Trng THPT Chuyn Lo Cai

T Ha hc

CHUYN : HIN TNG CHUYN V TRONG PHN NG HU C Trong hu ht cc phn ng ha hc hu c, trung tm phn ng l cc nhm chc v ch c s bin i v cu to (cu trc) . Tuy nhin, nhiu phn ng c s bin i khng ch v tr nhm chc m c s tham gia ca c gc hidrocacbon to ra nhng sn phm khc d kin, l hin tng chuyn v trong phn ng hu c. Chuyn v gm 3 loi ch yu: + Chuyn v 1,2 (Thuc dy no). + Chuyn v 1,3 (Thuc dy khng no no). + Chuyn v t nhm chc vo vng thm (Thuc dy thm). I. CHUYN V 1,2 I.1. Chuyn v 1,2 Nucleofin L s chuyn v m nhm nguyn t hoc nguyn t chuyn i mang theo c cp electron. I.1.1. Chuyn v n nguyn t Cacbon a. Chuyn v Vannhe-Mecvai: Chuyn v nguyn t Hidro, gc Ankyl, Aryl n v tr C+ (To cacbocation bn hn). Loi chuyn v ny thng gp : Ancol/H+(P th, phn ng tch nc), dn xut/Ag+, amin/HNO2, hidrocacbon (Anken/H+)... VD:
CH3 CH3 C CH3 + HCl CH2OH - H2 O CH3 CH3 C CH3 CH2Cl

CH3 CH3 C CH3 CH2OH - H2 O

(CH3)2C=CH-CH3 CH2=C-CH2CH3 CH3

b. Chuyn v pinacol-pinacolon: Chuyn v to cacboncaction bn hn (Do c s tng tc ca cp e ca nguyn t O vi C+). VD:

CH3 CH3 CH3 C OH C OH CH3 CH3 CH3 + H+ - H2O CH3 C OH C + CH3 + Chuyn v CH C 3 OH CH3 C CH3 CH3 CH3 C Pinacolon O C CH3 CH3 CH3

Pinacol

Hay tng t trn (To cacbocation trung gian ging nhau)

Phm Duy ng - Chuyn hu c

Trng THPT Chuyn Lo Cai

CH3 CH3 CH3 C OH CH3 C OH C Br C + NaNO2,HCl -NaCl, -N2 -H+ CH3 CH3 + Ag+ - AgBr -H+ CH3 C O CH3 C O C CH3 CH3 C CH3

T Ha hc
CH3

CH3 CH3 CH3

CH3

NH2

c th lp th: Do to ra cacbocaction trung gian dng cu ni nn chuyn v Vanhe-Mecvai v chuyn v Pinacol-Pinacolon u lm quay cu hnh sn phm (C). Hng chuyn v: + Nhm dch chuyn mang theo c cp electron (Nh mt tc nhn Nu) nn nhm no c tnh y electron mnh hn s b chuyn dch. VD:
CH3C6H4 C6H5 C OH C6H4 CH3 C C6H5 OH +H - H2O
+

C6H4 CH3 C6H5 + C OH C C6H5 C6H4 CH3 SPC

+ Vi Pinacol khng i xng, Cacbocation no cng bn s u tin c to ra. VD:

C6H5 C6H5 C6H5 C OH C6H4 OCH3 C C6H4OCH3 OH + H+ - H2O C6H5 C + Chuyn v C C6H4 OCH3 -H+ SPC

OH C6H4OCH3 C6H5 OH C6H5 C + C C6H4 OCH3 C6H4OCH3

Chuyn v

-H+

SPP

+ nh hng khng gian: o-Anizyl kh nng dch chuyn km p-Anizyl 1500 ln. c. Chuyn v Vonfer Chuyn ha -diazoxeton thnh xeten, tc dng vi H2O (Ancol) to ra axit (este). VD:
RCOCHN2 +Ag2O -N2 RCOCH Cacben

..

Chuyn v

+H2O RCH=C=O +R'OH

R-CH2COOH R-CH2COOR'

Chuyn v Vonfer dng trong tng hp axit , xeton. VD:

R-COOH
O

+SOCl2

R-COCl

+CH2N2

RCOCHN2
O

+Ag2O

RCH2COOH + H2O, Vonfer

+CH2N2

CV

Phm Duy ng - Chuyn hu c

Trng THPT Chuyn Lo Cai d. Chuyn v benzylic (Chuyn v Benzyl-axit benzilic) L s chuyn ha -dixeton/HO- thnh -Hidroxi axit.
ArCOCOAr HOAr Ar - C - C - OH
O O
-

T Ha hc

Ar O CV Ar - C - C - OH
O-

H3O+

Ar O Ar - C - C - OH
OH

I.1.2. Chuyn v n nguyn t Nit a. Chuyn v Hopman: Amit chuyn ha thnh amin di tc dng ca BrO-/HO-. .. CV -BrHOBrOR-CO-NH2 R-CO-NHBr R-CO-N Br R-CO-N :

R-N=C=O

+ H2O -CO2

R-NH2

b. Chuyn v Curtius
R-CO-N3 -N2, to R-CO-N : CV R-N=C=O + H2O -CO2 R-NH2

(Azit) Nu phn ng trong dung mi khng c hidro linh ng, phn ng dng li giai on to isoxianat. c. Chuyn v Lotxen
R-CO-NH-OH + HO-H2O R-CO-N - OH -HOR-CO-N : CV R-N=C=O + H2O -CO2 R-NH2

(Axit Hidroxamic) d. Chuyn v Schmidt

Nh vy, cc chuyn v Hopman, Curtius, Lotxen v Schmitdt u qua h/c isoxianat, ch khc iu kin v cht ban u. e. Chuyn v Backman Chuyn ha xetoxim (V cc dn xut O-Axyl ca chng) thnh cc amit th. Xc tc thng axit nh: H2SO4; PCl5; RSO2Cl; BF3; P2O5... C ch:
R C
N OH

R' +H
+

R' +C
N

HO + H2 O -H
+

R' C
N

O C
NH

R'

-H2O, CV

V mt lp th: Trong chuyn v Backman, vi cc xetoxim khng i xng (c phh), nhm b chuyn v v tr anti (i) vi nhm -OH. VD:

Phm Duy ng - Chuyn hu c

Trng THPT Chuyn Lo Cai

C6H5 C=N p-CH3OC6H4
p-CH3OC6H4 C=N C6H5 OH

T Ha hc
PCl5 O C - NH p-CH3OC6H4
O C6 H 5 C - NH C6H4OCH3 - p

C6H5

OH

ete
PCl5 ete

I.1.3. Chuyn v n nguyn t Oxi a. Chuyn v Bayer-Viliger Nm 1899, nh ha hc c Baeyer v nh ha hc Thy S Villiger trong lc nghin cu v phn ng m vng hp cht Xeton vng bng peroxi axit hoc hydro peroxit, h pht hin ra Xeton s c chuyn ha thnh este v Xeton vng chuyn ha thnh lacton hoc hydroxi axit tng ng. V vy loi phn ng ny c dt tn l Phn ng oxi ha chuyn v Baeyer-Villiger

Xeton C ch phn ng

Este

Xeton

Lacton

Phn ng Baeyer-Villiger c nhng c im sau: + S chuyn v u tin xy ra so vi nhng phn ng khc. VD: Hp cht , bt bo ha xeton cho phn ng oxi ha chuyn v vi nhm carbonyl thay v oxi ha ni i. + Nhm tham gia chuyn v thng theo th t: alkyl bc 3> xyclohexyl> alkyl bc 2 > aryl > alkyl bc 1 > metyl. + S chuyn v xy ra c lu gi cu hnh lp th ca nhm chuyn v. + Nhiu loi tc nhn oxi ha c th s dng cho phn ng ny vi hot tnh gim dn tng i nh sau: axit CF3COOH >axit monopermaleic > axit monoperphtalic > axit 3,5-dinitroperbenzoic > axit p-nitroperbenzoic > axit mclo peroxi benzoic ~ axit performic > axit perbenzoic >axit peracetic >> H2O2. + Vi -dixeton c th b oxh B-V thnh anhidrit axit, cn -dixeton th khng. a. Chuyn v Hidropeoxit: Chuyn v ny xy ra khi phn hy hp cht peoxit, bn cht tng t chuyn v Bayer-Viliger. VD:

Phm Duy ng - Chuyn hu c

Trng THPT Chuyn Lo Cai

CH3 C6H5 C O-O-H CH3 H
+

T Ha hc
CV (CH3)2C+-O-C6H5 + H2 O (CH3)2C=O + C6H5OH

-H2O

CH3

C 6 H5 C O+ CH3

Andehit salixilic + H 2O2/NaOH

o-Hidroxi phenol (pyrocatechol)

I.1. Chuyn v 1,2 electronfin, ng li Nhm chuyn v khng mang theo cp electron lin kt (ng vai tr nh tc nhn electronfin), to lin kt mi vi cp eletron ca nguyn t chuyn n. a. Chuyn v Steven:
+ Z-CH2-N(CH2)2 R HO-H2O Z-CH-N(CH2)2 R

(Z ht e: RCO; ROOC ...

R: Anlyl;

Benzyl...) b. Chuyn v Wittig: Chuyn ha ete di tc nhn baz mnh: C6H5Li; NaNH2... VD:
CH3 - O - CH2C6H5 + C6H5Li -C6H6 CH3 - O - CH C6H5

CV

O - CH C6H5 CH3

+ H2O -HO-

HO - CH C6H5 CH3

Kh nng chuyn dch ca cc gc: Anlyl, benzyl > metyl; etyl > phenyl. c. Chuyn v 1,2 Halogen ( Chuyn v 1,2 ng li ) t-C4H 9OCl CH3CHClCH2Br (SPP) + CH 3-CBr(Cl)CH3 (SPC) VD: (CH3)2CHBr (Sn phm chnh u tin hng to ra gc t do bn hn) II. CHUYN V 1,3 a. Chuyn v Anlylic Trong phn ng th ca dn xut Anlyl: RCH=CH-CH2X /NaOH VD:
CH3CH=CHCH2OH (40%) CH3CH=CH-CH2Cl + NaOH CH3CH(OH)CH=CH2 (60%) CH3CH=CHCH2OH (15%)

(CH3)2C=CH-CH2Cl + Na2CO3

H2 O

CH3CH(OH)CH=CH2 (85%)

b. Chuyn v Xeton-Enol (Hin tng Tautome) Xut hin hp cht c H linh ng: Hp cht Cabonyl; hp cht cha nhm: -NH-CO- ; > CH-NO2 ; > CH-NO ... Nhng s chuyn ha Xeto-Enol c nhiu ngha hn c. Di xc tc H+ hoc HO-, hp cht Cacbonyl b Enol ha nhanh to ra mt cn bng. T l Xeto/Enol trng thi cn bng ph thuc vo nhit , nng , dung mi v c bit l cu trc. Nu trong phn t c nhm gy -C mnh lin hp vi h Enol th dng Enol chim t l ln. VD: Phm Duy ng - Chuyn hu c 5

Trng THPT Chuyn Lo Cai

CH3COCH3 CH3C(OH)-CH2 0,00025%
CH3COCH2COCH3 CH3COCH2COH=CH2 80%

T Ha hc

Cn bng Xeto-Enol

Xeto ha xt axit

Enol ha xt axit

Enol ha xt bazo

III. CHUYN V VO VNG THM Chuyn v vo vng thm ch yu l cc phn ng mang c th th Electronfin vo vng benzen (Nhm chuyn v ng vai tr nh mt tc nhn elctronfin). Cc chuyn v vo vng thm thng t cc nguyn t d t nh Oxi, Nit. III.1. Chuyn v t nguyn t oxi vo vng thm a. Chuyn v Frai (Fries) Chuyn v nhm axyl trong este ca phenol vo vng thm di xt axit Lewis (AlCl3, ZnCl2, FeCl3...) nhit thp, u tin chuyn v vo v tr Para. Khi vng hm c sn nhm y e (Hot ha vng) th chuyn v Frai cng d thc hin.

Phm Duy ng - Chuyn hu c

Trng THPT Chuyn Lo Cai VD:

OH
AlCl3, 25oC

T Ha hc
OCOCH3
AlCl3, 165oC

OH CH3CO

CH3 CH3CO
80%

CH3
95%

CH3

b. Chuyn v Claizen Khi un nng ete Anlyl chuyn ha thnh o-Anlyl phenol.
OCH2CH=CH2
200oC

OH CH2CH=CH2

90%

III.2. Chuyn v t nguyn t Nit vo vng thm a. Chuyn v nhm Ankyl un nng mui Halogen ca Aryl ankyl amin, nhm ankyl s chuyn dch n v tr o- hoc p- ca nhn thm. VD:
NR2
HHal, to

NHR

NHR

R
NHR
HHal, to

NH2

NH2

b. Chuyn v Octon (Chuyn v nguyn t Halogen) un N-Clo axetanilit vi HCl (HBr), thu c o- hoc p- Clo (Brom) axetanilit.
N(Cl)COCH3
HHal, to

NHCOCH3

NHCOCH3

Hal

Hal

c. Chuyn v nhm Aryl azo Chuyn v nhm Aryl azo ca diazo aminobenzen thnh p-aminoazobenzen

Phm Duy ng - Chuyn hu c

Trng THPT Chuyn Lo Cai

N=N-NH-Ar
HHal, to

T Ha hc
N=N-Ar

NH2 Nu v tr p- c nhm th, s chuyn v vo v tr od. Chuyn v Fis - Hep(Chuyn v nhm Nitrozo ) Cho hp cht c nhm Nitrozo ca amin thm tc dng vi HCl, to.
N(NO)CH3
HHal, to

NHCH3

NHCH3

NO

NO

e. Chuyn v benzydin Cho Hidrazobenzen/H+ to ra Benzidin

H+

-NH-NH-

H2N

NH2

(70%)

Phm Duy ng - Chuyn hu c

Trng THPT Chuyn Lo Cai T Ha hc IV. BI TP VN DNG Bi 1: Hy d on sn phm to thnh trong cc qu trnh chuyn v sau: Xiclo heptanon. a. Xiclo hexanon + CH2N2 b. Xyclohexanon + 1. H2N-OH; 2. H+ Caprolactam (CH3)3CCH2NH2 c. (CH3)3CCH2CONH2 + NaOBr
H3C
-NH-NHH+

CH3
H2N

NH2

d.

CH3

H3C
H
+

(C6H5)2C-C(CH3)2

e.

(C6H5)2C-C(CH3)C 6H5

f.

g.

h. p-CH3OC6H4-COCOC6H5

i. 2,2-dimetyl propan-1-ol + H+ k. Xiclopentyl metanol + H+ Bi 2: Hy gii thch 1. 3-metylbuten-1 tc dng vi axit clohidric to ra cc sn phm, trong c A l 2-clo-3-metylbutan v B l 2-clo-2-metylbutan. Bng c ch phn ng, hy gii thch s to thnh hai sn phm A v B. 2. 2-metylbuten-2 phn ng vi axit clohidric. Trnh by c ch ca phn ng, cho bit sn phm chnh v gii thch? 3. But-3-en-2-ol tc dng vi dd HBr to thnh 3-brombut-1-en v 1-brombut-2en. Hy gii thch? 4. Ho tan hexa-1,4-dien-3-ol (A) trong H2SO4 ri sau mt thi gian pha long dd th thu c A v 2 ancol ng phn cu to ca n. (BT1,2 HS t gii) Bi 3. Cho ancol A c CTCT:
H3C CH3 C CH3 OH

Khi ehiat ha ancol A thu c 3 ankaien lin hp. Vit CTCT, gi tn 3 ankaien lin hp? Trnh by c ch phn ng? HD: Phm Duy ng - Chuyn hu c 9

OH
OH

OH
H+

OH

OH

OH
HO-

Trng THPT Chuyn Lo Cai

H+ -H2O OH -H+

T Ha hc

-H+

-H+

Bi 4. Tin hnh phn ng gia 3,5,5-trimetyl xiclohex-2-enon v n-butyl magi ioua. Sau , thu phn hn hp bng dung dch HCl 4M thu c hp cht B. B b chuyn thnh nm ng phn, k hiu t D1 n D5 c cng thc phn t C13H22. Vit cng thc cu to ca cc ng phn D1, D2, D3, D4, D5 v gii thch s hnh thnh chng? HD:
O
1 .BuMgBr 2. H 2 O

Hb HO H+
- H2O

Ha

- Hb - Ha

D2

D3

CV
D1 H+
- H O 2 +

D5

D4

Bi 5. X l - halogen xeton Vi baz mnh to thnh cc sn phm chuyn v. S chuyn v ny gi l phn ng Favorski. - cloxiclohexanon s chuyn v thnh metylxiclopentancacboxilat khi c mt CH3ONa trong ete. Hy xc nh c ch ca phn ng ny.
O Cl CH3ONa ete COOCH3 NaCl

HD:

Phm Duy ng - Chuyn hu c

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Trng THPT Chuyn Lo Cai

O Cl CH3O CH3OH O Cl O O CH3O OCH3

T Ha hc

OCH3 H2O OH

OCH3

Bi 6. Hy vit cu to cc cht t A n E:
O COOH OH
(CH3CO)2O CH3COOH (CH3)3CNH2 HBr

thay i v tr chuyn v Fries

C H3C

COOH
Br 2 H+

(B: sn phm chnh) D

LiAlH4

OH

(Trong ph hng ngoi khng cn cc m C= O na)

HD:
COOH
OOCCH3

COOH
OH

COOH
OH

A:

; B

CH3CO
COOH
OH

;C

BrCH2CO
CH2OH
OH

D: (CH3)3CNHCH2CO ; E: (CH3)3CNHCH2CH(OH) Bi 7. Anlylmagie bromua (A) phn ng vi acrolein to thnh cht B, sau khi thy phn B s c sn phm C duy nht. un nng C nhn c cht D. Cho D phn ng vi C6H5Li thu c sn phm E. un nng E khi c vt iot th c F c cng thc C12H14. 1. Hon thnh s dy phn ng trn (vit cng thc cu trc ca cc cht hu c trn t C n F). 2. Ghi k hiu c ch cc giai on ca phn ng di dng cc mi tn trong s , tr giai on to thnh F. HD:

Phm Duy ng - Chuyn hu c

11

Trng THPT Chuyn Lo Cai

+ CH2=CH-CH2-MgBr
+ CH2 = CH-CH = O
thu phn AN cng 1, 4

T Ha hc
CH2=CH-CH2-CH2-CH=CH2-OMgBr B
tautome ho H3O+

CH2=CH-CH2-CH2-CH=CH-OH C

CH2=CH-CH2-CH2-CH2-CH=O D

Hoc:
CH2=CH-CH2-MgBr AN H2O + CH2=CH-CH2-CH-CH=CH2 CH2=CH-CH2-CH-CH=CH2 cng 1, 2 -MgBr(OH) CH2=CH-CH=O B OMgBr C OH
t Chuyn v 3, 3
o

H bin

H D O

OH

OH
H2O

xeto-enol

C6H5Li AN

C6 H 5 H OLi

C6 H 5 H E OH

Vt iot, to - H2O

C6 H5

TI LIU THAM KHO [1] C s l thuyt ha hc hu c - GS.TS Trn Quc Sn - NXBGD 1979. [2] Bi tp ha hu c - GS.TSKH Ng Th Thun - NXBKHKT 2001 v 2008. [3] thi HSGQG cc nm. [4] Advanced Oganic Chemistry - Part B - Reactions and Synthesis - Kluwer Academic Publishers - New York - 2002. [5] Name Reactions - Phil S.Baran - La Jollan - 2006

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