1

LI NI U

Cun sch Hp cht hu c hidrocacbon c bin son theo ni dung ca
chng trnh o to h chnh quy mn hc ny bc i hc v cao ng c
ging dy trong nhiu nm trng i hc S phm i hc Nng.
Ni dung cun sch gm c 4 chng: Hidrocacbon no; Hidrocacbon khng
no; Hidrocacbon thm; Hidrocacbon thin nhin. Sau mi chng c mt s cu hi,
bi tp cho sinh vin t gii nhm cng c thm cc kin thc v l thuyt.
Cun sch l ti liu hc tp cho sinh vin cc chuyn ngnh ha hc s phm,
ha dc, ha sinh mi trng; lm ti liu tham kho cho cn b lm cng tc
ging dy, nghin cu khoa hc, cho cc hc vin cao hc, nghin cu sinh cc chuyn
ngnh ha hc.
Trong qu trnh bin son chc chn cn nhiu thiu st cha tht lm hi lng
bn c; Chng ti rt mong nhn c nhng kin ng gp hon thin hn.

Tc gi
















2


CHNG 1. HIROCACBON NO

Hirocacbon l tn chung ca tt c cc hp cht hu c m thnh phn phn t
ch cha hai loi nguyn t l cacbon v hiro. Hirocacbon l nhng hp cht hu c
n gin nht.
Da trn c s cu to ho hc, c th phn hirocacbon thnh nhng loi sau:
- Khi mch hirocacbon l mch h, ta c cc loi hirocacbon no (ankan),
hirocacbon cha no cha cc lin kt i (anken), hidrocacbon cha no cha cc lin
kt ba (ankin).
- Khi mch hirocacbon l mch vng, ta c cc loi hirocacbon vng no
(xyclo ankan), hirocacbon cha no cha lin kt ba (xyclo ankin), hp cht thm
cha nhn benzen trong phn t (aren).

1.1. Ankan, gii thiu metan
1.1.1. Dy ng ng metan, ng phn
1) Dy ng ng metan
Ankan thuc loi hirocacbon mch h, trong phn t ch c cc lin kt CC,
CH nn gi l hirocacbon no hay cn gi l parafin (do c t i lc trong cc phn
ng ho hc).

Cng thc chung l: C
n
H
2n+2
hay H(CH
2
)
n
H.
Khi n = 1, l hirocacbon n gin nht: CH
4
c gi l metan.
n = 2: ta c etan C
2
H
6
.
n = 3: propan C
3
H
8

n = 4: butan C
4
H
10
.

Nh vy, mi khi tng n thm mt n v, ta c mt hirocacbon no mi ch
khc cht ng trc mt nhm CH
2
gi l nhm metylen.
Ton b cc hirocacbon no mch h khc nhau trong thnh phn phn t bi
mt bi s cc nhm metylen hp thnh dy ng ng ca metan.

2) ng phn
a)Cu trc ca ankan
-Cng thc phng:
Trong phn t ankan, cc nguyn t cacbon u c lai ho sp
3
nn phn t c
biu din bng ng ziczc.

H
3
C
H
2
C
C
H
2
C H
3
H
3
C
H
2
C
C
H
2
H
2
C
C H
3


n gin, ngi ta ch biu din mch cacbon bng ng zizc, n cc nguyn
t cacbon gc cn hiro khng c biu din.
3




C H
3
C H
2
C H
2
C H
2
C H
2
C H
2
C H
3
n _ h e p t a n


Cc ankan c nhnh cng c biu din tng t.


2 , 2 _ d i m e t y l h e p t a n
3 e t y l h e c x a n


Nu cc nhm th khng phi l hirocacbon phi ghi r.

C l
C l C l
2 _ c l o _ 3 _ m e t y l b u t a n
2 , 2 _ d i c l o p e n t a n


- Cng thc khng gian:
Cu trc khng gian gy ra bi cu trc t din ca cacbon, c biu din theo
hnh t din.
C
H
H
H
H
C


Nu 4 nhm th u ging nhau ta c hnh t din u, nu cc nhm th khc nhau
th hnh t din s lch.

b)ng phn
- ng phn cu to:
Ankan c ng phn cu to l ng phn mch cacbon. Bt u t butan C
4
H
10
l
xut hin ng phn v mch cacbon

H
3
C
H
2
C
H
2
C C H
3
H
3
C
H
C C H
3
C H
3
n _ b u t a n i z o b u t a n

Khi s nguyn t cacbon tng th s ng phn tng ln rt nhanh.
4



S nguyn t cacbon: 1 2 3 4 5 6 7 8
S ng phn: 1 1 1 2 3 6 9 18

- ng phn cu dng:
Ngoi cc ng phn cu to trn, ankan c ng phn cu dng l do kh nng
quay xung quanh lin kt
C-C
. Cc ng phn cu dng thng c biu din m
hnh lp th: phi cnh v newman.
Do kh nng quay xung quanh lin kt CC vi cc gc quay khc nhau nn c v
s ng phn. Song ngi ta ch quan tm ti hai dng: ng phn che khut c nng
lng cao nht v ng phn xen k c nng lng thp nht.
-Cng thc phi cnh: biu din s phn b nhm th hai nguyn t cacbon
chn theo hng ng cho t tri sang phi.


C H
3
H
H
C H
3
H
C H
3
H
H
H
C H
3
H
H


Nu cc nhm th trng nhau ta c dng che khut, nu nhm th sau nm gia hai
nhm th trc ta c dng xen k.
- Cng thc chiu Newman: phn t c nhn dc theo lin kt CC. Cacbon sau
che khut cacbon trc biu din bng ng trn cn cacbon trc l giao im ca
cc nhm th. Cc nhm th trng nhau l che khut, cn cc nhm th gia gc ca
nhau gi l xen k hay km hm.


C H
3
H
3
C
H
H
H
H
C H
3
C H
3
H
H
H
H


1.1.2. Danh php
-Bn cht u dy ng ng mang tn gi c tnh cht lch s:

CH
4
: metan C
2
H
6
: etan
C
3
H
8
: propan C
4
H
10
: butan.
-T ng ng th 5 tr i, tn mi cht xut pht t tn ch s Hilp tng ng +
an:
5


C
5
H
12
: pentan C
6
H
14
: hecxan
C
7
H
16
: heptan C
8
H
18
: octan
C
9
H
20
: nonan C
10
H
22
: ecan

-Tn gc: nu bt i mt nguyn t hiro t mi phn t ankan ta s thu c mt
gc hirocacbon no tng ng gi chung l ankyl. Tn c th ca mi gc xut pht t
tn ca ankan tng ng nhng i ui an thnh ui yl.

CH
3
: metyl C
2
H
5
: etyl.

2) Danh php hp l
- Chn nguyn t cacbon c bc cao nht trong cu to phn t lm cacbon trung
tm mang tn mtan. Ln lt gi tn cc gc chung quanh nguyn t cacbon , gc
nh trc, gc ln sau v cui cng l mtan.


H
3
C
H
C C H
3
C H
3
T r i m e t y l m e t a n
H
3
C
H
C
H
2
C
H
2
C C H
3
C
2
H
5
m e t y l e t y l - n - p r o p y l m e t a n


-i khi, c th chn nguyn t cacbon trung tm mtan khng nht thit phi l
nguyn t cacbon c bc cao nht.

C H
H
2
C C H
H
3
C
H
3
C
C H
3
C H
3
d i i z o p r o p y l m e t a n


Do , cch gi hp l i vi hyrocacbon no cn gi l danh php mtan.
-Trng hp c bit, c th chn hai nguyn t cacbon lin nhau lm trung tm
etan gi tn mt hirocacbon no.


H
3
C C H
3
C H
3
C H
3
C H
3
C H
3
h e c x a m e t y l e t a n


3) Danh php quc t IUPAC
gi tn ankan, danh php IUPAC ra mt s nguyn tc sau:
- Gi nguyn tn gi cc ankan thng khng phn nhnh theo cc tn gi lch s v
tn gi xut pht t ch Hilp.
6


- Gi nguyn tn gi mt s ankan c cu to izo hoc neo nh mt s ankan sau
y:
(CH
3
)CHCH
3
: izo butan
(CH
3
)
2
CHCH
2
CH
3
: izo pentan
(CH
3
)
4
C: neopentan
(CH
3
)
2
CHCH
2
CH
2
CH
3
: izo hecxan

- i vi ankan phn nhnh, chn mch chnh l mch cacbon di nht.
- nh s th t cacbon trong mch chnh sao cho tng s ch v tr cc mch nhnh
l nh nht v phi theo th t tng dn hay gim dn t u ny n u kia. Cc s
trong mt dy c coi l nh nht khi trong dy c s u tin nh hn so vi s
tng ng trong dy kia.
Nguyn tc ny c p dng khng ph thuc vo bn cht cc nhm th.
-Trong mch nhnh li c nhnh nh th cng phi nh s th t trong mch nhnh
bt u t nguyn t cacbon dnh vo mch chnh.

H
3
C
H
2
C
H
2
C
H
2
C
H
2
C
H
2
C C
H
H
2
C
H
C
H
2
C
H
2
C
H
2
C C H
3
1
2 3 4 5 6
7
8 9
1 0
1 1 1 2
1 3
C H
H
3
C C H
3
H
C H
3
C
H
2
C
H
2
C
H
2
C C H
3
5 4 3
2 1
5 _ i z o p r o p y l _ 7 ( 1 , 2 _ d i m e t y l p e n t y l ) t r i d e c a n


-Khi gi tn ankan phn nhnh, c th gi tn cc nhnh theo trt t A, B, C hoc
theo trt t tng dn tnh phc tp ca nhnh, cui cng l tn ankan ng vi mch
chnh.

1.1.3. Tnh cht vt l
Trong phn t ankan gm nhng lin kt khng phn cc, s phn b ca in tch
l i xng. Do , tng cc mmen phn cc bng 0. Vy, tng tc quan trng trong
ankan l tng tc Vanderwaals. Tng tc ny ph thuc vo din tch tip xc v
khong cch gia hai phn t. V vy, khi phn t cng ln th lc tng tc cng
mnh. Thc nghim chng minh rng nhit si v nhit nng chy ca ankan
tng theo chiu tng ca s nguyn t cacbon trong phn t. Theo kinh nghim, t mt
s ankan thp, nu mch ca phn t tng thm mt nguyn t cacbon th nhit si
ca ankan tng ln 20 n 30
0
C.
Trong thc t, 4 ankan u t mtan n butan l nhng cht kh nhit thng.
13 ankan tip theo (C
5
n C
17
) l cht lng, t ankan C
18
tr i l cht rn. Cc ankan
c mch cacbon phn nhnh c im si thp hn cc ankan ng phn c mch
cacbon khng phn nhnh. S nhnh cng nhiu th nhit si cng thp v nht l
khi cc nhnh cng mt nguyn t cacbon.
Ankan khng phn cc nn tan tt trong dung mi khng phn cc, khng tan trong
nc. Ankan thp d tan trong ru, cc thnh phn cao kh tan. Ankan d tan trong
te, trong cc hiocacbon khc v trong cc dn xut halogen.
7


T trng ca cc ankan tng ln khi phn t lng tng nhng khng qu 0,8 g/cm
3
.
trng thi kt tinh, mch cacbon ca cc ankan thng c dng zizc, cc nguyn
t cacbon nm trn mt mt phng cn gc ho tr th gn bng gc ca t din u.
Trong tinh th, cc phn t ny sp xp song song thnh tng b cch nhau mt
khong cch nh.

1.1.4. Cc phng php iu ch
Thng thng, cc phng php iu ch cc hp cht hu c c chia lm 2 loi:
phng php cng nghip v phng php phng th nghim. Hai phng php ny c
nhng im khc nhau sau y:
- Phng php cng nghip: thng thu nhn mt khi lng ln hp cht vi gi
thnh thp trong khi phng php phng th nghim cn tng hp mt vi trm
gam, mt vi gam hoc t hn v khng quan tm ti gi thnh sn phm v thi gian
tng hp.
- Phng php cng nghip thng chn cch thu nhn hp cht sao cho tin li v
vic tn dng dy chuyn cng ngh v thit b. V vy, phng php cng nghip ch
c ngha vi cch thu nhn mt hp cht nht nh. Tri li, phng php phng th
nghim quan tm n vic s dng cho c mt lot hp cht cng loi vi nhau.

1) Phng php cng nghip.
a) Ngun thu nhn chnh ca ankan l kh thin nhin v du m
Tri qua hng triu nm, cc cht hu c phc tp ca ng vt v thc vt
chuyn ho thnh hn hp ankan c thnh phn t 1 cho n 30, 40 nguyn t cacbon.
Kh thin ch cha nhng ankan nh (c phn t lng b) 75% mtan, 15% tan,
5% propan, phn cn li l cc ankan cao hn v nhiu cht khc. Du m c thnh
phn ankan phc tp hn. Bng phng php chng ct du m, ngi ta tch loi
ankan ra khi nhau v c ng dng rng ri trong i sng cng nh cng nghip.
Cc ankan l kh c s dng lm cht t, ankan lng dng lm nhin liu cho
cc ng c, ankan cao hn dng du dng lm cht bi trn, nha ng, cc ankan
rn dng lm nn.
T cc ankan cao, c th iu ch ankan thp bng cc phn ng cracking.

C
n
H
2 n + 2
C r a c k i n g
C
m
H
2 m + 2
+ C
( n - m )
H
2 ( n - m )


b)Phng php tng hp t cacbon oxit CO
Cho hn hp cacbon oxit v H
2
nhit 200
0
C v p sut cao i qua xc tc l Fe
(hay Co) th thu c hn hp ankan gm ch yu l cc ankan mch thng v mt t
ankan mch nhnh.

n C O + ( 2 n + 1 ) H
2
C
n
H
2 n + 2
+ n H
2
O

2) Phng php phng th nghim
a)Phng php tng hp khng thay i mch cacbon cht ban u
- Hyro ho anken v ankin.
8


C
n
H
2 n - 2
H
2
, P t ( P d , N i )
C
n
H
2 n + 2
C
n
H
2 n
H
2
, P t ( P d , N i )
C
n
H
2 n + 2


Trong thc t ngi ta hay dng Ni nhit trn 100
0
C
-Kh dn xut halogen bng kim loi trong mi trng axit.

RX + Zn + H
+
RH + Zn
2+
+ X
-

-Kh cc dn xut khc nhau ca hirocacbon nh cc dn xut halogen, ancol, c
th l c axit bng axit ioic nhit cao:

RX + 2HI RH + HX + I
2

RCOOH + 6HI RCH
3
+ 2H
2
O + 3I
2

Phn ng ny iu ch ankan c mch cacbon ln.
-Thu phn hp cht c kim hay kh ho cc dn xut halogen bng tc nhn
grinha RMgX:

C
n
H
2n+1
Br + Mg C
n
H
2n+1
MgBr
C
n
H
2n+1
MgBr + H
2
O C
n
H
2n+2
+ MgBr(OH)

b)Phng php lm gim mch cacbon ban u
Phng php kim nng chy hay phng php uma: ct khan mui kim hoc
kim th ca axit cacboxylic vi vi ti xt s thu c hirocacbon c mch cacbon
gim i mt nguyn t so vi axit cacboxylic.

RCOONa + NaOH RH + Na
2
CO
3

c)Phng php tng hp lm tng mch cacbon ban u
-Phn ng tng hp Vuyc (Wurtz):

2RX + 2Na RR + 2NaX

Nu dng hai loi dn xut halogen c gc khc nhau ta s thu c hn hp ba sn
phm:

3RX + 3RX + 6Na RR + RR + RR + 6NaX

- Phn ng in phn dung dch mui axit: phn ng Kolbe:

9


[ R C O O ]
-
N a
+
R C O O
.
- C O
2
R
.
+ C O
2
R
.
+ R
.
R R
a n o t
- e
- e
c a t o t
N a
.
H
2
O
N a O H + 1 / 2 H
2

Trong tt c cc phng php trn y, phng php hir ho anken c
ngha nht v phn ng tin hnh n gin (ch cn khuy anken vi hir p sut
va phi v mt lng xc tc nh ta s thu c mt ankan c khung cacbon ging
anken ban u), nguyn liu r v d thu nhn bng nhiu phng php khc nhau.
Kh ho hp cht c kim cng l mt phng php c ngha thc t ln v cc
ankyl halogenua d dng c thu nhn t cc hp cht khc. Tuy nhin, trong trng
hp yu cu iu ch mt cht no m c th s dng c hai phng php th nn
chn phn ng hir ho anken v n n gin v cho hiu sut phn ng cao hn.
Phn ng Vuyc ch c ngha iu ch hirocacbon i xng.
* Mt s phng php iu ch mtan:
- T cacbua nhm:

Al
4
C
3
+ 12H
2
O 4Al(OH)
3
+ 3CH
4

-T sunfua cacbon:

CS
2
+ 2H
2
S + 8Cu CH
4
+ 4Cu
2
S
-T axtat natri:

CH
3
COONa + NaOH CH
4
+ Na
2
CO
3

1.1.5. Tnh cht ho hc ca ankan
Trong cu to phn t ca ankan, ch c hai loi lin kt CC v CH. l
nhng lin kt cng ho tr khng phn cc. Kh nng phn ng ca cc lin kt ny
ni chung l rt km. Do , cc ankan th hin mt phn no tr v mt ho hc
nn trc y ngi ta gi ankan l parafin (t i lc ho hc). Tuy nhin, ankan ch
tr i vi cc tc nhn ion nh cc baz, cc axit v c trung tnh v cc cht oxy ho
trong dung dch nc. Tri li, chng phn ng tng i d dng vi nguyn t v
cc gc t do v s phn ct d li cc lin kt CH i hi mt nng lng qu ln, s
phn ct lin kt CH c trng bi s phn ct ng li. V ankan khng c kh nng
kt hp vi hir nn c gi l hirocacbon no.
1) Phn ng thuc lin kt CH, phn ng th
a) Phn ng halogen ho
- Nghin cu phn ng clo ho metan:
10


Hn hp kh metan v clo di tc dng ca nh sng hoc nhit (250400
0
C)
th chng s tc dng mnh lit vi nhau to thnh phn t metyl clorua. Metyl clorua
c th tip tc tham gia phn ng clo ho to metylen clorua. Phn ng c th tip tc
xy ra to triclometan (clorofoc) hoc tetraclo metan (cacbon tetraclorua).

CH
4
+ Cl
2
CH
3
Cl + HCl
CH
3
Cl + Cl
2
CH
2
Cl
2
+ HCl
CH
2
Cl
2
+ Cl
2
CHCl
3
+ HCl
CHCl
3
+ Cl
2
CCl
4
+ HCl

Nh vy, khi clo ho metan c nh sng xc tc s thu c hn hp 4 sn phm:
mtyl clorua, metylen clorua, clorofoc v tetraclo metan. C 4 cht ny u l nhng
cht c ng dng v mt k thut.
Ta nhn thy phn ng clo ho metan xy ra vi nhng c tnh: khng tc dng
vi nhau trong bng ti v nhit thp. Phn ng d dng xy ra trong bng ti
nhit cao (250
0
C) hoc nhit thng khi c chiu sng. Nu phn ng c
khi mo bng nh sng th c hng ngn phn t metyl clorua c to thnh khi
phn ng hp th mt photon nh sng. Khi c mt lng nh oxy th tc phn ng
s gim i mt khong thi gian v thi gian ny ph thuc vo lng oxy c trong
phn ng.
V phn ng xy ra vi iu kin c nh sng v nhit, halogen hp th nng lng
ny ch c th phn li ng li thnh gc X

, khng c kh nng phn li thnh ion v

phi cn mt nng lng cao hn. Do , phn ng xy ra theo c ch gc S
R

nguyn t cacbon no.

b) Phn ng nitro ho
Ankan khng phn ng vi axit nitric c nhit thng, khi nng nhit ln,
HNO
3
c s oxy ho chm cc ankan b gy lin kt CC v cho sn phm chnh l
cc axit cacboxylic.
Tuy nhin, dng axit nitric long v tin hnh phn ng nht cao, p sut cao
th c th nitro ho c ankan:

R H + H N O
3
1 1 0 - 1 4 0
0
C , P c a o
R N O
2
+ H
2
O


Phn ng cng xy ra theo c ch gc thng km theo sn phm oxy ho ct
mch, do ngoi sn phm th gi nguyn mch cacbon cn c sn phm mch ngn
hn

C H
3
C H
2
C H
3
+ H N O
3
C H
3
C H
2
C H
2
N O
2
+ ( C H
3
)
2
N O
2
+ C H
3
C H
2
N O
2
+ C H
3
N O
2
1 5 %
4 0 % 1 0 % 2 5 %

c) Phn ng sunfo ho
11


Tng t nh axit nitric, cc ankan khng phn ng vi axit sunfonic c nhit
thng. Cc ankan khi un nng vi axit sunfuric bc khi (oleum 15% SO
3
t do) d
b sunfo ho trc tip to ankansunfo axit u tin cacbon bc 3:


H
3
C
H
C
H
2
C C H
3
+ H
2
S O
4
C H
3
H
3
C C
H
2
C C H
3
+ H
2
O
C H
3
C H
3


Trong thc t, ngi ta thng khng dng sunfo ho trc tip bng H
2
SO
4
c m
hay dng phn ng sunfo clo ho hoc sunfo oxi ho.

d) Phn ng sunfo- clo ho
Khi cho SO
2
v clo cng tc dng ln ankan 20 30
0
C c chiu sng bng n t
ngoi hoc c mt cht khi mo l peoxit ta s thu c sn phm l ankan.


C l
2
A S
2 C l
.
R H + C l
2
R
.
+ H C l
R
.
+ S O
2
R S O
2
.
R S O
2
.
+ C l
2 R
O
2
S C l + C l
.


trnh to ra nhng sn phm ph (RCl) ta dng d SO
2
v thng dng t l
l 2:1. Khi thu phn dn xut ankansunfo clorua c mch cacbon kh di (hn 10
nguyn t C) bng NaOH s thu c mui sunfonat l nhng cht c tc dng ty ra
tt. V vy, phn ng sunfo clo ho ankan c ngha thc t l tng hp cc cht
ty ra:


R
O
2
S C l + 2 N a O H R S O
3
N a + H
2
O + N a C l


e) Phn ng sunfo oxy ho
Khi cho SO
2
v oxi vi t l 1:1 tc dng vi ankan c mch 68 nguyn t cacbon
nhit 2030
0
C ng thi chiu sng bng n t ngoi s thu c sunfoaxxit.


R H + S O
2
+ O
2 R S O
3
H


S sunfo oxi ho cng c th tin hnh khi c mt anhydric axetic nhng phi tin
hnh nhit 45
0
C v di p sut 1518 at.

2) Cc phn ng thuc lin kt CC
a)Phn ng t chy v oxy ho
12


nhit thng, oxi v cc cht oxi ho khc (c nhng cht oxi ho mnh nh
axit crmic v kali pemanganat) u khng tc dng vi hirocacbon no.
nhit cao, hirocacbon no chy trong khng kh to nhit v pht sng.
Phng trnh phn ng t chy hon ton nh sau:

2 C
n
H
2 n + 2
+ ( 3 n + 1 ) O
2
2 n C O
2
+ 2 ( n + 1 ) H
2
O + 2 Q


Phn ng t chy l phn ng quan trng ca ankan, thng xy ra vi mt hn
hp ankan, sn phm ca phn ng khng quan trng song yu t quan trng l nhit
nng nn ankan c s dng lm nhin liu rt tt.
Tuy nhin, trong nhng iu kin thch hp, c th thc hin phn ng oxi ho
ankan bng oxi khng kh hoc oxi nguyn cht s thu c cc hp cht hu c c
cha oxi nh ancol, anehyt, axit cacboxylic v.v V d, khi oxi ho metan bng
khng kh di p sut thng nhit 400600
0
C vi xc tc l nit oxit s thu
c andehyt formic, cn p sut 150 at, nhit 400
0
C s thu c ch yu l
metanol. Oxy ho cc ankan cao th rn bng khng kh 100130
0
C c mt 0,3%
KMnO
4
s xy ra s b gy lin kt CC v cho cc axit bo cao. Cc phn ng trn
u p dng trong cng nghip ch b m nhn to, x phng v.v
b)Phn ng nhit phn v cracking
Cc ankan tng i bn vng vi nhit cho ti khong 300400
0
C (metan c th
bn ti 900
0
C). Trn khong nhit ny, cc lin kt CC trong phn t c th b b
gy to thnh nhng phn t nh hn. 1000
0
C, cc ankan b phn hu thnh C v H.
Tu thuc vo nhit phn ng ta phn bit: phn ng nhit phn (trn 650
0
C) v
phn ng cracking (di 650
0
C).
Cracking (crack: b gy) c 2 phng php: cracking nhit v cracking xc tc:
+ Cracking nhit: tin hnh trong pha kh nhit 600
0
C di p sut thng
hoc trong pha lng 550
0
C v p sut vi chc atmostphere. Sn phm l hn hp
cc ankan v anken c mch ngn hn do nhiu phn ng xy ra ni tip nhau hoc
xy ra ng thi.
V d:
Cracking nhit hecxaecan C
16
H
34
:
C
16
H
34
C
8
H
18
+ C
8
H
16
C
8
H
18
C
4
H
10
+ C
4
H
8

C
4
H
10
C
2
H
6
+ C
2
H
4

C
4
H
10
H
2
+ C
4
H
8

Vi metan, khi khng c xc tc c th bn ti nhit 900
0
C. Khi c xc tc,
nhit ny xy ra phn ng:

C H
4
C + 2 H
2


Khi CH
4
i qua thch anh nung ti 10001200
0
C trong thi gian ngn 0,3s
s thu c sn phm: axetilen, tilen, butaien, nhit ln hn 1200
0
C ch thu
c l axetilen:
13



2 C H
4
C
2
H
2
+ 3 H
2
- 9 1 k c a l


+ Cracking xc tc: c th tin hnh nhit thp hn cracking nhit
(450500
0
C) vn tc phn ng nhanh hn v sn phm tt hn (xng). Xc tc thng
dng: cc loi nhm silicat thin nhin hoc tng hp nh zelithe hoc
aluminosilicat.
Trong phn ng craking xc tc, bn cnh phn ng b gy mch cn xy ra s
ng phn ho chuyn cc hirocacbon mch thng thnh cu to phn nhnh. Sn
phm thu c c lng hirocacbon cha no t hn cracking nhit.

c)Phn ng vi iazo metan v keten

R C H + C H
2
N
2 R C
H
2
C H + N
2

V d:

H
3
C
H
2
C
H
2
C
H
2
C C H
3
+ C H
2
N
2
A S
H
3
C
H
2
C
H
2
C
H
2
C
H
2
C C H
3
+ N
2
+ H
3
C
H
C
H
2
C
C H
3
H
2
C C H
3
H
3
C
H
2
C
H
C
H
2
C C H
3
C H
3


1.1.6. Cht tiu biu CH
4

Thnh phn chnh ca kh thin nhin 9799% metan. Metan cng c trong kh du
m (3985%) hay trong cc m than . Hn hp metan v khng kh khi gp la s
n rt mnh. Metan cng c to thnh do s phn hu ym kh cc b ng, thc vt
di tc dng ca vi khun hoc c th c to thnh khi kh kh cacbonic:

CO
2
+ 4H
2
CH
4
+ 2H
2
O

1) Cc phng php iu ch metan
a) Tng hp t C v H
Bt tia la in gia hai in cc cacbon trong kh H
2
s to ra mt lng nh
metan cng vi hirocacbon khc nh etan, axetilen


C + 2 H
2
1 2 0 0
0
C H
4
( 1 , 2 5 % ) + i t e t a n + C
2
H
2

Khi tng p sut th s tng hiu sut thu CH
4
. Khi c mt xc tc v nhit thp
hn:

14


C + H
2
C H
4

300
0
C, cn bng hu nh dch chuyn sang phi (90% CH
4
) v 800
0
C cn bng
li dch chuyn sang tri (4,4% CH
4
).

b) Kh cacbon oxit v kh cacbonic
Cho hn hp kh gm cacbon oxit v hiro hoc cacbonic v hiro i qua xc tc
bt niken 250400
0
C:

CO + 3H
2
CH
4
+ H
2
O
CO
2
+ 4H
2
CH
4
+ 2H
2
O

c) Thu phn cacbua kim loi

C
3
Al
4
+ 12H
2
O 3CH
4
+ 4Al(OH)
3

Ngoi ra, c th thu phn cacbua kim loi khc nh: cacbua berili, thori, urani,
mangan.

d) i t cacbon isunfua v ng kim loi
Bng cch cho hn hp kh hiro sunfua, hi cacbon sunfua i qua Cu nung s
thu c kh mtan v ng I sunfua.

CS
2
+ 2H
2
S + 8Cu CH
4
+ 4Cu
2
S

e) i t axetat natri v vi ti xt
un nng hn hp axetat natri vi vi ti xt c th thu c kh CH
4
:

CH
3
COONa + NaOH CH
4
+ Na
2
CO
3

Phng php ny c th dng trong phng th nghim iu ch mt lng nh
CH
4
.
Ngoi ra, trong thc t, ngi ta c th iu ch CH
4
bng cch phn v rc trong
hm xy c np y kn.

2) Tnh cht v ng dng
Metan l mt kh khng mu, khng mi, t tan trong nc, chy vi ngn la mu
xanh nht v to nhiu nhit nn dng lm kh nhin liu.
t metan trong iu kin khng khng kh trong nhng thit b c bit s to
ra cacbon dng bt than mn.
CH
4
+ O
2
C + H
2
O
Bt than l nguyn liu quan trng dng lm cht n trong ch ho cao su.
Cho metan v hi nc i qua xc tc niken 850
0
C s thu c hn hp hiro v
cacbon oxit dng lm nguyn liu tng hp.
15



C H
4
C + 2 H
2


Cho hn hp sn phm i qua xc tc st oxit 400
0
C, CO s chuyn thnh CO
2
,
tch CO
2
thu c H
2
dng tng hp amnic.
Metan cng c dng lm nguyn liu tng hp axetilen, iu ch cc dn xut,
axit xianhiric.
Tnh cht ho hc ca metan c tm tt nh sau:

CH
3
Cl
metyl clorua
CH
2
Cl
2
metylen clorua
CHCl
3
clorofom
CCl
4
tetraclorua cacbon
CH
3
OH
HCHO
formandehyt
HCN
axit xyanhydric
C
H
2
NH
3
V
2
O
5
, 300
0
C
CH
4
Cl
2
O
2
NH
3
+ O
2


1.2. Phn ng th theo c ch gc: S
R
v kh nng phn ng
1.2.1. c im ca c ch gc S
R

Nt c trng ca cc hirocacbon no l tham gia phn ng theo c ch gc S
R
,
trong nguyn t hyro nh vo cacbon no c thay th bng halogen hay mt
nhm nguyn t khc. Quan trng hn c l phn ng halogen ho theo c ch gc.
Ngoi ra, cn c nhng phn ng th khc cng theo c ch S
R
nh nitro ho, sunfo
clo ho, t oxy ho.
S cc phn ng theo c ch gc t do (S
R
):

R H + X Y
R X + H Y


XY: halogen, SO
2
Cl
2
, R
3
COCl, CCl
3
Br, CF
3
I.

Phn ng xy ra khi c chiu sng hoc c mt cht khi mo l cc peoxit.
1.2.2. C ch phn ng
Phn ng th theo c ch gc S
R
cn c gi l phn ng dy chuyn (hay
phn ng chui) l phn ng xy ra qua nhiu giai on m trong giai on ny lm
sinh ra nhng trung tm c kh nng phn ng mnh gy ra cc phn ng tip theo.
y cng l phn ng c trng cho ankan.
- Giai on to gc giai on khi mo:
ru etylic
mc in, ch ho cao su
16


Cl
2
AS hay 200-400
0
C
2Cl
.
(1)


giai on (1) xy ra do s ph v phn t clo thnh gc t do do cn mt
nng lng ph v lin kt. Nng lng c cung cp bng s chiu sng hay
s un nng. Gc t do Cl

cng nh cc gc t do khc c kh nng phn ng rt
mnh v do n tm cch kt hp vi mt e
-
lm y lp 8 e ca mnh. t
c iu , gc Cl

cn phi v chm vi cc nguyn t hay cc phn t khc. S va

chm vi gc Cl

khc c xc sut rt b v nng ca chng mt thi im bt k

rt t. S va chm gia gc t do Cl

vi mt phn t clo ch dn ti s thay i mt

gc t do ny bng mt gc t do khc:

Cl

+ Cl
2
Cl:Cl + Cl


-Giai on pht trin mch:

Cl
.
+ RH
R
.
+ HCl (2)
R
.
+ X
2
RCl + Cl
.
(3)


Nguyn t clo vi mt electron t do hot ng nh mt gc t do, tn cng vo
lin kt CH ca ankan mi dn n vic to gc t do mi (giai on 2). Gc R
.
mi
sinh ra cng tng t nh gc clo trc y, tm cch lm y lp e
-
ngoi cng bng
s va chm vi cc phn t khc hoc nguyn t khc. S va chm ny ch c ngha
vi Cl
2
v to thnh ankyl clorua v Cl

. Gc t do mi sinh ra ny li tham gia vo

phn ng (2), tip theo l phn ng (3). Qu trnh lp i lp li nhiu ln to ra nhiu
phn t ankyl clorua.
Nguyn t clo c th tn cng vo phn t ankyl clorua mi to thnh, cho mt gc
t do khc l
.
RCl ri thnh ankyl diclorua:

RHCl + Cl
.

.
RCl + HCl
.
RCl + Cl:Cl RCl
2
+ Cl
.

Phn ng c th tip din cho n khi to thnh sn phm th hon ton cc nguyn
t hidro ca ankan.
- Giai on tt mch:
Tuy nhin, cc qu trnh trn y xy ra khng phi l vnh cu v s va chm ca
cc gc t do vi nhau, tuy rt t nhng vn c th xy ra v c th dn n s mt i
ca gc t do:
X
.
+ X
.
X
2
( 4 )
R
.
+ R
.
R
2
( 5 )
R
.
+ X
.
R X ( 6 )

17



Trong phn ng trn, giai on quyt nh tc phn ng l giai on hnh
thnh gc R

(xy ra rt chm). Gc R

l mt tiu phn trung gian c hnh thnh

qua trng thi chuyn tip: [RHX]
*
.
Trng thi chuyn tip ny c th chuyn v cht ban u hay v pha sn
phm. Giai on ny l thun nghch.
Giai on tip theo, gc R

tng tc vi X
2
qua trng thi chuyn tip:
[R

XX]
*

S chuyn t R

n trng thi chuyn tip l thu nhit nhng t trng thi

chuyn tip n sn phm l to nhit mnh. Do , giai on ny l to nhit.
Giai on tt mch cng l giai on to nhit.

1.2.3. nh hng ca cu to n phn ng th S
R

Trong phn ng vi propan ca clo, gc n-propyl c to thnh khi tch i 1
hydro bc , izo propyl c to thnh khi tch i mt H bc 2. Ta nhn thy rng trong
phn t propan c 6 H bc 1 v 2 H bc 2 nn xc sut va chm ca Cl

vi cc loi
hiro ny l 6:2 (3:1) c ngha l n-propyl clorua: izo-propyl clorua l 3:1. Nhng
trong thc t t l ny l 1:1 (45:55). iu ny c ngha l kh nng phn ng ca
izopropan gp 3 ln n-propan. V ch c gii thch bng nng lng hot ho E
a

dng tch H bc 3 nh hn rt nhiu so vi H bc 1. V ngi ta i n kt lun
rng kh nng tham gia phn ng halogen ho ca cac nguyn t H c thay i theo
dy sau:
H bc 1 < H bc 2 < H bc 3

Kh nng tham gia phn ng khc nhau ca cc loi H trong phn ng halogen ho
c gii thch da vo trng thi nng lng v bn ca cc gc t do trung gian
hnh thnh. V phn ng theo c ch gc nn t izopentan hnh thnh cc gc t do:

H
3
C
CH
H
3
C
C CH
2
.
C C
.
C H
H
H
H
3
C
H
3
C
C
.
C CH
3
C
C
H
H
H
H
H
H
H
H
H
H
H
H


Phn tch so snh v hiu ng siu lin hp gia cc electron ca cc lin kt C
H vi electron t do trong 3 gc t do trn v hiu ng +I ca cc nhm th, c th
a ra nhn xt: trng thi nng lng ca gc III l thp nht (c s lin hp ca 8
electron vi electron t do) nn bn nht v d hnh thnh nht, sau n gc II (c s
lin hp ca 4 electron vi electron t do) v cui cng l gc I (ch c s lin hp
ca 2 electron vi electron t do). Do ta c trt t sp xp v bn v kh nng
hnh thnh ca cc gc t do nh sau: bc 3 > bc hai > bc nht > CH
3
.

S ph thuc ca kh nng phn ng S
R
vo bn ca gc cacbo t do trung
gian biu hin rt r cc ng ng ca benzen. Phn ng halogen ho toluen xy ra
18


d hn metan rt nhiu. Trong etyl benzen, izpropyl benzen v cc ankyl benzen
khc, nguyn t hiro v tr anpha thng c kh nng phn ng cao nht.

C
6
H
5
C H
2
H
C
6
H
5
C C H
2
H H
C H
3
1 , 0
4 , 0 0 , 3 1


l do nh hng lin hp +C ca gc phenyl lm tng bn ca gc t do
sinh ra bng cch ngt nguyn t hiro anpha. nh hng ca nhm th trong trong
vng benzen phn t toluen n kh nng phn ng clo ho (th S
R
) tun theo phng
trnh Hammet (t hp vi
-
hoc
+
) vi 76 , 0 = . Du (-) chng t nhm th
y electron nhn thm lm tng kh nng phn ng v nguyn t halogen c tnh
cht electronphin s tn cng vo v tr giu mt electron hn.
V vy, trong phn ng halogen ho cc dn xut halogen ca ankan (cc
halogen c hiu ng I) nhng nguyn t hyro cng gn nhm th halogen th kh
nng phn ng cng gim.
Quy lut ny c tnh tng qut v p dng c cho c cc axit cacbxylic v
dn xut ca chng.

1.2.4. Ho hc lp th ca phn ng S
R

Trong phn ng clo ho butan, c sn phm thu c l sec-butyl clorua c
nguyn t C
2
bt i:
Tuy nhin, thc nghim chng minh rng sec-butyl clorua l mt hp cht
khng quang hot. Bi v, giai on 2, gc Cl

tch i mt nguyn t H bc 2 to
Sec-butyl radical. Nguyn t cacbon trong gc t do lc ny c lai ho sp
2
. Giai on
tip theo l hnh thnh lin kt CCl, gc Cl

c th tn cng t hai pha ca mt

phng cha obitan lai ho sp
2
. Xc sut tn cng vo hai pha ca mt phng nh nhau
nn to ra mt lng bng nhau cc sn phm quay tri v quay phi do gc quay
ca nh sng phn cc b trit tiu nn hn hp sn phm thu c khng quang hot
v ta gi l bin th Raxemic.

1.2.5. nh hng ca tc nhn
Phn ng clo ho nu tin hnh qu mnh lit c th xy ra n. trnh iu
, ngi ta thng cho d ankan hoc pha long clo bng nit hoc cho hn kh vo
dung mi lng.
Phn ng brm ho ankan tin hnh tng t clo ho nhng thc t yu hn v
t c p dng hn.
Phn ng iot ho ankan l qu trnh thun nghch:

R H + I
2
3 H
2
O + 3 I
2


19


Trong iu kin thng, phn ng c khuynh hng chuyn dch v pha tri ti
to ankan. Mun cho phn ng chuyn dch v pha phi to ra dn xut iot cn dng
cc cht oxy ho mnh nh axit iodic HIO
3
tch HI ra khi hn hp phn ng:

5 H I + H I O
3
3 H
2
O + 3 I
2


Phn ng flo ho ankan b hn ch do phn ng xy ra mnh lit gii phng HF
v CF
4
v cc sn phm phn hu khc v thng kt thc bng s n. Nguyn nhn
c bn ca phn ng th flo mnh lit l do nng lng to thnh ca HF v ca lin
kt CF rt cao.

C H
+ F
2
C F
+ H F + 1 0 3 k c a l / m o l


Nhit phn li lin kt CC bng 58,6 kcal/mol nn d lm phn hu cc
hirocacbon.

1.3. Xycloankan
L loi hirocacbon vng no. V c im cu to, n ging ankan ch trong
phn t ch c lin kt n CC v CH v n khc ch c cu to mch cacbon
l vng kn. Do c vng kn trong phn t nn ny sinh nhiu c im mi c bit l
phng din ho lp th.
Xycloankan bao gm cc loi cha mt vng hay nhiu vng. Loi mt vng no c
cng thc phn t chung l C
n
H
2n
(n3). Loi nhiu vng: c th l vng ri rc hay
vng ngng t. Cc vng gi l ngng t khi chng c mt hay nhiu cnh chung. Cc
xycloankan c nhiu vng ngng t c t l hiro t hn so vi loi mt vng nn c
cng thc phn t khc C
n
H
n.

1.3.1. Danh php
1) Xycloankan khng mang nhm th
Cc xycloankan khng mang nhm th c gi tn nh ankan tng ng (da trn
s cacbon trong vng) bng cch thm ch xyclo vo trc tn ankan. V d:
xycloheptan, xyclo octan.

2) Xyclo ankan c mang nhm th
C hai cch gi tn xyclo ankan c mang nhm th.
+ Cch 1: m s nguyn t C trong vng v trn nhm th ankyl ln nht. Nu s
nguyn t C trong vng tng ng hoc ln hn s nguyn t C trn nhm th th
coi hp cht l xycloankan c nhm th ankyl cn ngc li l ankan c mang nhm
th l xycloankyl.

20


C H
3
H
2
C
H
2
C
H
2
C C H
3
m e t y l c y c l o p e n t a n
1 - c y c l o p r o p y l b u t a n


-Vi xycloankan mang nhm th ankyl, C
1
c chn l cacbon mang nhm th,
cc nhm th cn li c nh s theo nguyn tc tng cc s th t l nh nht.

C H
3
C H
3
C H
3
C H
3
1
2
3
4
5
6
1
2
3
4
5
6
1 , 3 - d i m e t y l c y c l o h e c x a n
1 , 5 - d i m e t y l x y c l o h e c x a n ( s a i )
C
2
H
5
C
2
H
5
C H
3
C
2
H
5
C H
3
C H
3
H
3
C H
3
C
H
3
C
1
2
3
4
5
6
7
1
2
3
4
5 6
7
1
2
3
4
5
6
7
2 - e t y l - 1 , 4 - d i m e t y l c y c l o h e p t a n 1 - e t y l - 2 , 6 - d i m e t y l c y c l o h e p t a n
6 - e t y l - 1 , 5 d i m e t y l c y c l o h e p t a n
( s a i )
( s a i )


-Khi c nhiu nhm th ankyl khc nhau c cng cch nh s th s u tin theo
mu th t A, B, C.

C H
3
C
2
H
5
C H
3
C
2
H
5
1
5
4
3
2
1
2
3
4
5
2 - e t y l - 1 - m e t y l c y c l o p e n t a n
1 - e t y l - 2 - m e t y l c y c l o p e n t a n
( s a i )


-Nu c s hin din ca halogen, coi chng nh nhm ankyl trong cch nh s
th t.
C H
3
B r
C H
3
B r
1
2
2
1
1 - b r o m o - 2 - m e t y l c y c l o b u t a n
1 - m e t y l - 2 - b r o m o c y c l o b u t a n ( s a i )


3) Danh php cis trans trong xycloankan
21


Nhng xycloankan c t hai nhm th tr ln, cu hnh tng i ca hai nhm th
ny i vi nhau c xc nh bng danh php cis trans trc tn ca xycloankan.


M e
H
M e
H
B r
H
H
E t
C i s - 1 , 3 - d i m e t y l x y c l o b u t a n
t r a n s - 1 - b r o m o - 3 - e t y l x y c l o p e n t a n


4) Danh php xycloankan nhiu vng
Mt s polixycloankan c gi tn thng thng.

d e c a l i n
N o r b o r n a n
b a s k e t a n
c u b a n


Gi tn theo IUPAC:
-Xc nh s vng: s vng c suy ra t s ni i CC phi ct t thu c
hp cht mch h. Lc danh php s bt u bng bixyclo, trixyclo, tetra

b i x y c l o
t r i x y c l o
t e t r a x y c l o


- Xc nh s vng cacbon nm gia hai u cu (im ni cc vng). S
nguyn t cacbon ny c vit gia hai du ngoc [] cch nhau bi du chm v
c xp theo th t t ln n nh. i khi, bn phi cu, ngi ta thm hai con s
cch nhau bi du phy pha bn trn ca nhng con s ny xc nh v tr cacbon
ti hai u ca cu ny.
- nh s cacbon: cc u cu c nh s th t nh nht. Vng ln c nh
s u tin. S nguyn t C c trong hp cht c vit lin sau du ngoc theo
cchgi tn hp cht ankan. Cc cacbon mang nhm th trn h thng vng cng c
gi tn hp cht ankan. Cc cacbon mang nhm th trn h thng vng cng c
nh s th t theo quy tc nh nht nhng u tin sau cc nguyn t C u cu.

22


b i x y c l o [ 3 . 1 . 0 ] h e c x a n
1
2
3
4
5
6 1
2
3
4
5
6 7
8 C l
B r
1
2
3
4
8
5
7
6
1
2
3
4
5
6
7
8
9
1 0
1
2
3
4
7
5
6
1
2
3
4
5
6
7
8
9
1 0
1 1
1 2
1 3
8 - c l o r o b i x y c l o [ 4 . 2 . 0 ] o c t a n
b i x y c l o [ 2 . 2 . 2 ] o c t a n
4 - b r o m o - 9 - m e t y l t r i x y c l o [ 5 . 3 . 0
1 , 7
. 0
2 , 6
] d e c a n
t r i x y c l o [ 2 . 2 . 1 . 0
2 , 6
] h e p t a n
t e t r a x y c l o [ 7 . 3 . 1 . 0
3 , 1 3
. 0
7 , 1 3
] t r i d e c a n


1.3.2. ng phn
Mt hp cht vng gm cc loi ng phn sau y:
1) ng phn do s thay i s nguyn t cacbon ca vng

V d: C
5
H
10

C H
3 C H
3
C H
3


2) ng phn do s thay i cu to ca mch nhnh

C
2
H
5
C
2
H
5
C H
3
C
H
C H
3
C H
3
H
3
C
C H
3


3) ng phn do s sp xp cc nhm th khc nhau cc v tr khc nhau
23


H
3
C C H
3
C H
3
C H
3
R
R '
R R '
R
R '


4) ng phn hnh hc

C H
3
C H
3
C H
3
C H
3
t r a n s
c i s


5) ng phn quang hc
Xut hin khi trong phn t c cacbon bt i.
R
H
R
H


6) ng phn cu dng



1.3.3. Cc phng php iu ch
1) Phng php cng nghip
T du m, ta c th thu nhn mt s hp cht vng nh: xyclohexan, metyl xyclo
hecxan, metyl xyclo pentan Cc dn xut ca xyclo hecxan c th iu ch bng
cch hyro ho cc dn xut ca cc dn xut benzen.

2) Cc phng php tng hp
Mun iu ch cc xycloankan ngi ta thng xut pht t cc hp cht khng
vng, bng phn ng khp vng. Phn ng thng tin hnh d dng v cho hiu sut
cao khi to thnh cc vng 5 v 6 cnh. Vic to thnh cc vng ln hoc nh hn
thng tin hnh kh khn v cho hiu sut thp.
24


a)Vng ho cc dn xut ankan

n
( H
2
C )
H
2
C
C
H
2
B r
B r
+ 2 N a
n
( H
2
C )
C H
2
C H
2
+ 2 N a B r

C H
2
C l + 2 N a
H
2
C
H
2
C + 2 N a C l


Phn ng tin hnh theo c ch Vuyc.
C th thay natri kim loi bng bt km.

H
2
C
H
2
C
C
H
2
Cl
Cl
+ Zn H
2
C
CH
2
CH
2
+ ZnCl
2


Dng phn ng tng t iu ch xyclobutan, xycloheptan nhng vi hiu sut
thp.

b)Cng cacben vo anken

C
C
+ C H
2
N
2
C
C C
H
2
N
N
C
C
C H
2
C u , t
0
+ N
2



c)Phn ng quang ho

C O
a s
+ C O
H C
H C
C
H
R
C
H
R
H C
H C
C H R
C H R
a s


d)ime ho cc hirocacbon khng no
25


H
2
C C C H
2
t
0
H
2
C
C C H
2
H
2
C C
C H
2
2
+
H
2
C C
H
2
C C
C H
2
C H
2


e)Nhit phn mui ca axit icacboxylic
Khi chng ct khan mui canxi ca axit adipic (mch 6 cacbon) s thu c mt
xeton vng l xyclopentanon. C th chuyn ho d dng xeton ny thnh xycloankan
tng ng bng nhiu phng php khc nhau. n gin nht l cch kh bng hn
hng km trong axit clohidric (phng php Clemmensen).

H
2
C
H
2
C
H
2
C
O O
C
H
C C
O O
C a
H
2
C
H
2
C
H
2
C
C
C
H
2
O + C a C O
3
t
0


H
2
C
H
2
C
H
2
C
C
H
2
O + 4 [ H ] C
Z n / H g + H C l
( H
2
/ N i )
H
2
C
H
2
C
H
2
C
C
H
2
C H
2
+ H
2
O


C th p dng phng php ny iu ch cc vng to hn.

f) Kh cc hp cht thm
C
6
H
6
+ 3 H
2
N i , 1 9 0
0
C , 2 5 a t

g) iu ch xyclopropan
Xyclopropan l cht kh, c kh nng gy m, c dng rng ri trong gii phu,
khng c hi cho c th v khng li hu chng. c sn xut bng phn ng
Gustabcon:


C l
H
2
C C
H
C H
2
C l
H
2
C
H
2
C
H
2
C B r
+ H B r C l
H
2
C
H
2
C
H
2
C B r
+ Z n + Z n B r C l


1.3.4. Tnh cht vt l
S thay i nhit si, nhit nng chy ca xycloankan cng tun theo quy lut
nh ankan. Tuy nhin, nhit si v nng chy ca xycloankan cao hn ankan
tng ng mt t v ankan c tnh un do hn lm cho s t hp mng li tinh th
kh khn hn v tng tc gia cc phn t cng kh khn hn.

26


1.3.5. Tnh cht ho hc
1) Tnh cht chung
+ Cc xyclo ankan c c tnh no tng t nh cc ankan. Chng tham gia cc phn
ng th nh halogen ho, nitro ho. Tuy nhin, cc xycloankan vng nh ch yu l
xyclo propan v dn xut li c c tnh khng no, vng d m ra tham gia cc
phn ng cng.
+ Tnh cht ho hc ca cc xyclo ankan khng bin thin dn dn tun t nh
trong cc dy ng ng khc. Chng c mt s tnh cht c trng ph thuc vo cu
to ca vng. V vy, cc xycloankan c chia thnh 4 nhm: nhm vng nh (C
3
,
C
4
), nhm vng thng (C
5
, C
6
, C
7
), nhm vng trung bnh (C
8
C
12
) v nhm vng
ln (>C
12
).

2) Tnh cht ring
a)Tnh cha no ca cc vng nh
+ Xyclo propan tc dng vi brom ngoi nh sng mt tri cho sn phm cng
khng vng:

H
2
C
H
2
C
C H
2
+ B r
2
B r
H
2
C
H
2
C
H
2
C B r


+ Tc dng vi axit iot hiric khi un nng cho n-ropyl ioua:

H
2
C
H
2
C
C H
2
+ H I H
3
C
H
2
C
H
2
C I


+ Tc dng vi H
2
c xc tc l Ni 80
0
C to ra propan.

+ H
2
N i , 8 0
0
C
H
3
C
H
2
C C H
3


+ Cho xyclo propan i qua Al
2
O
3
100
0
C n s ng phn ho to ra propilen:

A l
2
O
3
, 1 0 0
0
H
3
C C
H
C H
3


+ Xyclo butan c kh nng phn ng km hn so vi xyclo propan. N khng tham
gia phn ng m vng khi tc dng vi halogen, hidro halogenua. Vng no m ra khhi
hiro ho c xc tc 120
0
C:

+ H
2
N i , 1 2 0
0
H
3
C
H
2
C
H
2
C C H
3

27


+ Cc dn xut ca xyclobutan c khuynh hng chuyn thnh vng 5 cnh:

H
2
C
H
C
H
2
C O H
H
2
C C H
2
a x i t o x a l i c
H C
H C
C
H
2
C H
2
+ H
2
O
H
2
C
x y c l o p e n t e n

b) Tnh bn vng ca cc vng 5, 6 cnh
Nhm clorua v brmua gy ra phn ng ng phn ho xycloankan lm cho vng
c th m rng ra hoc thu hp li.
V d: 3080
0
C, vi xc tc l AlCl
3
, xyclohecxan s chuyn ho thnh metyl
xyclo pentan.

A l C l
3
3 0 - 8 0
0
C
C H
3


Phn ng khng tin hnh mt chiu hon ton v pha phi. Phn ng t trng
thi cn bng khi thu c 75% xyclo hecxan v 25% metyl xyclo hecxan. Ngc lai,
nu i t metyl xyclopentan ta cng thu c hn hp tng t nh vy. Vy, khi c
mt nhm halogenua, gia hai hirocacbon ny thit lp mt trng thi cn bng. Cc
cn bng ho hc khng ph thuc vo cht xc tc v c ch phn ng m ch ph
thuc vo tnh bn nhit ng ca c hai thnh phn. Hn hp cn bng thu c
chng t rng vng 5 v 6 cnh c tnh bn gn nh ng nht.
Kt lun ny vn ng vi trng hp cn bng gia metyl xyclo hecxan v imetyl
xyclo pentan v xyclo heptan li chuyn hon ton thnh hn hp cn bng.

C H
3
H
3
C
C H
3


Tng t nh trn, xyclooctan chuyn hon ton thnh imetyl hecxan cn etyl
xyclo butan th chuyn thnh hn hp cn bng xyclo hecxan v metyl xyclo pentan.
T , ta kt lun rng cc vng 5 v 6 cnh l bn vng nht trong tt c cc vng.
Cc vng 5 6 cnh cng d c to thnh hn nhiu so vi cc vng nh v to. V
vy, trong thin nhin thng gp nhiu dn xut ca xyclohecxan v xyclopentan,
cn rt t gp cc dn xut ca cc xycloankan khc.
Khi tc dng vi halogenua, cc xyclo ankan loi vng 5, 6 cnh cng nh cc vng
ln hn khng b v vng m ch tham gia phn ng th.
28


+ C l
2 C l + H C l


Cc xyclopentan, xyclohecxan cng nh cc vng to hn khng chu tc dng ca
cc hiro halogenua, vng ca chng vn c bo ton. Khi c nhm cacboxyl nh
vo vng th vng tr nn bn vng hn.
Vng 5, 6 cnh cng khng cng c vi hiro khi c xc tc platin hoc niken
nh cc vng nh. Xyclo heptan v xyclo octan khi tc dng vi hiro c xc tc cng
khng b v vng nhng ch b ng phn ho thnh metyl xyclo hecxan v imetyl
xyclo hecxan. Cng tng t t xyclooctan s thu c metylxycloheptan v
dimetylxyclohecxan.

1.3.6. Cc thuyt gii thch v cu to cc hp cht vng
1) Thuyt A.Baye
gii thch tnh bn ca cc xyclo ankan trn y, nm 1885 gio s Baye Adong
a ra mt thuyt thng gi l thuyt sc cng gii thch tnh bn vng tng
i ca cc vng xycloankan.
Ta bit rng, gc lp bi lai ho trung tam hnh t din ca nguyn t cacbon no
(lai ho sp
3
) bng 109
0
28. Baye cho rng, tt c cc nguyn t ca vng u nm
trong mt mt phng, do cc gc ho tr ca nguyn t cacbon b lch i khi
hng bnh thng, v gc trong xyclo propan l 60
0
C, xyclo butan l 90
0
C, xyclo
pentan l 108
0
, xyclo hecxan l 60
0
. V vy, trong cc xyclo butan, gc t din ca
nguyn t cacbon b xm phm gy ra mt sc cng gi l sc cng Baye. Theo Baye,
lch ca gc ho tr cng ln, sc cng ny cng to th vng cng km bn. Trn c
s , Baye gii thch nhng c im khc nhau trong tnh cht ca cc xycloankan
c ln ca vng khc nhau.


2
' 28 109
0

= o l gc a din u ca vng.

Gi tr sc cng Baye c tnh cho cc xyclo ankan c n nguyn t C nh sau:

n 3 4 5 6 7 8 9
24
0
44 9
0
44 0
0
44 -5
0
16 -9
0
33 -12
0
46 -36
0
16

Nh vy, theo Baye, vng c sc cng ln nht l xyclopropan ri n xyclobutan
v cc vng ln. Vng c sc cng nh nht l xyclo pentan. Thc nghim cho thy
rng, i vi cc vng nh xyclo propan, xyclo pentan, xyclo butan sc cng ca vng
(Baye) ph hp vi cc tnh cht ca vng. Nhng i vi xyclo hecxan v cc vng
ln hn, sc cng Baye khng cn ngha. Xyclo hecxan c vng ln hn xyclo
pentan nhng n li rt bn, bn hn xyclo pentan. iu ny ch c th gii thch rng
trong khi a ra thuyt ca mnh, Baye phm sai lm l coi tt c cc cu t cu to
nn vng u nm trong mt mt phng.
29


2) Quan nim hin i v cu to ca hp cht vng
Theo quan nim ny, bn ca hp cht vng ph thuc vo sc cng Baye (sc
cng gc lin kt), sc cng Fitze (lc tc dng tng h ca cc nguyn t hay nhm
nguyn t k nhau ca vng), lc Vandervaals ca cc nhm khng k nhau. Cc
nguyn t cacbon trong ankan c lai ho sp
3
, do , hnh thnh lin kt chng
hng cc obital ny li vi nhau v c s xen ph cc i, cc gc lin kt phi l
109
0
28.
Trong phn t xyclo propan, gc lin kt khng th l 109
0
28 m ch c th l 60
0
,
do nguyn t cacbon khng th hng cc obitan lai ho sp
3
thng hng li vi
nhau nn s xen ph s t hn, lin kt km bn hn.
Trong trng hp phn t xyclo butan, gim bt sc cng, mt nguyn t cacbon
ca vng nm ngoi mt phng ca 3 nguyn t cacbon cn li nn to ra kh
nng xen ph cao hn v vng bn hn.



trnh cc sc cng, xyclopentan c cc cu dng thun li nht l dng na gh
v dng phong b.



Xyclo hecxan c cc cu dng: gh, xon, thuyn.




Nu phn t xyclo hecxan tn ti di dng gh th trong c hai loi hyro lin
kt khc nhau: 6 lin kt thng gc vi mt phng gh l lin kt axial (a) cn 6 lin
kt nm trong mt phng gh l lin kt equatorial (e)
.
1.3.7. Xycloankan tiu biu: xyclohecxan
Vng xyclohecxan c th c hai dng ng phn, trong tt c cc nguyn t
cacbon u c gc ho tr bnh thng bng 109
0
28, l dng gh v dng thuyn.
Cc cu dng c nng lng khc nhau: trong dng gh, tt c cc nhm CH
2

lin nhau c cu dng km hm, trong khi dng thuyn cha 4 cu dng km hm v
hai cu dng che khut. Do , dng gh bn vng hn dng thuyn. Nng lng dng
thuyn ln hn dng gh khong 5kcal/mol. Tuy vy, khng th tch c hai ng
30


phn ny ra khi nhau v chng chuyn ho ln nhau d dng v tn ti trng thi
cn bng.
Cc phng php nghin cu quang ph cho thy kt qu l cc phn t
xyclohecxan trong iu kin thng hu ht u dng gh. Dng thuyn ch xut
hin mt lng nh nhit cao.
Khi kho st cc m hnh phn t xyclohecxan dng gh, ta thy cc nguyn t
cacbon trong vng nm trn hai mt phng song song: cc nguyn t 1, 3, 5 mt
phng trn, cc nguyn t 2, 4, 6 mt phng di, khong cch gia hai mt phng l
0,5 A
0
.

4
2
3
6
1
5

hai mt phng song song trong phn t xyclohecxan

Xyclohecxan dng gh c 12 lin kt CH c th chia thnh hailai khc nhau: su
lin kt CH nh hng song song vi hai mt phng ni trn gi l cc lin kt
ngang (equatorial) k hiu l lin kt e, su lin kt CH cn li nh hng song
song vi trc ca vng, ba hng ln trn, ba hng xung di gi l lin kt trc
(axial) k hiu l lin kt a.

a
e
e
e
e
e
e
a
a
a
a
a


Cc dn xut mt nhm th ca xyclohecxan nh metylxyclohecxan c th tn ti
di dng hai ng phn c nhm metyl hoc lin kt trc hoc lin kt ngang.
Hai dng ny d chuyn ho ln nhau m khng cn b gy lin kt no, ch cn thay
i dng lin kt CC ca vng. S chuyn ho ny i hi mt nng lng hot ho
rt nh. V vy, cc ng phn ny khng th tch ra khi nhau c. Tuy nhin, dng
Cc lin kt trc (a) v lin kt ngang (electron) trong xyclohecxan
`trc i xng
bc 3
31


lin kt ngang v mt nng lng thun li hn v bn vng hn so lin kt trc vo
khong 2kcal/mol cho nn nhm metyl thng tn ti dng lin kt ngang e.
C H
3
e
e
e
e
e
e
a
a
a
a
a
H
3
C
a
e
e
e
e
e
a
a
a
a
a




































32


CU HI V BI TP

Bi 1. Nu c tnh ha hc ca ankan (minh ha bng cc phn ng) v nguyn nhn
dn ti c tnh , gii thch?
Bi 2. So snh tnh cht ha hc ca ankan v xicloankan. Gii thch v sao c s
ging nhau v khc nhau gia chng?
Bi 3. Nhit nng chy v nhit si ca cc ankan bin i theo cu trc phn t
ca chng nh th no, cho v d minh ha?
Bi 4. V sao nhit si v nhit nng chy ca xicloankan u cao hn hn so
vi n-henxan?
Bi4. Ion kiu metoni v cabocation ging v khc nhau nh th no (cu trc v
chuyn ha)?
Bi 6. Nhng yu t no (sc cng no) nh hng n bn xiclan? Cho v d?
Trong dy xiclan (CH
2
)
n
n = 313, v sao k hi n = 6 th entapi hnh thnh i vi mt
nhm CH
2
l nh nht?
Bi 7. Tm quan trng ca ankan v xiclo ankan trong th gii ngy nay?
Bi 8. a) Vit cng thc cu to, gi tn theo danh php thng v danh php IUPAC
cc hidrocacbon ng phn c cng cng thc C
4
H
10
v cc gc ankyl c cng cng
thc C
4
H
9
.
b) Vit cc phng trnh phn ng tng hp ra n-butan t:
- Than v vi
- 2 butin
- 2 Iotbutan
- Axit valeric CH
3
CH
2
CH
2
CH
2
COOH
- Axit propionic CH
3
CH
2
COOH
c) Cho bit ti sao phn ng ha hc c trng ca ankan l phn ng th theo
c ch gc. Vit phng trnh phn ng xy ra khi cho clo tc dng vi n-butan c
chiu sng.
Bi 9. a)Vit cng thc cu to ca tt c cc hidrocacbon c cng thnh phn nguyn
t C
5
H
12
v gi tn chng theo danh php thng v IUPAC. Cho bit bc ca tng
nguyn t cacbon tng ng.
b) T metan v cc hp cht v c cn thit hy tm cc phng php iu ch
ra izopentan.
Bi 10. a)T ru metylic v cc cht v c cn thit hy iu ch ra 2-metylpropan
v 2,2,4-trimetylpentan.
b) Trn 2-metylpropan vi clo theo t l 1:1 v th tch v tin hnh phn ng
khi un nng. Cc sn phm ca phn ng l 2-clo-2-metylpropan v 1-clo-2-
metylpropan c to ra theo t l phn t gam l 1:2. Cho bit nguyn t hidro
cacbon bc nht hay bc ba d phn ng hn.
Vit cng thc cu to ca cc dn xut monoclo sinh ra khi clo ha 2,2,4-
trimetylpentan.
Bi 11. a) Vit cng thc v gi tn cc ng phn cu to v ng phn lp th ca
nhng hp cht c cng thnh phn C
5
H
8
(CH
3
)
2
.
33


b) Khi hidro ha mt trong cc ng phn trn l 1,2-dimetylxiclopentan nh
xc tc niken v nhit 300
0
C thu c heptan, 1,2-dietylpentan v 3-
metylhecxan.
Vit cc phng trnh phn ng v ch v t lin kt cacbon-cacbon trong vng
b t.
Bi 12. a) Bng cc phn ng ha hc hy phn bit cc hp cht trong tng cp cht
sau:
- Xiclopropan v propan
- 1,2-dimetylxiclopropan v xiclopentan
- Xiclopentan v 1-peten
b) Hai hp cht hu c A v B u lm mt mu dung dch brm trong
tetraclorua cacbon. Cht A cho sn phm l 1,3-dibrombutan. Cht B cho sn phm l
1,2-dibrom-2-metylpropan. Xc nh cu to ca A v B.
34


TI LIU THAM KHO
1. Nguyn Hu nh, nh Rng Ha hc Hu c Tp 1, Nh xut bn Gio
dc, 2003.
2. Phan Tng Sn, Trn Quc Sn, ng Nh Ti, C s l thuyt ho hu c, tp
1,2, NXB i hc v trung hc chuyn nghip H Ni, 1980
3. Chu Phm Ngc Sn, Nguyn Hu Tnh, Bi tp ha hc hu c, NXB Hn
Thuyn, Thnh ph H Ch Minh, 1995.
4. ng Nh Ti, C s l thuyt ha lp th, NXB Gio dc, H Ni, 1998.
5. Thi Don Tnh, C s ho hc hu c, Tp 1, 2, NXB Khoa hc v K thut, H
Ni, 2006.
6. Ng Th Thun Ho hc hu c phn bi tp (tp 1,2), NXB Khoa hc v k thut,
H Ni, 2006.
7. Hong Trng Ym, Ho hc hu c, NXB Khoa hc & K thut, H Ni, 2002.
35


CHNG 2. HIROCACBON KHNG NO

2.1. Anken, c ch phn ng tch: E
1
, E
2
, E
i
, E
1cb
, hng tch, quan h gia
phn ng tch v th; phn ng cng A
E
, kh nng v hng cng

2.1.1. Dy ng ng ca etylen
Anken l loi hirocacbon cha no mch h c cha mt lin kt i C=C trong
phn t. So vi thnh phn cc phn t ankan c cng s nguyn t cacbon tng ng,
anken lun c t hn hai nguyn t hyro. Cng thc phn t chung ca anken l
C
n
H
2n
vi n 2 > . Khi n = 2, ta c dn xut u tin ca dy ng ng gi l etilen
C
2
H
4
; khi n = 3 ta c propilen C
3
H
8
; n = 4 ta c butilen C
4
H
8
Tt c hp thnh dy
ng ng ca etilen.
Anken cn c gi l hidrocacbon cha no loi etylen hoc l olefin.

2.1.2. Cch gi tn
- Tn gi thng thng hay tn lch s ca cc anken xut pht t tn gi ca
hirocacbon no tng ng nhng thay i ui an thnh ilen: etan etilen, propan
propilen, butan butilen, pentan pentilen hoc amilen.
- Cch gi tn hp l: coi tt c cc alken nh dn xut ca etilen, bng cch thay
th cc nguyn t hyro ca etilen bi cc gc hirocacbon khc. V d: cch gi tn
hp l ca mt s ng phn ca butilen.


H
3
C
H
2
C C
H
C H
2
H
3
C C
H
C
H
C H
3
H
3
C C
C H
2
C H
3
e t y l e t i l e n
d i m e t y l e t y l e n d o i x u n g
d i m e t y l e t i l e n k h o n g d o i x u n g


-Cch gi tn theo IUPAC. Cc anken c tn quc t ca cc alkan tng ng
nhng i ui an thnh en. V tr ca lin kt i c k hiu bng mt ch s. Vic
nh s mch cacbon theo trt t t u mch gn ni i. Cc ch s vit trc tn
nhnh v tn mch chnh. V d:


H
3
C
H
C
H
2
C C
H
C
H
C H
3
C H
3
5 - m e t y l - 2 - h e c x e n


Cc gc hirocacbon cha lin kt i c ui enyl, vic nh s mch cacbon
trong gc bt u t nguyn t cacbon c ho tr t do.
V d:
36


H
3
C C
H
C
H
H
2
C H
2
C C
H
H
2
C
H
2
C
2 - b u t e n y l
4 3 2 1
3 2 1 4
3 - b u t e n y l


Mt s gc ankenyl c tn gi thng thng c s dng ph bin hn. l
cc gc vinyl, alyl, izpropenyl.


C
H
H
2
C C
H
H
2
C H
2
C
C
C H
3
H
2
C
v i n y l a l y l
i z o p r o p e n y l


2.1.3. ng phn
1) ng phn cu to
Ngoi ng phn v mch cacbon nh i vi ankan, cc anken cn c cc ng
phn v v tr ca lin kt i, do s ng phn cu to ca anken nhiu hn ca
ankan c cng s nguyn t cacbon.
V d: buten C
4
H
8
c 3 ng phn trong khi butan C
4
H
10
ch c 2 ng phn,
penten C
5
H
10
c 5 ng phn trong khi pentan C
5
H
12
ch c 3 ng phn, hecxen
C
6
H
12
c 12 ng phn trong khi hecxan C
6
H
14
c 5 ng phn.
S nguyn t cacbon trong phn t cng tng th s chnh lch v s ng phn cu
to gia anken v ankan tng ng cng nhiu.

2) ng phn hnh hc hay ng phn cis trans
S c mt ca lin kt i trong anken lm xut hin mt loi ng phn lp th,
l ng phn hnh hc hay ng phn cis trans. c im ca ng phn ny l hai
nhm th nh hai cacbon mang ni i v cng mt pha hoc khc pha vi ni
i, thc cht l cng pha hoc khc pha i vi mt phng t ca lin kt i. Khi
hai nhm th cng pha ta c ng phn cis, khi hai nhm th khc pha cho dng
ng phn trans.
V d: 2-buten cho hai dng ng phn cis trans nh sau:

H
C H
3
H
H
3
C
C H
3
H
H
H
3
C
c i s - 2 - b u t e n
t r a n s - 2 - b u t e n


Nguyn nhn tn ti hin tng ng phn cis-trans l do cc nhm th khng th
quay t do xung quanh lin kt i nh lin kt n, v khi quay nh th, lin kt i
s b ph v.
37


Cc ng phn cis trans c tnh cht vt l v ho hc khc nhau nh cc ng
phn thng thng. Ta c th thy r s khc nhau v tnh cht vt l gia cc ng
phn cis trans trong trng hp ca iclotilen.



C l
H
C l
H
C l
H
H
C l
c i s - d i c l o e t i l e n
t r a n s - d i c l o e t i l e n


Nhit si
0
C 60,2 48,3
Nhit nng chy
0
C -80,5 -50
15
4
d 1,289 1,265
Momen lng cc 1,89 0

V tnh cht ha hc, ta thy s khc nhau r rt gia axit maleic (cis) v axit
fumaric (trans). Khi ung nng ch c axit maleic mi chuyn thnh dng anhiric:


H C C O O H
C H C O O H
H C
O
C
C H C
O
O
H O O C C
C H
H
C O O H
1 5 0
0
C
- H
2
O
a x i t m a l e i c
a n h i d r i c m a l e i c
a x i t f u m a r i c


Ni chung l dng trans bn hn dng cis do trng thi nng lng thp hn.

2.1.4. Tnh cht vt l
Ba cht u tin trong dy ng ng nhit thng l cc cht kh, cc anken
trung bnh l nhng cht lng, cc anken cao hn l cc cht rn. Nhit si ca cc
anken gn vi nhit si ca cc ankan c cng s nguyn t cacbon trong phn t.
T khi ca cc anken hi cao hn so vi t khi ca cc ankan tng ng.
Tnh cht vt l c ngha quan trng ca anken l khc x phn t MR. MR c
tnh cht cng tnh, ngha l khc x ca phn t bng tng s khc x cc
nguyn t c trong phn t y. Cho nn MR ca cc ankan bng tng s khc x
ca cc nguyn t C v H c trong thnh phn phn t. Tuy nhin, trong trng hp
cc anken, MR c xc nh bng thc nghim (theo cng thc Lorentz-Lorenz) ln
hn tr s tnh l thuyt khi ch da vo khc x nguyn t. Do , i vi cc
anken c mt i lng b sung gi l s gia k hiu l F th hin c im cu to ca
anken l s c mt ca lin kt i trong phn t. Trung bnh, s gia F i vi mt lin
kt i bng 1,7 1,9.
Nh vy, bng cch so snh khc x phn t MR thc nghim vi khc x
phn t MR tnh theo l thuyt c th khng nh s c mt hay khng ca lin kt i
trong phn t.
38


Ph hng ngoi ca cc anken cho vch hp th gn 1650 cm
-1
, c trng cho dao
ng ho tr ca lin kt i C=C. Tuy nhin, cng v v tr ca vch ny cn ph
thuc vo cu to phn t ca anken, n thay i vi phn nhnh lin kt i v
vi s c mt ca lin kt cha no th hai lin hp vi lin kt i th nht.

2.1.5. Cc phng php iu ch
1) Tch nc ra khi ancol
Khi tch H
2
O ra khi ancol no, s thu c anken. C th tin hnh vic tch H
2
O
bng hai phng php:

a) Trong pha lng
un nng ancol vi axit mnh nh axit sunfuric hoc axit photphoric hoc vi kali
sunfat axit. Axit s tng tc vi ancol trc ht to ra este (este v c), sau b
phn hu s cho anken. S chung nh sau:

R
H
2
C
H
2
C O H + H
2
S O
4
d
t
0
c
R
H
2
C
H
2
C O S O
3
H + H
2
O
R
H
2
C
H
2
C O S O
3
H R C
H
C H
2
+ H
2
S O
4


V d: un nng ancol etylic vi H
2
SO
4
c nhit trn 170
0
C s thu c
etylen.


H
3
C
H
2
C O H + H O S O
3
H
H
2
O +
H
3
C C H
2
O S O
3
H
H
3
C C H
2
O S O
3
H H
2
C C H
2
+ H
2
S O
4


Phn ng ny dng iu ch cc anken c s cacbon thp trong cng nghip. c
bit l cc ancol bc 1 v bc 2, phn ng loi nc bng H
2
SO
4
cho hiu sut rt cao.
i vi cc ancol bc cao, thng c sn phm ph km theo cho cc anken ng
phn do s tch nc theo cc hng khc nhau v cng c th do s di chuyn ni
i trong olefin di tc dng ca H
2
SO
4
.

b) Trong pha hi
Cho hi ancol i qua xc tc rn nh nhm oxyt, nhm silicat nhit 300
400
0
C, s tch mt phn t H
2
O ra khi phn t ancol v ta thu c anken. Hiu sut
phn ng t ti gn hiu sut l thuyt. Phn ng ny c th tin hnh lin tc v c
th s dng trong cng nghip. S chung nh sau:


R
H
C
H
C R '
O H H
A l
2
O
3
3 0 0 - 4 0 0
0
C
R C
H
C
H
R ' + H
2
O


39


Phn t nc c tch ra d dng nht t cc ancol bc 3 ri n cc ancol bc 2,
cc ancol bc 1 bn vng hn c, kh tch H
2
O nht. Phn t H
2
O c tch ra c
bit d dng t cc ancol bc 2 v bc 3 c cha nhm phenyl bn cnh cacbon
mang nhm OH. V d:


C
6
H
5
H
C C H
2
O H H
C
6
H
5
C
H
C H
2
p h e n y l m e t y l c a c b i n o l
+ H
2
O
s t i r e n


Khi tch nc bng cc phng php trn, c th xy ra s di chuyn lin kt i,
lin kt i c th v tr khc vi v tr d kin t cng thc ca ancol ban u. V
d, khi tch H
2
O t ancol n-butylic c mt H
2
SO
4
(hoc ZnCl
2
) s thu c mt hn
hp cha lng 2-buten nhiu hn hn 1-buten:

H
3
C
H
2
C
H
2
C C H
2
O H H
3
C C
H
C
H
C H
3
H
3
C
H
2
C C
H
C H
2
+


2) Tch hyro halogenua t cc dn xut mnohalogen no
Cc dn xut monohalogen no, c bit l dn xut bc 3, khi tng tc vi cc
dung dch baz mnh nh KOH, NaOH trong ancol v un nng, s b tch mt phn
t hyro halogenua cho anken tng ng.


R C C H
2
C H
3
X H
R C
C H
2
+ H X
C H
3
d d K O H , a n c o l


Cc dn xut halogen bc 2 b tch HX kh hn dn xut bc 3.
Ngoi tc nhn l dung dch KOH trong ancol, c th tch HX ra khi dn xut
halogen bng cch cho hi dn xut halogen i qua t st nung hoc canxi oxit,
bari oxit nung .
So snh kh nng tch HX ca cc dn xut clo, brm, it, flo ta c trt t sau:

RI > RBr > RCl > RF

Ta nhn thy rng dn xut it d b tch HX hn c ri n dn xut brm, dn
xut clo v kh nht l dn xut flo. Nguyn nhn l do nng lng lin kt ca cc
lin kt CX khc nhau. Nng lng lin kt ca CI l 51 kcal/mol, ca CBr l
68, ca CCl l 81 v ca CF l 116 kcal/mol.

3) i t dn xut ihalogen
40


Tng tc gia cc dn xut ihalogen c hai halogen nh vo hai cacbon lin
nhau vi bt km trong dung dch axit axetic, s tch hai hal to ra anken. Phn ng
ny thng dng tch cc anken ra khi cc hirocacbon khc. S chung ca
qu trnh nh sau:

R
H
C
H
C R ' + Z n
X X
R C
H
C
H
R ' + Z n X
2


4) cacboxy ho axit cha no
Khi un nng cc axit cha no, nhm cacboxyl b tch d hon cc axit no, to ra
anken. V d t axit xinnamic to ra stiren:


C
6
H
5
C
H
C
H
C O O H
C
6
H
5
C
H
C H
2
+ C O
2
t
0
C


5) hiro ho ankan
Trong cng nghip cc anken thng iu ch bng cch ehiro ho cc ankan
di tc dng xc tc ca crm trioxit 450
0
C. Bng phng php ny, c th iu
ch c cc buten i t n-butan v izobutilen t izobutan.
Cc anken cng c to thnh khi nhit phn cc ankan v cc hirocacbon khc
trong phn ng cracking.

2.1.6. Tnh cht ho hc
1) Bn cht, c im ca lin kt i C=C
Lin kt i C=C c to nn bi hai nguyn t cacbon trng thi lai ho sp
2
, tc
l kiu lai ho tam gic. Trong lin kt i c mt lin kt o do s xen ph trc ca
hai electron lai ho v mt lin kt t do s xen ph bn ca hai electron p. Tt c cc
nguyn t ni vi hai cacbon mang lin kt i u nm trn cng mt mt phng vi
hai cacbon gi l mt phng phn t v gc ho tr mi cacbon mang lin kt i
bng 120
0
. Hai trc ca hai electron p song song vi nhau to thnh mt phng t
thng gc vi mt phng ni trn. Thc cht ca lin kt t to thnh l obitan lin kt
t c mt electron bao ph c pha trn v pha di hai nguyn t cacbon mang ni
i.
Lin kt i c di bng 1,34 A, ngn hn so vi lin kt n (1,54 A). Nng
lng lin kt i C=C bng 145,8 kcal/mol, trong khi nng lng lin kt n
CC bng 82,6 kcal/mol. Gi thit nng lng lin kt o trong lin kt i bng nng
lng ca lin kt n th nng lng ca lin kt t bng 145,8 82,6 = 63,2
kcal/mol. Nh vy, nng lng lin kt o ln hn nng lng lin kt t, chnh
lch vo khong 20 kcal/mol, iu ny gii thch tnh km bn ca lin kt t v kh
nng phn ng cao ca lin kt i. So vi ankan, anken c kh nng phn ng ln
hn nhiu. Cc phn ng c trng ca anken thng tp trung vo lin kt i, do
ni i c coi l trung tm phn ng ca cc anken.
Cc phn ng quan trng nht i vi anken l phn ng cng, phn ng oxi ho v
phn ng trng hp.
41


2) Phn ng cng
Cc phn ng cng c trng nht i vi anken l phn ng cng vo lin kt i.
Trong phn ng ny, mt na lin kt i thc cht l lin kt t b b gy v kt hp
vi hai nguyn t hoc hai nhm nguyn t mi to ra hp cht no. S chung ca
phn ng cng vo lin kt i:


C C + X Y
C C
X Y


So vi vic b gy mt lin kt n CC trong ankan, vic b gy lin kt t trong
anken d dng hn nhiu:
V d:

H
2
C C H
2
+ B r B r H
2
C C H
2
B r B r
H
3
C C H
3
+ B r B r
H = - 2 7 k c a l
2 C H
3
B r H = - 7 k c a l


l do nng lng lin kt t nh hn nng lng lin kt o.
Kh nng phn ng cao ca anken so vi ankan cn c th gii thch l do trong lin
kt i ca anken mt electron c tri rng hn so vi lin kt n trong ankan.
Cc electron trong lin kt i b y ra xa do sc y nhau ca chng. Do , nhng
v tr ca lin kt i c mt electron bng vi ch c mt electron nh th ca
lin kt n th xa trc lin kt n.

a)Cng hyro hay hyro ho
* Hyro ho xc tc d th:
Kt qu phn ng cng hyro vo anken cho ta ankan tng ng. S chung ca
phn ng cng hyro vo anken:

C C C C + H
2


y l phn ng pht nhit (H = -30 kcal). Tuy nhin, mt hn hp hyro v
etylen bn vng v hn nhit 200
0
C. Cc anken cng khng th cng c vi
hyro mi sinh, nh bng km tc dng vi axit, hoc natri trong ru. Tuy nhin, c
th cho hyro phn t trng thi kh c mt xc tc cng vo lin kt i ca anken.
Xc tc hyro ho truyn thng thng dng l kim loi chuyn tip nh Pt, Pd,
Ru,Ni nghin nh dng tinh khit hoc tm trn cc cht mang nh C, BaSO
4
,
42


CaCO
3
, Al
2
O
3
Chng khc pha vi cc cht kh. Chng u khng tan trong mi
trng phn ng (dung mi hu c) v th gi l xc tc d th.
Pd/C xc tc cho s hyro ho anken thnh ankan trong dung dch etanol di p
sut thng, ngay 020
0
C. Trong iu kin , nhn benzen, nhm C=O, CN
khng b kh. V d:

H
C
C H
2
+ H
2
H
2
C C H
3
P d / C
2 0
0
C
O + H
2
P d / C , 1 a t m
2 0
0
C , C
2
H
5
O H
O
C
H
C
H
C O O C H
3
+ H
2
P d / C
2 0
0
C , C
2
H
5
O H
H
2
C
H
2
C C O O C H
3


Hyro ho dng xc tc Pt thng c tin hnh trong etanol, trong etyl axetat
hoc trong axit axetic di p sut thng, nhit 2050
0
C.
Xc tc Ni c iu ch bng cch cho hp kim Ni-Al tc dng vi dung dch
NaOH nng nhm ho tan ht Al, li Ni dng ht xp, mn. Niken r hn nhiu so
vi cc kim loi qu nh Pd, Pt nhng n hot ng yu hn nn phi tin hnh hyro
ho nhit cao hn, 50 100
0
C, di p sut 510 atm. Niken hnh thnh theo
phn ng:

2NiAl + 2OH
-
+ 2H
2
O 2Ni + 2AlO
2
-
+ 3H
2

Cc hp cht ca lu hunh, phtpho, asen lm t lit kh nng hot ng ca cc
xc tc hyro ho ngay vi nhng nng nh.
Phn ng ho xc tc d th thng xy ra theo kiu cng syn (cng vo cng mt
pha ca lin kt C=C).
V d:


C H
3
C H
3
+ H
2
P t / C , 1 a t m
2 0
0
C , C H
3
C O O H
C H
3
C H
3
H
H
1 , 2 - d i m e t y l x y c l o h e c x a n
c i s - 1 , 2 - d i m e t y l x y c l o h e c x a n


Phn ng hyro ho xc tc d th cng theo kiu syn m khng cng theo kiu anti
l do phn t H
2
b hp ph trn b mt kim loi lm cho lin kt HH b yu i.
43


Obitan t ca lin kt i C=C tng tc vi b mt lin kt (vi obitan d ca kim
loi) to ra trng thi hot ho rt d cng hp vi phn t H
2
c hot ho.

N i N i N i
H
2
C C H
2
H H
N i N i N i
N i N i N i
H
2
C C H
2
H H
N i N i N i
N i N i N i
H
3
C C H
3
N i N i N i


* Hyro ho xc tc ng th:
Hyro ho xc tc d th c mt vi hn ch nh thng km theo phn ng ng
phn ho v phn ng lm t lin kt CC. Mt thnh tu quan trng trong lnh vc
hyro ho anken l vic pht minh ra cc phc cht kim loi chuyn tip tan c
trong dung mi hu c, xc tc cho phn ng hyro ho anken iu kin thng
trong h ng th. Xc tc thng dng l [(C
6
H
5
)
3
P]
3
RhCl (clorotris-(triphenyl
photphin)rodi) v [(C
6
H
5
)
3
P]
3
Ru(H)Cl (clorohidridotris-(triphenyl photphin) ruteni).
Phc cht [(C
6
H
5
)
3
P]
3
RhCl (xc tc Wilkinson) c iu ch d dng t RhCl
3
v
triphenyl photphin nn c dng ph bin hn c.
u im ca xc tc ng th l n kh la chn ch cc lin kt i cha 1 hoc 2
nhm th khi c mt cc lin kt i cha 3 hoc 4 nhm th. V d:

O H
H
2
/ [ ( C
6
H
5
)
3
P ]
3
R h C l
B e n z e n
O H
L i n a l o o l

O
H
2
/ [ ( C
6
H
5
)
3
P ]
3
R h C l
B e n z e n
O
C a r v o n


Xc tc Wilkinson lm cho s cng hyro xy ra theo kiu cng syn. V d t
cis buten sau khi teri ho ta thu c ng phn meso:
S s hyro ho etylen xc tc bi niken
44


C a r v o n
C
C
H C H
3
H C H
3
D
2
/ [ ( C
6
H
5
)
3
P ]
3
R h C l
B e n z e n
C H
3
C H
3
H D
H D


Tnh lp th ca phn ng c c l do c hyro v anken u tin u to phc
vi Rh, trong cu phi tr ca phc trung gian , chng nhng v tr thun li cho
s cng syn.
Phng php hyro ho xc tc do Sabachi v Senren pht minh ra nm 1899,
hin nay vn cn c s dng rng ri v tr thnh mt trong nhng phng php
quan trng nht ca ho hu c, trong phng th nghim cng nh trong cng nghip.
Phng php ny khng nhng ch p dng cho cc anken n gin m c cho nhng
trng hp cha no khc cha ni i, ni ba.

b) Cng electrophin vo anken (A
E
)
Cc tc nhn phn ng nh cc halogen (Cl
2
, Br
2
, I
2
), cc hyro halogenua (HCl,
HBr), cc axit hipohalogen (HOCl v HOBr), nc, axit sunfuric u c th cng
c vo ni i ca anken cho cc hp cht no tng ng. C th biu din bng s
chung nh sau:

C C
C C
B r B r
C C
C l O H
+ B r
2
+ H O C l


C C
C C
H O S O
3
H
C C
H C l
+ H
2
S O
4
+ H C l
+ H
2
O , H
+
C C
H O H


45


Cc phn ng trn c nhng c im chung v mt c ch, l c ch cng
electrphin (tc l c ch cng i in t, k hiu A
E
) v cc tc nhn u l
electrphin.

* C ch phn ng:
Khi tc nhn electrphin tin li gn phn t anken, trong phn t anken c s di
chuyn mt electron t ca lin kt i lm phn cc ho lin kt i:


R
2
C C R
2 R
2
C C R
2
o ooo


C ch cng electrphin tin hnh qua 2 giai on: giai on 1, tc nhn electrphin
(phn mang in tch dng ca tc nhn) tin cng vo ni i, kt hp vi cacbon
mang ni i giu electron t hn, lm t lin kt t v hnh thnh lin kt o mi to
ra ion cacboni (cacbocation). Sau , trong giai on 2, cacbocation s kt hp vi
phn cn li ca tc nhn tch in m:
Giai on 1:


C C
+ X Y
X C C C C
X
+ Y
+


Giai on 2:

X C C
+ Y
X C C Y
n h a n h


Nh vy, XY khng tin cng ng thi vo ni i m qua nhiu giai on ni
tip nhau, trong giai on chm quyt nh tc chung ca phn ng cng l giai
on tn cng ca

X to thnh cacbocation.
chng minh rng phn ng cng xy ra theo nhiu giai on, ngi ta cho brm
tc dng vi etylen, c mt natri hoc nitrat natri. Nu s cng hp l mt giai on th
ta ch thu c 1,2-ibrmtan, cn nu phn ng xy ra theo nhiu giai on th ta s
thu c mt hn hp sn phm l 1-brom-2-clo etan v nitrat brom etan.


H
2
C C H
2
H
2
C
H
2
C B r B r
H
2
C
H
2
C B r C l
+ N a C l
+ N a N O
3
H
2
C
H
2
C B r O N O
2
+ B r
2

chm
hoc
46



Thc nghim cho thy rng, phn ng cng to ra nhng sn phm nh trong s
trn, ph hp vi c ch nhiu giai on.
C ch phn ng ny i hi dung mi phn cc, v trng thi chuyn tip v cc
sn phm ca giai on 1 c in tch ion, trong khi tc nhn li khng phn cc.
C C + B r B r C C B r B r
ooo
C C B r
+ B r

Trng thi chuyn tip ny ch c th to thnh trong dung mi c kh nng ion ho
rt mnh nh nc, ru.
xc nhn rng giai on cng phn mang in tch dng to thnh cacbcation
trung gian quyt nh vn tc chung ca phn ng, ta c th xt phn ng cng HBr
vo ni i ca xyclohecxen.


C
6
H
1 0
+ H B r
C
6
H
1 1
B r


Nu giai on chm ca phn ng l giai on tn cng ca

H th khi chuyn t
dung mi tr khng c tc dng vi

H sang dung mi c tnh baz tc dng c vi

H th vn tc ca phn ng gim i v nng ca

H b gim. Tri li nu giai

on chm l giai on tn cng ca Br
-
th hin tng trn khng th xy ra. Thc
nghim cho bit rng khi dng dung mi l te hoc ioxan (l nhng cht d b
prton tc dng) vn tc phn ng cng nh hn nhiu so vi vn tc cng trong dung
mi heptan hoc benzen. iu ny ph hp vi c ch cng electrophin.

* Tin trnh lp th:
V mt l thuyt, X v Y c th cng vo cng mt pha ca ni i, gi l kiu
cng cis hay syn, cng t hai pha khc nhau - cng trans hay cng anti. Tuy nhin,
nu X cng vo trc n ng mt pha, nht l khi to ra cation vng ni (X l
halogen), Y s phi i v pha i lp.


C C
C C
H a l
+
H a l
H a l
H a l
H a l


Nh vy, phn ng cng electrophin thng xy ra theo kiu trans hay kiu anti.
V d: Khi cho (E)-anken (trans) cng XY cho cp erytr (nu X=Y cho ta c ng
phn mz), cn (Z)-anken (cis) cho cp tre. iu ny chng minh tin trnh cng
anti ca phn ng.
dung mi
47


R
R
H
H
X Y
Y
H R
X
R H
R
R
H
H
X Y
X
H R
Y
R H


* Mt s phn ng A
E
ca anken:
- Phn ng cng halogen:
Cc halogen cng vo ni i ca cc anken mt cch d dng to ra dn xut
ihalogen, c hai halogen nh hai nguyn t cacbon cnh nhau.
V d:

H
2
C C H
2
+ C l
2
C l
H
2
C
H
2
C C l


Flo hot ng qu mnh nn khi tng tc vi anken ngay nhit thp cng gy
ra phn ng phn hu anken. It hot ng yu nn phn ng vi anken l thun
nghch v cn bng chuyn hn v pha cc cht u. Phn ng cng ca clo v brm
vo anken vi hiu sut gn 100%. Do phn ng cng vo anken lm mt mu nhanh
dung dch Br
2
nn phn ng ny thng c dng nhn bit anken. Ngi ta dng
CCl
4
lm dung mi v n ho tan tt c Br
2
ln anken nh vy m phn ng nhanh
hn, mu sc bin i r rt hn. Cng c th dng phn ng ny tch anken ra
khi cc hirocacbon khc. Cc hp cht khng no nh ankin, anehyt cng lm mt
mu dung dch nc brm.
- Phn ng cng hyro halogenua:
Cc hyro halogenua (HCl, HBr, HI) cng vo lin kt i ca anken cho cc dn
xut monohalogen. Phn ng xy ra d dng nht vi hyro ioua, kh nht i vi
hyro clorua.
H
2
C C H
2
+ H I H
3
C
H
2
C I


Phn ng thng bt u bng s hnh thnh phc t. Tnh c th lp th khng
cao. V d: DCl cng trans vo mtyl xiclopenten-1 nhng li cng cis vo
propenylbenzen.
Tc dng ca cc dung dch nc clo hoc brm vi anken cho sn phm l cc
halogenhirin. Trong trng hp ny, tc nhn hot ng l axit hipclor hoc axit
hipbrm. V d:
H
2
C C H
2
+ H O C l H O H
2
C
H
2
C C l
e t y l e n c l o h i d r i n


- Phn ng cng axit:
Khi sc kh etilen qua axit sunfuric m c (>95%), dung dch b nng ln v
khng thy bt kh thot ra, axit sunfuric cng vo etilen.
48


H
2
C C H
2
+ H O S O
3
H H
3
C
H
2
C O S O
3
H
e t y l s u n f a t a x i t


Cc anken lng khng tan trong dung dch axit nhng tan trong H
2
SO
4
m c l
do phn ng cng xy ra. Cc ankyl hirosunfat to thnh d b thu phn khi un
nng vi nc to thnh ancol, chng hn:

C
H
C H
2
+ H O S O
3
H
H
C C H
3 R
R
O S O
3
H
H
2
O
t
0
C
H
C C H
3
R
O H


Phn ng ny cng c dng tch anken kh ra khi hn hp vi cc kh khc
v l giai on trung gian trong vic iu ch ru t anken.
- Phn ng cng nc.
Nc l mt cht lng tnh v so vi hyro halogenua n ch l mt axit rt yu
nn thc t coi nh khng tc dng trc tip vi anken trong iu kin bnh thng.
Tuy vy, nu dng dung dch long ca axit mnh ta c th hyrat ho anken theo s
sau:

+ H
3
O
- H
2
O
C C
H
H
2
O
C C
H
O H
2
- H
C C
H
O H


Cht xc tc axit dng trong phn ng hyrat ho thng l HNO
3
, H
2
SO
4
. Dng
Hhal khng thun tin v bn thn Hhal c th cng vo ni i.
Khi mun hyrat ho nhng anken c t nhm th ni i ngi ta thng
dng H
2
SO
4
m c cng vo ni i, sau thu phn axit alkyl sunfuric thu
c. Nu dng d anken axit alkyl sunfuric c th cng vo ni i to ra sunfat
ialkyl.
V d:
H
2
C C H
2 + H
2
S O
4
C H
3
C H
2
O S O
3
H
H
2
C C H
2
H
2
O
C H
3
C H
2
O H + H
2
S O
4
( C H
3
C H
2
O )
2
S O
2


Ngoi ra, ta cng c th hyro ho gin tip bng phng php hyrobo ho ri sau
xy ho trialkyl bo mi thu c. V d:

H
3
C C
H
C H
2
6 + B
2
H
6
2 ( C H
3
C H
2
C H
2
)
3
B
2 ( C H
3
C H
2
C H
2
)
3
B
+ 3 H
2
O
2
3 C H
3
C H
2
C H
2
O H + H
3
B O
3


hyrbo ho
oxy ho
NaOH
49


Hyrobo ho l mt phn ng cng kiu cis. C ch ca phn ng ny cha c
nghin cu y . C th BH
3
sinh ra t B
2
H
6
cng vo ni i qua trung tm chuyn
tip vng:

H
3
C C
H
C H
2
H B H
2
H
3
C
H
C C H
H B H
2
o
o
o
o
H
3
C
H
2
C C H
2
B H
2


Hoc BH
3
tc dng nh mt tc nhn electrphin vo ni i ca anken to ra mt
cacbcation vi nhm th
3
H B

, sau s xy ra s chuyn dch ion hyrua t nguyn

t B
-
n nguyn t C
+
, sn phm thu c (monoalkyl bo) li tc dng vi cc phn
t anken khc to ra trialkyl bo:

H
3
C C
H
C H
2 + B H
3
H
3
C
H
C
H
2
C B H
3
H B H
2
C H
2
H
C H
3
C
C H
3
C H C H
2
B H
2
C H
3
C H C H
2
B H
2
+
2 H
3
C C
H
C H
2
( C H
3
C H
2
C H
2
)
3
B


* Kh nng phn ng:
Kh nng phn ng cng lin quan n tc nhn, cht xc tc v c bit l cu
trc ca hp cht cha no.
Theo c ch cng electrophin trnh by trn th giai on quyt nh vn tc
chung ca phn ng l giai on tn cng ca tiu phn mang in tch dng vo ni
i v to ra mt cation trung gian. V vy, ta c th on rng nu mt electron
lin kt i cng cao v nu cation trung gian cng n nh th phn ng cng d xy
ra. Nh th, nhng nhm th y electron ni i s lm tng kh nng phn ng ca
anken, cn nhng nhm th ht electron s c nh hng ngc li bi v cc nhm
th y e lm tng bn ca cacbcation v gim G:


C C
H
H
H
H
3
C
B r
C C
H
H
H
H
B r
C C
H
C
H
H
B r
O
O H



Quy lut trn v kh nng phn ng c thc nghim xc nhn l ng, c th
l nhm cacboxyl v nguyn t brm lm gim vn tc phn ng, trong khi cc
nhm metyl v phenyl lm cho vn tc tng ln. ng ch l nhm phenyl gy nh
hng mnh hn mt nhm mtyl nhng yu hn hai nhm.
d hn kh hn
50


So snh kh nng phn ng cng electrphin ca cc axit o, | - cha no ta cng
thy nh vy.

(CH
3
)
2
C=CHCOOH > trans-C
6
H
5
CH=CHCOOH
> trans-CH
3
CH=CHCOOH > CH
2
=CHCOOH

S d nhm phenyl c nh hng mnh n phn ng electrophin v nh c hiu
ng +C, n lm tng bn ca cacbocation trung gian.

* Hng cng electrophin:
S cng hp mt tc nhn khng i xng (ICl, HCl, HI, H
2
SO
4
) vo phn t
anken i xng th ch to ra mt sn phm cng. Nhng nu anken c cu trc khng
i xng, th d CH
3
CH=CH
2
, th phn ng cng c th xy ra theo hai hng khc
nhau:

H
3
C C
H
C H
2
+ X Y
H
3
C
H X
C C H
2
Y
H
3
C
H Y
C C H
2
X
( I )
( I I )


Phn ng s u tin xy ra theo hng nguyn t hyro ca HX s tn cng vo
nguyn t cacbon ca ni i cha nhiu hyro hn (cacbon bc thp), cn X s tn
cng vo nguyn t cacbon cn li ca ni i cha t hyro hn (cacbon bc cao) to
ra sn phm (II).
gii thch iu ny, ta c th xt cc yu t tnh (cu to phn t hp cht cha
no ban u, cu to ca tc nhn) nhng quyt nh hn, ta phi xt cc yu t ng
(phc hot ng hay l trng thi chuyn tip).
- Gii thch theo trng thi tnh.
Trong phn t propilen, do tc dng y electron ca nhm metyl v pha lin kt
i lm cho lin kt ny tr nn phn cc, mt electron t dch chuyn v pha
nhm CH
2
(cacbon bc thp) lm cho nhm ny mang mt phn in tch m v giu
mt electron hn cn nhm CH (cacbon bc cao) mang mt phn in tch dng.
Do , s phn b mt electron trong phn t propilen c th biu din nh sau:

C
H
H
H
H
C H
o
o


Khi cho H
+
Cl
-
tc dng vi propilen, phn cation ca tc nhn (prton H
+
) s tn
cng vo cacbon mang in tch m, cn phn anion Cl
-
s tn cng vo cacbon mang
in tch dng.
- Gii thch theo trng thi ng:
51


Phn ng xy ra theo c ch cng electrophin (A
E
) nn giai on quyt nh tc
phn ng l giai on ca H
+
tn cng vo propilen, c th gi thit c hai qu trnh
xy ra nh sau:

H
3
C C
H
C H
2
+ H H
3
C
H
C C H
3
( I )
H
3
C
H
C C H
3
C l
i z o p r o p y l c l o r u a
H
3
C C
H
C H
2
+ H H
3
C
H
2
C C H
2
( I I )
H
3
C
H
2
C
H
2
C
n - p r o p y l c l o r u a
C l
C l
C l


Trong qu trnh 1, H
+
tn cng vo nhm CH to ra ion cacboni trung gian (I); cn
trong qu trnh 2, H
+
tn cng vo nhm CH
2
to ra ion cacboni (II). Phn ng xy ra
theo qu trnh no l ph thuc vo nng lng v bn ca ion cacboni trung gian.
Dng ion cacboni c nng lng cng thp v c bn cng ln khi in tch dng
nguyn t cacbon cng c gii to. iu ny xy ra khi in tch dng nguyn
t cacbon lin hp vi cng nhiu electron o ca cc lin kt CH. Ion cacboni c
bn cng ln th cng d hnh thnh.
So snh c im cu to ca 2 ion cacboni I v II, ta nhn thy ion I c nng lng
thp hn ion II v trong ion I c s lin hp ca in tch dng vi 6 lin kt o
CH, cn trong ion II ch c s lin hp vi 2 lin kt o CH. Do , ion I bn hn
v d hnh thnh hn ion II.
iu ny gii thch c trong phn ng cng ca propilen vi HCl to thnh
ch yu l sn phm izopropyl clorua.
Trn c s s gii thch v trng thi tnh v s phn b mt electron ca phn t
cha phn ng, c th pht biu qui tc Maccpnhicp nh sau:
Tc dng ca mt tc nhn khng i xng (HX chng hn) vo mt anken khng
i xng, phn cation ca tc nhn s tn cng vo nguyn t cacbon mang ni i
giu mt electron tch in m, cn phn anion s kt hp vi nguyn t cacbon
mang ni i tch in dng.
Trn c s gii thch theo trng thi ng, c th pht biu khi qut qui tt
Maccpnhicp nh sau:
Phn ng cng electrophin vo anken s din ra ch yu qua dng ion cacboni
trung gian c bn ln nht.
Cch gii thch theo trng thi ng hin nay c p dng ph bin hn c.

* Hiu ng peoxit hay hiu ng Kharats.
Kharats v My nhn thy rng, khi cho HBr cng vo alyl brmua, nu loi tr
s cmt ca peoxit bng cch cho thm mt lng nh cht chng oxy ho vo hn
hp phn ng th phn ng cng xy ra bnh thng, tc chm, theo quy tc
Maccopnhicop. Nhng nu trong hn hp phn ng c sn peoxit hoc cho thm
peoxit mi vo th phn ng s din ra tri vi qui tc Maccopnhicop, tc nhanh:

52


H
2
C C
H
C H
2
B r + H B r
H
3
C
H B r
C C H
2
B r
B r H
2
C
H
2
C C H
2
B r
p e o x i t
n h a n h


C th dng cht chng oxi ho nh hidroquinon; cn peoxit xc tc cho phn ng
bt thng c th dng peoxit benzoyl chng hn. Ngoi trng hp alyl bromua
ngi ta nhn thy phn ng cng bt thng vi HBr khi c mt peoxit cng din ra
vi cc anken. V d: phn ng cng ca HBr c mt peoxit vo propylen s to thnh
n-propylen s to thnh n-propyl bromua, hiu sut phn ng t ti 80%.

H
2
C C
H
C H
3
+ H B r
H
3
C
H B r
C C H
3
H
3
C
H
2
C C H
2
B r
p e o x i t


Ta gi nh hng ca peoxit gy ra phn ng tri vi qui tc Maccopnhicop ny l
hiu ng peoxit hoc hiu ng Kharats.
Phn ng din ra theo c ch gc nh sau:
-Giai on khi mo: peoxit phn li cho cc gc t do:

R O O R R O
.
2


Cc gc t do c th tc dng vi hidro bromua theo hai cch:

RO
.
+ HBr ROH + Br
.
H = -23 kcal
RO
.
+ HBr ROBr + H
.
H = +39 kcal

V mt nng lng, phn ng to ra ROH v nguyn t brom thun li hn.
- Giai on pht trin mch:
Nguyn t brom s tn cng vo anken to ra mt gc t do mi, ri gc t do ny
li tc dng vi HBr to ra n-propyl bromua v nguyn t brom:

H
3
C C
H
C H
2
+ B r
.
H
3
C C C H
2
B r
. .
H
H
3
C C C H
2
B r
. .
H
+ H B r C H
3
C H
2
C H
2
B r + B r
.


- Giai on tt mch:

R
.
+ R
.
RR
cng bnh thng
cng khng bnh thng
chm
cht chng oxy ho
H = -5kcal/mol
H = -11kcal/mol
53



Nguyn t brom tn cng vo nhm CH
2
ca ni i l v nguyn t brom c tnh
electrophin, n tn cng vo nguyn t cacbon giu mt electron hn.
Mt khc, so snh bn hai gc t do trung gian c th to ra:

H
3
C C C H
2
B r H
3
C
H
C C H
3
B r
.
H
.
( I ) ( I I )


V mt nng lng, gc (I) bn vng hn gc (II), do s lng lin kt CH lin
hp vi electron t do trong gc (I) nhiu hn trong gc (II). V vy, gc (I) d hnh
thnh hn gc (II).
iu ny gii thch s hnh thnh sn phm n-propyl bromua khi cng HBr vo
propilen c mt peoxit.

* Quy tt Zaixep Vanhe:
Tng tc ca mt tc nhn khng i xng HX vi mt anken, trong , nguyn t
cacbon mang ni i l ng bc, lin kt vi 2 nhm ankyl khc nhau, mt l gc
metyl, th phn anion X
-
ca tc nhn s kt hp vi cacbon ca ni i mang nhm
metyl:

H
3
C
H
2
C C C C
H
H
H
+ H X
H
3
C
H
2
C
H
2
C
H
C C H
3
X
o
o


Kt qu ca phn ng c gii thch bng hiu ng siu lin hp cc cc gc
ankyl. Trong hiu ng siu lin hp, kh nng y electron ca cc gc ankyl ngc
vi trong hiu ng cm ng:

Hiu ng cm ng (+I): (CH
3
)
3
C > (CH
3
)
2
CH > CH
3
CH
2
> CH
3

Hiu ng siu lin hp: CH
3
> CH
3
CH
2
> (CH
3
)
2
CH > (CH
3
)
3
C

Do , trong 2-penten, mt electron t lch v pha C
3
lmcho mt electron
C
3
giu ln v tch in m. Khi tc dng vi HX, prton s tn cng vo C
3
, do
phn anion X
-
s kt hp vo C
2
mang nhm metyl.
Cng c th gii thch qui tt trn theo trng thi ng da vo bn ca ion
cacboni trung gian. Ion cacboni bc 3 bn hn.

3) Phn ng oxy ho
Cc hirocacbon cha lin kt i nhy cm hn nhiu i vi cc cht oxy ho so
vi cc hirocacbon no. iu kin tin hnh phn ng oxy ho rt khc nhau, sn
54


phm phn ng cng khc nhau, tu theo iu kin tin hnh phn ng v c tnh ca
tc nhn.

a)Tc dng ca kali permanganat
Di tc dng ca kali permanganat, trong dung dch trung tnh hoc kim, lin kt
i ca anken s kt hp vi hai nhm hidroxi nh khi cng vi hyro peoxit
HOOH, to ra 1,2-diol.

R C
H
C
H
R
+ 2 [ O H ] R
H
C
H
C R
O H O H

Trc ht ion pemanganat kt hp vo lin kt i to ra mt este mch vng. Este
ny khng th tch ra c, b thu phn chuyn ho ngay thnh dng cis-diol:

C
C
+ M n
O
O
O
O
-
C
C
M n
O
O
O
O
-
C
C
O H
O H
+
O
M n
O
O
O
-

Ion
2
4
MnO to thnh c mu l, khng bn, s tc dng ngay vi ion pemanganat
to thnh ion manganat:

+
2
4 4
3
4
MnO 2 MnO MnO .
V d: oxy ho xyclopenten bng dung dch kali pemanganat ta s thu c sn
phm l cis-cyclo pentandiol:
K M n O
4
O H
O H


Phn ng ny dng trong phn tch nhn ra ni i. Cho anken tc dng vi dung
dch kali pemanganat trong mi trng kim (thuc th Baye) dung dch s mt mu.
Trong iu kin mnh lit hn, dung dch axit v un nng, s xy ra phn ng b gy
phn t ch ni i to ra axit cacboxylic.

b)Tc dng cua axit cromic
Axit cromic c s dng rng ri oxi ho lin kt i hoc di dng dung dch
Cr
2
O
3
trong axit aetic m c c mt H
2
SO
4
hoc khng., hoc di dng dung dch
natri hoc kali bicromat. Phn ng b gy lin kt i to ra xeton hoc axit
cacboxilic. S to thnh xeton chng t s c mt nhm R
2
C=, cn s to thnh axit
cacboxilic chng t s c mt ca nhm RCH=:

R
2
C C
H
R + 3 [ O ]
R
2
C O + R C O O H

55



Nh phn ng ny c th xc nh v tr ca lin kt i trong anken.

c)Peaxit hu c
Cc axit pebenzoic, axit peaxetic v.v oxi ho cc anken to ra o-oxit:


C C + R C O O H
O
C C
O
R C O O H
+


Axit peaxit dng trong phn ng ny di dng dung dch trong axit axetic v c
tng hp t hiro peoxit v anhiric axetic.
un nng lu nhit cao, ng l thu c anken oxit, ta li thu c sn phm
thu phn ca n, tc l iol.

C C
O
+ H
2
O
O H
O H


Cc diol thu c t anken mch vng l cc trans diol, khc vi cc diol thu
c khi dng tc nhn l permanganat l cc cis diol.
Trong dung dch Hcl pha long cha PdCl
2
v ng, etylen b oxy ho n
axetaldehyt:

C
2
H
4
+ PdCl
2
[C
2
H
4
PdCl
2
] CH
3
CHO + Pd + 2H
+
+ 2Cl
-


Pd + 2CuCl
2
2CuCl + PdCl
2

c CuCl
2
, ngi ta oxi ho CuCl trong khng kh hoc oxy:

2CuCl + 2HCl + 1/2O
2
2CuCl
2
+ H
2
O

Phn ng tng qut:

C
2
H
4
+ O
2
CH
3
CHO

d)Ozon
Phn ln cc anken tc dng mt cch d dng vi ozon, ngay c khi nhit
thp, lin kt i b b gy, to ra sn phm gi l ozonit. Phn ng tin hnh ht sc
o-oxit
H
2
O
56


nh nhng so vi khi dng cc cht oxi ho thng thng v v vy c dng rng ri
thit lp cu to.
zonit l nhng cht lng nh du hoc cht rn v nh hnh, rt d n v khng
th chng ct c. Phn ng vi nc, ozonit s b phn hu thnh andehyt hoc
xeton, tu theo cu to ca anken ban u:
R
2
C C
H
R + O
2
R
2
C C H R
O O
O
+ H
2
O
R
2
C O + R C H O + H
2
O

loi tr mt s phn ng ph, ngi ta thay th giai on thu phn cui
cng bng cch kh, dng natri bisunfit hoc tt hn dng hyro c xc tc:

R
2
C C H R
O O
O
+ H
2
R
2
C O + R C H O + H
2
O


V d: khi ozon ho izobutilen, ta thu c sn phm l axeton v formandehyt:

C C H
2
H
3
C
H
3
C
+ O
3
C
H
3
C
H
3
C
O O
C H
2
O
+ H
2
O
H
3
C
C
H
3
C
O
+ H C H O + H
2
O
2


Phn ng ozon ho cho hiu sut kh cao, t 60-7-%.

4) Phn ng th v tr alil v vinyl
Trong thi gian gn y, ngi ta ch n mt s phn ng ca cc anken trong
lin kt i vn c duy tr. Trong trng hp ny, nguyn t hyro ca nhm
CH
2
v tr o i vi ni i thng gi l v tr alyl, c thay th:

C
H
C
H
H
2
C
o


Nguyn t hyro ny c kh nng phn ng c bit, th hin r trong nng lng
lin kt CH ca n l nh mt cch bt thng so vi hyro nh vo cc nguyn t
cacbon no khc (nng lng lin kt CH trong CH
4
bng 102 kcal/mol cn ca
CH alyl bng 77 kcal/mol).
Nguyn t hyro v tr vinyl tc l hyro nh trc tip vo cacbon mang ni i,
tuy c nng lng lin kt CH ln (104 kcal/mol) nhng trong nhng iu kin c
bit vn c th tham gia phn ng th.

57


a) Th v tr alyl
Trong nhng iu kin xc nh, tc dng ca clo n anken khng to ra dn xut
diclo m cho sn phm th kiu alyl theo s sau:


H
2
C C C
H
+ C l
2
C
H
C
H
C
C l
+ H C l


Phn ng ny tin hnh rt d dng i vi cc anken phn nhnh. V d, clo ho
izobutilen ngay nhit phng:

C C H
2
H
3
C
H
3
C
+ C l
2
H
2
C
C
C H
3
C H
2
C l + H C l


Sn phm ph l 1,2-diclo-2-metyl-propan.
Thc cht c s di chuyn ni i theo c ch phn ng sau y: trc ht c phn
ng cng bnh thng ca cation clo Cl
+
vo mt cacbon mang ni i; sau cation
ny hoc s cng vi anion clo Cl
-
cho sn phm cng bnh thng hoc s tch mt
proton H
+
cho sn phm th alyl:

C C H
2
H
3
C
H
3
C
+ C l : C l
H
3
C C
C H
3
C H
2
C l
H
3
C C
C H
3
C H
2
C l
H
3
C C
C H
3
C H
2
C l
C l
H
2
C
C
C H
3
C H
2
C l
+ C l
- H


i vi cc anken khng phn nhnh, nh propilen chng hn, phn ng cho sn
phm th alyl tin hnh trong iu kin kh khn hn.


H
3
C C
H
C H
2
+ C l
2
C l H
2
C C
H
C H
2
5 0 0 - 6 0 0
0
C
a l y l c l o r u a


b)Th v tr vinyl
Sn phm chnh
Sn phm ph
58


Nguyn t hyro nh vi cacbon mang ni i (hyro vinyl) bng lin kt CH c
nng lng lin kt ln hn nhiu so vi lin kt CH khc. l do m in kh
ln ca nguyn t cacbon lai ho sp
2
. Do , vic thay th nguyn t hyro vinyl bng
halogen tin hnh trong iu kin kh khn nh nhit cao. Cn trong iu kin
thng, tc dng ca halogen vi anken ch cho phn ng cng.
Phn ng th clo vo hyro trong etilen tin hnh nhit cao (200-600
0
C) cho
sn phm l vinyl clorua:

H
2
C C H
2
+ C l
2 C l C
H
C H
2
2 0 0 - 6 0 0
0
C


Phn ng ny dng trong cng nghip sn xut vinyl clorua lm nguyn liu tng
hp mt polime c gi tr l PVC. Hiu sut sn phm phn ng clo ho tng ln (n
90%) nu tin hnh phn ng 250-350
0
C c mt 0,5% oxi (oxi lm gim phn ng
cng clo).
C ch phn ng clo ho etilen nhit cao cng l c ch gc dy chuyn kiu
nh clo ho ankan.
C l : C l
t
0
2 C l
.
H
2
C C H
2 + C l
.
H
2
C C H
.
+ H C l
H
2
C C H
.
+ C l : C l
H
2
C C
H
C l + C l
.


5) Phn ng trng hp v telome ho
a)Phn ng trng hp
Mt trong nhng phn ng quan trng bc nht trong k thut hin nay ca cc
anken v cc hp cht cha no khc l phn ng trng hp to ra sn phm l polime
(cht cao phn t). Qu trnh trng hp to nhit rt ln, i vi etylen l 800 cal/g
(trng hp th kh), sau l izobutilen 228 cal/g (trng hp trong dung dch).
S chung ca phn ng trng hp nh sau:

nA (A)
n

n l h s trng hp.
A l mnme.
V d:
H
3
C C
H
C H
2
H
C
H
2
C
C H
2
n
n


Tu theo bn cht c im ca monome, tu iu kin tin hnh phn ng, s
trng hp s xy ra theo c ch khc nhau, cho polime c cu to khc nhau v h s
trng hp khc nhau.
b) Phn ng telome ho
59


Mt trong nhng dng trng hp c bit ca etilen l phn ng telome ho. Di
tc dng ca cacbon tetraclorua ln etilen p sut cao c mt peoxit lm xc tc, xy
ra qu tnh trng hp etilen nhng ch cho c mt polime c h s trng hp nh, do
s kt hp vi phn t CCl
4
lm tt mch sm hn phn ng trng hp bnh thng.
Qu trnh ny cng l mt chui cc phn ng dy chuyn theo c ch gc:


R C O O C R
O O
R
.
+ C O
2
+
.
O C O R
R
.
+ C C l
4 R C l +
.
C C l
3
H
2
C C H
2
+
.
C C l
3
H
3
C
H
2
C C C l
3
.
H
3
C
H
2
C C C l
3
.
C l C H
2
C H
2
C C l
3
+
.
C C l
3
H
2
C C H
2
H
2
C
H
2
C
H
2
C
H
2
C C C l
3
C l ( C H
2
C H
2
)
2
C C l
3
+
.
C C l
3
+ C C l
4
+ C C l
4
v . v . . .


Phn ng tng qut c th biu din nh sau:

n CH
2
=CH
2
+ CCl
4
Cl(CH
2
CH
2
)
n
CCl
3

trong n = 1,2,3

S to thnh nhng sn phm phn ng khc nhau c cha s gc etilen khc nhau
ph thuc vo iu kin phn ng.
Thu phn dn xut tetracloankan thu c s to ra ankyl cacboxylic.

C l ( C H
2
C H
2
) n C C l
3
+ 2 H
2
O
C l ( C H
2
C H
2
) n C O O H + 3 H C l


Phn ng telome ho etilen cho cc dn xut tetracloankan v cho axit tng ng c
cha s l nguyn t cacbon.
Phn ng telome ho c ngha thc tin iu ch tng hp cc mnme trong k
thut tng hp cc cht cao phn t cng nh cho nhiu qu trnh tng hp hu c
khc.

2.1.7. Phn ng tch
Khi hai nguyn t hay nhm nguyn t b tch ra khi mt phn t m khng c s
thay th bng nhng nguyn t hay nhm nguyn t khc ta c phn ng tch. Quan
trng v ph bin nht l nhng phn ng tch mt nhm X v nguyn t hyro v
tr | to ra lin kt i C=C.
60


H C C X
- H X
C C C C
H
X
- H X
C C


1) C ch phn ng tch
Phn ln nhng phn ng tch | quan trng l nhng phn ng nucleophin xy ra
trong dung dch (cc c ch E2, E1, E1cb) v phn ng theo c ch vng (Ei) xy ra
trong tng hi nhit cao.

a) C ch E2
C ch phn ng tch nucleophin lng phn t E2 c nhng nt tng t c ch
phn ng th S
N
2 v cng l phn ng mt giai on v i qua trng thi chuyn tip l
mt phc hot ng.
Khc vi phn ng S
N
2, trong phn ng E2, phc hot ng sinh ra do tng tc
gia tc nhn Y
-
v nguyn t | -hyro trong phn t cht p: phc ny tch prton
cng vi Y
-
v nhm X ng thi to ra sn phm cha no:

Y + H C
H
C X
Y H X
C C
o o
C C
+ Y H + X



y X c th l F, Cl, Br, I, OSO
2
R, N
+
R
3
v.v, cn Y
-
l mt anion hay phn t
trung ho vi cp electron cha s dng (baz) nh OH
-
, C
2
H
5
O
-
, C
6
H
5
O
-
, NR
3
v.v
V d: phn ng tch HBr t bromua propyl nh tc dng ca etylat natri trong
etanol:

C C
H
B r
H
H
H
3
C H
C C
H
B r H
H
H
H
3
C H
C
2
H
5
O
o
o
C C
H
3
C H
H
H
+ B r + C
2
H
5
O H

chng minh c tnh lng phn t ca c ch E2, ngi ta kho st vai tr
ca tc nhn Y
-
v thy rng trong phn ng E2 cn dng baz mnh v vn tc phn
ng thng ph thuc vo c hai thnh phn tham gia vo phn ng.

V = k[RX] [Y
-
]

trng thi chuyn tip
61


Mt khc, nu thay nguyn t | -hyro bng teri th thy c hiu ng ng v t 3
n 8, iu chng t lin kt CH b t giai on quyt nh vn tc phn ng.
Xt ho lp th ca phn ng ta thy v mt l thuyt nhm X c th b tch ra
cng vi nguyn t | -hyro cng pha (tch kiu cis hay syn) hoc khc pha vi n
(tch kiu trans hay kiu anti).

H
R
X
R
Y
H
R
X
R
Y
o
o
- X
- H Y
R
R


H
R
X
R
Y
H
R
X
R
o
- X
- H Y
R
R
Y
o


Do
o
X v
o
Y gn nhau s y nhau nn ttct syn khng n nh bng ttct anti.
Mt khc, t ttct anti d to ra obitan t hn v cc trc obitan ttct anti song song vi
nhau.
V vy, phn ng E2 xy ra theo kiu trans hay anti, tc l khi trung tm tham gia
phn ng (HCCX) trn mt mt phng, trong cc nguyn t hay nhm
nguyn t b tch (H v X) v tr anti i vi nhau.
Quy lut ny cng c p dng cho dy xiclohecxan: phn ng E2 ch xy ra d
dng khi hai nguyn t hay nhm nguyn t b tch v tr trans-(a,a). Cc ng phn
trans-(e,e) khng tham gia phn ng; cn cc ng phn cis-(a,e hoc e,a) ch phn
ng rt chm hoc khng phn ng.
Thc t, khi tch HBr t cis-dibrometylen trong dung dch kim etanol vn tc
tch ln gp 135 ln so vi phn ng tng t ca trans-dibrometylen.
Thc t, khi tch HBr t cis-dibrometylen trong dung dch kim-etanol, vn tc tch
ln gp 135 ln so vi phn ng tng t ca trans-dibrometylen.

C H
C
B r
H B r
H B r
H B r
B r H


Nhng s kin k trn chng t phn ng E2 xy ra theo kiu trans. Tnh c th
lp th ny c nhiu nguyn nhn:
nhanh
chm
-HBr
-HBr
ttct anti
ttct syn
62


-Nu so snh nng lng ca cc trng thi chuyn tip th trng thi ng vi s
tch kiu trans n nh hn trng thi ng vi s tch kiu cis v khng c s y nhau
gia cc nhm C. . .H. . .
o
Y v C. . .
o
X .

H
X
Y
o
o
H
X
o
Y
o





- S to thnh cc obitan t s thun li hn, nu phn ng tch xy ra theo kiu
trans. Tht vy, trng thi chuyn tip bt u hnh thnh ni i, obitan t ca ni
i ny sinh ra bng cch xen ph cc obitan vn l sp
2
nguyn t cacbon trong phn
t cht u. Cho nn s xen ph s thun li hn nu cc nhm b tch v tr trans
i vi nhau v khi y cc obitan sp
3
trn mt mt phng.


s p
3
s p
3
p
s p
3
p
s p
3



Ta c th pht biu mt quy lut chung nh sau: s tch lng phn t ch xy ra d
dng khi no bn trung tm tham gia phn ng (HCCX) nm trong mt mt
phng, ngha l cc nhm b tch v tr trans (hay anti) i vi nhau.
Tuy nhin, quy lut tch kiu trans ch p dng c cho cc hnh th (cu dng) c
nhng nhm b tch v tr trans kiu trc (axial). Cc hnh th kiu trans c nhng
nhm b tch v tr bin (equatorial) khng tham gia phn ng tch lng phn t v
bn trung tm HCCX khng nm trong mt mt phng.
minh ho quy lut va nu trn, ta xt phn ng tch ca clorua mentyl v clorua
nometyl. Clorua mentyl c hai hnh th gh trong I tng i bn hn, cn i vi
clorua nomentyl hnh th bn l III. Phn ng tch ca clorua neomentyl ch to ra
mt anken l menten-2 v xy ra vi vn tc rt chm. V tho mn iu kin tch
lng phn t phi chuyn cn bng t dng I sang dng II t bn hn. i vi clorua
neomentyl, nguyn t clo c th b tch cng vi nguyn t hyro C
2
hoc C
4
to ra
hn hp hai anken, trong menten-3 chim ty l cao hn (theo quy tt Zaixep) v
phn ng tch c vn tc tng i ln v III l dng bn ng thi tho mn iu kin
ca quy lut tch kiu trans.
trng thi chuyn tip trans trng thi chuyn tip cis
cht u trng thi chuyn tip sn phm
63


H
i - C
3
H
7 C l
H
3
C
H
H
( I )
H
C H
3
C l
H
H
i - C
3
H
7
( I I )
H
3
C i - C
3
H
7
H
C l
i - C
3
H
7
H
3
C
H
H
H
3
C i - C
3
H
7
( I I I )
1 0 0 %
7 5 %
2 5 %
m e n t e n - 3
m e n t e n - 2

S u tin tch theo kiu trans trong phn ng E2 l quy lut c ngoi l. V d,
phn ng E2 ca hyroxit trans-2-phenylxyclohexen tc l tch theo kiu cis.

N ( C H
3
)
3
H
C
6
H
5
H
H O
C
6
H
5


Nguyn nhn ca trng hp ngoi l ny l nh hng ca gc phenyl lm cho
nguyn t | -hyro tr nn hot ng.
Nhng phn ng debrom ho cc dn xut 1,2-dibrom bng anion iot cng chy
theo kiu trans:



H
B r
R
B r
H R
I B r + C C
R
H
H
R
+ B r
I B r + I
I
2
+ B r


b)C ch E1
C ch phn ng tch n phn t E1 tng t c ch n phn t S
N
1 v giai on
chm to ra cacbocation, nhng giai on sau th khc ca phn ng. Trong phn
ng E1 cacbocation tch prton to ra sn phm cha no.
64


H C C X H C C + X
H C C C C + H
X : C l , B r , I , O S O
2
R , S R
2
, O H
2 .
. .


Trong cc giai on phn ng trn, dung mi gi vai tr solvat ho rt quan trng.
V d: c th m t phn ng tch ca bromua t-butyl nh sau:

( C H
3
)
3
C B r + s o l
( C H
3
)
3
C s o l + B r s o l
( C H
3
)
3
C s o l
( C H
3
)
2
C H C H
2
+ H s o l

Sol: dung mi.

Vn tc ca phn ng E1 ch ph thuc vo nng ca cht phn ng ch khng
ph thuc vo nng ca tc nhn nucleophin: trong v d trn v [(CH
3
)
3
CBr].
Nhng yu t lm thun li cho phn ng S
N
1 ni chung cng lm thun li cho phn
ng E1.
V phng din ho lp th, cc phn ng E1 trong dung dch khng c tnh c th
nh phn ng E2 v cacbocation trung gian sinh ra c cu trc phng hoc gn nh
phng, do s tch khng ph thuc vo cu hnh phn t ban u. Tuy vy, nu
nhm X cha ri khi nguyn t cacbon mang in dng mt khong cch xa m
xy ra s tch proton hoc nu trong phn ng ch to ra nhng cp ion trung gian
[R
+
X
-
] th s tch theo kiu trans s chim u th hn.
Trong thc t, nhng iu kin ca phn ng E1, t hai ng phn cis trans
ca 1-metyl-2-cloxyclohexan u to ra 1-metylxyclohexen l chnh, cng vi 3-
metylxyclohecxen nhng t ng phn cis (tch kiu trans) t l 1-metylxyclohecxen
cao hn.

c) C ch E1cb
Theo c ch E1, nhm X b tch trc proton. Trong c ch E2, nhm X v hyro
b tch ng thi. C mt c ch th ba na: u tin, hyro b tch bi baz to ra
cacbanion, sau n lt X tch ra to thnh sn phm cha no:
chm
nhanh
65


H C C X
C C
C C + X
+ Y X + Y H
C C X


Qu trnh hai giai on trn c gi l c ch E1cb hay c ch cacbanion.
C ch E1cb ch xy ra d dng khi X km hot ng cn | -H rt linh ng (th d:
CHCl
2
CF
3
, NCCH
2
COHR
2
,), Y
-
l baz mnh (HO
-
, RO
-
...). V cacbanion sinh
ra c n nh nh nh hng ca nhng nhm ht electron mnh. l trng hp
ca cc phn ng hydrat ho | -hydroxyxeton, | -hydroxynitrin, deamin ho (tch
NH
3
hoc amin), | -aminoxeton v.v

R
O
C
H
2
C C
O H
R
O
C C
H
C
- H
2
O

N C
H
2
C C
O H
N C C
H
C
- H
2
O
R
O
C
H
2
C C
N H
2
R
O
C C
H
C
- N H
2


V mt ho lp th E1cb khng c tnh c th.
S xut hin cacbanion nh mt sn phm trung gian c xc minh bng phn ng
trao i ng v gia 1,1-diclo-2,2,2-trifloetan vi D
2
O. Vn tc trao i ng v ln
hn vn tc tch:


H C C l
2
C F
3
N a O D
C C l
2
C F
3
- H
D
2
O
- F
C l
2
D C C F
3
C l
2
C C F
2


Mt khc, kho st s tch CH
3
COOH t 2-phenyl-2-axetoxy-1-nitroxyclohecxan
ngi ta thy ng phn I phn ng nhanh hn ng phn II ti bn ln (nu theo c
66


ch E2 th II d b tch hn I) v thng s v nh hng ca nhm th gc phenyl
trong phng trnh Hammet c gi tr dng, iu ph hp vi c ch cacbanion:

H
C
6
H
5
O C O C H
3 N O
2
N O
2
C
6
H
5
H
O C O C H
3
C
6
H
5 N O
2
( I )
( I I )


C ch E1cb v cc c ch E1, E2 ch l ba trng hp in hnh trong mt dy
lin tc cc c ch tch nucleophin:




d)C ch Ei
C ch Ei thng gp trong cc phn ng nhit phn ankyl axetat (to ra anken v
CH
3
COOH), ankyl xantogenat (to anken, CH
3
SH v COS), oxit amin bc 3 (to
anken v hyroxylamin) V d:

C H
3
C H
2
C H
2
O C O C H
3
H
3
C H C C H
2
+ C H
3
C O O H
5 0 0
0
C
C H
3
C H
2
C H
2
O C S S C H
3
H
3
C H C C H
2
+ C O S + C H
3
S H
3 0 0
0
C
C H
3
C H
2
C H
2
( C H
3
)
2
N O
H
3
C H C C H
2
+ ( C H
3
)
2
N O H
1 5 0
0
C


Phn ng Ei l phn ng mt giai on, i qua trung tm chuyn tip vng kiu
perixilic. V d:


C C
H O
C O
R
C C
H O
C O
R
C C
O
C H O
R



2) Cc quy tt v hng tch
a)Quy tt v hng tch | -H
E1
cc c ch
trung gian
E2
cc c ch
trung gian
E1cb
67


i vi cc dn xut bc mt, nguyn t | -hyro ch c mt mt nguyn t
cacbon. V vy, nu khng xy ra s chuyn v th phn ng tch ch cho anken 1 l
sn phm duy nht. V d: C
6
H
5
CH
2
CH
2
Br ch c th cho C
6
H
5
CH=CH
2
.
i vi cc dn xut bc 2 v bc 3 th khng nh vy, y c kh nng hnh
thnh ng thi hai hoc ba sn phm. V d: sec-butyl c th to ra buten-1 v buten-
2, trong s c mt sn phm chnh. Trong nhng trng hp nh vy, c mt s
quy tt cho php xc nh sn phm chnh, c ngha l xc nh hng ca phn ng
tch. Cc quy tt l:
-Trong cc phn ng theo c ch Electron, nhm X b tch ra cng vi nguyn t
| -hyro cacbon bc cao nht v to ra ni i c nhiu nhm th nht. Quy tt ny
c gi l quy tt Zaixep. V d:

C H
3
C H C H
2
C H
3
O H
E 1
C H
3
H C C H C H
3
+
H
2
C C H C H
2
C H
3
C H
3
C H C H
2
C H
2
C H
3
O H
E 1
C H
3
H C C H C H
2
C H
3
+
H
2
C C H C H
2
C H
2
C H
3


H
3
C
H
C C H C H
3
C H
3
S ( C H
3
)
2
E 1
H
3
C H C
C C H
3
C H
3
+ H
2
C
C H C H C H
3
C H
3


- Nu X l mt nhm th khng mang in tch nh Cl, Br, I v khng c s
n ng khng gian th phn ng E2 cng xy ra theo hng nh phn ng E1 ngha l
X b tch cng nguyn t | -hyro cacbon bc cao nht (quy tt Zaixep). V d:


C H
3
C H C H
2
C H
3
B r
E 2
C H
3
H C C H C H
3
+
H
2
C C H C H
2
C H
3
C
2
H
5
O


Trong trng hp X l nhm th mang in dng v kh b tch hoc cng
knh nh
N R
3
, S R
2
, S O
2
R . . .
phn ng tch E2 xy ra theo hng tri ngc vi quy tt
Zaixep ngha l X b tch cng vi nguyn t | -hyro cacbon bc thp hn (quy tt
Hopman). Nh vy, quy tt Hopman ngc vi quy tt Zaixep v ch yu p dng cho
phn ng E2. V d:

C H
3
C H C H
2
C H
3
N ( C H
3
)
3
C H
3
H C C H C H
3
+
H
2
C C H C H
2
C H
3
E
2
H O

chnh ph
ph chnh
chnh ph
ph chnh
chnh ph
68




C H
3
C H C H
2
C H
2
C H
3
S O
2
C H
3
b a z o
C H
3
H C C H C H
2
C H
3
+
H
2
C C H C H
2
C H
2
C H
3
E 2


- Trong cc phn ng theo c ch E1cb, nhm X b tch ra cng vi nguyn t
| -hyro no c tnh axit tng i cao hn c.
- Bt k phn ng xy ra theo c ch no, nu trong phn t c sn ni i
(C=C hoc C=O) c th lin hp vi ni i sinh ra th sn phm lin hp thng l
sn phm chnh.
- Bt k l c ch phn ng no, tun theo quy tt Hopman hay Zaixep, phn
ng tch khng xy ra theo hng to sn phm km bn.
Trong nm quy tt k trn, quy tt Hopman v Zaixep c ngha quan trng v
ph bin hn c.

b)nh hng ca cu to n hng tch v vn tc tch
Nu nhm X b tch v tr o, cn proton b tch v tr | trong phn t th cc
nhm th nhng v tr c th gy nn nhng nh hng khc nhau nh sau:
- Chng lm n nh hay mt n nh ni i ang hnh thnh (cc nhm v tr o
hay | ).
- Chng lm n nh hay mt n nh cacbanion v lm thay i tnh axit ca | -
proton (cc nhm v tr | ).
- Chng lm mt n nh hay n nh cacbocation sinh ra (ch cc nhm v tr o).
- Chng gy cc hiu ng khng gian (cc nhm v tr o v | ).
Hai hiu ng th nht v th t c hiu lc c ba c ch tch song hiu ng th t
c hiu lc cao nht phn ng E2. Hiu ng th hai khng c hiu lc i vi phn
ng E1 cn hiu ng th ba khng c hiu lc i vi phn ng E1cb.
Bng thc nghim, vn tc ca phn ng E2 ca cc halogenua ankyl bc mt
RCH
2
CH
2
Br ph thuc vo bn cht ca nhm th R v tr | theo th t:

CH
3
> CH
3
CH
2
> CH
3
CH
2
CH
2
> H


Khi a mt nhm ankyl vo v tr | hoc o ca halogenua ankyl bc hai v bc ba
ta cng thy vn tc phn ng E2 tng ln, nht l khi cc nhm ny v tr o. Mt
khc, ta cn thy s tch | -proton cc dn xut bc hai v bc ba c th xy ra
pha mch ankyl ngn hay pha mch ankyl di hn. Khi y vn tc ca phn ng tch
pha mch ankyl di v hiu sut ca anken tng ng thng ln hn hn so vi s
tch pha mch ankyl ngn ngha l phn ng tun theo quy tt Zaixep.
Nu a nhm th ankyl vo phn t hp cht oni, s bin thin vn tc phn ng
E2 s theo chiu ngc li, cc nhm th ankyl v tr | lm gim vn tc phn ng,
khi y, vn tc E2 mch di gim rt nhanh v phn ng tun theo quy tt Hopman.
ph chnh
69


Vn tc ca phn ng tch E2 cng ph thuc vo bn cht ca nhm b tch X.
Trong dy cc dn xut halogen vn tc tch gim theo th t I > Br > Cl > F. Mt
khc, hng c trng ca phn ng theo quy tt Zaixep cng gim theo chiu
ng thi hng to ra sn phm Hopman tng ln. V d, khi cho 2-halogenpentan
CH
3
CHHalCH
2
CH
2
CH
3
tc dng vi etylat natri trong etanol ngi ta thu c cc
penten theo t l phn trm nh sau:


I Br Cl F
Penten-2 80 75 64 18
Penten-1 20 25 36 82

i vi cc phn ng tch E1, khi nghin cu nh hng ca cc nhm ankyl v
tr | n phn ng ca dn xut (RCH
2
)
2
CHBr ngi ta thy vn tc cng nh hiu
sut anken bin thin th t sau:

R: CH
3
> CH
3
CH
2
> H

Kho st nh hng ca cc nhm ankyl cc dn xut bc ba RCH
3
CBr(CH
3
)
2
ta
cng thy quy lut nh trn. Trong trng hp , | -hyro b tch t mch ngn
(CH
3
) hay mch di (RCH
2
). Hiu sut anken v vn tc tch mch di ln hn
nhiu so vi mch ngn, ph hp vi quy tt Zaixep.
Phn ng E1 ca cc hp cht oni cng tun theo quy lut tng t dn xut
halogen ngha l cc nhm ankyl v tr | lm tng vn tc v hiu sut anken. Mt
khc, phn ng cng tun theo quy tt Zaixep.
Nhng iu trn cho thy hng ca phn ng tch ngoi ph thuc vo c im
c ch cn ph thuc vo cc yu t cu to.
c)C s l thuyt ca quy tt tch
Trong phn ng tch nucleophin, s u tin to thnh mt anken ng phn no
(theo quy tt Zaixep hay quy tt Hopman) khng phi do s ng phn ho anken gy
nn v trong iu kin phn ng tch khng gy nn. Yu t c bn chi phi
hng ca phn ng tch l cc yu t ng hc.

- Quy tt Zaixep trong phn ng E2
gii thch quy tt Zaixep ngi ta thng da vo nh hng khc nhau ca cc
nhm th cc v tr o v | n n nh ca trng thi chuyn tip cng nh
bn ca anken. Trng thi chuyn tip trong phn ng E2 ca cc dn xut halogen
(X-Cl, Br, I) v nhiu dn xut RX khc, c cu to:


C C R
R
X
H
B
R
R
o
o

70



Nu R l nhm ankyl c hiu ng siu lin hp th n nh ca trng thi chuyn
tip cng nh bn ca anken tng ng s cao hn so vi trng hp R l hyro.
Theo quy lut chung, phn ng s u tin xy ra theo hng no c trng thi chuyn
tip n nh hn v sn phm cng bn hn. V d: c phn ng ehydrobrom ho 2-
brombutan trong dung dch kim-etanol.

C C H
C H
2
C H
3
B r
H
H O
H
H
o
o
H O
-
H
3
C H C C
H
H
C H
2
B r
H
C C H
C H
3
B r
H
H O
H
3
C
H
o
o
H O
-
- H
2
O
- B r
- H
2
O
- B r
H
3
C H
2
C H
H
H
b u t e n - 1
H C H
3
H
3
C
H
b u t e n - 2



Nhn vo s c ch v gin nng lng, trung tm chuyn tip theo quy tt
Zaixep n nh hn trung tm chuyn tip theo quy tt Hopman nh vo hiu ng siu
lin hp ca hai nhm metyl nn phn ng din ra u tin theo quy tt Zaixep. V mt
nng lng buten-2 sinh ra cng bn hn buten-1.

- Quy tt Hopman trong phn ng E2
V kch thc ca cc nhm R
3
N
+
, R
2
S
+
v.v rt ln nn cu dng tch anti (trans)
theo quy tt Zaixep khng bn bng cu dng tch anti theo quy tt Hopman. Mt
khc trung tm chuyn tip T
Z
cng khng n nh bng trung tm chuyn tip T
H
. V
vy, phn ng din ra u tin theo quy tt Hopman.

o
E t
N M e
3
H
M e
H
M e
H O
E t
N M e
3
H
M e
H
M e
O
- H O H
- N M e
3
H
M e M e
E t


trng thi chuyn tip km bn trng thi chuyn tip bn hn
(km bn) 20%
(bn hn) 80%
T
Z
cu dng km bn
Sn phm Zaixep
71


o
P r - i
N M e
3
H
M e
H
H
H O
P r
N M e
3
H
M e
H
H
O
- H O H
- N M e
3
H
M e H
P r - i


Cng c th gii thch quy tt Hopman da theo hiu ng electron ca nhm th
trung tm chuyn tip.

- Quy tt Zaixep trong phn ng E1
Phn ng E1 ca mi dn xut RX d hng tch theo quy tt Zaixep hay theo quy
tt Hopman cng sinh ra mt cacbocation trung gian. Nh vy, yu t quyt nh
hng tch khng phi l trng thi chuyn tip I (ca bc to thnh cacbocation) m
l trng thi chuyn tip II (ca bc chuyn ho cabocation thnh sn phm tch) v
bn tng i ca sn phm tch.
C C
H
X
o
o
C C
H
o
S
o
( I )
( I I )


Xt bn tng i ca cc trng thi chuyn tip cng nh bn ca cc
sn phm ta u thy phn ng phi xy ra theo quy tt Zaixep.
Tuy vy, quy tt Zaixep c th b vi phm v cc l do v khng gian. V d, phn
ng E1 ca 2,4,4-trimetyl-2-clopentan to ra anken-1 l chnh:

H
3
C C
H
2
C C
C H
3
C H
3
C l
C H
3
C H
3
H
3
C C
H
2
C C
C H
2
C H
3
C H
3
C H
3
H
3
C C C
H
C
C H
3
C H
3
C H
3
C H
3
E 1
+
a n k e n - 1 8 1 % a n k e n - 2 1 9 %

Nguyn nhn lm cho phn ng trn u tin to ra anken-1 c th l s n ng
khng gian ca cc nhm metyl trong bc tch proton ra khi cacbocation trung gian
v quan trng hn nal anken-2 km bn hn so vi anken-1.
V d: phn ng tch (CH
3
)
2
CHCH(CH
3
)S
+
(CH
3
)
2
trong etanol-nc (S l dung
mi).
T
H
cu dng bn
Sn phm Hopman
72



H
3
C
H
C
H
C C H
3
C H
3
S ( C H
3
)
2
H
3
C
H
C
H
C C H
3
C H
3
C C
H
3
C
H
3
C
H
o
S
C H
3
H
o
C C
( H
3
C )
2
H C
H
H H
S
o
o
H
3
C C H
3
H
3
C
H
( H
3
C )
2
H C H
H
H
- S H
- S H
9 1 %
9 %




Trong v d trn, trung tm chuyn tip T
Z
(ca giai on tch proton) n nh
hn trung tm chuyn tip T
H
. Sn phm tch theo quy tt Zaixep cng bn hn sn
phm theo quy tt Hopman. V th mi phn ng E1 ni chung u theo quy tt
Zaixep.
- T l hai ng phn cis-trans trong sn phm tch
Khi tch HX t CH
3
CXR
1
R
2
hoc R
1
R
2
CHCXR
3
R
4
, anken sinh ra khng
c dng phn cis-trans nhng t R
1
R
2
CHCXR
3
R
4
v R
1
CH
2
CXR
2
R
3
c th to ra
nhng ng phn trans v cis tng ng.
Phn ng E2 xy ra theo kiu trans, trong trng hp ny yu t hnh th c
ngha quyt nh. Cc phn ng E2 thng sinh ra (Electron)-anken v phn ng ny
din ra vi cu dng anti (cho ng phn Electron) thun li hn vi cu dng syn
(cho ng phn Z) xt v bn ca cc cu dng u cng nh ca cc trung tm
chuyn tip tng ng.
V d: c phn ng ehydroclo ho 1-clo-1,2-diphenyletan. Dn xut clo ny c 3
hnh th xen k, trong s ch cc hnh th I v II mi c H v Cl v tr anti i
nhau.
trng thi chuyn tip bn hn trng thi chuyn tip km bn
Anken km bn
Anken bn hn
73


C l
H C
6
H
5
H
H C
6
H
5
C l
H C
6
H
5
H
C
6
H
5
H
C l
H C
6
H
5
C
6
H
5
H H
( I )
( I I ) ( I I I )


Khi c tc dng ca baz, I s b dehydroclo ho thnh trans-stilben cn II s
to ra cis-stilben:


C l
H C
6
H
5
H
H C
6
H
5
( I )
H O
C l
H C
6
H
5
H
H C
6
H
5
O
o
o
o
- H O H
- C l
H C
6
H
5
C
6
H
5
H
t r a n s - s t i l b e n
C l
H C
6
H
5
H
C
6
H
5
H
( I I )
H O
C l
H C
6
H
5
H
C
6
H
5
H
O
o
o
o
- H O H
- C l
H C
6
H
5
H C
6
H
5
c i s - s t i l b e n


Gin nng lng ca hai qu trnh trn c trnh by hnh sau. So snh
cc gin , nht l so snh cc nng lng hot ho ta thy hng to thnh trans-
stilben thun li hn hng to thnh cis-stilben. Thc nghim xc nhn lp lun
trn l ng.
i vi cc phn ng E1, nu cacbocation trung gian sinh ra t quay t do c
th bt k hai dng hnh hc ca cht u nh th no, trng thi bn ca ion cng s l
trng thi m trong nhm ln hn ca cp nhm th L-N s i din vi nhm nh
hn ca cp nhm th L-N (L: ln, N: nh).

H
L ' N '
N
L
h a y
N ' L
H
L N


T trng thi bn s sinh ra anken tng ng.
74


Mt khc, nu cacbocation khng hon ton t do th phn ng c khuynh
hng tng t phn ng E2. Ngoi ra, nu c mt nhm gy hiu ng k th nhm
c th nh hng n t l ca cc sn phm cis-trans-anken.

3) Nhng yu t nh hng n quan h gia cc phn ng tch v th
nucleophin
Cc phn ng tch v th nucleophin nguyn t cacbon no thng xy ra song
song. Tu iu kin c th m mt phn ng no chim u th hn. C nhiu yu
t nh hng n mi quan h .

a)nh hng v cu to ca cht phn ng
- Phn ng lng phn t
Trong iu kin phn ng lng phn t, khi bc ca gc hirocacbon tng ln th
vn tc ca phn ng S
N
2 gim trong khi vn tc ca phn ng E2 li tng. Nh
vy, khi tng bc ca gc hirocacbon hiu sut to ra anken s tng. C th:

CH
3
CH
2
X < (CH
3
)
2
CHX < (CH
3
)
3
CX.

V d: khi tc dng vi etylat natri trong etanol, bromua etyl cho ta sn phm ch
yu l dietyl ete v ch 1% etylen. Tri li, bromua t-butyl cho ta sn phm chnh l
izobutylen, cn bromua izopropyl li to ra propylen v etyl i-propyl ete theo t l 3:1.

- Phn ng n phn t:
i vi cc qu trnh n phn t, giai on quyt nh t l gia cc sn phm th
v tch l giai on nhanh khng quyt nh tc ca c qu trnh. V th, kh m
thy c mi quan h gia vn tc ca phn ng S
N
1 v phn ng E1.
Khi mc cng knh R tng ln, t l sn phm E1/S
N
1 s tng. Mt trong
nhng nguyn nhn quan trng y l nh hng khng gian. Ta bit rng gc ho
tr cacbocation l 120
0
, gc ln hn gc ho tr hp cht no ban u (109
0
).
Nh vy, s to thnh cacbocation l thun li v mt khng gian. Khi chuyn
cacbocation thnh anken vn cn s thun li nhng nu chuyn thnh sn phm
th th cc gc b thu nh li lm cho s y nhau gia cc nhm th tng ln do
chiu hng th l kh khn hn.
Bn cht ca nhm X b tch ni chung khng nh hng n s cnh tranh gia
hai phn ng E1 v S
N
1. Tuy vy, trong iu kin phn ng lng phn t t l
S
N
2/E2 bin i cht t theo bn cht ca halogen. Nu X l Ots phn ng th thng
chim u th. V d: n-C
18
H
37
Br tc dng vi t-C
4
H
9
OK cho 85% l sn phm tch
trong khi n-C
18
H
37
Ots li cho 99% l sn phm th. Ngoi ra, nhng nhm X mang
in dng cho sn phm tch nhiu hn.

b) nh hng v nng v bn cht ca tc nhn
- Phn ng lng phn t
+ C hai phn ng u ph thuc nng Y
-
, E2 ph thuc vo lc baz ca Y
-
,
cn S
N
2 li ph thuc vo lc nucleophin. Cho nn nu chn baz yu m c tnh
nucleophin mnh nh I
-
ta d dng tng hiu sut sn phm th v ngc li.
75


+ C hai phn ng u chu nh hng khng gian ca Y
-
, song nh hng i
vi S
N
2 ln hn rt nhiu so vi E2. V vy, chn Y
-
cng knh th d
etyldiizopropylamin c th khng ch ch cho E2 xy ra.
- Phn ng n phn t:
Ni chung, phn ng n phn t khng ph thuc vo nng Y
-
. Tuy vy, lc
baz ca Y
-
cng ln th kh nng tch prton ca R
+
cng tng, do t l E1/S
N
1 s
tng. Mt khc, nu tng kch thcY
-+,
th kh nng phn ng S
N
1 s gim r rt,
trong khi kh nng phn ng E1 t thay i. V vy, chn Y
-
rt cng knh, th d
2,6-di-t-butyl-piridin c th khng ch ch cho E1 xy ra.

c)Dung mi
Nguyn tt chung l nu mc tp trung in tch trung tm chuyn tip cao hn
trng thi u th s tng phn cc ca dung mi lm cho phn ng thun li hn.

- Phn ng lng phn t
i vi h Rhal + HO
-
, v d CH
3
CH
2
Br + HO
-
, c hai trung tm chuyn tip
u c in tch gii to ra ba nguyn t (OCBr), so vi h u, song in tch
trung tm chuyn tip ca E2 gii to rng hn c phn b trn 5 nguyn t
(OHCCBr)

o
H O H C
H
2
C
H
2
B r
o
H O C
H
2
B r
C H
3
o o


V cc dung mi phn cc lm n nh in tch tm trung ca ion hydroxyl
h u hn l in tch gii to cc trng thi chuyn tip, nht l trng thi chuyn
tip E2, cho nn khi tng phn cc ca dung mi c hai phn ng u tr nn kh
khn hn, nht l phn ng E2 v t l E2/S
N
2 s gim. iu ny c tnh cht tng
qut v c cc kt qu thc nghim xc minh.

- Phn ng n phn t.
Trong cc phn ng tch ca nhng dn xut vi X l nhm trung ho, s tng
phn cc ca dung mi v tng lc ion lun lun d dng cho cc c ch E1 v
E1cb.
Phn ng S
N
1 cng chu nh hng ca dung mi nh phn ng E1 nu xt giai
on to ra cacbocation. Nhng giai on sau, nh hng khng ging nhau.
V d, phn ng n phn t ca bromua t-butyl vi ion hydroxyl:

76


o
H
3
C C B r
C H
3
C H
3
- B r
H
3
C C
C H
3
C H
3
H O
H O
S
N
1
E 1
H
3
C C
C H
3
C H
3
O H
o
H
3
C C O H
C H
3
C H
3
H O H C
H
2
C
C H
3
C H
3
o
o
H
2
C C
C H
3
C H
3
- H O H

H gm cacbocation v HO
-
cng nh cc trng thi chuyn tip u b solvat ho,
nhng cc trng thi chuyn tip, nht l trng thi chuyn tip E1 b solvat ho yu
hn v in tch nh v gii to ra nhiu nguyn t hn. Nh vy, tc dng n nh bi
dung mi phn cc th hin r nht h cc ion ((CH
3
)
3
C
+
v HO
-
) v km nht
trng thi chuyn tip E1. Ni khc i, tc dng km hm s to thnh trung tm
chuyn tip E1 ln hn i vi s to thnh trung tm chuyn tip S
N
1 cho nn vn tc
v hiu sut ca phn ng E1 km phn ng S
N
1.
Do nh hng khc nhau ca dung mi nh trn, khi thc hin phn ng
ehydrohalogen ho, ngoi vic chn nhng baz mnh, ngi ta dng nhng dung
mi tng i t phn cc. Theo nguyn tt ny, ta c th xp mt s cp baz-dung
mi theo th t tng dn kh nng dehydrohalogen ho nh sau:

K O H
K O H C
2
H
5
O K t - C
4
H
9
O K
H O H C
2
H
5
O H C
2
H
5
O H
t - C
4
H
9
O H


d) nh hng ca nhit
i vi mt cht hu c nht nh, hai phn ng song song v cnh tranh nhau
thng khc nhau v nng lng hot ho.
Theo phng trnh Areniut
RT / E
a
BZe k

= , mt nhit nht nh, nng lng hot
ho cng ln phn ng s cng chm nhng nu nhit tng vn tc ca phn ng
no c nng lng hot ho ln hn s tng nahnh hn. Cho nn, c th c nhng
phn ng nhit phng th xy ra chm (E
a
ln) nhng nhit cao li xy ra rt
nhanh.
Cc phn ng tch v th nucleophin thuc loi nhng phn ng song song v cnh
trnah nhau. Phn ng tch thng c nng lng hot ho ln hn phn ng th
mol / kcal 1 2 . V d cc phn ng lng phn t gia bromua izopropyl v etylat natri
c nng lng hot ho ln lt l S
N
2: 20,8 kcal/mol; E2: 22,1 kcal.mol.
V l do ny, khi tng nhit phn ng ln th t l gia cc sn phm tch v th
E/S cng tng ln tc l tng hiu sut anken.
V d: un EtOH vi axit sunfuric m c nhit < 140
0
C tao c Et
2
O l
chnh, nng nhit ln th hiu sut ete gim, hiu sut etylen s tng, ti >180
0
C th
sn phm chnh l etylen.

2.1.8. Anken tiu biu: etilen C
2
H
4

1) Cch iu ch
77


Trong phng th nghim, etilen thng c iu ch t ru etylic bng cch dng
H
2
SO
4
c trong tng lng hoc bng cch cho hi ru i qua Al
2
O
3
nhit cao.

H
3
C C H
2
O H
H
2
C C H
2
+ H
2
O
+ H
2
S O
4
d d
t
0
> 1 7 0
0
C
H
3
C C H
2
O H
H
2
C C H
2
+ H
2
O
A l
2
O
3
, 3 5 0
0
C


Trong cng nghip, etylen c th thu c t l kh than cc v c bit l t kh
crackinh du m.
Cng c th iu ch etylen bng cch hyro ho axetylen c xc tc:


H C C H + H
2
H
2
C C H
2
N i


2) Tnh cht v ng dng
Etylen l mt cht kh, ho lng -105
0
C, khng mu, khng mi, khng tan trong
nc ( 0
0
C, 100 th tch nc c th ho tan c 0,25 th tch etylen).
Etylen c tt c nhng tnh cht ho hc nh cc anken khc nh trnh by
trn. Trong khng kh, etylen chy vi ngn la sng hn ngn la metan to thnh
CO
2
v H
2
O. Hn hp etylen v oxi l hn hp n mnh v phn ng t chy to
nhiu nhit. Do cng c th dng etylen v oxi ct v hn kim loi nh axetylen.
Khi kt hp vi nc, etylen to thnh ru etylic. Phn ng ny c th thc hin
nh H
2
SO
4
qua sn phm trung gian l etylsunfataxit hoc cng c th cng trc tip
hi nc vo etylen nh xc tc (nh Al
2
O
3
) nhit 250-260
0
C v di p sut 50-
80 at.
Tc dng ca etylen vi dl clo trong nc s to thnh etylen clohidrin, t clohidrin
c th iu ch etylen oxit:

H
2
C C H
2
+ C l
2
+ H O H H
2
C C H
2
C l O H
H
2
C C H
2
O
K O H
e t y l e n c l o h y d r i n
e t y l e n o x i t


Tc dng ca etylen vi benzen c xc tc AlCl
3
s to ra etylbenzen, t cht ny ta
iu ch ra stiren:

+
H
2
C C H
2
H
2
C C H
3
C
H
C H
2
A l C l
3 - H
2
e t y l b e n z e n
s t i r e n


Stiren c dng iu ch nha cao phn t polistiren v cao su tng hp buna - S.
78


Etylen trng hp to thnh polietylen cng l mt cht cao phn t c nhiu
ng dng trong k thut v i sng.
Ngoi ng dng trong tng hp hu c vi rt nhiu sn phm qu, etylen cn
c dng gim qu xanh v etylen c tc dng kch thch s hot ng ca cc
men lm qu mau chn.
C th tm tt cc hng ng dng chnh ca etylen trong s sau.


H
3
C C H
2
O H
H
3
C C H
2
C l
B r
H
2
C
H
2
C B r
C l
H
2
C
H
2
C C l
C l
H
2
C
H
2
C O H
H
2
C C H
2
O
C
6
H
5
C
2
H
5
C
6
H
5
C
H
C H
2
e t y l e n c l o h i d r i n
e t y l e n o x i t
e t y l b e n z e n
s i r e n
*
H
2
C
H
2
C
n
p o l i e t y l e n
+ H O H
+ H O H
+ H C l
+ B r
2
+ C l
2
+ H O C l
+ O
2
, x t
+ C
6
H
6
, x t
H
2
C C H
2


2.2. Ankadien-tecpenoit
2.2.1. Ankadien
1) Cu to v gi tn
Cc hirocacbon cha no cha nhiu ni i trong phn t gi chung l polien hoc
poliolefin.
Tu theo v tr tng i ca cc ni i trong mch cacbon, c th chia thnh ba
loi polien chnh sau y:
+ Polien c ni i cch bit:
Trng hp
ru etylic
Etyl clorua
dibrometan
cht chng chy n cho xng
Diclo etan
Dng iu ch cao su polisunfua,
dng iu ch etylen diamin
79


Trong loi polien ny, cc ni i nm xa hn nhau, t nht cch nhau t hai ni n
tr ln, cc ni i ny ni chung khng nh hng g n nhau, chng vn duy tr
nhng tnh cht ca lin kt i nh trong anken.
V d: squalen l mt polien c cc ni i cch bit.


H
3
C C C
H
C H
3
H
2
C ( C H
2
C
C H
3
C
H
H
2
C
H
2
C C
H
C C H
3
C H
3


+ Polien c cc ni i lin nhau:
Cc ni i trong loi polienny st bn nhau, mi nguyn t cacbon gia mch
u mang hai ni i.
V d: CH
2
=C=CH
2
: alen.
+ Polien c ni i lin hp (hay lun phin).
Trong loi polien ny, cc lin kt i nm cch nhau bng mt lin kt n. H
thng cc ni i cch nhau mt lin kt n nh th gi l h cc ni i lin hp.
V d: CH
2
=CHCH=CH
2
: 1,3-butadien.
Trong ba loi polien ni trn, loi c cc ni i l c nhiu ngha quan trng v l
thuyt v thc tin. Di y, kho st ch yu loi ankandien lin hp.

a)Cu trc
Cu trc ca cc alen v polien lin hp c nhng nt rt khc bit so vi anken v
polien c ni i cch bit.
cc anlen, hai nguyn t cacbon mang ni i u mch trng thi lai ho sp
2

cn cc nguyn t cacbon gia mch th trng thi lai ho sn phm. Cc nguyn t
cacbon nm trn mt ng thng. Nguyn t cacbon ny lin kt vi nguyn t
cacbon kia bng mt lin kt o v mt lin kt t. Mt phng t lin kt i ny
vung gc vi mt phng t lin kt i lin vi n. Ging nh lin kt i ca
anken, cc nhm nguyn t nh vi nhau bi cc ni i lin khng quay t do quanh
trc cha cc lin kt i .
polien lin hp, tt c cc nguyn t cacbon mang ni i u trng thi lai
ho sp
2
. Nhng nguyn t Csp
2
ny v tt c cc nguyn t lin kt tc tip vi chng
nm trn cng mt mt phng gi l mt phng phn t. Trc ca cc obitan p mi
Csp u song song vi nhau. Cc obitan p khng ch xen ph vi nhau tng i
mt to ra cc lin kt t ring r m cn xen ph lin tip vi nhau to thnh
obitan t chung cho ton h lin hp.
V d phn t 1,3-butadien c bn nguyn t cacbon trng thi lai ho sp
2
.
Chng lin kt vi nhau v vi cc nguyn t hyro bng lin kt o. Cc lin kt o
to thnh do s xen ph ca cc obitan lai ho sp
2
ca cacbon (lin kt CC) v do s
xen ph ca cc obitan lai ho vi obitan s ca hyro (lin kt CH).
Tt c cc nguyn t cacbon v hyro u nm trn mt mt phng. mi
nguyn t cacbon cn mt obitan (chon bi mt electron p), chng c trc thng gc
vi mt phng phn t. Bn obitan p ho vo nhau thnh bn obitan phn t
(
4 3 2 , 1
, , ) l nhng t hp tuyn tnh ca cc obitan nguyn t. Nng lng ca
80


chng tng ln t
1
n
4
. Obitan phn t
1
c nng lng thp nht, c bn
ln nht, phn b my electron c bn nguyn t cacbon, tng cng lin kt gia
bn cacbon. Obitan phn t
2
c mt phng ct gia cc nguyn t C
2
v C
3
, n tng
cng lin kt gia C
1
C
2
v C
3
C
4
lm yu lin kt C
2
C
3
. Obitan phn t
3
c
hai mt phng ct, n tng cng lin kt C
1
C
2
v C
3
C
4
. Cn obitan phn t
4

c cc mt phng gia ct gia tt c bn nguyn t cacbon, n lm yu tt c cc lin
kt CC.


C
C
C
C
H
H
H
H
H
H
C C
C
C
H
H
H
H
H
H




trng thi c bn, phn t 1,3-butadien tn ti vi hai loi obitan phn t
1
,

2
bn vng hn c, cc obitan ny xc nh cu to electron ca phn t. Cc obitan
c nng lng cao (
3
,
4
) ch c electron trong cc phn t trng thi kch thch.
Thc t, mt electron t l ln nht gia cc lin kt C
1
C
2
v C
3
C
4
, cn
lin kt C
2
C
3
khng phi hon ton l lin kt n o, n c mt mt electron t
nht nh nn n c c tnh yu ca lin kt i.
Bng phng php vt l hin i, ngi ta xc nh c di lin kt ca
cc lin kt CC trong phn t 1,3-butadien: di lin kt C
1
C
2
v C
3
C
4
bng
nhau v bng 1,37A
0
, ln hn di lin kt i C=C bnh thng (1,34A
0
); cn
di lin kt C
2
C
3
bng 1,46A
0
n hn di lin kt n CC bnh thng
(1,54A
0
).
Tng tc ca cc electron t trong h cc ni i lin hp nh trong phn t
1,3-butadien gi l lin hp t- t. S lin hp ny lm cho phn t tr nn bn vng
n nh v san bng cc lin kt.
Tuy nhin, s lin hp khng phi l nguyn nhn duy nht lm thay i
khong cch gia cc nhn nguyn t. di lin kt cn ph thuc vo trng thi lai
ho ca cacbon. V vy, s ngn li ca lin kt n C
2
C
3
trong phn t butadien do
kt qu ca hai yu t lin hp v lai ho.
S lin hp ca cc lin kt t ca phn t cha phn ng, c trng bng hiu
ng lin hp tnh. C th biu din lin hp cc lin kt t trong 1,3-butadien bng
mi tn cong hoc bng chm tng trng s san u cc lin kt:

s to thnh lin kt o
trong phn t 1,3-butadien
s xen ph cc obitan trong
phn t 1,3-butadien
81


H
2
C C
H
C
H
C H
2
H
2
C C
H
C
H
C H
2


Di nh hng ca cc tc nhn, s lin hp c tng cng v xut hin
hiu ng lin hp ng (C

) cn c gi l hiu ng E (electrone). Hiu ng lin hp

tnh (C
t
) cn c k hiu bng hiu ng M (hiu ng mezome). Bn cht hai loi hiu
ng ny ng nht, tuy nhin hiu ng lin hp ng thng c ngha quan trng
hn.
V lin kt C
2
C
3
c mt electron t nh nht nh nn kh nng quay t do
b hn ch. V mt c to lp th, butadien c th tn ti di cc cu dng sau y: s-
trans (a) v s-cis (b), trong dng s-trans (a) c nng lng thp nht v bn vng
nht:
C
H
C
C
C
H
H
H
H
H
C
H
C
C
H
C
H
H
H
H
s - c i s - b u t a d i e n - 1 , 3
s - t r a n s - b u t a d i e n - 1 , 3


b) ng phn v danh php
Cch chn mch chnh i vi polien cng tun theo nhng nguyn tt ging nh
i vi anken. Phn nn ch tn mch chnh ca polien phi thm ch a. V d:
prop+a=propa, but+a=buta, pent+a=penta V th dien c gi l ankadien, trien
c gi l ankatrien. Sd ch v tr ni i t trc phn nn. Ngoi ra mt s tn
thng thng vn c dng. V d:

H
2
C
C C
H
C H
2
C H
3
C C
H
H
3
C
H
3
C
H
2
C C H
2
C C H
2
C
H
H
2
C
1
2 3 4 5
6
7 8
i s o p r e n
2 - m e t y l - 1 , 3 - b u t a d i e n
x i c l o p e n t a d i e n
x i c l o - 1 , 3 - p e n t a d i e n
m i r x e n
6 - m e t y l e n - 2 - m e t y l - 2 , 7 - o c t a d i e n


i vi cc allen cha s chn lin kt i, nu mi nguyn t cacbon u mch
c hai nhm th khc nhau th phn t tr thnh bt i (khng c mt phng v tm
i xng) tc l c tnh khng trng nh vt. Khi s xut hin ng phn quang
hc. V d:

82


C C C
H
3
C
H
H
C H
3
H C H
3
H
H
3
C
C H
3
H
H C H
3
C H
3
H
H
3
C H
( S ) - 1 , 3 - d i m e t y l a l l e n
( R ) - 1 , 3 - d i m e t y l a l l e n


i vi cc allen cha s l lin kt i th s c ng phn hnh hc nu mi
nguyn t cacbon u mch c hai nhm th khc nhau. V d:


C C C C
C H
3
H
H
3
C
H
C C C C
H
C H
3
H
3
C
H
c i s - 2 , 3 , 4 - h e c x a t r i e n
t r a n s - 2 , 3 , 4 - h e c x a t r i e n


i vi cc polien lin hp hoc polien bit lp cha n lin kt C=C th s chn
ng phn hnh hc s nh hn hoc bng 2
n
tu thuc vo cu to ca chng. V d:
2,4-heptadien c 4 ng phn hnh hc:

2) Tnh cht vt l
a)Tnh cht vt l thng thng
S bin i cc tnh cht vt l thng thng ca polien cng tun theo nhng quy
lut nh i vi anken v ankan. V d:

Polien: CH
2
=C=CH
2
CH
2
=C=CH=CH
3
CH
2
=CHCH=CH
2

C , t
0 0
s
-34,3 -10,8 -4,7
C , t
0 0
nc
-146 -136 -108,9
d,g/ml 0,662 (-35
0
C) 0,667 (0
0
C) 0,650 (-6
0
C)

b)Tnh cht ph
Ph electron ca cc polien lin hp c nghin cu kh k v rt c ch trong
vic xc nh cu to ca cc polien lin hp thin nhin cng nh tng hp. Khi mch
lin hp ko di, c
max
v c
max
u tng mnh. Cc nhm th gn vo h lin hp
lm tng
max
theo nhng gia s ring c tnh cht cng tnh. Chng hn, mi nhm
ankyl lm tng
max
thm 5nm, mi nhm RO lm tng 6nm, nhm RS lm tng
ti 30nm.
Gi tr
C C=
v ca cc polien lin hp nh hn
C C=
v polien thng cng nh
C C=
v
anken. Tt c chng u nm trong vng 1600-1650 cm
-1
.
C C=
v ca allen th ln ti
1950 cm
-1
tc l nm trung gian gia anken v ankin (2100-2300 cm
-1
). Dao ng ho
83


tr ca lin kt Csp
2
H polien thng v polien lin hp ging nh anken (3000-
3100 cm
-1
).
chuyn dch ho hc ca proton gn vi Csp
2
polien thng v polien lin hp
khng khc my so vi anken (khong 4,5-6 ppm) cn ca proton allen th thp hn
hn (khong 4-5 ppm).

3) Cc phng php iu ch v ng dng
Butadien l mt trong nhng nguyn liu quan trng nht tng hp cao su nhn
to v c iu ch bng nhng phng php khc nhau.

a)Nhit phn du m
Khi nung nng mt s phn on du m n 700-800
0
C, s thu c butadien vi
hiu sut 3-4%.V vy, khi cracking du m trong cc kh cracking thu c, thng
lun c cha mt lng nh butadien.
Mt s hirocacbon b nhit phn cho butadien vi hiu sut cao. Chng hn, khi
cho xiclohecxen trng thi kh i qua mt dy kim loi nung bng dng in s
cho butadien v etylen. (phng php Zelinski).

C H
2
C H
2
C H
2
C H
2
+


b)ehydro ho xc tc cc n-buten v n-butan
Khi cho cc n-buten i qua xc tc crom oxit trn nhm oxit nhit 650
0
C, s
thu c butadien vi hiu sut trn 70%.

H
3
C C
H
C
H
C H
3 H
2
C C
H
C
H
C H
2
+ H
2


Do phn ng lm tng th tch nn tin hnh trong iu kin p sut thp s thun
li hn. trnh phn ng trng hp c th xy ra ng thi, xc tc c ph mt
lp cacbon mng. Xc tc mi c bit hot ng l canxi niken photphat kp
Ca
8
Ni(PO
4
)
6
c hot ho bi crom oxit cho hiu sut 87%.
Vic ehydro ho n-butan thc hin qua hai giai on. Trc ht, n-butan b
ehydro ho trong iu kin nh nhng thnh cc n-buten; cc n-buten c tch ra
khi hyro v cc hirocacbon C
3
v C
2
, sau cc n-buten b ehydro ho thnh
butadien nh m t trn.

c) i t axetylen
T axetylen, c th iu ch butadien bng nhiu cch khc nhau:
-Trng hp thnh vinylaxetilen ri hyro ho.

HCCH + HCCH CH
2
=CHCCH CH
2
CHCH=CH
2
84


-Cng HOH qua axetandehyt, qua andol, qua butilen glicol ri thnh butadien.

H C C H
+ H O H
C H
3
C H O
+ K O H
H
3
C C H O H
H
2
C C H O
H
3
C C H O H
H
2
C C H
2
O H H
2
C C
H
C
H
C H
2

-Cng fomandehyt thnh butindiol, qua butindiol, qua tetrahydrofuan ri thnh
butadien (phng php Repp):

H C C H
+ 2 H C H O
H O H
2
C C C C H
2
O H
+ H
2
H O H
2
C
H
2
C
H
2
C C H
2
O H
- H
2
O
O
- H
2
O
H
2
C C
H
C
H
C H
2
t e t r a h y d r o f u r a n


d)i t etanol
- Phng php Ostromlensli: cho hn hp etanol v axetandehyt i qua nhm oxit
300-400
0
C:

CH
3
CH
2
OH + CH
3
CHO CH
2
=CHCH=CH
2
+ 2H
2
O

Vi xc tc ziecconi oxit hoc tantan oxit c th t ti hiu sut 60% butadien
v khong 5% buten.
-Phng php lebedep: cho hi etanol i qua xc tc gm magie oxit v kaolin vi
mt lng nh oxit st, titan v km ng vai tr cht khi mo. Hiu sut butadien
thu c ti 50-60% c cha khong 10% buten. Xc tc va c tc dng ehyro
ho, va dehydrat ho. Phn ng tin hnh qua cc giai on sau:

CH
3
CH
2
OH CH
3
CHO + H
2

2CH
3
CHO CH
3
CH=CHCHO + H
2
O
CH
3
CH=CHCHO + CH
3
CH
2
OH CH
3
CH=CHCH
2
OH + CH
3
CHO
CH
3
CH=CHCH
2
OH CH
2
=CHCH=CH
2
+ H
2
O

e)ng dng
Trong dy polien th cc dien lin hp c ng dng quan trong hn c. Dien lin
hp nh butadien, izopren, cloropren c dng iu ch cao su tng hp. Cao su
tng hp thng khng n hi bng cao su thin nhin nhng li c th iu chnh
thnh phn to ra nhng tnh cht khc vt tri hn cao su thin nhin. Chng hn,
cao su butadien-acrilonitril, cao su silicon bn vi du m, cao su butadien-stiren c
bn c hc cao.
Trong thin nhin, cc hirocacbon loi polien v cc dn xut ca chng rt ph
bin gii thc vt v ng vt thng dng lm cc cht hng liu hay dc liu
qu. Chnh cao su thin nhin l mt polien cao phn t c vai tr quan trng trong
nn kinh t.
85


4) Tnh cht ho hc
Tnh cht ho hc ca polien thng (polien bit lp) hon ton tng t nh anken.
Do c im cu trc electron, tnh cht cc allen khc hn cc anken v c phn no
ging vi cc ankin. Cn polien lin hp th v c bn tng t nh anken nhng n
cng c nhng nt c o ring.
Polien lin hp, nht v ien lin hp c ngha thc t v l thuyt quan trng hn
c, v th trong chng ny ch yu xem xt cc phn ng ca chng.
Butadien l mt cht kh, izopren v dimetyl butadien l nhng cht lng nhit
thng.
nh hng lin hp th hin r kh nng phn ng tng ln trong cc phn ng
cng v c bit l cc phn ng cng 1,4. Loi phn ng vo cc u mch ny
khng gii hn trong cc dien m cn th hin trong nhiu hp cht hu c khc c
cha h ni i lin hp. Ngoi ra, cc ankadien c ni i lin hp cn rt d tham
gia phn ng trng hp thnh cc polime dng ch cao su nhn to.

a) bn ca dien lin hp
bn ca cc dien lin hp c xc nh bng nhit hyro ho cc dien. Kt qu
thc nghim cho thy rng nhit hyro ho ca cc anken nh sau:

RCH=CH
2
R
2
C=CH
2
RCH=CHR R
2
C=CHR
~30 kcal/mol ~28kcal/mol ~28kcal/mol ~27kcal/mol

Da vo cc s liu trn y ta tnh c nhit hyro ho cho 2 cht:

CH
2
=CHCH=CH
2
CH
3
CH=CHCH=CH
2

Theo tnh ton 30 + 30 = 60 kcal/mol 28 + 30 = 58 kcal/mol
Thc nghim 57 kcal/mol 54 kcal/mol

So snh cc kt qu tnh ton theo l thuyt v thc nghim ta thy cc dien lin
hp bn hn cc ien khng lin hp.

b)Phn ng cng
- Cng brom.
Khi cho butadien tc dng vi brom s thu c sn phm cng 1,4 l 1,4-
dibrombuten v mt lng nh 3,4-dibrom-1-buten l sn phm phn ng cng vo
ni i:
Cho butadien cng vi clo trong dung dch cacbon disunfua s thu c sn

H
2
C C
H
C
H
C H
2
+ B r
2
B r
H
C C
H
C
H
C H
2
B r B r
H
2
C
H
C C
H
C H
2 +
B r
1 , 4 - d i b r o m 2 - b u t e n
3 , 4 - d i b r o m 1 - b u t e n

phm cng 1,2 v 1,4 vi t l bng nhau.
86


Trc y, Thil gii thch phn ng cng 1,4 bng thuyt ho tr d: Thil
cho rng trong butadien mi nguyn t cacbon c mt ho tr d, cc ho tr d C
2

v C
3
kt hp vi nhau cn cc ho tr d C
1
v C
4
trng thi t do nn d kt hp
vi cc nguyn t khc cho sn phm cng 1,4. Gi thuyt ca Thil gii thch c
phn ng cng 1,4 nhng khng gii thch c s hnh thnh sn phm cng 1,2.
Theo quan im hin i, c ch phn ng cng brom tin hnh theo hai giai
on nh khi cng brom vo mt lin kt i ring bit. Phn ng cng brom l mt
phn ng cng electrophin, khi cation Br
+
tin li gn butadien s gy ra s phn cc
trong phn t butadien v Br
+
tn cng vo mt u ca h lin hp to ra mt ion
cacboni trung gian:

H
2
C C
H
C
H
C H
2
+ B r
o o
H
2
C C
H
C C H
2
B r
H


Ion cacboni to thnh c cha mt h gm ba nguyn t cacbon, trong hai
cacbon lin kt bng ni i cn mt mang in tch dng, l cation alyl. Trong
cation alyl c s phn b li mt electron t to thnh mt obitan phn t bao trm
c ba nguyn t cacbon.

H
2
C C
H
C C H
2
B r
H
H
2
C C
H
C
H
C H
2
B r


S phn b iu ho mt electron t nh th lm cho cation alyl c nng lng
thp hn cation c in tch dng tp trung mt cacbon v do n bn vng hn.
Sau cation alyl tc dng vianion Br
-

hoc vo v tr 4 hoc vo v tr 2 (khng th
vo v tr 3 v trng hp ny khng to ra ni i):


H
2
C C
H
C
H
C H
2
B r
+ B r
B r
H
C C
H
C
H
C H
2
B r
B r
H
2
C
H
C C
H
C H
2
B r


Trc khi thit lp cn bng, cc sn phm cng 1,2 v 1,4 d dng chuyn ho ln
nhau. Hn hp cn bng cha khong 80% sn phm cng 1,4. S ng phn ho tin
hnh nh s phn li ca ion Br
-
. Trong s phn li , c hai dn xut dibrom u cng
cho mt cation alyl l sn phm trung gian ca phn ng cng brom, l cation c nng
lng thp v bn vng hn c.
T l cc sn phm cng 1,2 v 1,4 cng cn ph thuc vo iu kin tin hnh
phn ng. Trong dung mi phn cc nh trong axit axetic nhit 40
0
C t l sn
phm cng 1,4 t khong 70-80%,
- Cng hyro clorua.
87


Cho butadien tc dng vi hyro clorua cng to ra hai sn phm cng 1,2 v 1,4
nhng trong trng hp ny sn phm cng 1,2 t ti t l 75-80% cn sn phm
cng 1,4 ch chim t l 20-25%.
H
2
C C
H
C
H
C H
2
B r H
2
C C
H
C
H
C H
3
H
C l
C l
H
2
C C
H
C
H
C H
3
H
3
C
H
C C
H
C H
2
C l
2 0 - 2 5 %
7 5 - 8 0 %

- Hyro ho.
Phn ng cng hyro vo butadien thng tin hnh bng cch dng hyro mi
sinh do tc dng ca kim loi vi dung mi proton ha c nh nc, ru hoc axit.
Khi kim loi cho phn t butadien hai electron ng thi chuyn thnh ion trong
dung dch, phn t butadien b phn cc ho v ln lt nhn hai proton t dung dch.
Phn ng hyro ho tin hnh theo s sau:

2 e H
2
C C
H
C
H
C H
2
H
H
2
C C
H
C
H
C H
3
. .
H
H
3
C C
H
C
H
C H
3


Cc polien c hai nhm phenyl hai u mch d b hyro ho bng hn hng
natri trong etanol:
C
H
C
H
C
H
C
H
C
6
H
5
C
6
H
5
H
2 e
H
2
C C
H
C
H
H
2
C C
6
H
5
C
6
H
5
d i p h e n y l b u t a d i e n 1 , 4 d i p h e n y l - 2 - b u t e n


c)Phn ng cng 1,4 khp vng-tng hp Dinx-Ande
Mt trong nhng phn ng thng dng nht trong vic tng hp hu c l phn ng
ca mt h ni i lin hp vi mt hp cht c ni i khc c hot ho gi l
dienophin. Tc nhn dienophin thng c cha lin kt i ni vi cc nhm ht
electron nh COOH, COR, CN, v.v
Kt qu phn ng cng 1,4 to ra mt vng su cnh, cn ni i v tr 2,3 ca
cht u. Phn ng thng tin hnh khng cn xc tc, ch cn un nng hn hp
phn ng ti nhit 100-120
0
C.
Dienophin thng dng l anhydric maleic, c th tc dng vi nhiu dien lin hp
khc nhau.

H C
H C
C H
2
C H
2
+
H C
H C
O
C
C
O
O
O
C
C
O
O
b u t a d i e n
a n h y d r i c m a l e i c a n h y d r i c t e t r a h i d r o p h t a l i c

88



C nhiu dienophin khc nh acrolein, crotonadehyt, axit acrylic, cc este v
nitrin ca n, axit xinnamic C
6
H
5
CH=CHCOOH, quinon v.v Cc anken n
gin cng c th dng lm dienophin nhng hiu sut thp v phi tin hnh nhit
cao hn.
i vi dien lin hp c th dng cc dn xut v ng ng ca butadien c
cha cc nhm metyl, phenyl, halogen v.v Cc dien mch vng nh xyclopentadien,
xiclohecxadien cng d dng tham gia phn ng Dinxo-Ande, to ra nhng hp cht
nhiu vng c cu ni khc nhau.
H C
H C
C H
C H
+
H C
H C
O
C
C
O
O
x y c l o p e n t a d i e n
a n h y d r i c m a l e i c
C H
2
O C
O C
O
H
H


d) Phn ng trng hp ca ankadien lin hp
Cc ankadien lin hp rt d tham gia phn ng trng hp trong nhiu iu kin
khc nhau theo kiu phn ng cng 1,4 to thnh cc polime c khi lng phn t rt
cao. V vy, phn ng trng hp ankadien lin hp c ngha thc tin rt quan trng
ch to cao su tng hp.
V d: khi trng hp 1,3-butadien nh natri kim loi lm xc tc s thu c
polibutadien.


H
2
C C
H
C
H
C H
2
N a
H
2
C C
H
C
H
H
2
C
n
n
p o l i b u t a d i e n

Qu trnh trng hp c th biu din nh sau:

2Na + CH
2
=CHCH=CH
2
NaCH
2
CH=CHCH
2
Na
NaCH
2
CH=CHCH
2
Na + CH
2
=CHCH=CH
2

NaCH
2
CH=CHCH
2
CH
2
CH=CHCH
2
Na v.v

Phn ng tip tc din ra nh trn n khi to ra polime c phn t lng cao. Cng
c th to ra polime c cu to phn nhnh do phn ng xy ra va theo kiu 1,4 va
1,2:
89


N a H
2
C C
H
C
H
C H
2
N a +
H
2
C
C H
C H
C H
2
N a H
2
C C
H
C
H
H
2
C
H
2
C C H N a
C H
C H
2
H
2
C C
H
C
H
C H
2
N a H
2
C C
H
C
H
H
2
C
H
2
C
H
C
C H
C H
2
H
2
C C
H
C
H
C H
2
N a

Cao su tng hp ch t polibutadien nh phn ng trn gi l cao su buna.

5) Gii thiu cao su
a) Cao su thin nhin
C nhiu loi cy (trn 500 loi) c th cho cao su. Cc loi cy ny thuc cc h
Moraceae, Parthenium argentatum, Euphorbiaceae. Thuc h Euphorbiaceae c cy
Hevea brasiliensis c ngun gc tman M trn b Amazon. Danh t cao su c
ngha l nc mt ca cy l ting a phng ca ngi da Nam M. Lin X
c cc cy cho cao su nh taraxacum Kok-saglug, taraxacum megalorhigon.
Cn gutta-percha cng l mt loi cao su ly t v v l cy h Sapotaceae
(Palaquium v Payena)n mc nhiu Malaisia. Balata l cao su ly t cy mc
Trung Nam M, balata chnh l ng nht vi gutta-percha.
Cc rng cao su nc ta hin nay ch yu l thuc loi cy Hevea brasiliensia do
thc dn Php bt u a sang trng th ri lp n in cao su t cui nhng nm
70 ca th k 19.
Nhng ngi da l nhng ngi u tin s dng cao su. H ph bc cao su
bng nhng khun t st v sy. Sau khi thu c nhng mu cao su n hi v
khng thm nc, h p v vn khun t st thnh cc mnh v ko cc mnh
qua mt l ming bnh to thnh cc loi bnh dng ng nc.
nc Anh, ngi ta dng cao su th ho tan vo hirocacbon ca nha than v
thu c mt dng keo cao su. Ngi ta s dng keo cao su ny ph ln b mt ca
vi lm vi khng thm nc. b mt c ph bng nha cao su khng thm
nc khng b dnh bn ngi ta gp i chng li. Loi o ma c hai lp du nh
vy do Makintosh lm ra nn c gi l o mng t. V sau, khc phc s dnh
bn ny ngi ta cho thm cc loi bt khc nhau. Mt trong nhng loi bt l lu
hunh v nh pht hin ra s lu ho cao su.

b) M cao su v cao su th
T cy cao su ngi ta trch thu nha hay m cao su hay latex. M cao su l mt
h phn tn trong nc ca cc tiu phn c ng knh trung bnh 0,5 micromet
(0,0005 mm). Khi cho m cao su bay hi th thy, ngoi nc ra trong m c 30-40%
thnh phn rn. Trong c ti 90% l hirocacbon cao su v 10% l cc thnh phn
khc nh protit, nha, sp, cht bo, cc mui v c v mt s loi men.
Mc du kch thc cc tiu phn trong m ln, h phn tn vn bn v cc tiu
phn c bao bc bi mt lp phn t protit ng vai tr l keo bo v. Nh cc
90


tiu phn tch in m v khi in di th chuyn dch v pha anot. M cao su c pH
trong khong 6,4-6,8.
Trc y, ngi ta lm ng t m cao su ly cao su th bng cch xng khi.
Hin nay, ngi ta dng axit axetic hoc axit focmic lm ng t m cao su.
Cao su mi ly t m ra bng cch lm ng t gi l cao su th hay cao su sng, c
mu hi en do thng c hun khi st trng. Mt dng ca cao su th l crep.
Cao su th c thnh phn ch yu l hirocacbon (C
5
H
8
)
n
v cn cha lng nh
mt s cht khc. Thnh phn trung bnh ca cao su th nh sau:
Hirocacbon (C
5
H
8
)
n
(cao su) 92-94%
Nc 0,5-1,2%
Cht chit c bng axeton 2,5-3,2%
Protit 0,15-0,5%
Sau khi tinh ch loi b cc tp cht trong cao su th s thu c cao su tinh khit
hn.

c) Cu to ca cao su thin nhin
- Cao su c cng thc nguyn n gin nht l C
5
H
8
ng nht vi izopren. Tuy
nhin, vi nhng tnh cht nh p sut hi bng 0 v dung dch c c tnh keo chng
t cao su c cu to i phn t.
- Cao su khng chng ct c, nhit trn 300
0
C n b phn hu cho izopren.
Trong iu kin thun li c th cho hiu sut ti 58% bin thnh izopren. Nh vy,
cao su c th coi l polime ca izopren (C
5
H
8
)
n
.
- Phn t cao su th hin tnh cht cha no qua cc phn ng cng vi hyro thh
(C
5
H
10
)
n
, cng vi brom thnh sn phm trng khng tan (C
5
H
8
Br
2
)
n
, cng vi hyro
clorua, hyro bromua v.v Thc t chng t rng c mi n v mc xch C
5
H
8
trong
phn t cao su c cha mt lin kt i.
- C ngha c bit l phn ng vi ozn (O
3
) thnh ozonit (C
5
H
8
O
3
)
n
ri thu
phn cho mt sn phm (hiu sut ti 90%) l mt cht dicacbonyl: andehyt levulic:

O
C
H
2
C
H
2
C C
H
O
C H
3


Trn c s d kin ny, ngi ta i n kt lun v cu to ca cao su nh sau:


H
2
C C C
H
C H
3
H
2
C
H
2
C C C
H
C H
3
H
2
C
H
2
C C
C H
3
C
H
H
2
C
. . . . . .


Khi tc dng vi ozon, s to thnh ozonit c cu to nh sau:

91


H
2
C C O
C H
3
. . .
H
C
H
2
C
H
2
C C O
H
C
H
2
C
H
2
C C O
H
C
O O
C H
3
O O
C H
3
O O
H
2
C
. . .


Sau khi thu phn ozonit ni trn s thu c andehyt levulic.
Nh vy, cc i phn t cao su c coi nh to ra do s trng hp ca
izopren cc v tr 1,4 mt cch iu ho v ni vi nhau theo kiu u vi ui.

H
2
C
C C
H
C H
2
C H
3
H
2
C
C C
H
C H
2
C H
3
H
2
C
C C
H
C H
2
C H
3
+ n +
H
2
C C C
H
H
2
C
C H
3
. . .
H
2
C C C
H
H
2
C
C H
3
H
2
C C C
H
H
2
C
C H
3
. . .
n


- Phn t lng ca cao su c xc nh bng nhiu phng php dng cho
cc cht cao phn t. Cao su ca cy hevea c khi lng phn t trong khong
50000-3000000. Tuy nhin, trn 60% c phn t lng vt qu 1300000 (h s trng
hp n trn 20000).
- Gutta-percha v balata c thnh phn phn t v ho tnh gn nh ng nht
vi cao su. Khi ozon ho ri thy phn cng thu c andehyt levulic. Tuy nhin, tnh
cht vt l khc nhau nhiu. Khi lng phn t o bng php o nht v thm
thu cho kt qu bng 40000-50000, vi h s trng hp n = 600-700.
- V mt cu hnh: quang ph Roentgen ca cao su trng thi khngko cng
cho thy c nhng vng c trng cho cc ct th v nh hnh. iu chng t rng
trong cao su khng ko cng khng c s nh hng xc nh ca cc i phn t,
cn trong cao su c ko cng chng c nh hng song song nhau. Khi lm lnh
trng thi ko cng n cng li v vn gi trng thi sau khi loi b sc ko cng.
Quang ph Roentgen ca cc loi cao su u ng nht, cn quang ph ca
gutta percha th khc vi ca cao su. Gutta percha c th tn ti di hai dng o v | .
Trong mch cao phn t ca cao su, c mi n v gc izopren c mt lin kt
i v do c th tn ti hai dng ng phn cis v trans. Trong dng trans cc lin
kt 1,2 v 3,4 s hai pha khc nhau i vi ni i, cn trong dng cis, chng sp
xp trong cng mt pha.
S c mt ca ni i trong phn t cao su rt quan trng v n cho php ta tin
hnh lu ho. Cao su lu ho c cu to mng khng gian nn cng hn. Nu lu ho
nhiu s cho sn phm l ebonit dng lm cht cch in.
Trong dng trans, cc khong ng nht ch l mt gc izopentan c di
bng 5,0A cn trong dng cis khong ng nht gm hai gc izopentan c di bng
9,1A.
Thc nghim chng t rng khong ng nht trong cao su bng 8,1A cn
trong gutta percha bng 4,7 A (dng | ).Nh vy chc chn rng cc i phn t cao su
c cu hnh cis cn i phn t gutta percha c cu hnh trans.
92




C
H
2
C C H
H
3
C
C
H
2
H
2
C
C C H
H
3
C
H
2
C
C
H
2
C C H
H
3
C
9 , 1 A
C
H
2
C
H
3
C
C H
H
2
C
C
H
2
C
H
3
C
C H
H
2
C
C
H
2
C C H
H
3
C
5 , 0 A 5 , 0 A



d)Tnh cht ca cao su thin nhin
- Cao su c th tn ti di 4 trng thi: kt tinh, rn v nh hnh, n hi v do.
Hai trng thi trn l nhng trng thi cng c trng cho s khng linh ng ca cc
i phn t ging nh tinh th v thu tinh thng thng. Trng thi n hi l trng
thi trung gian gia v nh hnh v do, n c th xut hin do s d un ca cc i
phn t.
- Tnh tan: cao su tan trong cc hirocacbon (nh benzen, etxang, du thng) v
trong cc dn xut halogen (nh clorofom) nhng khng tan trong cc dung mi phn
cc (nh ru, axeton). Ru lm cao su kt ta t dung dch. Trc khi ho tan sao
su thng phng ln rt mnh. Cc dung dch cao su long c nht cao, nht t
l vi h s trng hp.
Tnh tan ca cao su ph thuc rt nhiu vo s ch bin s b. Cao su hevea ch tan
mt phn trong te. Phn tan (65-75%) gi l cao su sol v phn khng tan gi l cao
su gel. Tnh khng tan ca cao su gel l do trong phn c h s trng hp ln.
- S t oxi ho (hay lo ho). Cao su lu ngoi khng kh s gim tnh bn c
hc, tnh n hi. ng thi tnh tan ca cao su tng ln nhiu ngay trong nhng dung
mi phn cc (ru, axeton). Cao su lu ho cng tng t
cu hnh ca phn t cao su (dng cis)
cu hnh ca phn t gutta percha (dng trans)
93




Hin tng ny c xc tin khi un nng v nht l khi chiu sng v khi c mt
ca mt s cht xc tc nh ng v.v
S t oxy ho l mt phn ng dy chuyn, tng t phn ng t oxi ho cc olefin.
Ngi ta nhn thy giai on cm ng rt di (ti vi nm) cao su th, nhng rt
nhanh cao su c x l vi dung mi tch mt s cht km hm thin nhin (cc
cht phn oxi ho). Sn phm u tin l peoxit, cht ny c th nhn ra nh phn ng
vi kali iodua. C l nhm CH
2
b tn cng s hot ho cc lin kt i bn cnh.
Trc ht, to ra nhm >CHOOH, sau chuyn thnh cc nhm >CHOH v
>CO, ng thi xy ra s b gy i phn t, iu ny gii thch s gim bn, gim
h s trng hp v lm thay i cc tnh cht c l ca cao su.

Ti sao cao su c tnh n hi?
Ta bit rng mch cao su c phn t ln. Mt khc, do cc nguyn t cacbon c gc
lai ho l 109
0
28 cng vi s quay t do cc lin kt o cacbon-cacbon to thnh v
s cu dng khc nhau nhng v tr ni i trong phn t khng thay i. mt phn
t ln, s xp t ca mch phn t s khng iu ho m rt tu tin v cu dng. Khi
b ko mnh nhng ch sp xp khng trt t b ko ra lm cho mch cao su b gin.
Nu b lc ko n li tr v trng thi bnh thng.

e)Cao su tng hp
Cao su tng hp l polibutadien. thay i tnh cht ca n, cao su tng hp
thng s dng cc phn ng ng trng hp: butadien vi styren, acrilonitrin

H
2
C C
H
C
H
C H
2
+ H
2
C C
H
C
H
C H
2
+ H
2
C
C H
C
6
H
5
H
2
C C
H
C
H
C H
2
+
x t
H
2
C C
H
C
H
H
2
C C
H
C
H
H
2
C
H
2
C
H
C
H
2
C C
H
C
6
H
5
C
H
H
2
C
. . . . . .
c a o s u b u t a d i e n s t y r e n ( b u n a S )


trng thi khng ko cng ca phn t cao su
trng thi ko cng ca phn t cao su
94


2.2.2. T ecpenoic
T c xa xa, loi ngi u thch v quan tm ti du thm tch ra t thc vt.
Tuy nhin, mi n u th k XIX mi c nhng nghin cu u tin v thnh phn
ho hc ca tinh du. V vo nm 1818 ngi ta xc nh c rng t l nguyn t
C: H tinh du l 5:8. Tip theo , mt s hirocacbon khng no, khng vng hoc
c vng c tch ra. Chng c cng thc chung l (C
5
H
8
)
n
(n2) v c gi l
tecpen. Khi n=2 ta c cng thc l C
10
H
16
l monotecpen thng gi gn l
tecpen; khi n=3 ta c C
15
H
24
l setkitecpen, n=4 c C
20
H
32
l ditecpen, n=6 c
C
30
H
48
l tritecpen v.v
T nm 1887, Otto Wallach nhn thy c im chung trong cu trc ca tcpn
l gm cc mt xch ging nh isopren hp thnh. Sau , nh nhng nghin cu tng
kt cc tecpen bit, L.Rugiska nu ra quy tt isopren ni rng tecpen dng nh
c to thnh do isopren kt hp vi nhau theo kiu u ni vi ui. V d:

C
5
H
8
, isopren
C
10
H
16
, Oximen C
10
H
16
, Silvestren
C
15
H
24
, Xingiberen


Trong a s trng hp, c ngha quan trng trong thc t khng phi l cc
hirocacbon loi tecpen m l dn xut cha oxi ca chng nh cc ancol, andehyt,
xeton, este. Tecpen v cc dn xut ca n c gi chung l tecpenoit. Tecpen v
tecpenoit i khi cn c gi l isoprenoit nhn mnh rng n gm cc mt xch
c khung cacbon ging vi isopren.
Ngi ta cng tm thy nhiu hp cht thin nhin m b khung cacbon gm t
cc mt xch ging isopren nhng c ch kt hp vi nhau khng theo kiu u ni
vi ui nhng cng vn c xp vo loi tecpen. V d:

C
30
H
50
squalen


Vy, tecpen l nhng hp cht cha C, H v O m b khung cacbon gm nhiu
mt xch ging vi b khung cacbon ca isopren, tc l n c th biu din bi cng
thc (iso-C
5
)
n
vi (n2).
Tecpen v cc dn xut cha oxi ca chng thng c mt trong nhiu loi tinh du
c hng thm. Tinh du l nhng sn phm c tch ra t cc b phn ca thc vt.
C loi tinh du tch ra t hoa nh tinh du hoa hng, hoa nhi, hoa ngc lan. C loi
tch ra t l nh s. C loi tch ra t c hoa v l nh hng nhu, bc h, hng qu.
Khng theo kiu u ni vi ui
95


C loi tch ra t v nh cam, chanh, qut, bi. C loi tch ra t g ca thn, cnh
cy nh tinh du long no. C loi tch ra t c nh tinh du gng, ring. C loi ly
ra t r nh hng lau, pmu. C loi tch ra t nha cy nh tinh du thng v.v
Tinh du c mt s c tnh chung, khc vi du bo p t cc ht qu thc vt
nh sau:
- Tinh du si nhit kh cao (thng trong khong 150-250
0
C) nhng li
d bay hi to mi thm d chu. Nh mt git tinh du ln mt giy thy xut hin vt
trong m nh khi nh git du bo nhng vt ca git tinh du th bin i kh nhanh,
mt giy tr li bnh thng trong khi vt m ca git du bo th tn ti mi.
- Tinh du thng khng tan hoc t tan trong nc, tan nhiu trong cc dung
mi hu c nh ru, ete, benzen v.v a s tinh du nh hn nc nh s, bc h
v.vcng c loi tinh du nng hn nc nh qu, inh hng v.v Tinh du
thng khngmu hoc mu vng nht nhng lu mu sc tinh du thng thay i
do mt s thnh phn trong tinh du b oxi ho trong khng kh v bin mu.
- Tinh du thng l mt hn hp phc tp gm hng chc cht khc nhau, mi
cng nh gi tr tinh du do mt s thnh phn trong quyt nh. Tinh du c nhiu
ng dng quan trng trong nhiu ngnh kinh t nh dc phm, thc phm, m phm
v hng phm. Do , n l loi sn phm thin nhin c gi tr kinh t cao.

1) Monotecpen
Cc tecpen c thnh phn C
10
H
16
c th chia thnh hai nhm ln:
- Nhm th nht l cc tecpen mch h khng vng.
- Nhm th hai l cc tecpen mch vng: gm cc tecpen mt vng v hai vng.
a)Tecpen mch h v nhng dn xut ca chng
Cc tecpen mch h t gp trong thin nhin v ngi ta tm c hai
hirocacbon loi monotecpen khng vng (axiclicmonotecpen) l mirxen v oximen.
Chng c ba lin kt i trong phn t.

H
3
C C
C H
3
C
H
H
2
C
H
2
C C C
H
C H
2
C H
2
H
2
C
C
C H
3
H
2
C
H
2
C C
H
C C
H
C H
3
C H
2
m i r x e n
o x i m e n


Mirxen c tch t tinh du cy Myria (nguyt qu) cn oximen c tch t l
cy Ocimum basilicum (mt loi hng qu).
Cc dn xut cha oxi ca tecpen mch h c ngha quan trng hn. Cc dn xut
l cc ancol, andehyt.
- V ancol:
Geraniol C
10
H
18
O (t
0
si: 229-230
0
C) l ru bc nht c chung cng thc cu
to vi nerol (t
0
si: 225-226
0
C) v cho cng sn phm oxi ho v cc dn xut chung
96


khc. T suy ra cc ancol ny l ng phn cis-trans v mi ancol cn li l mt
hn hp hai dng ng phn izopropyliden v izopropenyl.

H
C H
2
O H
C H
2
O H
g e r a n i o l
C H
2
O H C H
2
O H
N e r o l


Nerol c dng cis v n khp vng nhanh hn 10 ln so vi geraniol cho o-
tecpineol. C th thu nhn c nerol khi un nng geraniol vi etylat natri.
Geraniol l thnh phn chnh tinh du hoa hng, tinh du s v cng c trong
nhiu tinh du khc. Geraniol v nerol c hng thm mi hoa hng.
Xitronelol C
10
H
20
O cng l ru bc nht c cha mt ni i l hn hp ca
hai ng phn izopropyliden v izopropenil.

C H
2
O H
C H
2
O H
X i t r o n e l o l


V c cacbon bt i trong phn t nn xitronelol c tnh quang hot. Dng
quay tri (-) c mt trong trong tinh du hoa hng. Dng quay phi (+) c trong tinh
du s. Dng quay tri rt c gi tr ch nc hoa.
Linalol (t
0
si: 198 199
0
C) l mt ru bc ba c hai ni i l ng phn ca
geraniol v nerol.

L i n a l o l
O H
O H


97


Linalol c mt cacbon bt i nn c hai i quay, c hai u ph bin trong
thin nhin. Dng (-) trng thi t do cng nh trng thi este trong tinh du ngc lan
ty, hoa hng, dng (+) c trong tinh du cam, du ht mi. Dng raxemic ( ) linalol
thu c khi ng phn ho geraniol di tc dng ca axit, phn ng tin hnh rt d
dng.
- V andehyt:
Xitral C
10
H
16
O l mt andehyt ng vi geraniol, thng gp di dng hai
ng phn cis-trans gi l xitral-a (tcl geranial) v xitral-b (tc l neral). Sn phm
thin nhin l mt hn hp ca hai dng v mi dng l hn hp ca hai ng phn
kiu izopropiliden v izopropenil.
Xitral l mt trong nhng hp cht quan trng nht ca nhm tecpenoit mch
h. Xitral c mt trong nhiu loi tinh du nh trong tinh du s, chanh, tinh du mng
tang v.v T xitral c th thc hin vic chuyn ho thnh hydroxixitronelal thnh
cc ionon v.v l nhng cht c hng thm d chu c gi tr kinh t cao.

b)Tecpen mt vng v cc dn xut ca chng.
Cc hp cht loi tecpen mt vng c b khung cacbon ging p-ximen hoc
mentan:

p - x i m e n m e n t a n


Chng c cha hai lin kt i trong phn t. Cc tecpen mt vng cn gi l
cc mentadien. V l thuyt c th tn ti 14 mentadien ng phn do s khc nhau v
v tr tng h ca hai lin kt i.
V d:
Limonen c trong thin nhin di cc dng (+) limonen, (-) limonen v ( )
limonen (tc l dipenten). (+) limonen c th tch ra t tinh du v cam, chanh v.v
(-) limonen c mt trong tinh du thng, trong tinh du m tc. Chng u c mi
thm d chu. ( ) limonen (dipenten) c trong tinh du long no, tinh du l chanh,
tinh du becgamot v.v



98


Trong cc dn xut cha oxi ca tecpen mt vng, ng ch nht l cc ancol,
trong s c mentol, tecpineol v.v
Mentol C
10
H
20
O c cng thc cu to sau y ng vi mt ru bc hai.

O H


Trong thin nhin thng gp dng mentol quay tri. Cht ny l thnh phn
chnh ca tinh du bc h (mentha piperita); c th tch ra d dng t loi tinh du ny
(-) mentol kt tinh, nng chy 43
0
C, si 216
0
C, [ o]
D
= -49
0
.
Mentol c cha ba nguyn t cacbon bt i trong phn t v vy c 8 ng
phn quang hc vi 4 cp i quang v 4 bin th raxemic ( ). Chng c tn: ( )
mentol, ( ) neomentol, ( ) izomentol v ( ) neoizomentol.
Mentol c nhiu ng dng trong i sng v y hc: ch thuc nh rng, lm
bnh ko, thuc ho v.v
Tecpineol C
10
H
18
O l ancol bc ba cha mt ni i gm cc ng phn:

O H
O H
O H
O H


Trong s cc ng phn ni trn, o-tecpineol l c hng thm d chu hn c nn
c dng nhiu sn xut nc hoa.
c)Tecpen hai vng v cc dn xut
Tecpen hai vng chia thnh nhiu nhm tu theo b khung cacbon khc nhau. V
d:



*
*
*
o-tecpineol
| -tecpineol 1-tecpineol
4-tecpineol
Nhm pinan Nhm camphan
99


- Nhm pinan:
Cht tiu biu chnh ca nhm ny l o-pinen. cng l tecpen ph bin nht
trong thin nhin. N c mt trong nhiu tinh du cng vi | -pinen, ch yu trong
tinh du thng, c khi chim ti 70-90% thnh phn tinh du.




Tinh du thng l sn phm thu c khi em chng ct li cun bng hi nc
nha thng th trch t thn cy thng. Phn nha rn cn li sau khi ct tinh du gi
l nha tng hng hay colophan.
Tinh du thng cng nh nha tng hng u c nhiu ng dng quan trng.
Trc y tinh du thng thng dng lm dung mi pha sn nhng ngy nay
tinh du thng tr thnh mt loi nguyn liu quan trng ca cng nghip ho hc. T
o-pinen tch c t tinh du thng, ngi ta c th thc hin vic chuyn ho n
thnh hng trm cht khc nhau, trong s c nhng cht c gi tr cao dng lm
dc phm, hng liu, thuc tr su v.v
Nha tng hng l hn hp phc tp trong thnh phn axit nha chim t
l cao, i khi ti trn 90%. N c dng trong nhiu ngnh cng nghip nh giy,
vi, cao su, mc in, xi, x phng v.v
Nc ta c rt nhiu rng thng ln c hai min Nam v Bc vi nhiu loi
thng khc nhau nh thng ui ng (Pinus massoniana), thng nha, thng ba l,
thng nm l v thng hai l dt. Cc vng thng tp trung min bc nh Qung
Ninh, Ngh An, Bc Thi, Thanh Ho v.v min Nam nh Lm ng, Gia Lai.
- Nhm Camphan.
Cht tiu biu quan trng nht ca nhm ny l dn xut cha oxi gi l campho
hay long no.
Campho C
10
H
16
O l mt xeton hai vng c cng thc cu to nh sau:

O


(+) Campho hoc campho thng c iu ch bng cch ct li cun vi hi
nc g cy long no Cinnamoum camphora. Loi cy ny mc nhiu Cao Bng v
H Tuyn, Bc Thi v.v
(+) Campho c mi thm c trng, v nng v hc, thng ho c nhit
thng, khng tan trong nc, d tan trong a s dung mi hu c.
o-pinen | -pinen
100


Campho c nhiu tc dng v mt sinh l: kch thch hot ng ca tim nn
dng ch thuc hi tnh c tim, h st, gim au, kch thch nim mc, c tnh st
trng, cha au bng v.v Ngoi ra campho cn dng nhiu lm cht ho do trong
cng nghip nha xenluloit.

2) Seckitecpen (izo-C
5
)
3

Seckitecpen cmch cacbon l (izo-C
5
)
3
. Chng c loi mch h, loi mch vng
thng gp trong thin nhin dng hirocacbon, ancol hoc xeton.
a)Axilic seckitecpen (seckitecpen khng vng
Seckitecpen khng vng gp trong thin nhin t hn so vi loi c vng. Tiu biu
cho loi axiclic seckitecpen l farnezen v ancol tng ng l farnezol (tch c t
tinh du cam qut).

C H
2
O H
F a r n e z e n ( C
1 5
H
2 4
) F a r n e z o l ( C
1 5
H
2 4
)


Farnezol tch c t tinh du mt s loi ho. Cng thc cu to ca n c
thit lp nh da vo sn phm phn ng ozon phn, vo quy tt izopren v c
khng nh bng qu trinh tng hp geraniol.

H
3
C C
H
H
2
C C C
H
C H
3
H
2
C
H
2
C C C
H
H
2
C O H
C H
3
C H
3
H
3
C C
O
C H
3
O C
H
H
2
C
H
2
C C
O
C H
3
O C
H
H
2
C
H
2
C C
O
C H
3
O C
H
C H
2
O H
O
3
Z n / H C l
+
+
+
F a r n e r o l
A x e t o n A n d e h y t l e v u l i n o i c
A n d e h y t g l i c o l i c


b)Xiclic seckitecpen (seckitecpen vng)
Hirocacbon seckitecpen c vng gp rt ph bin trong gii thc vt. Chng c
cu to kh phc tp, phn t gm cc vng t 3 n 9 cnh hoc ln hn. V d:

Bisabolen
Cadinen
Copaen
Selinen
Cedren

101


Cc dn xut cha oxi ca hidrocacbon xiclic secquitecpen rt phong ph. C
nhng cht c hot tnh sinh hc cao nh xantonin c dng lm thuc tr giun
a rt hiu nghim.

O
O
O
o
-Cadinol
Cedrol
Xantonin


3) Cc tecpen khc
a)Dictecpen (iso-C
5
)
4

C gi tr quan trng l hai ancol ditecpen: phitol (C
20
H
39
OH) v retinol
(C
20
H
29
OH). Phitol dng este to thnh mt nhnh ca clorophin c trong cht dip
lc ca cy xanh. Retinol hay vitamin A c trong lng trng, du gan c

CH
2
OH
CH
2
OH
Phitol
Retinol (vitamin A)


Gc phityl c trong thnh phn ca vitamin E v vitamin K
1
v trong clorophinal
(cht dip lc). Retinol (vitamin A) khi vo trong c th s b ehydro ho thnh poli-
trans-retinal. vng mc, poli-trans-retinal kt hp vi protein v tr thnh tc nhn
tip nhn nh sng ng phn ho thnh 11-cis-retinal. Chnh phn ng quang ng
phn ho retinal lm c s ho hc ca th gic.

CHO
Poli-trans-Retinal
CHO 11-cis-retinal


b)Tritecpen, (iso-C
5
)
6
, v tetratecpen, (iso-C
5
)
8

Hidrocacbon tritecpen quan trng nht l squalen (C
30
H
50
) (c nhiu trong du gan
c mp), c dng lm nguyn liu trong sinh tng hp nhiu steroit.

squalen

102



Hidrocacbon tetratecpen, C
40
H
56
gp rt ph bin trong thin nhin. Chng c mu
t vng n v to ra sc t ca hoa qu. V d:




gia mi phn t squalen, licopen v | -caroten u c mt lin kt m s hnh
thnh chng khng theo quy tt isopren u ni vi ui. Trong c th, di tc dng
ca enzim carotenaza, mi phn t caroten c chuyn ho thnh 2 phn t vitamin
A. Lin kt duy nht b t l lin kt tri quy tt isopren.
Cc dn xut cha oxi ca tritecpen v tetratecpen c kh nhiu v thng dng
a vng. Chng hn, dng 5 vng su cnh rt hay gp trong t nhin m i din l
fridelin. Khi cho fridelanol tc dng vi axit, ngi ta thy xy ra s chuyn v
cacbocation nhiu ln rt th v vi hiu sut 55%.


O
HO
H
-H
2
O
Fridelin (C
30
H
50
O) Fridelanol (C
30
H
52
O) C
30
H
50
(55%)


Cn ch rng cc tritecpen 5 vng trn trng gn ging vi loi hp cht gi l
steroit. Tuy nhin, b khung cacbon ca steroit khng phn thnh cc mt xch iso-C
5

theo quy tt isopren c.

c) Politecpen
Trong thin nhin, ngi ta gp mt s polime m phn t ca chng gm hng
chc ngn mt xch iso-C
5
to thnh. l cc politecpen. Quen thuc nht l cao su
thin nhin m mi mt xch iso-C
5
c mt lin kt i u cu hnh cis:

Licopen (sc t mu qu c chua)
| -caroten (sc t mu da cam c c rt)
103


CH
2
H
3
C
H
2
C
H
n


ng phn cu hnh ca cao su thin nhin l nha gutapecha, m mi mt xch
iso-C
5
c mt lin kt i cu hnh trans:

CH
2
H
3
C
H
H
2
C
n


Chnh do s khc nhau v cu hnh ca mt xch iso-C
5
m cao su thin nhin th
n hi cn gutapecha th dn.

4) Sinh tng hp tecpenoit
Di tc dng ca nh sng, nh c cht dip lc, t CO
2
v H
2
O, cy xanh tng
hp c cc cht hu c n gin. Sau , nh cc enzym, cc phn t n gin
c bin i v kt hp vi nhau thnh nhng phn t phc tp hn. S tng hp
tecpenoit cy xanh cng xy ra theo cch thc .

2.3. Ankin
Ankin cng l loi hirocacbon cha no mch h, nhng c lin kt ba trong phn
t. Mi phn t ankin so vi phn t ankan tng ng c t hn bn nguyn t hyro,
do cng thc phn t chung ca ankin l C
n
H
2n-2
, 2 n > . Khi n = 2 ta c cht u
tin ca dy ng ng ny l C
2
H
2
tc l axetylen; n = 3 c metyl axetylen C
3
H
4

v.v Tt c hp thnh dy ng ng axetylen.

2.3.1. Cu to v gi tn
1) Cu trc
Hai nguyn t cacbon ca lin kt ba trng thi lai ho sp. Mi nguyn t C
sp

dng mt obitan lai ho to lin kt vi mt nguyn t hyro v mt obitan lai ho
khc to lin kt o vi nguyn t C
sp
kia. mi nguyn t C cn hai obitan 2p khng
lin hp (obitan p thun khit) m trc ca chng vung gc vi nhau v vung gc
vi trc lin kt. Hai obitan 2p c trc song song nhau ( hai nguyn t C khc nhau)
li xen ph vi nhau tng i mt to thnh hai lin kt t. Nh th, lin kt gia hai
nguyn t C axetylen c m bo bi mt lin kt o v hai lin kt t l lin
kt ba. lin kt ba, mt electron t phn b u c bn pha ca trc lin kt,
chng hp vi nhau thnh dng gn ging hnh tr. di lin kt ba CC l 120 pm
ngn hn nhiu so vi lin kt CC (154 pm) v lin kt i C=C (133pm). di
lin kt HC
sp
cng ngn hn so vi lin kt HC
sp3
v HC
sp2
. Hai nguyn t C
ca lin kt ba v hai nguyn t khc lin kt trc tip vi chng to thnh mt ng
thng.
104


H C C H
1 2 0 p m
1 0 6 p m



Ta nhn thy rng
) C ( ) C ( ) C (
3
sp
2
sp
sp
r r r < < l do kch thc ca obitan lai hoa sp nh hn
obitan sp
2
v sp
3
. iu lm cho m in ca C
sp
ln hn ca
2
sp
C v
3
sp
C .
Ankin vi lin kt ba gia mch (vit gn l ankin gia mch) bn hn ankin vi
lin kt ba u mch (vit gn l ankin u mch) nhng c hai loi u km bn
hn so vi dien ng phn v tt nhin cng km bn hn so vi anken c cng s
nguyn t C.

2) ng phn v danh php
Do c im v cu trc, ankin khng c ng phn hnh hc v t C
5
tr ln mi
c ng phn mch cacbon. V ng phn cu to, cc ankin tng t nh anken,
ngoi cc ng phn v mch cacbon cn c ng phn v v tr ca lin kt ba.
Nhng khc vi lin kt i ca anken, lin kt ba trong ankin khng to ra ng phn
lp th.
Theo danh php hp l, tn gi cc hirocacbon cha lin kt ba xut pht t tn
ca axetylen bng cch gi tn cc gc ankyl hai bn ni ba sau thm tn
axetylen.
V d:
CH
3
CCH: metyl axetylen
CH
3
CCCH
3
: dimetyl axetylen.

Theo danh php quc t IUPAC, cc hirocacbon cha lin kt ba gi chung l
ankin, chng u c ui tn cng l in. Vic nh s mch chnh bt u t nguyn t
cacbon u mch gn lin kt ba.

V d:
CH
3
CCCH
2
CH
2
CH
2
CH(CH
3
)CH
3

7-metyl-2-octin
TN GI MT S ANKIN N GIN
Cng thc Tn lch s Tn hp l Tn quc t IUPAC
CHCH Axetylen axetylen Etin
CHCCH
3
Anlilen Metylaxetylen Propin
CHCCH
2
CH
3
Crotonilen Etylaxetylen 1-butin
CH
3
CCCH
3
Crotonilen imetylaxetylen 2-butin
CH
3
CCCH
2
CH
3
Valerilen Metyletylaxetylen 2-pentin
CH
3
CH(CH
3
)CCH Valerilen Izopropylaxetylen 3-metyl-1-butin
CHCCH
2
CH
2
CH
3
Valerilen Propylaxetylen 1-pentin

105


Cc gc hirocacbon cha lin kt ba gi chung l ankinyl.
V d: CHC etinyl
CHCCH
2
2-propinyl

2.3.2. Tnh cht vt l
Cc thnh phn thp C
2
-C
4
trong dy ng ng ankin l nhng cht kh khng
mu. Cc ng ng cao hn l nhng cht lng hoc rn.
T khi ca cc ankin cao hn so vi cc anken tng ng.
Cc ankin tan trong nc nhiu hn cc hirocacbon khc.
Cc ankin c nhit si cao hn so vi cc anken v ankan tng ng.
Ph hng ngoi ca cc ankin c di hp th 2100 cm
-1
ng vi dao ng ho tr
ca lin kt ba CC. Cc monoankylaxetylen RCCH c di hp th mnh gn
3300 cm
-1
c trng cho dao ng ho tr ca lin kt CH trong nhm CH. Nh
vy, s c mt ca nhm CCH trong phn t ankin c th nhn ra d dng nh ph
hng ngoi. Tuy nhin, lin kt ba trong ankin kiu RCCR li kh pht hin do
khng c di hp th ca nhm CH gn 3300cm
-1
v s hp th ca lin kt CC
i khi qu yu kh nhn ra.

2.3.3. Cc phng php iu ch v ng dng
1) i t dn xut dihalogen
Cc dn xut dihalogen no c hai halogen nh hai nguyn t cacbon bn cnh
nhau, hoc cng c th dng dn xut dihalogen khi tng tc vi dung dch KOH-
ru, s b tch hai phn t hyro halogenua to ra lin kt ba:


R
H
C
H
C R '
X X
2 K O H / r u o u
R C C R ' + 2 H X

R
H
2
C C H X
2
2 K O H / r u o u
R C C H + 2 H X


Nh phn ng tch hai phn t HX to ra lin kt ba, c th chuyn ho lin kt
i thnh lin kt ba.
V d:
H
3
C C
H
C H
2
+ B r
2 H
3
C
H
C C H
2
B r B r
2 K O H / r u o u
H
3
C C C H
- 2 H B r


Phn ng tch hyro bromua c th tin hnh qua hai giai on. V d, dn xut
dibromphenyl d b tch mt phn t hyro bromua to thnh bromstiren, sau li
tch phn t hyro bromua th hai, giai on ny kh khn hn giai on trc to ra
phenylaxetylen:


106


C
6
H
5
C
H
C H
2
+ B r
2 C
6
H
5
H
C C H
2
B r B r
2 K O H / r u o u
C
6
H
5
C
H
C H
B r
+ B r
2
S t i r e n
1 , 2 - d i b r o m p h e n y l e t a n
b r o m s t i r e n
2 K O H / r u o u
C
6
H
5
C C H
p h e n y l a x e t y l e n


2) i t dn xut tetrahalogen
Cho dn xut tetrahalogen c bn halogen nh vo hai cacbon lin nhau tc dng
vi bt km cng to ra c lin kt ba.


R R '
X
X
X
X
+ 2 Z n R C C R ' + 2 Z n X
2


3) iu ch ng ng ca axetylen i t axetylen
Nh kh nng c th chuyn ho axetylen thnh dn xut c kim (dn xut natri)
nn c th tng hp c cc ng ng cao ca axetylen khi cho dn xut ny tc
dng vi dn xut halogen theo s sau:

H C C H + N a H C C N a H C C R
I R


V d: t axetylen v etyl bromua c th tng hp ra etylaxetylen.

H
3
C
H
2
C B r
N a C C H
H
3
C
H
2
C C C H
+


4) iu ch axetylen
Trong dy ng ng ankin, axetylen l thnh phn u tin, ng thi cng ng
vai tr quan trng nht trong thc t nn c sn xut vi qui m ln trong cng
nghip.

a)i t canxi cacbua
Phng php quan trng nht v thng dng nht trong cng nghip cng nh trong
phng th nghim l thu phn canxi cacbua, thng gi l t n. Cho canxi cacbua
tip xc vi nc s gii phng kh axetylen bay ln:

CaC
2
+ 2H
2
O HCCH + Ca(OH)
2

Trong cng nghip s thu phn c th tin hnh theo phng php t (c) hoc
theo phng php kh (mi). Phng php t dng nhiu nc. Phng php kh
107


dng t nc hn, ch cn lng nc bng 1/10 lng nc dng trong phng php
t. Trong l phn ng theo phng php kh, ngi ta cho nc vo canxi cacbua,
phn ng pht nhit v lm cho ton khi nng ln ti 115
0
C, nc d cng bay hi
ch cn li khi vi rn. Hi nc ln vi kh axetylen bay ra s c ngng t trong
thp ngng.
Canxi cacbua c iu ch t than v vi sng trong l in nhit gn
2500
0
C:

CaO + 3C CaC
2
+ CO mol / kcal 111 H
0
298
+ = A

y l mt phn ng thu nhit, i hi phi cung cp mt nng lng ln.
Canxi cacbua l nhng tinh th rn. Mng li tinh th gm nhng ion Ca
2+
v
2
2
C
(CC); cc ion
2
2
C rt khng bn khi gp nc, chng s lp tc chim ly cc
ion H
+
ca phn t H
2
O to ra axetylen v cc ion HO
-
.
Axetylen iu ch t canxi cacbua thng c cha mt lng nh cc kh khc nh
NH
3
, PH
3
, AsH
3
, S(CH=CH
2
)
2
, vinylaxetylen v.v Cc tp cht ny c th c loi
tr ra bng cch cho hn hp kh i qua dung dch kali bicromat trong axit sunfic
hoc qua cc dung dch oxi ho khc.

b) i t metan
Trong l in ( nhit khong 1500
0
C), kh metan b nhit phn to thnh
axetylen:


2 C H
4
1 5 0 0
0
C
C
2
H
2
+ 3 H
2


Tnh ton nhit ng cho thy rng iu kin cn bng lm thun li cho s to
thnh axetylen nng trn 1200
0
C. Tuy nhin, nhit ny, axetylen li d b
phn hu thnh cacbon v hyro. Mt khc, di 1200
0
C c mt hyro axetylen cng
khng bn v mt nhit ng. V vy, cn lm lnh ngay hn hp kh sau khi ra khi
khu vc phn ng. nhit di 100
0
C, axetylen khng ph phn hu nh tnh tr
ca phn t.
Phn ng nhit phn metan lm tng th tch, v vy, s tin hnh phn ng di p
sut thp thun li cho s to thnh axetylen.
Phn ng ny c p dng trong cng nghip vi nhiu phng php tin hnh
c th khc nhau. Chng hn, ngi ta cho metan i vo l di p sut thng, cho
bt tia la in gia hai in cc kim loi trong mt thi gian ngn (bng mt phn
giy), sau lm lnh ngay hn hp kh i ra bng nc. Kh thu c cha 12-15%
axetylen (v l thuyt c th t ti 25%), axetylen li c tch ra bng cch ho tan
trong nc di p sut cao. Sn phm ph l diaxetylen C
4
H
2
c tnh n d dng.
Cng c th dng phng php t chy tng phn bng cch cho hn hp metan
v oxi i qua nhng ngn la c bit. Nhit to ra do phn ng t chy dng
cung cp cho phn ng nhit phn thu nhit. Trong hn hp kh to thnh, ngoi 8-
10% axetylen, cn c H
2
, CO, CO
2
.

mol / kcal 5 , 95 H
0
298
+ = A
108


c)Tng hp trc tip
Nm 1860, Bectlo l ngi u tin tin hnh tng hp axetylen t cacbon v
hyro:

2C + H
2
C
2
H
2
mol / kcal 9 , 54 H
0
298
+ = A

Phn ng din ra trong vng cung la in gia hai in cc bng than. Tnh
ton nhit ng chng t rng, cn bng ch lch v pha phi nhit rt cao (trn
3000
0
C). Do , phn ng ny khng c p dng trong thc t v ch c ngha v
mt l thuyt.

5) ng dng
a)Lm nhin liu
Khi axetylen chy trong oxi nhit ngn la c th t ti 3000
0
C v th n
x axetylen-oxi c dng hn v ct kim loi. Ngun cp axetylen cho n x c
th l mt thng phn ng n gin thu phn canxi cacbua k thut (gi l t
n) hoc c th l cc bnh thp cha cht xp v axeton ho tan axetylen p sut
12 n 15 at ( p sut 1 th tch axeton ho tan c 300 th tch axetylen).
Axetylen chy trong khng kh cho ngn la sng chi. V th trc kia ngi
ta dng canxi cacbua k thut np vo bnh thp c van cho nc nh xung t t ri
t kh axetylen sinh ra thp sng. Canxi cacbua k thut cha nhiu tp cht c
mu en nn c gi l t n.
Khi t n phn ng vi nc, ngoi C
2
H
2
cn to ra H
2
S, PH
3
, NH
3
chng
to ra mi hi gi l mi t n.

b) Lm nguyn liu cho cng nghip tng hp hu c
Trc nhng nm nm mi ca th k 20, cng nghip tng hp hu c da trn
nguyn liu chnh l axetylen. T axetylen ngi ta iu ch c axetandehyt (cng
nc), vinyl clorua (cng HCl), vinyl axetylen (dime ho) ri butadien v cloropren,
acrilonitril (cng HCN), vinyl axetat (cng CH
3
COOH), ankyl vinyl ete (cng
ancol) Cc cht ny dng sn xut ho cht hu c c bn khc v quan trng
hn l tng hp cc polime sn xut ra cc cht do v cao su tng hp.
Ngy nay, nh s pht trin vt bc ca cng ngh ho du, cc ho cht hu c
c bn trn u c sn xut t etylen hoc t cc hirocacbon thu c khi cracking
du m bng cc phng php kinh t hn v t nh hng n mi trng hn.

c)Tng hp cc hp cht c hot tnh sinh hc
Nu nh ngnh cng nghip ho hc trn c s axetylen ngy ny hu nh b
thay th bi cng nghip ho hc trn c s etylen th vic tng hp cc hp cht c
hot tnh sinh hc t axetyeln li c nhng bc pht trin mnh m v thu c
nhng thnh tu to ln.
Dn chng tiu biu l vic tng hp cc pheromon. l cc hp cht ha hc do
sinh vt tit ra thng tin cho nhau. Pheromon c tnh cht hp dn, li cun ng
loi khc gii gi l pheromon hay l cht d dn gii. S dng cht dn d gii ngi
109


ta c th tp trung cn trng (chng hn bm c) n a im t thuc tiu dit
chng m khng cn phi phun thuc trn lan trn ng rung.
Rt nhiu pheromon gii ca cn trng c cha trong phn t nhng lin kt i
bit lp hoc lin hp c cu hnh xc nh (E hoc Z). Phng php thun li tng
hp ra chng l iu ch ra cc ankin tng ng bng cc phng php kh la cn
lp th. Hy xem mt v d tng hp pheromon gii d dn bm su hai cam qut
vi hai lin kt i cu hnh Z.
H
3
C H
2
C C C C C ( C H
2
)
1 0
O H
1 ) ( x i c l o - C
6
H
1 1
)
2
B H
2 ) C H
3
C O O H , 0
0
C
H
3
C H
2
C H C C
H
C
H
C H ( C H
2
)
1 0
O H
Z Z
H
3
C H
2
C H C C
H
C
H
C H ( C H
2
)
9
C H O
Z Z C
5
H
5
N H C r O
3
C l

Ngoi vic s dng trong tng hp peromon, axetylen v cc ankin cn c
dng trong tng hp mt s hot cht tng t hocmon dng trong y dc.

2.3.4. Tnh cht ho hc
1) Bn cht, c im ca lin kt ba CCC
Lin kt ba CC c to nn bi hai nguyn t cacbon trng thi lai ho sp tc
l kiu lai ho ng thng. Trong lin kt ba c mt lin kt o do s xen ph trc
ca hai electron lai ho cn hai lin kt t do s xen ph bn ca hai cp electron t.
Cc trc ca cc electron t to thnh hai mt phng thng gc vi nhau, giao tuyn
ca hai mt phng l ng ni tm hai nguyn t cacbon.
Mc lin kt ca cc nguyn t cacbon trong lin kt ba ln hn trong lin kt
nn lm cho lin kt ba ngn hn. di lin kt ba CC bng 1,20A
0
trong khi
di lin kt i C=C l 1,34 A
0
v di lin kt n CC l 1,54A
0
. V nng lng
lin kt, i vi lin kt ba l 199,6 kcal/mol, ca lin kt i l 145,8 kcal/mol v ca
lin kt n l 82,6 kcal/mol. Mt electron t tp trung ch yu khong gia hai
ht nhn ca hai nguyn t cacbon, nn khu vc bn ngoi ca hai ht nhn tng i
ngho mt electron. iu gii thch kh nng phn ng km ca lin kt ba so
vi lin kt i trong cc phn ng cng electrophin.
Mt c im ng ch na l cc nguyn t cacbon trng thi lai ho sp c
m in ln hn ca cacbon lai ho Csp
2
v cacbon lai ho Csp
2
li c m in ln
hn Csp
3
. Kt qu l trong lin kt CH v s phn cc mnh CH lm tng
momen lng cc ca lin kt v lm tng kh nng ca hyro tch ra di dng
proton. Thc t, tnh axit ca axetylen ln hn so vi etylen v etan.
Di y l mt s c im v cu to v lin kt trong cc phn t etan, etylen v
axetylen:

Hirocacbon Lai
ho
m
in ca
C (eV)
Bn knh
nguyn t C
(A
0
)
di lin
kt CH
(A
0
)
Momen
lng cc
(D)
Hng s
phn li
axit K
a

CH
3
CH
3
sp
3
2,50 0,722 1,102 0,307 <10
-40
CH
2
=CH
2
sp
2
2,69 0,74 1,081 0,692 10
-40
CHCH sp 2,75 0,69 1,064 1,05 10
-22
110


Cc phn ng ca ankin c th chia thnh ba loi: phn ng cng, phn ng trng
hp. V i vi nhng ankin RCCH v axetylen th c thm nhng phn ng
ca nguyn t hyro nh vi cacbon mang ni ba.

2) Phn ng cng
Cc phn ng cng vo lin kt ba din ra qua hai giai on: giai on th nht
chuyn ni ba thnh ni i v giai on th hai chuyn ni i thnh ni n.
a)Phn ng hyro ho
* Hyro ho xc tc.
Khi c xc tc kim loi nh Ni, Pt, Pd, ankin cng vi hyro u tin to ra anken
nhng anken li phn ng ngay vi hyro to thnh ankan:

R C C R ' R C
H
C
H
R ' R
H
2
C
H
2
C R '
H
2
x t
H
2
x t


Mun phn ng dng li giai on to ra anken th cn lm gim hot tnh ca
xc tc, lm yu xc tc bng nhng tc nhn thch hp. Chng hn Pd/CaCO
3
phn
hot ho bng (CH
3
COO)
2
Pb (xc tc Lindlar) hoc Pd/C tm quinolin hay piridin u
xc tc cho phn ng ch n giai on to ra anken cu hnh cis. V d in hnh l
vic to ra cu hnh cis trong tng hp cht d dn b ry (pheromon) hoc cis-stilben:


H
C
C H
3
C
2
H
5
( C H
2
)
4
C C ( C H
2
)
6
C H
2
O H
H
2
/ x t L a n d l a r
2 0
0
C , C
2
H
5
O H
( C H
2
)
6
C H
2
O H
H
H
3
C H
2
C H C ( H
2
C )
4
H
C H
3
9 2 % c i s
C r O
3
, C
5
H
5
N , H C l
C H
2
C l
2
, 2 0
0
C
( C H
2
)
6
C H
H
H
3
C H
2
C H C ( H
2
C )
4
H
C H
3
9 2 % c i s
O


C
6
H
5
C C C
6
H
5
P d / C , q u i n o l i n
H
C
6
H
5
H
C
6
H
5
c i s - S t i l b e n


* Kh bng Na/NH
3
lng.
c anken cu hnh trans, ngi ta kh ankin bng Na trong amonic lng. V
d:
C
3
H
7
C C C
3
H
7
N a / N H
3
l o n g
- 3 3
0
C
C
3
H
7
H
H
C
3
H
7
+ N a N H
2
9 7 %


cht d dn b ry
111


Tnh c th lp th ca phn ng kh ankin bng Na/NH
3
lng c gii thch bi
c ch phn ng. Natri cng nh cc kim loi kim khc khi ho tan vo trong
amonic lng to ra dung dch mu xanh thm l do to thnh electron solvat ho
e(NH
3
)
n
(vit gn l e
-
(sol)).

Na + NH
3
(lng) Na
+
(NH
3
)
m
+ e
-
(NH
3
)
n

Electron sonvat ho (c bn cht nh gc t do) cng vo lin kt ba bin ankin
thnh anion gc (va mang in tch m va mang electron c thn). Anion gc ny
ly mt proton t NH
3
to gc vinyl bn hn.

R C C R
( s o l ) N a
+
( s o l )
- N a
+
( s o l )
R C C R
H N H
2
.
. .
e
-
R C C
H
R
+ N H
2
-
.


Dng cis v dng trans ca gc vinyl c th chuyn i cho nhau qua trng thi
chuyn tip m nguyn t cacbon mang electron c thn trng thi lai ho sp.
Cng ging nh anken, gc dng trans bn hn:

C C
R H
R
.
R C
H
C
H
R
.
C
H
R
C
R
.



Gc trans-vinyl nhn mt electron solvat ho ( ghp i electron) tr thnh anion
trans-vinyl. Tip theo anion vinyl ngt ly mt proton t amonic v to thnh trans-
anken:

( s o l ) N a
+
( s o l )
- N a
+
( s o l )
e
-
C C
R
H R
.
C C
R
H
. .
-
H N H
2
R
H
H
R
+ N H
2
-


b)Cng halogen
Cng nh phn ng hyho, phn ng cng halogen xy ra theo hai giai on. V d,
khi cho brom cng vo axetylen, giai on u s cho trans-1,2-dibrometylen v giai
on sau cho 1,1,2,2-tetrabrometan:

gc vinyl
gc trans-vinyl
trng thi chuyn tip
gc cis-vinyl
112


H C C H + B r
2
C C
H
B r
B r
H
B r
2
B r
2
H C C H B r
2
t r a n s - 1 , 2 - d i b r o m e t y l e n
1 , 1 , 2 , 2 - t e t r a b r o m e t a n


i vi clo, trong iu kin thng, phn ng xy ra qu mnh lit to nhiu nhit
nn gy phn ng phn hu. Trong iu kin k thut, ngi ta thc hin c phn
ng cng clo trc tip vo axetylen trong nhng khi xp.

c)Cng hyro halogenua
Phn ng cng hyro halogenua kh hn phn ng cng halogen. Tc dng ca
hyro florua khan vo axetylen bt u cho vinyl florua v sau cho 1,1-difloetan.

H C C H + H F
H
2
C C
H
H F
H
3
C C H F
2
v i n y l f l o r u a
F
1 , 1 - d i f l o e t a n


Trong k thut tng hp nha polivinyl clorua (PVC), mun iu ch ra vinyl
clorua ngi ta cho axetylen tc dng vi hyro clorua trn xc tc thu ngn clorua
120 150
0
C:

H C C H + H C l
H
2
C C
H
v i n y l c l o r u a
C l
H g S O
4


d)Cng nc
Phn ng cng HOH vo axetylen v ng ng ca n c Kucherop nghin cu
nm 1881. Phn ng tin hnh bng cch cho ankin i vo dung dch axit sunfuric
long c cha thu ngn sunfat ng vai tr xc tc. Phn ng qua giai on trung
gian l dng enol khng bn nn n ng phn ho thnh hp cht cacbonyl theo s
chung sau:

C C
+ H O H
H g S O
4
C
H
C
O H
H
2
C C
O


Nu i t axetylen, giai on trung gian l ancol vinylic khng bn, cui cng ta
c axetandehyt:

dng enol dng cacbonyl
113


H C C H + H O H
H g S O
4
H
2
C
C H
O H
H
3
C C
H
O



Cc ng ng ca axetylen khi cng HOH s to ra xeton theo quy tt
Maccopnhicop. V d:


C C H
+ H O H
H g S O
4
C
C H
2
H
3
C C C H
3
H
3
C
H
3
C
O H O
a x e t o n
Theo Kucherop, trc ht thu ngn sunfat kt hp vi phn t ankin to ra mt hp
cht phc t tan:

C C + H g S O
4
C C O
H g O S O
2


Sau , hp cht phc ny b thu phn, cho hp cht cacbonyl v li gii phng
thu ngn sunfat:

C C O
H g O S O
2
- H g S O
4
H
2
O
C
H
C O H
H
2
C C
O

Phn ng kucherop c ngha quan trng trong k thut. Nh phn ng ny,
xut pht t axetylen cng nh t cc ankin khc, c th tng hp ra nhiu hp cht
hu c lm nguyn liu trong cng nghip ho hc.

e)Cng ancol v cng axit cacboxylic
Tng t phn ng cng HOH, di tc dng xc tc ca thu ngn sunfat (hoc
tt hn dgn xc tc CCl
3
COOH, BF
3
v HgO), axetylen c th cho phn ng cng
vi ancol to ra ete vinylic, cng vi axit cacboxylic to ra este ca ancol vinylic.
V d:

CHCH + HOC
2
H
5
H
2
C=CHOC
2
H
5

CHCH + HOOCCH
3
H
2
C=CHOCOCH
3

Ancol vinylic khng bn
andehyt axetyic
Etyl vinyl ete
vinyl axetat
114



Cc ete vinylic cng nh este vinylic u c th dng lm nguyn liu tng hp
polime c nhiu ng dng trong k thut.

3) Phn ng trng hp
a)Trng hp mch vng
Khi cho axetylen i qua ng nung ti 600-800
0
C, axetylen s trng hp li cho
mt cht nh nha, c cha sn phm chnh l benzen (ti 28%), cng vi nhng sn
phm ph nh toluen, naphtalen v cc hirocacbon thm ngng t khc tng t cc
sn phm chng ct nha than :
H C
C H
H C
C H
C H
C H
H C
H C
C
H
C H
C H
H
C


Cc ng ng ca axetylen trng hp trong iu kin nh nhng hn, di tc
dng xc tc ca axit sunfuric c. Trong iu kin , metylaxetylen trng hp cho
trimetylbenzen i xng:



H C
C
C
C H
C H
C
H C
C
C
H
C
C H
C
C H
3
H
3
C
C H
3
C H
3
H
3
C C H
3


Khi c xc tc iu ch t tetracacbonyl niken v triphenyl photphin
(CO)
4
Ni[P(C
6
H
5
)
3
]
2
nhit 60-70
0
C, axetylen s trng hp thnh benzen vi hiu
sut 80%.
Di tc dng xc tc ca niken xianua 20at v 60-70
0
C, axetylen trng hp
nhanh chng thnh xiclooctatetraen vi hiu sut cao:


H C C H
C H
C H
C H
C H
H C C H
H C
H C
C
H
C
H
C H
C H
C H
H
C


b)Trng hp mch thng
115


Di tc dng xc tc ca mui ng I, axetylen trng hp hai phn t (dime ho)
to ra vinylaxetylen:

H C C H +
H C C H
C C C C H
H
H
H
v i n y l a x e t y l e n


Phn ng ny c ngha quan trng v t vinylaxetylen, c th iu ch ra butadien
CH
2
=CHCH=CH
2
(cng hyro) v cloropren CH
2
=CHCCl=CH
2
(cng HCl) l
nhng nguyn liu tng hp cao su nhn to.
* Axetylen cng c th trng hp ba phn t to thnh CH
2
=CHCCCH=CH
2

hoc bn phn t cho CH
2
=CHCCCH=CHCH=CH
2
.
Khi c mt bt ng v vt oxi 200-250
0
C, axetylen trng hp thnh mt polime
(CH)
n
gi l cupren. l mt cht bt v nh hnh, khi lng phn t rt ln,
khng tan trong nc v cc dung mi hu c. Thng thng dng lm cht cch in.

4) Tnh axit yu v phn ng th vi kim loi
a)Tnh axit yu
Nguyn t hyro nh vo nguyn t cacbon mang lin kt ba rt linh ng, n c
tnh axit yu v c th tham gia phn ng th vi kim loi. Phn ng ny l phn ng
c trng nht ca cc ankin c hyro nh vo cacbon mang ni ba.
Trong axetylen HCCH c hai nguyn t hyro u nh vo cacbon mang ni
ba. Axetylen c tnh axit yu hn ca nc nhng li mnh hn ca amonic (ti 10
13

ln) v hn ca etylen v etan t nht ti 10
18
ln.
Nguyn nhn tnh linh ng ln ca hyro trong axetylen so vi trong etylen v
etan l do m in ca cc nguyn t cacbon trng thi lai ho khc nhau. Ta bit
rng obitan s c kch thc nh hn obitan p (gn ht nhn hn) nn b ht nhn ht
mnh hn. Hm lng obital s orbital lai ho sp ln hn sp
2
v sp
3
. Do cacbon
lai ho sp c m in ln nht ri n cacbon lai ho sp
2
v km nht l cacbon lai
ho sp
3
. Do m in ca cacbon lai ho sp ln nn lin kt CH ca cacbon mang
lin kt ba phn cc mnh, tng cng kh nng proton ho ca nguyn t hyro cng
nh kh nng th vi kim loi.

C C R H
o o


b) Phn ng th vi kim loi kim v kim th
Khi cho axetylen i qua natri kim loi un nng nhit 150
0
C hoc i qua dung
dch lng natri amiua NaNH
2
s to ra dn xut th natri axetylennua.

HCCH + Na HCCNa + 1/2H
2

HCCH + NaNH
2
HCCNa + NH
3

116


un nng mononatri axetylenua ti khong 220
0
C s to ra dn xut dinatri
axetylenua Na
2
C
2
. Canxi cacbua CaC
2
thc cht l canxi axetylenua c cha ion
2
2
C .

c) Phn ng th vi kim loi khc
Khi cho axetylen i vo dung dch bc nitrat trong amonic s to ra kt ta bc
axetylenua mu xm bc Ag
2
C
2
:
H C C H
[ A g ( N H
3
)
2
]
C C A g A g


Cng tng t, khi cho axetylen i qua dung dch ng clorua trong amonic s to
ra kt ta v nh hnh mu gch ca ng axetylenua Cu
2
C
2
.

H C C H
[ C u ( N H
3
)
2
]
C C C u C u


Cc phn ng vi mui bc v mui ng dng nhn ra axetylen v cng c th
dng tch cc ankin c hyro nh cacbon mang ni ba ra khi cc ng ng
khc.
Cc axetylenua ng v bc bn vng trong nc. Chng ch b thu phn bi
axit mnh, ti to li axetylen. iu chng t cc lin kt cacbon kim loi trong
axetylen ua ny mang tnh cht cng ho tr nhiu hn so vi cc axetylenua kim loi
kim, kim th. Cc axetylenua bc v ng khi kh rt d n mnh, gii phng kim
loi v cacbon ng thi to ra mt nhit lng ln. V d:

Ag
2
C
2
2C + 2Ag + 87 kcal

5) Mt s phn ng cng khc
a)Cng gc
Khi c mt peoxit hoc chiu sng. HBr cng vo ankin tri vi quy tt
Maccopnhicop. So snh phn ng cng electrophin v phn ng cng gc:


H
3
C ( H
2
C )
3
C C H + H B r
( C
2
H
5
)
4
N B r
C H
2
C l
2
H
3
C ( H
2
C )
3
C
C H
2
B r
8 9 %
H
3
C ( H
2
C )
3
C C H + H B r
8 m o l p e o x i t
H
3
C ( H
2
C )
3
H C
C H 7 4 %
0 - 5
0
C , 1 h
B r


b) Cng bohidrua
Hydrobo ho ankin xy ra tng t nh hydrobo ho anken. im khc bit l sau
khi ch ho vi H
2
O
2
/HO
-
th khng thu c enol m thu c xeton.

117


C C R R 3 + B H
3
T H F
( R C H C R )
3
B
H
2
O
2
/ O H
-
R C H
C R
O H
R C C H
2
R
O


c) Cng nucleophin
Do nguyn t cacbon mang ni ba trng thi lai ho sp c m in ln hn
Csp
2
v vy, khc vi anken ankin c phn ng cng theo kiu nucleophin (A
N
) khi
c tc nhn Nucleophin tn cng giai on quyt nh tc phn ng. V d phn
ng ca axetylen vi ancolat kim loi kim nhit cao to ra vinyl ete.

H C C H + R O N a
2 0 0
0
C
R O H
R O C
H
C H
R O H
R O C
H
C H
2
v i n y l e t e


Tng t, ion thiolat cng vo ankin to thnh vinyl thioete.

H
3
C C C C H
3
N a O H
C
2
H
5
O H
+ R S H
H
3
C
H
S R
C H
3


Phn ng cng amin vo ankin hot ho nh nhm ht electron cng thuc loi
cng nucleophin. V d:

C
6
H
5
O
C C C H + ( C
2
H
5
)
2
N H C
6
H
5
O
C C
H
C
H
N ( C
2
H
5
)
2


6) Phn ng oxi ho
a) Oxi ho gi mch v ct mch cacbon.
Ankin lm mt mu tm ca dung dch KMnO
4
ging nh anken. u tin c l to
ra vixinal dienol. Nhng phi nhit thp v mi trng trung tnh phn ng mi
dng li giai on to thnh o-dixeton (gi nguyn mch cacbon). Cn nu khng
khng ch pH ca mi trng v khng lm lnh th mch cacbon b ct ti ch c lin
kt ba to ra axit cacboxylic. V d:

H
3
C C C C H
2
C H
3
K M n O
4
H
2
O
0
0
C , p H 7 , 5
H
3
C C C C H
2
C H
3
O O
t
0
H
3
C C O O H
+ C H
3
C H
2
C O O H

118


Phn ng ozon phn ankin lun dn ti sn phm l axit cacboxylic.

H
3
C
3
( H
2
C ) C C C H
3
1 ) O
3
, C C l
4
, 0
0
C
2 ) H
2
O
C H
3
( C H
2
)
3
C O O H + C H
3
C O O H


Phn ng oxi ho ct mch bng KMnO
4
cng nh phn ng ozon phn c dng
xc nh v tr ca lin kt ba trong mch cacbon. V d, khi oxi ho mt hp cht
thin nhin c cng thc phn t l C
18
H
32
O
2
ngi ta thu c axit laurinic v axit
adipic. Suy ra hp cht l axit octadeca-6-inoic:

H
3
C ( H
2
C )
1 0
C C ( C H
2
)
4
C O O H C H
3
( C H
2
)
1 0
C O O H + H O O C ( C H
2
)
4
C O O H
K M n O
4
H
2
O
a x i t l a u r i n i c a x i t a d i p i c


b)Oxi ho tng mch
Nm 1870, Glazer pht hin thy rng huyn ph ca ankinua Cu(I) trong ru b
oxi ho bi oxi khng kh to thnh diin lin hp:

C
6
H
5
C C H + C u
2
C l
2
N H
3
C
2
H
5
O H
C
6
H
5
C C C u
O
2
C
2
H
5
O H
C
6
H
5
C C C C C
6
H
5



C
4
H
9
C C H + C u
2
C l
2
+ O
2
C
5
H
5
N
6 0
0
C
C
4
H
9
C C C C C
4
H
9


Oxi ho tng mch ankin l mt phng php rt c gi tr trong tng hp cc cht
thin nhin loi diin v dien lin hp.

H
2
C C
H
( C H
2
)
4
C C H H C C ( C H
2
)
7
C O O H +
C u ( I )
O
2
H
2
C C
H
( C H
2
)
4
C C C C ( C H
2
)
7
C O O H


Nm 1959 Eglinton ci tin bng cch dng xc tc l ng (II) axetat trong
piridin 60-70
0
C.
Nh c xc tc loi ny m vo nhng nm sau ngi ta tng hp c
cc xiclopoliin vng ln. V d:

H
2
C C H
2
C C
C H C H
C u ( C H
3
C O O )
2
C
5
H
5
N
+


c) Phn ng chy
119


Ankin chy hon ton to thnh CO
2
v H
2
O to nhit mnh (H < 0).

C
n
H
2n-2
+
2
O
2
1 n 3
(

nCO
2
+ (n-1)H
2
O
CHCH +
2
5
O
2
2CO
2
+ H
2
O

Thiu nhit ca axetylen nh hn ca etylen v etan nhng nhit ngn la t
c cao hn v th ngi ta dng n trong ngn la n x axetylen- oxi hn v ct
kim loi.

2.3.5. Gii thiu axetylen
Cht tiu biu quan trng nht ca dy ng ng ankin l axetylen.
Axetylen hay etin l mt cht kh khng mu, nguyn cht, khng mi, nh hn
khng kh v t tan trong nc, iu kin thng mt th tch nc ho tan c mt
th tch kh axetylen, khi p sut tng ln tnh tan cng tng ln. Axetylen tan nhiu
hn trong cc dung mi hu c nh ru, ete, c bit tan rt nhiu trong axeton: di
p sut thng mt lt axeton ho tan c 25 lt kh axetylen. Mun chuyn ch
axetylen c nhiu v trnh n nguy him ngi ta cho axetylen ho tan trong axeton
di p sut cao 12-15 at. Di p sut ny, mt lt axeton ho tan c ti 300 lt kh
axetylen. Bnh thp cha dung dch axetylen trong axeton khng nguy him so vi
axetylen lng, nht l khi dng thm cc khi xp v c cht y trong bnh.
Axetylen l mt hp cht khng bn v mt nhit ng. N c th b phn hu to
ra cacbon v hyro km theo hin tng n. Phn ng n c th khi mo bng nhit,
bng thu ngn funmiat hoc t n di p sut cao. Phn ng n to nhiu nhit,
mol / kcal 9 , 54 H
0
298
= A , nhit ca kh lc c th ln ti hng nghn .
Axetylen chy trong khng kh cho ngn la c nhiu mui en. l v phn ng
chy khng hon ton, thiu oxi. C th dng phn ng t chy khng hon ton
axetylen cng nh nhiu hirocacbon khc ly mui en (cacbon) dng trong vic
ch ho cao su. Hn hp axetylen v khng kh vi t l oxi theo phng trnh t
chy hon ton l mt hn hp n rt mnh. Phn ng t chy hon ton ta rt nhiu
nhit:

HCCH + 5/2 O
2
2CO
2
+ H
2
O mol / kcal 315 H
0
298
= A

Chnh nh lng nhit rt ln ny m axetylen c dng mt cch rng ri hn
v ct kim loi. Ngn la n x axetylen oxi c nhit vo khong 3500-4000
0
C.
nhit ny hu ht cc kim loi u chy lng. Nhit cao khng phi ch l
nhit t chy ca axetylen (nhit t chy ca axetylen cao hn ca metan 45% trong
cng nhng th tch kh bng nhau v hi nh hn nhit t chy ca butan) m cn
do tc phn ng rt ln. Phn ng t chy axetylen tin hnh theo hai giai on
m giai on u tin hnh theo phng trnh phn ng sau:

HCCH + O
2
2CO + H
2
120



Chnh giai on u ny xy ra trong khu vc ngn n x c nhit cc i. Giai
on sau l giai on t chy cacbon oxi v hyro.
Ngoi ng dng trn, axetylen c s dng vi qui m ln lm nguyn liu tng
hp sn xut ra nhiu sn phm hu c quan trng trong cng nghip ho hc.
C th tm tt cc hng chnh tng hp hu c t axetylen:

H
2
C C H
2
e t y l e n
C l
2
H C C H C l
2
1 , 1 , 2 , 2 - t e t r a c l o e t a n
H
2
C C
H
C l
v i n y l c l o r u a
H
2
C C
H
C N
a c r i l o n i t r i n
H
3
C C
H
O
a x e t a n d e h y t
H
2
C C
H
O C O R
e s t e v i n y l i c
H
2
C C
H
C O O R
a c r i l a t a n k y l
H C C C H
2
O H
a n c o l p r o p a c g i l i c
C C C H
2
O H
1 , 4 - b u t i n d i o l
H
2
C C
H
C
H O H
2
C
C H
v i n y l a x e t y l e n
+ H
2
+ C l
2
+ H C l
+ H C N
+ H O H
+ R C O O H
+ C O + R O H
+ H C H O
+ H C C H
H C C H




121


CU HI V BI TP
Cu 1. Nhm chc ca anken, ankin, ankadien l nhm nguyn t no? Trnh by cu
trc v c tnh ca chng (cu trc electron, cu trc khng gian, nng lng, di
v gc lin kt, bn nhit ng)?
Cu 2. So snh tnh cht ha hc ca anken, ankin v ankadien?
Cu 3. Hy a ra bng chc thc nghim chng t rng lc axit ca axetylen,
etilen, etan v amonic c sp xp nh sau: CH CH > NH
3
> CH
2
=CH
2
> CH
3

CH
3
. Gii thch?
Cu 4. Hy lp s ni ln mi quan h gia ankan, anken, ankin v ankadien?
Cu 5. Hy nu phng php thc nghim phn bit ankan, anken, ankin v
ankadien (phng php ho hc v phng php vt l)?
Cu 6. Hy dng 3 s phn ng vi axetilen, etilen v metan ln lt l trung
tm gii thch th no l nn cng nghip ho cht hu c da trn axetilen, da
trn etilen v da trn metan?
Cu 7. Tecpen l g? Phn loi tecpen?
Hy pht biu quy tt isopren v minh ho bng cc trng hp sau: o-pinen,
camphen, cedren, xantonin v vitamin A?
Cu 8. Hy trnh by s sinh tng hp tecpenoit v cho bit giai on no ging
vi phn ng trong phng th nghim, giai on no khc?
Cu 9. Khi dn hi ru n-propilic qua Al
2
O
3
nhit 300
0
C thu c anken.
Cho anken tc dng vi dung dch brm c cha kali clorua v natri nitrat.
Cho bit nhng sn phm no c hnh thnh? Vit cc phng trnh
phn ng xy ra v gii thch?
Cu 10. Xut pht t cc cht u l etilen, propilen, izobutilen v cc cht v c
thch hp hy vit cc phng trnh phn ng tng hp ra nhng hp cht sau:
a) (CH
3
)
3
C OH d) CH
3
CH
2

CH
2
OH
b) (CH
3
)
2
CH CH
2
Br e) ClCH
2
C(CH
3
)
2
CH
2
CH(CH
3
)
2

c) CH
3
CH(OH) CH
2
Br f) (CH
3
)
3
C CH
2
C(CH
3
)
2
I
Cu 11. a) Cho bit ti sao cc ankadien lin hp c kh nng tham giai phn ng
cng 1,2 v 1,4.
b) Vit phng trnh phn ng cng gia 1,3-butadien vi tng tc nhn sau
(theo t l 1:1 v phn t gam): Br
2
, HCl, Icl, CH
2
= CH CN
c) Khi oxy ha (trong iu kin thch hp) sn phm cng hai nguyn t
brm vo 1,3-butadien thu c axit bromaxetic (BrCH
2
-COOH). Hy cho bit
hng ca phn ng cng xy ra?
Cu 12. Mt ankadien c cng thc phn t C
6
H
10
, sau khi ozon ha ri thy phn
ozonit to thnh thu c mt trong cc sn phm l andehyt sucxinic (O=CH-CH
2
-
CH
2
-CH=O). Hy suy ra cu to ca ankadien ban u.
Cu 13. Hai hidrocacbon u lm mt mu dung dch nc brm v u c kh nng
tc dng vi ozon. Khi thy phn ozonit ca chng thy t mt phn t gam ozonit
ca A cho mt phn t gam CH
3
-CO-CH=O v hai phn t gam CH
2
=O; t mt phn
t gam ca B cho mt phn t gam O=CH-CH=Obitan v hai phn t gam CH
2
=O.
Xc nh cu to ca A v B. Vit cc phn t phn ng ha hc xy ra.
122


Cu 14. Hai hidrocacbon A v B c cng cng thc C
6
H
10
, cng lm mt mu nc
brm. Hidrocacbon A cho kt ta vi dung dch amoniac ca bc nitrat v khi b oxi
ha trong iu kin thch hp cho dioxit cacbon v axit trimetylaxetat (CH
3
)
3
C-
COOH. Hodrocacbon B khng phn ng vi dung dch amoniac ca bc nitrat, khi b
oxy ha cho axit axetic v axit izobutiric.
Xc nh cng thc cu to ca A v B gi tn chng.
Cu 15. Mt hidrocacbon c cng thc C
5
H
8
c kh nng cng 4 nguyn t clo, phn
ng vi dung dch amonic ca bc nitrat. Khi hidrat ha c mt mui thy ngn (II)
cho metylizopropyl xetn CH
3
-CO-CH(CH
3
)
2
. Cho bit cu to ca hidrocacbon, gi
tn v vit cc phng trnh phn ng xy ra.

123


TI LIU THAM KHO

1. L Huy Bc, Nguyn Vn Tng, Bi tp ha hc hu c, NXB Quc gia H Ni,
1986.
2. Nguyn Hu nh, nh Rng Ha hc Hu c Tp 1, Nh xut bn Gio
dc, 2003.
3. nh Rng, ng nh Bch, Nguyn Th Thanh Phong Ho hc hu c 2,
NXB Gio Dc, 2006.
4. Phan Tng Sn, Trn Quc Sn, ng Nh Ti, C s l thuyt ho hu c, tp
1,2, NXB i hc v trung hc chuyn nghip H Ni, 1980
5. Trn Quc Sn, ng Vn Liu Gio trnh c s ha hc hu c, Tp 1, 2, NXB
i hc s phm, 2007.
6. ng Nh Ti, C s l thuyt ha lp th, NXB Gio dc, H Ni, 1998.
7. Nguyn Minh Tho, Tng hp hu c, NXB i hc quc gia H Ni, .2005.
8. Thi Don Tnh, C s ho hc hu c, Tp 1, 2, NXB Khoa hc v K thut, H
Ni, 2006.
124


CHNG 3. HIDROCACBON THM

S khc nhau v cu to v kh nng phn ng ca hirocacbon no v khng no
r rng. Nhng hirocacbon vi lin kt n khng c kh nng phn ng vi i b
phn tc nhn ngoi tr phn ng th hyro bng halogen trong iu kin nghim ngt.
Trong khi cc anken v ankin phn ng vi axit, vi cht oxi ho, kt hp vi
halogen v cc tc nhn khc. Hirocacbon thm (loi hirocacbon th ba) khng th
xp vo loi hp cht cha lin kt i v ba. Tn gi thm xut pht t ch nhng
hp cht u tin tm c thuc loi ny c mi thm khc nhau. Tn thm vn c
gi cho n ngy nay mc du ho hc ca hirocacbon thm bao gm c nhng hp
cht khng c mi thm.
Aren hay hirocacbon thm l loi hirocacbon c c trng trong phn t bi
s c mt ca mt hoc nhiu nhn benzen.
Benzen, cng thc phn t C
6
H
6
l hirocacbon thm n gin nht ng thi cng
l cht tiu biu c ngha l thuyt v thc tin quan trng nht trong cc hp cht
thm.

3.1. Benzen v ng ng
Benzen c Faraday tm ra ln u tin nm 1825 trong thnh phn kh thp. Nm
1834, Mitseclic iu ch c benzen khi decacboxyl ho axit benzoic thu c t
nha cy Styrax benzoin bng cch ct khan axit benzoic vi vi ti xt:

C
6
H
5
COOH + 2NaOH C
6
H
6
+ Na
2
CO
3
+ H
2
O

Nm 1845, Hopman li tm ra benzen trong nha than , t benzen tr thnh
ngun nguyn liu phong ph ca cng nghip ho hc.
Benzen l cht lng, khng mu, si 80
0
C, l nguyn liu quan trng ca cng
ngh ho hc. Cng thc cu to m ta vn dng ngy nay c Kekule ngh t
nm 1865. Mi n khong nm 1931 (sau s xut hin ca l thuyt v obitan phn
t) ngi ta mi hiu tng i y v bn cht lin kt, v cu trc ca benzen.

3.1.1. Cu to ca vng benzen
1) Cng thc phn t, ng phn, cu trc phn t theo Kekule
Cng thc phn t ca benzen c xc nh l C
6
H
6
da vo vic xc nh phn t
khi v phn tch nguyn t. Nm 1858, Kekule cho rng cc nguyn t cacbon c
th kt hp vi nhau to thnh mch. Sau vi nm (1865), ng b sung thm l
mch cacbon cng c th ng thnh vng. ng a ra cu trc ca benzen nh sau:

H
H
H
H H
H


125


Song cng thc phn t C
6
H
6
cng cn c th ng vi nhng cu trc khc:


H
H
H
H H
H
C H
2
H
H
H
H
H
3
C C C C C C H
3
H
2
C C
H
C C C
H
C H
2


Trong s nhng cu trc trn th cu trc ca Kekule l tng i hp l, nhng
thuyt phc hn cn phi xem xt v s ng phn.
i vi benzen th mt ln th ch c mt sn phm duy nht nhng nu th hai ln
th cho ba ng phn. Nh vy, ch c cng thc ca Kekule l ph hp:

X
X
X
X
X
X


Tuy nhin khi nghin cu chi tit cu trc ca Kekule th thy c kh nng c hai
ng phn th 1,2. gii quyt vn ny, Kekule cho rng phn t benzen lun
lun chuyn ho v trong mt trng thi cn bng khng th phn chia.


X
X
X
X
X
X
X
X



2) S n nh ca vng benzen
Cn li mt s vn m cu trc ca Kekule khng gii quyt c. Chng hn,
cu trc ny th hin s khng no rt ln, ngha l n phi d dng tham gia phn ng
cng v kh tham gia phn ng th nh anken. Nhng ngc li, benzen tng i tr
vi cc tc nhn oxi ho, thc hin phn ng th d dng nhng rt kh tham gia phn
ng cng. Ngoi ra, ngi ta cn xc nh vng benzen bn vng hn nhiu so vi
nhng g d on t xiclohecxatrien. Nhit hyro ho ca xiclohecxen l 118 kJ/mol,
ca xyclohecxadien-1,3 l 231 kJ/mol, ngha l ln hn hai ln. Vy, i vi
xyclohecxatrien phi l 358 kJ/mol, song hyro ho benzen ch to ra 208 kJ/mol, t
hon 150 kJ/mol theo d on. iu c ngha l benzen bn hn xiclohecxatrien 150
kJ/mol.

3) di lin kt trong benzen
126


di lin kt CC trong benzen ging nhau v c tr s trung gian gia lin kt
n v i. Trong nhiu hp cht khc nhau, di ca lin kt i C=C bng 134
pm. Lin kt n CC c di 154 pm trong etan, 150 pm trong propilen v 148
trong butadien-1,3. Nu theo cu trc Kekule th benzen phi c ba lin kt ngn (134
pm) v ba lin kt di (148 pm) nhng cc s liu phn tch cho thy rng tt c su
lin kt trong benzen u bng nhau (139 pm), ngha l trung gian gia lin kt n v
i.

4) Cu to vng benzen theo thuyt obitan phn t
Theo quan nim hin i, phn t benzen l mt h vng kn lin hp su cnh u,
tt c cc nguyn t cacbon v hyro u nm trn cng mt mt phng. Cc nguyn
t cacbon u trng thi lai ho sp
2
. Mi nguyn t cacbon lin kt vi hai nguyn
t cacbon bn cnh v vi nguyn t hyro nh s xen ph cc obitan lai to ca
chng vi nhau v vi obitan s ca hyro to thnh cc lin kt o trong phn t
benzen.

C C
C
C C
C
H
H
H
H
H
H
C
C
C
C
C
C
H
H H
H
H H
+ +
+
+ +
+
-
-
-
-




Nh vy, mi nguyn t cacbon trong vng benzen cn mt obitan 2p, c trc
thng gc vi mt phng phn t benzen. Su obitan 2p c th t hp thnh su obitan
phn t t (t
1
+ n
6
+ ). trng thi c bn su electron t chim cc obitan c
nng lng thp nht, l cc obitan lin kt (
1
-
3
). Ba obitan cn li c nng
lng cao l nhng obitan phn lin kt, l nhng obitan trng, chng ch c mt
electron khi phn t trng thi kch thch (
4
-
6
). Trong cc obitan , obitan lin
kt c nng lng thp nht l bn vng nht l obitan
1
, n c mt electron t
gia tt c cc lin kt CC v bao trm tt c cc nguyn t cacbon ca phn t
benzen. Khi nim hin i v s lin hp cc electron t trong phn t benzen tng
ng vi obitan lin kt
1
. Hai obitan lin kt
2
v
3
, c nng lng cao hn,
cng tham gia vo h lin hp t tng cng ca phn t.
biu th cu to benzen theo quan nim hin i, hin nay ngi ta s dng rng
ri cc cng thc sau:



S to thnh lin kt o
trong phn t benzen
Cc obitan 2p trong
phn t benzen
127


3.1.2. ng phn v danh php
1) ng phn
ng ng u tin ca benzen l metylbenzen hoc l toluen C
6
H
5
CH
3
. V tt c
cc nguyn t hyro trong benzen u tng ng nhau nn toluen cng nh tt c
cc dn xut th mt ln u khng c ng phn.
Khi nhn benzen c hai nhm metyl nh ni phn cu to benzen s to ra ba
ng phn 1,2; 1,3; 1,4-dimetylbenzen v cng cn gi l ng phn octo, mta v
paraxilen.

C H
3
C H
3
C H
3
C H
3
C H
3
C H
3 1 , 2 - d i m e t y l b e n z e n
( o c t o - x i l e n )
1 , 3 - d i m e t y l b e n z e n
( m e t a - x i l e n ) 1 , 4 - d i m e t y l b e n z e n
( p a r a - x i l e n )


2) Danh php
a)Tn benzen l tn ring c IUPAC lu dng v l hyrua nn gi tn
cc ng ng v dn xut khc theo danh php thay th. Nhiu ankyl v
ankenylbenzen c tn ring:

Hp cht Tn thay th Tn thng
C
6
H
5
CH
3
Metylbenzen Toluen
*

C
6
H
5
C
2
H
5

Etylbenzen

C
6
H
5
CH(CH
3
)
2

Isopropylbenzen Cumen
**


o-C
6
H
4
(CH
3
)
2

(ba ng phn o-, m-, p-)
o-dimetylbenzen
1,2-dimetylbenzen
o-Xylen
**

PCH
3
C
6
H
4
CH(CH
3
)
2

(ba ng phn o-, m-, p-)

4-isopropyl-1-metyl benzen hay
4-isopropyl toluen
p-Ximen
**
C H
3
H
3
C
C H
3





1,3,5-Trimetyl benzen



Mesitilen
**
C
6
H
5
C
H
C H
2

Etenybenzen hay Vinylbenzen Siren
*

C
6
H
5
C C H

Etinylbenzen
128


* Tn c dng khi khng c nhm th hoc c nhm th trong vng di
dng tin t.

V d:

p-(CH
3
)
2
CHC
6
H
4
CH
3
p-isopropyl toluen

p-C
2
H
5
C
6
H
4
CH=CH
2
p-Etylstiren.

** Cc tn ch c dng khi khng c nhm th

b) Cc tn gc.
- Cc tn c dng khi c hoc khng c nhm th:

C
6
H
5
phenyl

C
6
H
4
phenylen (o-, m-, p-)

-Cc tn c dng khi khng hoc ch c nhm th trong vng:


C
6
H
5
CH
2
benzyl

C
6
H
5
CH= benzyliden

C
6
H
5
C benzylidin

C
6
H
5
CH=CH stiryl

-Cc tn c dng khi khng c nhm th:

CH
3
C
6
H
4
tolyl (o-, m-, p-)

2,4,6-(CH
3
)
3
C
6
H
2
mesityl

3.1.3. Quy tt (4n+2) ca Huycken
Ngoi nhng hp cht c cha vng benzen cn c rt nhiu hp cht khc cng
c gi l hp cht thm mc du b ngoi chng khng ging benzen. Vy, c tnh
chung cho tt c cc hp cht thm l g?
Nu nhn nhn di gc thc nghim, cc hp cht thm l phi l nhng hp
cht m phn t ca n phi c tnh khng no ln nhng li khng tham gia cc phn
ng cng hp c trng cho cc hp cht khng no. Tri li, chng d dng tham gia
cc phn ng th ging benzen, c bn cacbon so vi hirocacbon tng ng v c
cu to phng, c mch vng.
Nu nhn nhn di gc l thuyt, mt hp cht thm c cc c im sau:
- L hp cht vng cha mt s lin kt t lin hp.
129


- Mi nguyn t cacbon ca vng phi c orbital p khng lai ho (mi nguyn t
cacbon ca vng trng thi lai ho sp
2
hay sp).
- Cc orbital p song song vi nhau, xen ph nhau to thnh vng chung. t
c iu , cu trc ca vng phi phng (hoc gn phng).
- S gii to (hay khng khu tr) ca cc electron t trong vng phi dn ti vic
lm gim nng lng electron ca h, thng gi l nng lng thm (benzen l 150
kJ/mol).
Nghin cu ho hc lng t cc hp cht vng, E.Hucken nhn thy cc h thng
vng annulen v vng tng t c bn c bit khi chng c 4n + 2 electron t
trong vng vi n l cc s t nhin. Nm 1931, ng cng b quy tt m sau ny gi l
quy tt Hucken: Nu s electron t trong h thng vng l 4n+2, vi n l cc s t
nhin th h thng l thm. H thng vng c 4n electron t l phn thm.
Quy tt Hucken l mt cn c quan trng xt cc hp cht thm v phn thm,
trong cn hiu rng cc h thng vng phi xem xt c phi l vng xem ph cc
orbital p khp kn v c cu dng phng.
Da vo quy tt Huycken, ta xt mt s hp cht sau y:

( I H ) ( I I )
( I I I )
( I V ) ( V )
( V I )
+
.
-
+ . -


Trong cc hp cht trn y, ta nhn thy:
(I)-Xyclopentadienyl-cation c 4 in t t nn khng thm.
(II)-Xyclopentadienyl-radical c 5 in t t nn khng thm.
(III)-Xyclopentadienyl-anion c 5 in t t nn khng thm.
Tng t nh vy, trong cc cu to (IV, (V), v (VI) c cation (IV) c 6 in
t t nn l hp cht thm.

3.1.4. Phng php iu ch
1) Chng ct than trong cng nghip
Khi em chng than (loi than bo) nhit 900 1100
0
C luyn tthan cc
dng trong cng nghip luyn kim hoc nhit 10001300
0
C ly kh t, ta thu
c ba phn: phn kh, phn lng v phn rn cn li l than cc.
Phn kh vn thng gi l kh than hay kh l than cc. Kh than l mt
ngun nguyn liu rt tt dng trong cng nghip, dng un v thp sng v dng
chy my. Nhng trc khi em dng, kh than cn c x l loi b nhng
kh c, thi nh hyro sunfua H
2
S, axit xianhiric HCN, amonic NH
3
, cacbon
isunfua CS
2
v kh CO
2
. Trong kh than cn c c benzen, c th thu c bng
cch cho kh than qua thp hp th c ti du nng t trn xung. Trong thp hp
th thu c khong 2% benzen th. Mt tn than cho khong 300m
3
khthan .
Trong kh than cha khong 3050% kh metan (theo th tch) v 3050% kh
hyro.
Phn lng thu c khi chng than gm hai lp:
130


- Lp nc c tnh kim l dung dch amonic, thng c tch ra v dng trong
cng nghip phn bn amoni sunfat v mt s cht khc.
- Lp nha l mt th du nu sm hay gn en (khong 5% lng than em
chng ct). em chng ct phn on du ny c nhng phn sau:
+ T 80 170
0
C: phn ny l du naphta tho hay du nh. T khi d = 0,9, nh
hn nc. Trong phn ny c cha cc hidrocacbon thm nh benzen, toluen, xilen,
etylbenzen v.v, cc cht phenol, crezol, cc amin thm nh anilin, toluidin, cc
cht d vng nh thiophen, piridin v cc dn xut ca n..
+ T 170 240
0
C: phn ny l du cacbolic hay du trung bnh, t khi d xp
x bng 1. Phn ny gm cc cht nh phenol, crezol v nhng hidrocacbon thm
vng ngng t nh naphtalen v dn xut ca n.
+ T 240 270
0
C: phn ny l du creozot hay du nng. T khi d vo
khong 1,04. Phn ny gm cc crezol, xilenol, diphenil, cc baz quinolin v.v Du
creozot thng dng tm g chng mi mt.
+ T 270 400
0
C: phn ny l du antraxen hay du lc gm nhng
hidrocacbon thm nhiu vng ngng t nh antraxen, phenantren, axenaphten. Ngoi
ra cn c cc cacbazol, acridin v nhiu hp cht khc.
Cui cng, cn li cht b gi l hc n thng luyn lm vt liu ri ng,
lm in cc trong cc l in v.v
Mun tch nhng hidrocacbon thm trong phn du nh, trc ht cn loi b
nhng cht c tnh baz nh piridin, anilin v.v bng cch ra vi axit sunfuric,
sau loi b phenol bng cc ra vi dung dch kim. em ct phn on du nh
cn li s thu c benzen (c t
0
si: 110
0
C), hn hp cc xilen v etylbenzen (c t
0

si: 135 145
0
C). Phn cn li ca du nh l dung mi naphta dng pha sn mau
kh. C th loi b thiophen ra khi benzen bng cch x l vi axit sunfuric c,
thiophen b sunfo ho trc tch ra; cng c th dng AlCl
3
khan ph hu thiophen.
Trung bnh t 1000kg nha than , thu c:

Benzen 16 kg
Toluen 2,5 kg
Cc xilen 0,3 kg
Phenol, cc crezol 20 kg
Naphtalen 20 60 kg
Antraxen 5 20 kg
Hc n 300 600 kg.

2) i t cc hidrocacbon mch h. (thm ho ankan v anken)
Hidrocacbon thm c th c iu ch t cc ankan bng cch cho ankan i qua
xc tc dehidro ho khp vng. Nm 1936 1937, nhiu nh bc hc Lin X chng
minh rng, nhit 300 310
0
C, trn xc tc cabon platin (Kaznki, plate) hoc
450 470
0
C trn xc tc crom oxit (Mondapski, Kamusa) hoc 500 550
0
C trn
xc tc cromo phtpho (Caczep, Severianop), cc hidrocacbon no v etylenic c th
bin thnh hidrocacbon thm.
Ngi ta c th chng minh thm, i vi phn ng thm ho ankan v anken, c
th dng nhiu loi xc tc khc nh cc oxit ca vndi, molipden, thori, urani, xeri
131


v.v v mt s ln cc xc tc hn tp khc. Trong thnh phn cc xc tc hn tp
ny, c th thy hu ht cc nguyn t ca bng tun hon Mendelep c th tham gia
vi cc t l khc nhau.
V mt c ch ca qu trnh thm ho, c th tm tt trn s chung nh sau:












Nhiu cng trnh nghin cu chng minh rng, c ch ca qu trnh thm ho
ankan ph thuc bn cht ca cht xc tc.
Trn xc tc platin, phn ng tin hnh qua giai on to thnh sn phm trung
gian l cc hidrocacbon loi xiclohecxan. V d:


H
2
C
H
2
C
C
H
2
CH
3
CH
3
H
2
C
- H
2
H
2
C
H
2
C
C
H
2
CH
2
CH
2
H
2
C
- 3H
2
HC
HC
C
H
CH
CH
H
C
n-hecxan cyclohecxan benzen


Giai on sau din ra nhanh hn giai on trc rt nhiu (100 ln) do
khng th tch xiclohecxan trung gian ra.
Trong qu trnh thm ho ankan trn xc tc platin, khng c s to thnh
anken v khi thm anken vo, qu trnh thm ho s ngng li. V vy, s thm ho
ankan trn xc tc platin ch thc hin theo pha bn phi ca s trn.
Tri li, trn xc tc l cc oxit kim loi, thng lun lun c s to thnh cc
anken trung gian, sau cc anken ny li tip tc chuyn ho thnh cc hidrocacbon
thm (pha bn tri s trn). Mt phn ankan trn xc tc oxit kim loi c th
chuyn ho trc tip thnh hidrocacbon thm (pha gia s ).

3) Tch hidrocacbon thm t du m
Du m cha mt lng ln hidrocacbon thm, ch yu trong cc on si trung
bnh v on si cao (khong 30%). Vic tch hidrocacbon thm bng chng ct
khng thc hin c v hn hp qu phc tp. Tuy nhin, cng c th tch c
hidrocacbon thm bng cch dng SO
2
lng chit ra (phng php Edelian).
nhit thp (-60
0
C), SO
2
lng ch ho tan hidrocacbon thm v khng ho ln vi
cc loi cht khc.
ankan
Hidrocacbon thm
Anken
Xiclohecxan
132


Benzen v toluen cng c th tch c trong xng bng cch ct ng ph vi
axeton, vi metyletylxeton hoc bng cch lc qua silicagen c tnh cht hp ph chn
lc cc hidrocacbon thm.

4) Tng hp Vuyc Fictic
Khi cho hn hp ankyl halogenua v dn xut halogen thm tc dng vi natri kim
loi, ta s thu c ng ng ca benzen (Fictic, 1863). Phn ng din ra tng t
phn ng Vuyc trong tng hp hidrocacbon no. V d, khi cho brombenzen v
etylbromua tc dng vi natri kimloi, s thu c etylbenzen:

C
6
H
5
Br + 2Na + BrC
2
H
5
C
6
H
5
C
2
H
5
+ 2NaBr

Phng php Vuyc-Fictic c s dg tng hp p-metylizoproylbenzen, tc l
ximen, mt hidrocacbon thm c mt trong mt s loi tinh du. Ngi ta cho p-
bromtoluen v izopropyl bromua tc dng vi natri kim loi:



H
3
C Br Br CH
CH
3
CH
3
H
3
C CH
CH
3
CH
3
+ 2Na +
p-bromtoluen izopropyl bromua
ximen


S chung ca phn ng tng hp Vuyc-Fictic nh sau:

ArX + 2Na + XR ArR + 2NaX

5) Tng hp Friden Crap (1877)
Tng tc ca hidrocacbon thm vi dn xut halogen mch thng c xc tc l
nhm triclorua khan s xy ra phn ng th vo nhn benzen cho ng ng ca
benzen v gii phng hidro clorua. Trong phn ng ny, AlCl
3
ch cn mt lng nh
(1/20 1/5 mol). S phn ng nh sau:

Ar H
+ X R
AlCl
3
Ar R + HX


V d, tc dng ca benzen vi etyl clorua, xc tc AlCl
3
s cho sn phm l
etylbenzen:

+ Cl C
2
H
5
AlCl
3
C
6
H
5
C
2
H
5
+ HCl
C
6
H
6


Sn phm phn ng li c kh nng tc dng vi dn cut halogen to ra cc ng
ng cao hn. Trong v d ca benzen vi etylclorua, ngoi etylbenzen, s to ra c
dietylbenzen, trietylbenzen v.v Nu d etyl clorua th c th to thnh sn phm th
su ln l hecxaetylbenzen. Mun c sn phm th l dn xut mt ln th phi dng
tht d lng benzen.
Phn ng Friden-Crap c tnh cht thun nghch. Tc dng ca etylbenzen vi hidro
clorua c mt xc tc AlCl
3
, c th ti to ra benzen v etylclorua.
133


Nh vy, phn ng Friden-Crap thc cht l mt h thng cc phn ng thun
nghch ni tip nhau:

C
6
H
6
+ RX C
6
H
5
R + HX
C
6
H
5
R + R X C
6
H
4
(R
2
) + HX
C
6
H
4
R
2
+ RX C
6
H
3
(R
3
) + HX
v.v

Trong phn ng Friden-Crap, i vi hidrocacbon thm ngoi benzen ra, c th
dng tt c cc ng ng khc c mt nhn hoc nhiu nhn, cc hidrocacbon thm
c nhiu nhn ngng t cng nh nhiu hp cht thm khc.
i vi tc nhn dn xut halogen c t ba cacbon tr ln trong halogen nh
vo cacbon bc nht, khi tham gia phn ng Frien-Crap s xy ra phn ng ng
phn ho to ra dn xut halogen bc cao hn nh xc tc AlCl
3
. V d, tc dng ca
n-propylbenzen m l izopropylbenzen; t izobutyl clorua v benzen s thu c
tecbutylbenzen:


CH
3
CH
2
CH
2
Cl
AlCl
3
H
3
C
H
C CH
3
Cl
C
6
H
6
C
6
H
5
CH
CH
3
CH
3
n-propyl clorua
izopropyl clorua
izopropyl benzen

AlCl
3
H
3
C C CH
3
Cl
C
6
H
6
C
6
H
5
C(CH
3
)
3
izobutyl clorua
tecbutyl clorua
tecbutyl benzen
CH CH
2
Cl
H
3
C
H
3
C
CH
3


Trong phn ng Friden-Crap, ngoi dn xut halogen, c th dng cc anken lm
tc nhn phn ng. V d, t benzen v etylen s thu dung dch etylbenzen:

C
6
H
6
+ H
2
C CH
2
AlCl
3
C
6
H
5
C
2
H
5


Nu anken l ng ng ca etylen, anken s kt hp vi nhn thm nguyn t
cacbon mang ni i c bc cao hn. V d:

H
3
C
C
6
H
6
+
C
H
CH
2
AlCl
3
C
6
H
5
CH
CH
3
CH
3


Thc cht qu trnh phn ng din ra nh sau: trong giai on u c phn ng
cng hidro clorua (c di dng vt do AlCl
3
b thu phn mt phn) vo lin kt i
cu anken to ra dn xut halogen; sau phn ng Friden-Crap tin hnh bnh
thng gia hidrocacbon thm v dn xut halogen nh m t trn.
134


Ngoi ankyl halogenua v anken, c th dng cc ancol v mt s dn xut ca
chng lm tc nhn ankyl ho nhn thm. Trong trng hp ny, cc ancol bc ba c
kh nng phn ng ln nht ri n ancol bc hai, km nht l ancol bc nht.
V cht xc tc, ngoi nhm triclorua c th dng cc halogenua kim loi sau y
(sp xp theo trt t gim dn hot tnh):
AlBr
3
, AlCl
3
, GaCl
3
, SbCl
5
, FeCl
3
, SnCl
4
, TiCl
4
, BiCl
3
, BCl
3
, ZnCl
2
, HgCl
2

Khi ankyl ho bng ancol cn dng cht xc tc khc nh HF khan, BF
3
, H
2
SO
4
,
P
2
O
5
, H
3
PO
4
.

3.1.5. Tnh cht vt l
a s aren loi benzen l nhng cht lng, mt s l nhng cht rn nhit
thng, khng mu, chng c mi thm d chu c trng nhng li gy c cho c
th. Chng d bay hi nn d bt la, chy vi ngn la sng, khi en do c nhiu
mui than. Nhng aren ng phn c nhiu nhnh (ng phn v tr) c im si gn
nhau, do thng khng th tch chng ra khi nhau bng chng ct phn on. Tuy
nhin, im nng chy ca chng li tng i khc xa nhau, trong cc ng phn c
hai nhnh ankyl, ng phn para c im nng chy cao hn c, do c th dng
phng php kt tinh phn on tch hn hp cc ng phn meta v para-xilen ra
khi nhau.
Khi s nhnh ankyl tng ln, nhit nng chy ca cc aren cng tng theo.
Cc ng phn c mch thng c im si cao hn cc ng phn c nhnh phn
nhnh. V d: n-propylbezen c im si cao hn izopropylbezen.
Cc aren u khng tan trong nc nhng tan trong dung mi hu c nh ru,
ete vi bt k t l no. Cc aren lng nh benzen, toluen c s dng rng ri
lm dung mi nh kh nng ho tan nhiu loi cht v c cng nh hu c.

V tnh cht ph ca benzen:
Khc vi cc dien lin hp mch h, ph hp th ca benzen tng i phc tp.
Trong ph t ngoi, bebzeb th hin ba vn hp th c trng: vn B 254 nm c
cng yu, vn K 204 nm c cng mnh hn v vn 184 nm c cng
mnh. C ba vn hp th u lin quan n s chuyn mc t t
*
. Tuy nhin, vn
184 nm vng kh o nn t c ch . Cc vn hp th ny s chuyn hn v pha
sng di hn nu h lin hp ca vng c m rng hn khi vng c cc nhm th
khng no (nh CH=CH
2
, CH=O) hoc cc nhm th c cp electron cha lin kt
(nh NH
2
, OH,) trong vn K chuyn nhanh hn,c khi che lp c vn B.
Trong ph hng ngoi, cc dao ng ho tr ca cc lin kt CC trong nhn
benzen c c trng bi hai vch hp th gn 1600 cm
-1
v 1500 cm
-1
, trong mt s
hp cht c thm vch gn 1580 cm
-1
. Nhng vch nhn sc gn 3030 cm
-1
c trng
cho cc lin kt CH ca nhn benzen. Nhng vch khc trong ph hng ngoi, c
bit l nhng vch gia 1650 v 2000 cm
-1
, gia 1225 v 950 cm
-1
v di 900 cm
-1
,
tng ng vi s lng v v tr cc nhm th ca nhn benzen.

3.1.6. Tnh cht ho hc
Do s lin hp ca cc electron t trong nhn benzen, nn cc aren c nhng tnh
cht ho hc c trng, gi chung l tnh thm. l khuynh hng ca nhn benzen
d tham gia cc phn ng th, kh tham gia cc phn ng cng v tnh bn vng ca
nhn benzen i vi cc tc nhn oxi ho v i vi nhit.
135


A. Phn ng th electrophin vo nhn benzen (S
E
)
1) C ch chung ca phn ng th electrophin vo nhn benzen
a) S chung ca cc phn ng th electrophin vo nhn thm nh sau
Cc phn ng th tin hnh nh cc cation (hay u mang in tch dng ca lin
kt phn cc mnh) tn cng gi l phn ng th electrophin.
S chung ca cc phn ng th electrophin vo nhn thm nh sau:

X + ArH ArX +

H

Cc phn ng th electrophin vo nhn thm lun lun tin hnh trong iu kin c
mt mt axit mnh hoc mt cht xc tc. Axit mnh hoc cht xc tc c tc dng
chuyn ho tc nhn thnh dng electrophin hot ng, k hiu

X . V vy, ta phn ra
thnh hai giai on ln trong phn ng th: giai on u l giai on to ra dng
electrophin hot ng ca tc nhn do kt qu phn ng ca tc nhn vi mi trng
phn ng (vi axit mnh hoc vi cht xc tc); giai on sau mi chnh l giai on
xy ra phn ng th vo nhn.

b) Giai on th vo nhn
Trong giai on th vo nhn, xut hin vn s th vo nhn xy ra theo mt
bc, trong c s trao i trc tip (tng t c ch S
N
2) qua trng thi chuyn tip
trung gian:

X + Ar H
X Ar H X Ar + H
(1)


Hoc tri li, s th xy ra theo hai bc, bc th nht l s kt hp tc nhn
electrophin vi nhn thm to ra sn phm trung gian, sau trong bc th hai xy
ra s tch proton:

X + Ar H Ar
H
X
Ar
H
X
Ar X
+ H
(2)


Trong c hai c ch trn, proton t nhn thm c tch ra khng di dng t do
m kt hp vi mt thnh phn trong mi trng phn ng.
Nu ch dng cc phng php n gin v ng hc, khng th no phn bit c
hai loi c ch . Tuy nhin, nh vic s dng cc hp cht thm, c cc ng v
nh du ca hyro, ngi ta chng minh rng, phn ng tin hnh qua hai bc,
to ra sn phm trung gian tn ti c trong mt thi gian ngn.
Phn ng th electrophin bt u xy ra vi s hnh thnh phc t do tng tc ca
cc obitan phn ng t ca hp cht thm cha nhn benzen vi obitan t do ca tc
nhn electrophin. Sau phc t chuyn dn thnh phc trung gian o tch in dng
do s to thnh lin kt cng ho tr o gia tc nhn electrophin vmt nguyn t
cacbon ca nhn thm. Nguyn t cacbon ny chuyn t trng thi lai ho sp
2
sang
136


trng thi lai ho sp
3
vi cu to t din ca cacbon, do nhm th X v nguyn t
hyro ni cacbon nm ngoi mt phng ca vng v to thnh mt phng thng gc
vi mt phng ca vng. Khi trong nhn thm cn li bn electron t lin hp vi
in tch dng v phn b u gia nm nguyn t cacbon cn li ca nhn thm to
ra cayion pentadienic (phc o). l giai on chm ca qu trnh. Sau phc o b
tch nhanh proton to thnh sn phm th vi s hon nguyn li nhn thm bn vng
n nh v mt nng lng (giai on nhanh):

+
X X
X H X H
nhanh
- H
X


S to thnh phc o i hi tiu th mt t nng lng v nng lng lin hp ca
h lin hp ny (theo tnh ton c lng t bng 26 kcal/mol) b tr mt phn ln s
mt nng lng lin hp ca nhn benzen (36 kcal/mol), nh vy, phn ng ch i
hi khong 10 kcal/mol. Trong thc t, nhiu phn ng th vo nhn thm tin hnh
vi nng lng hot ho tng i nh. Gn y, nhiu loi phc trung gian kiu nh
trn c tch ra di dng nguyn cht.
Phn ng th electrophin vo nhn thm c th biu din dng mt gin nng
lng nh hnh bn.



Cc tiu nh th nht ng vi phc t t bn, cn cc tiu th hai ng vi phc o.

2) nh hng ca cu trc n s th electrophin vo nhn thm
Trong cc phn ng th vo nhn benzen, phn ng th electrophin (cation tn
cng) l loi phn ng c bn nht, ph bin nht v c nhiu ngha quan trng nht.
a) Quy lut th
chm
phc t
phc o
hoc
137


i vi phn t benzen, do su nguyn t cacbon cng nh su nguyn t hidro ca
vng hon ton tng ng nhau cho nn phn ng th mt ln ch cho mt loi sn
phm duy nht.
Khi trong nhn benzen c sn mt nhm th, th nhm th ny c nh hng ln
n s th tip sau vo nhn benzen. Ngi ta ni rng, nhm th c sn c tc dng
nh hng cho nhm th mi vo nhn benzen.
Cn c vo kt qu cc phn ng th, ngi ta chia cc nhm th thnh hai loi
chnh:
-Cc nhm th loi I chnh gm c:
CH
3
, C
2
H
5
, C
3
H
7
v.v (cc nhm ankyl), OH, OR, OCOR,
SH, SR, NH
2
, NHR, NR
2
, CH
2
Cl, NHCOR, CH
2
OH, CH
2
NH
2
,
CH
2
COOH, C
6
H
5
, F, Cl, Br, I.

- Cc nhm th loi II chnh gm c:
NO
2
, SO
3
H, COOH, CHO, COR, COOR, COCl, CONH
2
,
CN, CCl
3
, CF
3
,
3
H N

,
2
HR N

, R H N
2

,
3
R N

.

Ngoi hai loi nhm th chnh, cn c nhng nhm th c tc dng nh hng hn
tp.
V d:
NO, COCH
3
, CH
2
F, CHCl
2
, CH
2
NO
2
,
3 2 2
R N CH CH



Cc nhm th ny xc nh nhng quy tt th hoc quy tt nh hng nh sau:
-Nu trong nhn benzen c sn mt nhm th loi I, th nhm th ny s nh
hng cho nhm th mi vo v tr octo v para trong nhn benzen. V d: khi nitro
ho toluen (nhn cha nhm metyl thuc loi I) s thu c hn hp sn phm chnh
l o- v p-nitrotoluen:

CH
3
+ HNO
3
CH
3
NO
2
CH
3
NO
2
+
o-nitro toluen
p-nitro toluen

-Nu trong nhn benzen c sn mt nhm th loi II th nhm th ny s nh
hng cho nhm th mi vo v tr meta trong nhn benzen. V d: khi nitro ho
nitrotoluen (nhn cha sn nhm NO
2
thuc loi II) s thu c sn phm chnh l
m-dinitrobenzen.

138


NO
2
+ HNO
3
NO
2
m-dinitro benzen
NO
2


- Cc nhm th hn tp inh hng khng u tin r rt vo v tr octo, para hoc
meta m thng cho hn hp sn phm gm c ba loi v tr vi t l khng chnh
lch nhau nhiu.

* Mt s nhn xt
- Cc nhm th loi I thng ch cha cc lin kt n, c bit l nguyn t lin
kt trc tip vi nhn benzen. Cn cc nhm th loi II thng cha cc lin kt i
nguyn t lin kt trc tip vi nhn benzen hoc nguyn t ny mang mt in tch
dng.
- Cc nhm th loi I (tr cc halogen) thng lm d dng cho s th tip sau vo
nhn benzen, tng cng kh nng phn ng ca nhn. Ta ni rng, cc nhm th loi
I hot ng ho nhn benzen.
- Tri li, cc nhm th loi II lm kh khn cho s th tip sau vo nhn benzen,
lm gim kh nng phn ng ca nhn. Ta ni rng, cc nhm th loi II lm b ng
ho nhn benzen. V d: nitro ho toluen d dng hn nitro ho benzen, tri li nitro
ho nitrobenzen lo kh hn nitro ho benzen.
Nhng quy tt ny ch c tnh cht tng i, t c trng hp thu c 100% loi
sn phm octo hoc para hoc 100% loi sn phm meta.
- Khi trong nhn benzen c sn hai nhm th th v tr ca nhm th mi th ba
cng s ph thuc vo bn cht v v tr tng i ca hai nhm th c sn.
Nu hai nhm th c sn thuc loi khc nhau, mt nhm loi I, mt nhm
loi II th nhm th th ba chu nh hng nh hng ca nhm th loi I.
Nu hai nhm th cng loi I c hoc cng loi II c th nhm th th ba
chu nh hng ca nhm th no c lc nh hng mnh hn.
Lc nh hng tng i ca cc nhm th c sp xp theo mt trt t c tnh
cht kinh nghim ca Hlman nh sau:

i vi nhm th loi I: NH
2
> OH > Halogen
i vi nhm th loi II:
3 3
) CH ( N

> COOH > SO

3
H > NO
2


b) Gii thch quy tt th
* S phn b mt electron trong phn t dn xut th ca benzen (trng
thi tnh)
Khc vi trng hp phn t benzen, trong cc dn xut th ca benzen, mt
electron trong vng benzen phn b khng iu ho na. S ri lon tnh cht i
xng ca my electron trong nhn benzen khi c mt nhm th c sn, c th xy ra
theo hai cch ngc nhau.
-Nu nhm th thuc loi I nh cc nhm NH
2
, OH, CH
3
th mt electron
trong vng benzen ni chung u tng ln v c bit tng nhiu cc v tr octo v
para. S d c s tng mt electron trong nhn l do hiu ng lin hp +C ca nhm
139


th, thc cht l ca cp electron t do hoc ca cc electron o ca cc lin kt CH
vi h thng electron lin hp thm ca nhn benzen. Mt electron t nhm th di
chuyn v pha vng benzen to ra mt h lin hp mi ca phn t hp cht thm.
Trong h lin hp mi ny, mt electron cc v tr octo v para l tng i cao
hn cc v tr khc. V d:

N
H H
:
o
o
o
O
H
:
o
o
o
C
o
o
o
H
H H


S phn b mt electron trong cc dn xut th ca benzen c xc nh
chnh xc bng nhiu phng php vt l hin i. S phn b in tch cng c th
tnh ton bng nhiu phng php orbital phn t.
-Nu nhm th c sn thuc loi II nh NO
2
, COOH,
3 3
) CH ( N

th mt
electron trong vng benzen ni chung gim i v c bit cc v tr octo v para.
Nguyn nhn ca s gim mt electron trong nhn benzen l do hiu ng C ca
cc nhm th, mt electron t trong nhn di chuyn ra ngoi v pha nhm th ht
electron. cc v tr meta, mt electron tng i cao hn:



N
O O
o
o
o
o
N
o
o
o
CH
3
CH
3
H
3
C C
O O
o
o
o
H



* S phn b mt electron trong nhn thm lc tham gia phn ng th
electrophin (trng thi ng)
- Trng hp dn xut benzen cha nhm th loi I.
Kho st phn ng nitro ho vo ete ca phenol.
Trong phn t cha tc dng ca ete ca phenol, do hiu ng lin hp +C ca nhm
OR vi nhn thm, cc v tr octo v para c mang mt phn in tch m (I). Do
, cation nitroni NO
2
+
tin li gn cc v tr octo v para s thun li v mt nng
lng hn l khi tin li gn v tr meta. Nh vy, cc yu t tnh lm thun li cho s
th octo v para. Ngoi ra, khi tc nhn electrophin tn cng cc v tr octo v para s
xut hin trng thi chuyn tip (II), trong san u in tch dng, ngoi cc
nguyn t cacbon ca vng benzen, cng c s tham gia ca nhm th OR. Khi tn
cng vo v tr meta, s xut hin trng thi chuyn tip (III), trong , do c im
cu to, nhm th OR khng th tham gia vo vic san u in tch dng.
140



O
R
:
o
o
o
O
R
:
H NO
2
1/3
1/3
1/3
O
R
:
1/3
1/3
1/3
H
NO
2
(I) (II) (III)


Nh vy, trong trng thi chuyn tip (II), in tch dng c gii to nhiu hn,
nng lng hot ho nh hn so vi trong trng thi chuyn tip (III). Do , trong v
d trn, s nh hng u tin vo v tr octo v para l do kt qu tc dng cng
hng ca cc yu t tnh v cc yu t ng.
Cng do cc nhm th loi I lm tng mt electron ca ton b nhn benzen, c
bit cc v tr octo, para cho nn ta hiu c v sao phn t th electrophin vo cc
hp cht nh anilin, phenol v.v li tin hnh d dng hn so vi bn thn benzen.
- Trng hp dn xut benzen cha nhm th loi II:
Kho st phn ng nitro ho vo nitrobenzen.
Do s phn b mt electron trng thi tnh ca phn t nitrobenzen, s tin li
gn ca tc nhn electrophin vo v tr meta thun li v nng lng hn so vi cc v
tr octo v para (IV).

N
O
H NO
2
1/3
1/3
1/3
1/3
1/3
1/3
H
NO
2
(IV) (V) (VI)
N
O O
o
o
o
o
O
o
N
O
O
o



Trong cc trng thi chuyn tip, khi th vo octo v para (V), cng nh khi th vo
meta (VI), s san u in tch dng ch xy ra bn trong nhn benzen khng c s
tham gia ca nhm th. Do , nng lng cc trng thi chuyn tip ny l nh nhau.
Trong trng hp ny, s nh hng v c bn do yu t tnh quyt nh c ngha l
nhm th mi s hng vo v tr meta.
Cng do nhm th loi II lm gim mt electron ca vng benzen, v tr meta
tng i gim t cho nn ta hiu v sao phn ng th hngd vo v tr meta v tin
hnh kh khn hn so vi bn thn benzen.
Cc quy tt th electrophin trong nhn benzen c ngha thc tin rt ln. Nh cc
quy tt ny, c th tin on kt qu phn ng ng thi cng cho php chn nhng
con ng hp l nht trong tng hp hu c.

3) Mt s phn ng th electrophin
a)Phn ng halogen ho
Tng tc ca halogen nh clo, brom vi benzen khan nhit thng, c mt
ca xc tc nh bt st hoc cc halogenua kim loi nh FeCl
3
, FeBr
3
, AlCl
3,
AlCl
3
,
141


SbCl
3
hoc iot v.v s xy ra phn ng mnh lit v cho sn phm phn ng l dn
xut halogen thm nh clobenzen, brombenzen:

+ Br Br
Fe
Br
+ HBr


Vi lng ln halogen, s to ra cc dn xut octo v para-diclo benzen hoc
dibrom benzen. Trong nhng iu kin mnh lit v halogen, c th thu c dn
xut th hon ton hecxaclobenzen C
6
Cl
6
.
Iot khng cho phn ng th vi benzen trong iu kin tng t nh khi clo hoc
brom ho; ch khi c mt cht oxi ho mnh nh axit nitric c, hyro v.v tc dng
ca iot vi benzen mi to ra iotbenzen C
6
H
5
I. c bit, cation Ag
+
cng c th xc
tc phn ng iot ho benzen.
Cc ng ng ca benzen cng tc dng vi halogen tng t nh benzen. Tu
theo iu kin tin hnh, phn ng th c th xy ra nhn hoc nhnh. V d,
toluen khi tc dng vi clo c mt xc tc FeCl
3
s to hn hp octo v para-clotoluen:

CH
3
+ Cl
2
FeCl
3
CH
3
Cl
CH
3
Cl
+
o-clo-toluen
p-clo-toluen



Khi khng c cht xc tc v ngoi nh sng mt tri hoc c chiu sng bng
tia t ngoi, nhit si, phn ng th s tin hnh mch nhnh. Tu theo s
nguyn t hidro nhnh c th bng clo, s thu c cc dn xut mono, di v
trihalogen.
C
6
H
5
CH
3 + Cl
2
hv, t
0
cao
C
6
H
5
CH
2
Cl + HCl
C
6
H
5
CH
2
Cl
+ Cl
2
hv, t
0
cao
C
6
H
5
CHCl
2
+ HCl
C
6
H
5
CHCl
2 + Cl
2
hv, t
0
cao
C
6
H
5
CCl
3
+ HCl
benzyl clorua
benzyliden clorua
phenyltriclo metan
phenylclorofom


Trong iu kin tin hnh nh vy, phn ng th nhnh xy ra theo c ch gc,
tng t phn ng th halogen vo hidrocacbon no.

* C ch phn ng th halogen vo nhn thm
Phn ng th halogen vo nhn thm xy ra theo c ch th electrophin, tri vi
phn ng th nhnh, theo c ch gc. V d, phn ng th brom vo benzen c xc
tc l bt st.
142


Giai on u to ra dng hot ng ca tc nhn

X ; cn nu xc tc l bt st
hoc v bo bt st th trc ht to ra mt lp st halogenua trn b mt st kim loi
v sau mi to c

X :

3Br
2
+ 2Fe 2FeBr
3

Br Br + FeBr
3
Br Br FeBr
3
o
o
Br
+ [FeBr
4
]


Giai on tip theo l s tn cng ca

Br vo nhn thm to ra phc o trung gian,

sau phc ny tch proton cho brombenzen:

+ Br
Br H
Br
+ H
brom benzen


Proton c gii phng li tng tc vi anion phc [FeBr
4
]
-
ti to FeBr
3

H + [FeBr
4
]
-
FeBr
3
+ HBr

Tc dng xc tc ca iot trong phn ng clo ho hoc brom ho nhn thm cng
chnh l iot lm d dng cho s to thnh cc cation clo hoc cation brom:

I
2
+ Cl
2
2ICl
ICl

I + Cl
-

ClCl +

I ICl +

Cl

Phn ng iot ho benzen nh xc tc Ag
+
tin hnh nh sau: khi ho tan iot vo
benzen khng nhn thy c phn ng g. Khi cho thm bc sunfat vo hn hp phn
ng, ri thm sxxit sunfuaric vo, s to ra kt ta bc ioua v iot benzen. Trong bc
iodua cha anion I
-
nn ch c I
+
c th tc dng vi benzen:

II + Ag
+
AgI + I
+

I
+
+ C
6
H
6
C
6
H
5
I + H
+

b)Phn ng nitro ho
Nitro ho nhn thm l mt trong nhng phn ng th c nhiu ngha quan trng.
Tng tc ca hn hp axit sunfuric c v axit nitric c vi benzen s xy ra phn
ng nitro ho gn mt nhm nitro NO
2
vo nhn benzen cho sn phm l
nitrobenzen:

C
6
H
6
+ HONO
2
H
2
SO
4
C
6
H
5
NO
2
+ H
2
O
nitrobenzen


chm nhanh
143


Khi a nhm NO
2
th hai vo nhn, cn phi dng hn hp axit c nng cao
hn v tin hnh nhit cng cao hn, sn phm thu c l dn xut meta-
dinitrobenzen.
Cng c th gn nhm NO
2
th ba vo nhn benzen, nhm ny cng vo v tr
meta so vi hai nhm u nhng phi tin hnh trong iu kin mnh lit hn:

NO
2
NO
2
NO
2
NO
2
O
2
N NO
2


Khng th gn nhm NO
2
th t bng cch nitro ho trc tip.
Khi nitro ho toluen s thu c hn hp gm ch yu cc o- v p-nitrotoluen v
mt lng nh m-nitrotoluen. Nu tip tc nitro ho s c th thu c 2,4-
dinitrotoluen v cui cng ti 2,4,6-trinitrotoluen:

CH
3
CH
3
CH
3
CH
3
CH
3
NO
2
NO
2
NO
2
O
2
N NO
2
NO
2 NO
2
+
2,4,6-trinitro toluen


V tc nhn nitro ho, ngoi hn hp sunfonitric, c th dng nhiu loi tc nhn
khc tu tng trng hp. i khi c th nitro ho ch bng axit nitric c hay long;
hoc thnh thong c th dng hn hp axit nitric vi anhidric axetic lm tc nhn
nitro ho.
Tc phn ng nitro ho tng nhanh khi tng nng H
2
SO
4
t 80 n 90% l do
trong khong nng , s tng nng
4 2
SO H lm cho cn bng lch v pha phi
to ra ion nitroni NO
2
+
. Khi nng
4 2
SO H t ti 90%, axit nitric chuyn hon ton
thnh ion nitroni. Khi nng
4 2
SO H vt qu nng thch hp cc i l 90% s
gy phn ng to mui gia hp cht thm vi axit c v phn ng ny cn tr mt
phn phn ng nitro ho.
Khi ch dng axit nitric c lm tc nhn nitro ho, s hnh thnh ion nitroni xy ra
theo phng trnh phn ng t ba phn t axit nitric nh sau:

O
2
NOH + 2HNO
3

-
3 2
2NO O H NO + +



Sau giai on to ra ion nitroni, phn ng ca ion nitroni vi hidrocacbon thm tin
hnh theo hai bc, bc th nht to ra phc o trung gian v bc th hai tch
proton theo c ch chung ca s th electrophin vo nhn thm:

144


+ NO
2
O
2
N H
NO
2
+ H


Bc th nht, cng ion nitroni l giai on chm xc nh tc phn ng, bc
th hai l tch proton l giai on nhanh. Tc ca cc bc ny c xc nh
da vo kt qu o hiu ng ng v.
Cn ch phn ng nitro ho xy ra theo c ch electrophin ch trong trng hp
s dng cc tc nhn nitro ho mnh, khi nitro ho bng axit nitric long phn ng tin
hnh theo c ch khc.
c)Phn ng sunfo ho
Sunfo ho l phn ng gn nhm sunfonic SO
3
H vo phn t mt hp cht hu
c. Cng nh phn ng nitro ho, phn ng sunfo ho cc hp cht thm c nhiu
ngha quan trng.
Phn ng sunfo ho c tin hnh bng tng tc ca
4 2
SO H vi hidrocacbon
thm theo s chung nh sau:

ArH + HOSO
3
H ArSO
3
H + H
2
O

Khc vi trng hp nitro ho, phn ng sunfo ho c tnh cht thun nghch. Nc
c gii phng ra, khng nhng lm gim nng axit sunfuric ti gii hn lm
ngng phn ng sunfo ho m cn gy ra phn ng nghch, thu phn sunfoaxit to
thnh:

ArSO
3
H + H
2
O ArH + H
2
SO
4

Nh vy, khi sunfo ho hidrocacbon thm bng
4 2
SO H s thit lp mt cn bng
gia hai phn ng thun v nghch nh sau:

ArH + HOSO
3
H ArSO
3
H + H
2
O

Do , khi sunfo ho ngi ta thng dng mt lng
4 2
SO H d rt ln khong t
hai n nm ln. Phn ng thu phn (desunfo ho) khng th xy ra c, nu khi
sunfo ho dng oleum vi nng SO
3
lin kt vi nc gii phng ra v duy
tr nng tc nhn sunfo ho khng thp hn
4 2
SO H 100%.
Trong phn ng sunfo ho, tc nhn thng dng l axit sunfuric c hoc oleum.
Khi tin hnh phn ng sunfo ho nhit thp th cn dng d nhiu axit ht
nc nhng khi tin hnh nhit cao th khng cn dng d axit v nc to thnh
s bc hi i.
Mun sunfo ho benzen trong iu kin nhit thng, cn dng oleum cha
58% SO
3
. Cng c th sunfo ho benzen bng axit sunfuric c d nhng cn un
nng nhit 80
0
100
0
C. Mun gn hai nhm sunfonic tr ln vo nhn benzen c
th tin hnh ngay mt lc vi lng
4 2
SO H hoc oleum cn thit hoc thc hin
tng bc vi iu kin v nng axit v nhit thch hp. Nhm sunfonic th hai
gn vo v tr meta i vi nhm th nht.
chm nhanh
145


V d, ngi ta thng iu ch m-benzendisunfoaxxit bng cch sunfo ho benzen
n monosunfoaxit, sau li sunfo ho tip theo ln th hai bng oleum 80
0
C:

H
2
SO
4
80
0
SO
3
H
H
2
SO
4
+ SO
3
80
0
SO
3
H
SO
3
H
monobenzen sunfo axit
m-benzendisunfo axit

Meta-benzendisunfoaxit cng c th iu ch bng tc dng ca
4 2
SO H c d
nhiu v nhit cao 240250
0
C.
Mun gn nhm th ba phi tin hnh iu kin mnh lit hn: dng oleum
nhit 300
0
C.
Sunfo ho toluen cho hn hp o-v p-toluensunfoaxit, trong t l sn phm para
chim nhiu hn.
Sunfo ho naphtalen nhit di 100
0
C cho sn phm ch yu l o-
naphtalensunfoaxit. Nu tin hnh sunfo ho nhit 160
0
C tr ln th s to ra | -
naphtalensunfoaxit. Khi un nng o-naphtalensunfoaxit vi
4 2
SO H ti 160
0
C cng
xy ra s ng phn ho mt phn ln sn phm o thnh | (85% ng phn | v
15% ng phn o).

160
0
160
0
H
2
SO
4
<100
0
naphtalen
-naphtalen sunfoaxit o
-naphtalen sunfoaxit |
SO
3
H
SO
3
H

d)Phn ng axyl ho (Friden-Crap)
Tng tc ca clorua axit hoc anhidric axit vi hidrocacbon thm c mt AlCl
3

khan xc tc s to ra xeton thm. S chung nh sau:

Ar H + Cl C R
O
AlCl
3
Ar C R
O
+ HCl
Ar H
+ (R CO)
2
O
AlCl
3
Ar C R
O
+ RCOOH

V d:
AlCl
3
H
+ Cl C C
6
H
6
O
C
O
+ HCl
H
+
Cl C
O
CH
3
AlCl
3
C
O
CH
3
+ HCl
axetophenol
benzophenol
axetyl clorua

146


Ngoi benzen, c th dng cc ng ng nh toluen, xilen, cc hidrocacbon thm
nhiu vng ri hoc ngng t nh diphenyl, naphtalen v nhiu dn xut khc lm cht
phn ng trong phn ng axyl ho.
V cht xc tc phn ng, ngoi AlCl
3
khan, c th dng nhiu loi xc tc
electrophin khc nh AlBr
3
, GaCl
3
, FeCl
3
, SbCl
5
, SbCl
3
, SnCl
4
, BCl
3
v.v

4) S chuyn v theo kiu th nhn thm
Trong cc phn ng th - chuyn v loi ny, tc nhn phn ng trc tip thng l
nhm nguyn t ngay nhm th c sn trong vng benzen. Trong qu trnh chuyn
v, nu nhm nguyn t tch ri khi phn t cht u ta c chuyn v lin phn t,
tri li nu nhm khng tch ri hn ra ta c chuyn v ni phn t.
a)Chuyn v t oxi vo vng thm
- Chuyn v lin phn t - chuyn v Frai.
Khi c tc dng ca axit Liuyt (AlCl
3
, ZnCl
2
, FeCl
3
v.v) nhm axyl trong este
ca phenol chuyn dch vo cc v tr octo v para ca vng.

O
C
O
R
1) AlCl
3
2) H
3
O
OH
OH
C
O
R
+
C
O R


R l alkyl hoc alyl.
Cc kt qu th nghim cho thy rng chuyn v Frai c tnh cch lin phn t.
Tuy vy, c ch ca s chuyn v ny cha c xc nh hon ton y . Ngi ta
cho rng qu trnh chuyn v Frai tng t qu trnh axyl ho theo Friden Crap. Di
tc dng ca xc tc, este to ra cation axyli O RC

, cation ny s tin cng cc v tr

octo v para ca vng thm.
O
C
O
R
OAlCl
2
OH
C
O
R
C
O R
AlCl
3
OAlCl
3
CR
O
OH
C
O
R
OAlCl
2
C
O R
H
3
O
H
3
O


Do tnh cht electron ca qu trnh chuyn v nn khi trong vng thm c nhm th
y electron, phn ng s tr nn d dng hn.
Phn ng Frai lun lun to ra mt hn hp hai sn phm ng phn; nhit thp
l iu kin thun li cho s to thnh ng phn para, cn nhit cao sn phm
chnh l ng phn octo. V d:

147


AlCl
3
, 25
0
C
OCOCH
3
80%
AlCl
3
, 165
0
C
95%
OH
CH
3
COCH
3
COCH
3
CH
3
OH
CH
3


Khi v tr para b chim th ch to thnh sn phm octo. V d:

OCOCH
3
AlCl
3
nitrobenzen
OH
CH
3
COCH
3
CH
3


- Chuyn v ni phn t - chuyn v Claizen.
Khi un nng cc alylaryl ete s chuyn thnh octo alylphenol theo mt phn ng
gi l phn ng chuyn v Claizen. V d:

OCH
2
C
H
CH
2
200
0
C
90%
OH
CH
2
CH CH
2


Nghin cu s chuyn v cc alylphenyl ete c nh du bng
14
C hoc nhm th
v tr para, ngi ta ngh mt c ch ni phn t nh sau:
O
CH
2
CH
H
2
C
O
CH
2
H
CH
H
2
C
OH
CH
2
CH
H
2
C


Trong trng hp cc v tr octo b chim nhm alyl ca ete s chuyn dch n
v tr para. Ngi ta gi l s chuyn v para-Claizen. Nu tt c cc v tr octo v
para u b chim th khi un nng khng xy ra s chuyn v no c.
Rt c th s chuyn v para Claizen cng phi qua bc chuyn v octo, sau
mi xy ra s chuyn v tip n v tr para:

O
CH
2
CH
H
2
C
O
CH
2
H
CH
H
2
C
OH
CH
2
CH
H
2
C


b)Chuyn v t nit vo vng thm
148


- Chuyn v nhm alkyl.
Khi un nng cc mui halogenhydrat ca arylalkylamin, nhm alkyl s chuyn
dch n v tr octo hoc para ca nhn thm. V d:

C
6
H
5
NR
2
HHal
t
0
o or p-RC
6
H
4
NHR
C
6
H
5
NHR
HHal
t
0
o or p-RC
6
H
4
NH
2


Phn ng bt u bng mt qu trnh th nucleophin tch dn xut halogen Rhal
ra khi mui halogenhydrat, sau Rhal s tc dng vi nhn thm theo c ch th
electrophin. V d:
C
6
H
5
NHR HHal RHal + C
6
H
5
NH
2
C
6
H
5
NH
2
+ RHal RC
6
H
4
NH
3
Hal


Phn ng chuyn v nhm alkyl nh trn c th xy ra khi un amin t do vi
CoCl
2
nhng c ch cha r rng.
- Chuyn v nguyn t halogen - chuyn v lin phn t.
S chuyn v nguyn t halogen t nguyn t nit vo vng benzen gi l chuyn
v Octn. V d, khi un N-cloaxetanilit trong axit axetic hoc nc c mt clorua
hidro ta c o- v p-cloaxetanilit.

C
6
H
5
N
Cl
COCH
3
HCl
Cl C
6
H
4
H
N COCH
3

Ngi ta cho rng trong phn ng trn, clorua hidro tc dng vi cloaxetanilit
sinh ra axetanilit v clo, sau clo tc dng vi vng thm ca axetanilit theo c ch
electrophin:

C
6
H
5
N
Cl
COCH
3
+ HCl C
6
H
5
HN COCH
3
+ Cl
2
ClC
6
H
4
HN COCH
3
+ HCl


- Chuyn v nhm arylazo.
V d tiu biu v chuyn v nhm arylazo l phn ng chuyn ho
diazoaminobenzen thnh p-aminoazobenzen:

C
6
H
5
N N NHC
6
H
5
HCl
or C
6
H
5
NH
2
+ HCl
p-H
2
NC
6
H
4
N NC
6
H
5

Trong trng hp v tr para b chim, nhm arylazo s chuyn dch n v tr
octo. V d:

149


H
N N p-H
3
CC
6
H
4
N CH
3
H
2
N
CH
3
N p-H
3
CC
6
H
4
N
p-CH
3
C
6
H
4
NH
2
HCl

Nu thay p-CH
3
C
6
H
4
NH
2
bng C
6
H
5
NH
2
trong phn ng trn ta s c 4-
metyl-4aminoazobenzen. iu ny cho thy phn ng chuyn v nhm arylazo thuc
loi chuyn v lin phn t.
Phn ng ca clorua phenyldiazoni vi anilin c th xy ra hai hng khc nhau tu
thuc vo pH ca mi trng:


C
6
H
5
N
2
Cl
+ H
2
NC
6
H
5
C
6
H
5
N N NHC
6
H
5
C
6
H
5
N N NHC
6
H
5


Da trn cc d kin thc nghim trn ngi ta cho rng s chuyn v nhm
arylazo xy ra qua giai on to thnh ion aryldiazoni s tc dng vo nhn thm ca
amin theo c ch electrophin:

C
6
H
5
N N NHC
6
H
5
HCl
C
6
H
5
N
2
+ C
6
H
5
NH
2
C
6
H
5
N NC
6
H
4
NH
2
-p

-Chuyn v nhm nitrozo (chuyn v Fiso-Hep).
Khi c mt axit clohyric, nhm nitrozo ca nitrozamin thm s chuyn dch vo
nhn thm. V d:

C
6
H
5
N
NO
CH
3
HCl
o- and C
6
H
4
H
N CH
3
p-ON


C ch chuyn v Fiso-Hep tng t c ch chuyn v Octn. Di tc dng ca
axit, nitrozamin b phn tch thnh amin v clorua nitrozyl (NOCl) hoc ion nitrozoni
(

NO ), sau l qu trnh nitrozo ho nhn thm theo c ch electrophin:

C
6
H
5
N
CH
3
NO
+ H
C
6
H
5
N
CH
3
H
+ NO O N C
6
H
4
NHCH
3
+ H


-Chuyn v benzidin: Khi cho axit mnh tc dng ln hydrazobenzen s xy ra s
chuyn v lm t lin kt nit-nit v hnh thnh lin kt cacbon-cacbon to ra
benzidin (4,4-diaminobiphenyl):

pH ln hn
pH nh hn
150


H
N NH
H
H
2
N NH
2
benzidin
hydrazobenzen


Trong phn ng chuyn v ca hydrazobenzen, ngoi benzidin l sn phm ca s
t hp p,p (chim 70%) ngi ta cn c diphenylin l sn phm ca s t hp o,p
(chim gn 30%) v nhng lng rt nh cc sn phm t hp khc:

NH
2
diphenylin
NH
2
NH
2
o-benzidin
NH
2
NH
2
NH
2
N
H
p-xemidin
N
H
o-xemidin
H
2
N

Nu c hai v tr para trong phn t hydrazobenzen ban u u b chim c bi
cc nhm th, th sn phm chnh thng l cc o-xemidin c nhm th. Cn nu ch
c mt v tr para b chim th phn ng c th to ra cc dn xut th ca diphenyl, p-
xemidin v o-xemidin.

B. Phn ng cng
Nh ni trn, nhn benzen tuy rt cha no, nhng do c h lin hp thm rt
bn vng nn kh nng tham gia cc phn ng cng c phn kh khn. Tuy nhin, khi
to iu kin phn ng thch hp, vn c th thc hin c phn ng cng.

1) Cng hidro
Vi cc tc nhn kh ho mnh nh axit iot hidric chng hn cng c th kh c
mt cch kh khn nhn benzen thnh vng no. Tuy nhin, phn ng kh c th tin
hnh thun li hn khi dng hidro phn t c xc tc l cc bt kim loi (niken, platin,
paladi). Phn ng din ra hu nh cng mt lc vo c ba ni i trong nhn benzen:
+ 3H
2
Ni
benzen
cyclohecxan


Nu xut pht t toluen, kt qu phn ng kh s to ra metylxyclohecxan:

+ 3H
2
Ni
metyl cyclohecxan
CH
3
CH
3


Nhn chung, phn ng kh cc ng ng v cc dn xut ca benzen tin hnh d
dng hn chnh bn thn benzen.
151


Phn ng kh tin hnh tt nht khi dng bt platin lm xc tc di p sut kh
quyn hoc dng bt niken di p sut ca hidro.

2) Cng halogen
Khi cho clo i qu benzen ung nng nhit 4050
0
C hoc cho hi brm i qua
benzen si c nh sng mt tri trc tip chiu sng hoc dng n thch anh pht tia
t ngoi chiu vo hn hp phn ng, s xy ra phn ng cng su nguyn t halogen
vo nhn benzen. V d:


C
6
H
6
+ 3Cl
2
C
6
H
6
Cl
6
hecxaclocylohecxan

Sn phm cng to thnh l mt hn hp phc tp ca nhiu ng phn lp th.
V mt l thuyt, hn hp gm 8 ng phn khc nhau. Trong thc t, dn dn
ngi ta tch c y c 8 ng phn .
C ch ca phn ng cng halogen vo nhn thm c trnh by nh sau: khc vi
trng hp phn ng th halogen vo nhn thm trong iu kin c halogenua kim
loi xc tc xy ra theo c ch electrophin, y trong iu kin c nh sng xc tc,
phn ng cng halogen vo nhn thm xy ra theo c ch gc:

Cl : Cl 2Cl
.

+ Cl
.
.
Cl
Cl : Cl
Cl
Cl
+ Cl
.
Cl
Cl
Cl
.
Cl : Cl
Cl
Cl
Cl
Cl
+ Cl
.
Cl
Cl
Cl
Cl
Cl
.
Cl
Cl
Cl
Cl
Cl
Cl
+ Cl
.


C) Phn ng oxi ha
Trong iu kin thng, nhn benzen t ra ht ssc bn vng i vi tc dng ca
cc cht oxi ho, ngay c nhng cht oxi ho mnh nh kali pemanganat, axit cromic
v.v Ch trong iu kin rt mnh lit, nhn benzen mi b oxi ho cho nhiu sn
phm khc nhau.
l iu khc bit nht phn bit hidrocacbon thm vi cc hp cht thng
thng mang ni i.
v h
152


Tc dng ca cht oxi ho mnh vi cc ng ng ca benzen th nhn benzen bn
vng hn mch nhnh (cc gc ankyl). Kt qu ca s oxi ho l d mch nhnh di
hay ngn th no chng u b tch ra khi nhn benzen, ch nguyn t cacbon gn
nhn benzen nht (cacbon o) l cn tn ti v bin thnh nhm cacboxyl cho axit
cacboxylic thm. Phn ng ny dng xc nh s mch nhnh v v tr ca chng
trong nhn benzen. Khi c mt nhnh ta c axit benzoic, nu c hai nhnh ta c
axit dicacboxylic thm (octo, meta, para):

CH
3
+ 3 [O]
dd KMnO
4
COOH
+ H
2
O
toluen axit benzoic

H
2
C
H
2
C CH
3
o
|
+ 5 [O]
COOH
axit benzoic
+ CH
3
COOH + H
2
O
n-propyl benzen
izopropyl benzen
CH
CH
3
CH
3
+ 7 [O]
COOH
axit benzoic
+ 2HCOOH + H
2
O
o-xilen
CH
3
CH
3
+ 6 [O]
axitH-phtalic
COOH
COOH
+ 2H
2
O


3.1.7. Aren loi benzen tiu biu: Benzen
Ngoi cc phng php chung iu ch cc hidrocacbon thm ni trn, benzen cn
c th tng hp t kh axetylen (phng php Bectlo).
Benzen l mt cht lng, khng mu, linh ng, c chit sut cao, c mi thm c
bit. im si cu benzen l 80,4
0
C, im ng c l 5,4
0
C.
Benzen khng tan trong nc nhng tan trong ru, ete, du ho. Benzen ho tan
c nhiu cht nha, m, lu hunh v nhiu cht khc khng tan trong nc. Do ,
benzen l mt dung mi rt thng dng.
V ho tnh, ngoi nhng tnh cht chung ca hidrocacbon thm, di tc dng ca
nhit cao (500600
0
C) v c xc tc kim loi nh ch, st, benzen bin thnh
diphenyl v gii phng hidro:

C
6
H
6
+ C
6
H
6
C
6
H
5
C
6
H
5
+ H
2
diphenyl


153


Kh benzen bng photpho v axit iot hidric s c metylxyclopentan do s ng
phn ho sn phm trung gian l xyclohecxan. Tuy nhin, khi kh benzen tng hi
trn xc tc platin hoc paladi hoc trn niken 150200
0
C s thu c xiclohecxan.
Phn ng ny thun nghch v 300
0
C, xiclohecxan b tch hhi cho li benzen.
i vi cc cht oxi ho mnh, vng benzen rt bn vng. Vi hidro peoxit, bnh
thng khng c phn ng nhng nu c thm mt t FeO, phn ng s xy ra mnh
lit to thnh cc phenol, pirocatechol v cc sn phm oxi ho xa hn. c bit,
benzen c th tc dng vi ozon to thnh triozonit v khi thu phn cho ba phn t
glioxal:
+ 3O
2
O
3
O
3
O
3
+ 3 H
3
O
OHC CHO 3
triozonit
glioxan


Benzen ch yu c dng iu ch nitrobenzen, anilin, clobenzen, phenol,
etylbenzen, izopropylbenzen, stiren v.v V vy, n l mt nguyn liu quan trng
trong cng nghip phm nhum anilin, dc phm, trong vic sn xut cao sunfuric
tng hp v cht do, trong vic sn xut cc cht ph gia nng cao ch s octan i
vi nhin liu ng c t v my bay.
Nhng tch cht ho hc v hng ng dng chnh ca benzen c th tm tt trong
s sau:

154


C
6
H
5
NO
2
nitrobenzen
Fe + HCl
C
6
H
5
NH
2
anilin
C
6
H
5
Cl
clobenzen
C
6
H
5
OH
phenol
C
6
H
5
SO
3
H
benzensunfoaxit
C
6
H
5
OH
phenol
C
6
H
5
C
2
H
5
etylbenzen
C
6
H
5
C
H
styren
C
6
H
5
CH
izopropylbenzen
C
6
H
5
O
C
axetophenon
C
6
H
6
Cl
6
hecxaclocyclohecxan
C
6
H
12
cyclohecxan
C
6
H
5
C
6
H
5
diphenyl
CH
2
CH
3
CH
3
C
6
H
5
C
H
styren
CH
2
CH
3
HNO
3
+ H
2
SO
4
Cl
2
, FeCl
2
H
3
PO
4
H
2
C CH
2
H
2
C C
H
CH
3
AlCl
3
H
2
SO
4
CH
3
COCl
AlCl
3
3Cl
2
, h
3H
2
, Ni
Pb, 500-600
0
C
benzen


3.2. Cc aren khc v cc hp cht thm khng c vng benzen
3.2.1. Hidrocacbon thm nhiu nhn
Hai vng thm c hai nguyn t chung gi l vng ngng t. Hidrocacbon thm
ngng t tiu biu nht l naphtalen, antraxen, phenantren. C ba hidrocacbon ny u
c tch t nha than , hm lng naphtalen trong nha than l 5% vt cc
cu t khc.
1) Naphtalen
Trong cng thc cu to, cc v tr c nh du nh sau:

1
2
3
4 5
6
7
8
9
10
o
|
o
o o
| |
|


a)Cu trc phn t
Naphtalen c xem nh l hp cht thm v tnh cht ca n ging benzen. Vi
cng thc C
10
H
8
, naphtalen c th tn ti mc cha no ln nhng n li bn vi cc
phn ng cng, phn ng in hnh ca n l th electrophin.
V mt l thuyt, naphtalen c cu trc ca mt hp cht thm, n c cu to vng
phng vi cu trc cho php to nhng m my electron t gm 10 electron (mng
155


thm). Nhng electron t ny to nhng m my xen ph trn v di mt phng
cha 10 nguyn t cacbon. Mi nguyn t cacbon lin kt vi ba nguyn t khc bng
lin kt o.
Theo phng php lin kt ho tr, naphtalen c xem nh l lai ho ca ba cu
trc I, II, III.

I II III


thun tin, c th biu din naphtalen dng cu trc IV


b)Tnh cht ho hc
* S th electrophin.
Naphtalen cho sn phm vi nhm th v tr 1 hay o. V d khi brom ho
naphtalen.
Br
2
/CH
3
CO
2
H
-HBr
Br


gii thch s nh hng, ta xt cu trc ca phc o. Gi s, tc nhn th vo v
tr mt v hai:


Ta thy rng, s th vo C
1
s c s cu trc c cha vng benzen ln hn th vo
C
2
.

S tng hp mt vi dn xut ca naphtalen.
156


HNO
3
/H
2
SO
4
CH
3
COOH/H
2
O
CH
3
COCl,C
6
H
5
NO
2
Br
2
AlCl
3
H
2
SO
4
60
0C
H
2
SO
4
150
0C
NO
2
Br
COCH
3
SO
3
H
SO
3
H
COCH
3
+
75%
25%


* Phn ng oxy ho.
Thng thng hp cht thm nhiu nhn c kh nng phn ng cao hn benzen.
iu ny c gii thch bi nng lng n nh ca h ngng t thp hn ca mt
vng:

K
2
Cr
2
O
7
H
2
SO
4
COOH
COOH


Nu trong phn t naphtalen c nhm th th vng no c hot ho hn s b oxy
ho:
K
2
Cr
2
O
7
H
2
SO
4
COOH
COOH
NO
2 NO
2
K
2
Cr
2
O
7
H
2
SO
4
COOH
COOH
NH
2


* Phn ng kh.
157


Cng nh benzen, s kh naphtalen c mt xc tc ch xy ra trong nhng iu kin
nghim ngt. S kh tng phn naphtalen n tetralin c th t c bng tc dng
ca hn hng natri trong etanol.

H
2
/Ni
t
0
, p

Na, Hg
C
2
H
5
OH


2) Antraxen v phenantren
Trong phn t antraxen v phenantren, cc v tr c nh s nh sau:

1
2
3
4 5
6
7
8 9
10
1
2
3
4
5
6
7
8
9
10
Antraxen
Phenantren


Antraxen v phenantren c mt s tnh cht ho hc nh sau:
-Antraxen v phenantren km bn i vi phn ng oxi ho - kh so vi naphtalen.
C hai hp cht trn u b oxy ho n 9,10-quinon v b kh n 9,10-dihidro:

O
O
K
2
Cr
2
O
7
, H
2
SO
4
Na, C
2
H
5
OH

K
2
Cr
2
O
7
, H
2
SO
4
Na, C
2
H
5
OH
O O


Antraxen v phenantren cng tham gia phn ng th electrophin nhng n khng c
ngha v mt tng hp v sn phm to thnh hoc l hn hp hoc l b th nhiu
ln. V d v tr s 1 ca antraxen tham gia phn ng th d dng:

158


+ H
2
SO
4
d
SO
3
H
+ H
2
O
t
0
C


Phenantren phn ng vi clo (hoc brm) khi c mt AlCl
3
cho sn phm th v
tr s 9 hoc 10 km theo sn phm cng do phc o cng Cl
-
bn cnh vic tch H
+


+ Cl
2
AlCl
3
Cl
Cl H
Cl H
+
9-clophenantren
9,10-(trans)-Diclo-9,10-dihidrophenantren

Antraxen v phenantren cn tham gia phn ng cng clo hoc brom di tc dng
ca nh sng cho 9,10-dihalogen-9,10-dihidroaren:

+ Cl
2
hv
H Cl
H Cl

+ Cl
2
hv
Cl H
Cl H


3.2.2. Hp cht thm khng cha vng benzen
1) Mt s hp cht thm khng cha vng benzen
Ngoi cc hp cht thm cha vng benzen, ngi ta cn nhn thy nhiu hp cht
vng khc v ion vng khc c nhng c im ca hp cht thm.
a)Cc hp cht thm
annulen
azulen


b)Cc ion thm
159


:
:
:
cation
xyclopropenyl
anion
xyclopentadienyl
cation
xycloheptatrienyl
(ion tropoli)
dianion
xyclooctatrienyl


c)Cc hp cht d vng thm

N
N
..
O
..
S
..
..
H .. ..
piridin
pirol furan thiophen


2) Hp cht phn thm v khng thm
a)Hp cht phn thm
Hp cht phn thm l hp cht tho mn ba tiu chun u ca hp cht thm v
khng t tiu chun th t: s gii to electron t trong vng dn ti vic gim nng
lng electron.
Cc hp cht annulen c 4n electron t phn ln thuc loi phn thm nh A, B v
C nu C phng (nhng thc t C khng phng)

xyclobutadien
cation
xyclopentadien
annulen


b)Hp cht khng thm
Hp cht khng thm l nhng hp cht vi phm mt trong ba tiu chun u ca
hp cht thm. l cc hp cht c nguyn t cacbon trng thi lai ho sp
3
trong
vng, cc hp cht annulen c 4n electron t v cc hp cht annulen c 4n+2 electron
t nhng khng phng nh cc hp cht sau:
xyclohecxadien-1,3 annulen ditrans-annulen xyclononatetraen
annulen


A c hai nguyn t cacbon trng thi lai ho sp
3
, B c cu dng thuyn, C c 4n+
2 electron t nhng c hai nguyn t hidro hng vo pha trong vng nn y nhau
lm phn t khng thng. D c mt nguyn t cacbon trng thi lai ho sp
3
, E c 4n
160


electron t v khng phng. Tt c cc hp cht khng thm tham gia phn ng nh
cc polien.































161


CU HI V BI TP

Cu 1. Hy nu c im cu to ca vng benzen. Benzen c tnh cht thm in
hnh, l nhng tnh cht no?
Cu 2. Hy trnh by c ch phn ng electron, hiu ng nhm th v quy tt th trong
vng benzen, gii thch?
Cu 3. Tnh cht khng no ca vng benzen cng biu hin tnh cht bn ca vng?
Cc phn ng no biu hin tnh cht ?
Cu 4. V tr o ca ankylbenzen c kh nng phn ng c bit g? Hy gii thch
phn ng th halogen v tr benzylic bng thuyt cng hng?
Cu 5. Hy gii thch ti sao naphtalen kh nng th vo vi tr o > |? Trnh by kh
nng phn ng c bit v tr 9 v 10 ca antraxen v phenantren?
Cu 6. T benzen, metan v cc hp cht v c cn thit, hy vit cc phng trnh
phn ng tng hp ra cc hp cht sau:
- 2,6-dibrom-4-nitrotoluen
- Axit 2-nitro-4-brombenzoic
Cu 7. Hy suy ra cng thc cu to ca hai hidrocacbon A v B c cng cng thc
phn t C
9
H
12
. Bit khi oxy ha A thu c axit benzoic cn B thu c axit
terephtalic p-HOOC-C
6
H
4
-COOH.
Cu 8. Hai hidrocacbon A v B c cng cng thc phn t C
6
H
6
. Hidrocacbon A lm
mt mu nhanh dung dch nc brm v dung dch kali permanganat. Hidrocacbon B
khng phn ng c vi hai dung dch trn. C A v B u khng phn ng c vi
bc nitrat trong dung dch amoniac.
Xc nh cng thc cu to ca A v B.
Cu 9. a) Trnh by c im cu to ca naphtalen. C bao nhiu ng phn i vi
dn xut th mt ln ca naphtalen.
b) T naphtalen, hy iu ch ra:
- 4-brom-1-nitronaphtalen
- 5-brom-1-nitronaphtalen
Cu 10. Hidrocacbon A c cng thc phn t C
8
H
10
. B c cng thc phn t C
10
H
8
.
Khi oxy ha A v B bng oxi khng kh c xc tc V
2
O
5

400
0
C u cho anhidric
phtalic.
Xc nh cu to ca A v B.
Cu 11. Vit cng thc cu to ca cc hp cht cho di y tha mn cc iu
kin sau:
a) C
8
H
10
khi nitro ha ch cho mt dn xut mononitro
b) C
6
H
3
Br
3
khi nitro ha cho ba dn xut mononitro.
c) C
6
H
3
Cl
3
khi nitro ha ch cho mt dn xut mononitro
Cu 12. Mt hp cht hu c A c cng thc phn t C
8
H
6
lm mt mu nc brom,
phn ng vi oxit bc trong NH
4
OH cho kt ta, khhi oxy ha thu c mt trong cc
sn phm l axit benzoic.
Vit cng thc cu to ca A.

162


TI LIU THAM KHO

1. L Huy Bc, Nguyn Vn Tng, Bi tp ha hc hu c, NXB Quc gia H Ni,
1986.
2. Nguyn Hu nh, nh Rng Ha hc Hu c Tp 1, Nh xut bn Gio
dc, 2003.
3. nh Rng, ng nh Bch, Nguyn Th Thanh Phong Ho hc hu c 2,
NXB Gio Dc, 2006.
4. Trn Quc Sn, ng Vn Liu Gio trnh c s ha hc hu c, Tp 1, 2, NXB
i hc s phm, 2007.
5. ng Nh Ti, C s l thuyt ha lp th, NXB Gio dc, H Ni, 1998.
6. Nguyn Minh Tho, Tng hp hu c, NXB i hc quc gia H Ni, .2005.
7. Thi Don Tnh, C s ho hc hu c, Tp 1, 2, NXB Khoa hc v K thut, H
Ni, 2006.
8. Ng Th Thun Ho hc hu c phn bi tp (tp 1,2), NXB Khoa hc v k thut,
H Ni, 2006.

163


CHNG 4. HIDROCACBON THIN NHIN
4.1. Du m
4.1.1. Ngun gc ca du m
Du m l mt cht lng, snh, c trong lng t c mu t nu sm n en, c
mi c trng, nh hn nc, khng tan trong nc v chy c. Thnh phn ch
yu ca du m l hn hp cc ankan, xicloankan v aren. Ngoi ra cn c mt lng
nh dn xut cha oxi, lu hunh v nit.
Du la v kh t c con ngi bit n t hng nghn nm trc. Su nghn
nm trc y, ngh du la v nha ng tn ti trn b sng Orat, vo thi i
, s pht hin ra du la, s thot ra ca kh t c l l l do th phng ca thn
la huyn b. Nhng ch n gia th k XIX, khi xut hin k thut khoan du v
cc loi ng c t trong, ngi ta mi ni n du la nh mt ngun nng lng.
Cng t thi gian ny, vic nghin cu thm d du m v kh t pht trin mnh.
Nhng nm 20 -30 ca th k XX, vic khai thc du la c tin hnh rm r. Vic
x l kh t c ch mun hn, v vy cng nghip kh t n nm 40 ca th k
XX mi c tch cc gii quyt .
Cho n nay, vn ngun gc du m vn cha c gii thch mt cch tho
ng. Cc gi thuyt v ngun gc du m c hnh thnh trn hai hng: ngun gc
v c v ngun gc hu c. Mt s nh bc hc tip tc cc cng trnh theo hng v
c nh thuyt cacbon kim loi ca Meneleep (1877), th nhng chnh ng cng tha
nhn du m Baku thuc ngun gc hu c. Hin nay, a s cc nh khoa hc u cho
rng du m c ngun gc hu c. Thuyt ny da trn c s nhiu kim loi du m
c cha cht ca nit nh clorophin, hemin cng nh cc hirocacbon hot ng
quang hc. iu ny chng t du la khng th chu tc dng ca nhit trn
250
0
C.
Nh vy, du m c to thnh t ng vt hoc thc vt tch lu lu ngy
nm su di y i dng, m h dng bn v chu tc dng ca vi khun trong
iu kin thiu khng kh.
Hi ngh Quc t v Ho du Matxcva nm 1958 cng phi cng nhn s
song song tn ti ca hai gi thuyt v c v hu c v ngun gc du m.

4.1.2. Thnh phn v phn loi du m
1) Thnh phn
a)Thnh phn nguyn t
Thnh phn nguyn t ca du m nh sau:
Cacbon: 8287, nit: 0,012, oxi t 0,017, ngoi ra cn c mt s nguyn
t khc chim hm lng khng ng k .
b)Cc cht ho hc
Du m l hn hp phc tp cc cht hu c. Thnh phn ca n thay i ph
thuc vo ngun gc v a cht ca tng vng, song u cu thnh t hai loi hp
cht chnh: hp cht Hidrocacbon v hp cht khng thuc loi hidrocacbon c cha
cc nguyn t oxy, lu hunh, nit, trong cc hp cht hidrocacbon l ch yu v
quan trng nht ca du m.
- Cc hp cht hidrocacbon trong du m gm:
- Hidrocacbon loi parafin
- Hidrocacbon loi mch vng (xicloankan hay naphen).
164


- Hidrocacbon loi thm (aren n vng hoc a vng ngng t).
- Hidrocacbon loi hn tp naphen thm.
Trong du m khng c aken v ankin. Bng cc phng php phn tch hin i,
cho n nay pht hin c khong 425 hidrocacbon trong du m.
- Cc hp cht khng thuc loi hidrocacbon trong du m gm:
- Cc hp cht cha lu hunh nh: mecaptan, sunfua, thiophen .
- Nhng hp cht cha oxy nh axit, phenol, xeton, este, lacton .
- Cc hp cht cha nit thuc loi piriin, quinolin, isoquinolin, cc cht c 4
nguyn t nit thuc nhm porphirin di dng phc cht vi V hoc Ni.
- Nha v atphan:
- Cc cht nha l nhng cht lng nht, qunh, mu nu en. V cu trc, trong
phn t nha ng c cha nhng h a vng ngng t trong c b phn l
vng thm, b phn l vng naphten. Nhng h vng ngng t c mang cc
nhnh bao quanh, lin kt vi nhau qua cc d t (S,O).
- Atphan l hp cht rn ca du m c mu nu thm hoc en, l cc sn
phm ngng t oxi ho v trng hp ha cc hidrocacbon thm cao. T l
cacbon/hidro trong atphan kh ln, chng t mc ngng t rt cao. Khi
lng phn t t 2500-3500. Atphan c kt ta t mazut.

2) Phn loi
C nhiu cch phn loi du m.
a)Phn loi da trn c s t khi
- Loi du nh, t khi d
15
15
0,828.
- Loi du trung bnh, t khi d
15
15
= 0,829-0,884. Du m Bch H Vit Nam
thuc loi ny.
- Loi du nng, t khi d
15
15
0,885

b)Phn loi theo thnh phn ho hc
Theo thnh phn tri hn , ngi ta phn ra cc loi du :
- Du parafin c thnh phn parafin trn 61% nh du Cn ng, Nam Bocneo,
Vit Nam, Grozni ( Lin X c).
- Du naphten c thnh phn xicloparafin khong t 61 n 76%.
- Du aren c thnh phn hidrocacbon thm khong 40% nh Bocneo.
- Du atphan, loi du c nhiu hp cht cha oxi v khi ch bin n b nha ho
nhiu.

4.1.3. Ho hc ca qu trnh ch bin du m
1) X l ban u v ch bin s cp
a)Giai on x l ban u chuyn du th thnh du gc
Trc khi a vo ch bin s cp, du m c x l ban du, kh nc, ph hu
nh nc bng cch un nng n 50160
0
C di p sut 510 atm, dng cc cht
hot ng b mt, cht ph hu nh tng. Khi kh nc, cc mui clorua vn cn
ho tan trong du nn phi dng cc thit b kh mui bng in. Sau khi tch nc v
cc tp cht ta c du gc a vo ch bin s cp.

165


b)Giai on ch bin s cp
Ch bin s cp l giai on chng ct du m bng nhit thu cc phn on du
m khc nhau. Qu trnh chng ct c tin hnh trong cc thp hnh ng hot ng
lin tc theo nguyn tt chng ct phn on. Nhng phn on tch c c th c
s dng trc tip ch bin thnh cc sn phm tng ng: phn on xng c s
dng sn xut xng t hoc my bay, phn on du ho sn xut nhin liu
cho ng c phn lc hoc du ho dn dng, phn on du diezen sn xut cc
loi du nhn, phn on mazut sn xut cc loi du nhn. Phn cn mazut
(500
0
C) cn li chin khong 30 45% du th sn xut parafin, atphan.Qu trnh
chng ct phn on du m thu c cc phn on c ghi bng sau:

Cc sn phm du m thu c khi chng ct
Cc sn phm Nhit si,
0
C S nguyn t C
Kh du m di 20 C
1
C
4
Ete du ho 20 60 C
5
C
6

Xng 40 250 C
5
C
14
Du ho 170 270 C
10
C
15
Du diezen 220 360 C
12
C
20
Mazut, cn mazut t 360 tr ln C
20
C
60

2) Nhin liu
a)Phn on xng
Xng l nhin liu dng cho ng c t trong c b ch ho kh. Yu cu quan
trng l chy u n v khng b kch n.
- Nguyn nhn ca hin tng kch n c lin quan n cu to ca hidrocacbon
trong xng. Bi v cc hidrocacbon di tc dng nhit ca xi lanh s b oxi ho do oxi
ca khng kh to thnh cc hidro peoxit (ROOH). Hp cht ny khng bn, rt d
b phn hu thnh cc gc t do, to iu kin pht trin nhanh phn ng chy, lm
tng t ngt p sut v kch n trc khi c nh la. Nghin cu hin tng ny
cho thy, cc hidrocacbon khng nhnh (n-parafin) rt d to cc peoxit. Cc naphten
v olefin nm trung gian, cc hidrocacbon thm v cc hidrocacbon c nhnh c kh
nng chng kch n tt. Bi vy, khi s dng xng cn phi quan tm ti tnh chng
kch n ca xng.
- Ch s octan: tnh chng kch n c c trng bng ch s octan. V tr s n
c biu th bng % th tch ca izooctan (2,2,4-trimetylpentan) trong hn hp vi n-
heptan. Thc t cho thy izooctan chng kch n tt nht, c quy c l 100, cn n-
heptan l km nht c ch s l 0. Nh vy, mt loi xng c kh nng chng kch n
tng tng vi hn hp gm 70% izooctan v 30% n-heptan th c ch s octan l 70.
Xng thu c t phn on chng ct trc tip du m c ch s octan thp v c
nhiu parafin v naphten, c rt t hidrocacbon thm v izoparafin.
- nng cao ch s octan ca xng, ngi ta phi dng thm cc xng cracking
nhit v cracking xc tc hoc pha thm vo xng cc cu t c ch s octan cao hay
chng chng kch n nh ru etylic, ete diizopropylic, anilin, toluidin v tt hn l
ch tetraetyl (C
2
H
5
)
4
Pb. Ch tetraetyl chng kch n hiu qu nht v ch cn thm vo
xng 0,5% khi lng l lm tng ch s octan ln 12 20 n v. Song tnh c
ca ch cng cn phi lu . Ngi ta phi pha mu hoc xanh vo xng nhn
bit v phng. Hin nay, cm sn xut v s dng cc loi xng c ch, thay vo
166


l cc loi xng pha cc cht c ch s octan cao hn nh cc parafin phn nhnh,
hidrocacbon thm, ancol, ete.

b)Phn on du ho
Phn on du ho c s dng lm nhin liu cho cc ng c my bay phn lc
v lm nhin liu sinh hot (du ho).
Nng sut to nhit v hiu qu chy ln l tiu chun rt quan trng v c bn
nh gi cht lng nhin liu phn lc. Nng sut to nhit ph thuc vo hm lng
hidro v t s C/H ca phn t, song t ph thuc vo khi lng phn t. V vy, cc
anken v cycloankan c nng sut to nhit dao ng trong mt gii hn hepk (gn
bng nhau). Cc hidrocacbon thm, khi tng khi lng phn t th nng sut to nhit
tng, cn i vi cc ankan th ngc li. Tiu chun quy nh, nng sut to nhit ca
nhin liu phn lc khng c di 10250 kcal/kg.
V mt hiu qu chy (chy hon ton), kinh nghim cho thy nhin liu c nhiu
hidrocacbon thm thng rt km. Nh vy, tho mn c nhng yu cu trn ch
c hn hp hidrocacbon parafin mch nhnh v cc naphtenic c nhnh ankyl l thch
hp nht.
V d, thnh phn ca nhin liu phn lc ca Lin X c nh sau:
- Gii hn si 155 -271
0
C.
- Thnh phn: hidrocacbon thm 19,4%, naphten c nhnh 38,2%, parafin c
nhnh 41,4%, olefin 1,0%.
nng cao kh nng bc chy ca nhin liu phn lc, khi s dng ngi ta
thng cho thm vo nhm bohidrua Al(BH
4
)
3
.
i vi du ho thp n v bp: du ho thng ly phn on trong khong
nhit d t 170 270
0
C gm t C
10
C
15
. Yu cu du phi d dng ln theo bc,
ngn la sng, khng khi v tn. Cc hidrocacbon thm hai vng ngng t, hp cht
cha lu hunh, nit khng m bo yu cu cht lng. Ngc li, cc parafin gp
phn nng cao cht lng du ho. Cht lng du c nh gi bng chiu cao ca
ngn la khng khi tnh bng mm.

c)Phn on du diezen
Du diezen c s dng lm nguyn liu cho qu trnh cracking v nhit phn.
ng thi bn thn n c trc tip s dng lm nhin liu cho ng c diezen.
Ch s xetan: yu cu ca nhin liu diezen l nhit t bc chy thp, thi gian
chm bc chy c cng ngn ng c lm vic cng tt. Cc hidrocacbon c nhit
t bc chy cao khng ph hp. Cc parafin c nhit t bc chy thp lm tng
cht lng ca nhin liu. n-Xetan C
16
H
34
l nhin liu l tng cho ng c diezen
nn ngi ta quy c ly xetan lm chun v quy nh ch s l 100, cn | -
metylnaphtalen quy nh bng 0. nh gi cht lng ca nhin liu diezen, ngi
ta dng ch s xetan l hm lng % (tnh theo th tch) ca xetan trong hn hp vi
| -metylnaphtalen. Mt nhin liu c ch s xetan 80 tc l n c cht lng nh mt
nhin liu chun c 80% xetan.

3) Cc phng php ch bin th cp
a) Cracking
167


- Khi nim: cracking, ngha ca t l s ct. V mt ho hc du m l phn
ng phn ct phn t hidrocacbon thmh cc phn t nh hn. V mt k thut ch
bin du m, y l mt phng php iu ch xng t phn on c nhit si cao
hn.
- C hai phng php cracking: cracking nhit v cracking xc tc. Cracking
nhit tin hnh khong trn 500
0
C v vi p sut thay i t 10 n 70 atm.
Cracking xc tc tin hnh nhit khong di 500
0
C v vi p sut thp t 1,0
n 1,5 atm vi xc tc nh A
2
O
3
.4SiO
2
.
- Phn ng cracking: trong qu trnh cracking, cc phn ng ho hc xy ra
phc tp, thng l phn hu, ehidro ho, vng ho, m vng.
V d:
C
10
H
22
C
5
H
10
+ C
5
H
12

C
10
H
22
C
2
H
4
+ C
8
H
8

C
10
H
22
C
8
H
16
+ C
2
H
6

C
10
H
22
C
10
H
20
+ H
2

C
2
H
4
+ C
4
H
8
2C
3
H
6
-H
2
-H
2 -H
2


Cc sn phm to ra th kh chim t 10 n 15%, th lng l xng t 30 n 55%,
cn li l cht lng nht v rn.
Xng cracking c ch s octan cao nhng km n nh v cha nhiu hidrocacbon
khng no, khi dng cn phi loi ra.
- C ch phn ng cracking:
+ Cracking nhit:
Cracking nhit xy ra theo c ch gc. Gc hnh thnh do s ct lin kt CC
cc ankan cao thnh cc gc t do nh hn. Cc gc t do ny bin i theo ba cch:
gc ny ly H ca gc kia hnh thnh mt ankan v mt anken (phn ng 1), hoc hai
gc kt hp vi nhau to thnh ankan (phn ng 2) hoc gc ln b phn ct | thnh
etylen v gc nh hn ri gc ny li chuyn ho tip (phn ng 3).
V d vi hexan:
CH
3
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
3
CH
3
+ CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
3
CH
3
CH
2
+ CH
2
CH
2
CH
2
CH
2
CH
2
CH
3
CH
3
CH
2
CH
2
+ CH
2
CH
2
CH
2
CH
2
CH
3
CH
3
CH
2
CH
2
CH
2
+ CH
2
CH
2
CH
2
CH
3
.
.
.
.
. .
. .
CH
3
+ CH
2
CH
3
. .
CH
4
+ CH
2
=CH
2
CH
2
CH
3
+ CH
2
CH
3
. .
CH
3
CH
2
CH
2
CH
3

CH
2
CH
2
CH
2
CH
2
CH
2
CH
3
.
CH
3
CH
2
CH
2
CH
2
+ CH
2
=CH
2
.

168


Nh vy, cracking nhit to ra mt lng ln metan, etylen, cc ankan khng phn
nhnh nn xng thu c c ch s octan thp.
+ Cracking xc tc:
Cn c nhiu kin khc nhau v c ch ca qu trnh cracking xc tc, song nhiu
kin cho rng phn ng ny xy ra theo c ch ion. Ta ly v d cracking xc tc n-
ankan. Ion cacboni c to thnh khi n-ankan tc dng vi trung tm axit ca xc tc,
sau l qu trnh ng phn ho ion cacboni, cui cng l s ct mch v tr | ca
ion v hnh thnh sn phm.
V d:
CH
3
CH
2
CH
2
CH
2
CH
2
CH
3
CH
3
CHCH
2
CH
2
CH
2
CH
3
A (H )
-H
2
A

CH
3
CHCH
2
CH
2
CH
2
CH
3
CH
3
CH
2
CHCH
2
CH
2
CH
3
CH
3
CH
2
CCH
2
CH
3
CH
3
CCH
2
CH
2
CH
3
CH
3
CH
3

CH
3
CCH
2
CH
2
CH
3
CH
3
H
3
C C
CH
2
CH
3
+ H
2
C CH
3
AH
2
AH
2
-AH
2
A(H )
H
2
C CH
2
H
3
C CH
3
+ A(H )
H
3
C
H
C CH
3
CH
3


Qu trnh cracking xc tc to ra cc ankan v anken c mch phn nhnh v mch
khng phn nhnh, ngoi ra cn c cc qu trnh vng ho v thm ho nn sn phm
c ch s octan cao hn ca sn phm cracking nhit.
- Hidrocracking: khi cracking nhit hoc xc tc, ngoi thnh phn kh v lng cn
to ra cc sn phm phn t ln ngho hidro.
Nh vy, c th ch bin du m thnh cc loi nhin liu dng cho ng c m
khng cn cn du, cn phi a vo qu trnh ch bin mt lng hidro t ngoi vo.
Lng hidro mi a vo lm no tt c cc mnh phn t b phn hu, dn n hiu
sut sn phm lng tng. Thm vo , khi c mt hidro th cc phn ng ngng t b
hn ch. i vi loi nguyn liu c nhiu lu hunh th lu hunh s b kh v c
lm sch, nh vy li cng c ngha.
Thc t, phng php cracking di p sut hidro c hiu qu cao v mt l thuyt
cng nh v kinh t. Song mt hn ch ca n l vn u t ln gp 2, 3 ln so vi
169


cracking xc tc. Phng php ny dng ch bin phn on nng nhm thu nhin
liu cho cc l, nhin liu xng hoc nguyn liu cho cc qu trnh cracking tip theo.
b) Nhit phn
Nhit phn l s phn hu cc hidro hoc phn on ca du m di tc dng ca
nhit trn 650
0
C trong p sut thp (khong p sut ca kh quyn). Nhit phn cho
cc sn phm kh l cc anken v ankan t C
1
n C
4
cng H
2
v sn phm lng trong
cc hidrocacbon thm chim ti 70%. T cc phn on sn phm kh v lng ny,
ngi ta s tch c cc ho cht tinh khit l cc cht u quan trng ca ngnh ho
du.

c)Reforming xc tc
Phng php ny nhm lm thay i cu trc ca hidrocacbon theo hng ng
phn ho (tng ch s octan) m khng gy ra nhng thay i ng k v khi lng
phn t. Nguyn liu l cc phn on xng chng ct c. Qu trnh tin hnh
p sut hidro t 35 n 65 atm, nhit 450 500
0
C trn cc xc tc a chc nng
nh Pt, Pd, Ir, Ni hoc cc oxit kim loi gn trn cht mang l nhm oxit hoc nhm
silicat.
Khi dng h xc tc platin nhm oxit (Pt/Al
2
O
3
) ngi ta gi l phng php
platforming.
Cht xc tc cho reforming phi m nhim c hai chc nng, hidro ho,
ehydro ho v ng phn ho. Nhng cht xc tc ny gip cho phn ng ng phn
ho n-ankan thnh isoankan, vng ho n-ankan thnh naphten, dehidro ho naphten
thnh hidrocacbon thm. Thm vo , cc hp cht cha lu hunh trong xng b
kh ho n H
2
S bay i.
Ni chung, reforming lm cho ch s octan ca xng tng ln t 50 n 80,
vi platforming c th ln n 90. Mt khc, sau khi reforming ta cng thu c mt
s hidrocacbon thm cho cng nghip ho cht.
C ch phn ng reforming n-ankan: phn ng reforming bt u bng s
dehidro ho ankan thnh anken, sau din ra theo hai hng: hng th nht l ng
phn ho to cc anken mch phn nhnh, hng th hai l vng ho ri thm ho. V
d: reforming n-hecxan:

+ CH
4
+
AH
+
+H
2
/M
-H
+
+HA
M
-H
2
AH
+
AH
+
M/(-H
2
)
AH
+
AH
+
+H
2
/M
-3H
2
/M

Nh vy, t n-hecxan, sau qu trnh reforming thu c izohecxan,
metylxiclopentan, xiclohecxan v benzen. Tt c cc hp cht ny u l cc cu t c
ch s octan cao t 80 n 111 (benzen).

170


4.1.4. Du m Vit Nam
1) Tnh hnh du m Vit Nam.
Thm lc i Vit Nam rng 1,3 triu km
2
, c chia thnh hng trm l,
mi l hng nghn km
2
tm kim, thm d du kh. Kh nng l c du kh sut dc
thm lc a ny. Hin ti, nhng kho st ban u cho thy, vng trin vng c du
tp trung thm lc a pha nam. Trn t lin, vng ng bng sng Hng v ng
bng sng Cu Long ang tip tc c thm d.
Nm 1986, ngn la tn hiu u tin khi c du bng chy trn dn khoan m
Bch H. Tnh n nay, ba m c xc nh c du l Bch H, i Hng v
Rng. Sn lng du m Bch H nm 1992 khong 5 triu tn v tnh n nm
1992 sn xut khong 14 triu tn du th. M Rng v i Hng i vo khai
thc. y l nhng m c tr lng ln.
Ngoi lin doanh Vit X, ti nay ta k nhiu hp ng tm kim, khai thc vi
hu ht cc cng ty du kh ln trn th gii nh Shell, BP (Anh), Total (Php), EOE
(Anh), Statoil (Nauy), Petrocanada (Canada), PHP (c), Petrofia (B), Petronas
Carigali (Malaixia), Pedeo (Nam Triu Tin), AEDC, Indematsu (Nht Bn)
Nm 2000, ta sn xut c trn 20 triu tn du th, sau nm 2000, sn lng
du th c th t trn 34 triu tn. Ngnh du kh Vit Nam chn phng n v k
hp ng thit k tng th cng trnh du kh vi mt nhm cc cng ty nc ngoi.
y l vic lm cp thit bi v hng ngy trn vng bin Bch H phi x i 200 ngn
m
3
kh t c gi tr tng ng 3 4 chc ngn la M. Nh my lc du v ho
du ang c khn trng xy dng ti Dung Qut (Qung Ngi). Theo d kin cui
nm 2010 s a vo hot ng.

2) Tim nng du kh Vit Nam
Bch khoa ton th Du kh th gii nm 1994 a con s c thc tr
lng du v kh quy i ca cc nc vng Ty Thi Bnh Dng th Vit Nam ng
hng th 6 (1,9 t thng, 1 thng = 150 lit), sau cc nc Malaixia (18,5), Inonexia
(18), Oxtraylia (5,3), Brunay (4,0) v Singapo (3,1), trn Thi Lan v cc nc khc.
Du kh Vit Nam, cn c vo kt qu kho st ca cc cng ty nc ngoi, d
kin tr lng tim nng c th t 5 n 6 t tn.

3) c im ca du th Vit Nam v kh nng ch bin
Trong s cc m du ang khai thc, sn lng du ca hai m Bch H v i
Hng chim 80 n 90% tng sn lng du th ca Vit Nam, nn c th xen du th
ca hai m Bch H v i Hng l tiu biu ca Vit Nam. Du th Vit Nam c cc
c im nh sau:
- Du th Vit Nam thuc h du parafinic, cha nhiu n-parafin C
10
C
40
.
Trong du i Hng c 17,8% parafin cn trong du Bch H c ti 29% parafin lm
cho ng c ca du hi cao. im ng c ca du i Hng l 27
0
C, cn ca
du Bch H l 33
0
C. Do vy, kh khn trong vic bc rt, tn cha, truyn dn trong
ng ng nn phi thm ph gia h im ng. Mt khc, do hm lng n-parafin
cao m du th Vit Nam c ch s octan thp (t 45 n 62), nn sn xut xng ta
cn phi tin hnh refoming hoc pha thm cc cht ph gia lm tng ch s octan.
Vic sn xut du diezen li thun li v ch s cetan cao (47 n 65,85, tiu chun l
45). V phng din nhin liu dn dng (du ho), du m Vit Nam li c li th:
du ho cho ngn la khng khi di t 20 n 30 mm. Phn on lm nhin liu cho
171


phn lc ca du Bch H li khng thun li bng ca du i Hng v im ng
c cao: -39
0
C i vi nhin liu ly t du Bch H v -47
0
C i vi nhin liu ly t
du i Hng (tiu chun l -47
0
C).
Du m Vit Nam cn c gi tr trong vic sn xut du nhn, sp, cc ho cht
hu c phc v cho nhiu ngnh cng nghip, hng tiu dng.
- Du th Vit Nam thuc loi du nh va phi.
T khi ca du th Vit Nam nm trong khong 0,830 0,850 (du nng c d
0,865, du nh c d 0,830). Du cng nh, tng hiu sut cc sn phm trng cng
cao v du cng c gi tr. Du th Vit Nam cho tng hiu sut cc sn phm trng
trong khong 50 60%.
- Du th Vit Nam l loi du sch, cha t cc hp cht cha lu hunh, nit,
kim loi nng, cha t nha v atphan. Cc cht bn s u c xc tc, gy cn tr
cho qu trnh ch bin v lm bn cc sn phm ch bin gy nhim mi trng.
Du th Vit Nam cha rt t lu hunh (0,03 0,08%, tiu chun du sch l
0,5%). Hm lng nit khong 0,03 0,04%, hm lng Vndi khong 0,09 ppm
0,15 ppm, hm lng Niken khong 2,54 2,64 ppm (du th Venezuela cha khang
1350 ppm).
Do cha rt t cht bn nh vy, nn du th Vit Nam thuc loi du c gi tr
cao trn th trng th gii. Tuy nhin, du th Vit Nam c t nha v atphan nn
khng th s dng sn xut nha ng (bitaum) hoc than cc c cht lng tt.

4.1.5. Tng hp nhin liu lng
Nhin liu tng hp c th thu c bng cch hiro ho than v nhng phn
cn li ca du m cng nh kh cacbon oxit. Phng php ny c pht trin vi
nhng nc khng c du m nhng li giu v than.
1) Sn xut nhin liu bng cch hiro ho thu phn than : hiro ho phn hu
than l phng php qu gi khng dng mc nghin cu phn ng ho hc c
bn m cn to ra k thut mi v p sut cao
Nm 1924, ngi ta tng hp c xng t nha bn cc ca than bn bng
cch hiro ho c xc tc molipen 450
0
C v 200atm. Qu trnh hiro ho din ra
theo hai giai on: Bt u ngi ta nghin than hay nha vi du nng thnh hn hp
c snh, sau hiro ha nhit 450
0
C p sut t 200-700 atm vi st oxit lm
xc tc. Ngi ta ct sn phm tng t nh du m v phn c nhit si cao hn
350
0
C c dng li. cn sn phm c nhit thp c chuyn thnh xng khi n i
qua xc tc ( Mo-Zn-Mg-Al
2
O
3
hay WS2-NiS-Al
2
O
3
) nhit gn 400
0
C v p sut
200-300atm.
Nu dng 3,6 tn than ngi ta thu c 0,8 tn xng(tt) v nhin liu iezen cng
vi 0,2 tn kh t.

2) Sn xut nhin liu bng cch kh ha kh than t (phng php Fis Trop):
Kh than t l hn hp cac bon monoxit v hiro c iu ch bng cch cho tc
dng ca hi nc ln than cc nhit cao :
C + H
2
O CO +H
2
O
Nm 1902, Xabati nhn thy rng cacbon oxit c th bin thnh mtan bng cch
hiro ho c xc tc nhit cao:

CO + 3H
2
CH
4
+ H
2

t
o

Ni
172



Nm 1923, Fis v cng s cho kh than t qua xc tc st oxit hc cacbon thu
c mt hn hp hirocacbon gm ch yu l n-parafin. Qu trnh c th thc hin
di p sut bnh thng (hoc khong 10-15 atm), nhit khong 200
0
C. do thnh
phn ch yu l n-parafin t C
5
- C
6
v C
13
- C
17
nn xng thu c c ch s octan
thp, vo khong 40. Do cn phi tin hnh refoming tip theo v thm ch tetraetyl
tng ch s octan mi dng c.
Trng hp l tng l s kh cacbon oxit din ra theo phng trnh :


CO + 2H
2
CH
2
+ H
2
O

Gc metylen s c polime ho trn xc tc cc bon. Kh dng xc tc st v
di p sut 10atm th thu c cc sn phm ph l hp cht oxi.
V cht lng s dng v hiu qu kinh t, phng php ny khng th cnh tranh
c vi cng ngh du m.

4.2. Kh thin nhin
4.2.1. Ngun kh thin nhin, phn loi, thnh phn v quy lut phn b cc
cu t trong cc kh
1) Ngun kh thin nhin
Kh thin nhin l ngun nhin liu v nguyn liu qu gi trong i sng v trong
Cng ngh Ho hc hin nay
V ngun gc, cho dn nay vn tn ti hai gi thuyt cho rng kh c hnh thnh
do ngun gc hu c v v c nh du m. Kh thin nhin c cc m ring bit vi
p sut ln, khong 200 atm. Kh cng c phn trn cc m du to thnh cc m
kh, nhng m kh ny rt linh ng iu ho, n inh p sut trong m du. Khi
khai thc du, kh phun ra, cho nn ngi ta cn gi l kh ng hnh trong Cng ngh
Du kh. Ngay trong du la cng c mt lng nh kh ho tan.
Kh thin nhin cn ho tan trong nc ngm vi tr lng rt ln gp ba bn ln
tr lng du la v kh m. Vic khai thc ngun nng lng ny khng phi l n
gin.
Ngoi cc m, trong thu quyn ngm, kh thin nhin cn cha cc ch trng
trong cc m than, c bit gia cc va than. Hn hp kh thin nhin ny (ch yu l
metan) vi khng kh, khi t ti t l thch ng l nguyn nhn gy ra s c n cc
hm l khi khai thc.
Kh thin nhin c ngay c di y h ao. Ngi ta cn gi l kh bn ao.
Kh metan l thnh phn quan trng ca kh quyn Hnh tinh H Mt Tri. l
lp sng m metan bao quanh h hnh tinh th 7 Uranus, do cc nh du hnh v tr
khm ph trong nhng nm gn y. ui sao chi cu to phn ln bi metan rn.
Nh vy, kh thin nhin c trong lng t, thu quyn ngm, trong V Tr vi tr
lng khng l. Kh thin nhin trong lng t di dng m kh v du m c
nghin cu nhiu v c a vo khai thc v s dng
2) Phn loi v thnh phn
nghin cu v ngun kh thin nhin trong lng t, ngi ta phn bit ba loi
kh sau:
173


- Kh thin nhin: l nhng kh thot ra t cc m kh. Thnh phn ch yu l metan
t 90 - 95%, cn li l cc ng ng ca metan, CO
2
, N
2
, i khi cn c H
2
S. Nhng
loi kh thin nhin no c cha nhiu Ni t thng li c km theo heli v agon.
- Kh ngng t: l nhng kh thot ra t nhng m kh ngng t, khc vi kh thin
nhin, ngoi metan y cn c cc ng ng ca n cho n C
5
v trn na vi mt
lng kh ln. Nhng hiroccbon ny khi thot ra ngoi do p sut gim, chng s
ngng t v c thnh phn nh kh thin nhin. S to thnh cc m kh ngng t ch
yu xy ra trong cc iu kin p sut cao v nm su trong lng t ( lc ny mt s
hirocacbon nh etan, propan s chuyn sang trng thi lng ca du m s ho vi
kh b nn lng v to nn cc m kh ngng t ).
- Kh m du: l nhng kh ho tan trong du v thot ra cng vi du t cc m
du khai thc. Thnh phn kh m du khc vi kh thin nhin ch hm lng etan,
propan, butan v cc hirocacbon nng chim mt s ln.
V d: c th thy r s khc nhau qua nhng s liu v thnh phn kh ca m kh
( kh thin nhin ) v kh m du Lin X (c) (Xem bng VII.4)

Bng VII.4. Thnh phn kh vi m ca Lin X (c)
(theo % khi lng)
Tn m: CH
4
C
2
H
6
C
3
H8 C
4
H
10
C
5
H
12
CO
2
N
2
H
2
S
Kh m Dusavo:
Kh m du m
Romaskinski
97,8
39,1
0,5
18,7
0,2
21,4
0,1
9,5
0,05
4,1
0,05
0,4
1,3
6,7
0,1
0,2

4.2.2. ng dng ca kh thin nhin
Trong cng ngh du kh, ngi ta phn bit lm 3 loi kh nh trn, nhng trong i
thng th ngi ta gi khi qut tt c l kh thin nhin. C th ni rng, v nhiu
phng din kh thin nhin chng t l dng nhin liu hp dn v hiu qu nht.
Ngi ta ang nghin cu s dng metanol v kh thin nhin ho lng lm nhin liu
t. N c dng lm nhin liu sn xut in cc nh my in cng nh
nhin liu un nu, thp sng nh v ng ph. Tng t nh in cc nh
my in, kh c th np vo v ly ra theo mun, c th kim tra k lng khi cn
thit v c th gi lu di. c bit thun tin v c hiu qu cao khi dng trong sn
xut thu tinh v gm.
-Kh thin nhin cn c dng nh l nguyn liu ban u tng hp cc sn
phm ho hc khc. Metan l thnh phn chnh ca kh thin nhin dng sn xut
amoniac, phn bn, metanol, cht do cng nh b hng v cao su tng hp. Etan,
prpan, butan l cc hidrocacbon nh c trong kh thin nhin c vo sn xut
eten, propen v em polime ho c cc vt liu quan trng. Nhng thnh phn
cn li trong kh thin nhin c tch ra v ng dng rt a dng. Do , nhu cu v
kh thin nhin trn th gii ngy cng ln. M, 1930, kh m bo ti 33%,
cn Lin X c ti 25% v nhu cu nng lng. cc nc ng v Ty u, Trung
Quc, n , Nht Bn... hng nm tiu th ti hng trm t met khi kh. Nhu cu s
dng kh thin nhin ngy cng tng song vic vn chuyn cng kh khn. T cui th
k XIX u th k XX, ngi ta sn xut c ng dn kh chu c p lc ln,
thit k mng li d kh trong quc gia v xuyn quc gia, m ra mt trin vng mi,
p ng c nhu cu ca con ngi. Ngoi ra ch to c cc tec bng thp dung
tch ln, chu p lc cao ch kh ho lng ti cc vng cha c h thng dn kh.
174



4.2.3. Kh thin nhin nc ta
Nc ta c thm lc a rng, c c di t ven bin theo chiu di ca t nc vi
nhiu du hiu c m kh v m du.
vng thm lc a nc ta c c ba loi kh, l kh thin nhin (m kh), kh
ngng t, kh m du. T nm 1985, trn cc vng m Bch H, i Hng v Rng c
hng chc gin khoan lm vic tm kim v khai thc. Vi gn 50 gin khoan khai
thc, song song vi lng du thu c, trc y hng ngy c hong 200.000 m
3
kh
thot ra t i lm lng ph ti 30 n 40 ngn la M. Ngy nay, ta c h thng
dn kh v t lin. Nh my x l kh Dinh C Vng Tu ngoi vic cung cp kh
ho lng cn cung cp kh metan cho nh my in, cho nh my sn xut phn m.
y l khu cng nghip Kh - in - m u tin nc ta. m Rng c ging
khoan su ti 3411 - 3476m nhn c dng kh t phun 520,7m
3
/ngy v 194,7m
3

kh ngng t trong ngy.
Sau 30 nm kho st hng chc ngn km
2
tuyn a - vt l vng ng bng sng
Hng, khoan hng chc ging thm d, c ging su ti 4.300m, nhiu ni cho
nhng tn hiu c m kh v m du. c bit, nm 1970 tm c m kh Tin
Hi (Thi Bnh) v a vo khai thc vi quy m 40 triu m
3
/nm. Thi Bnh
dng kh thin nhin ny phc v cho cng nghip a phng nh chy tua bin
my pht in, lm nhin liu cho cc nh my gm, s, thu tinh.
V tr lng kh thin nhin nc ta, Saclo Gioxn, ngi lm vic cho cc
chng trnh ti nguyn ca Trung tm ng - Ty Haoai nh gi: hi t t
nhin Vit Nam c th nhiu, tr lng c th ti 300 n 400 t m
3
hoc hn th
na.
Kh thin nhin nc ta cn c th khai thc cc vng m than ko di 200 km
t o Ci Bu (Cm Ph) ln Bc Giang, Qun Triu, Phn M... Cng ngh chng
than , luyn cc cng l ngun cung cp kh ng k.

4.3. Chng ct than
Ngoi kh hidrocacbon trong cc ti kh cc m than, khi chng ct than m,
ngi ta thu c mt lng ng k hidrocacbon v dn xut ca chng.

4.3.1. Chng ct than m
Than m (than bo) c chng ct trong l cc khng c khng kh khong
1000
0
C. Cc cht hu c c trong than m s b phn hu, thot ra cng hi nc.
Phn rn cn li trong l l than cc, dng cho cng nghip luuyn kim, iu ch canxi
cacbua hoc lm cht t.
Phn cc cht thot ra c lm lnh, phn lng ngng ng li, cn li l phn kh,
gi l kh than hay kh l cc. Kh l cc l mt hn hp kh gm: metan (khong
20%), cc hidrocacbon sau metan dng kh (khong 7%) , hiro (khong 55%), cc
kh cacbon oxit CO, cacbon ioxit CO
2
, cacbon iunfua H
2
S, amoniac NH
3
,.... Sau khi
loi b cc kh c, kh l cc c dng vo cc mc ch sau :
- Tch ly tng loi hiro cacbon ring bit nh metan, etan, tn,... v hiro.
- Lm nhin liu trong cng nghip hay thp sng.
- Tng hp amoniac.
Phn lng c tch ra lm hai lp:
175


- Lp nc l dung dch amoniac, thng c axits ho iu ch phn
bn amoni.
- Lp nh mu en hoc nu sm, ch yu l hn hp hirocacbon thm, d
vng thm v dn xut ca chng, gi l nha than .
-
4.3.2. X l nha than
Ngi ta em ct lp nha than thnh tng phn on ri x l cc phn on
c cc cht tinh khit hoc s dng c hn hp ca phn on vo mt mc ch
no .
V d, ngi ta c th chng ct c cc phn on sau :
- T 80 n 170
0
C c du nh, ch yu cha Benzen, Toluen...
- T 170 n 240
0
C c u trung, ch yu cha Phenol, crezol,
naphtalen,...
- T 240 n 270
0
C c u nng, ch yu cha antraxen, phennantren...
Cht b cn li l hc n, thng c dng ri ng hoc lm in cc.
Tng phn on c x l ring. Nh phn on du nh c em x l vi axits
loi cc baz nh analin, piriin, sau x l vi baz loi cc cht c tnh axit
nh phenol, crezol. Cui cng, em ct phn on dc cc cht tinh khit nh
bezen, toluen...
Trung bnh t mt tn than m qua l cc c th thu c 780 kg than cc, 30 kg
nha than v 190 kg (325 m
3
) kh l cc. T 30 kg nha than em x l v ct
phn on c 2,5 kg naphtalen, 0,1 kg antraxen, 6 kg benzen, 1,2 kg toluen, 0,1 kg
xilen, 15 kg hc n.






















176


CU HI V BI TP

Cu 1. Trn th gii c cc ngun hidrocacbon thin nhin quan trng no? C bao
nhiu cch phn loi du m? Du m Vit Nam thuc loi no?
Cu 2. Phn bit cc khi nim: du th, du gc, ho du, ch s octan v ch s
cetan.
Cu 3. Phn bit cc phn ng cracking, refoming v nhit phn. Cc sn phm chnh
ca cc phn ng trn l g? Th no l phn ng platfoming?
Cu 4. Trnh by c ch cc phn ng cracking nhit, cracking xc tc v refoming?







































177


TI LIU THAM KHO

1. L Huy Bc, Nguyn Vn Tng, Bi tp ha hc hu c, NXB Quc gia H Ni,
1986.
2. Nguyn Hu nh, nh Rng Ha hc Hu c Tp 1, Nh xut bn Gio
dc, 2003.
3. nh Rng, ng nh Bch, Nguyn Th Thanh Phong Ho hc hu c 2,
NXB Gio Dc, 2006.
4. Phan Tng Sn, Trn Quc Sn, ng Nh Ti, C s l thuyt ho hu c, tp
1,2, NXB i hc v trung hc chuyn nghip H Ni, 1980
5. Trn Quc Sn, ng Vn Liu Gio trnh c s ha hc hu c, Tp 1, 2, NXB
i hc s phm, 2007.
6. Chu Phm Ngc Sn, Nguyn Hu Tnh, Bi tp ha hc hu c, NXB Hn
Thuyn, Thnh ph H Ch Minh, 1995.
7. ng Nh Ti, C s l thuyt ha lp th, NXB Gio dc, H Ni, 1998.
8. Nguyn Minh Tho, Tng hp hu c, NXB i hc quc gia H Ni, .2005.
9. Thi Don Tnh, C s ho hc hu c, Tp 1, 2, NXB Khoa hc v K thut, H
Ni, 2006.
10. Ng Th Thun Ho hc hu c phn bi tp (tp 1,2), NXB Khoa hc v k
thut, H Ni, 2006.
11. Hong Trng Ym, Ho hc hu c, NXB Khoa hc & K thut, H Ni, 2002.
12. John D. Roberts, Marjorie C. Caserio, Ha hc hu c hin i, tp 1,2,3, NXB
Khoa hc v K thut, H Ni, 1984.
13. Francis A Carey, Organic Chemistry, Mc-Graw Hill Companies, 2001.
14. R. Morrison and R. Boyd, Organic Chemistry, Prentice-Hall International (UK)
Limited, London, 2001.
178


MC LC
Trang
Li ni u ............................................................................................................. 1

Chng 1. Hidrocacbon no ................................................................................... 2
1.1. Ankan, gii thiu metan ................................................................................... 2
1.1.1. Dy ng ng metan, ng phn ............................................................ 2
1.1.2. Danh php ............................................................................................... 4
1.1.3. Tnh cht vt l ........................................................................................ 6
1.1.4. Cc phng php iu ch ....................................................................... 7
1.1.5. Tnh cht ho hc ca ankan .................................................................... 9
1.1.6. Cht tiu biu CH
4
................................................................................... 13
1.2. Phn ng th theo c ch gc: S
R
v kh nng phn ng .................................. 15
1.2.1. c im ca c ch gc S
R
..................................................................... 15
1.2.2. C ch phn ng ...................................................................................... 15
1.2.3.nh hng ca cu to n phn ng th S
R
............................................. 17
1.2.4. Ho hc lp th ca phn ng S
R
............................................................. 18
1.2.5. nh hng ca tc nhn .......................................................................... 18
1.3. Xycloankan ...................................................................................................... 19
1.3.1. Danh php ............................................................................................... 19
1.3.2. ng phn ............................................................................................... 22
1.3.3. Cc phng php iu ch ....................................................................... 23
1.3.4. Tnh cht vt l ........................................................................................ 25
1.3.5. Tnh cht ho hc .................................................................................... 26
1.3.6. Cc thuyt gii thch v cu to cc hp cht vng .................................. 28
1.3.7. Xycloankan tiu biu: xyclohecxan.......................................................... 29
Cu hi v bi tp .............................................................................................. 32

Chng 2. Hidrocacbon khng no ........................................................................ 34
2.1. Anken, c ch phn ng tch: E
1
, E
2
, E
i
, E
1cb
, hng tch, quan h gia phn ng
tch v th; phn ng cng A
E
, kh nng v hng cng ........................................ 34
2.1.1. Dy ng ng ca etylen ........................................................................ 34
2.1.2. Cch gi tn ............................................................................................. 34
2.1.3. ng phn ............................................................................................... 35
2.1.4. Tnh cht vt l ......................................................................................... 36
2.1.5. Cc phng php iu ch ....................................................................... 37
2.1.6. Tnh cht ho hc .................................................................................... 39
2.1.7. Phn ng tch .......................................................................................... 58
2.1.8. Anken tiu biu: etilen C
2
H
4
....................................................................

75
2.2. Ankadien-tecpenoit .......................................................................................... 77
2.2.1. Ankadien ................................................................................................. 77

179


2.1.2.T ecpenoic ................................................................................................ 93
2.3. Ankin ............................................................................................................... 102
2.3.1. Cu to v gi tn .................................................................................... 102
2.3.2. Tnh cht vt l ........................................................................................ 104
2.3.3. Cc phng php iu ch v ng dng ................................................... 104
2.3.4.Tnh cht ho hc ..................................................................................... 108
2.3.5.Gii thiu axetyle ..................................................................................... 118
Cu hi v bi tp ................................................................................................... 120

Chng 3. Hidrocacbon thm ............................................................................... 122
3.1. Benzen v ng ng ....................................................................................... 122
3.1.1. Cu to ca vng benzen ......................................................................... 122
3.1.2. ng phn v danh php.......................................................................... 125
3.1.3. Quy tt (4n+2) ca Huycken .................................................................... 126
3.1.4. Phng php iu ch .............................................................................. 127
3.1.5. Tnh cht vt l ........................................................................................ 132
3.1.6. Tnh cht ho hc .................................................................................... 132
3.1.7. Aren loi benzen tiu biu: Benzen .......................................................... 150
3.2. Cc aren khc v cc hp cht thm khng c vng benzene ........................... 151
3.2.1. Hidrocacbon thm nhiu nhn ................................................................. 151
3.2.2. Hp cht thm khng cha vng benzene ................................................ 155
Cu hi v bi tp ................................................................................................... 158
Chng 4. Hidrocacbon thin nhin ..................................................................... 159
4.1. Du m ............................................................................................................ 159
4.1.1. Ngun gc ca du m ............................................................................ 159
4.1.2. Thnh phn v phn loi du m.............................................................. 159
4.1.3. Ho hc ca qu trnh ch bin du m .................................................... 160
4.1.4. Du m Vit Nam ................................................................................. 166
4.1.5. Tng hp nhin liu lng ......................................................................... 167
4.2. Kh thin nhin ................................................................................................ 168
4.2.1. Ngun kh thin nhin, phn loi, thnh phn v quy lut phn b cc cu t
trong cc kh ........................................................................................................... 168
4.2.2. ng dng ca kh thin nhin .................................................................. 169
4.2.3. Kh thin nhin nc ta ......................................................................... 170
4.3. Chng ct than ....................................................................................... 170
4.3.1. Chng ct than m ................................................................................... 170
4.3.2. X l nha than .................................................................................. 171
Cu hi v bi tp ................................................................................................... 172
Ti liu tham kho .................................................................................................. 173
Mc lc ................................................................................................................. 174