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CHNG IA: NG PHN

nh

ngha: l hin tng cng mt cng thc c nhiu cht khc nhau loi:

Phn

ng phn cu to (phng): cng cng thc phn t nhng khc cng thc cu to. ng phn lp th (khng gian gian) ): cng cng thc cu to nhng khc nhau v cch thc sp xp cc nguyn t trong khng gian gian. .

Phn loi ng phn phng


ng phn phng
ng phn mch cacbon
CH3 CH CH3 CH3 CH2 CH CH3 CH2 CH3 CH3 CH2 CH2 CH3

ng phn v tr
CH3 CH OH CH2 CH2 OH CH3

ng phn nhm chc


CH3 CH2 OH

CH3

CH3

ng phn v tr tr: : tnh cht vt l khc nhau (khng nhiu), tnh cht ha hc tng ng. ng phn nhm chc: tnh cht vt l ha hc hon ton khc nhau nhau. .

Phn bit gia h bin v ng phn


C O C H C OH C C O N H C OH N

Ceton

Enol

Amid

Imid

CH

NH

CH

OH

Imin

Enamin

Nitroso

Oxim

Trong mt s trng hp cht hu c c th tn ti cng mt lc hai dng cn bng khc nhau nhau. . S h bin c c l do s dch chuyn ca nguyn t H t nguyn t ny sang nguyn t khc Hai dng h bin khng th tch c do chng chng chuyn ha (bin i) lin tc qua li nh vy h bin khng phi hin tng ng phn phn. .

ng phn lp th (khng gian)

ng phn lp th (khng gian gian) ): cng cng thc cu to nhng khc nhau v cch thc sp xp cc nguyn t trong khng gian gian. . Cn c tn l ng phn cu hnh do cu hnh c nh ngha l cch thc sp xp trong khng gian ca cc nguyn t trong mt phn t. V d: phn t metan c cu hnh t din u.
H H

o C 109 28'

H H H

H H H

M HNH PHN T

biu din (trnh by by) ) cu hnh ca mt phn t hp cht hu c trn mt phng ngi ta c th dng cng thc chiu:
1. 2. 3.

Cng thc phi cnh Cng thc chiu Newman Cng thc chiu Fisher

Cng thc phi cnh


Hai Ni nt Ni

ni trong mt phng c biu din bng nt lin nm pha trc mt phng c biu din bng m nm sau mt phng c biu din bng nt t

=
Sai

* Biu din cng thc phi cnh cho nhiu cacbon cacbon: :
-

Ni sang phi hng ra bn ngoi mt phng Ni sang tri hng ra pha sau mt phng Cc ni c v vung gc nhng tht ra gc ni l 109o28 28 Ni C-C gia v di ra cc nhm th ca 2 tm C sp3 khng chp ln nhau

Thuyt quay gii hn ca ni n s

Ni s c c l do s xen ph gia hai vn o theo hng trc lin nhn. Nh vy ni s c tnh i xng trc ngha l khi xoay 2 vn o xen ph, xen ph hay bn (nng lng) lin kt khng i. Do , 2 nguyn t ca ni s c th xoay quanh lin kt s.

sp3 s

sp3

sp3

C-H

C-C

Dn n hin tng phn t hu c c th tn ti di nhiu cu trng (cu dng khc nhau) nhau). . Cu trng: l cc dng khc nhau ca cu hnh c c do s quay quanh ni n s. V d: xt phn t n-butan

Cu trng i lch

Cu trng che khut bn phn

Cu trng bn lch

Cu trng che khut ton phn

CH3

H H CH3

H H H

CH3

CH3 H

CH3

CH3

CH3 CH3

Cu trng lch bn hn cu trng che khut rt nhiu, trong bn nht l cu trng i lch, cu trng che khut ton phn km bn nht.

Ni l gii hn v khng phi ni s quay t do hon ton m phi quay sao cu trng bn chim lng nhiu hn. S quay trong phn t hp cht hu c l lin tc do ta c th c v s cu trng khc nhau nhau. . Cn phn bit r gia hin tng cu trng v ng phn. phn .

Cu trng bn nht ?

Cng thc chiu Newman


-

Trc C-C c t thng gc vi mt phng chiu (t giy hoc tm bng). C xa c biu din bng ng trn trn, , C gn c biu din bng du chm tm ng trn . Cc ni ca C gn xut pht t tm ng trn trn, , Cc ni ca C xa xut pht t trn ng trn trn. . Cc ni to vi nhau gc 120o.
H H H CH3 H H H H H H CH3 H H

CH3

CH3

CH3 CH3

H H

H CH3

H H H H CH3 CH3 CH3 H H H H

HCH3

Cng thc chiu Fisher


-

Ni dc (Bc-nam nam) ) hng ra pha sau mt phng. Ni ngang (ng-ty ty) ) hng ra pha trc mt phng. Mch cacbon c t trn trc dc, cc ni vit bnh thng. Giao im gia ng ngang v ng dc chnh l tm cacbon cacbon. .
C A B D A D C B A D C B C

A D

C D

A C D

A C

G F G E C D A

A F G E

=
F G E

Trong trng hp nhiu C (t 2C tr ln ln), ), nu dng cu trng lch chiu th d ng t pha no chiu th u khng tha mn cng thc chiu Fisher (khng phi tt c cc ni ngang hng ra pha trc mt phng) do vy thu c hnh chiu sai sai. .

C1

C2

A2

A1

A D1 D1 D2 C1 B1 B1 B2 A2 A D2 C2 B2 A1

Nh vy chiu cng thc chiu Fisher ng ngoi vic chn gc nhn (hay mt phng chiu ng) trong mt s trng hp nu phn t cu trng lch th phi xoay v cu trng che kht ri mi chiu.

A A

D F G

C G E

F E

D A C

Phn loi ng phn lp th

ng phn lp th

ng phn hnh hc

ng phn quang hc

ng phn hnh hc

nh ngha: l nhng hp cht c cng CTCT nhng cch sp xp ca nhng nguyn t hay nhm nguyn t khc nhau i vi mt mt phng quy chiu. Ty vo mt phng qui chiu l mt phng p (mt phng cha ni s v p) hay mt phng vng (xicloankan xicloankan) ) m ta ng phn hnh hc tng ng:
ng phn hnh hc ng phn ca ni i ng phn xiclan

ng phn hnh hc ca ni i
Hin tng ng phn c c l do c cu cng nhc ca ni i khc vi ni n khng th xoay c (nu khng s mt i s xen ph bn ca 2 vn o p). Nh vy nu trn 2 cacbon ni i c 2 nhm th khc nhau th ta s c 2 cch sp xp cc nhm th trong khng gian (i vi mt phng p - mt phng cha ni s v p 2 ng phn hnh hc.

H H H COOH

HOOC

COOH

HOOC

Axit cis-2-butenoic Axit maleic

Axit trans-2-butenoic Axit fumaric

Ban u ngi ta s dng tn gi cis cis-trans, nhng tn gi ny c nhc im l trong trng hp trn 2 cacbon ni i c khng c 2 nhm th ging nhau c nn khng c c tn 2 ng phn quang hc c th c c. .

Cl

Cl

Br

Br

Do cc nh ha hc phi ra mt cch gi tn khc tt hn. l tn gi E-Z.

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Cch gi tn E-Z
Bc 1: So snh u tin ca 2 nhm th trn mi cacbon ni i theo quy tc Cahn Cahn-Ingold Ingold-Prelog Prelog. . Bc 2: Gi tn - 2 nhm th u tin cng pha (Z) - 2 nhm th u tin khc pha (E) - (E), (Z) c t trong du ngoc n v t trc tn cht bi du gch ngang () - Trong trng hp c nhiu ni i th ta phi vit km theo s th t ni i. V d: (2E, E,4 4Z) (theo s th t t nh m ln).

Quy tc Cahn-Ingold Ingold-Prelog


- Nguyn t c bc s nguyn t ln hn th u tin hn: H<C<N<O<F<Cl H<C<N<O<F< Cl<Br<I <Br<I - Nu 2 nguyn t ni trn C ni i ging nhau th ta xt n nguyn t k cn.
Cl CH2 CH2OH CH3 F CH2 C CH3 CH3

- Nhm th c ni i hay ni ba c xem nh tng ng vi 2 ni n, 3 ni n.


H C C O C C C C

H C C C

O C C O

C C C C

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V d:
CH3
Cl F Cl I

CH3 H

H
Br I Br F

CH3

(Z)

(E)

(2E, E,4 4E )

Lu l tn gi cis cis-trans v tn gi E-Z trong mt s trng hp s khng trng nhau nhau. . V d:


CH3 H Cl CH3 H CH3 Cl

CH3

trans (Z)

cis (E)

ng phn xiclan
-

Cc hp cht vng no c th c 3, 4, 5, 6, 7, 8, cacbon Nhng vng 3,4 rt km bn (qu cng), trn thc t cc cht vng ch yu l vng 5,6 (bn nht). Vng 7 tr ln rt t gp.

Mo hnh phan t

Cau trang u ai thc te

Dang n gian

Cong thc khai trien phang

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- V d: Hp cht 1-Hidroxi Hidroxi-4-brom brom-ciclohexan c 2 ng phn hnh hc c trnh by dng n gin v cu trng gh.
OH Br H OH H Br

cis-1-Hidroxi-4-bromociclohexan
Br H OH H

trans-1-Hidroxi-4-bromociclohexan
H Br OH H

ng phn quang hc

Nm 1815 1815, , Jean Jean-Baptiste Biot pht hin mt s cht hu c lng hoc dung dch cc hp cht thin nhin nh: ng, axit tartic (dd dd), ), tinh du thng (l) c kh nng lm quay mt phng nh sng phn cc. (trc y ngi ta cng tm thy hin tng ny mt s tinh th v c bt i xng).

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Nhng hp cht ny c gi l nhng cht c tnh trin quang hay c tnh quang hot. Tnh quang hot ca mt s hp cht hu c c gii thch l do tnh bt i xng trong phn t hp cht . C mt s nguyn nhn dn n tnh bt i xng nhng ph bin nht l trong phn t hu c c cha t nht mt C phi i xng hay cn gi l C th tnh (k hiu C*) C*). .

C PX

BX

HTQH

Tnh bt i xng

C nhiu cch bit (hay nh ngha) vt no i xng hay bt i xng. Vt bt i xng l vt khng c bt k yu t i xng no (nh tm i xng, trc i xng, mt phng i xng, ). Mt cch nh ngha khc khc, , vt i xng l l vt trng vi nh ca n qua gng. Ngc li, vt bt i xng l vt khng trng vi nh ca n qua gng.

14

C phi i xng : l C sp3 c cha bn nhm th khc nhau nhau. .

Khng C*

C C*

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- V d: Xt phn t axit lactic

CH3

CH COOH OH

- ng vi mt C*, c th c hai cch sp xp 4 nhm th trn C , hai cch sp xp ny nu trnh by trong khng gian l hai hnh i xng vi nhau qua gng phng v khng trng kht ln nhau nhau. . Nh vy, chng khng phi l cng mt cht m l hai cht khc nhau tc hai ng phn phn. . Trong ha hc ngi ta gi chng l hai i phn.

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GI TN NG PHN QUANG HC R-S

Bc 1: Da trn quy tc Cahn Cahn-Ingold Ingold-Prelog sp xp th t u tin 4 nhm th trn C phi i xng v nh s 1>2>3>4. Bc 2: Chn hng quan st ngc vi nhm c u tin thp nht (4) (tc nhn t C phi i xng n (4). Xem xt nhm 1 2 3 theo chiu kim ng h hay ngc li. Nu cng chiu kim cu hnh R, ngc chiu kim ng h cu hnh S.

Th t u tin tin: : a>b>c>d

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Trng hp c 2 cacbon phi i xng, v d xt hp cht 2-Brom Brom-3clobutan .ng vi 1 C phi i xng ta c 2 cch sp xp l R, S. Nh vy ng vi 2 C phi i xng ta c th c 4 cch sp xp trong khng gian tc c 4 ng phn quang hc.
CH3 Br

Br

CH3 H

i phn
Cl H CH3

Cl CH3

(2S,3S)-2-Bromo-3-clorobutan
H CH3 Br

(2R,3R)-2-Bromo-3-clorobutan
Br CH3 H

i phn
H Cl CH3
Cl H CH3

(2S,3R)-2-Bromo-3-clorobutan

(2R,3S)-2-Bromo-3-clorobutan

Khi trnh by 4 ng phn quang hc trn di dng cng thc chiu Fisher ta thy cng thc chiu ca hai i phn cng i xng vi nhau qua gng phng. Hai ng phn quang hc m khng phi l i phn ca nhau c gi l hai xuyn lp th phn phn. . (1), (2): cu hnh treo treo; ; (3), (4): cu hnh eritro
1CH3 H Cl 2 3 Br H

CH 3 Br H H Cl CH 3

(1)

4CH3

Xuyn lp th phn

(2)

CH3 H H Br Cl CH3
Br Cl

C H3 H H C H3

(3)

(4)

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Nh vy cng nhiu C* ta cng c th c nhiu ng phn quang hc. Quy tc Van Hoff Hoff: : Nu c nC nC*, *, ta s c 2n ng phn quang hc. Nhng quy tc Van Hoff trong mt s trng hp li khng ng. V d: xt hp cht 2,3-Dibrombutan CH3 CH CH CH3

Br
CH3 H Br

Br

CH3 Br

CH3 Br H
Br

CH3 H

Br

H CH3

Br CH3

Hai i phn treo

H CH3

Br

Br CH3

(2S,3S)-2,3-Dibromobutan
C H3 H Br H CH 3 Br

(2R,3R)-2,3-Dibromobutan
CH3 Br H
Br CH3 H

L mt
H Br C H3 H CH 3 Br

Br CH3

Br

H CH3

l do ng phn ny c mt mt phng i xng vung gc vi ni C2-C3. V cng v vy ng phn ny khng c tnh quang hot (khng c tnh trin quang) quang). . Ngi ta khng dng tn gi eritro na m gi ng phn ny l meso meso. .
CH3 Br CH3 Br Meso CH3 H Br

H CH3

Br

Nh vy quy tc Van Hoff khng ng m phi pht biu li l nu mt cht c nC* th c th c ti a 2n ng phn quang hc. Bt k yu t i xng no cng s lm gim s ng phn quang hc. ng phn quang hc no c cha t nht mt yu t i xng s khng c tnh quang hot (khng c tnh trin quang) quang). .

19

Lu khi c tn eritro eritro, , treo treo, , meso cho cc hp cht c 2C*: - Mch cacbon chnh phi t trn trc dc ca cng thc chiu Fisher. Fisher . t C s 1 ln trn cng cng. . - Nu 2 nhm th ging nhau cng bn eritro eritro, , khc bn treo. treo . Nhng khng phi lc no ta cng c c tn eritro eritro, , treo treo. .
1 CH3
Br

Br

Cl

CH 3

CH3

3 4 CH3

CH3

Br H Br CH3

H CH3

Cl

Cl
CH 3

H Cl

Sai

Cl

1 CH3 2
Br

Cl

Br

3 4 CH3 1 CH3

3 4 CH3
H CH3 Br

2 1 CH3

CH3 Cl H

Br

3 4 CH3

Cl

Cch gi tn D,L cho cacbohidrat v amino axit

i vi nhng hp cht ha sinh quan trng nh cacbohidrat v amino axit (ngay c trong trng hp 2C*), phn bit cc ng phn quang hc ngi ta khng dng tn gi eritro eritro, , treo treo, , meso m dng tn gi D,L . Tn gi D,L bt ngun t lc ban u khi nghin cu glicerandehit, glicerandehit , Hermann Emil Fischer chn mt cch c on hp cht hu trin l D-(+) (+)-glicerandehit v hp cht t trin l (L)(L) -(-)-glicerandehit glicerandehit. .
CHO H OH CH2OH D-(+)-glicerandehit OH CHO H CH2OH (L)-(-)-glicerandehit

Da theo quy c ny ny, , ngi ta gi tn cc cacbohidrat khc khc. . Nh vy mun s dng tn gi D,L bt buc phi s dng cng thc chiu Fisher Fisher. .

20

Gi tn D,L cho cacbohidrat cacbohidrat: :


t mch cacbon chnh trn trc dc. t cacbon c mc oxi ha cao nht v tr trn cng (COOH>CHO>(COOH>CHO> -C-OH) (chnh l C s 1). Da trn nhm OH cacbon phi i xng mang s nh v cao nht, nu nm bn tay phi hp cht c cu hnh D, nu nm bn tay tri hp cht c cu hnh L.
H HO H H CHO OH H OH OH CH2OH HO H HO HO CHO H OH H H CH2OH H HO HO H CHO OH H H OH CH2OH H HO HO H CHO OH H H OH CH2OH

D-(+)-glucose CHO OH OH OH CH2OH

L-(-)-glucose CHO H H H CH2OH L-(+)-ribose CHO H H CH2OH

D-(+)-galactose CHO H OH OH CH2OH D-(+)-arabinose HO H H CHO H OH CH2OH

L-(-)-galactose CHO OH H H CH2OH L-(+)-arabinose H HO HO CHO OH H CH2OH

H H H

HO HO HO

D-(-)-ribose CHO OH OH CH2OH D-(-)-eritrose H H

HO HO

HO H

H HO

L-(+)-eritrose

D-(-)-treose

L-(+)-treose

H HO H H

CHO OH S3 H R4 OH R5 OH CH2OH
R2 6

HO H HO HO

CHO H R3 OH S4 H S5 H CH2OH
S2 6

D-(+)-glucose

L-(-)-glucose

(2R,3S,4R,5R)-2,3,4,5,6-pentahidroxihexanal

(2S,3R,4S,5S)-2,3,4,5,6-pentahidroxihexanal

Gi tn D, L cho amino axit axit: : - t mch cacbon chnh trn trc dc. - t cacbon c mc oxi ha cao nht v tr trn cng (chnh l nhm COOH tc C s 1). - Da trn nhm NH2 C* mang s nh v thp nht, nu nm bn tay phi hp cht c cu hnh D, nu nm bn tay tri hp cht c cu hnh L.
COOH COOH H2N H CH2OH L-(-)-serin H COOH H2 N NH2 H CH2OH CH3 D-(+)-serin L-(-)-threonin OH H

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Quy tc s dng cng thc chiu Fisher

Quy tc 1: Nu i ch 2 nhm th bt k ca mt C* trn cng thc chiu Fisher th ta s lm thay i cu hnh ca C* (chuyn sang dng i hnh hnh) ).
H Br R CH3 CH2CH3

i ch ln 1

CH3CH2

S CH3

Br

i ch ln 2
H CH3CH2 R Br CH3

- M rng:

Thay i v tr hai nhm th s l ln lm thay i cu hnh (chuyn sang dng i hnh hnh) ). Thay i v tr hai nhm th s chn ln khng lm thay i cu hnh hnh. .

- Tuy nhin cn lu l nhng iu trn ch ng vi trng hp mt C*, trong trng hp nhiu C th tnh th kt qu s phc tp hn.
CHO H HO H H R S R R OH H OH OH HO HO H H CHO S S R R H H OH OH

CHO H HO H H R S R R OH H OH OH HO H HO HO

CHO S R S S H OH H H

CH2OH (D)-(+)-glucose

CH2OH (D)-(+)-mannose

CH2OH (D)-(+)-glucose

CH2OH (L)-(-)-glucose

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- Quy tc ny rt hu ch trong mt s trng hp khi ta v cng thc chiu Fisher c tn cu hnh, c th chiu ng th gc nhn li v cng kh khn d dn n nhm ln, khi ta c th chn gc chiu d chiu ri i ch s chn ln (thng l 2 ln) c c cng thc Fisher ng ca cht ri c tn cu hnh hnh. .
OH OH

CHO

CH 2OH

CHO

CH2OH H CHO H

OH

CH2OH D

Quy tc 2: Nu xoay cng thc chiu Fisher 1800 trong mt phng th ta s khng lm thay i cu hnh ca cht .
H Br R CH3 CH2CH3

CH3
Xoay 1800 trong mt phng

CH3CH2

R H

Br

Quy tc 3: Nu xoay cng thc chiu Fisher 1800 ngoi mt phng th ta s lm thay i cu hnh ca cht .
H Br R CH3 CH2CH3

Xoay 1800 ngoi mt phng

CH 3 CH 2

S CH 3

Br

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Quy tc 4: Nu xoay cng thc chiu Fisher 900 trong mt phng th ta s lm thay i cu hnh ca cht .
H Br R CH3 CH2 CH3

Br

Xoay 900 trong mt phng

CH3

CH2CH3

Tnh cht ng phn lp th

Cc ng phn lp th: Tnh cht vt l (nhit si si, , nhit nng chy, t khi, ha tan, ch s khc x, ) hon ton ging nhau nhau. . Tnh cht ha hc: hon ton ging nhau nhau. . ng phn quang hc c hot tnh quang hc khc nhau, nhau , hai i phn nu o cng iu kin th mt cht s lm quay mt phng nh sng phn cc sang tri tri, , mt cht s lm quay mt phng nh sng phn cc sang phi, vi tr tuyt i s gc quay bng nhau nhau. . Hot tnh sinh hc khc nhau nhau. .

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CHNG IB: CC HIU NG IN T

Trong ha hu c c hai hiu ng v cng quan trng l hiu ng in t v hiu ng lp th. Hiu ng in t quan trng v n quyt nh phn cc do nh hng n tnh cht vt l, tnh cht ha hc ca hp cht hu c. Hiu ng in t c chia lm 3 loi: hiu ng cm, hiu ng lin hp (cng hng) v hiu ng siu lin hp (siu tip cch).

1. Hiu ng cm (hiu ng ca ni s): 1.1. nh ngha: l hiu ng dch chuyn in t sinh ra do s sai bit v m in ca hai nguyn t hoc nhm nguyn t.

C5 > C4 > C3 > C2 > C1 > X

- X c m in ln hn C X ht i in t ni C1-X, ht i in t ni ca C1-C2, nh hng truyn ngang qua cc ni ha tr lc ht gi l hiu ng cm (nh vy nhm gy hiu ng cm khng ch nh hng ln nguyn t gn trc tip gn n m cn nh hng n nguyn t xa hn).

1.2. Biu din:

+ C > X
1.3. c im: L s phn cc thng trc trng thi cn bn ca mt phn t. Hiu ng cm truyn dc trn dy carbon, cng cng yu dn khi cng xa X, trn thc t hiu ng cm s bng 0 khi lan truyn qua 3 hoc 4 ni (hiu ng cm gim rt mnh theo khong cch v bn cht n l lc Coulomb t l nghch vi bnh phng khong cch). Do C v H c m in gn bng nhau nn xem nh ni C-H khng c hiu ng cm (mc d C-H c phn cc mt t). H < C < I < Br < N < Cl < O < F

1.4. Phn loi: gm c 2 loi


-

Hiu ng cm dng: cho hiu ng y in t (+I), thng l ankyl hoc nhng nhm mang in tch m. Hiu ng cm m: cho hiu ng rt in t (-I), thng l nhng nhm c m in ln hoc nhng nhm mang in tch dng.
CH3 H > < C < CH3
<

<

+I

< S

>

< O

>

C < CH3 CH3

>

< CH2 < CH3 >

< CH3

<

CH3
> C N > > F > > Cl > > C O OH > > Br >

-I

> NR3 >

> NO2 O N O

>

> SO3H O S O O

>

> I>

> OH >

> OR >

> NH2 >

> C O

R >

> C O

OR >

> C C >

>

>

> C CH 2

1.5. ng dng: So snh mnh axit, baz. Gii thch bn ion: ion cng bn khi gn trng thi trung ha in (ngc li, trng thi cng mang in nhiu cng km bn) nhm no cng lm ion gn trng thi trung ha in s lm ion cng bn ngi ta ni nhm c tc dng an nh (lm n nh) ion.
C C carbanion

carbocation
-

Hot tnh hp cht tc (ng hc) phn ng (v d: phn ng cng thn hch ca carbonyl). nh hng phn ng tc thnh phn sn phm chnh, ph (v d: phn ng th thn in t ca cc dn xut ca benzen).

Gii thch tnh axit, baz:

HA cng mnh

H+ + A-

X cng bn

cng giu e- cng mnh

V d:
CH3 CH 2 COOH

4,90 4,76

CH3 CH2 CH2 COOH


CH2 CH2 CH2 COOH

4,82

H CH2 COOH

4,52

CH2

CH CH2 COOH
CH2 COOH

4,35 3,00

Cl
CH3 CH CH2 COOH

HC C

4,05

Br

CH2 COOH

2,86

Cl

V d gii thch bn ion:


CH3 > C < CH3 CH3 III > H

V d gii thch hot tnh ( phn ng) hp cht:

< <
Cl CH2 COOH
CF3 COOH
2,83

CH3 CH2 CH Cl

COOH

2,85

Rt mnh

C < CH3 CH3 II

>

CH2 < CH3

>

CH3

V d gii thch ng hc v nh hng phn ng:

[AB] trng thi trung gian

AB

[A1B1] A + B [A2B2]

A1B1 A2B2

2. Hiu ng lin hp (cng hng) (hiu ng ca ni p): 2.1. Thuyt cng hng: i vi nhiu cht hu c nu ch biu din chng bng mt cng thc Lewis s khng gii thch c rt nhiu tnh cht vt l ha hc ca chng. V d:
Ngn hn ni n thng thng
C O

Mang mt phn tnh ni i


O H

CH2

CH

CH

CH2

Di hn ni i thng thng

H H

H H H H
C

CH 2

CH

CH

CH 2

CH2

CH

CH

CH2

C O

C O

2.2. c im:
-

Phn bit gia h bin v lin hp: cng thc lin hp khng c tht (ch l cng thc) tng tng trnh by mt phn t di dng nhiu cng thc lin hp. Phn t hp cht hu c thc cht l s lai tp hay l trung bnh cng ca tt c cc cng thc lin hp. Tuy nhin s c nhng cng thc lin hp quan trng hn (bn hn) chim t l nhiu hn, c cng thc t quan trng hn chim t l t hn. c im khc vi hiu ng cm: lan truyn lin tip mnh khng gim theo ni, chng no cn tip cch ni p.

2.3. Cc h thng lin hp: a) p-s-p: (ni p tip cch vi nhau bi ni s) Nu ch i in t p no khi u cho s dch chuyn cng c tng ng nhau.
CH2 CH CH CH CH3
CH2 CH CH CH CH3

CH2
-

CH

CH

CH

CH3

CH2

CH

CH

CH

CH3

Nhng nu c nhm gy hiu ng cng hng m (-R) s bt u t nhm ny.


CH3 CH CH C O CH3

CH3

CH

CH

C O

CH3

b) p-s-p:
C O O H

C O

c) p-s-C+:
C CH C

CH

d) p-s-C+:
Cl C

Cl

e) Gc t do - in t p:

CH

CH

2.4. Cch trnh by cng thc lin hp:


-

Tt c cc cng thc lin hp l cng thc Lewis Cch nhau bi du . Du ch chiu di chuyn in t Trong cc cng thc lin hp ch c i in t p hay p l dch chuyn cn tt c cc nguyn t khng thay i v tr. Phi tnh li s in t t suy ra in tch trn tng nguyn t (tuy nhin tng in tch th khng i). Thng ngi ta vit tt hai cng thc lin hp u v cui.
OH
OH OH

OH

OH

OH

OH

2.5. Phn loi:


-

Cng hng m (-R): cho hiu ng rt in t, thng l nhng nhm chc bt bo ha. Cng hng dng (+R): cho hiu ng y in t, thng l nhng nhm mang in tch m hoc nhng nhm c cha nguyn t c i in t t do.
-R NO2 O N O O C O +R S > HN C O > > R > C O OR > C O NH2 > C C > C CH2 > SO3H O S O > C N > C O H > C O OH >

O R

NR F

> >

NH2 Cl

> >

OR Br >

> I

OH

>

* Nhn xt:
-

C ch 2 hiu ng khc nhau. C nhng nhm ch c mt hiu ng. a s cc nhm c hai hiu ng cng chiu, nhng mt s nhm cho hai hiu ng ngc chiu.

+R +I

-R -I

NO2 ,

SO3H ,

N ,

C O

H ,

C O

OH

C O

C O

OR ,

C O

NR2

+R -I

NR2

NH2

OR

OH ,

Cl

Br

HN C O

2.6. ng dng:
-

nh hng ln tnh axit, baz. nh hng ln di ni. nh hng ln hot tnh (kh nng phn ng) hp cht t quyt nh (ng hc) phn ng. nh hng ln nh hng phn ng (v d: phn ng th thn in t ca cc dn xut ca benzen).

3. Hiu ng siu lin hp (siu tip cch):


(sn phm chnh)

CH3 CH2 CH

CH

CH3

HCl

CH3 CH2 CH2 CH Cl

CH3

H H C H
H H C H C C > H

C H

H C C C C > C

H C C C C > C

C C C C C

CHNG II: HIDROCACBON


CHNG IIA: ANKAN
Trong phn t hp cht hu c ngi ta phn bit lm hai phn: phn khung sn cacbon (R) nh ankan, anken, akin, aren (hydrocacbon) to nn phn xng sng cho cc hp cht hu c. Mc d chim khi lng ln nhng cc hydrocacbon t quyt nh tnh cht vt l v c bit l tnh cht ha hc ca hp cht hu c.

Phn nhm chc li quyt nh tnh cht vt l v ha hc ca hp cht hu c.


H C C C

Phn ln cc ni trong hp cht hu c l ni cng ha tr thun ty rt bn, kh ct t hu nh tr v mt ha hc. Phn khung sn cacbon ny phn cc km nn khng tan trong nc, dy cacbon cng di cng km tan. Ngi ta gi chng l u k nc hay a du. Ngc li, phn nhm chc ha hc nu phn cc mnh c gi l u k bo hay a nc.

* Cc bc gi tn quc t ca hp cht hu c: - Trc y tn ca hp cht hu c thng l do nh ha hc tm ra n t cho, tn ny thng c gc Latinh xut pht t ngun gc hay c tnh ni bt ca hp cht . V d: Ure (urine), Morphin (morpheus), acid barbatiric (Barbara), - Nhu cu t ra phi c mt h thng c tn thng nht cho tt c cc hp cht hu c. Hip hi Ha hc thun ty v ng dng quc t quy tc c tn chun (danh php quc t hay IUPAC). - c tn quc t ca hp cht hu c, chng ta phi tin hnh 4 bc.

Bc 1: Xc nh nhm chc chnh. Th t u tin ca cc nhm nh chc c sp xp theo th t sau -COOH > -SO3H > -CO-O-COR > -COOR > -COX > -CONH2 > -CN > -CHO > -COR > -OH > -NH2 > -OR > -O-O-R
CH2 CH OH OH CH2 CH CH CH3 CH3 Cl
CH3 CH OH CH2 CH2 COOH

Bc 2: Xc nh mch chnh l mch cacbon di nht c cha nhm chc chnh. Trong trng hp c nhiu nhm chc chnh th mch chnh phi l mch cha tt c cc nhm chc chnh (hoc cha nhiu nhm chc chnh nht c th).
CH3 CH2 CH2 CH3 CH CH3 CH3 CH2 CH CH2 CH CH3

CH3

CH2 CH

CH2 CH2 CH3

COOH

CH2 COOH HOOC CH2 CH2 CH CH2 CH2 COOH

Bc 3: nh s trn mch chnh theo tun theo cc quy tc u tin di y - nh s sao cho nhm chc chnh c s th t nh nht (trong trng hp c th nhiu nhm chc chnh th phi nh s sao cho tng s th t cc nhm chc chnh l nh nht). - nh s sao cho tng s th t nhm th l nh nht. - Khi va c nhm ankyl v nhm halogen th u tin nhm halogen c s th t nh hn. - Khi c nhiu nhm th tng ng th nh s sao cho nhm th c ch ci u tin ng trc trong vn a,b,c s th t nh hn.

1 2

1
CH2

2
CH

3
CH

4
CH

5 4

6 3

7 2

8
CH2

OHC CH CH2 CH CH CH3 CH3 Cl

CH2 CH2 CH

5
CH3

4
CH3

2
Cl

1
CH3

5
CH3

4
Cl

2
Br

1
CH3

CH CH2 CH

CH CH2 CH

Bc 4: c tn tun theo cc quy tc sau - STT nhm th-tn nhm th + tn mch chnh. - Gia s v s l du phy (,) ; gia s v ch l du gch (-) - Nu c nhiu nhm th ging nhau th thm tip u ng : di, tri, tetra, penta, hexa, ... vo trc tn nhm th v phi lp li STT ca nhm th (STT c vit t nh n ln). i vi cc nhm th phc tp th s dng tip u ng bis, tris, tetrakis, - Cc nhm th c vit theo th t a,b,c (da vo ch ci u tin ca cc nhm th m khng bao gm cc tip u ng di, tri, tetra,

Nhm th
F Cl Br I

Tn gi
Flo(ro) Clo(ro) Brom(o) Iod(o)

Nhm th
OH NH2 NO2 NO CN

Tn gi
Hidroxi Amino Nitro Nitroso Ciano

- Gc hidrocacbon: gc xut pht t ankan tn ankan b an thm yl(il), nhng gc xut pht t anken, akin th ch cn thm yl(il).

Gc
CH3 CH2 CH3 CH2 CH2 CH3 CH CH3 CH2 CH2 CH2 CH3 CH2 CH CH3 CH CH2 CH3 CH3 CH3 C CH3 CH3 CH2 C CH3 CH3 CH3 CH3 CH3

Tn gi
Metyl Etyl n-propyl Isopropyl (i-propyl)

Vit tt
Me Et n-Pr i-Pr

Gc

Tn gi
Ciclohexyl

Vit tt

Phenyl

Ph

CH2 n-butyl Isobutyl (i-butyl) n-Bu i-Bu CH3

Benzyl

o-Tolyl

sec-butyl (s-butyl)

s-Bu

CH3 m-Tolyl

tert-butyl (t-butyl)

t-Bu CH3

p-Tolyl

Neopentyl

Gc
CH2 CH 1 CH 1 CH2 CH2 2 CH 2 CH 3 CH3 3 CH2

Tn gi
Metilen Etenyl (Vinyl) 1-Propenyl 2-Propenyl (Alyl)

Gc

Tn gi

C 1 C 1 CH2

CH 2 C 2 C 3 CH3 3 CH

Etinyl 1-Propinyl 2-Propinyl

i vi cc gc phc tp th ta nh s t u gc ri i tip v ng theo quy lut trn:


CH3 Cl

u gc

1 2 3 CH2 CH2 CH
8

4 CH2

8-(4-clo-3-metylbutyl)

Gc c cha oxi:
Gc Tn gi

OCH3 OCH2 CH3 OCH2 CH2 CH3 CH3 O C CH3

Metoxi Etoxi Propoxi tert-butoxi

CH3 O Phenoxi

Tip u ng ch s C
1 Met 2 3 4 5 6 7 8 Et Prop But Pent Hex Hept Oct 10 Dec 11 Undec 12 13 14 15 16 17 18 Dodec Tridec Tetradec Pentadec Hexadec Heptadec Octadec 20 (E)Icos 30 Triacont 21 Hen(e)icos 31 Hentriacont 22 23 24 25 26 27 28 Docos Tricos Tetracos Pentacos Hexacos Heptacos Octacos 32 40 50 60 70 80 90 Dotriacont Tetracont Pentacont Hexacont Heptacont Octacont Nonacont

9 Non 19 Nonadec 29 Nonacos

100 Hect

II. Gi tn: 1. Tn thng thng: p dng vi cc ankan c mch n gin


CH3 CH CH3
Isopentan

CH2 CH3

CH3

CH CH3

CH2 CH2 CH3

Isohexan

2. Tn quc t: - Cc ch n-, s-, t-, i- (vit tt ca normal, sec-, tert-, iso-) khng c tnh n khi sp th t theo vn a,b,c. Tuy nhin Iso (khng vit tt) v neo (khng c dng vit tt th c tnh)

3. Tn cicloankan: - Nu s cacbon trn dy nhnh s cacbon trn vng th xem vng l mch chnh.
CH CH3 CH3

Isopropylxiclohexan

- Nu s cacbon trn dy nhnh > s cacbon trn vng th dy nhnh l mch chnh.
CH2 CH Cl CH2 CH3

1-Xiclopropyl-2-clobutan

II. Tnh cht vt l: - Khng tan trong nc, ch tan trong cc dung mi hu c khng phn cc, khng tan trong axit, baz long, dung dch H2SO4 lnh. - Nh hn nc. - Nhit si, nng chy thp. S C tng, nhit si, nng chy tng. - Cng s C, ng phn c nhiu dy nhnh hn s c nhit si, nng chy thp hn. C1-C4 : kh C5-C17 : lng C18 : rn

III. iu ch: 1. Hidro ha anken, akin:


C C + H2 Ni t0 C H C H

2H2

Ni t0

C H H

C H H

2. Kh Halogenua ankyl (RX): a. Dng H2 xc tc Pt hoc Ni:


RX + H2 Pt RH + HX

b. Dng H ang sinh:


RX + 2[H] Zn/HCl RH + HX

c. Dng LiAlH4 (Liti nhm hidrua):


RX + LiAlH4 4RH + LiX + AlX3

H Li H Al H H

H Al H H + H + Li

C H

3. Tng hp Wurtz:
2RX + Na t0 R-R + 2NaX

- Ch thch hp iu ch ankan i xng, khi dng 2 halogenua ankyl khc nhau th s to hn hp sn phm hiu sut thp.
RX + RX ' + Na t0 R-R + R'-R' + R-R + NaX

10

4. Phn ng kh cacbonyl (Clemensen):


R C O R C O R' Zn-Hg/HCl R CH2 R' H Zn-Hg/HCl R CH3

5. Kh CO2 ca mui RCOONa:


RCOONa + NaOH CaO to R-H + Na2CO3

IV. Tnh cht ha hc: 1. Phn ng t chy:


C nH 2n+2 + O2 to nCO 2 + (n+1)H 2 O

- Ankan cho kh nng chy tt: cho ngn la sng, khng khi. - Tuy nhin khi s C tng th kh nng chy cng gim. - So snh gia cc ankan > anken > ankin > aren. - Trong trng hp t chy nhng hydrocacbon c kh nng chy km hoc t chy trong iu kin thiu oxy th qu trnh t chy cho nhiu khi, mui than.

11

2. Phn ng halogen ha: - iu kin: nh sng t ngoi hoc 200-400oC - C ch: gc t do qua 3 giai on + Giai on khai mo (nhanh):
Cl Cl

Gc t do

hn

Cl

Cl

+ Giai on truyn (chm):


H
Cl

H
H

+ H

C H

C H

HCl

H H C H

+ Cl

Cl

C H

Cl

Cl

+ Giai on kt thc:
Cl
CH 3

+
+

Cl
Cl

Cl 2
CH 3Cl

CH 3

CH 3

CH 3-CH 3

CH4

+ Cl2

hn

CH3-Cl

HCl

- Trong trng hp ankan c nhiu loi hidro ta s thu c nhiu sn phm halogen ha. Sn phm chnh s l sn phm xut pht t gc t do bn nht .
H Cl C H H C H H C H
C C C C > C H C C > H H C C > H H C H

12

- phn ng: Cl2 > Br2 > I2 (I2 hu nh khng phn ng). Tuy nhin Br2 li c chn lc cao hn Cl2.
CH3 CH2 CH2 CH3 Cl2 CH3 CH2 CH2 CH2 Cl (30%) CH3 CH2 CH2 CH3 Br2 CH3 CH2 CH2 CH2 Br (2%) + + CH3 CH2 CH CH3 Cl (70%) CH3 CH2 CH CH3 Br (98%)

III II I Cl 5 : 3,5 : 1 Br 1600 : 82 : 1

3. Phn ng nitro ha: - Xy ra pha kh, nhit cao, mch cacbon c th b ct t cho hn hp sn phm.
RH + HNO3 RNO2 + H2O

4. Phn ng cracking:
R CH2 CH2 R' to R CH CH2 + R'H

13

CHNG IIB: ANKEN


I. Gi tn:
1. Tn thng thng:
CH2 CH2 CH2 CH Propylen CH3 CH2 CH CH2 CH3 Etylen -butylen CH3 CH3 CH CH CH3 CH3 CH Isobutylen CH2

-butylen

2. Tn quc t:

CH3

Cl

4-Metylxiclohexen

5-Cloxiclohexadien-1,3

II. Tnh cht vt l:


-

Khng tan trong nc, ch tan trong cc dung mi hu c khng phn cc, khng tan trong axit, baz long nhng tan trong dung dch H2SO4 lnh. Nh hn nc. Nhit si, nng chy thp. S C tng, nhit si, nng chy tng. Cng s C, ng phn c nhiu dy nhnh hn s c nhit si, nng chy thp hn. C2-C4 : kh C5-C18 : lng C19 : rn

III. iu ch:
1. Hidro ha ankin:
C C
+ H2 Pd to

C H

C H

2. Kh nc ancol:
-

iu kin: H2SO4 (170oC) hoc Al2O3 (400800oC) Kh nng phn ng: ancol III > ancol II > ancol I

3. Kh HX ca RX (halogenua ankyl):
-

iu kin: KOH/EtOH, to (un nng mnh) Kh nng phn ng: R-I > R-Br > R-Cl > R-F III > II > I

nh hng phn ng: tun theo quy tc Zaixep

4. Kh X2 ca -dihalogenua (vic-dihalogenua):
C X C X + Zn to C C + ZnX2

ng dng: bo v ni i

IV. Tnh cht ha hc:

- Ni p km bn v giu in t d cho in t cho cc tc nhn thn in t phn ng c trng l phn ng cng.

Cng i xng Phn ng cng Cng bt i xng Phn ng ca anken KMnO4 Phn ng oxi ha O3

* Cng cc tc nhn i xng: 1. Phn ng cng H2: 2. Phn ng cng X2:


-

Thng s dng dung mi CCl4 (CHCl3, CH2Cl2). Phn ng xy ra d dng nhit phng. Khng nn s dng d X2 hoc thc hin trong iu kin nh sng v phn ng th s quan trng. Mt in t trn ni i cng ln, phn ng cng xy ra nhanh (cng nhiu nhm y in t gn ni i). ng dng: dng nhn bit ni i.

* Cng cc tc nhn bt i xng: 3. Phn ng cng HX (hidracid):


-

Tin hnh: c th sc kh HX vo anken hoc phn ng trong dung mi chung l axit acetic. Ring HI (KI + H3PO4) nh hng phn ng: quy tc Markonikov. C ch: cng thn in t qua 2 giai on. + Giai on 1: cng thn in t proton vo ni p to carbocation (chm). + Giai on 2: X tc kch vo C+.

Br
C C
H d+

H C C

Br d-

H C C

Br

d+
CH2 CH CH CH2
H

dCl

Butadien-1,3

CH2

CH

CH

CH3

CH2

CH

CH

CH3

(Cng hng p-s-C+)

Cl

Cl

CH2

CH

CH Cl

CH3

CH2 CH Cl

CH

CH3

Sn phm cng 1,2

Sn phm cng 1,4

Quy tc Markonikov
Nm 1869, Vladimir Markonikov kho st nhiu phn ng cng hidracid vo anken v a ra quy tc mang tn ng : Trong s cng hidracid vo ni i C=C, H s gn vo carbon mang nhiu H nht .
C
a b
a

H
a b

C
H+
CH3 CH 3 C CH3

C C H

> CH3

C CH3

> CH3

CH2 >

CH3

Tuy nhin, quy tc Markonikov ch l quy tc kinh nghim, cha tnh n hiu ng in t do trong mt s trng hp s khng d on c hoc d on sai sn phm chnh.
CH2 CH C O
CH2 CH C O H

HCl

CH2 CH2 C Cl
CH2 CH

(Sn phm chnh)

O
C O H

d+

d-

(Hiu ng cng hng)

CH3 CH > C

CH2

CH

C O

H+
CH2

CH2 > C O

(bn hn)

CH2

CH

CH2 Cl

HCl

CH2 CH2 CH2 Cl Cl

(Sn phm chnh)

Cl
CH2 C Cl
CH 3

CH3

HCl

CH3

C Cl

CH3

(Sn phm chnh)

CH

CH 2 > Cl

CH2

CH

CH2 Cl

H+
CH2 CH2 CH2 > Cl

(bn hn)

CH2
CH2 C Cl
CH3

CH
>

CH3

CH3

H+

Cl

C Cl

CH3

(bn hn)

Nm 1933, Morrish S. Kharash v Frank R. Mayo kho st phn ng anken vi HBr vi s c mt ca peroxit (R-O-O-R):
CH2 CH CH 3

HBr Peroxit

CH2 CH2 CH3 Br

(sn phm chnh)

Sn phm chnh khng tun theo quy tc Markonikov m tun theo quy tc Kharash (phn Markonikov). Lu : peroxit ch c nh hng vi HBr (khng c tc dng vi cc tc nhn bt i xng khc nh HCl, HI, H2SO4, H2O, ) C ch: Gc t do.

+ Giai on khi mo:


R O O R
2RO

RO + H

Br

ROH

Br

+ Giai on truyn (chm):


C C
+

Br

C Br

C Br

Br

C Br

C H

Br

+ Giai on kt thc:

C
a b

Br
a b

C
Br

.
H H > H C C >

C Br

C C C C > C

H H C H

C C

4. Phn ng cng H2SO4 v cng H2O: a. Phn ng cng H2SO4 (m c lnh):


-

Tin hnh: sc kh anken vo H2SO4 , lnh hoc trn anken lng vo axit to thnh dung dch ng nht.
O

O
OH

S O

C H

S O

OH

Hidrosunfat ankyl (tan trong H2SO4 d)

Nu tip tc cho hn hp sn phm phn ng vi H2O un nng (thy gii):


O C H C O S O OH
H2O to

C H

C OH

H2SO4

ng dng: + iu ch ancol t anken thu c trong s cracking du ha + Tch mt hp cht ra khi anken - nh hng: tun theo quy tc Markonikov
-

b. Phn ng cng H2O (xc tc H2SO4 l):


-

C ch:
C C

d+ H

dA

C H

+
H O H

C OH

C H

H-A
H

C O H

C H

nh hng: tun theo quy tc Markonikov

10

Nm 1959, H.C. Brown tm ra phn ng cng H2O theo quy tc phn Markonikov - phn ng hidrobor ha
-

C ch: 2 giai on
H
C C
H BH2 C C

+
H

Boran
H C C 3 B
H 2O 2 OH -

H C C

OH

Triankyl boran

H
H

H
H

B
C

H C C

BH2

L phn ng hai giai on nn phi trnh by:


1)BH3 (B2H6) 2)H2O2, OH

11

* Phn ng oxi ha: 5. Phn ng oxi ha vi KMnO4: a. iu kin oxi ha yu (KMnO4 long, lnh):
-1 -2 +7 0 -1 +4

3R

CH

CH2 + 2KMnO4 + 4H2O

3R

CH OH

CH2 + OH

2MnO2 + 2KOH

-diol

b. iu kin oxi ha mnh (KMnO4 , to):


CH3 CH2 CH CH C CH3

CH3

CO2

HOOC-COOH +

C CH3

6. Phn ng Ozon gii:


-

C ch: 3 giai on
O
R1 C R2 C R4 R3

O
O3 CH2Cl2

O C C
chuyn v

R1 R2

R3 R4

Molozonid (khng bn)

R1 C R2 O

O C

R3 R4 O

H2O,Zn hoa c H3O+

R1 C R2 O
+

R3 O C R4

Ozonid

12

Tin hnh: sc kh O3 vo dung dch anken trong dung mi (CH2Cl2, CCl4). Sau cho dung mi bay hi thu c ozonid du st (khng bn, d n) ngi ta khng c lp m cho tc dng ngay vi H2O vi s c mt ca Zn (s c mt ca Zn l ngn H2O2 oxi ha andehit thnh axit). ng dng: Xc nh cu trc anken
H C H H C H
CH CH

CH3 C CH3

CH3

CH

CH

C CH3

Phn ng ozon gii phi tri qua hai giai on nn phi trnh by:
1)O3 2)H2O, Zn

7. Phn ng th H:
CH3 CH CH2 + Cl2 450oC Cl CH2 CH CH2 + HCl

13

CHNG IIC: ANKIN


Ty cu trc ankin m ngi ta chia ankin lm 2 loi l ankin cui dy v ankin gia dy:
R C CH R C C R'

Akin cui dy

Akin gia dy

Axetilen l ankin cui dy duy nht c cu trc i xng. HC CH

I. Gi tn:
1. Tn thng thng: xem nh dn xut ca axetilen
CH3 C CH CH3 CH2 C CH

Metylaxetilen

Etylaxetilen CH3

CH3

CH3

CH3

CH

CH

Dimetylaxetilen

Isopropylaxetilen

2. Tn quc t: - Nu hp cht va c ni i v ni ba th phi nh s u tin ni i c STT nh hn.

II. Tnh cht vt l: - Ging ankan, anken (tan trong H2SO4 lnh). III. iu ch: 1. iu ch axetilen: a. T than v vi:
Than vi CaC2 + 2H2O Than cc 2000oC Cao Ca(OH)2 + C2H2 CaC2 H2O C2H2

b. Oxi ha metan:
6CH4 + O2 1500oC 2C2H2 + 2CO + 10H2

2. Kh 2HX ca dihalogenua ankyl (vic hoc gem): - Tc cht: NaNH2/NH3l (NaNH2 pkb -19; KOH pkb = 0,5).
2Na + 2NH3
H R C H X CH X

Fe(NO3)3 -33oC

2NaNH2 + H2

KOH EtOH

HX

C H

CH X

NaNH2 NH3l

halogenua vinyl

- Phn ng ny thng c dng iu ch ankin cui dy. Nhng v ankin cui dy c tnh axit nn ngi ta thng dng d NaNH2 (3:1) v s thu c mui axetilua natri thay v ankin. Sau cng phi thm vo dung dch axit chuyn ha mui natri thnh akin tng ng.

CH

CH2

X2

CH X

CH2 X

NaNH2 NH3l

CH

+ 2HX

vic-dihaloankan

H R C H

X CH X

NaNH2 NH3l

CH

+ 2HX

gem-dihaloankan

3. Kh X2 ca tetrahalogenua ankyl:
X C X X C X + Zn to

2ZnX2

- ng dng: bo v ni ba

4. Phn ng th axetilua natri vi RX (halohenua ankyl): - L phn ng tng mch


R C CH

NaNH2 NH3l

+ CNa + R' > X

R' + NaX

Ankin cui dy

Axetilua natri

IV. Tnh cht ha hc:

Cng i xng Phn ng cng Cng bt i xng Phn ng ca ankin Phn ng oxi ha (KMnO4)

Phn ng th hin tnh axit yu (ankin cui dy)

* Cng cc tc nhn i xng: 1. Phn ng cng H2: 2. Phn ng cng X2:


X X C X

X2

C X

C X

X2

C X

Dihaloanken

Tetrahaloankan

* Cng cc tc nhn bt i xng: 3. Phn ng cng HX (hidracid): - i vi ankin cui dy:


R C CH

HX

C X
X

CH2

(sn phm chnh)

C X

CH2

HX

C X

CH3

(sn phm chnh)

gem-dihaloankan
R
R C X
R C X CH3

CH
>

CH2

CH2

H+

(bn hn)

- i vi ankin gia dy i xng hoc axetilen:


R C C R

HX

CH

C X

(sn phm duy nht)

X
R C X CH R

HX

C X

CH2

(sn phm chnh)

gem
X
HC CH

HX

CH2 CH X

HX

H3C

CH X

(sn phm chnh) gem

- i vi ankin gia dy (bt i xng):


R C C R'

HX

C X

CH

R'

CH

C X

R'

(hn hp sn phm)
X
R C X CH R'

HX

C X

CH2

R'

(sn phm chnh) gem

X
R CH C X R'

HX

CH2 C X

R'

(sn phm chnh)

4. Phn ng cng H2O (xc tc HgSO4): - i vi axetilen:


HC CH

H2O HgSO4

H2C

CH HO

c/v

H3C

CH O

Axetandehit

- i vi akin cui dy:


R C CH

H2O HgSO4

CH OH

CH2

c/v

C O

CH3

(sn phm chnh)

Metylceton

- i vi akin gia dy:


R C C R'

H2O HgSO4

C OH

CH

R'

CH

C HO

R'

c/v
R C O CH2 R'

c/v +
R CH2 C O R'

Hn hp 2 ceton H2O HgSO4

CH

C HO

c/v

CH2 C O

(sn phm duy nht)

1 ceton

- Lu :
R C CH

1)BH3 2)H2O2, OH-

CH

CH HO

c/v

CH2

CH O

(sn phm chnh)

Andehit

5. Phn ng cng HCN v CH3COOH: - HCN v CH3COOH ch cng mt ln.


R C CH

HCN

C CN

CH2

CH

CH3COOH

CH2

OCOCH3

* Phn ng oxi ha: 6. Phn ng oxi ha bi KMnO4 :


R C C R'

KMnO4

RCOOH

RCOOH

* Th hin tnh axit yu ca ankin cui dy: - Tnh axit ca akin cui dy c gii thch:
HA
R C CH

H+ H+

+ +

AR C C

rt e-

- Tnh axit ca akin cui dy rt yu (axetilen pka = 25)

7. To axetilua kim loi kim vi NaNH2 :


R
R

C
C

CH
CNa

+ NaNH2 + H2O

NH3l

CNa

+ +

NH3 NaOH

CH

8. To axetilua kim loi nng vi CuCl/NH3 v AgNO3/NH3 : - Dng nhn bit ankin cui dy
R R C C CH CH

+ +

[Cu(NH3)2]+ [Ag(NH3)2]+

R
R

C
C

CCu
CAg

+ +

NH3 NH3

+ +

NH4+ NH4+

CHNG IID : ANREN

Quy tc Huckel : + C cu vng phng. + Cng hng lin tc trong vng vng. . + C 4n+ n+2 2 in t p.

CiclooctatetraenCiclooctatetraen -1,3,5,7

Hp cht hydrocarbon thm quan trng nht l benzen. benzen . Vo u th k 15 15, , t vng ng Nam xut qua Chu u mt loi nha (benzoin) c chit xut t mt loi cy b (hoa cnh kin trng - hoa benzoin) lm hng liu. c rt nhiu nh ha hc quan tm nghin cu. Nm 1833 Eilhard Mitscherlich qua s chng ct nha benzoin (axit axetic) iu ch c mt cht m ng t tn l benzin benzin. . 1845, 1845 , Charles Mansfield c lp c benzen t hc n than . Bn nm sau ng pht trin thnh sn xut quy m cng nghip.

Mc d CTPT (C6H6) c xc nh t lu nhng trong mt thi gian di cc nh vn cha xc nh c CTCT ca n n. . 1865 1865, , Friedrich August Kekul ng trn mt bi bo ca Php ngh cu trc ca benzen. benzen . Nm sau, ng vit mt bi bo chi tit hn c trong cp nhiu bng chng c th : ch c 1 ng phn dn xut th mt ln v c 3 ng phn dn xut th hai ln. Cng v sau cc nh ha hc cng tm c nhiu hp cht c lin quan quan. . Hofman ngh t tn nhm hp cht ny l hidrocarbon thm (hng phng).

H H H

1,397

H H

>

Thiu nhit mol chun ca 1,3,5-ciclohexatrien l thuyt l 827 kcal/mol, benzen : 789 kcal/mol thp hn 38 kcal/mol (nng lng cng hng).

CH

CH2

CH2

CH3

CH2

CH3

H2/Ni, 20OC 2-3 atm, 75 pht

H2/Ni, 125OC 110 atm, 100 pht

Benzen khng phn ng vi Br2/CCl4; khng lm mt mu KMnO4 long lnh. Nh vy benzen bn hn mt xiclohexatrien l thuyt v khng th xp vo anken a chc.

I. Gi tn : 1. Tn quc t : - Nu trn nhn thm ch cha nhm th nh : ankyl, halogen, NO2,


Et
Pr
t-Bu

NO 2

Br

Etylbenzen

- Nu trn nhn thm cha nhiu nhm th th phi nh s (theo quy tc) :
Me Me

NO 2 Cl

Br

NO 2

- Tuy nhin nu trn nhn thm cha nhm nh chc ha hc th mch chnh lc ny (bao gm benzen v nhm nh chc ) s c tn ring v nhm nh chc ng nhin nh s 1.
COOH 1
SO 3H 1

CHO 1

Acid benzoic

Acid benzensulfonic

Benzandehit

OH 1

NH 2 1

CH3 1

Phenol

Anilin

Toluen

Me NO2 1 NO 2
Br

OH 1 Br

COOH 1

OH

NO2

2. Tn thng thng :
Me

Me

Ph

Me

Toluen
8 7 6 5 4 1

o,m,p-Xilen
9 1 2 3 5 10 4
2 3

Biphenyl
6 5 7 8

8
2 3

7 6

9 4 10

Naptalen
CH CH2

Antrancen
Me

Phenantren

Me

CH

CH

Me

Me

Stiren

Cumen

o,m,p-Cimen

Mestilen

Stilben

- Ngoi cch nh s ch v tr 2 nhm th trn nhn thm vi nhau ngi ta cn dng cc tip u ng : orto, meta, para vit tt o-, m-, p- (c x nh s.
Y

orto

meta para
Cl Cl

Me

CHO

Br
Cl

- Trong mt s trng hp gi tn aren gp kh khn, c th xem nhn thm lm nhm th.


CH 3 CH (CH2 )4 CH3
C CH
CH 3 C CH CH3

II. II . Tnh cht vt l :


-

a s l cht lng tr cc hp cht a nhn l cht rn. ng phn para thng c im chy cao hn v tan km hn ng phn orto, meta meta. .

III. iu ch : III. 1. Phn ng Wurtz - Fittig :


C6H5Br + CH3Br + 2Na ete khan C6H5CH3 + 2NaBr

2. Phn ng ankyl ha Friedel - Craft :


R + RX AlCl3 to HX +

3. Phn ng ancyl ha Friedel - Craft :


O C + R C O Cl AlCl3 to HCl + R Zn, Hg/HCl CH 2 R

IV. IV . Tnh cht ha hc :


Phn ng trn nhn thm - Phn ng th thn in t Th trn dy nhnh Phn ng Phn ng trn dy nhnh Oxi ha Phn ng cng ca benzen

* Phn ng th thn in t :
-

Cc phn ng th thn in t u c c ch ging nhau. nhau . Chng ch khc nhau bn cht v cch to ra tc nhn thn in t.
E+

E H

H
E+

Cng hng p-s-C+

1. Phn ng nitr ha : - iu kin : HNO3/H2SO4


O O H N O
H O O H N O

H2SO4 H+ HSO4-

H2O

N O

Nitronium

NO2 H

NO2

2. Phn ng sulfon ha : - iu kin : H2SO4 bc khi


H

O S O O

H2SO4
O

S O

HSO4-

H O S O O

HSO4SO3 H H

SO3H

+ H2SO4

Axit sulfonic khng bn c th b thy phn cho ra vng thm v H2SO4.


CH3 CH3 SO3H H2SO4 to + CH3

SO3H
CH3 CH3

H3 O+ to

H2SO4

SO3H

10

3. Phn ng halogen ha :
-

iu kin : Cl2/FeCl3, Br2/FeBr3, I2/CuCl2


Br Br

FeBr3

d+ dBr3Fe...Br...Br

d+ dBr3Fe...Br...Br
Br H

Br

FeBr4-

+ FeBr3 + HBr

4. Phn ng ankyl ha Fridel Fridel-Crafts :


-

iu kin : xc tc AlCl3, to
R + RX AlCl3 to HX +

CH3

Cl

AlCl3

CH3 AlCl4

CH3
CH3 H

CH3

AlCl4-

+ AlCl3 + HCl

11

Phn ng ny rt kh dng n ankyl ha v nhm ankyl l nhm tng hot nhn thm lm cho nhn thm c th nhn thm nhiu nhm ankyl na dn n s a ankyl ha ha. . trnh s a ankyl ha ngi ta thng s dng lng tha benzen benzen. .
C(CH3)3 C(CH3)3

(CH3)3CCl AlCl3, to

C(CH3)3

Nu s dng halogenua c nhiu nhm halogen ta s thu c sn phm c nhiu nhn thm (a nhn) :
2
+ CH2 Cl CH2 Cl AlCl3 to

CHCl3

AlCl3 to

12

Phn ng ankyl ha Fridel Fridel-Crafts khng xy ra trong cc trng hp sau : + Khi R = vinyl hoc phenyl :
Cl +

Cl

+ Khi trn nhn thm c nhng nhm rt in t mnh nh : -NR3, -NO2, -SO3H, -CN, -CHO, COR, -COOH, -COOR hoc cc nhm amino nh : -NH2, -NHR, -NR2.

Phn ng ankyl ha Fridel Fridel-Crafts c mt nhc im l rt kh dng tng hp nhn thm c dy nhnh di do carbocation R+ c th chuyn v t bc I sang bc cao hn (bn hn) :
CH3
CH3

CH2
CH2

CH2
CH2

CH2
CH2

Cl

AlCl3 c/v

CH3 CH3

CH2 CH2

CH2 CH

CH2 AlCl4 CH3

CH3 CHCH2CH3 CH3(CH2 )3Cl AlCl3, to CH2(CH2)2CH3

13

5. Phn ng ancyl ha Fridel Fridel-Crafts :


O C + R C O Cl AlCl3 to HCl + R

C O

Cl

AlCl3

AlCl4

O
CO H

COR

AlCl4-

+ AlCl3 + HCl

Quy tc nh hng trn nhn thm Quy tc Hollowman


H H H
Y

orto

H H

meta para

* Nhm Y nh hng ln phn ng th thn in t ln nhn thm hai yu t : a) phn ng b) nh hng

14

a) phn ng :
OH
Cl
NO2

1000

1 0,033 Vn tc phn ng nitro ha

6x10-8

- Nh vy c 2 loi nhm : + Nhm lm tng vn tc phn ng th thn in t tip theo c gi l nhng nhm tng hot. + Nhm lm gim vn tc phn ng th thn in t tip theo c gi l nhng nhm gim hot.

Nhng nhm tng hot l nhng nhm y t vo trong nhn thm lm cho nhn thm in t hn phn ng tt hn. Nhng nhm gim hot l nhng nhm rt t ca nhn thm lm cho nhn thm km in t hn phn ng km hn.
OCH3 NH C CH3 O R -H F Cl Br I NO CH O C O OR C O OH C O R SO3H

in giu in giu

NH2

OH

C N

NO2

R R R

QUY TAC HOLLEMAN Nho m tang hoat Nho m giam hoat

-I, +R

-I, -R

15

b) nh hng :
-Y -NO2 -COOH -SO3H -Cl -Br -I -Me -OH orto 7 22 21 35 43 45 63 50 meta 91 76 72 1 1 1 3 0 para 2 2 7 64 56 54 34 50

Hiu sut sn phm phn ng nitro ha C6H5Y (%)

NH2 OH

C nhng nhm quyt nh phn ng th thn in t tip theo cho sn phm ch yu l ng phn orto, para c gi l nhng nhm nh hng orto, para para. . C nhng nhm quyt nh phn ng th thn in t tip theo cho sn phm ch yu l ng phn meta c gi l nhng nhm nh hng meta meta. . Hon ton quyt nh bi hiu ng cng hng.
OCH3 NH C CH3 O R -H F Cl Br I NO CH O C O OR C O OH C O R SO3H C N NO2 N R R R

QUY TAC HOLLEMAN Nhom nh hng orto, para Nho m nh hng meta

+R

-R

16

Gii thch :
OH OH OH OH OH

O N

O N

O N

O N

O N

O N

NH2

OH

OCH3

NH C CH3 O

-H

Cl

Br

NO

CH

C O

OR

C O

OH

C O

SO3H

C N

NO2

R R R

QUY TAC HOLLEMAN Nho m tang hoat nh hng orto, para Nhom gia m hoat nh hng orto, para Nhom giam hoa t nh hng meta

Trng hp hai nhm th (C6H4XY)


-

Trng hp 1 : 2 nhm h tr nhau


Me Me

HNO3 H2SO4

NO2

NO2

p-Nitrotoluen

17

Trng hp 2 : 2 nhm nh hng khc nhau


OH OH

Br/FeBr3 to

Me

Me

p-Metylphenol (p(p -Cresol)

* Phn ng trn dy nhnh : 6. Phn ng halogen ha : - c im : phn ng th ti H


Cl CH2 CH2 CH3 CH CH2 CH3

Cl2 as

18

7. Phn ng oxi ha (KMnO4) :


-

c im : oxi ha (ct t mch) ti tt c C


CH2 CH2 CH3 COOH

KMnO4 to

CH3COOH

CH3 CH3 C CH3

KMnO4 to

* Phn ng cng ca benzen (t c) : 8. Phn ng cng H2 :


H H Ni, to p cao H H H H

9. Phn ng cng Cl2 :


Cl Cl Cl2 a s Cl Cl Cl Cl

Hexaclociclohexan

19

CHNG III: ANCOL

Ngi ta phn loi ru lm 3 loi:


R' R CH2 OH R CH OH
Ru I Ru II

R'

C OH
Ru III

R''

OH

Phenol

I. Tn gi: 1. Tn thng thng: rt nhiu cch a) Cch 1: Ancol + tn gc hidrocarbon


MeOH EtOH Me3OH CH2 CH CH2 OH

Ancol metyl

Ancol etyl

Ancol t-butyl

Ancol alyl

CH3

CH

CH

CH2 OH

CH2 OH

Ancol crotyl

Ancol benzyl

HC

CH2OH

Ph

CH

CH

CH2 OH

Ancol propagyl

Ancol cinamyl

- Cch ny cn dng c tn ancol bo


CH3 (CH2)6 CH2OH CH3 (CH2)10 CH2OH

Ancol capryl

Ancol lauryl

b) Cch 2: Ru + tn gc hidrocarbon + ic
CH3 CH3 OH CH3 CH2 OH CH3 C CH3 OH

Ru metylic

Ru etylic

Ru t-butylic

CH3 CH CH2 CH2 OH CH3

CH2 OH

Ru isoamylic

Ru benzylic

c) Cch 3: ly C-OH lm mch chnh v c tn metanol hoc carbinol (t thng dng) :


CH3 CH2 CH CH OH CH3 Ph CH2 OH CH3 C CH3 OH

Metylvinylmetanol

Phenylmetanol

Trimetylcarbinol

- Ngoi ra mt s ancol a chc c tn c bit:


CH2OH CH2 CH2 OH OH CH2 OH CH OH CH2 OH OHCH2 C CH2OH

CH2OH

Etilen glycol

Glycerin

Pentaeritritol

2. Tn quc t:
-

Tn mch hidrocarbon+ol-s th t Ru a chc: diol, triol, tetraol, (-STT)


CH2 CH2 OH OH CH2 OH CH OH CH2 OH

Etandiol-1,2

Propantriol-1,2,3

Ancol vng: Xiclohexanol, xiclopentanol,


OH CH3 OH

Et OH

2-Metylxiclohexanol

2-Etylxiclohexandiol-1,4

Lu : cch gi tn quc t cn cho php mt cch c tn na - xem nhm OH l nhm th (hidroxi) trn mch chnh l hidrocarbon.
CH2 OH CH2 CH2 CH Cl CH2 Cl

1,2-Diclo-5-hidroxipentan

1
CH3

2
CH OH

3
CH Br

4
CH3

4
CH3

3
CH OH

2
CH Br

1
CH3

3-Brombutanol-2

2-Brom-3-hidroxibutan

OH CH2 CH CH2 OH CH2 CH CH OH CH3

2-Propenol-1 (Prop-2-en-1-ol)

3-Butenol-2 (But-3-en-2-ol)

2-Xiclohexenol

II. Tnh cht vt l: 112C: lng, >12C: rn - C kh nng to lin kt Hidro: + Lin phn t nhit si, nng chy cao hn hydrocarbon, halogenua, ete c cng s carbon .V d: etanol (78,9oC), hexan (69oC), Dietylete (34,6oC). + Vi H2O ancol tan rt tt. Tuy nhin s C tng th tan gim. - Metanol v etanol c kh nng ha tan rt nhiu cht hu c k c nhng cht km phn cc dng lm dung mi.
-

II. iu ch: 1. T anken:


H2O/H2SO4l Markonikov

C
1)BH3 2)H2O2, OH phn Markonikov

2. Thy phn halogenua ankyl (mi trng kim):


R-X + H2O NaOH to R-OH + HX

phn ng : R-I > R-Br > R-Cl.

3. T andehit, ceton (kh):

C O

H2

Ni to

CH2

OH

Ru I

C O

R'

H2

Ni to

CH OH

R'

Ru II

4. T hp cht Grignard (c magie):


-

Victor grignard (Php) (Nobel 1912)


R-X + Mg ete khan to RMgX (hp cht Grignard)
- + R-MgX

Mg

MgX

Hp cht Grignard rt hot ng


Ca + MgX

+ Cb

Ca

Cb

tm giu in t

tm thiu in t to ni C-C tng mch

H
- + R MgX +

H+ H2O

R-CH2OH

XMgOH

O -

OMgX
H

1 Mg(OH)2 MgX 2 2

- + R MgX +

R'

R'

H+ H2O

CH OH

R'

XMgOH

O -

OMgX
R'

R'
R''

- + R MgX +

R'

R''

H+ H2O

C OH

R''

XMgOH

O-

OMgX

- + R MgX +

CH2

CH2 O -

CH2

CH2 OMgX

H+ H2O

R-CH2-CH2-OH

XMgOH

RMgX

1) HCHO 2) H3O+

R-CH2OH

Ru I (+1C)

RMgX

1) RCHO 2) H3O+

CH OH

R'

Ru II

R'

RMgX

1) RCOR 2) H3O+

C OH

R''

Ru III

RMgX

1) O 2) H3O+

R-CH2-CH2-OH

Ru I (+2C)

Lu khi thc hin phn ng vi hp cht Grignard khng c c mt cc hp cht c cha hydro axit (d yu) nh : RCOOH, H2O, ROH, RCCH,
R'COOH + RMgX

RH
RH

+
+

R'COOMgX
OHMgX

OH R'OH
R'C

+ +

RMgX RMgX
RMgX

RH

R'OMgX

CH

RH

R'C

CMgX

V hp cht Grignard phn ng vi hi H2O v kh CO2 trong khng kh nn khi va iu ch phi s dng ngay.

III. Tnh cht ha hc:


H O

1. Tnh axit:
ROH RO- + H+

CH3OH > Ru I > II > III pka = 15,4 EtOH(16) Me3COH(18,6) CF3CH2OH: pka = 12,43

Ch phn ng vi kim loi kim m khng phn ng c vi NaOH, KOH,


ROH + Na RONa + 1/2H2
ancolat

RONa + H2O

ROH + NaOH

CH3

CH2

ONa

Etoxit natri

CH3 CH3 C CH3 OK

Baz rt mnh kh proton t-Butoxit kali

2. Phn ng ester ha: - iu kin: xc tc acid proton (H2SO4), to


R-OH
-

RCOOH

H2SO4 to

RCOOR + H2O

phn ng : CH3OH > I > II > III

Phenol khng phn ng este ha vi axit cng iu kin. Mun thc hin phn ng este ha phenol ngi ta phi dng hp cht c hot tnh mnh hn : anhidric axit hoc clorua axit.
OH
+ CH3COOH

H2SO4 to
OCOCH3

OH

CH3 C O C CH3 O O

piridin
OCOCH3
CH3 C Cl O

CH3COOH

piridin

HCl

3. Phn ng vi cc hidracid (HX):


R-OH + HX RX + H2O

Tin hnh: sc kh HX vo ancol hoc un ancol vi HX . phn ng :


III > II > I HI > HBr > HCl

HCl phn ng rt yu phi c thm ZnCl2 lm xc tc. Lu l HCl khng phn ng vi ru I.

ZnCl2 pha trong dd HCl c gi l thuc th Lucas ng dng nhn bit bc ca ancol. Ru III: phn ng nhanh Ru II: chm Ru I: khng phn ng
R-OH + HCl ZnCl2 RCl + H2O

khng tan trong nc

Phn ng xy ra s cho hin tng : ban u hn hp phn ng s c yn mt lc s t t tch lm hai lp cht lng.

10

Phn ng ca ru vi HX to halogenua c nhc im l tnh axit qu mnh ca HX c th nh hng n cc nhm chc khc trn hp cht hu c. Ngoi ra khng th iu ch clorua ankyl bc I t ru bc I.

4. Phn ng halogen ha vi SOCl2, PX5, PX3:


R-OH R-OH R-OH + + + SOCl2 PCl5 PBr3 R-Cl R-Cl R-Br + + + SO2 POCl3 H3PO3 + + HCl HCl

11

5. Phn ng kh nc:
-

iu kin: H2SO4 (170oC) hoc Al2O3 (400-800oC). Kh nng phn ng: ancol III > ancol II > ancol I nh hng phn ng tun theo quy tc Zaixep. Tuy nhin khi dng d ancol v thc hin phn ng nhit thp th 2 phn t ancol c th kh mt phn t nc cho ete.
2CH3-CH2-OH H2SO4 140oC CH3-CH2-O-CH2-CH3 Dietylete Etoxietan + H2O

* Phn ng oxi: 6. Phn ng oxi ha hu hn:


R-CH2-OH + CuO to R-CHO + Cu + H2O

CH OH

R'

CuO

to

C O

R'

Cu

H2O

12

7. Phn ng vi cc tc nhn oxi ha mnh:


-

KMnO4 (long, lnh, trung ha), CrO3/ceton, H2CrO4 , K2Cr2O7, ...

8. Phn ng haloform (phn ng oxi gim mch):


CH3 CH R' OH

X2/NaOH

lng d

CHX3

RCOONa

CHCl3 : Cloroform CHBr3 : Bromoform CHI3 : Iodoform


CH3 CH R OH
CH3 C O R

I2 + 2NaOH

CH3 C R O

2NaI +

2H2O

+ 3I2 + 4NaOH

RCOONa + CHI3 + 3NaI + 3H2O

13

Do I2 tan rt km trong nc nn thng phi thm iodua (I-),v d KI. Cc phn ng haloform nht l phn ng idoform dng nhn bit ru c cu trc l: CH3 CH R v iodoform l cht rn mu vng
OH
CH3 CH CH3 OH
Propanol-2

CH3

CH2 CH CH2 CH3 OH


Pentanol-3

Lu : R = H

CH3 CH H OH

CH3 CH2 OH
Ru I

14

CHNG IIIB : PHENOL


OH

Va l tn ca hp cht va l ch mt loi nhm chc

I. Tn gi: - Phenol l mch chnh, nu l nhm th hidroxi. - Hu ht cc phenol c tn thng thng.


OH

OH CHO
Me

OH

o-,m-,p-Cresol

Salicilandehit

NH C O

CH3

Axetaminophen

OH OH

OH

OH

OH

Catechol

Resorcinol

OH

Hidroquinon

OH Cl

OH Cl

OH Cl Cl

Cl Cl Cl Cl

Cl Cl

Cl

Hexaclorophen

Pentaclophenol

II. Tnh cht vt l: - Cc phenol u l cht rn c nhit nng chy thp (do c lin kt H lin phn t). - Tan km trong nc. - Thng b chy nc, b xn mu do b oxi ha trong khng kh. - Gy bng lnh. - ng phn para c nhit nng chy, nhit si cao hn ng phn orto, meta.

III. iu ch: 1. T Clobenzen (quy trnh Dow):


Cl
ONa OH

NaOH, 360 C p rt cao

HCl

C6H5Cl

+ 2NaOH

C6H5ONa + NaCl + H2O C6H5OH + NaCl

C6H5ONa + HCl

2. Phng php kim chy (PTN):


SO3H

OH

SO3 H2SO4
CH3
CH3

1) NaOH, to 2) H3O+

Axit p-toluensunfonic

C6H5SO3Na + 2NaOH C6H5ONa + HCl

C6H5ONa + Na2SO3 + H2O C6H5OH + NaCl

- Nhc im: thc hin nhit cao t nhm chc no tn ti sau phn ng (ch thch hp iu ch cc ankyl phenol.

IV. Tnh cht ha hc:


OH

Phn ng ca nhm OH phenol (th hin tnh axit)

Phn ng ca nhn thm (phn ng th thn in t)

OH

OH

OH

OH

OH

* Phn ng ca OH phenol: 1. Tnh axit:


O H
+ HOH

O
+ H3O+

bn nh cng hng

- Cc phenol c ka khong 1,3x10-10 tc pka 10 (mnh hn ancol nhng yu hn axit carboxylic).

- Nhng nhm rt in t v tr orto, para lm tng tnh axit, ngc li nhng nhm cho in t v tr ny lm gim tnh axit.
OH NO2 NO2

pka = 0,6
NO2

- Khc vi ancol, phenol phn ng c vi NaOH, KOH, (dung dch kim long):
C6H5OH + NaOH C6H5ONa + H2O

2. Phn ng to ete:
ArOH
NaOH

ArO

+ R

ArOR +

OH

O Na

OCH3
+ CH3 I

NaOH

Metoxibenzen (Anisol)

3. Phn ng este ha: - Phenol hu nh khng phn ng este ha vi axit carboxylic xc tc H2SO4 phi dng tc cht c hot tnh mnh hn: clorua axit hoc anhidric axit.
R C O Cl

C O

C O

COOMe

COOH OH

CH3OH to

OH

+ H2O Metyl salicilat


COOH O C O

Axit salicilic

Ac2O to Aspirin

CH3

+ AcOH

HO

HO

O N CH3

Ac2O to

O N CH3

Morphin

Heroin

4. Phn ng nhn bit phenol bng FeCl3:

* Phn ng ca vng thm: - OH l nhm tng hot mnh, nh hng orto, para.
OH
Br OH Br

Br2

Br

(rt kh dng n halogen ha)

Chng IV
Hp cht Carbonyl

C O
Andehit

C O
Xeton (R, R H)

R'

I. Tn gi: 1. Tn andehit: a) Tn thng thng: - Xut pht t tn thng thng ca axit


Tn thng thng ca axit b ic (oic) + andehit. Andehit + tn thng thng ca axit (b axit)
H C O H CH3 C O H
CH3 CH2 CHO

Formandehit Andehit formic

Axetandehit Andehit axetic

Propionandehit Andehit propionic

CH3

CH Cl

CH2

CHO

CH3

CH CH3

CH2

CHO

Ph

CH

CH

CHO

b-Clobutirandehit

Isovalerandehit

Xinamandehit

CHO OH

CHO

OMe

CH3

Salicilandehit

o,m,p-Toluandehit

CHO

Anisandehit (ngoi l)

b) Tn quc t: - Tn mch hidrocarbon + al (khng STT)


H C O H CH3 C O H

CH3-CH2-CHO

Metanal

Etanal

Propanal

CH3

CH2

CH Cl

CHO

CH3

CH CH3

CH2

CHO

2-Clobutanal

3-Metylbutanal

- Nh chc: dial
HOC CH2 CH2 CH2 CH2 CHO

Hexandial

- Andehit vng: Tn vng + carbandehit


CHO

CHO Cl

CH3

Xiclopentancarbandehit
CHO

2-Clo-3-metylxiclohexancarbandehit

CHO

Benzencarbandehit (Benzandehit)

2-Naptalencarbandehit

- Khi l nhm th (Ankanoil):


H C O
CH3 C O

C O

Metanoil (Formil)

Etanoil Acetyl (Ac)

Benzoil

CH3

C O

C O

CH3

Ac2O

Anhidric axetic

2. Tn xeton: a) Tn thng thng: - Tn 2 gc hidrocarbon (vit cch) + xeton


CH3 C O CH2 CH3 CH3 C O CH3

Etyl metyl xeton

Dimetyl xeton

CH3

C O

CH CH3

CH3

CH3

CH CH3

C O

CH CH3 CH3

Isopropyl metyl xeton

Diisopropyl xeton

- Tn xeton thm: tn thng thng axit b ic + ophenon


O C CH3
O C CH2 CH3

Axetophenon
O C CH2 CH2 CH3

Propiophenon
O C

n-Butirophenon

Benzophenon

b) Tn quc t: - Tn mch hidrocarbon + on-STT (nu cn) - a chc: dion, trion,


CH3 C O CH3
CH3 CH CH3 CH2 C O CH3

Propanon

4-Metylpentanon-2

CH3

CH

CH

C O

CH3

3-Pentenon-2

Xiclohexanon

CH3

C O

C O

CH3

Butandion

- Khi l nhm th: oxo


CH3 C O CH2 C O OCH3

3-Oxobutanoat metyl

I. iu ch: 1. T ru:
R-CH2-OH + CuO to R-CHO + Cu + H2O

CH OH

R'

CuO

to

C O

R'

Cu

H2O

2. Ozon gii:
CH3 CH2 CH CH C CH3
CH3

HCHO + HOC-COH + O

C CH3

3. T ankin:
HC CH

H2O HgSO4

H3C

C O

Axetandehit
R C C R'

H2O HgSO4

C O

CH2 R'

CH2 C O

R'

Hn hp 2 xeton
R C CH

H2O HgSO4

C O

CH3

Metyl xeton 1)BH3 2)H2O2/OH


R CH2 C O H

4. Thy phn gem-dihalogenua:


OH

R-CHCl2

2NaOH

CH OH

2NaCl

R-CHO

H2O

R-CHCl2 R-CCl2-R

+ +

2NaOH 2NaOH

R-CHO
R C O

+
R' +

H2O H2O

+ +

2NaCl 2NaCl

5. Phn ng kh Rosenmund (iu ch andehit):


R C O Cl

H2

Pd-BaSO4 to

R-CHO

HCl

III. Tnh cht ha hc :


Phn ng cng thn hch

Phn ng ca carbonyl

Phn ng do tnh axit (yu) ca Ha

Phn ng oxh-kh

* Phn ng cng thn hch:


C d+ O d:Nu Tm giu in t (tc nhn thn hch)

- C=O cng phn cc, carbonyl cng c hot tnh vi cc tc nhn thn hch
H C O H

>

C O

>

C O

R'

Chiu tng hot tnh

- Yu t lp th cng quyt nh hot tnh:


CH3
CH3 C CH3 O
CH3 CH3

>

CH3

C O

CH CH3

> CH3 CH C CH CH3


O

Chiu tng hot tnh

- C ch: c 2 hng c ch chnh


O

OH

O C R R'

:Nu (a)

R R'

C Nu

H+

R R'

C Nu

OH

Nu

:Nu-H (b)

R R'

C Nu H

H+

R R'

C Nu H

-H2O
R

C R'

- V d:
CH3 C CH
NaNH2 NH3l

CH3

C Na

CH3

CH3

C O

CH3

CH O

CH3

H2O

CH3

CH OH

CH3

1. Phn ng vi HCN: - Phn ng c xc tc bng baz tng nng CNC O

HCN+KCN

C O

CN

HCN

C OH

CN

Xiahidrin (2-Hidroxinitrin) H3O+ to


C OH CN C a COOH

OH

ng dng

Acid a-hidroxicarboxylic 1)LiAlH4 2)H2O

C OH

CH2

NH2

2. Phn ng vi NaHSO3 (ch vi andehit v metyl xeton):


R C O H

SO2Na OH

CH

OH

SO2ONa
CH3

C O

CH3 +

SO2Na OH

OH

Sn phm cng bisunfit (Tan trong nc nhng khng tan trong NaHSO3 bo ha d)

SO3Na

- ng dng: tch andehit v metyl xeton ra khi mt hn hp

CH OH
Me

SO3Na

HCl

C O

+ NaCl + SO2

+ H2O

C OH

SO3Na

Na2CO3

C O

CH3

+ Na2SO3 + NaHCO3

3. Phn ng vi tc cht Grignard: (xem li phn iu ch ancol - Chng 3)

10

4. Phn ng ancol gii: - Xc tc: axit (do ROH c tnh thn hch yu)
H

H O C

O C

H+

ROH
H O C O H R
OH2

OH C OR

H3O+

Hemiaxetal Hemixetal

- Nu cho Hemiaxetal/Hemixetal tip tc phn ng vi ancol(d) vi xc tc axit s thu c sn phm Axetal/Xetal.


H O C OR
H O H O C OR R

H+

+
ROH
R

H2O

OR

O C
OR

H3O+

R O H

H 2O

Axetal Xetal

11

O C

OH

ROH

H+

C OR

Hemiaxetal Hemixetal
OH C OR

OR

ROH

H+

C OR

H2O

Axetal Xetal

OR C OR

H3O+

2ROH

- ng dng: bo v nhm carbonyl. V d:


O O C OCH3 OH CH2OH

1) LiAlH4 2) H3O+

CH2
C OCH3

CH2 OH

O C OCH3

OH

H+

1) LiAlH4 2) H3O+

O CH2OH

H3O+

CH2OH

CH2

CH2 OH

+
OH

12

5. Phn ng vi NH3 v cc dn xut:


O

OH C NH2

+ NH3

-H2O

C NH2 H

NH

Imin
OH C NHR
-H2O

+ RNH2 Amin I

C NHR H
H

NR

Imin

H Ca C O

+ RNHR' Amin II

Ca C R

H
O N R' H

Ca C

OH R N R'

-H2O

C C N

R R'

Enamin

O + R N R' R''

Amin III

+ NH2 OH Hidroxilamin

OH

Oxim

+ NH2 NH2 Hidrazin

NH2

Hidrazon

NH2 NH

N NH

Phenylhidrazin
NO2
C O

Phenylhidrazon
NO2

NH2 NH

NO2

N NH

NO2

2,4-Dinitrophenylhidrazin (DNP)

2,4-Dinitrophenylhidrazon

13

- Cc sn phm ca cc phn ng trn thng l nhng cht rn, kt tinh c nhit nng chy xc nh nn thng c dng nhn bit carbonyl c bit l DNP. Carbonyl phn ng s cho kt ta mu vng ti cam

* Phn ng do tnh axit ca Ha:


O C H C H C H C H C

pka khong 17 (andehit) 19 (xeton)


O
O

O C C H

H+

cng mnh

cng bn

cng hng p-s-p

C O

C H

C O

1,3-Dixeton (pka 9)

C O

C H

C O

1,3-Dieste (pka 13)

C O

C H

C O

1,3-Xetoeste (pka 11)

14

- Lu : + Khng phi carbonyl no cng c Ha. V d:


CH3 CH3 C C CH3 CH3

C O

C O

CH3

CH3 O

+ Andehit c ti a 1 loi Ha , ceton c th c ti a 2 loi Ha:


CH3 C O CH3
CH3 C O CH2 CH3

6. Phn ng ankyl ha:


C O a CH3

NaNH2 - Ha

C O

CH2

C O

CH2

Carbanion
R

1)NaNH2 2)RX

C O

CH R

1)NaNH2 2)RX

C O

C R

- V d: iu ch Axit 2,2-dimetylpropanoic t etanol

15

7. Phn ng halogen ha:


H C O Ca Br
OH
-

Br2

C O

Ca

HBr

8. Phn ng haloform: (ch vi metyl xeton)


R C O a CH3

X2/NaOH chm

C O

CH2X

X2/NaOH nhanh

C O

CHX2

X2/NaOH nhanh hn

C O

CX3

O
OH

O
O C R CX3 OH

C R CX3

C R OH

CX3

O C R O

CHX3

16

C O

CH3

X2 +

NaOH

C O

CH2X

NaX +

H2O

C O

CH3

+ 3X2 + 3NaOH

C O

CX3

+ 3NaX + 3H2O

C O

CX3

+ NaOH

C O

ONa

CHX3

C O

CH3

+ 3X2 + 4NaOH

C O

ONa

+ 3NaX + 3H2O +

CHX3

- Lu : trng hp c bit khi R = H


CH3 C O
Axetandehit

9. Phn ng andol ha: - iu kin: un nng vi kim


HO

H H Ca H C O H

CH3

C O

H
CH3 CH O a CH2 C O H

-H+

Ca H

C O

carbanion
H2O
a CH

CH3

CH

C O

-H2O

CH3

CH OH

a CH2

C O

b-Hidroxiandehit

- Phn ng ch c mt carbonyl tham gia nh trn c gi l phn ng t andol ha.

17

CH3

CH OH

CH2

C O

CH3CHO + HCHO

OH

to
CH2 CH 2 OH C O H

C O

Ca H

C O

a CH2 CH2 O

C O

H2O

CH2 OH

a CH2

C O

carbanion

- Phn ng andol gia 2 carbonyl khc nhau c gi l phn ng andol ha cho.

CH3

CH3

CH OH
CH3

CH2

C O

CH3

C OH

CH2

C O

CH3

CH3

C O

+ CH3

C O

CH3

OH

to
CH3

C OH

CH2

C O

+ CH3 CH
OH

CH 2

C O

CH3

CH3 C CH 3

CH3 CH3 C O a CH 2 C O CH3

CH3

Ca H

C O

CH3

H2O

CH3

C OH

a CH2

C O

CH3

CH3 C CH 3
H Ca H C O H

CH3 CH3 C O a CH2 C O H

CH3

H2O

CH3

C OH

a CH2

C O

CH3 C H
H Ca H C O CH3

CH3

CH O

a CH2

C O

CH3

H2O

CH3

CH OH

a CH2

C O

CH3

18

* Phn ng oxh - kh: 10. Phn ng kh thnh hidrocarbon (Clemensen):


R C O R C O R' Zn-Hg/HCl R CH2 R' H Zn-Hg/HCl R CH3

11. Phn ng kh thnh ancol:


R C O
R C O R' + H2 Ni to R CH OH R'

H2

Ni to

CH2

OH

Ru I

Ru II

- Lu nu dng LiAlH4:
O C R R'
H

O R R' C H

OH

H3O+

R R'

C H

H2/Ni

to
CH3 CH CH C O H

CH3

CH2

CH2

CH2 OH

1) LiAlH4 2) H3O+

CH3

CH

CH

CH2 OH

4RCHO + LiAlH4 + 4H2O

RCH2OH + LiOH + Al(OH)3

19

- LiAlH4 l cht kh rt mnh (kh c axit, este thnh ru I) NaBH4 kh yu hn v chn lc hn (ch kh andehit, xeton). 12. Phn ng oxi ha: - Xeton xem nh khng b oxi ha. iu kin oxi ha mnh lit b ct t cho hn hp axit khng c gi tr tng hp.
CH 3 CH2 CH2 CH 2 C O CH2 CH 3

KMnO4

to

CH3-CH2-CH2-COOH + CH3-CH2-COOH + CH3-CH2-CH2-CH2-COOH + CH3COOH

- Andehit c th tc dng vi tc nhn oxi ha mnh nh : KMnO4, H2CrO4,K2Cr2O7


3RCH=O + 2H2CrO4 + 6H+ 3RCOOH + 2Cr3+ + 5H2O

- Andehit phn ng vi mt s thuc th c tnh oxi ha yu nh : Tollens, Fehling, Benedict (Cu2+), ... Ngoi ra, nhng thuc th ny cn c dng nhn bit cc ng kh.

20

- Thuc th Tollens (AgNO3/NH3) trng gng.


RCH=O 1) [Ag(NH3)2]+ 2) H3O+

phn ng

RCOOH + Ag

- Thuc th Fehling: Fehling A (CuSO4) + Fehling B (Natri kali tartat)


COOH H H OH OH COOH
O H H O C C O H O O O Cu2+ O O H O O C C O OH OH O

RCH=O

1) phc Cu2+ 2) H3O+

RCOOH + Cu2O ( gch)

- Ch phn ng vi andehit bo.

21

- Thuc th Benedict: CuSO4 + Natri citrat


O O OH O

HO OH

OH

22

C O

OH

I. Tn gi: 1. Tn thng thng:


Xut pht t ngun gc (hu ht t gc Latin, mt s

gc Hy Lp). Thng s dng: iso, sec, tert, neo. Cn s dng nh s theo mu t Hy Lp: a, b, g

C O

OH

CH3

C O

OH

CH3-CH2-COOH

Axit formic (formica kin)

Axit axetic (acetum dm)

Axit propionic (proto u tin pion bo)

CH3-CH2-CH2-COOH Axit butyric (butyrum b)

CH3

CH

CH2

COOH

CH3 Axit isovaleric (Axit b -metylbutyric) (valerian cy n lang)

CH3-(CH2)4-COOH Axit caproic (caper d) CH3-(CH2)10-COOH Axit lauric (laurus nguyt qu) CH3-(CH2)16-COOH Axit stearic (stearin m ng vt)

CH3-(CH2)6-COOH Axit caprilic

CH3-(CH2)8-COOH Axit capric

CH3-(CH2)12-COOH Axit myristic

CH3-(CH2)14-COOH Axit palmitic (palmitin du c)

H H

OH

Axit oleic (du oliu) (oleum du)

Axit cis-9-octadecenoic
O

HO

Axit cis,cis-9,12-octadecadienoic
O

Axit linoleic (linoleum ht lanh)

HO

a (ALA) : all-cis-9,12,15-octadectrienoic acid


O

Axit linolenic

HO

g (GLA) : all-cis-6,9,12-octadectrienoic acid

CH3

C O

C O

COOH

CH3

C O

CH2 COOH

Axit axetoaxetic (Axit 3-oxobutanoic)

Axit pyruvic (Axit axetylformic) (Axit 2-oxobutanoic)

COOH

COOH OH

CH3

Axit o,m,p-toluic

Axit salicilic

COOH COOH

COOH

COOH

COOH
COOH

Axit phtalic

Axit isophtalic

Axit terephtalic

HOOC-COOH Axit oxalic

HOOC-CH2-COOH Axit malonic (malum to)

HOOC-(CH2)2-COOH Axit succinic (succinium h phch)

HOOC-(CH2)3-COOH

HOOC-(CH2)4-COOH

Axit glutaric (gluten)

Axit adipic (adipis bo)

COOH

HOOC

COOH

HOOC

Axit maleic

Axit fumaric

COOH

COOH
CH3 CH OH COOH

OH OH COOH

HOOC

CH2

C OH

CH2

COOH

Axit lactic (lactum sa)

Axit citric

Axit tartic (tartarum cn ru nho)

2. Tn quc t:
Axit + Tn mch hidrocarbon + oic (khng cn STT)
HC C COOH
CH3 HC CH COOH

Axit propinoic

Axit 2-butenoic

Nh chc: Axit + tn mch hidrocarbon + dioic (khng cn STT)


Et CH3 CH2 COOH

HOOC-(CH2)8-COOH Axit decandioic

HOOC CH2 CH CH2 CH2 CH

Axit 3-etyl-6-metyloctandioic

a chc:
CH2 COOH HOOC CH2 CH2 CH CH2 CH2 CH2 COOH

Axit 4-carboximetyloctandioic

COOH HOOC CH2 C OH CH2 COOH


HOOC CH2 CH2

COOH CH CH2 CH2 COOH

Axit 2-hidroxipropan-1,2,3-tricarboxylic

Axit pentan-1,3,5-tricarboxylic

Axit vng: Axit + tn vng + carboxylic


COOH
COOH COOH

Br

Axit 3-brombenzencarboxylic

Axit benzen-1,2-dicarboxylic

COOH COOH

COOH

Axit xiclohexan-1,2-dicarboxylic

Axit 1-xiclopentencarboxylic

3. Tn este, mui: Tn este: tn gc axit b ic thm at + tn gc ankyl (p dng vi c tn thng thng v tn quc t) carboxylat ankyl.
CH3 C O O CH2 CH2 CH CH3 CH3

Axetat isoamyl Etanoat isoamyl

Tn mui: tn gc axit b ic thm at + tn cation


COONa

CH3COONH4 Axetat amoni

Benzoat natri

II. Tnh cht vt l:


Cc axit n chc u l cht lng hoc cht rn. Cc

axit thm u l cht rn. To lin kt hidro lin phn t nn c nhit si, nhit nng chy cao hn cc nhm chc hu c khc c cng s C. To lin kt hidro vi H2O nn tan tt trong nc.
O R C O H O H O C R

III. iu ch: 1. Phn ng oxi ha: a. T anken, ankin:


R CH CH R'

KMnO4 to
R C C R'

RCOOH

RCOOH

b. T aren (c dy nhnh): iu ch axit thm


a b CH2 CH2 CH3

COOH

KMnO4 to

CH3COOH

b. T ru I, andehit:
R-CH2-OH R-CH=O

[O]

RCOOH

2. iu ch t cc dn xut ca axit: Dng phn ng thy phn trong mi trng axit


R C O
R C O
R C
H+

Cl

H 2O

RCOOH + HCl

C O
N

H 2O

H+

2RCOOH

+ H+ + 2H2O H 2O

RCOOH + NH4+ RCOOH + NH4+

C O

NH2 + H+ +

C O

OR'

NaOH

to

RCOONa + ROH
H+

RCOOH

C O

OR'

H+

to

RCOOH

+ ROH

3. T tc cht Grignard:
- + R MgX
+O
C O

C O

OMgX

H+ H2O

C O

OH

RMgX

1) CO2 2) H3O+

RCOOH

Axit (+1C)

RMgX

1) HCHO 2) H3O+

R-CH2OH

[O]

RCOOH

4. Tng hp malonic:
pka 17-19
H C O a C
R

NaNH2 -Ha

C O

C O

a C

pka 13
H EtO C O C H C O OEt

EtOOC

EtOOC

NaOEt EtOH

CH EtOOC

X
EtOOC

CH

COOH

H3O+ to

CH COOH

-CO2

R-CH2-COOH

EtOOC CH EtOOC R

EtOOC

EtOOC

NaOEt EtOH
EtOOC

X
EtOOC

C R

H3O+ to

COOH R C R COOH

-CO2

CH R

COOH

EtOOC CH EtOOC R

EtOOC

EtOOC

NaOEt EtOH
EtOOC

R'

X
EtOOC

C R'

COOH

H3O+ to

C R' COOH

-CO2

CH R'

COOH

IV. Tnh cht ha hc:


+

- O

Tuy cng cha nhm C=O nhng axit carboxylic li khng cho phn ng cng thn hch nh carbonyl (phn ng vi CN-, NaHSO3, NH3, )

10

1. Tnh axit:
R C O O H

H+ +

C O

C O

(cng hng p-s-p)

ka ca axit carboxylic khong 10-5 (pka5). Tnh axit mnh hn phenol, ancol nhng yu hn cc axit v c mnh nh: HCl, H2SO4,
R-COOH > HOH > ROH > RC CH > R-H

Nhng nhm rt in t lm tng tnh axit, nhng nhm y in t lm gim tnh axit. i vi axit thm nhng nhm rt in t v tr orto, para lm tng tnh axit, ngc li nhng nhm cho in t v tr ny lm gim tnh axit.
Axit carboxylic th hin tnh axit qua cc phn ng : + Phn ng vi kim loi: Na, Zn, + Phn ng vi oxit kim loi: CaO, + Phn ng vi baz: NaOH, NH3, + Phn ng vi mui ca axit yu: CaCO3,

11

2. Phn ng to cc dn xut ca axit: a. Clorua axit:


R C O
R C O OH

OH

PCl5

C O

Cl

POCl3 + HCl

+ SOCl2

C O

Cl

SO2

HCl

b. Anhidric axit:
2R C O OH

P2O5 - H 2O

C O

C O

c. Amid:
RCOOH + NH3 to RCOONH4

RCOONH4

RCONH2 + H2O

d. Nitril:
R C O NH2

P2O5

e. Este (xem li ancol):

12

3. Phn ng th Ha (Hell-Vohhard-Zelinsky):
R CH2 COOH

+ Br2

CH Br

COOH

+ HBr

NH3 ng dng

CH NH2

COOH

CH Br

COOH

a-amino acid

OH

CH OH

COOH

a-hidroxi acid

4. Phn ng kh:
RCOOH LiAlH4 RCH2OH

13

CHNG VI: AMIN

NH2

NH

R'

N R''

R'

Amin I

Amin II

Amin III

I. Tn gi: 1. Tn thng thng: Mt s diamin c tn thng thng:


NH2-CH2-CH2-NH2 Etylendiamin NH2-(CH2)6-NH2 Hexametylendiamin
NH2 NH2

p-Phenylendiamin

Mt s amin thm c tn thng thng:


NH2 OCH3
NH2

CH3

o-Anisidin

m-Toludin

Piridin

Piperidin

2. Tn quc t: a. Amin I:

Cch 1: Xem NH2 l nhm th amino


NH2-CH2-CH2-NH2 1,2-Diaminoetan

Cch 2: Ankylamin (tn gc hidrocarbon + amin) ch thch hp cho cng thc n gin
CH3

CH3-CH2-NH2

NH2

CH NH2

CH2 CH2 CH3

Etylamin

Xiclohexylamin

1-Metylbutylamin

Cch 3: Ankanamin-STT (nu cn)


CH3

CH3-CH2-NH2

NH2

CH NH2

CH2 CH2 CH3

Etanamin

Xiclohexanamin

2-Pentanamin
NH2

CH2 CH CH3 NH2 NH2

NH2-(CH2)6-NH2

H2N

NH2

1,2-Propandiamin

1,6-Hexandiamin

1,2,4-Benzentriamin

b. Amin II,III: Cch 1: Tn cc gc hidrocarbon + amin


NH

CH3 CH2 N CH2 CH3 CH3

Diphenylamin

Dietylmetylamin

Cch 2: Chn dy di nht lm mch chnh. Cc nhm th cn li xem nh dn xut ca amino.

CH3 CH2 N CH2 CH2 CH2 CH3 CH3

ClCH2 CH2 NH CH2 CH2 CH3

N-Etyl-N-metylbutanamin

N-(2-cloetyl)propanamin (2-cloetylpropylamin)

c. Amin thm: mch chnh l anilin


CH3
NH CH3

N CH3

N-Metylanilin

N,N-Dimetylanilin

d. Khi amin l nhm th amino


CH3 NH CH2 CH2OH
NH2 COOH
NH2 CH2 CH2 C O CH3

2-Metylaminoetanol

Axit 4-aminobenzoic

4-Amino-2-butanon

e. Mui amoni:
CH3 CH3 CH2 N CH3 OH CH3 CH2 CH3

Etyldimetylpropylamonium hidroxit

II. Tnh cht vt l: Phn cc hn ankan nhng km hn ancol, axit. Tr amin III, amin I, II c kh nng to lin kt hidro lin phn t. Nhit si, nng chy cao hn cc nhm chc khc nhng thp hn ancol, axit. Gia cc ng phn amin I c im si cao nht, amin III c im si thp nht. Mi kh chu: c, nc tiu (ging m phn hy).

III. iu ch: 1. T halogenua ankyl (RX):


R X + NH3
RNH3X

NH3, to

RNH2 + NH4X

X + RNH2

R2NH2X

NH3, to

R2NH + NH4X

X + R2NH

R3NHX

NH3, to

R3N

+ NH4X

X + R3N

R4NX

Rt kh dng phn ng u v cng v sau N cng c hot tnh cao hn hp sn phm. Mun thu c sn phm n ankyl ha phi dng d NH3. V d:
CH3(CH2)6CH2Br + (2)NH3 I (45%) + II (43%) + III,IV(t) PhNHCH2Ph (85-87%)

(4)PhNH2 + (1)PhCH2Cl

Aryl halogenua phn ng kh khn, phi thc hin phn ng nhit cao, p sut cao.
C6H5Cl + 2NH3 340oC 340atm C6H5NH2 + NH4Cl

C th thay halogenua ankyl bng ancol vi xc tc axit v c hoc oxit nhm.


C2H5OH + 2NH3 xc tc xc tc C2H5NH2 + H2O

C2H5OH + C2H5NH2

(C2H5)2NH + NH4Cl

2. T nitro:

Dng H ang sinh: Fe/HCl, Sn/HCl,


NO2

NH2

Fe/HCl

H2O

3. T nitrin, amid, imin (phn ng kh):


Na/EtOH
R C N

LiAlH4 H2/Ni

R-CH2-NH2

C O

NH2

LiAlH4

R-CH2-NH2

H2NR -H2O

H2/Ni

CH

NH R

Imin

4. Phn ng Gabriel:
O C N C O H

O C

O C

KOH C2H5OH

N C O

X
C O

phtalimit

Kali phtalimit
O

H3O+

OH

+
C O OH

RNH2

IV. Tnh cht ha hc: 1. Tnh baz: N ca amin c i in t t do Xt v tnh baz: III > II > I > amin thm Amin phn ng vi axit cho ra mui v c cho mui ha tan trong nc. Ngi ta li dng iu ny tch amin ra khi nhng hp cht trung ha khc.
RNH2
+ HCl

RNH3Cl

2. Phn ng ankyl ha (xem li phn iu ch) : 3. Phn ng ancyl ha :

Axit carboxylic:
R C O
R C O OH

OH

+ 2RNH2

to

C O

NHR' + H2O

+ 2R2NH

to

C O

NR'2

+ H2O

Clorua axit :
R C O R C O Cl
+ 2RNH2
R

Cl

+ 2NH3

C O
C O

NH2

+ NH4Cl

NHR'

R'NH3Cl

C O

Cl + 2R2NH

C O

NR'2

R'2NH2Cl

Anhidric axit:
(CH3CO)2O + RNH2
CH3 C O NHR

+ CH3COOH

(CH3CO)2O c th vit tt thnh Ac2O.

Sn phm ca phn ng ancyl ha - amid thng c dng bo v nhm amin. Anilin khng th phn ng trc tip trong cc phn ng th thn in t (tr phn ng halogen ha) m phi bo v nhm amino trc ri mi tin hnh phn ng, sau kh nhm bo v tr li nhm amino.

NH2

NH3 NO3

NH2

NH3 HSO4

HNO3 H2SO4

SO3 H2SO4

Anilinium nitrat

Anilinium hidrosunfat

NH2
AlCl3

NH2AlCl3

tnh baz rt yu

NH

C O

CH3

Ankyl/ancyl ha Fridel-Crafts

Cng hng p-s-p

NH2

NHCOCH3

NHCOCH3

(CH3CO)2O - CH3COOH

HNO3 H2SO4

NH2

NO2

H3O+ - CH3COOH
NO2

4. Phn ng vi axit nitro HNO2 (nitroso ha):

HNO2 rt km bn nhit thng nn phi to ra bng cch cho mui (NaNO2, KNO2) phn ng vi axit mnh (HCl, H2SO4, o HNO3) nhit thp 0-5 C.
O N O

H+ o 0-5 C

H+

O H

-H2O

ion nitronium

10

Amin no bc I:
RNH2 + HNO2 ROH + N2 + H2O

Amin no v Amin thm bc II:


(CH3)2NH + HNO2 (CH3)2N-N=O + H2O N-Nitrosodimetylamin

Amin no bc III: khng phn ng

Amin thm bc III:


N(CH3)2
HNO2
N(CH3)2

NO

p-Nitro-N,N-dimetylanilin

11

Amin thm bc I:
H
N O

ArNH 2

ArNH

H+

ArN

- H+

ArN

-H2O

ArN

O H

H+

ArN

OH

NH2

N Cl

NaNO2/HCl 0-5 C
o

Diazonium clorua

NCl

tng i bn do cng hng nhng d cho phn ng th gii phng kh N2


OH

H2O
I

N2 +

HCl

KI
Cl

N2

CuCl

+
Br

N2

CuBr

N2

12

CN

CuCN

N2

H3O+
COOH

H3PO2

N2

V d: iu ch 1,3-Dibrombenzen t benzen
Br
Br2 FeBr3 HNO3 H2SO4
NO2 Br
Br

Fe/HCl

NH2

Br

Br

Br

Br2 FeBr3
Br NH2

NaNO2/HCl o 0-5 C
Br N NCl

H3PO2
Br

13

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