Bài Tập Hóa Học Hữu Cơ Tập 1

volcmttl@yahoo.com.
vn copyright 2009

Ti liu dnh cho:
Hc sinh chuyn Ha.
Sinh vin cc trng i hc.
Gio vin Ha hc.

08 2009

Li ni u
Ha hc hu c l mt trong nhng b mn rt quan trng trong lnh
vc Ha hc ni ring v phm tr Khoa hc t nhin ni chung. Tuy nhin
hin nay, cc ti liu tham kho v bi tp ha hc hu c l khng nhiu. V
vy vic tng hp cc t liu c mt ti liu tham kho b ch v d tip
thu hn l vic rt cn thit.
Bi tp Ha hc hu c l mt ti liu c bin son da trn vic
tng hp li t nhiu ngun t liu khc nhau theo tng chuyn hc
sinh, sinh vin d nm bt. Ti liu gm hai phn: Phn bi tp theo tng
chuyn v phn hng dn gii. Cc bi tp trong tng chuyn c
tuyn chn k lng nhm mc ch m bo cho cc dng bi tp khng
trng lp v hc sinh, sinh vin c th tip cn nhiu hng ra khc nhau
t cng mt d liu kin thc.
Bi tp Ha hc hu c bao gm hai tp:
- Tp 1: Gm by chuyn tng ng vi ni dung thuc phn i cng
ha hc hu c v phn kin thc ha hu c t bi alkane n cetone
(theo chng trnh ha hc ph thng).
- Tp 2: Gm cc phn t acid carboxylic n cc hp cht d vng. Ngoi
ra cn minh ha thm mt s bi tp nng cao tng hp cc chuyn .
V l ti liu tng hp li cc bi tp nm trong cc gio trnh, sch tham kho bi tp
hu c, cc thi hc sinh gii nn p n cho tng bi khng thay i theo p n ca
tng ti liu tham kho. V vy Bi tp Ha hc hu c khng phi l mt ti liu do mt
nhm tc gi bin son m ch l ti liu tng hp c chn la t cc ngun t liu sn
c. (Tng hp t ngun Internet copyright volcmttl@yahoo.com.vn).
Bi tp Ha Hu C Ti liu dnh cho sinh vin cc trng i hc

Copyright 2009 volcmttl@yahoo.com.vn 1
Part: 1 HIU NG HA HC

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Bi 1: Sp xp cc nhm nguyn t sau theo chiu tng dn hiu ng tng ng, bit trong cu a th R
ni trc tip vi S.
a. Hiu ng I ca: (1) SR (2) SO
2
R (3) SOR
b. Hiu ng C ca: (1) R
2
NCO (2) R
2
NC(=NR) (3) (R)
2
NC(=
+
NR
2
)
c. Hiu ng +C ca: (1) RCON(R) (2) RC(=NR) N(R) (3) RCH
2
N(R)
Bi 2: Da vo hin tng cng hng, vit cng thc gii hn (nu c) ca cc cht sau y:
a. CH
2
=CHCH
2
Cl.
b. p-NO
2
C
6
H
4
NH
2
.
c. C
6
H
5
CN.
d. C
6
H
5
CH
3
.
Bi 3: Gii thch ti sao nhng v tr o- hay p- ca hp cht C
6
H
5
CH
2
Cl tng i giu in t trong khi
ti cc v tr o- hay p- ca C
6
H
5
CCl
3
th thiu in t.
Bi 4: Da vo hiu ng in t, hy so snh tnh acid ca cc cht sau y:
a. C
6
H
5
OH (1), p-CH
3
OC
6
H
4
OH (2), p-NO
2
C
6
H
4
OH (3), p-CH
3
COC
6
H
4
OH (4), p-CH
3
C
6
H
4
OH (5).
b. CH
3
CH
2
COOH (1), ClCH
2
COOH (2), ClC
2
H
4
COOH (3), IC
2
H
4
COOH (4), ICH
2
COOH (5).
Bi 5: Sp xp cc cht sau theo th t gim dn tnh base:

(1) (2) (3) (4) (5)
Bi 6: So snh tnh acid ca cc hp cht sau: (1) (CH
3
)
3
CCOOH ; (2) CH
3
CH=CHCH
2
COOH ;
(3) CH
3
CH
2
CH=CHCOOH ; (4) (CH
3
)
2
CHCOOH ; (5) CH
2
=CHCH
2
CH
2
COOH.
Bi 7: So snh tnh base ca cc hp cht sau:

(1) (2) (3) (4) (5)

Bi 8: Ngi ta nhn thy rng alcohol tertbutylic tc dng ngay lp tc vi acid HCl m c to
thnh tertbutylchloride bn vng trong khi alcohol nbutylic trong cng iu kin phn ng rt chm.
Bi 9: Xc nh hiu ng ca cc nhm th sau khi lin kt vi gc phenyl: Cl, C(CH
3
)
3
, CHO, NO
2
,
CN, CH
2
CH
3
, N
+
(CH
3
)
3
.
Bi 10: Da vo hin tng cng hng, vit cng thc gii hn (nu c) ca cc cht sau y:
a. Aniline.
b. Buta1,3diene.
c. Vinyl Bromide.
d. Acrolein.
Bi 11: So snh bn ca cc ion sau:
a. (1) CH
2
CH
3
, (2) CH(CH
3
)
2
, (3) C(CH
3
)
3
.
b. (1) CH
2
CH
3
, (2) CH
2
OCH
3
, (3) CH
2
NHCH
3
.
c. (1) C(CH
3
)
3
, (2) CH
2
C
6
H
5
, (3) CH(C
6
H
5
)
2
.
Bi 12: Xc nh base lin hp ca cc acid sau theo quan im ca Brnsted: H
2
O, C
6
H
5
NH
3
(+)
,
C
2
H
5
OH, H
3
O
(+)
.
Bi 13: So snh di lin kt CCl trong CH
3
CH
2
Cl v CH
2
=CHCl. Gii thch.
Bi 14: Gii thch s tng dn nhit si ca cc alcohol sau:
Alcohol CH
3
OH C
2
H
5
OH C
3
H
7
OH C
4
H
9
OH
Nhit si (
o
C) 65 78,5 97,2 138
Bi 15: Cho ba gi tr nhit si: 240
o
C, 273
o
C, 285
o
C. Gn ba gi tr trn vo ba ng phn o-, m-, p-
ca benzenediol cho ph hp. Gii thch ngn gn.
Bi 16: Gii thch s khc nhau v nhit si trong dy cc cht sau:
(1) (2) (3) (4)

115
o
C 117
o
C 256
o
C 187
o
C
Bi 17: So snh kh nng tan trong nc ca cc cht sau
a. (1) HO(CH
2
)
4
OH, (2) HO(CH
2
)
3
CHO, (3) C
3
H
7
CHO.
b. (1) C
6
H
5
NH
3
Cl, (2) C
6
H
5
NH
2
, (3) C
2
H
5
NH
2
.
Bi 18: Acid fumaric v acid maleic c cc hng s phn li nc 1 (k
1
), nc 2 (k
2
). Hy so snh cc cp
hng s phn li tng ng ca hai acid ny v gii thch.
Bi 19: So snh nhit nng chy v tr s pK
a
ca 2 acid sau:

(1) acid iso-Crotonic (2) acid Crotonic

Bi 20: Xc nh tm base mnh nht trong cc alkaloid sau:

Nicotine Vindoline

************************************************
Part: 1 HNG DN GII
Bi 1: Sp xp theo chiu tng dn hiu ng in t:
a. (1) < (3) < (2).
b. (2) < (3) < (1).
c. (1) < (2) < (3).
Bi 2: Vit cng thc gii hn:
a. Cht (a) khng c cng thc gii hn.
b. Cng thc gii hn ca (b)

c. Cng thc gii hn ca (c)

d. Cng thc gii hn ca (d)


Bi 3: Gii thch:
- hp cht C
6
H
5
CH
2
Cl c hiu ng siu lin hp dng +H ca nhm CH
2
Cl vi vng
benzene lm cho nhng v tr o- hay p- ca vng tr nn giu in t.
- Trong khi nhm CCl
3
ht in t mnh (hiu ng siu lin hp m H) nn nhng v tr o-
hay p- ca C
6
H
5
CCl
3
th thiu in t.
Bi 4: So snh:
a. (3) > (4) > (1) > (5) > (2). b. (2) > (5) > (3) > (4) > (1).
Bi 5: Chiu gim dn tnh base: (3) > (1) > (4) > (5) > (2).
Bi 6: Chiu tng dn tnh acid: (1) < (4) < (3) < (5) < (2).
Bi 7: Chiu gim dn tnh base: (3) > (4) > (5) > (1) > (2).
Bi 8: Xt 2 phn ng sau:
(1) (CH
3
)
3
COH + HCl
+
H
(CH
3
)
3
CCl + H
2
O c vn tc phn ng l v
1

(2) CH
3
CH
2
CH
2
CH
2
OH + HCl
+
H
CH
3
CH
2
CH
2
CH
2
Cl + H
2
O c vn tc phn ng l v
2

C ch phn ng d l S
N
1
hay S
N
2
u tri qua giai on to carbocation. Carbocation cng bn th phn
ng xy ra cng u tin. S d v
1
>> v
2
l do carbocation (CH
3
)
3
C bn hn CH
3
CH
2
CH
2
CH
2
nhiu.
iu ny gii thch da vo +I ca (CH
3
)
3
C ln hn nhiu so vi +I ca CH
3
CH
2
CH
2
CH
2
.
Bi 9: Khi lin kt vi gc phenyl th:
- CHO, NO
2
, CN gy hiu ng I, C
- Cl gy hiu ng I, +C
- N
+
(CH
3
)
3
gy hiu ng I
- C(CH
3
)
3
gy hiu ng +I
- CH
2
CH
3
gy hiu ng +I, +H
Bi 10: Cng thc gii hn:
a. Aniline

b. Buta1,3diene:
+
CH
2
CH=CHCH
2

c. Vinyl Bromide:
CH
2
CH=Br
+

d. Acrolein:
+
CH
2
CH=CHO

Bi 11: So snh bn:
a. (3) > (2) > (1).
b. (3) > (2) > (1).
c. (3) > (2) > (1).

Bi 12: Xt bng:
acid H
2
O C
6
H
5
NH
3
(+)
C
2
H
5
OH H
3
O
(+)

base lin hp OH

C
6
H
5
NH
2
C
2
H
5
O

H
2
O
Bi 13: di lin kt CCl trong CH
2
=CHCl ngn hn trong CH
3
CH
2
Cl v:
- CH
3
CH
2
Cl c hiu ng I.
- Ngoi hiu ng I cn c thm hiu ng +C lm gim di lin kt CCl
(lm di lin kt CCl ngn hn lin kt CCl bnh thng ng thi lm lin kt C=C di
hn di lin kt C=C bnh thng).
Bi 14: Do c 4 alcohol u to c th to c lin kt hydro lin phn t nhng do khi lng phn t
ca cc alcohol tng dn nn nhit si cng tng dn.
Bi 15: Ta c ba ng phn o-, m-, p- ca benzenediol

(1) 240
o
C (2) 273
o
C (3) 285
o
C
(1) c lin kt hydro ni phn t nn nhit si l b nht.
(2), (3) u c lin kt hydro lin phn t nhng lin kt hydro ca (3) bn hn ca (2) do t b cn tr v
mt khng gian.
Bi 16:
- Ta c nhit si ca (1) < (2) l do hai cht ny khng to c lin kt hydro nn nhit si
ph thuc vo khi lng phn t.
- Li c, nhit si ca (4) < (3) l do mc d c hai cht u c lin kt hydro lin phn t
nhng lin kt hydro ca (3) dng polymer cn ca (4) dng dimer.
Bi 17: Kh nng tan trong nc ca:
a. (1) > (2) > (3). b. (1) > (3) > (2).
Bi 18: Xt cc chuyn ha:
H
H HOOC
COOH - H
+
H
H HOOC
COO
-
- H
+
F
F
,
F
,,
Axit fumaric
H
H
-
OOC
COO
-

H H
O OH
OH O
- H
+
- H
+
H
COO
- -
OOC
H
...
H H
O O
O OH
.
.
.
. ....
...
M Axit maleic M
,
M
,,


- k
1
(M) > k
1
(F) l do M c kh nng to lin kt hydro ni phn t, lin kt OH ca M trong qu
trnh phn li th nht phn cc hn so vi F v base lin hp M' cng bn hn F'.
- k
2
(M) < k
2
(F) l do lin kt hydro ni phn t lm cho M' bn, kh nhng protone hn so vi
F'. Ngoi ra, base lin hp M'' li km bn hn (do nng lng tng tc gia cc nhm COO

ln hn) base lin hp F''.
Bi 19: So snh
- Nhit nng chy ca (2) > (1).
- Tnh acid ca (1) > (2).
Bi 20: Xc nh tm base mnh nht

Nicotine Vindoline
- Alkaloid l cc base t nhin, tnh base tp trung ti d t N cho nn nguyn t N cng giu
electron th tnh base cng mnh.
- Vi Vindoline th N(b) trong nhn indole c tham gia qu trnh cng hng nn ngho electron
hn N(a) nn tm base mnh nht ca vindoline l N(a).
- Vi Nicotine th tnh base ca N(a) v N(b) gn bng nhau tuy nhin N(a) tham gia vo qu
trnh cng hng cho nn tm base mnh nht ca Nicotine l N(b).

************************************************

Part 2 NG PHN


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Bi 1: Vit cc ng phn cu to ca cc cht sau:
a. C
5
H
10
(cha mt vng).
b. C
5
H
11
OH.
c. C
6
H
14
.
d. C
4
H
9
Cl.

Bi 2: Cht no sau y c ng phn hnh hc, gi tn cc ng phn theo danh php Z, E.
a. (CH
3
)
2
CHCH=CH
2

b. CH
3
CH=CHCH
3

c. CH
3
CH=CHF
d. C
2
H
5
C(CH
3
)=CHCH
3

e. CH
3
CH=C=CHCH
3

f. Cao su thin nhin
g. Nha Guttapercha
h. CH
3
CH=C=C=C=CHCH
3

i. 1,2dimethylcyclopropane
Bi 3: Da theo gi tr momen lng cc ca cc ng phn hnh hc, hy cho bit trong cc cht A, B
sau y ng phn no l cis, ng phn no l trans
a. FHC=CHF
A
= 0 D
B
= 2,42 D
b. CH
3
CH=CHBr
A
= 1,57 D
B
= 1,69 D
c. pNO
2
C
6
H
4
CH=CHC
6
H
4

A
= 3,11 D
B
= 4,52 D
Bi 4: Nhng cht sau y c th tn ti bao nhiu ng phn lp th.
a. 1phenylethanol.
b. 2chlorobut2ene.
c. 1,2dibromopentane.
d. Alanine.
Bi 5: Trnh by cng thc chiu Fischer v xc nh cu hnh tuyt i ca cc ng phn c cu to sau

(a) (b) (c)

Bi 6: Vit cng thc chiu Newman dng bn ca:
a. (CH
3
)
2
CHCH
2
CH
3
.

b. CH
3
CH=CH
2
.
c. CH
3
CHO.
Bi 7: Cht A l mt acid hu c c ni i C=C v khng quang hot. Tuy nhin A c ng phn hnh
hc v c cng thc phn t l C
5
H
8
O
2
. Khi hydro ha A thu c sn phm B c tnh quang hot. Xc
nh hai cht A, B v vit phng trnh phn ng xy ra.
Bi 8: Vit cc cng thc h bin ca:
a. CH
3
COCH
2
CH
3
.
b. CH
3
COCH
2
COCH
3
.
c. C
6
H
5
NHCONHC
6
H
5
.
Bi 9: Hy ghi du * vo bn cnh nguyn t carbon bt i v xc nh cu hnh tuyt i ca Serine,
Adrenaline, Menthone.

Serine Adrenaline (Corticoid) Menthone
Bi 10: Vit cng thc dng h bin v cho bit loi h bin trong hai trng hp sau:
a. Cyclohexanone. b. (CH
3
)
2
CHN=O.
Bi 11: Xc nh cu hnh ca A, B (dng cis, trans) v vit cu dng gh tng ng

H H
H

H H
H

A B
Bi 12: Cho cc phn ng sau:
(1) C
6
H
5
CH
2
CH(CH
3
)OH + ClSO
2
C
6
H
4
CH
3
-p
pyridine
(E) +
+

[ ]
D
= +33
o
H Cl

(2) (E) + CH
3
COOK TsOK + (F) (Ts l k hiu vit tt ca SO
4
C
6
H
4
CH
3
-p)
(3) (F) + KOH CH
3
COOK + C
6
H
5
CH
2
CH(CH
3
)OH
[ ]
D
= 32,2
o

a. Xc nh cu trc ca (E) v (F) v cho bit phn ng (2) thuc loi phn ng g.
b. Cho bit phn ng thy phn cc ester loi nh (F) trong mi trng kim vi s hin din ca
H
2
O
18
nh sau: RCOOR + H
2
O
18

OH
RCOO
18
H + ROH

Da vo cc kt qu trn, hy gii thch s thay i du nng sut quay cc [ ]
D
ca alcohol ban u
v sn phm.
Bi 13: Vit tt c cc ng phn ca phc cht [Co(bipy)
2
Cl
2
]
+
vi bipy l:
N N

Bi 14: Quang ph hp th in t ca formaldehyde c ba cc i 295 nm, 185 nm v 155 nm. Nu
cho formaldehyde tc dng vi H
2
c xc tc Pt th ba cc i ny cn khng. Gii thch.
Bi 15: Vit cng thc cu to cc ng phn mch h c cng thc phn t C
3
H
4
BrCl, c ng phn
quang hc v ch c mt carbon phi i xng trong phn t.
Bi 16: Styryllactone c phn lp t thc vt. Vit cng thc cu dng cc cp ng phn i quang v gi
tn styryllactone theo danh php IUPAC.
O
O
O
HO
1
2
3
4 5 6
7
8
9

Bi 17: Khung carbon ca cc hp cht terpene
c to thnh t cc phn t isoprene kt ni vi
nhau theo quy tc u ui. V d, nu tm quy
c: (u) CH
2
=C(CH
3
)CH=CH
2
(ui) th phn
t mycrene c kt hp t 2 n v isoprene.
Da vo quy tc trn hy cho bit trong cc cht sau mycrene
y, cht no l terpene v ch ra n v isoprene trong khung terpene .
Bi 18: Vit cng thc Fischer ca cc cht C v D trong dy chuyn ha sau:

Bi 19: Vit cng thc chiu Fischer cc ng phn lp th ca acid 2bromo3methylsuccinic v ch ra
cc cp ng phn i quang v cc cp ng phn khng i quang trong cc ng phn lp th .

Bi 20: C ba hp cht: A, B v C

a. Hy so snh tnh acid ca A v B.
b. Hy so snh nhit si v tan trong dung mi khng phn cc ca B v C.
c. Cho bit s ng phn lp th c th c ca A, B v C.
Part 2 HNG DN GII
Bi 1: Vit cc ng phn cu to:
a. bt bo ha
5 2 2 10
1
2
+
= = , theo C
5
H
10
c cha mt vng ( 1 = ) nn l cycloalkane.
C
5
H
10
(c 1 vng) c 5 ng phn cu to ph hp:

b. C
5
H
11
OH c bt bo ha
5 2 2 12
0
2
+
= = nn l alcohol no n chc. C 8 ng phn.
c. C
6
H
14
c 0 = , c 5 ng phn.
d. C
4
H
9
Cl c 0 = , c 4 ng phn.
Bi 2: Cc cht c ng phn hnh hc l b, c, d, f , g, h, i
- Vi b, c, d ch c 2 ng phn hnh hc.
- f (cispolyisoprene) c ng phn l g (transpolyisoprene) v ngc li.
- h c ng phn hnh hc v c s l lin kt C=C lin nhau nh mt h c nh.

- i c hai ng phn hnh hc do vng cyclopropane phng (mt c nh).

Bi 3: Xt bng

Cu
ng phn
a b c
Cis B A B
trans A B A
Bi 4:
a. (A) c 1 C
*
nn c 2
1
= 2 ng phn quang hc, (A) khng c ng phn hnh hc. Vy (A) c 2
ng phn lp th.
b. (B) c 2 ng phn lp th l 2 ng phn hnh hc.
c. (C) c 2 ng phn lp th l 2 ng phn quang hc.
d. (D) c 2 ng phn lp th l 2 ng phn quang hc.
Bi 5: Cu hnh tuyt i
(a) (2S)(3S)dichlorobutane.
(b) Acid (2R)(3R)2,3dihydroxy2,3dimethylbutane4al1oic.
(c) (2R)(3S)2bromo3chlorobutane.

(a) (b) (c)
Bi 6: Vit cng thc chiu Newman
a. (A) c 2 dng bn:

b. (B) c 1 dng bn:

c. (C) c 1 dng bn:


Bi 7:
A l CH
3
CH=C(CH
3
)COOH.
B l CH
3
CH
2
CH(CH
3
)COOH.
Bi 8: Cng thc h bin
a. H bin cetoenol ca dng ceto CH
3
COCH
2
CH
3
l cc dng enol
CH
3
C(OH)=CHCH
3
; CH
2
=C(OH)C
2
H
5

b. H bin cetoenol ca dng ceto CH
3
COCH
2
COCH
3
l cc dng enol
CH
3
C(OH)=CHC(=O)CH
3
; CH
2
=C(OH)CH
2
C(=O)CH
3

c. H bin cetoenol ca dng ceto C
6
H
5
NHCONHC
6
H
5
l dng enol
C
6
H
5
N=C(OH)NHC
6
H
5

Bi 9: Ghi du * vo bn cnh nguyn t carbon bt i v xc nh cu hnh tuyt i:

S R

R
Bi 10: Cng thc dng h bin
a. Cyclohexanone. H bin cetoenol

b. (CH
3
)
2
CHN=O. H bin nitro-axi

Bi 11: Xc nh cu hnh ca A, B (dng cis, trans) v vit cu dng gh tng ng
*
*
*

- A l cisdecalin - B l transdecalin
- Cu dng gh ca (A), (B)

(A) (B)
Bi 12:
a. Gi s alcohol ban u c [ ]
D
= +33
o
cu hnh R => (E) cng c cu hnh R v phn ng
khng xy ra ti C
*
m ti O, trong khi (F) c cu hnh S ti phn ng xy ra ti C
*
.
- Gi s cu trc ban u ca alcohol l:

- Cu trc ca (E) l: Cu trc ca (F) l:

- Phn ng (2) l phn ng S
N
2
=> sn phm alcohol ca phn ng (3) c cu hnh nghch vi
cu hnh alcohol ban u.
b. Phn ng (1) v (3) khng lm nghch cu hnh, ngc li phn ng (2) c s nghch o cu hnh
do phn ng xy ra theo c ch S
N
2

Bi 13: Quy c biu din bipy bng mt cung li.
a. ng phn cis, trans:
Trans
Co
Cl
Cl Cis
Co
Cl
Cl

b. ng phn quang hc:

Co
Cl
Cl Co
Cl
Cl

Bi 14: Ba cc i hp th 295 nm, 185 nm v 155 nm tng ng vi s chuyn di in t mc nng
lng:
* * *
n , n , . Khi tc dng vi H
2
/Pt to ra nhm OH nn lin kt khng cn, do vy
ba cc i khng cn.
Bi 15: ng phn quang hc:

Bi 16:
- Tn: 8hydroxy7phenyl2,6dioxabicyclo[3.3.1]nonane3one
- Cng thc cu dng:
9
9
O
O
O
1
2
3 4
5 6
7
8
OH
C
6
H
5
1
2
3
4
5
6
7
8
HO
H
5
C
6 O
O
O
O
O
1
2
3
4
5
6
7
8 9
HO
H
5
C
6 O O
O
O
1
2
3
4
5 6
7
8 9
OH
C
6
H
5

Bi 17: Acoron v acid abietic l terpene

Bi 18: Cng thc Fischer ca cc hp cht C, D


Bi 19: Ta c 4 ng phn lp th

(I) (II) (III) (IV)

Bi 20: So snh, gii thch
a. Tnh acid c nh gi bi s d dng phn li protone ca nhm OH. Kh nng ny thun li
khi c cc hiu ng ko electron (I hoc C) nm k nhm OH. A va c hiu ng lin hp (C)
v hiu ng cm ng (I) ; B ch c hiu ng (I). Tnh acid ca (A) > (B).
b. Lin kt hydro lm tng im si. Cht C c lin kt hydro ni phn t, B c lin kt hydro lin
phn t nn nhit si ca (C) b hn nhit si ca (B). (C) c tan trong dung mi khng
phn cc ln hn (B).
c. (A), (B) u c 2 tm bt i, hai nhm th c th nm 2 pha khc nhau ca vng
cyclohexene v chng c th tn ti 4 ng phn lp th. (C) c 4 tm bt i c 16 ng phn.


Part 3 C CH PHN NG

- H
+
OEt
S
O
C
O
O
2
N CH
3
N
N N
O
N HN
OEt
S
O
C
O
2
N CH
3
N
N N
O
N
N
O
+ H
+
+ CO
2
+

OEt
S
O
O
2
N CH
3
N
N N
N HN
(-)

-------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
Bi 1: Cho bit cc phn ng sau xy ra theo c ch g. Vit c ch phn ng.
a. CH
3
MgCl + C
2
H
5
COCH
3

b. CH
3
CH
2
Cl + KCN
c. CH
3
Cl + H
2
NCH
3

d. CH
3
CH
2
Cl + H
2
O
OH

e. C
6
H
5
ONa + CH
3
I
f. C
6
H
5
OH + CH
3
OH
g. 2C
2
H
5
OH
H
+

h. Pyridine + C
2
H
5
I
i. C
6
H
5
OH + HCHO
H
+

j. C
6
H
5
CHO + CH
3
CHO
OH

k. CH
3
CH
2
CH(OSO
3
H)CH
3
+ H
2
O
o
t

l. CH
3
COOC
2
H
5
+ OH

Bi 2: Xc nh cc cht cn li trong cc s sau v nu c ch to ra chng
a. Hon thnh s sau:

b. Hon thnh s sau:

c. Hon thnh s sau:

Bi 3: Cho bit sn phm to thnh trong cc phn ng sau, nu c ch phn ng
a. CH
3
CH=CH
2
+ Cl
2

o
600 C
1:1

b. CH
2
=CH
2
+ Br
2

4
CCl
1:1

c. H
2
C=CHCH=CH
2
+ Br
2

4
CCl
1:1

d. C
6
H
5
CH
3
+ Cl
2

o
t C
1:1,Fe,xt


Bi 4: So snh kh nng phn ng ca cc cp cht sau:
a. Theo S
N
1
: CH
3
CH
2
CH
2
Cl (1) ; CH
2
=CH
2
CH
2
Cl (2).
b. Theo S
N
2
: CH
2
=CHCl (1) ; CH
3
CH
2
Cl (2).
c. Theo S
N
1
: p-NO
2
C
6
H
4
CH
2
Cl (1) ; p-CH
3
OC
6
H
4
CH
2
Cl (2) ; CH
3
CH
2
CH
2
Cl (3).
Bi 5: Dng mi tn cong ch r c ch chuyn 7-dehydrocholesterole (I) thnh vitamine D
3
(II) v cho bit
cu dng bn ca n. Bit trong cng thc di y: R l: -CH(CH
3
)-(CH
2
)
3
-CH(CH
3
)
2

HO
R
(I)

HO
R
(II)

Bi 6: Cho s phn ng:

CH
3
C=O
C
3
H
7
C
2
H
5 H
1
. C
6
H
5
MgBr
2
. H
2
O
B
HBr ac
C
(A)

a. Vit c ch phn ng v cng thc cu to cc sn phm.
b. Gi tn cu hnh ca B, C theo danh php R, S.
Bi 7: Hy gii thch s to thnh nhanh chng 2,4,6-Br
3
C
6
H
2
NH
2
(D) khi cho p-H
2
N-C
6
H
4
-SO
3
H (A)
hoc p-H
2
N-C
6
H
4
-COOH (B) tng tc vi dung dch nc Br
2
.
Bi 8: Hy ch ra c ch phn ng v sn phm cui ca phn ng cng Br
2
(1:1) vi nhng cht sau:
a. Acid maleic (1).
b. Acid fumaric (2).
c. But-2-ine (3).

3 3
H C C C CH
(1) (2) (3)
Bi 9: Xt phn ng th: RCl OH ROH Cl

+ + c biu thc tc phn ng l: v = k[RCl] hoc
v k[RCl][OH ]
=
a. Cho mt v d c th v RCl trong mi trng hp, gii thch.
b. S dung mi gii ca tertButyl bromide trong acid acetic xy ra theo c ch nh sau:

3 3 3 3
3 3 3 3 3 3
(CH ) CBr (CH ) C Br (1)
(CH ) C CH COO (CH ) COCOCH (2)
+
+
+
+

Hy gii thch ti sao, khi tng hm lng Sodiumacetate (CH
3
COONa) th khng lm tng tc
phn ng.

Bi 10: Hp cht 2,2,4-trimethylpentane (A) c sn xut vi quy m ln bng phng php tng hp
xc tc t C
4
H
8
(X) vi C
4
H
10
(Y). A cng c th c iu ch t X theo hai bc: th nht, khi c xc
tc acid v c, X to thnh Z v Q ; th hai, hydro ho Q v Z.
a. Vit cc phng trnh phn ng minh ha v tn cc hp cht X, Y, Z, Q theo danh php IUPAC.
b. Ozone phn Z v Q s to thnh 4 hp cht, trong c acetone v formaldehyde, trnh by c ch.
Bi 11: Gii thch:
a. Ti sao phn ng sau khng dng tng hp tert-butyl propyl ether.
CH
3
CH
2
CH
2
ONa + (CH
3
)
3
CBr (CH
3
)
3
COCH
2
CH
2
CH
3

b. Sn phm chnh ca phn ng ny l g.
c. Hy ngh phng php tng hp tert-butyl propyl ether tt hn.
Bi 12: X l - halogen cetone vi base mnh to thnh cc sn phm chuyn v. S chuyn v ny gi
l phn ng Favorski: - chlorocyclohexanone s chuyn v thnh methylcyclopentanecacbocylate khi c
mt CH
3
ONa trong ether. Hy xc nh c ch ca phn ng ny.

Bi 13: Cho cc phn ng sau:
4 2
3
LiAlH H
Pd/ CaCO
But 2 ine A (1) ; But 2 ine A (2) . Trong
A, B l 2 ng phn lp th. Khi ch ha ring bit A v B bng acid mnh th chng u chu s chuyn
ha sau: ng phn ha v tr, ng phn ha khng gian.
a. Xc nh A, B v cc sn phm chuyn ha nu trn.
b. Vit c ch cho qu trnh chuyn ha trn.
Bi 14: Khi un nng 2methylcyclohexane1,3dione vi but3ene2one trong dung dch kim
ngi ta thu c mt hp cht hu c (sn phm chnh) c cng thc C
11
H
14
O
2
. Hy vit cng thc cu
to ca sn phm ny v gii thch qu trnh to ra n.
Bi 15: C mt phn ng chuyn ha theo phng trnh sau:

a. Gii thch c ch.
b. Nu thay cht ban u l pxylene th sn phm no to thnh.

Part 3 HNG DN GII
-------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
Bi 1:
a. CH
3
MgCl + C
2
H
5
COCH
3

N
A
(CH
3
)
2
C(C
2
H
5
)OMgCl
b. CH
3
CH
2
Cl + KCN
2
N
S
CH
3
CH
2
CN + Cl

c. CH
3
Cl + H
2
NCH
3
2
N
S
CH
3
HNCH
3
+ HCl
d. CH
3
CH
2
Cl + H
2
O
2
N
S
CH
3
CH
2
OH + HCl
e. C
6
H
5
ONa + CH
3
I
2
N
S
+ NaI
f. C
6
H
5
OH + CH
3
OH
E
S
CH
3
C
6
H
4
OH (o-, p-) + H
2
O
g. 2C
2
H
5
OH
2
N
S
C
2
H
5
OC
2
H
5
+ H
2
O
h. Pyridine + C
2
H
5
I
2
N
S
[pyridine(N+) C
2
H
5
]I

i. C
6
H
5
OH + HCHO
E
S
(o-, p-) CH
2
OHC
6
H
4
OH
j. C
6
H
5
CHO + CH
3
CHO
N
A
C
6
H
5
CH=CHCHO + H
2
O
k. CH
3
CH
2
CH(OSO
3
H)CH
3
+ H
2
O
1
N
S
CH
3
CH
2
CH(OH)CH
3
+
l. CH
3
COOC
2
H
5
+ OH

2
N
S
CH
3
COO
+ C
2
H
5
OH
Bi 2:


Bi 3:
a. CH
3
CH=CH
2
+ Cl
2

o
R
600 C
2 2 S
Cl CH CH CH HCl = +
b. CH
2
=CH
2
+ Br
2

4
E
CCl
A
BrCH
2
CH
2
Br
c. H
2
C=CHCH=CH
2
+ Br
2

4
E
CCl
A
(1) (2) + ;
(1) ClCH
2
CH(Cl)CH=CH
2
; (2) ClCH
2
CH=CHCH
2
Cl
d. C
6
H
5
CH
3
+ Cl
2

o
E
t C,1:1,Fe,xt
3 6 4 S
p CH C H Cl HCl +
Bi 4:
a. (2) > (1) b. (2) > (1) c. (2) > (3) > (1)
Bi 5:
R
HO
H
C H
2
HO
R
R
HO
as
t
o
HO
R Cu d ng bn: S-trans
.

Bi 6:
a. C ch A
N
. Cng thc ca B v C

b. B: (2R)(3S)2phenyl3ethylhexane2ol, C: (2R)(3S)2phenyl2bromo3ethylhexane
Bi 7: Trong nc (A), (B) tn ti dng ion lng cc:
- p-H
2
N-C
6
H
4
-SO
3
H (A) p-
+
H
3
N-C
6
H
4
-SO
3
(A)
- p-H
2
N-C
6
H
4
-COOH (B) p-
+
H
3
N-C
6
H
4
-COO
(B)
Mt nhm SO
3
trong A hoc COO
trong B l do: Br
2
Br
+
+ Br

Cu dng bn

Sau tc nhn electronphile (Br
+
) s tn cng vo nguyn t carbon ca nhn thm th nhm SO
3

trong A hoc COO
trong B. Sau xy ra qu trnh tch H

+
to thnh nhm NH
2
. Nhm NH
2
vi
hiu ng C s nh hng nhm th tip theo vo v tr ortho- theo s sau:

Bi 8: C ch cng Bromine vo ni i C=C xy ra theo c ch cng hp electronphile A
E
, gm 2 bc:

Trng hp a, b xy ra theo c ch A
E
nu trn.
a. Phn ng to thnh hn hp raxemic gm 2 acid: acid (2R)(3R)2,3dibromobutanedioic v acid
(2S)(3S)2,3dibromobutanedioic
b. C 4 cch tn cng u cho 1 sn phm duy nht l acid (2R)(3S)2,3dibromobutanedioic
c. Cng tng t c ch A
E
nhng sn phm l: (E)2,3dibromobut2ene.
Bi 9: a. Ta c:
- v = k[RCl] phn ng th n phn t S
N
1
, trng hp thun li l halogenide bc III nh
(CH
3
)
3
CCl.
- v = k[RCl][OH
] phn ng th lng phn t S

N
2
, trng hp thun li l halogenide bc I nh
CH
3
CH
2
CH
2
Cl
b. Phn ng theo S
N
1
, m giai on (1) l giai on chm quyt nh tc phn ng v biu thc
tc phn ng khng ph thuc [CH
3
COO
] nn tng nng CH
3
COONa khng lm thay i
tc phn ng.


Bi 10:
a. Sn phm phn ng
+
H
3
C C CH
2
CH
3
C
CH
3
H
CH
3
CH
3
t
o ,
p
C
CH
3
CH
3
CH
3
H
3
C C
CH
3
C
H
H
H
2-Metylpropen (X) 2-Metylpropan (Y) (A)

Phn ng qua 2 bc:
Bc th nht gm tng tc gia hai phn t trong mi trng acid:
H
3
C
C CH
2
CH
3

H
3
C
C
CH
3
C
H
H
C
CH
3
CH
3
CH
2
H
3
C
C
CH
3
C
H CH
3
CH
3
CH
3
C
2,4,4-trimetyl pent-1-en
2,4,4-trimetyl pent-2-en
H
+
2

Bc th hai hydro ho Q v Z

+ H
2
+ H
2
H
3
C C
CH
3
C
H
H
C
CH
3
CH
3
CH
2
Ni , t
o
H
H
CH
3
H
3
C
C
CH
3
C
H
CH
3
CH
3
C
CH
3
H
3
C
C
CH
3
C
H CH
3
CH
3
C

b. C ch phn ng

(0,75 m).
Z
Zn/H
3
O
+
O
3
R
1
C CH
2
CH
3
R
2
HC
O +
CH
3
COCH
3
H
CH
3
Zn/H
3
O
+
O
3
CH
3
Q
H
CH
3
CH
3
R
2
C C
H
CH
3
CH
3
O
C O
C
O
R
2
O
C C
O
O
R
2
O
C O
CH
2
O
CH
3
R
1 R
1
C O + O CH
2
CH
3
O
C CH
2
O
O
CH
3
R
1


Bi 11:
a. Phn ng sau khng dng tng hp tert-butyl propyl ether.
CH
3
CH
2
CH
2
ONa + (CH
3
)
3
CBr (CH
3
)
3
COCH
2
CH
2
CH
3

Natri propoxide tert-butyl bromide tert-butyl propyl ether.
Do phn ng th S
N
2
khng thc hin vi alkyl halogenide bc ba
b. Ion Alcoholate l mt base mnh, l tc nhn nucleophile nn phn ng tch chim u th nn
sn phm chnh ca phn ng ny l sn phm tch E
2

c. Phng php tng hp hiu qu l dng phn t phn ng S
N
2
c nhm alkyl t cn tr hn v
alcoholate cn tr nhiu hn:

Bi 12:
O
Cl
CH
3
O
CH
3
OH
O
Cl
O
CH
3
O
O
OCH
3
H
2
O
OH
O
O
OCH
3
OCH
3

Bi 13:
a. Gii thch cu hnh A, B
- Do phn ng cng LiAlH
4
l phn ng cng trans nn A l transBut2ene.
- Do phn ng cng H
2
xc tc Pd/CaCO
3
l phn ng cng cis nn B l cisBut2ene.

b. C ch chuyn ha A B

- ng phn ha v tr

- ng phn ha khng gian
Hai cation trung gian hnh thnh khi protone ha A v B l ng nht nn c th chuyn ha A
thnh B v ngc li.

(B) cation trung gian (A)

Bi 14: Khi un nng 2methylcyclohexane1,3dione vi but3ene2one trong dung dch kim
ngi ta thu c mt hp cht hu c (sn phm chnh) c cng thc C
11
H
14
O
2
.

Bi 15: C ch phn ng
a. Phn ng xy ra qua 4 bc
- Bc 1: To carbocation
2
H O
+ +
3 3 3 3 2 3 3
(CH ) C OH + H (CH ) C O H (CH ) C
+


- Bc 2: To isobutene v isobutane

V

- Bc 3: To carbocation trung gian

- Bc 4: To sn phm

b. Nu thay bng p-xylene th phn ng theo c ch S
E
thng thng v s ly ion hydride t nhm
methyl l khng th c. Sn phm l:


Part 4 ALKANE, CYCLOALKANE

-------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
Bi 1: Tnh nhit phn ng H cho cc phn ng sau y:
a. (CH
3
)
3
CH + F
2
(CH
3
)
3
CF + HF.
b. (CH
3
)
3
CH + Cl
2
(CH
3
)
3
CCl + HCl.
c. (CH
3
)
3
CH + Br
2
(CH
3
)
3
CBr + HBr.
d. (CH
3
)
3
CH + I
2
(CH
3
)
3
CI + HI.
Cho bit cc gi tr nng lng phn ly lin kt (Kcal/mol):
(CH
3
)
3
CH = 93,60
F
2
= 37,20
Cl
2
= 58,32
Br
2
= 46,32
I
2
= 36,14
(CH
3
)
3
CF = 110,64
(CH
3
)
3
CCl = 81,36
(CH
3
)
3
CBr = 67,44
(CH
3
)
3
CI = 52,32
HF = 135,84
HCl = 103,68
HBr = 87,60
HI = 71,29

Bi 2: Hon thnh cc phng trnh phn ng sau y:
a. CH
3
CH
2
CH
2
CH
2
CH
3
+ O
2

o
t

b. CH
3
CH
2
CH
2
CH
2
CH
3
+ HNO
3

c. (CH
3
)
2
CHCl + Na
d. CH
3
CH
2
I + HI
( red)
P

e. CH
3
CH
2
C(=O)CH
3

Zn / HCl

f. CH
3
CH
2
CH(CH
3
)
2
+ Br
2

h

Bi 3: Cho bit sn phm to thnh khi un nng hn hp kh CH
3
I

v HI. Trnh by c ch v tnh ton
gi tr H cho tng giai on. Bit cc gi tr phn ly lin kt (Kcal/mol): II = 36,24 ; CH
3
H = 105,26 ;
HI = 71,29 ; CH
3
I = 57,17.
Bi 4: Vit qu trnh phn ng Br ha cc cht sau vi s c mt ca benzoylperoxide
a. Isopropylbenzene.
b. pchlorotoluene.
Bi 5: Cho isopentane tc dng vi Cl
2
(nh sng h ) thu c 4 sn phm vi thnh phn t l nh sau:
1chloro2methylbutane (30%), 1chloro3methylbutane (15%), 2chloro3methylbutane (33%) v
2chloro2methylbutane (22%).
a. Cho bit sn phm no d hnh thnh hn, gii thch.
b. Tnh kh nng phn ng tng i ca cc nguyn t hydro gn vi carbon bc I, II, III.
Bi 6: Vit c ch phn ng ca 2methylpropane v CCl
4
c thc hin
o
130 140 C vi s c mt
ca tert-butylperoxide.

Bi 7: T cyclopropane, hy iu ch 2,3dimethylbutane.
Bi 8: Kh nng phn ng tng i ca cc hydro bc I, II, III i vi phn ng chloridize (phn ng Cl

ha) l 1: 3, 8: 5 tng ng.
a. Tnh lng tng i ca monochlorobutane nhn c khi Cl ha nbutane
b. Tnh phn trm ca cc sn phm khc nhau.
c. Tnh phn trm cc sn phm monochlorated (c Cl ha mt ln) khi Cl ha 2methylbutane.
Bi 9: Ngi ta chuyn ha 100 g CH
4
thnh CH
3
Cl vi hiu sut l 40%. Sau cho ton b lng
CH
3
Cl va to thnh tc dng vi Na thu ethane (Hiu sut 50%). Sau ngi ta Br ha ethane, sau
khi phn ng kt thc thy thu c 60% bromoethane. Tnh lng bromoethane sau phn ng Br ha.
Bi 10: T isoamyl chloride, hy vit s iu ch 2,3,4,5tetramethylhexane.
Bi 11: Vit cng thc cu to ca cc hp cht sau:
a. 2,6dimethylspiro[4,5]decane.
b. 1,4dimethylspiro[2,2]pentane.
c. Spiro[4,4]nonane.
d. Spiro[3,4]oct1ene.
e. Bicyclo[3.2.1]octane.
f. 2,3dimethyl9isopropylbicyclo[5.3.0]decane.
Bi 12: T hp cht c 3 nguyn t Carbon, vit phng trnh tng hp bicyclo[4.1.0]heptane.
Bi 13: Hon thnh cc phng trnh phn ng sau v cho bit trong mi phn ng, cht no l cht
trung gian hot ng. Gi tn loi phn ng:
a. CH
2
=CH
2
+ CH
2
N
2

b. CH
3
CH=CH
2
+ CH
2
I
2

Cu Zn

Bi 14: Vit cng thc cu trc cc sn phm ca cc phn ng sau:
a. 2methylcyclopent1ene + CHCl
3

3 3
(CH ) COK
A + B.
b. 1 methylcyclopent1ene + CHClBr
2
3 3
(CH ) COK
C + D.
Bi 15: Cho nbutane phn ng vi Cl
2
theo t l 1 : 1 c chiu sng thu c hn hp A v hn hp kh
B. hp th ht kh HCl trong B cn va 1,6 l dung dch NaOH 1,25M.
a. Vit phng trnh phn ng th ca nbutane vi Cl
2
(1 : 1) v nu c ch phn ng.
b. Tnh khi lng hn hp A.
c. Sn phm chnh trong phn ng th trn chim 72,72% khi lng hn hp A. Tnh khi lng
ca sn phm chnh v ph.
d. Hy cho bit nguyn t H nguyn t carbon bc II tham gia phn ng th vi Cl
2
d hn nguyn
t H nguyn t carbon bc I bao nhiu ln.
Bi 16: Hai cycloalkane A v B u c t khi hi so vi methane bng 5,25. Khi Cl ha (1 : 1, askt) th
A cho 4 cht cn B ch cho 1 cht. Xc nh A, B v vit cu dng bn nht sn phm Cl ha t B.

Bi 17: Phn ng gia spiropentane vi Cl
2
c chiu sng l mt phng php iu ch
Chlorospiropentane (mt sn phm monochlorated):

a. Gii thch ti sao phn ng trn thng c s dng iu ch chlorospiropentane.
b. Nu c sn phm dichlorated (sn phm Cl ha 2 ln) to thnh. Hy nu phng php tch hai
sn phm .
c. Trnh by c ch phn ng Cl ha trn.
Bi 18: Cho s sau:

a. Vit cc phng trnh phn ng theo s chuyn ha trn.
b. giai on chuyn B
2
thnh B
3
, trong iu kin c rt t Br
2
, ngoi B
3
ngi ta cn thu c mt
lng nh alkane B
4
khc. Hy xc nh B
4
v gii thch s to thnh B
4
.
Bi 19: Hon thnh s phn ng sau:

Trong s trn: Cc cht A, A
1
, B, B
1
, B
2
D
2
u l cc hp cht hu c.
Bi 20: T cyclopropane v cc cht v c thch hp, vit cc phng trnh phn ng iu ch cc
cht sau:
a. Diphenyl. b. Teflon (CF
2
CF
2
)
n
.
************************************************

Part 4 HNG DN GII
-------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
Bi 1: Tnh nhit phn ng H (Kcal/mol):
a. (CH
3
)
3
CH + F
2
(CH
3
)
3
CF + HF H = 115 (Kcal/mol)
b. (CH
3
)
3
CH + Cl
2
(CH
3
)
3
CCl + HCl H = 33 (Kcal/mol)
c. (CH
3
)
3
CH + Br
2
(CH
3
)
3
CBr + HBr H = 15,12 (Kcal/mol)
d. (CH
3
)
3
CH + I
2
(CH
3
)
3
CI + HI H = 6,24 (Kcal/mol)
Bi 2: Hon thnh cc phng trnh phn ng:
a. CO
2
+ H
2
O.
b. CH
3
CH
2
CH(CH
3
)NO
2
, CH
3
CH
2
CH
2
CH
2
NO
2
, CH
3
CH
2
CH
2
NO
2
, CH
3
CH
2
NO
2
, CH
3
NO
2
.
c. (CH
3
)
2
CHCH(CH
3
)
2
.
d. CH
3
CH
3
.
e. CH
3
CH
2
CH
2
CH
3
.
f. CH
3
CH
2
[(Br)C(CH
3
)]CH
3
.
Bi 3: C ch tng giai on v hiu ng nhit phn ng:
o
t
3 3
CH I CH I

+
3 4
3 2 3
1. CH HI CH + I ; H = 71, 29 105, 0 = 33, 71 (Kcal / mol)
2. I CH I I + CH ; H = 57, 00 36, 00 = 21, 00 (Kcal / mol)

+
+

Cng (1) v (2) ta c phn ng: CH
3
I + HI I
2
+ CH
4
; H = 12,71 (Kcal / mol)
Bi 4:
a. Ta c cc qu trnh
6 5 2
R
(C H COO)
6 5 3 2 6 5 3 2 6 5 S
6 5 3 2 2 6 5 3 2
6 5 3 2 6 5 3 2
6 5 3 2 2 6 5 3 2
C H CH(CH ) C H C(CH ) C H COOH
C H C(CH ) Br C H CBr(CH ) Br
C H CH(CH ) Br C H C(CH ) HBr
C H C(CH ) Br C H CBr(CH ) Br...

+
+ +
+ +
+ +

b. C ch tng t cu a.
Bi 5:
a. 2chloro2methylbutane d to thnh nht v trong phn ng th gc S
R
, gc t do cng bn th
sn phm cng u tin, m gc
3 2 2 3
(CH ) CCH CH
c electron t do nm trn carbon bc III nn

bn nht. V vy s kt hp ca gc Cl
vi gc
3 2 2 3
(CH ) CCH CH
l d xy ra nht.
b. Kh nng phn ng tng i ca cc nguyn t hydro gn vi carbon bc I : bc II : bc III
tng ng t l: 1 : 3,3 : 4,4.

Bi 6: Phn ng c thc hin theo c ch gc t do:
3 2 3
3 3 3 3
3 4 3 3
3 3 3 3
(Me CO) 2 Me CO
Me CO Me CH Me COH Me C
Me C CCl Me CCl CCl
CCl Me CH CHCl Me C
+ +
+ +
+ +

Qu trnh pht trin dy chuyn cho n khi cc gc t do gp nhau => xy ra s ngt mch.
Bi 7: iu ch
HBr Ca / NaOH HBr Na
3 3 2 3 2 3 3
Cyclopropane CH CH CH Br CH CH CH CH CHBrCH = sn phm.
Bi 8:
a. C 6 nguyn t H hnh thnh 1chlorobutane (A) v 4 H hnh thnh 2chlorobutane (B). T
l nguyn t ca H (I) : H (II) l 3 : 2. Lng tng i ca sn phm l:
(A) = 3 1 = 3 v (B) = 2 3,8 = 7,6
b. Phn trm (A) v (B) l:
3
% A = 100% 28%
10,6
7,6
% B = 100% 72%
10,6

c. C 4 sn phm monochlorated khc nhau:
1chloro2methylbutane (C)
2chloro2methylbutane (D)
2chloro3methylbutane (E)
1chloro3methylbutane (F)
Ta c lng tng i v % cc sn phm l:
Cht Lng tng i Phn trm
(C) 6 1 = 6
6
100% 28%
21, 6

(D) 1 5 = 5
5
100% 23%
21, 6

(E) 2 3,8 = 7,6
7, 6
100% 35%
21, 6

(F) 3 1 = 3
3
100% 14%
21, 6

Bi 9: p s: 40,9 g
Bi 10: iu ch:


Bi 11: Vit cng thc cu to:

(a) (b) (c)

(d) (e) (f)
Bi 12:

4
3
2 5 2 5
3
LiAlH 1.KCN HBr
2 3 2 3 2 5 2 5
2.H O
C H OH C H O 1.KCN
2 5 2 5 2 5 2 5 Claisen Condensation 2.H O H
Br(CH ) Br HOOC(CH ) COOH HO(CH ) OH Br(CH ) Br
HOOC(CH ) COOH C H OOC(CH ) COOC H
+
+ +

Bi 13:
- (a) cyclopropane ; (b) methylcyclopropane.
- Cht trung gian hot ng ca phn ng:
(a) l carbene :CH
2
.
(b) l carbenoid ICH
2
ZnI (tin cht ca carbene :CH
2
).
- Loi phn ng ny l: Phn ng cng hp ng vng.

Bi 14:
a. :CCl
2
cng hp cis vo C = C, nhng kt qu l vng ba cnh c th v tr cis hoc trans vi
nhm CH
3
to (A) hoc (B):

(A) (B)

b. Anion ClBr
2
C: c to thnh s mt Br
cho carbene ClBrC: ; carbene ny cng vo C = C v

Cl hoc Br s v tr cis so vi nhm CH
3
c (C) hoc (D):

(C) (D)

Bi 15:
a. Phng trnh phn ng:
CH
3
CH
2
CH(Cl)CH
3
(X) + HCl
CH
3
CH
2
CH
2
CH
3
+ Cl
2

CH
3
CH
2
CH
2
CH
2
Cl (Y) + HCl
C ch phn ng l c ch th gc t do S
R
: sn phm chnh l (X), sn phm ph l (Y).
b.
A
m = 1,6 1,25 92,5=185
c. Khi lng mi sn phm:

X Y
185 72, 72
m 134, 532g ; m 185 134, 532 50, 468g
100
= = = =
d. Gi kh nng phn ng th bi Cl
2
ca mt nguyn t H lin kt vi nguyn t carbon bc II l a,
bc I l b ta c:

4a a
100 72, 72 109,12a 436, 32b 3, 998 4
4a 6b b
= = =
+

Bi 16:
a. M
A
= M
B
= 16.5,25 = 84 g/mol A v B l ng phn ca nhau (v u l cycloalkane). Gi
CTPT ca A, B l C
x
H
y
( x 3 ; 6 y 2x ) 12x + y = 84 CTPT ca A, B l C
6
H
12
.
- Khi mono-Cl ha B thu c mt hp cht duy nht B l cyclohexane.
- Khi mono-Cl ha A thu c 4 hp cht V vy A c th l methylcyclopentane hoc
A l iso-propylcyclopropane.
b. Cu dng (gh) bn nht ca sn phm mono-Cl ha t B l echlorocyclohexane.

askt

Bi 17:
a. Do cu trc ca spiropentane l i xng, cc nguyn t H trn nhm methylene u nh nhau,
do phn ng mono-Cl ha c th xy ra trn bt c nhm methylene no.
b. Tch bng phng php chng ct phn on v sn phm mono-Cl ha c nhit si thp hn
sn phm di-Cl ha.
c. Phn ng xy ra theo c ch th gc t do S
R
.

Bi 18:
a. Hon thnh s phn ng:
(1) C
4
H
10

o
t
CH
3
CH=CH
2
+ CH
4

(2) CH
3
CH=CH
2
+ H
2

o
Ni / t
CH
3
CH
2
CH
3

(3) CH
3
CH
2
CH
3
+ Br
2

askt
CH
3
CHBrCH
3
+ HBr
(4) CH
3
CHBrCH
3
+ Mg
Ether khan
(CH
3
)
2
CHMgBr
(5) (CH
3
)
2
CHMgBr + C
2
H
5
Br (CH
3
)
2
CHCH
2
CH
3
+ MgBr
2

(6) (CH
3
)
2
CHCH
2
CH
3

o
xt ,t
CH
2
=CCH
3
CH=CH
2
+ 2H
2

(7) n CH
2
=CCH
3
CH=CH
2

o
xt ,t
(CH
2
CCH
3
=CHCH
2
)
n

(8)
o
1500 C
4 2 lanh nhanh
2CH HC CH + 3H

(9)
o
Ni / t
2 3 3
HC CH 2H CH CH +
(10) CH
3
CH
3
+ Br
2

askt
CH
3
CH
2
Br + HBr
(11)
o
Carbon,600 C
3HC CH C
6
H
6

(12) C
6
H
6
+ CH
2
=CHCH
3

2 4
H SO
C
6
H
5
CH(CH
3
)
2

(13) C
6
H
5
CH(CH
3
)
2
+ Br
2
o
Fe,t
p-BrC
6
H
4
CH(CH
3
)
2
+ HBr
(14) p-BrC
6
H
4
CH(CH
3
)
2
+ Br
2

askt
p-BrC
6
H
4
CBr(CH
3
)
2
+ HBr
(15) C
6
H
5
CH(CH
3
)
2
+ HNO
3

2 4
H SO
p-O
2
NC
6
H
4
CH(CH
3
)
2
+ H
2
O
b. B
4
l n-butane
To thnh B
4
l do phn ng th gc t do S
R
ca C
2
H
6
vi Br
2
nh sau:

askt
3 3 3 2
3 2 2 3 2
3 3 3 2
3 2 3 2
2
3 2 2 3 3
(1) Br Br 2Br
(2) CH CH Br CH CH HBr
CH CH Br CH CH Br Br
CH CH Br CH CH HBr...
(3) CH CH Br CH CH Br
Br Br Br
CH CH CH CH CH C

+ +
+ +
+ +
+
+
+
2 3 2
H CH CH


Bi 19:
Cht Cng thc cu to Cht Cng thc cu to
A CH
2
=CH
2
B
1
CH
2
=CHCH
2
Cl
B C
2
H
5
OH C
1
ClCH
2
CHOHCH
2
Cl
C CH
3
CHO D
1
HOCH
2
CHOHCH
2
OH
D CH
3
COOH B
2
CH
3
CHClCH
3

G CH
2
=CHCH=CH
2
C
2
(CH
3
)
2
CHMgCl
A
1
CH
3
CH=CH
2
D
2
(CH
3
)
2
CHCH
2
CH
2
OH
Ngoi ra:
- Nu C l CH
3
COOH th D l (CH
3
COO)
2
Ca
- Nu A l CH
4
th B l HC CH , C l CH
3
CHO
Bi 20:
a.
o o
2 2
o o
H Cl ,askt t 1500 C C
3 8 4 2 2 6 6 1:1 600 C xt ,t
C H CH C H C H cyclohexane methylcyclohexane
o
6 6
o
3
C H xt,t
AlCl ,t
phenylcyclohexane diphenyl
+

b.
o
2 2
o o o
5
H Cl HF Zn xt ,t ,p
2 6 2 6 2 2 2 2
Ni,t t SbCl ,t ,p
HC CH C H C Cl CClF CClF CF CF teflon =

************************************************

Part 5 ALKENE, ALKINE, DIENE, TERPENE
-------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------

Bi 1: Hon thnh cc phng trnh phn ng di y v biu din ng phn lp th ca cc sn phm
to thnh bng cng thc chiu Fischer.
a. cisbut2ene + Br
2

b. transbut2ene + Br
2

c. Acid fumaric + Br
2

d. Acid maleic + Br
2

Bi 2: Phn ng sau cho sn phm l hp cht mesomeric hay bin th racemic:
trans3,4dimethylhex3ene + H
2

2
PtO
sn phm.
Bi 3: Cho bit sn phm to thnh khi ozone ha cc hp cht sau y:
a. CH
3
CH=CH
2
.
b. CH
2
CHCH(CH
3
)CH=CH
2
.
c. 1methylcyclohexa1,4diene.
Bi 4: Vit cc qu trnh iu ch:
a. CH
3
CH
2
COCH(CH
3
)
2
t propene, HCl, Mg, BH
3
, H
2
O
2
, NaOH, CrO
3
.
b. Cyclopentanone t cyclobutene, O
3
, Zn/CH
3
COOH, LiAlH
4
,

PBr
3
, Mg, HCOOCH
3
, CrO
3
.
Bi 5: em dn xut halogen C
6
H
13
I un nng vi dung dch KOH/alcohol thu c sn phm (A). Cho
(A) tc dng vi O
3
thy to thnh hp cht ozonide (B). Thy phn (B) cho CH
3
CHO

v aldehyde
isobutyric. Xc nh cng thc cu to ca C
6
H
13
I, (A) v (B).
Bi 6: Vit phn ng DielsAlder ca Buta1,3diene vi cc hp cht sau y:
a. Anhydride maleic.
b. Methylvinylcetone.
c. Acid maleic.
d. Acid fumaric.
e. H
2
C=CHCH=CH
2
.
f. C
6
H
5
CH=CHNO
2
.
Bi 7: Cho bit sn phm to thnh khi cho isobutene tc dng vi cc cht sau:
a. HI.
b. HI (Peroxide).
c. Br
2
/H
2
O.
d. Br
2
+ NaCl (H
2
O).
e. KMnO
4
long (lnh).
f. 1. O
3
; 2. (CH
3
)
2
S.
g. 1. B
2
H
6
; 2. H
2
O
2
/OH
.
Bi 8: Cho bit sn phm chnh to thnh khi cho
3
CH C CLi tc dng vi cc hp cht sau y:
a. CH
3
CH
2
Br.
b. Cyclopentanal.
c. Cyclohexanone.
d. CH
3
CH CH
2

Bi 9: Hon thnh chui phn ng sau y:
3 3 2 5 2
3 3
1.CH COCH C H MgBr 1.CO HC CH
2.H O 2.H O
BrMgC CMgBr A B C D
+ +


Bi 10: Khi cho isobutene vo dung dch c ha tan HBr, NaCl, CH
3
OH c th to ra nhng cht g, gii
thch v vit c ch phn ng.
Bi 11: Cho dn xut halogen CH
3
CH=CHCH
2
Cl (A)
a. Cho (A) tc dng vi dung dch Cl
2
trong bng ti. Vit cng thc cu to ca sn phm.
b. Nu un nng (A) vi dung dch kim long thu c monoalcohol tng ng. Cho thm kim
vo, tc phn ng khng thay i. Hy cho bit c ch phn ng v so snh kh nng phn ng
ca (A) vi n-CH
3
CH
2
CH
2
CH
2
Cl v CH
2
=CHCH
2
Cl trong cng iu kin phn ng, gii thch.
Bi 12: Hydrocarbon (X) c trong tinh du tho mc. Khi cho (X) tc dng vi lng d acid HCl thu
c sn phm duy nht c cha 2 nguyn t chlorine trong phn t. Ozone phn (X) thu c hn hp
(CH
3
)
2
CHCOCH
2
CHO v CH
3
COCH
2
.
a. Xc nh cng thc cu to ca (X). Vit cc phng trnh phn ng xy ra.
b. Hydrocarbon (Y) cng c cng cng thc phn t vi (X). Khi ozone phn (Y) thu c (Z) c
cng thc phn t C
10
H
16
O
2
. Cho bit (Z) c cu to i xng v c mch carbon khng phn
nhnh. Xc nh cng thc cu to ca (Y) v (Z).
Bi 13: Khi un nng hn hp Buta1,3diene v ethene thy xy ra phn ng ng vng DielsAlder
to thnh cyclohexene. Phn ng ny tr nn d dng hn nu thay H trong ethene bng nhm ht
electron nh COOH, COOR, CHO, v thay H trong buta1,3diene bng nhm y electron nh
CH
3
, C
2
H
5
,
a. Vit phng trnh phn ng xy ra khi cho Buta1,3diene tc dng vi ethene, cho bit cu trc
ca Buta1,3diene trc phn ng (scis hay strans).
b. un nng transpenta1,3diene vi acid acrylic CH
2
=CHCOOH, vit cu to sn phm chnh.
c. So snh tc phn ng ca mi diene sau vi acid acrylic.
- 2methylbuta1,3diene v 2chlorobuta1,3diene.
- Cispenta1,3diene v transpenta1,3diene.
Bi 14: Khi trng hp Buta1,3diene to cao su Buna thng to ra sn phm ph l vng 6 cnh
cha no (phn ng DielsAlder), khi phn ng vi H
2
d xc tc Ni th to ra ethylcyclohexane. Vit cc
phng trnh phn ng v cho bit iu kin phn ng ng vng DielsAlder xy ra d dng.
Bi 15: C 2 hydrocarbon (A), (B) u c cng thc phn t l C
7
H
14
. Bit rng:
- Oxygen ha (A) bng dung dch KMnO
4
/H
2
SO
4
to ra 2 cht CH
3
CH
2
COCH
3
v CH
3
CH
2
COOH.
- (B) c cu to mch thng v khi oxygen ha bng dung dch K
2
Cr
2
O
7
/HCl to ra CO
2
.
Xc nh cng thc cu to ca (A), (B) v hon thnh cc phng trnh phn ng.
Bi 16: Mt alkene sau khi ozone phn to ra sn phm hu c duy nht l CH
3
CHO. Khi cng hp vi
Br
2
trong bnh lm bng vt liu phn cc th ch to ra mt sn phm l mt ng phn khng quang
hot. Hy cho bit cng thc phn t ca alkene v vit cng thc cu to ca sn phm theo Fischer,
Newman ri gi tn sn phm.

Bi 17: Alkene (A) c cng thc phn t l C
6
H
12
c ng phn hnh hc, tc dng vi dung dch Br
2
cho
hp cht dibromine (B). Cho (B) tc dng vi KOH trong alcohol un nng thu c alkadiene (C) v
mt alkine (D). Khi (C) b oxygen ha (oxygenize) bi dung dch KMnO
4
/H
2
SO
4
v un nng thu c
acid acetic v CO
2
. Xc nh (A), (B), (C), (D) v vit cc phng trnh phn ng xy ra.
Bi 18: Khi cyclotrimer ha buta1,3diene vi s c mt ca cht xc tc c kim, ngi ta iu ch
c (Z, E, E)cyclodeca1,5,9triene. y l mt phng php n gin iu ch hydrocarbon vng
ln. Khi dng cc cht xc tc thch hp l cc phc allyn ca kim loi chuyn tip, ngi ta iu ch
c (E, E, E)cyclodeca1,5,9triene v (Z, Z, E)cyclodeca1,5,9triene. Vit cng thc cu to ca
cc hp cht trn.
Bi 19: Ozone phn mt terpene (A) C
10
H
16
thu c mt cht (B) c cu to nh sau:
CH
3
C CH
2
CH CH CH
2
CH = O
C
H
3
C CH
3

Hydro ha (A) vi xc tc kim loi to ra hn hp sn phm (X) gm cc ng phn c cng thc phn
t C
10
H
20
.
a. Xc nh cng thc cu to ca (A).
b. Vit cng thc cc ng phn cu to trong hn hp (X).
Bi 20: T mt loi tinh du ngi ta tch c cht (A) v (B) l ng phn hnh hc ca nhau. Kt qu
phn tch cho thy (A) ch cha 78,95% C v 10,52% H v khi lng, cn li l O. T khi hi ca A so
vi H
2
l 76. (A) phn ng c vi dung dch AgNO
3
/NH
3
cho kt ta Ag v mui ca acid hu c. Khi
b oxygen ha (oxygenize) mnh, (A) cho mt hn hp sn phm gm acetone, acid oxalic v acid
levulinic CH
3
COCH
2
CH
2
COOH. Khi cho Br
2
/CCl
4
phn ng vi (A) theo t l mol 1 : 1 thu c ba dn
xut dibromine. Phn t (A) bn hn (B). Xc nh cng thc cu to ca (A), (B).
Bi 21:
1. Hp cht A (C
10
H
18
O) c phn lp t mt loi tinh du Vit Nam. A khng lm mt mu nc
bromine v dung dch thuc tm long, cng khng tc dng vi hydro c xc tc Ni, nhng li tc
dng vi HCl m c sinh ra 1chloro4(1chloro1methylethyl)1methylcyclohexane. Hy
xut cu trc ca A.
2. Hp cht B (C
10
H
20
O
2
) c trong mt loi tinh du Nam M. T B c th tng hp c A bng
cch un nng vi acid.
a. Vit cng thc cu to v gi tn B.
b. Dng cng thc cu trc, vit phng trnh phn ng v trnh by c ch y ca phn ng
tng hp A.
3. Hp cht B thng c iu ch t C (2,6,6trimethylbicyclo[3.1.1]hept2ene) c trong du
thng. Dng cng thc cu to, vit phng trnh phn ng v ch r cc lin kt ca C b t ra.
O

4. Trong cy long no c hp cht D tn l 1,7,7trimethylbicyclo[2.2.1]heptan2one. Vit s cc
phn ng tng hp D t C v cho bit c ch ca giai on u.
5. V cu to ha hc, cc hp cht A, B, C v D trn c c im g chung nht. Minh ha vn tt
c im trn cc cng thc cu to ca chng.
Bi 22: Anethole c phn t khi l 148,2 v hm lng cc nguyn t: 81,04% C, 8,16% H, 10,8% O.
(Bit H = 1,008 ; C = 12,000 ; O = 15,999). Hy:
a. Xc nh cng thc phn t ca anethole.
b. Vit cng thc cu trc ca anethole da vo cc thng tin sau:
- Anethole lm mt mu nc bromine.
- Anethole c hai ng phn hnh hc.
- S oxygen ha anethole to ra acid methoxybenzoic (M) v s nitro ha M ch cho duy nht acid
methoxynitrobenzoic.
c. Vit phng trnh ca cc phn ng: (1) anethole vi bromine trong nc ; (2) oxygen ha
anethole thnh acid methoxybenzoic ; (3) nitro ha M thnh acid methoxynitrobenzoic. Vit tn
ca anethole v tt c cc sn phm hu c nu trn theo danh php IUPAC.
d. V cu trc hai ng phn hnh hc ca anethole.
Bi 23: Tin hnh phn ng gia 3,5,5trimethycyclohex2enone v n-butylmagnesiumiodide. Sau ,
thy phn hn hp bng dung dch HCl 4M thu c hp cht B. B b chuyn thnh nm ng phn, k
hiu t D
1
n D
5
c cng thc phn t C
13
H
22
. Vit cng thc cu to ca cc ng phn D
1
, D
2
, D
3
, D
4
,
D
5
v gii thch s hnh thnh chng.
Bi 24: Mt monoterpenoid mch h A c cng thc phn t C
10
H
18
O (khung carbon gm hai n v
isoprene ni vi nhau theo qui tc uui). Oxygen ho A thu c hn hp cc cht A
1
, A
2
v A
3
.
Cht A
1
(C
3
H
6
O) cho phn ng iodoform v khng lm mt mu nc bromine. Cht A
2
(C
2
H
2
O
4
) phn
ng c vi Na
2
CO
3

v vi CaCl
2

cho kt ta trng khng tan trong acid acetic ; A
2

lm mt mu dung
dch KMnO
4

long. Cht A
3
(C
5
H
8
O
3
) cho phn ng iodoform v phn ng c vi Na
2
CO
3
.
a. Vit cng thc cu to ca A
1
, A
2
v A
3
.
b. V cng thc cc ng phn hnh hc ca A v gi tn theo danh php IUPAC.
Bi 25: T benzene v cc hp cht hu c c s C 3, vit s tng hp cis-1-phenylhex-2-ene.
Bi 26: Hon thnh s phn ng sau, xc nh cc hp cht t A n I:
o
5 3 2 2 2
2 3 6 13
PCl CH MgI 1.LiNH H Ac O 1.Mg,ether khan t
19 38 2 2. CH =C(CH )-CHO 2.C H Br Pd/C ether khan
X A B C D E F I(C H O )
Cho bit: X l:

A c 1H ethylenic, B c 5H ethylenic, D c 1H ethylenic.

Bi 27: A, B l hai hydrocarbon c tch t du m c cc tnh cht vt l v d kin phn tch nh sau:
t
s
(
o
C) t
nc
(
o
C) %C %H
A 68,6 -141 85,63 14,34
B 67,9 -133 85,63 14,34
A cng nh B lm mt mu nhanh chng dung dch KMnO
4
v nc bromine, khi ozone phn cho sn
phm ging nhau. Xc nh cu trc ca A, B.
Bi 28: Hon thnh s phn ng sau:
2
3(l)
3 2
2 4 2 2 2
N
2
3
1.NaNH
2.Na/NH
1.CH MgBr NaNH HC CNa NaI HC CNa
3 2 2 11 18 Br-(CH ) -Cl S 3.H O 2.CO
H (1mol)
12 20 2 Pd/CaCO
CH CH CH I A B C D E(C H ) F
F G(C H O ).

Bi 29: Pheromol (H) c Bestmann iu ch nm 1982 nh sau:
( )
2 8 2
2 4 3
Me(CH ) Br 2H 1.EtMgBr 1.EtMgBr bromine ha
16 29 2.HC C-CH -OTs 2.Epoxide Pd,Lindlar CBr +PPh
HC CLi A B C D E C H Br

3
2
Ph P NaI 1.Base
acetone 2.CH =CH-CHO
E F G H .
Xc nh cng thc cu to cc cht t A n G. Bit H l:
Bi 30: Acid Abscisic (ABA) thuc loi sesquiterpenoid c nhiu trong gii thc vt c tc dng iu
chnh gic ng ng ca cy ci v cho php cy tn ti trong mi trng bt li. C nhiu phng php
tng hp ABA. y dn ra phng php i t acetone.
+
2 2 2 2
3 6 4 3
3 2 4 4
- -
H
NaNH -2H O HOCH CH OH
3 3 19 13 11 18 2 11 18 2 p-CH C H SO H
CH SO Cl KMnO KMnO
11 20 4 11 18 4 11 15 3 pyridine OH OH
3CH COCH A B(C H O) C(C H O ) D(C H O )
D [E](C H O ) F(C H O ) G(C H O )

Tip theo s ni mch to thnh acid nh sau:
2 4
+
3 2 4
+
2
H O CrSO LDA G + -
7 7 2 18 22 5 DMF
1.CH ONa,H O NH
H O 2.H
Methyl - 3- methylpent - 2(Z) - ene - 4- inoate H (Li C H O ) I(C H O Li) K L
L M acid Abscisic (ABA).

a. Vit CTCT cc cht t A n M bit rng hn hp methanesunfonyl chloride/pyridine dng
tch nc alcohol bc ba.
b. Acid Abscisis c tnh quang hot hay khng, n c cu hnh nh th no.
************************************************
Part 5 HNG DN GII
-------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
Bi 1: Biu din cu hnh sn phm bng cng thc chiu Fischer:


Bi 2: Hn hp racemic

Bi 3:
a. CH
3
CHO + HCHO.
b. OHCCHCH
3
CHO + 2HCHO.
c. OHCCH
2
COCH
3
+ OHCCH
2
CHO
Bi 4:
3 3
2 2
3
HCl Mg
3 2 3 3 3 3
1.BH CrO
3 2 3 2 2 3 2
2.H O ,OH
H O
3 2
CH CH CH CH CHCl CH CH CH(MgCl) CH (1)
CH CH CH CH CH CH OH CH CH CHO (2)
(1) (2) CH CH CHOH
+
=
=
+
a.

3
CrO
3 2 3 2 3 2
CH(CH ) CH CH CO CH(CH ) .

3 3 4
3
3
+
3
1.O 1.PBr LiAlH
2 2 2 4 2 4 2.Zn/CH COOH 2.2Mg
CrO 1.HCHO
2.H O
cyclobutene OHCCH CH CHO HO(CH ) OH BrMg(CH ) MgBr
cyclopent an ol cyclopen tan one.

b.

Bi 5: C
6
H
13
I l

Bi 6:


Bi 7:
a. tert-butyliodide.
b. Tert-butyliodide.
c. 1bromo2methylpropanol.
d. 1-bromo-2-chloro-2-methylpropane, 1,2-dibromo-2-methylpropane, 1-bromo-2-methylpropanol.
e. 2methylpropan1,2diol.
f. Acetone v formaldehyde.
g. Isobutanol.
Bi 8:
a.
3 2 3
CH CH C C CH .
b. Sn phm l

c. Sn phm l

d.
3 2 3
CH CHOH CH C C CH
Bi 9:

A l HC CMgBr ; B l ; C l ; D l
Bi 10: Sn phm phn ng l hn hp gm:

(CH
3
)
3
CBr ; (CH
3
)
3
COH ; CH
3
[(HO-)C(-Cl)]CH
3
; (CH
3
)
3
COCH
3

Gii thch da vo c ch phn ng:
- Trong dung dch c cc qu trnh phn ly:
HBr H
+
+ Br
NaCl Na
+
Cl

- Do trong dung dch c 4 tc nhn l Br
, Cl
, H
2
O v CH
3
OH c kh nng kt hp vi
carbocation. Phn ng theo c ch cng electrophile (A
E
).
- u tin, H
+
tn cng vo C
to carbocation (CH
3
)
3
C (giai on chm.)
- Sau 4 tc nhn trong dung dch s kt hp carbocation to sn phm (giai on nhanh).
Bi 11:
a. CH
3
CHClCHClCH
2
Cl. C ch A
E
.
b. C ch S
N
1
: CH
3
CH=CHCH
2
Cl > CH
2
=CHCH
2
Cl > CH
3
CH
2
CH
2
CH
2
Cl.
Bi 12:
a. Cng thc ca X l:

b. Cng thc ca Y v Z ln lt l:

Bi 13:
a. Buta1,3dien dng s-cis. Phn ng:

b. Phn t penta1,3diene c nhm CH
3
y electron cn acid acrylic c nhm COOH ht electron
nn c s phn cc cc lin kt theo chiu mi tn cong. Sn phm chnh to thnh do cc nguyn
t C mang in tch tri du kt hp vi nhau.

c. So snh kh nng phn ng:

- 2methylbuta1,3diene > 2chlorobuta1,3diene.
- Cispenta1,3diene < transpenta1,3diene.
Bi 14:
a. Phng trnh phn ng:
+
t , xt
o
+ 2H
2
t , xt
o
;

b. iu kin: Hp cht diene (A) phi c cu hnh s-cis. Phn ng ny tr nn d dng hn nu thay
H trong dienophile bng nhm ht electron nh COOH, COOR, CHO, v thay H trong
diene bng nhm y electron nh: CH
3
, C
2
H
5
,
Bi 15:
A l 3methylhex3ene.
B l Hept1ene.
Bi 16:
- Alkene l But2ene
- Phn ng cng Br
2
vo But2ene l cng trans nn to ng phn khng quang hot th
alkene But2ene phi dng trans.Cng thc Fischer, Newman ln lt l:

Bi 17:
(A) l: CH
3
CH
2
CH=CHCH
2
CH
3
.
(B) l: CH
3
CH
2
CHBrCHBrCH
2
CH
3
.
(C) l: CH
3
CH=CHCH=CHCH
3
.
(D) l:
3 2 2 3
CH CH C CCH CH . =
Bi 18: Cng thc cu to:
Z, E, E
E, E, E Z, Z, E

Bi 19:

a. Cng thc cu to ca A:

b. Hn hp X:

Bi 20:
(A) l trans- (CH
3
)
2
C=CHCH=C(CH
3
)CH
2
CH
2
CHO.
(B) l cis- (CH
3
)
2
C=CHCH=C(CH
3
)CH
2
CH
2
CHO.
Bi 21:
1. Xc nh cng tc cu trc ca A(C
10
H
18
O). A c 2 = .
- A khng lm mt mu dung dch nc bromine v dung dch thuc tm long chng t trong A
khng c ni i hay ni ba.
- A khng tc dng vi hydro trn cht xc tc Ni chng t trong A khng c nhm chc carbonyl.
- A tc dng vi acid HCl c c 1chloro4(1chloro1mehylethyl)1methylcyclohexane
nn trong A c vng no v c lin kt ether.
- Suy ra cng thc cu trc ca A
O
CH
3
CH
3
CH
3
CH
3
H
3
C
CH
3
O
O
O

2.a. Vit cng thc cu to, gi tn B
B l mt diol c b khung carbon nh A
Gi tn B: 1-hydroxy-4-(-1-hydroxy-1-methylethyl)-1-methylcyclohexane.
H
+

H
2
O
A
OH
OH
B

2. b. Dng cng thc cu trc, vit phng trnh phn ng v trnh by c ch y ca phn ng.

- C 2 dng trans v cis ca B u cu dng gh bn vng, tuy vy cu dng gh khng th tham
gia ng vng m phi i qua dng thuyn km bn.
- Dng thuyn s tham gia phn ng S
N
1 ni phn t.

Cis-B
A
OH
OH
H O
OH
H O
H
+
O
H
+
H
+
(+)
OH
(+)

(+)
Trans-B
A
OH
OH OH
OH
(+)
OH
H
+
O
H
+
OH

3. Lin kt ca C b t cc ng chm chm:
H
+

2 H
2
O
OH
OH
+

HCl
D
H
+
(+)
chuyn v
H
2
O
O
O
HO
Cl
(+)
Cl
-
4.
C

5. c im chung nht v cu to ho hc: mi phn t gm 2 n v isoprene (hoc isopentane) ni
vi nhau.
Bi 22:

a. Xc nh cng thc phn t:
C = (81,04/12,00) = 6,75 ; H = (8,16/1,01) = 8,08 ; O = (10,8/16,0 = 0,675
C = 6,75/0,675 = 10 ; H = (8,08/0,675 ) = 12 ; O = 1 => C10H12O
b. Vit cng thc cu trc ca anethole:
Anethole lm mt mu nc bromine nn c lin kt i ; v tn ti dng hai ng phn hnh hc
(lin kt i, ) v khi oxygen ha cho acid nn c lin kt i mch nhnh ; v ch cho 1 sn phm sau
khi nitro ha nn nhm methoxy v tr 4 (COOH- nhm th loi 2, methoxy nhm th loi 1. l acid
4-methoxy-3- nitrobenzoic.
Vy anethole l:

c. Cc phng trnh phn ng:
(1) anethole vi Br
2
/H
2
O

(2) oxygen ha anethole thnh acid methoxybenzoic:

(3) nitro ha M thnh acid methoxynitrobenzoic:

Tn ca anethole v tt c cc sn phm hu c nu trn theo danh php IUPAC:
(2) 2-Bromo-1-(4-methoxiyphenyl) propan-1-ol.
(3) Acid 4-methoxybenzoic ; (4) Acid 4-methoxy-3-nitrobenzoic.
d. Hai ng phn hnh hc ca anetol:

(E)-1-methoxy-4-(1-propenyl)benzene (Z)-1-methoxy-4-(1-propenyl)benzene

hoc (E)-1-(4-methoxyphenyl) prop-1-ene hoc (Z)-1-(4-methoxyphenyl) prop-1-ene
Bi 23: Cng thc cu to ca 5 ng phn, k hiu t D
1
, D
2
, D
3
, D
4
n D
5

Bi 24: a. Xc nh A
1
, A
2
, A
3

- A l hp cht mch h nn c 2 ni i
- A
1
tham gia phn ng iodofom nn A1 l hp cht metyl xeton
CH
3
COCH
3

+ I
2

/KOH CHI
3

+ CH
3
COONa
- A
2
phn ng vi nn y l mt acid, da vo cng thc phn t y l mt diacid
HOOC-COOH + Na
2
CO
3
NaOOCCOONa + H
2
O + CO
2

- A
3
, C
5
H
8
O
3
, cho phn ng iodoform, phn ng c vi Na
2
CO
3
. A
3

va c nhm chc methyl
cetone va c nhm chc acid.
Vy A
1
: CH
3
COCH
3
, A
2
: HOOCCOOH, A
3
: CH
3
COCH
2
CH
2
COOH
b. A l monoterpene mch h nn c b khung carbon l:

Da vo cu to ca A
1
, A
2
, A
3
nn xc nh c v tr cc lin kt i trong mch carbon (hnh trn):
V c s hnh thnh acid oxalic nn A c th l: (E) hoc (Z)3,7dimethylocta2,6dienol

Bi 25: S tng hp:
2 2 2
3 2 2 6 5 2
1.NaNH 1.NaNH H
3 2 2 3 2 2 2 6 5 2.CH CH CH Br 2.C H CH Br xc tc Lindlar
HC CH CH CH CH C C H CH CH CH C CCH C H
cis-1-phenylhex-2-ene. Trong :
3 2
o
3
CH Br Br ,as C
6 6 6 5 3 6 5 2 AlBr 600 C
HC CH C H C H CH C H CH Br.

Bi 26:


Bi 27: Da vo kt qu phn tch nguyn t, A v B c cng thc C
6
H
12
. c th l ng phn
cis/trans ca hex2ene hoc hex3ene. Do ozone ha cho sn phm ging nhau nn l ng phn ca
hex3ene. A l ng phn cis v c nhit nng chy thp hn vo nhit si cao hn => B l trans.
Bi 28:
2
2 4 2
N
2
3(l)
3
2 2
NaNH HC CNa NaI
3 2 2 3 7 2 3 3 2 3 2 Br-(CH ) -Cl S
1.NaNH
2.Na/NH
1.CH MgBr HC CNa
2 4 2 4 3.H O 2.CO
CH CH CH I C H C CH n - PrC C(CH ) CH n - PrC C(CH ) CH I
n - PrC C(CH ) C CH Trans - n - PrCH = CH(CH ) C CH

2
3

H (1mol)
2 4 12 20 2 Pd/CaCO
Trans - n - PrCH = CH(CH ) C C- COOH Acid dodeca - 2Z, 8E- dienoic (C H O ).

Bi 29:
t R l CH
3
(CH
2
)
8
:
2
2
4 3
RBr 1.EtMgBr 1.EtMgBr
2 2 2 2 2.HC C-CH -OTs 2.Epoxide
2H bromine ha
2 2 2 Pd,Lindlar CBr +PPh
HC CLi HC CR(A) HC CCH C CR(B) RC CCH C CCH CH OH(C)
(Z, Z)RCH = CHCH CH = CHCH CH OH(D) (Z

3
2 2 2
Ph P NaI
2 2 2 2 2 2 3 acetone
, Z)RCH = CHCH CH = CH(CH ) Br(E)
(Z, Z)RCH = CHCH CH = CH(CH ) I(F) (Z, Z)RCH = CHCH CH = CH(CH ) PPh I (G)
+

Bi 30:
a. Cng thc cu to cc cht:



b. ABA l hn hp racemic khng c tnh quang hot, c cu hnh Z, E, Z.

************************************************

Part 6 HYDROCARBON THM, DN XUT

HALOGEN, HP CHT C KIM.
-------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
Bi 1: Gii thch cc d kin sau:
a. Kh nng phn ng ca chlorobenzene km benzene trong phn ng th i in t, d rng nh
hng vn u tin o-, p-.
b. Ion phenolate tham gia phn ng th i in t cc v tr o-, p-.
c. Phn ng th i in t ca acid benzoic u tin cho sn phm m-.
d. Phenol d b Br ha hn benzene.
e. Cc dn xut halogen ca hydrocarbon thm kh tham gia phn ng th i nhn hn dn xut
alkylhalogenide.
Bi 2: Ba hp cht trimethylbenzene sau, cht no c kh nng hot ha mnh nht trong phn ng th
in t S
E
: (1) 1,2,3trimethylbenzene ; (2) 1,2,4trimethylbenzene ; (3) 1,3,5trimethylbezene.
Bi 3: Vit cc sn phm to thnh ca cc phn ng sau y:
a. Phn ng sulfonic ha p-methylcumene. b. Phn ng sulfonic ha p-acetyltoluene.
Bi 4: Hon thnh cc phn ng chuyn ha sau:
a. Br(CH
2
)
3
pC
6
H
4
CH
2
Br
o
2
H O,t

b. C
6
H
5
CH
2
Cl
o
2
1.KCN,DMSO
2.H ,H O,t
+

c. C
6
H
5
CH
3

3 2 4
3 2 4
o
1.SO .H SO
2.HNO /H SO
3.NaOH,t

d.
3 2 3
6 5
o
3
1.CH (CH ) Li
2.C H CHO
3.H O ,t
+

e.
2 2 7 2 4
Na Cr O / H SO

f.
2
o
2
1.MnO
2.KOH,H O,t

Bi 5: T benzene hoc methylbenzene, hy vit phng trnh iu ch:
a. C
6
H
5
CH
2
CH
2
CCH.
b. p-ClC
6
H
4
CONH
2
.
c. C
6
H
5
COpC
6
H
4
COOCH
3
.
d. Acid 2,6dibromobenzoic.
Bi 6: Cht A c cng thc C
8
H
6
v lm mt mu nc Br
2
, phn ng vi AgNO
3
/NH
3
cho kt ta,
oxygen ha thu c acid benzoic. Xc nh cng thc cu to ca cht A.
Bi 7: Khi un nng 1,4dibromobutane vi Na
2
S s to thnh thiophene C
4
H
4
S. Bng phng php trn,
hy iu ch methylthiophene.
Bi 8: Trong phn ng Cl ha nh cht xc tc FeCl
3
, kh nng phn ng tng i ti cc v tr khc
nhau trong cc phn t biphenyl v benzene nh sau:


a. Trnh by c ch phn ng Cl ha biphenyl theo hng u tin nht.
b. Tc mono-Cl ha biphenyl v benzene hn km nhau bao nhiu ln.
c. Trong mt phn ng mono-Cl ha biphenyl thu c 10 grams 2chlorobiphenyl th s thu c
bao nhiu grams 4chlorobiphenyl.
Bi 9: Hon thnh cc chui phn ng sau:
a.
3 2
H O SO Cl KCN
3 3
CH CHOHCH (A) (B) (C).
+

b.
2 2
CH CH KCN/ alcohol
2 4
I(CH ) I (A) (B).
=

Bi 10: Vit phng trnh phn ng ca ethylmagnesiumbromide vi cc cht sau:
a. CH
3
CH
2
CN.
b. CH
3
COCl.
c. C
2
H
5
CHCH
3
C CH.
d. CH
3
COOC
2
H
5
.
e. C
2
H
5
COCH
3
.
Bi 11: Cho bit sn phm ca cc phn ng sau:

Bi 12: Indene C
9
H
8
c tch t nha than , c phn ng vi KMnO
4
v lm mt mu Br
2
/CCl
4
. Tin
hnh hydro ha xc tc trong iu kin m du s nhn c indan C
9
H
10
v trong iu kin mnh hn th
c C
9
H
16
. Khi oxygen ha indene c acid phthalic.
a. Xc nh indene, indan, C
9
H
16
v vit cc phng trnh phn ng xy ra.
b. T indene, hy iu ch azulene C
16
H
26
O.
Bi 13: Cho cumene tc dng vi CH
3
Cl/AlCl
3
thu c cc sn phm monomethyl ha trong c A.
Khi cho A tc dng vi KMnO
4
un nng thu c cht B c cng thc C
8
H
4
O
4
K
2
. Cho A tc dng vi
Br
2
(xc tc bt Fe) thu c hai sn phm mono-Br C v D. Vit cng thc cu to, gi tn A, B, C, D
v hon thnh cc phng trnh phn ng minh ha.
Azulene


Bi 14: Cho cetone (I) C
5
H
10
O tc dng vi ethylmagnesiumbromide ri tch nc hp cht carbonyl to
thnh thu c alkene (II), cht ny ozone ha ri thy phn cho diethycetone v acetaldehyde. Vit
cu trc ca cc hp cht (I), (II).
Bi 15: Vit phng trnh phn ng ca isobutylchloride vi:
a. AgOH.
b. H
2
O (khi un si).
c. KOH/C
2
H
5
OH.
d. 1. KCN ; 2. H
3
O
+
.
e. NH
3
(un trong ng hn kn).
f. Na kim loi trong hexane.
g. Mg trong ether khan.
h. CH
3
COONa.
i. KHS.
Bi 16: Methyl ether ca p-cresol (A) c cha O
18
l mt hp cht qu khng may b trn ln vi
iodobenzene. Hy dng phng php thun tin nht c th tch ring hai cht trn. Bit nhit si
ca hai cht gn bng nhau v lng cht qu t nn khng th dng phng php sc k iu ch.
Bi 17: Cht A c cng thc phn t l C
9
H
14
. Khi oxygen ha bng K
2
Cr
2
O
7
/H
2
SO
4
ta thu c
cetodiacid X mch thng (c t hn A mt carbon), A cng hp H
2
to ra n-propylcyclohexane. A phn
ng vi KMnO
4
long thu c Y (190 g/mol) c cng s carbon vi A. Y phn ng vi CH
3
COOH xc
tc H
2
SO
4
ch to cht Z (C
15
H
24
O
7
). Vit phng trnh phn ng, xc nh A.
Bi 18: Tm cc cht A, B, C, D, E, F v vit cc phng trnh phn ng xy ra theo s sau:
Na2Cr2O4

2 2
o
3
Cl ,1mol H O
FeCl t ,P
Benzen A B
(1 mol)

E
Fe / HCl
F
Bi 19: Oxygen ho hydrocarbon thm A (C
8
H
10
) bng oxygen c xc tc cobalt acetate cho sn phm B.
Cht B c th tham gia phn ng: vi dung dch NaHCO
3
gii phng kh CO
2
; vi ethanol (d) to thnh
D ; un nng B vi dung dch NH
3
to thnh E. Thy phn E to thnh G, un nng G nhit khong
160
o
C to thnh F. Mt khc, khi cho B phn ng vi kh NH
3
(d) cng to thnh F. Hy vit cc cng
thc cu to ca A, B, D, G, E v F.
Bi 20: 3iodo2,2dimethylbutane khi phn ng vi AgNO
3
trong C
2
H
5
OH s cho 3 sn phm. Vit
cng thc cu to ca 3 sn phm y v cho bit sn phm no chim t l ln nht.
Bi 21: m-Fluorisopropylbenzene (I) c tng hp theo 8 bc i t benzene (A). Hy hon thin s
phn ng ny:
o
2 3 3 2 2 2
4
+Me CHBr/AlCl HNO +Br /Fe HNO H O 6[H] t Mg
HBF
A B C D E F G H I
Bi 22: Xut pht t Bromobenzene cha C
14
v tr 1 v cc cht v c cn thit khng cha C
14
, hy
iu ch cc hp cht thm cha C
14
v tr 3.
a. Aniline.
b. Iodobenzene.
c. Acid benzoic.

HNO3 1:1
C
2[ H]
D

Bi 23: Ephedrine (G) l mt hot cht dng lm thuc cha bnh v h hp c chit t cy ma hong.
Ephedrine c tng hp nh sau: C
6
H
6
3
AlCl / HCl , CO
D

OH , NO CH CH
2 2 3
E
Ni / H
2
F
Br CH
3
G
a. Vit cng thc cu to ca D, E, F v G trong s trn.
b. Vit c ch phn ng ca cc giai on to thnh D v E.
c. i t benzene, acid propanoic v cc tc nhn cn thit khc, hy a ra mt s tng hp
ephedrine.
Bi 24: Vit cng thc cu to sn phm cui (nu c) ca cc phn ng sau:

Bi 25: Vit cc phn ng tng hp sn phm t cc cht ban u cho di y:

************************************************

Part 6 HNG DN GII
-------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------

Bi 1:
a. Do nguyn t Cl c hiu ng +C.
b. Do nh hng y in t ca O, cng hng lm cho cc v tr o-, p- c th mang in tch m
(cng thc gii hn).
c. Do nh hng ht in t ca nhm CHO lm cho v tr o-, p- c th mang in tch dng (cng
thc gii hn).
d. Do hiu ng +C ca nhm OH.
e. Do nguyn t Cl c hiu ng +C.
Bi 2: (3) > (2) > (1).
Bi 3: Vit cc sn phm to thnh:

Bi 4:
a. Br(CH
2
)
3
pC
6
H
4
CH
2
OH.
b. C
6
H
5
CH
2
OH.

Bi 5:
a. C
6
H
6

3 2 3
o
2
3 3
1.CH CH Cl / AlCl
2.Br ,t
3.(CH ) COOK
4.HBr,ROOR
5.HC CLi
C
6
H
5
CH
2
CH
2
CCH.
b. C
6
H
5
CH
3

2 3
2 2 7
2
3
1.Cl / FeCl
2.Na Cr O
3.SOCl
4.NH
p-ClC
6
H
4
CONH
2
.
c. C
6
H
5
CH
3

4
2
6 5 3 3
2 2 7
3 2 4
1.KMnO / OH
2.SOCl
3.C H CH /AlCl
4.Na Cr O
5.CH OH/H SO
C
6
H
5
COpC
6
H
4
COOCH
3
.
d. C
6
H
5
CH
3

3 2 4
2 3
o
2
2 2 7 2 4
1.SO ,H SO
2.Br ,FeBr
3.H O,t
4.Na Cr O / H SO
Acid 2,6dibromobenzoic.
Bi 6: Cng thc cu to ca A l: C
6
H
5
C CH .
Bi 7:
2
Na S HBr
2 2 2 3 2 2 2
CH CHCH CH OH CH CHBr CH CH CH Br Metylthiophene = .

Bi 8:

Bi 9: Hon thnh cc chui phn ng:
a.
3 2
H O SO Cl KCN
3 3 3 3 3 3 3 3
CH CHOHCH CH CHClCH CH CHCNCH CH CHCOOHCH .
+

b.
2 2
CH CH KCN/ alcohol
2 4 2 2
I(CH ) I CH CH CH CH cyclohexene.
=
= =
Bi 10:
a. CH
3
CH
2
COCH
2
CH
3
.
b. CH
3
COCH
2
CH
3
.
c. C
2
H
5
CHCH
3
C CMgBr + C
2
H
6

d. CH
3
COOC
2
H
5
.
e. (C
2
H
5
)
2
C(OH)CH
3
.
Bi 11: Cho bit san phm ca cc phn ng:

Bi 12:
a. Cng thc cu to:


b. iu ch:

Bi 13: A l p-methylcumene. Cc phn ng:
A + 8KMnO
4

o
t
p-KOOCC
6
H
4
COOK (B) + 2K
2
CO
3
+ 8MnO
2
+ 2KOH + 4H
2
0.
A
2
Br (Fe)
HBr
+
C + D
Trong : C l o-Bromo-p-methylcumene. D l m-Bromo-p-methylcumene.
Bi 14: Cng thc cu to cc cht: (I) l diethylcetone. (II) l 3ethylpent2ene.
Bi 15:
a. CH
3
CHCH
3
CH
2
OH.
b. CH
3
CHCH
3
CH
2
OH.
c. CH
3
CHCH
3
=CH
2
.
d. CH
3
CHCH
3
CH
2
COOH.
e. CH
3
CHCH
3
CH
2
NH
2
.
f. CH
3
CHCH
3
CH
2
CH
2
CHCH
3
CH
3
.
g. CH
3
CHCH
3
CH
2
MgCl.
h. CH
3
CHCH
3
CH
2
OCOCH
3
.
i. CH
3
CHCH
3
CH
2
SH.
Bi 16: Ha tan hn hp trong ether v thm mt lng Mg va , khi iodobezene chuyn thnh
phenylmagnesiumiodide. Thm nc vo hn hp sau phn ng, khi phenylmagnesiumiodide c th
chuyn thnh benzene trong khi methyl ether ca p-cresol khng thay i. Hn hp lc ny gm c
Benzene (
o o
s
t 80 C = ) v methyl ether ca p-cresol (
o o
s
t 175 C = ) c th phn tch d dng bng phng
php chng ct.
Bi 17:
- T d kin A cng hp H
2
n-propylcyclohexane v oxygen ha bng K
2
Cr
2
O
7
/H
2
SO
4
ta thu
c cetodiacid X mch thng (t hn A mt carbon) => A c t nht mt lin kt i u mch.
- V X l cetodiacid => A c 2 lin kt i hoc 1 ni i trong vng v phi c nhm:
C C = CH C
C
- A phn ng vi KMnO
4
long thu c Y (190 g/mol) c cng s carbon vi A => s nhm OH
trong Y l (M
Y
M
A
)/17 = 4 => CTPT ca Y l C
9
H
14
(OH)
4
.
- Y phn ng vi CH
3
COOH xc tc H
2
SO
4
ch to cht Z (C
15
H
24
O
7
) => Z c 3 nhm ester ca
acid acetic v trong phn t cn 1 nhm OH khng to ester. Nhm OH lin kt vi C (III).

- Vy cng thc cu to ca A l:

- Vit cc phng trnh phn ng da vo A l hp cht va tm c trn.
Bi 18: Hon thnh s phn ng:
A l chlorobezene.
B l phenol.
C l p-benzoquinone.
D l hydroquinone.
E l p-nitrophenol.
F l p-aminophenol.
Bi 19: Cng thc cu to ca cc cht:
A B
CH
3
CH
3
C
C
O
O
O

D
C
O
C
O
O
C
C
O
O
OC
2
H
5
OC
2
H
5
+ C
2
H
5
OH

ftalimit F
C
C
O
O
O
+ NH
3
(kh, d- )
C
C
O
O
N H

C
C
O
O
NH
2
OH
F
C
C
O
O
N H
160
O
C
G

Bi 20: (CH
3
)
3
CCHICH
3
+ Ag
+
(CH
3
)
3
CC
+
HCH
3
+ AgI.
- (CH
3
)
3
CC
+
HCH
3

2 5
C H OH
(CH
3
)
3
CCH=CH
2
(A).
- (CH
3
)
3
CC
+
HCH
3
(chuyn v CH
3
) CH
3
C
+
CH
3
CH(CH
3
)
2
2 5
C H OH
(CH
3
)
2
CH=CH(CH
3
)
2

Sn phm (B) l chnh.
- CH
3
C
+
CH
3
CH(CH
3
)
2
2 5
C H OH
CH
2
=C(CH
3
)CH(CH
3
)
2
(C).
Bi 21: Hon thnh s phn ng:
A l benzene.
B l cumene.
C l p-bromocumene.
D l p-bromo-m-nitrocumene.
E l p-bromo-m-aminocumene.
F l p-Br-m-
+
N
2
BF
4
C
6
H
3
CH(CH
3
)
2
.
G l p-bromo-m-fluorcumene.
H l m-fluor-p-magnesiumbromocumene.
Bi 22: S tng hp
a. Aniline:


b. Iodobenzene:

c. Acid benzoic:

Bi 23:
a. Tng hp ephedrine:

b. C ch phn ng:
C ch phn ng to thnh D: phn ng th electrophile vo nhn thm, S
E
:

C ch phn ng to thnh E: phn ng cng nucleophile vo nhm carbonyl, A
N
:

c. S tng hp khc i t acid propanoic v cc tc nhn cn thit khc:


Bi 24: Vit cng thc cu to sn phm cui (nu c) ca cc phn ng:

Bi 25: Vit cc phn ng tng hp:

************************************************


Part 7 ALCOHOL PHENOL
ALDEHYDE CETONE

-------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
Bi 1: Cho cc alcohol: (1) p-CH
3
-C
6
H
4
-CH
2
OH , (2) p-CH
3
O-C
6
H
4
-CH
2
OH, (3) p-CN-C
6
H
4
-CH
2
OH v
(4) p-Cl-C
6
H
4
-CH
2
OH. So snh kh nng phn ng ca cc alcohol trn vi HBr v gii thch.
Bi 2: Cho s cc phn ng sau:
HCHO H
2
O
OH
OH
-
A
B
NaCN
DMF
C
O
Cl
D1 + D2 + E (sn phm ph)

Hy vit cng thc cu to ca A, B, C, D1, D2 v E. Bit E c cng thc phn t C
19
H
22
O
5
N
2
.
Bi 3: Hp cht A (C
4
H
6
O
3
) quang hot, khng tham gia phn ng trng bc, tc dng vi anhydride
acetic to ra dn xut monoacetate. Khi un nng vi methanol, A chuyn thnh cht B (C
5
H
10
O
4
). Di
tc dng ca acid v c long, B cho methanol v C (C
4
H
8
O
4
). C tc dng vi anhydride acetic to ra dn
xut triacetate, tc dng vi NaBH
4
to ra D (C
4
H
10
O
4
) khng quang hot. C tham gia phn ng trng bc
to thnh acid carboxylic E (C
4
H
8
O
5
). X l amide ca E bng dung dch long sodium hypochlorite to ra
D-(+)-glyceraldehyde (C
3
H
6
O
3
) v ammonia.
Bi 4: Vit cng thc cu to cc sn phm hu c A, B, C v D trong s sau:

HBr
A
Br
3.
1. Li
2. CuI
B
(NBS)
C
N
2
H
4
/O
2
D
KOH
C
2
H
5
OH
CH
2
CH
2
C
O
C
O
NBr

Bi 5: Xc nh cc cht t A n G v hon thnh cc phng trnh phn ng trong chui bin ha sau:

KMnO
4
(c nng) H
2/
Pt 1. CH
3
MgCl

C
10
H
16
(G) Methyl cyclopentane 2. H3O
+

H
2
SO
4
(un nng)

C
10
H
18
O (F)
3
1.Mg,ether HBr
5 9 2.Cy
3.H O
C H Br( )
+
E

cl opentanone

6 5
C H COOOH
C
5
H
8
O (C)

Bi 6: Thc hin dy chuyn ha sau:

o
2 4
2 2
PhCHO 1.BuLi
2 3 2.Ethyl trans But 2 enoate H
H SO Ni,Raney H ,t
H H O
HS (CH ) SH
+
+

A B
C D E

Cyclohexanol
o o
3 2 4 2 4
3
1.CH MgCl H SO ,t H SO ,t
6 12 6 10 6 12
2.H O
C H O( ) C H ( ) C H O( )
+
A B D

Bi 7: T nha thng, ngi ta tch c cht hu c (X) v chuyn ha (X) theo s sau:

Bit A c cng thc phn t l C
9
H
14
O.
a. Vit cng thc cu to cc sn phm hu c A, B, C
1
, C
2
, C
3
, D, E.
b. Sn phm no c to thnh ng phn v ch r s lng ng phn ca mi sn phm.
Bi 8: Hp cht hu c A cha 79,59 % C ; 12,25 % H ; cn li l O ch chim mt nguyn t trong phn
t. Ozone phn A thu c HOCH
2
CH=O ; CH
3
[CH
2
]
2
COCH
3

v CH
3
CH
2
CO[CH
2
]
2
CH=O. Nu cho A
tc dng vi Br
2
theo t l mol 1:1 ri mi ozone phn sn phm chnh sinh ra th ch thu c hai sn
phm hu c, trong c mt cetone. un nng A vi dung dch acid d dng thu c sn phm B c
cng cng thc phn t nh A, song khi ozone phn B ch cho mt sn phm hu c duy nht.
a. Xc nh cng thc cu to v gi tn A.
b. Tm cng thc cu to ca B v vit c ch chuyn A thnh B.
Bi 9: Vit cc phng trnh phn ng theo s sau:
C (ethylene glycol diacetate)
2HCHO
o
P,t ,xt
A
2
H ,xt
B D (poliether)
E
2
O ,xt
F (acid a chc)
2( )
Ca(OH)

G
Bi 10: Khi cho cis v trans-3,3-imethyl-2-bromocyclohexanol phn ng nhanh vi base mnh s thu
c 2 sn phm ring bit. Sn phm to thnh t cis-bromoalcohol c vn hp th 1710 cm
-1
, cn sn
phm kia khng c vn hp th ny v cng khng c vn hp th 3350 cm
-1
. Xc nh cng thc cu
to ca cc sn phm trn.
Bi 11: Hp cht A phn ng vi PCl
3
cho ra B, kh ha B bng H
2
/Pd nhn c benzaldehyde. Mt
khc cho B tc dng vi NH
3
c C, x l C vi Br
2
trong mi trng kim c D. T B c th nhn
c E bng cch cho phn ng vi benzene xc tc AlCl
3
. E chuyn thnh F khi x l vi
hydroxylamine, trong mi trng acid F chuyn thnh G. Vit cng thc cu trc cc hp cht trn.
Bi 12: Vit cng thc cu trc ca cc sn phm trung gian v dng mi tn ch r s tng tc ca
nhn vi trung tm phn ng:
OEt ph vng HOEt OEt khp vng OEt OEt H
+
X A B C D E F G Y
Trong X, Y ln lt l:
(X) (Y)
d
Trng ngng
+X
+ CuO, t
o


Bi 13: Tin hnh ngng t gia benzaldehyde v ethyl methyl cetone ln lt trong mi trng acid v
mi trng base ngi ta thu c 2 sn phm khc nhau. Vit CTCT cc sn phm to thnh, gii thch.
Bi 14: Hp cht A C
4
H
8
O
3
quang hot, tan tt trong nc to thnh dung dch phn ng acid vi giy
qu. un mnh dung dch, A chuyn thnh cht B C
4
H
6
O
2
khng quang hot tan va phi trong nc v
cng cho phn ng acid vi giy qu. B phn ng vi KMnO
4
mnh lin hn A. Oxygen ha A bng
dung dch H
2
CrO
4
long s thnh cht lng bay hi C C
3
H
6
O. C khng phn ng vi KMnO
4
nhng cho
phn ng vi I
2
trong dung dch kim. Vit CTCT cc cht v phng trnh phn ng xy ra. Cc d kin
trn iu kin xc nh cu trc ca A cha, gii thch.
Bi 15: Hp cht hu c A c cng thc C
17
H
30
O b oxygen ha nh cho 2 acid l: acid octandioic v
acid nonandioic. Hy gi tn A theo danh php IUPAC v chuyn hn hp ng phn ca n thnh cis-A.
Bi 16: Hp cht X C
6
H
9
OBr phn ng vi methanol trong mi trng acid sinh ra Y C
8
H
15
O
2
Br. Cho Y
phn ng vi Mg trong ether khan, sau cho phn ng tip vi aldehyde formic c cht E. Thy phn
E trong mi trng acid c F, dehydrate ha F thu c 2-vinylcyclopentanone
a. Xc nh CTCT ca X
b. Nu mun iu ch F t X c nht thit phi qua cc giai on nh trn khng, v sao.
Bi 17: C 5 l khng nhn c k hiu t A n E cha ring l 5 hp cht thm sau:
C
6
H
5
COCH
2
CH
3
, C
6
H
5
COOH, C
6
H
5
COCH
3
, C
6
H
5
CH(OH)CH
3
v C
6
H
5
CHO. Da vo cc kt qu th
nghim sau y nhn bit ha cht c trong mi l:
Cho vo mi l 1 git dung dch K
2
Cr
2
O
7
/H
2
SO
4
ri lc u. Sau vi pht thy l A v C bin i
dung dch mu da cam thnh xanh lc.
Cho vo mi cht mt t dung dch NaOH long th ch ring l B tan c.
Khi cho tc dng vi I
2
trong dung dch kim th l A v E cho kt ta vng.
L C, D v E u tc dng vi 2,4-dinitrophenylhydrazine cho kt ta , da cam.
Bi 18: C 4 hp cht thm: C
6
H
5
OH ; C
6
H
6
; C
6
H
5
CH
3
; C
6
H
5
NO
2
. Xt bng sau:
Cht phn ng A B C D
Nc Br
2
Khng phn ng C phn ng Khng phn ng Khng phn ng
Br
2
/Fe C phn ng
Phn ng 0
o
C v
khng cn xc tc Fe
Ch phn ng khi
un nng
C phn ng
HNO
3
/H
2
SO
4
C phn ng
Phn ng vi c dung
dch HNO
3
long
Ch phn ng khi
un nng
C phn ng
khng cn H
2
SO
4

a. Xc nh k hiu A, B, C, D cho mi cht.
b. Hy sp xp cc cht theo th t tng dn v kh nng tham gia phn ng th vng benzene.
Gii thch s nh hng ca cc nhm th n kh nng .
Bi 19: T ht tiu ngi ta tch c hp cht A (C
17
H
19
NO
3
) l cht trung tnh. Ozone phn A thu
c cc hp cht: ethadial, B, D. Thu phn B thu c OHC-COOH v hp cht d vng 6 cnh
piperidine (C
5
H
11
N). Cho D tc dng vi dung dch HI c thu c 3,4-dihydroxybenzaldehyde. Hy
xc nh cng thc cu to ca A, B, D v cho bit c bao nhiu ng phn lp th ca A.

Bi 20: T cc cht ban u c s nguyn t carbon 3, vit cc phng trnh phn ng (ghi r iu kin
nu c) iu ch: Acid cyclobutanecarboxylic v Cyclopentanone.
************************************************
Part 7 HNG DN GII
-------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
Bi 1: Phn ng gia cc alcohol cho vi HBr l phn ng th theo c ch S
N
. Giai on trung gian
to carbocation benzylic. Nhm OCH
3
y electron (+C) lm bn ho carbocation ny nn kh nng
phn ng tng. Nhm CH
3
c (+I) nn cng lm bn ha carbocation ny nhng km hn nhm OCH
3

v (+C) > (+I) . Cc nhm Cl (-I > +C) v CN (-C) ht electron lm carbocation tr nn km bn do
vy kh nng phn ng gim, nhm CN ht electron mnh hn nhm Cl.
Vy sp xp theo trt t tng dn kh nng phn ng vi HBr l:
p-CN-C
6
H
4
-CH
2
OH < p-Cl-C
6
H
4
-CH
2
OH < p-CH
3
-C
6
H
4
-CH
2
OH < p-CH
3
O-C
6
H
4
-CH
2
OH.
Bi 2: S iu ch p-hydroxyphenylacetamide
HO HO
CH
2
CN
HO
CH
2
OH
HO
CH
2
CONH
2
HCHO
OH
-
H
2
O NaCN
DMF
A B C

OH
C D1 D2
H
2
NCOCH
2
+ O
Cl
O
H
2
NCOCH
2
O
O
H
2
NCOCH
2
Cl
OH

Sn phm ph:
C
19
H
22
O
5
N
2
O
H
2
NCOCH
2
O
OH
CH
2
CONH
2

Bi 3: S chuyn ha gia cc cht:
MeOH
M
e
O
H
CHO
CH
2
OH
H OH
C
CH
2
OH
CH
2
OH
CH
2
O
MeO
O
O
CHO
CH
2
OH

D-Glyxeraldehit E
COOH
CH
2
OH
CH
2
A B D

D-Glyceraldehyde

Bi 4: Cng thc cu to cc sn phm:

Bi 5: Cng thc cu to cc cht trong s :

Bi 6: Cng thc cu to cc cht trong s :


Bi 7:
a. Cng thc cu to sn phm:

b. Cc sn phm to thnh c ng phn:
- C
3
c 2 ng phn quang hc
- C
2
c 4 ng phn quang hc
- D c ng phn E, Z.
Bi 8:
79, 59 12, 25 8,16
13: 24:1
12 1 16
= = = => A c cng thc phn t l C
13
H
24
O
T sn phm ozone phn, tm ra 2 cng thc cu to c th ph hp:

T sn phm Br ha ri ozone phn => A
1
ph hp v:

Tn ca A: 3-Ethyl-7-methyldeca-2,6-diene-1-ol


b. B phi l hp cht mch vng cha mt ni i trong vng, B sinh ra t A do phn ng ng vng

Bi 9:

o
o
p,t ,xt
2
xt
2 2 2 2
3 2 4 2 3 2 2 4
trng ngung
2 2 2 2 n 2
t
2 2 2
xt
2
2HCHO HOCH CHO ( ).
HOCH CHO H HOCH CH OH ( ).
2CH COOH C H (OH) (CH COO) C H ( ).
HOCH CH OH ( OCH CH ) ( ) nH O.
HOCH CH OH 2CuO OHC CHO ( ) 2H O+2Cu.
OHC CHO O
+
+
+
+ +
+
A
B
C
D
E
2 2 4 2
HOOC COOH ( ).
HOOC COOH + Ca(OH) CaC O ( ) 2H O.

+
F
G

Bi 10:
- trans-3,3-imethyl-2-bromocyclohexanol khng b tch HBr m c th phn ng S
N
2
ni phn t

- cis-3,3-imethyl-2-bromocyclohexanol tch HBr to enol khng bn chuyn thnh cetone (h bin
ceto-enol) c vn hp th 1710cm
1
.

Bi 11:
- A l PhCOOH.
- B l PhCOCl.
- C l PhCONH
2
.
- D l PhNH
2
(+CO
2
).
- E l PhCOPh.
- F l Ph
2
C=NOH
- G l PhCONHPh.
(F G chuyn v Beckman)


Bi 12: Vit cng thc cu trc ca cc sn phm trung gian v dng mi tn ch r s tng tc ca
nhn vi trung tm phn ng:

Bi 13:
- Trong mi trng base:
o
OH
6 5 3 2 3 6 5 2 3 2
t
C H CHO CH COCH CH C H CH CHCOCH CH H O
+ = + .
H ca CH
3
c

tnh acid mnh hn H ca CH
2
.
- Trong mi trng acid:
o
H
6 5 3 2 3 6 5 3 3 2
t
C H CHO CH COCH CH C H CH C(CH ) COCH H O.
+
+ = +
Khi c xc tc acid, cetone s b enol ha m CH
3
=C(OH)CHCH
3
bn hn.
Bi 14:
- C l acetone CH
3
COCH
3
.
- A l CH
3
CHOHCH
2
COOH.
- B l CH
3
CH=CHCOOH (cis/trans).
- iu kin xc nh A v ch c cetoacid th nhm COOH mi d b decarboxyl ha
v vy A ch c th l acid 3hydroxybutanoic thay v acid 2hyroxybutanoic.
Bi 15:

Vy A l cycloheptadex9enone.

Chuyn hn hp cc ng phn v cis:
o
2
2 4 2
2 5
2 2 5
3
1.Br / 20 C
2.C H (OH) / H
3.KOH/ C H OH
4.H , Ni / C H OH
5.H O
(transv cis) cis
+
+
A A
Bi 16:
a. Cht Y cha nhiu hn X 2 nguyn t carbon, 6 nguyn t hydro v 1 nguyn t oxygen, suy ra X
phn ng vi 2 CH
3
OH v tch loi 1 phn t H
2
O dn n s hnh thnh acetal methylic t X.
Cht F sau khi dehydrate ha to ra 2vinylcyclopentanone. Vy F phi c cng thc cu to l:

b. Khi iu ch nht thit phi qua cc giai on trn v nu khng qua giai on to Y th hp cht
c magnesium s phn ng vi nhm C=O. Nu a 1 C qua phn ng vi KCN th nhm C=O
cng c th phn ng vi KCN.
Bi 17:
- A l C
6
H
5
CHOHCH
3

- B l C
6
H
5
COOH
- C l C
6
H
5
CHO
- D l C
6
H
5
COC
2
H
5

- E l C
6
H
5
COCH
3

Bi 18:
a. A l C
6
H
6
; B l C
6
H
5
OH ; C l C
6
H
5
NO
2
; D l C
6
H
5
CH
3

b. Kh nang phn ng th vng benzene tng dn theo th t: C < A < D < B
Gii thich:
- Phn ng th H vng benzene theo c ch S
E
.
- Tc nhn electrophile tn cng vo electron ca nhn thm. Do o nguyn t hay nhm nguyn
t no lm tng mt electron ca nhn benzene (nht l v tr ortho-, para-) phn ng cng d
dng.
- Ly C
6
H
6
lm mc so snh, ta thy nhm CH
3
c hiu ng +I v nhm OH c nhm +C y
electron mnh hn nhm CH
3
. Hai nhm ny lm tng mt electron ca nhn thm ti cc v tr
ortho-, para-. V vy ta c phn ng th ca B > D > A.
- Nhm NO
2
c hiu ng I, C ht electron mnh v lm gim mt electron ca nhn thm,
lm gim kh nng phn ng th H vng benzene so vi C
6
H
6
=> C < A.

Bi 19: Ozone phn A thu c ethadial chng t trong A c nhm =CHCH= . Thu phn B thu c
OHC-COOH v piperidine, suy ra B c lin kt O=CN v N nm trong vng 6 cnh. D phn ng vi
HI thu c 3,4-dihydroxybenzaldehyde. Vy c cc cng thc cu to:

Trong A c 2 lin kt i, s ng phn hnh hc l 4: ZZ , EE , ZE , EZ.
Bi 20: S iu ch:

************************************************



TI LIU THAM KHO:

1. Bi tp L thuyt v Thc nghim, tp 2: Ha Hc Hu C Cao C Gic NXB Gio Dc 2006.
2. Bi tp Ha Hu C Trn Th Vit Hoa, Trn Vn Thnh NXB i Hc Quc Gia TP H Ch
Minh 2003.
3. B thi HSG Quc gia lp 12 THPT.
4. B thi Olympic 30/4 cc tnh pha nam.
5. Bi tp Ha Hu C, tp 1 Ng Th Thun NXB i hc Quc Gia H Ni 1999.
6. Bi tp Ha Hu C, tp 2 Ng Th Thun NXB Khoa hc v K thut 2008.
7. Bi tp Ha Hu C i Hc Y Dc TP H Ch Minh 2001.
8. Tng hp Hu C Nguyn Minh Tho. NXB i hc Quc Gia H Ni 2001.
9. Mt s cu hi v bi tp Ho hu c - o Vn ch, Triu Qu Hng - NXB i Hc Quc Gia
H Ni.



************************************************
LI M U
Phn 1: HIU NG HA HC
BI TP ...................................................................................................................................... Trang 1
P N ....................................................................................................................................... Trang 3
Phn 2: NG PHN
BI TP ...................................................................................................................................... Trang 7
P N ....................................................................................................................................... Trang 10
Phn 3: C CH PHN NG
BI TP ...................................................................................................................................... Trang 15
P N ....................................................................................................................................... Trang 19
Phn 4: ALKANE CYCLOALKANE
BI TP ...................................................................................................................................... Trang 26
P N ....................................................................................................................................... Trang 28
Phn 5: ALKENE ALKINE DIENE TERPENE
BI TP ...................................................................................................................................... Trang 34
P N ....................................................................................................................................... Trang 39
Phn 6: HYDROCARBON THM DN XUT HALOGEN HP CHT C KIM
BI TP ...................................................................................................................................... Trang 49
P N ....................................................................................................................................... Trang 53
Phn 7: ALCOHOL PHENOL ALDEHYDE CETONE
BI TP ...................................................................................................................................... Trang 58
P N ....................................................................................................................................... Trang 61

TI LIU THAM KHO ...................................................................................................... Trang 64
MC LC ................................................................................................................................... Trang 65

- - - - - - - - - - Ht tp 1 - - - - - - - - - -

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trong A hoc COO

trong B. Sau xy ra qu trnh tch H

] phn ng th lng phn t S

c electron t do nm trn carbon bc III nn

cho carbene ClBrC: ; carbene ny cng vo C = C v

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