You are on page 1of 161

GS.TS.NGND.

O HNG CNG

CHUYN TNG HP HU C

2011

CHNG I
CCH A NHM CHC VO PHN T CHT HU C V S CHUYN HO GIA CHNG
Qa trnh tng hp cc hp cht hu c thc cht l qu trnh chuyn ho t mt hp cht ny thnh mt hp cht khc di tc dng ca cc yu t nh cc tc nhn phn ng v iu kin phn ng. Qa trnh chuyn ho c th thchin c bng hai phng php c bn: - a mt nhm chc vo phn t ca hp cht hyrcacbon. - Chuyn ho tng h gia cc nhm chc vi nhau. 1.1. A NHM CHC VO PHN T HYRCACBON 1.1.1. A NHM CHC VO ANKAN a mt nhm chc vo phn t ca cc hp cht ankan c th s dng mt trong cc phn ng sau y tu thuc vo yu cu v mc ch ca s tng hp. 1.1.1.1. Phn ng halogen ho:
C H + X2
250-4000c hoc chiu sng

X + HX

Phn ng xy ra theo c ch gc (SR) l thng to thnh hn hp nhiu sn phm khc nhau. Kh nng phn ng ca tc nhn halogen X2: Cl2 > Br2; cn kh nng phn ng ca nguyn t Hyr trong ankan l: Bc ba > Bc hai > Bc mt > CH3 - H
1.1.1.2.

Phn ng mtylen ho:


CH2N2 C H N2
Tia cc tm

hoc
CH2 = C = O

CH2 - H +

hoc
CO

Phn ng mtylen ho cc hp cht ankan thng to ra mt hn hp cc sn phm khc nhau. Mt khc, phn ng loi ny c th xy ra theo 2 c ch: 1. C ch mtylen ho trc tip:
CH2 + C H C A CH2 C CH2 - H

2. C ch tch - cng hp:


CH2 + C H C + CH3 C CH3

1.1.1.3.Phn ng nitr ho: Phn ng thng c tin hnh trong tng kh nhit cao vi axit nitric hoc nit tetraoxyt lm tc nhn nitro ho
CH2 + HNO3
0 470 C

CH3 - NO2 + H2O

Phn ng xy ra thng km vi oxi ho ankan to thnh CO 2 v H2O nn c hiu sut khng cao. Mt khc khi tin hnh phn ng nitr ho vi cc ng ng ca mtan thng xy ra s ct mch to thnh hn hp sn phm:
CH3CH2CH2NO2 + CH3 - CH - CH3 CH3CH2CH3
0 HNO3, 425 C

NO2 CH3CH2NO2 + CH3NO2

1.1.1.4. Phn ng synf ho Phn ng ny c th c thc hin bng tc nhn sunf ho l axit sunfuric c:
R - H + HO - SO3H R - SO3H + H2O

Tuy nhin phn ng ny t hiu sut rt thp nn trong thc t thng s dng phn ng thay th hyr bng gc SO2Cl to thnh ankynlsunfclorua nh sau:
R - H SO2, Cl2, t0C R - SO2Cl + HCl

1.1.1.5. Phn ng xy ho: Di nhng iu kin c bit, ankan c th b xy ho hp cht C H v chuyn v cc hp cht hyrxi hoc cc hp cht cacbonyl. V d:

CH3 H3C + C CH3 R - CH3 CH4


B2O3, khng kh
Khng kh, 6000C, NO

CH3 H
KMnO4

H3C

C CH3

OH

R - CH2 - OH H - CHO

1.1.2. A NHM CHC VO ANKEN: Vic a mt nhm chc vo phn t anken c th thc hin c bng phn ng cng hp electrophin, cng hp raddical phn ng thay th v oxy ho. Di y l s ca mt phn ng c bn thng c s dng trong tng hp cc hp cht hu c. 1.1.2.1. Phn ng cng hp:
C = C + XY C X C Y

Trong XY = H2, Br2, HCl, HBr, HI, H2SO4, HOH, HOCl... Cc phn ng xy ra c th c s tham gia ca cc xc tc thch hp cng c khi khng cn s c mt ca xc tc. Trong i a s cc trng hp, phn ng cng hp cn xy ra theo quy tc Macpnhicp: Phn ng cng hp xy ra theo c ch gc (khi c s tham gia ca cc cht xc tc c kh nng to thnh gc t do nh poxit, peaxit...) th hng ca phn ng ngc vi quy tc Macpnhicp.
Khng c pexit

CH3CHBrCH3 Theo Macpnhicp

CH3CH = CH2

HBr
C mt pexit

CH3CH2CH2Br

Phn Macpnhicp

Cc phn ng cng hp ca mt s hp cht anken ri hyrcacbon hoc mtylen s cho sn phm ankyl ho:

C = C

+ R

axit

C H

C R

CH2N2 C = C + CH2 = C = O Hv C CH2 C

Phn ng thay th nguyn t hyr v tr allyl ca cc hp cht anken c thc hin nhit cao (khong 6000C) vi cc tc nhn l clo Brm hoc N brmxucximit:
H C C = C + X2 X C C = C X2 = Cl2, Br2

V d:
CH3CH = CH2
Cl2, 600 C
0

Cl - CH2CH = CH2 Br2

+ Br2

600 C

1.1.2.3. Phn ng oxi ho: Phn ng oxy ho cc hp cht lephin thng to thnh cc sn phm cha xy l ancol hoc anhyt tu thuc vo tc nhn xy ha. V d nu xy ho cc hp cht lephin bng tc nhn KMnO4 lnh v long hoc dung dch peaxit HCOOOH th s thu c hp cht glycol nh sau:
C = C + KMnO4

hoc

HCOOOH

C OH

C OH

Mt khc s khc nhau gia cc phn ng xy ho ca 2 tc nhn ny l vic to thnh cc sn phm ng phn hnh hc khc nhau. Phn ng xy ho bng KMnO 4 thng to ra cc sn phm ng phn Cis tri li HCOOOH to ra cc sn phm ng phn trans.

KMnO4 OH OH cis - xyclopentadiol -1,2 H H H2O2, HCOOOH H OH + OH H

trans - xyclopentadiol -1,2

Nu tin hnh phn ng xy ho bng tc nhn l hp cht zn th sn phm thu c l cc anhyt hoc xtn:
O C = C + O3 C O C O H CH3CH2CH = CH2 CH3 CH3 C = CH2 O3 H2O, Zn CH3 O3 H2O, Zn H H2O,Zn C = O + O = C

V d:
CH3CH2C = O + O = CH CH3 H

C = O + O = CH

Phn ng ny thng c s dng xc nh cu to ca phn t olephin. 1.1.3. a nhm chc vo phn t ankin: Tng t nh cc phng php a mt nhm chc vo hp cht anken, vic a mt nhm chc vo phn t ankin cng c tin hnh bng phng php cng hp hoc thay th nguyn t hyrlinh ng ca ankin. 1.1.3.1. Phn ng cng hp:
Y C C + YZ C = C YZ C Y Z C Z

Trong : YZ = H2,Cl2, Br2, HCl, HI, H2O Cc phn ng xy ra theo hng c th v mt lp th tu thuc vo vic s dng cc hp cht xc tc. V d:

H C C + YZ 2H2
Ni, H hoc pd

H C H

C H

Na hoc Li,NH3

H C=C H

ng phn trans

C
H2, pd hoc Ni B

H C=C H

ng phn cis

Phn ng cng hp vi nc thng xy ra vi s c mt ca xc tc l mi thu phn trong mi trng axit v to thnh sn phm l cc hp cht xtn:
H C C + H2O HgSO4, H2SO4 C = C H OH C H C O

V d:
H H C C H + H2 O HgSO4, H2SO4 H C H H CH3 C C H + H2 O HgSO4, H2SO4 H C H C O C O H C H H H

1.1.3.2. Phn ng ankyl ho: Nguyn t hyr thuc lin kt ni ba ca ankin rt linh ng dn n cc hp cht ankin c tnh axit yu. V vy n c kh nng tham gia vi cc phn ng vi cc kim loi kim hoc vi cc ion kim loi nng. V d:
C C H + M C C H + H

Trong : Hoc:
C

M = Ag , Cu

H + Na

NH3 lng

Na + 1/2H2

Nu cho hp cht axetylua kim loi trn y tc dng vi cc dn xut halogen th s thu c cc sn phm ankyl ho:
-C C-M+X-R -C C - R + MX

1.1.4. a mt nhm chc vo phn t hp cht thm Vic a mt nhm chc vo nhn thm ca cc hp cht hyddrrocacbon thm c thc hin bi cc phn ng xy ra theo c ch th electrophin (S E). Di y l s ca mt s phn ng c bn thng gp: a, Nitrr ho:
ArH + HONO2
H2SO4

ArNO2 + H2O

b, Sunf ho:
ArH + HOSO3H
SO3

ArSO3 + H2O

c, Halogen ho
ArH + X2 Fe ArX + HX (X2 = Cl2, Br2)

d, Ankyl ho theo Frien Craf:


ArH + RCl
AlCl3

ArR + HCl

d, Ankyl ho theo Frien Craf:


ArH + ROCl
AlCl3

ArCOR + HCl

e, Nitrrz ho:
ArH + HONO ArN = O + H2O

g, Az ho:
ArH + Ar'N2X ArN = N - Ar' + HX

h, Phn ng Konbe:
OH + CO2 125 c, 7atm
0

OH

COONa

i, Phn ng Raim Timan:


OH + CO2 dung dich NaOH OH CHO

Trong bng s ca cc phn ng trn y, cc phn ng e v g ch xy ra i vi cc hp cht hyrocacbon thm hot ng mnh, cn cc phn ng h v i ch c ngha khi hp cht hyrocacbon thm tham gia vo phn ng l phenol. Vic a mt nhm chc th hai vo nhn thm ca hyrocacbon thm c tun theo mt s quy lut nh hng nht nh. Ngi ta chia cc nhm th thnh 2 loi: - Loi I: Cc nhm tng hot (c kh nng lm tng mt in t ca nhn thm) nh hng oct v para. - Loi II: Cc nhm gim hot (nhm ko in t ca nhn thm) - nh hng mta. Kh nng hot ng ca cc nhm th trong phn ng th electrophin rt khc nhau v c sp xp theo th t nh sau: NHM TH LOI I Tng hot mnh - NH2 (-NHR, -NH2) - OH Tng hot va - OCH3 (-OC2H5...) - NHCOCH3 Tng hot yu - C6H5 - CH3 (-C2H5,...)
9

NHM TH LOI II nh hng mta - NO2 - N(+) (CH3)2 - CN - COOH (COOR) - SO3H - CHO, COR nh hng Oct, para - F, - Cl, - Br, - I

Vic a nhm chc th ba vo nhn thm khi c mt ca 2 nhm th s lm phc tp s nh hng ca phn ng th electrophin. V vy ta c th phn thnh cc trng hp sau: 1. Nu hai nhm th cng nh hng vo mt v tr th s nh hng s xy ra theo chiu ca cc mi tn sau:
O2N CH3 O2N SO3H CN NHCOOCH3

2. Nu hai nhm th nh hng khc nhau th s theo quy tc: - nh hng ca nhm hot ho mnh (tng hoc gim hot) s quyt nh hng ca phn ng SE so vi nhm hot ho yu. - nh hng ca nhm tng hot s quyt nh hng ca nhm phn ng S E so vi nhm gim hot. S nh hng ny c thay i theo dy sp xp sau:
-

NH2 > - OH > - OCH3 > - NHCOCH3 > - C6H5 > - CH3 > Nhm nh hng mta V d:
HO CH3 HNO3/H2SO3 HO CH3 NO2 Br2/Fe

CH3CONH

CH3

CH3CONH Br

CH3

HO CHO Br2/Fe

HO

HO CHO + Br Br Br CHO

1.1.5. A MT NHM CHC VO PHN T D VNG THM N GIN Vic a mt nhm chc vo nhn thm d vng n gin c thc hin bng phn ng th eleectrophin. Cc phn ng th xy ra cc hp cht furan, tiophen, pirol u tin nh hng vo v tr s 2. V d:

10

+ O furan

: SO3

SO3H

furan 2O sunf axit


0

+ (CH3CO)2O + (C2H5)2O : BF3 O

0C O

COCH3

2- axtylfuran

+ C6H5COCl + SnCl4 O tiophen S

COC6H5 2 - Bezoyltiophen

+ C6H5N N H Pirol

NCl N H

N = NC6H5

2- (phenylaz) pirol

N H

+ CH3Cl + KOH N H

CHO

Tng t nh vic a mt nhm th vo hp cht d vng 5 cnh, vic a mt nhm chc vo hp cht d vng 6 cnh cng c th thc hin bng phn ng th electrophin. Trng hp ny hng th u tin vo v tr 3 (hoc )

11

KNO3, H2SO4, 300 C N H2SO4, 350 C N piridin Br2, 3000C N N Br +


0

NO2 SO3H Br N

Phn ng th nuclphin ca hp cht piriin s cho ra cc sn phm th vo v tr 2 hoc:


un nng
N H NH2 N NH2 + NaNH2 + H2

+ NaNH2

+ C6H5 - Li

un nng
N

H NH2 N

C6H5 + LiH

1.2. S CHUYN HO TNG H GIA CC NHM CHC 1.2.1. CHUYN HO NHM CHC HYRXYL CA ANOL V PHENOL S chuyn ho nhm hyrxyl ca cc hp cht ancol c th c thc hin bng mt s phn ng quan trng sau y: a, Phn ng halogen ho: Phn ng ny c th c thc hin bng cc tc nhn halogen ho nh hyrhalogenua HX, phtpho halogenua PX3, PX5, inyl clorua SOCl2. Phn ng vi hyrhalogenua:
ROH + HX RX + H2O

Phn ng xy ra theo c ch th Nuclphin, trong kh nng phn ng ca HX gim dn theo dy: HI > HBr > HCl, cn kh nng phn ng ca ROH thay i theo dy: Allyl benzyl > bc ba > bc hai > bc mt Nhiu khi phn ng xy ra vi s chuyn v.
12

V d:
CH3 H CH3 H CH3 C H C OH CH3 HCl CH3 CH3 C H C Cl CH3

CH3 H C Cl C H CH3

Hoc:
CH3 CH3 CH3 C CH3 CH2OH HCl CH3 CH3 C CH3 CH3 C Cl CH2 CH3 CH2 Cl

* Phn ng photpho halogennua:


R - OH +PX n RX +H3PO 3

Trong : PXn = PBr, PL3, PCl5 V d:


- CH - CH3 OH
PBr3

- CH - CH3 Br

CH 3CH 2OH CH3

P +I

CH3 CH 2I CH PCl5
3

CH3 CH2CHCH2OH

CH3 CH2 CHCH2Cl

* Phn ng vi tioonyl clorua:

13

R - OH +SOCl 2

piri in
-

R - O - SOCl HCl (khng b n)

R - Cl +SO 2

* Phn ng tch loi hyrt ho:


axit

C H

C OH

+H 2O

Phn ng tch loi ancol xy ra theo c ch E 1 v E2 vi s tham gia ca cht xc tc l axit. Kh nng tham gia phn ng tch loi ca ancol bin i theo dy: ROH: bc ba > bc hai > bc mt Hng ca phn ng tch loi xy ra sao cho to thnh anken l bn vng nht. Ngoi ra, phn ng tch loi cc ancol nhiu khi xy ra vi s chuyn v. V d:
CH3 CH2 CH 2CH 2OH H2SO4 CH 3CH =CHCH3v CH 3CH 2CH =CH nng (S ph ch un n m nh)
2

c, Phn ng oxy ho: Phn ng chuyn ho nhm hyrxyl ca hp cht ancol bng phng php xy ho to thnh cc sn phm khc nhau tu thuc vo loi ancol v tc nhn, iu kin cc phn ng. Di y l s c bn ca mt s phn ng: Bc mt:
H Cu, 2500C R - CH 2OH KMnO4 R - C =O Ho K 2Cr2O 7 c Ho K 2Cr2O7 c KMnO 4

R - COHH

Bc hai:
R R

, c 2 R - C - HOH KMnO4 ,CrO3 0 ho K Cr2O 7 R - C =O ho Cu, 250 C c

Bc ba:

14

R R - C - OH R Vd: CH 3CH 2CH 2OH CH3 CH 3CH2 CHCH2 OH KMnO4 Cu, 250 C
0

KMnO4 (trung t ho ki ) nh c m

Khng phn ng

H CH3 CH2 C =O +H2 3 CH3 CH3 CH2 CH COOH

OH

K 2Cr O7 2

=O

1.2.2. CHUYN HO NHM AMIN Tng t nh amnic, nguyn t nit trong nhm amni mang cp in t khng phn chia to nn kh nng tham gia cc phn ng nuclphin ca nhm chc ny. Sau y l s ca mt s phn ng chuyn ho c bn: a, Phn ng to mui:
+ RNH 2 +H R2NH R3N + +H + + H + RNH

+ R NH
2

+ R 3NH

b, Ph ng ankyl ho: n RX RX RX RX RX + R NX
4

RNH 2

R 2NH ArNHR

R 3N A rNR2

ArNH2 RX

+ ArNR X
3

V d:

15

(n - C H 9) 2NH +C H5 CH2Cl 6 4 H I n - C H 7NH2 CH3 3 n - C H7NCH 3 3

(n - C H ) NCH2 C H5 4 92 6 CH3 CH3 I n - C3H 7NCH 3 CH3 I CH3 + n - C 3H 7NCH3 I CH3

c, Phn ng to thnh amit: * Bc mt


O R O ArSO2 Cl Ar - S - N O R C N H R H

, R COCl RNH

* Bc hai:

, R COCl R2NH ArSO2 Cl

O R O Ar - S - N O R C N R R R

* Bc ba:
, R COCl R2N ArSO2 Cl

khng phn ng

V d:

khng ph ng n

16

H (CH 3CO)2O NH 2 C6 H5 SO2 Cl dung d NaOH ch - N - C - CH3 H O O - N - SO

C5 H6 COCl H C6 H5NCH3 n - CH3 C6 H5 SO2 Cl dung d NaOH ch

CH3 -C-N O O CH3 S- N C2 H5 CH3

CH3

d, Phn ng vi axit nit: * Amin thm bc mt:


ArNH2 HONO N Ar - N m ui ifini
+

* Amin bo bc mt:
RNH 2 HONO
+

R-N

H2O N +hn h p ancol v anken 2

* Amin thm v bo bc hai:


R ArNHR ho c R 2NH HONO Ar - N - N =O ho c R2 N - N =O N - Nitrozam in

17

* Amin thm bc ba:


NR 2 HONO O =N NR2

* Amin bo bc ba:

R3 N

HONO

R2N - N =O +an hyt, xtn

e, Phn ng tch loi: Phn ng tch loi cc hp cht amin to thnh cc anken ch c th thc hin c khi chuyn chng thnh ion amni bc bn. C 2 phn ng tch loi c bn sau y: * Phn ng tch loi theo Hpman:
H nng un - C - C - HO, NR3 >C =C < +R3 N +H2 O

V d:
CH3 CH3 un CH3 - N - CH2 CH2 CH3 HO, nng CH3 - N +CH2 = CHCH3 +H2O CH3 CH3

* Phn ng tch loi theo Kopu:


2 Am bc ba H O2 in

-C-C

nng un

>C =C <+R2 NOH

HO O O N

V d:

18

R - CH2 - CH 2 N H3C

H2O2

R - CH2 - CH2 ,

140 C

, RCH =CH +CH - N - CH2 CH R 2 3 2 OH

, H3C - N - CH2 CH2 R O

CH 2CH 2R

1.2.3. CHUYN HO NHM HALOGEN a, Do c nhng cp in t t do trn cc ocbital ca cc nguyn t halogen nn cc hp cht halogen tham gia phn ng th nuclophin. Di y l s ca mt s phn ng th nuclophin thng xy ra: Phn ng R: X + : Z R: X + : OH R: X + : H2O R: X + : OR R: X + : C CR R: X + : Na R R: X + : I R: X + : CN R: X + : ROO : R: X + : NH3 R: X + : NH2R R: X + : NH2RR
R : X +: P(C6 H5 ) 3

R : Z + : X R : OH + : X R : OH R : OR R : C CR R : R R : I R : CN R : COOR R : NH2 R : NHR R : NRR


R : P (C 6H 5)3 X

Sn phm ancol ancol ete ankin ankan ankyl iua nitri este amin bc nht amin bc hai amin bc ba
m photphoni ui

R: X + : SH R: X + : SR
R : X +: CH(COOC2H 5)2 R : X +: CH3 COCHCOOC2H 5

R : SH R : SR

Tiol(mcaptai) Tiete(sunfir)
T h p m ng alnic

R : CH (COOC2H 5)2

CH 3COCHCOOC 2H 5 T h p axtaxetat ng ... R

Phn ng th nuclphin xy ra theo c ch SN1 hoc SN2 tu thuc vo bn cht ho hc ca dn xut halogen. S ph thuc c hiu qua s bin i sau:
Tc phn ng SN 2 tng RX =CH3 X, bc m bc hai, bc ba t, Tc ph ng SN2 tng n 19

Mt khc, cn ch thm rng phn ng xy ra theo c ch S N1 thng km theo s chuyn v: V d:


CH 3 C2H5 O SN2
CH3 CH3 - C - CH2 Br CH 3

CH 3 - C - CH 2OC2H 5 khng c chuy v n CH 3 CH 3 CH3 - C - CH 2CH 3 OC2H5 ch sn phm c chuy v n

C2 H 5OH S 1 N

CH 3 CH3 - C =CH - CH 3

a, Phn ng tch loi: Cc dn xut halogen khng ch c tham gia ch yu vo cc phn ng th nuclphin m cn tham gia cc phn ng tch loi, to thnh cc hp cht khng no:
Baz

C H

C X

C =C

Phn ng tch loi ca cc dn xut halogen xy ra theo c ch E1 v E2. Khi ny tham gia phn ng tch loi ca chng theo c ch E1 v E2 thay i nh sau: Bc ba > Bc hai > Bc mt. c, Phn ng kh Phn ng kh cc dn xut halogen c th xy ra bng Hyr vi s tham gia ca cc xc tc kim loi cng c th bng Hyr mi sinh (kh ho hc): * Kh xc tc:
RX +H2 Ni RH +HX

* Kh ho hc:
RX +M +H RX +M + X

V d:
20

CCl4

Fe,H2 O

CHCl3 (CH3 ) CMgCl 3 (CH3 ) CD 3

(CH3 )3 CCl Br Br 7,7 - ibrm norcaran

Na, CH3 OH Norcaran

1.2.4. CHUYN HO NHM ANHYT V XTN: Ha hc ca cc hp cht anhyt v xtn c xc nh bi s c mt ca nhm cacbonyl > C = O. Chnh nhm ny l trung tm ca s tn cng nuclophin. V vy, phn ng chuyn ho c trng cho an hyt v xtn l phn ng cng hp nuclophin. Ngoi ra, anhyt v xtn cn tham gia mt s phn ng khc nh xi ho, kh ho, ngng t,... Sau y l s ca mt s phn ng c bn. a, Phn ng xi ho: * Anhyt:
Ag(NH3 )3 RCHO ho ArCHC c KMnO4 K2 Cr2O 7 RCOOH ho ArCOOH c

V d:
CH3 CHO +2Ag (NH 3)3 + 3HO Ag + 3COO +4NH 3+2 H 2O CH OX

* Mtyl xtn:
R - C - CH3 ho Ar - C - CH3 c O O RCOO ho ArCOO +CHX 3 c

V d:

21

C2 H5 - C - CH3 +3OI O CH3

C2 H5 COO +CHI3 + 2HO

CH3 KOCl 60
0

CH3 C =CH - C - CH 3 O

CHCl3 +CH3 C =CHCOOK

b, Phn ng th: - Kh ho thnh ancol:


H 2 +Ni, Pt ho Pd c C =O LiAlH4 ho NaBH4 ,ti theo H c p C OH

V d:
O H2 , Ni

OH

C O

CH

LiAl H 4

CH OH

CH3

- Kh ho thnh hyrcacbon:
Zn (Hg), HCl( ) - C- H H C =O NH2 NH2, Baz -C-H H kh Kizne - Vonfa kh Klem enxen

V d:

22

CH3 CH2 CH2 COCl 2 2 A lCl3 O NH2 NH , NaOH 2

CCH CH CH 2 2 3 O H H

Zn(Hg), HCl( )

CH2 CH CH CH 2 3 2

- Kh ho thnh pinacol:
C O kh ho l ng ph t n C C

OH OH Pinacol CH3 CH3 CH3 CH 3 CH3 H2 O CH3 C C CH3

V d:
2CH3CCH3 O Mg, Benzen CH3 C O

C O Mg

OH OH

C O

Mg +MgI , ete, benzen

C HO

C OH

Amin ho - kh ho:
>C =NH H2 , Ni >CH - NH 2

>C =O +NH 3

V d:
CH 3 (CH 2)5 CHO CCH 3 O NH3 , H2 , Ni CH 3 (CH 2) CH2 NH2 5 CH - CH3 NH2

NH3 , H2 , Ni

Phn ng cng hp Grinha:

23

C +RMgX O

H2 O

C OH

OMgX

Phn ng xy ra theo c ch cng hp nuclphin A N : vi focmanhyt to thnh ancol bc mt, vi cc anhyt khc to thnh ancol bc hai, vi xtn s to thnh ancol bc ba. V d:
H CH 3 CH 2 CHCH3 +H - C =O MgBr H MgBr +CH3 - C =O CH3 CHOMgBr H2 O CH3 CHOH CH3 CH3 CH2 CHCH2 OMgBr H2O CH 3 CH3 CH2 CHCH2 OH

CH 3 n - C H9 MgBr +CH3 - C =O 4

CH3

CH3

n - C4 H9 COMgBr H2 O n - C H9 C - OH 4 CH 3 CH 3

d, Phn ng cng hp to thnh xianhyric:


C + CN O H C OH CN

V d:

24

H CH3 - C =O +NaCN H2 SO4

H CH3 - C - CN OH CH3 H2O;HCl

H CH3 - C - COOH OH CH 3 H2O,H2SO4 CH3 - C - COOH OH CH3 CH2 =C - COOH

CH3 - C =O +NaCN O

CH3 - C - CN OH

e, Phn ng cng bisunfit:


C + Na HSO O
+ 3

C OH

SO Na 3

V d:

H C =O +Na HSO4

H C OH CH3 SO3 Na

CH 3 CH2 CCH3 +Na HSO4 O

CH3 CH2 C - SO3 Na OH

g, Phn ng cng hp vi cc dn xut ca amnic.

25

H2 N - G H2N - OH H2N - NH2 H2N - NHC6H 5 Hy rxilam in Hy razin Phenylhy razit C =NOH C =N - NH 2 C =NNHC6H 5 C =NNHCONH 2

S phm n xim Hy razon Phenylhy razit Sem icacbazit

H2N - NHCONH2 Sem icacbazit

V d:
CH3 OH =O +H2 N - OH H CH3 CH =NOH +H2 O H CH3 CH3 COOH3 +H2 N - NHCONH2 H CH3 C =NNHCONH2 +H2 O CH =NNHC H5 + 2 O H 6

CH =O +H2 N - NHC6 H5

h, Phn ng cng vi ancol to thnh hp cht axtal:


C +2ROH O H
+

- C - OR +H 2O OR

V d:

H HCl

H CH 3 - C - OC2H 5+H 2O OC2H5

CH3 - C =O + 2 H5 OH 2C

i, Phn ng Kaizar:
H 2 - C =O Bazm nh - COO + - CH 2OH
-

V d:
2HCHO dd 50% NaOH HCOO +CH 2OH

k, Phn ng ngng t:

26

R ArCHO +(RCH2 CO)2O Baz Ar CH =C - COOH

1.2.5. CHUYN HO NHM AXIT CACBOXYLIC V DN XUT CA CHNG Tnh cht ho hc ca axit cacboxylic c xc nh bi s c mt ca nhm cacbonxyl : - COOH. Nhm ny c cu to t nhm cacbonyl ( >C = O) v hyrxyl (OH), do phn ng chuyn ho nhm - COOH cng chnh l s chuyn ho ca hai nhm ny. Di y l s chuyn ho ca mt s phn ng c bn: a, Phn ng chuyn ho thnh cc dn xut axit:
O O R-C OH O R-C OH + Z SOCl 2 PCl 3 PCl 5 O R-C Cl (Z =Cl, OR ,'NH ) 2 R-C

* Chuyn ho thnh cloranhyrat:

V d:
3 CH3 COOH +PCl 3 O 50 C
0

3 CH 3 COCl +H 3PO 3 O R-C OR'

* Chuyn ha thnh este:


R-C + OH SOCl3 O ' R - C R OH Cl

Kh nng ph ng R' OH : Bc m >Bc hai >Bc ba n t O R-C +R' OH OH H O R-C OR + H2O

* Chuyn ho thnh amit:

27

R-C

O NH3 OH O

RCOONH

nng un - H2 O O

O R-C NH2 O

R-C + OH Vd:

SOCl2

R-C Cl

NH 3

R -C NH2

CH3COOH NH3 CH 3COONH 4 C6 H5 CH2 COOH SOCl2

NH3

CH 3 CONH 2 NH3 C 6H 5CH 2CONH

C6 H 5CH 2COCl

b, Kh ho:
RCOOH Vd: 4 (CH 3 )3 C COOH +LiAl H4 RCOOH Vd: 2 CH3 COOH +Zn CH3 (CH )10 COOH +NaOH ete (CH3 ) 3 C CH2 O
4

LiAl H 4

RCH2 OH H2 ,Li AlO 2

Al Li

(CH3 )3 C CH2 OH

c, Phn ng th hin tnh axit to thnh mui:


RCOO +H (CH3 COO) Zn +H2 2 CH3 (CH2 ) COONa +H O 2 10
0 tC

h, Phn ng cacboxyl ho:


C6 H5 COONa +NaOH (CaO) NO2 NO COOH NO2 H2 O, H si un O2 N C6 H6 +Na CO 2 3 NO2 +CO2 NO2

28

CHNG II: S PHN CT V TO THNH LIN KT CACBON CACBON Trong cc qu trnh phn ng ho hc, lin kt C X gia cacbon v mt nguyn t X khc (C th l cacbon, xy, halogen...) trong phn t cht hu c c kh nng t ra theo 3 kiu khc nhau:
a. - C : X -C
+

cacbcation b. - C : X -C
+

Ki ph cdly u n t X
-

cacbcation c. - C : X -C
+

Ki ph c ly u n t ng

hc cacb t do

Trong kiu phn ct th nht to ra mt ion vi nguyn t cacbon thiu mt electrn v mang in dng. Ion ny c gi l cacbcation. Trong kiu phn ct th hai ion sinh ra mang in tch m gi l cacbanion. l hai kiu phn ct d ly. Cong kiu phn ct th ba phn ct ng ly, to ra gc t do vi in t t do nguyn t cacbon gi tt l gc cacb t do. S phn ct nh trn c th xy ra c khng hoc c th xy ra theo kiu no, iu tu thuc ch yu vo cu trc ca phn t cha nhm C X v cc iu kin tin hnh phn ng. S kho st cc ion v gc t do ca cacbon c tm quan trng c bit trong vic tm hiu c ch cc phn ng hu c. 2.1.CACBCATION Ccbcation l nhng cation m trung tm in dng l nguyn t caacbon. C nhiu loi cacbcation khc nhau: Ccbcation c ba lin kt C(+) (ph bin nht). Th d (CH3)3C(+). Ccbcation ch c hai lin kt C(+). Th d CH2 = CH(+). C6H5(+). Ccbcation khng kinh in (nonlassical carboncation) hay l cacbcation cu ni. Trong in tich dng c gii to nh cc lin kt hoc v tr tng i xa nguyn t cacbon trung tm. Ccbcation c s phi tr 5 (rt t gp). Th d: CH 5(+). Trong phn ny ch yu cp n loi cacbcation th nht. 2.1.1. NHNG PHN NG TO THNH CACBCATION 2.1.1.1 Cc phn ng ct lin kt C X thnh cacbcation a. Phn ct lin kt C Hal. Mun cho lin kt C Hal b phn ct d ly iu kin tt nht l Hal c kh nng ht electron mnh, cacbcation sinh ra c cu trc tng i bn
29

v dung mi c kh nng ion ho cao. V d triphnylclomtan l mt cht rn kt tinh khng mu, khng tan trong nc v d tan trong C6H6 hoc CHCl3 cho dung dch khng mu v khng dn in do s phn ly:
(C6 H 5)3 C - Cl SO2lng (C6 H 5 ) 3 C
+

+Cl

L tt nhin cc ion sinh ra u b sonvat ha, trong cc dung mi nh nitrmtan, axtn... triphnylclomtan cng b phn ly nhng mc yu hn. V dung dch cacbcation dn in v c mu nn ngi ta c th dng cc phng php vt l kho st. Chng hn bng phng php quang ph ngi ta thit lp c rng 00c dung dch 0,1M (C6H5)3C-Cl trong SO2 lng c cha 3,2% dng ion cn dung dch 0,01M cha 21%. Trng thi ca lin kt C-Hal c th thay i r rt khi c tc dng ca cc mui halgenua kim loi c kh nng to mui phc vi halgen trong C-Hal, nh: SnCl4, AlCl3, SbCl5, HgCl2... Th d:
(C6 H5)3 C - Cl +SbCl 5 (C 6 H 5 )3 CCl +SbCl 5 (C6H 5)3C
+

+SbCl 6

Qa trnh phn ly trn c th xy ra ngay trong cc dung mi khng phn cc nh benzen, ttraclorua cacbon... ng ch l nhiu dn xut halgen, vi halgen nguyn t cacbon bt i, c th t raxemic ho trong dung mi c kh nng ion ha cao v qu trnh phn ly c tnh thun nghch. Nu dn xut halgen khng t phn ly thnh cacbcation raxemic ho c th ngi ta c th nhng mui halogen kim loi nh ni trn. Hin tng raxemic ho y l c s ca mt phng php kho st qu trnh phn ly, c bit l qu trnh phn ly ca nhng cht c phn ly km. b, Phn ct lin kt C-OH. Lin kt C-OH rt kh t phn ly thnh cacbcation v anion hyroxyl. Chng hn triphnylcation l mt cht khng mu v trung tnh, khng phn ly trong C6H6. Phn ly rt yu trong SO2 lng nhng trong axit sunfuric c hay axit fomic c phn ly mnh cho ta nhng dung dch mu vng da cam. Quang ph ca cc dung dch ny ging quang ph ca dung dch (C6H6)3C
( 6H 5)3COH +2H 2SO4 C (C 6H 5 3C +H 3 +2HSO 4 ) O
+ -

V phn ng trn chuyn dung dch mt cht khng mu thnh dung dch cht c mu (hoc mu thm hn) do hin tng to mui cho nn ngi ta cho l mt v d ca hin tng halcrm (Hal-mui, rm-mu)
30

Cc ancolloaij bo bc cao th d (CH3)3COH cng c kh nng to ra ion cacbni trong axit sunfuric c. Th d trimtylcacbinol c. Phn ct lin kt C-C. Lin kt C-C ni chung kh phn ly thnh ion. Tuy nhin nhng dn xut thm ca metan nh ttraphnylmtan, imtylphnylmtan,...trong axit sunfuric ddawcjlaij c th cho ta nhng dung dch c mu v c tnh hunh quang khi chiu tia t ngoi vo, do hin tng to thnh cacbocation. So snh quang ph electron ca dung dch trimtylcacbinol v dung dch imtylphnylcacbinol trong H2SO4 c vi dung dch trimtylphnylmtan ngi ta i n kt lun rng trimtylphnylmtan b phn ct thnh cation tecbutyl.
(CH3)2 C - C6H 5 (CH 3)3C
+

d. Mt s hp cht khc nh este ca axit v c mnh ROSO2H, ROSO2Ar, hoc hp cht az trong nhng iu kin thch hp cng c th phn ly thnh cacbcation. Th d:
+ +

R-N

R + N2

2.1.12. Cc phn ng cng vo ni i to thanh cacbcation a. Cng prtn vo ni i ca anken: Khi c mt axit mnh alken c th cng hp prtn thnh cacbcation.
R2C =CR 2 +HA R 2C - CHR 2 +A
+ -

nu ion ny rt t bn n s chuyn ho ngay. V d:


CH 2 =CH 2 +H 2SO4 CH 3 CH 2 HSO 4
+

CH 3 CH 2OSO 3H

chng minh rng qu thc cacbcation c sinh ra t ken ngi ta so snh ph electron ca 1,1- iphnyltylen v ca hai dung dch ny c ph kh kin rt ging nhau, iu chng t trong c hai dung dch u to ra cacbcation mtyliphnyl mtyl. b. Cng prn vo nhm cabnyl:

31

Cc anhyt v xtn , - cha no vi lin hp cao, c kh nng kt hp prtn to thnh cacbcation cha nhm hyrxy ngay nguyn t cacbon trung tm. Th d:
- CH =CH - C =O +H 2SO4
2 +

- CH =CH - 2C - OH +H 2SO4

Phn ng trn l mt phn ng halcrm. Trong s cc phn ng to thnh cacbcation chng ta cn phi k n cc qu trnh to thnh hp cht thm khng c vng bn nh ion triphnyl-xycclpropenili, ication ttraphenyl-xycclpropenili... 2.1.2.1. Cu trc khng gian: V mt l thuyt ta c th cho rng cacbcation c cu trc phng tng t R 3B hoc cu trc hnh thp tng t R3N. gii quyt vn ny ta c th a vo s bin i nng sut quay cc ca dung dch hp cht c cacbon bt i kiu R1R2R3C Hal. Ta bit rng khi ho tan hp cht trn vo SO2 lng s xy ra qu trnh thun nghch.
R1 R 2 - C - Cl R3 R1

R - C - Cl 2 R3

Nu cacbcation c cu trc phng nh triankyl bo th trong qu trnh nghch Cl(-) c th tn cng nguyn t cacbon mang in dng t hai pha vi xc sut nh sau:

R1 C R2
+

R1 +Cl R3 Cl - C R2 R3 v

R1 C - Cl R2 R3

32

kt qu s to ra bin th raxemic, v R1R2R3C-Cl trong SO2 lng s b raxemic ho. Ngc li nu ion c cu trc hnh thp nh R3N th trong qu trnh nghch Cl(-) ch c th tn cng t mt pha thi.
Cl
+

C R1 R2 R3

Cl

C R 1 R2 R 3

kt qu l cu hnh ca phn t phi c bo ton. Thc t cho thy rng cc phn ly thnh cacbcation nh trn i vi hp cht cacbon bt i lun lun km theo s gim nng sut quay cc. D kin ny cng vi cc d kin thc nghim khc chng t rng cacbcation c cu trc phng hay gn nh phng. Thuyt c lng t cng cho kt qu tng t. Trong trng hp cacbcation triarylmtyl ta hiu cu trc phng l ba trc xut pht t nguyn t cacbon mang in dng xuyn qua cc v tr 1,4 ca vng benzen u trn mt mt phng. Cn ba vng khng nht thit trn mt phng m b lch i trong khng gian (do nh hng khng gian) tng t nh ba cnh ca mt chic qut bn. Trong cc cation xyclpropy ba lin kit C-C trn mt mt phng, cn vng xyclpropan to thnh mt phng khc nhau thng gc vi mt phng va ni v song song vi trc ca obitan p cn trng ca nguyn t C(+). Th d:

CH3 C CH3

Cu trc phng l iu kin cn cho cacbcation tn ti . V th, khc vi triphnyclomtan, 1-brmtryptyxen (A) trong SO2 lng khng cho dung dch mu v cng khng dn in. Khc vi triphnylcacbinol, 1 hyrxytryptyxen (B) trong H2SO4 c cng khong cho dung dch mu. Nhng iu chng t chng rt kh to ra cacbcation hnh thp.

33

Br C -C H (A)

OH C -C H (B)

2.1.2.2. Cu trc tinh vi v bn vng tng i bn tng i ca cc ion cacbni c lin quan cht ch ti s phn b in tch (cu trc tinh vi) trong ton b ion. in tch cng c gii to rng ra nhiu nguyn t trong ion th bn tng i cng cao. Mun tng bn ca mt cacbcation c th a vo nguyn t cacbon mang in dng nhng nhm c hiu ng lin howph hoc lin hp dng:
H H H
+

C- C

V vy, trong dy cation ankyl cng nh trong dy cc cation arlmtyl, bc ca cation cng cao bn ca cation cng ln:
+ + + +

CH 3
+

<

CH2 CH 3
+

<

CH(CH3 )2
+

< C (CH3 )3
+

CH 3

<

CH2 C H 5 6

<

CH(C6 H 5 )2

< C (C6 H 5 )3

Dy th hai thng c bn tng i cao hn dy th nht v hiu ng +C ca nhm aryl mnh hn hiu ng +H ca nhm ankyl. Tng t nh vy, s c mt ca nhm viryl C (Cation alyl) lm cho bn ca cation tng ln r rt:
+ +

CH2 - CH 2 - CH 3

<

CH 2 - CH = CH 2

Kt qu tnh ton in tch dng theo cc phng php ho lng cng nh cc kt qu kho st bng cc phng php vt l xc nhn c s gii to in tch dng trong cacbcation lin hp trn. Th d theo phng php MO Hucken in tch dng mt s cacbcation c gii to nh sau:
34

CH 2 = CH - CH 2 +0,05 0 C C + 0,05 C +0,14 0 +0,14 0

C6 H 5CH + 0,14
+ 0,57

C6 H5C (CH3)2 0 +0,08


+ 0,31

C6 H 5 C C6 H 5

C +0,08 0 +0,08

Cc nhm th c hiu ng +C hay +H v tr para ca C6H5CH2 hoc v tr ca CH2 = CHCH2 lm cho bn tng ln; tri li cc nhm th c hiu ng -C hoc H nhng v tr lm chop bn gim i. Trong nhng trng hp cacbtion khng kinh in, s d chng c bn tng
+

i cao (So vi ca lin kt C C hoc electron ca lin kt C = C khng v tr lin hp i vi obitan trng m v tr xa hn. Th d:
CH
+

CH

chng hn) v c s gii to electron

CH 2
+

CH 2 CH 2

CH2 CH 2

CH

CH 2

(Sinh ra t CH3 = CHCH2Cl (Sinh ra t C6H5CH2CH2Br) hoc t xicl-C6H5CH2Cl) S xut hin tnh bn vng c bit ca cc cation thm (th d ion trpili) cng do s lin hp v cc c tnh khc ca vng thm gy nn. 2.2.CACBANION Khc vi cacbcation c nguyn t cacbn thit th electron v mang in tch dng, cacbanion c mt cp electron d nguyn t cacbon v mang in tch m. Gia loi ion ny c s lin quan cht ch; v iu kin to thnh v tnh cht c nhng im tng t nhau hoc i lp nhau; v th khi kho st cacbanion cn lin h vi cacbcation. 2.2.1 S PHN LY LIN KT C X THNH CACBANION 2.2.1.1. iu kin thun li cho s phn ly lin kt C X thnh cacbanion. Mun cho lin kt C X d b phn ct d ly thnh cacbanion iu kin tt nht l: a. Cp electron lin kt C X chuyn mnh v pha nguyn t cacbon, chng hn cc lin kt CK, CNa,... trong hp cht c kim; b. Cacbanion sinh ra c cu to tng i bn

35

nh cac anion triarrylmtyl chng hn; c. Dung mi c dng c kh nng ion ho cao, thng amniac lng, ete,... Triphnylclomtan ch d phn ly thnh cacbcation thi. Nhng nu ta chuyn nhng phn t ny thnh dn sut natri (C6H5)3CNa trong amnic lng chng li cho ta nhng dung dch dn in v c mu, do s to thnh cacbanion v ion kim loi.
(C6 H 5)3C - H Na
NH 3lng

(C6 H5 )3 C - CNa (C H5 )3C - Cl 6 Na

NH 3lng

(C6H 5)3C : Na

Cacbanion ca nhng ankan n gin c trong cc hp cht c nguyn t nh cc hp cht ca liti, natri, magi...; do ni chung cc hp cht ny tham gia phn ng nh nhng cacbanion. Tuy vy, khng nn ngh rng cc hp cht y l nhng mui n gin kiu R- M+ v rng cc lin kt gia cacbon vi kim loi phn no mang tnh cht cng ho tr. 2.2.1.2. S phn ly lin kt C H v lc C H tng i: Lin kt C H cng c th b phn ct d ly to thnh cacbanion nu nguyn t H c linh ng rt cao. Th d triphnylmtan thc t khng tc dng vi kim c nhng tri (p-nitrophnyl) mtan li tc dng c vi NaOH to ra dn xut natri d phn ly thnh cacbanion.
(p - NO2C6H 4)3CH + NaOH (p - NO 2 6H 4) 3 C CNa +HOH

Qa trnh phn ly lin kt C H y chnh l qu trnh phn ly ca nhng axit cho nn ngi ta c th dng cc gi tr pKa lm mc o s phn ct d ly ny. 2.2.2 CU TRC V BN TNG I CA CACBANION 2.1.2.1. Cu trc khng gian: Nhn vo cng thc ca cacbanion ta c th cho rng cc anion ny c cu trc mt phng nh cacbcation. Nhng cacbanion li c cp electron cn d, nn cng c th chop rng chng c cu trc hnh thp. gii quyt vn cu trc khng gian ca cacbanion ngi ta c dng phng php o s bin i tnh quang hot ca hp cht c cacbon bt i trong qu trnh to thnh cacbanion. Tuy vy phng php ny gp nhiu kh khn cn bn. V th trong tng thi gian, tng ngi c nhng nhn nh khc nhau. Hin nay ni chung ngi ta nht tr rng cacbanion c th c cu trc hnh thp hay cu trc gn nh thng tu theo bn cht ca cc nhm th nguyn t cacbon mang in tch m. Nu gia nhm th v cp electron C(+) khng c s lin hp th cacbanion c cu trc hnh thp theo mt cn bng gia hai dng:

36

R1 R2 R3 C C

R1 R2 R3

V th trong phn ng di y cu hnh ca phn t vn bo ton.


n - C6 H13 CH 3 C6 H5 SO2
( T khi quang hc) nh u

C-D

OCH3

n - C6 H13 CH3 C6 H5 SO2

n - C H13 6
HOCH 3

CH3 C H SO 6 5 2

* C-H

( tinh khi quang hc 90%) t

Tri li nu gia nhm th v cp electron C (-) c s lin hp cho anion tr v bn vng th anion c cu trc phng hay gn nh phng. V vy, ta thy trong qu trnh sau y c s raxmic ho:
CN
* C2 H5 - C - COO

C2 H 5

C . . C

CN C H5 - C - H 2

anion quang hot

cacbanion

bi thraxm n ic

2.2.2.2. Cu trc tinh vi v bn tng i Gia cu trc tinh vi (s phn b mt electron) v bn tng i ca cacbanion cng c mi lin quan: in tch m hay l mt electron nguyn t cacbon trung tm cng c gii to rng bn ca cacbon cng cao. Nhng nhm th vi hiu ng C c kh nng gii to in tch m nh vy, chng hn tnh ton cho thy trong cc anion alyl v benzyl in tch m nguyn t cacbon trung tm ch bng khong n v in tch.
-0,50 0 -0,05 0 -0,14

-0,14
0 -0,14

-0,17

37

V th tluen c pKa ( 38) nh hn ca tan ( 58) , triphnylmtan c pKa cn nh hn na ( 33). bn ca cc cacbanion nh C6H5 CH2(-), (C6H5)6C(-) s tng ln khi tng ln v tr para c nhm th gy hiu ng C ( th d NO 2, CN...) ngc li s gim i khi c nhm th +C. Nu nhng nhm th -C ni trc tip vi nguyn t ccbnion s tng ln r rt (biu hin pKa). Th d:
CH 3CN CH 3(CN) pKa 25 11 CH 2 (COOC2H 5) CH 2 (COCH 3) 2 pKa 13 9

Trong nhng trng hp , in tch ca cacbanion phn b 2 nguyn t khc nhau. Th d:


CH3 - C = CH ... COOC2 H . 5 . . O

Nhng nhm c hiu ng -1 hoc H ni vi C(-) cng lm tng mnh bn ca cacbanion. Th d: pKa(theo thang Xtrviz) ca CF3H : 28, (CF3)3CH : 11. Cc anion vng thm nh C3H5(-), C6H52 ... c tnh bn cao l do s lin hp v cc c tnh khc ca hp cht thm. 2.3 PHN NG TO LIN KT CACBON CACBON VI S THAM GIA CA CACBCATION V CACBONANION: 2.3.1. PHN NG TO LIN KT CACBON CACBON CA CACBCATION 2.3.1.1. Phn ng ankyl ho: a. Phn ng ankyl ho ca cacbcation to ra lin kt cacbon-cacbon l phn ng cng hp vi ankan. V d in hnh nht ca phn ng ny l s to thnh 2,2,4 trimtylpetan c dng lm nhin liu cho ng c t izbutan v izbutylen.

38

CH3 (1) CH 3 - C = CH2 CH3 (2) CH3 - C = CH2


+

CH 3 +H
+

CH 3 - C - CH 3
+

CH 3 C - CH3 CH3

CH3
+

CH3

CH3 - C = CH2 - C - CH 3 CH3

CH 3
+

CH 3

CH 3

CH 3

CH3

CH 3
+

(3) CH3- C =CH - C - CH +H - C- CH 2 3 3

CH - C =CH - C - CH +H - C - CH3 3 2 3 H CH 3

CH3

CH3

Sau phn ng li tip tc 2, 3; 2, 3... b. Phn ng ankyl ha ca cacbcation xy ra cc hp cht thm theo c ch S E (phn ng Faiden-Crap). Trong phn ng ny thit lp nn mt lin kt cacbon-cacbon mi:
RCl + AlCl 3
+

AlCl 4
+

+ R R

R
+

+ C6 H6 R
-

C6 H5 H C6H5 - R +HCl +AlCl 3

6 C H5

+ AlCl4 H

Bng phn ng ny c th iu ch c nhiu hp cht thm c mch nhnh khc nhau. V d:

39

C6 H6 +CH3 CH2 CH2 CH3 C6 H6 +CH3 C - CH3 +

AlCl 3

C H5- CH CH CH3 +H 6 2 2 CH3

AlCl 3

C6 H5 - C - CH3 +H CH3

2.3.1.2. Phn ng cng hp vo anken y l phn ng cng hp to thnh mt caacbcation mi vi s hnh thnh lin kt cacbon-cacbon:
+ +

+>C =C<

R -C-C

Phn ng ny c ngha quan trng trong qu trnh trng hp theo c ch cactionic. V d phn ng trng hp izbutylen trong axit xy ra nh sau:
(CH3 )2 C = CH 2 H
+

(CH3)2C CH2 =C(CH3)2CH 3) 2C =CH 2 - C(CH 3 )

...

Trong nhng iu kin xc nh di tc dng ca axit H2SO4 s xy ra phn ng ime ho:


CH 3 CH 3

CH2 =C - CH2 - C - CH 3 CH3 2CH3 - C =CH4 H2SO4 CH3 CH 3 CH 3 CH 3 CH 3

H2 /Ni CH3 - CH - CH 2 - C - CH 3 CH 3

CH 3- C =CH - C - CH 3 CH 3

2.3.1.3. Phn ng ngng t crtnic: Hp cht cacbonyl trong mi trng axit b prtn ho to thnh cacbocation:

40

CH3 C =O +H CH3
+

CH 3
+

CH 3 C =O - H
+

C =OH

CH 3

CH 3

Cc hp cht tham gia phn ng ngng t crtnic to thnh lin kt cacbon cacbon mi:
CH3 C - OH +CH 3 C -CH3 CH3 O
+

CH 3 C - CH 2 - C - CH 3 CH 3 +OH 2 O
- HOC

CH 3 C - OH +CH 3- C - CH3 CH3 O


-H
+

CH3 C =CH2 C - CH 3 CH 3 O

2.3.2. PHN NG TO LIN KT CACBON CACBON CA CACBANION: Cacbanion c to thnh bng s tch i nguyn t - hyr ca cc hp cht cacbonyl. V vy cacbonion l mt baz mnh tham gia cc phn ng to lin kt cacboncacbon nh mt tc nhn nuclphin. 2.3.2.1. Phn ng cng hp nuclphin vo hp cht cacbonyl: a. Phn ng ngng t anatol:
C =O + - C - C =O
+

-C-C-C= O O

V d: Phn ng to thnh hp cht - hyrxibutandehyt t axxetanehyt xy ra theo s sau:

41

CH 3CHO + HO H CH3 - C =O + CH2 CHO

CH 2CHO H

+ H 2O

CH - C - CH 2CHO O
-

H
-

H CH 3- C - CH 2CHO OH

CH3- C =O + CH2 CHO O-

b. Phn ng ngng t peckin: Phn ng ca anhyrit ca axit cacbonxylic vi cc anhyt thm to thnh mi lin kt cacbon-cacbon xy theo c ch cng hp nuclphin (phn ng Peckin).
O CH 3 - C O CH3 - C C6H5- CH =O + C6H 5- C - CH 2 C = O O
-

O CH 3 - C O

C6 H5 CH =CH - COOH +CH 3COOH -

Cc phn ng to lin kt cacbon cacbon xy ra theo c ch ny cn tm thy rt nhiu hp cht khc nhau nh cc hp cht c kim loi, phn ng Refocmatxki s c trnh by trong phn sau: 2.3.2.2. Phn ng th nuclephin nhm axyl a. Phn ng ngng t claizen y l phn ng to thnh lin kt cacbon cacbon hp cht -xtn. V d phn ng iu ch tyl axetaxtat xy ra nh sau:

42

CH 3COOC2H 5

+C2H 5O

C2H 5OH + CH 2COOC 2H 5 O


-

CH 3 - C - OC2 H 5+ CH2COOC2H 5 O

CH 3 - C - CH 2 COOC 2H 5 OC2H5
-

CH 3 - C - CH2COOC2H 5 + C2H 5O O

bTng hp malnic: Mt trong nhng phng php to lin kt cacboxylic c da trn c s ca hp cht etylmelonat gi l tng hp malnic. Trong phn ng ny nguyn t -hyr ca etylmalnat rt linh ng nn d dng b thay th bi cc ion natri to thnh cacbonion.
COOC2H 5 CH 2 COOC2H5
C2H5ONa

CH
Na

COOC 2 H 5 + C2 H5OH COOC2 H5

Cacbanion c to thnh rt d tham gia phn ng vi cc dn xut halogen to thnh cc sn phm khc nhau:
COOC2H 5 R - Ral + CH 2 COOC2H5 R - CH COOC2 H 5 COOC 2 H 5 + NaHal

Cc este malnic d b thu phn trong mi trng axit v sau b cacboxyl ho bi nhit to ra cc axit monocacboxylic:
COOC2H 5 R - CH 2 COOC2H5
+

COOH R - CH COOH
tC - CO2
0

HOH/H

+R - CH 2- COOH

Theo nguyn tc ca phn ng trn y khng nhng c th tng hp c axit kiu R CH2COOH, R CHCOOH m cn tng hp c cc iaxit kiu HOOC (CH2)n COOH.

43

R 2.4. TO LIN KT CACBON CACBON BNG CC HP CHT C KIM: 2.4.1. PHN NG CA HP CHT GRINHA: Khi cho Magi tc dng vi cc dung dch ca ankyl halogenua trong ityl ete khan (C2 H5 )2O Th phn ng s xy ra rt mnh lit kt qu l Magi b ho tan v thu c mt dung dch mi. Dung dch gi l tc nhn Grinha. Tc nhn Grinha l mt hp cht hot ng rt mnh, n tc dng nhiu cc hp cht v c k c nc, xy, CO2 v vi mt s lng rt ln cc hp cht hu c. Mt trong nhng hng quan trng cu phn ng cc hp cht Magi l to ra cc mi lin kt cacbon cacbon. 2.4.1.1. Phn ng cng hp ca tc nhn Grinha: Phn ng cng hp ca tc nhn Grinha vi cc hp cht Cacboxyl (anehyt v xtn). Cc este v cc dn xut ca tylenxit u cho ra sn phm l cc ancol vi s to thnh cc mi lin kt cacbon cacbon mi. Trong phng php ny sn phm ca loi ancol thu nhn c tu thuc vo c im ca cc tc nhn c cha xy c s dng. a.Phn ng ca tc nhn Grinha vi cc hp cht cacboxyl: T Focmandhyt HCHO s to thnh ancol bc 1, t cc anhyt to thnh ancol bc 2 0, v t xtn s to thnh ancol bc 30.

44

R H - C =O +RMgX H - C - OMgX H R
0

H - C - OH (Acol 1 ) H H R' - C =O +RMgx H ' R' - C - OMgx R '' R ' R - C =O +RMgx '' R
HOH

H H - C - OH (Acol 2 ) R '' R H - C - OH (Acol 3 ) R


0 0

R' - C - OMgx R

Vic vn dng phng php tng hp ny thu nhn mt hp cht cn thit theo mun cn phi cn c vo cu to ca sn phm ancol. Mt nhm ankyl lin kt vi nguyn t cabon mang nhm - OH to thnh t phn t ca cc tc nhn Grinha, hai nhm cn li t hp cht cacbonyl, v d c th thu nhn hp cht 2 phnylhecxanol -2 bng 2 s phn ng sau:

45

CH3 -C O Axtphennon n - butylm agi brm ua +CH 3CH2 CH2 CH2 MgBr

CH 3 - C - CH2 CH2 CH2 CH3 OH

CH 3 - MgBr +CH3 CH2 CH2 CH2 - C O Phnylm agi brom a Mty - n - butylxtn -

CH 3 C - CH2 CH2 CH CH3 2 OH

Nh vy c th thu nhn 2-phnylhecxanol -2 t mt xtr thm vi tc nhn Grinha c 4 nguyn t cacbon (1) hoc t mt xtn bo vi tc nhn Grinha (2). Tuy nhin thc nghim cho thy rng trong trng hp c th ny th tin hnh iu ch 2 -phnylhecxal -2 theo s (1) l tt nht. b. Phn ng cng hp ca tc nhn Grinha vi este l mt trong nhng phng php tt nht iu ch ancol bc 30. Phn ng xy ra theo hai giai on: Giai on 1 to ra hp cht xtn v giai on 2 l phn ng ca xtn vi tc nhn Grinha to ra ancol:
O R-C '' R '' R Mgx
1

'' R
HOH

'' R -C-R O

R'' Mgx
2

'' R -C-R '' R

'' R -C-R '' R

OR'

Nh vy ancol bc 30 c th thu nhn c t xtn hoc este bng phn ng cng hp vi tc nhn Grinha. Tuy nhin cc kt qu nghin cu cho thy phng php iu ch ancol bc 30 t este l tt nht. V d triphnycacbinol c th thu nhn bng phn ng ca phnylmagibromua vi este etylbenzoat hoc xtn benzphenon. C 2 qu trnh c th thc hin t axit benzic theo s sau:

46

- COOH C2 H5 OH, H PCl 5 - COCl


C6 H 6/AlCl3

- COOC H5 2

2C6 H5 MgBr

- C - OH

- CO

C6 H5 MgBr

R rng qua s cho ta thy rng phn ng chuyn ho axit benzic thnh triphnycacbinol bng tc nhn Grinha qua bc to thnh este xy ra n gin hn, t giai on hn. c. Phn ng to thnh lin kt cacbon cacbon ca tc nhn Grinha vi xi tylen l mt phng php quan trng iu ch cc ancol bc 10. Phng php ny c u im ln so vi phn ng iu ch ancol bc 10bng focmanhyt s to ra c sn phm c mch di hn 2 nguyn t cacbon so vi gc ankyl hoc aryl ca tc nhn Grinha:
R - MgX +CH2 - CH 2 O RCH 2 2 CH OMgx H
+

RCH 2CH 2OH

2.4.1.2. Phn ng ca cc nhn Grinha v phn t cacbon electrophin: a. Phn ng vi cc dn xut Halogen: V nguyn tc tc nhn Grinha c th tham gia phn ng vi cc dn xut halogen theo c ch SN2 to ra lin kt cacbon cacbon. y l mt trong nhng phng php thun tin nht iu ch hydrocacbon no bc bn:
Br (C6 H5 )3 C - Cl +C6 H5 MgBr (C H5 ) C +Mg 6 4 Cl Br (CH3 )3 C - Cl +C H5 MgBr 2 (CH3 ) C - C H +Mg 2 5 3 Cl

Phn ng ny cng c th dng iu ch cc hyrcacbon khng no:

47

Br CH3 CH2 - MgBr + ClCH2- CH =CH2 CH 3CH2 CH 2 - CH =CH 2 +Mg Cl

Phn ng ca tc nhn Grinha vi dn xut halogen ca axit cacboxylic s to thnh hp cht xtn. Trong thc t ngi ta c th li cho phn ng dng li giai on to ra xtn hoc i xa hn na to thnh amol bc 3.
' R RCOL ' RMgBr ' R - CO - R RMgBr, HOH R - C - OH ' R

b. Phn ng vi cc hp cht nitrin RC N Nhm xian trong cc nitri R C N phn ng vi hp cht magi to thnh lin kt cacbon cacbon tng t nh nhm cacbonyl:
R - MgBr +R' - C N R - C - R' HOH NMgBr R - C - R' +Mg NH Br Cl

Sau nhm Imin b thu phn to thnh hp cht xtn:


R - C - R' + HOH NH R - C - R' + NH 3 O

Phn ng ny c th s dng iu ch cc xtn bo. V d:


CH3CH2 MgCl + CH3 - C CH3CH2 - C - CH3 NH
HOH

CH3 CH2 - C - CH 3 HOH NMgBr

CH3 CH 2 - C - CH 3 O
Br

hoc cc xtn thm:


C6 H5 - C N + RMgBr C6 H5 - C - R NMgBr C6H 5 - C - R + Mg O Cl + 2 NH

Trong R - gc bo hoc thm.

48

c. Phn ng ca hp cht magi vi cc hp cht ankel, xy ra theo c ch cng hp. So vi lin kt C = O th lin kt i C = C kh tham gia phn ng cng hp vi hp cht phi kim hn:
R C C + RMgHal chm MgHal - C - O -

Trong khi :
C =O +RMgHal
nhanh

- C - O - MgHal R

Tuy nhin s cng hp vo lin kt i c th thc hin c khi lin kt c hot ho bng mt nhm ht in t: V d:
' OR x =C - C =O +RMgHal R OR'

- C - C =C - OMgHal H3O
+

OR'

OR'

- C - CH - C =O

- C - C =C - OH

2.4.2. PHN NG CC HP CHT C KIM VI CC PHN T CACBON ELETROPHIN. 2.5.2.1. Cc hp cht c Natri v c Liti: Cc hp cht ankyl natri v ankyl liti c nhiu im ging vi tnh cht ca cc hp cht c magi nhng c kh nng phn ng cao hn. to thnh lin kt cacbon cacbon, cc hp cht ankyl natri v ankyl liti c s dng trong nhiu phn ng khc nhau. V d phn ng tng hp Vuyc iu ch cc hp cht ankhan xy ra theo s sau:
R - Hal + 2 Na + Hal - R R - R + 2 NaHal

Trong phn ng ny cc ankyl halogenua c phn t lng cng cao thng cho hiu sut cao v phn ng thng c s dng iu ch cc hyrcacbon mch di:
2C20H41Br
nhanh

C40H82 Pehi rlicopin 49

ihy rphytyl Brom ua

Tuy nhin phn ng tng hp ny ch c ngha dng tng hp ankan i xng R R, cn i vi cc ankan bt i R Rs to ra mt hn hp nhiu sn phm. Cc hp cht ankyl c liti c th tc dng vi nhng hp cht c ni i, ni i lin hp vi nhn thm v cc ien:
CH3CH2 CH2 CH2 Li +nCH2=CH 2 (C H5 )2 C = CH2 + C4HgLi 6 CH 3CH 2CH 2CH 2(CH 2- CH 2 n ) Li (C6H 5) 2C =CH 2C 4Hg Li CH3 CH2 = C - CH =CH 2+ RLi CH 3 RCH 2 - C = CH = CH 2Li

Cc ankan liti cng vo butaien -1,3 cc v tr 1,4 v 1,2 nhng nu tin hnh nhit cao th phn ng cng vo v tr 1,4 l thun li. Phn ng c s dng tng hp polibutanien c cu trc iu ho tp th lm cao su ging cao su t nhin.
H3 C C =C R - CH 2 H CH3 +CH =C - CH =CH H3 C C =C R - CH2 CH2 H CH2 C =C CH 3 Polim ho e H CH2 Li

CH2 Li

H3C C =C R CH2

H CH2 CH2 C =C CH2 H n CH2 R

Khc vi hp cht c magi, c km tham gia phn ng vi cc hp cht cacbonnyl to thnh ancol bc ba c phn nhnh cao. V d: trizpropylcacbinol c th c iu ch t izpropylxtn v izpropyl liti nh sau:

50

H3C CH3 CH - C - CH CH3 O CH 3 H3C H3C CH CH - C - CH H 3C OH CH 3 CH3 + CH3 CH - Li CH3 CH3 CH 3 CH3 CH

CH3 CH 3

CH - C - CH CH3 OLi CH 3

HOH - LiOH

2.5.2.2. Hp cht c km, catmi: Tng t nh hp cht c magi, c km tham gia phn ng vi cc hp cht cacbonyl to thnh cc ancol khc nhau tu thuc vo tc nhn cacbonyl tham gia phn ng: focmahyt ancol bc mt; anhyt ancol bc hai; xtn, clorua axit ancol bc ba. iu ng lu l phn ng ca anhyt hoc xtn vi km v este ca cc axit halogen th ta c - hyrxiaxit (phn ng Refocmatxki).
BrCH2 COOCH2CH3 + Zn BrZn - CH 2COOCH2CH 3
HOH

CH3CH2 CH = O

CH3CH2 - CH - CH2 COOCH 2CH 3 OZnBr

CH3CH2 - CH - CH 2COOCH 2CH 3 OH

OHOH/H+

CH3 CH2 - CH - CH 2COOH OH

to mi lin kt cacbon cacbon c th sue dng phn ng ca hp cht c catmi vi hp cht clorua axit:
2RCOl + R'2Cd 2R - C - R' + CdCl 2 O

Khc vi phn ng ca hp cht c magi vi clorua axit l sau khi to ra sn phm xtn, hp cht magi tip tc tc dng vi hp cht ny to thnh ancol bc ba, trong khi hp cht c catmi c tnh hot ng ho hc yu hn nn sn phm thu c ch dng
51

li hp cht xtn. Mt khc hp cht c catmi cng khng phn ng vi nhiu nhm chc khn nhau nh NO2 CN - , - COOR. V vy s c mt ca cc nhm chc khc trong phn t clorua axit s khng gy cn tr n phn ng tng hp xtn. V d:
2O2 N COCl + (CH3 ) Cd 2 2O2 N COCl + (CH3 ) Cd 2

CH3 OCOCH2 CH2 COCl + (CH3 ) CHCH2 CH2 2Cd 2 CH2 OCOCH2 CH2 CO CH2 CH(CH3 )2

52

CHNG 3 PHNG PHP NG V M VNG 3.1. PHNG PHP TO VNG ANKAN Qa trnh thu nhn cc vng anken t cc hp cht hyrcacbon mch thng thng c thc hin qua 2 giai on phn ng: a. Chuyn ho mt hp cht mch h thnh hp cht mch vng bng phn ng n vng. b. Chuyn ho hp cht vng thu c thnh hp cht vng cn thit phi iu ch, v d chuyn ho xycloancol thnh xycloankan hoc xycloanken thnh xycloankan. 3.1.1. ANKYL HO TRC TIP: chuyn ho cc hp cht mch h thnh mch vng bng phng php ankyl ho trc tip th cc hp cht mch h cn phi cha 2 nhm chc nh halogen, ancol, cacboxyl... V d phn ng to cc hp cht vng nh c thc hin bng cc s sau y:
CH 2 - X (CH2 )n CH2 - X Xc tc ( CH2 )n CH2 CH2

Trong phn ng ny n = 1,2,3,4,5, - tc l c th iu ch t xyclopropan n xyclohecxan. X v Y l cc nhm halogen, cacboxyl. Xc tc thng hay dng l kim loi kim hoc cc hn hp kim loi. V d xyclpropan c iu ch t 1,3 ibrompropan vi xc tc natri kim loi theo phn ng sau:
CH 2Br CH 2 CH2 Br Na CH2 CH2 CH2 + 2NaBr

V thc cht y l phn ng ng vng ni phn t Vuyc nu phn ng ny c thc hin vi tc nhn tch loi l bt km trong ancol th s c hiu sut cao hn. iu ch xyclobutn vi hiu sut cao konor dng phn ng ca 1,4 dibrombutan vi hn hp Liti trong dung mi khng phn cc tetrarydofuran:
CH2 CH2 - CH2 Br +2 Li - Hg - CH2Br CH2 CH 2 CH2 - CH 2 + 2 Li - Hg

53

Bng phng php tng t cng c th iu ch xyclopental t 1,5 dibrompentan vi hiu sut 75%.
CH2CH2 Br H2 C CH2 CH2 Br +2Li - Hg H2 C CH 2 - CH 2 CH2 - CH2 +2LiBr + Hg

Tuy nhin trng hp cc hp cht vng c th iu ch bng phng php Peckin vi cc tc nhn phn ng l mui natri ca este nalnia v dn xut halogen:
CH2Br CH2 CH2 Br CH2
Na CH COOC2H 2 5
+

+Na CH COOC H5 2 -NaBr CH2 2 CH 2Br

CH 2 - CH 2 COOC 2H 5

H2 C CH2

C (COOC2 H5 )2 + NaBr + CH2(COOC2 H 5)2

iu ch cc vng 5, 6 v cc hp cht a vng thng s dng phng php Piria nhit phn mui canxi ca iaxit cacboxylic.
O CH2 - CH2 - C O Ca O CH2 - CH2 - C O CH2 - CH2 tC
0

CH2 - CH2 C = O + CaCO3

Phn ng loi ny nu dng iu ch xyclopentanon v xyclohecxanon th c hiu sut cao cn vi cc vng c s nguyn t cacbon ln hn th c hiu sut rt thp. Phn ng ny cng khng s dng c iu ch cc hp cht 3 hoc 4 vng. Phng php ngng t cc ieste v cc dn xut ca n cng thng c s dng iu ch cc hp cht vng - phn ng icmon:

54

O (CH2 )n - COOHC H5 2
C H5ONa 2

C (CH2 )n-- CH - COOC2 H5

CH2 - COOC H5 2

Trong iu kin tng t nh vy s xy ra phn ng ngng t ca hp cht nitrin:


CH2 CN (CH2 )n CH2 CN CH2 (CH2 ) n C = NH HOH CH2 (CH2)n C =O

CH - CN

CH - CN

Phn ng ngng t este lin phn t cng c th s dng iu ch hp cht vng. V d phn ng ca ietylxalat vi este glutariat hoc ng ng axtn ca n s to ra cc vng xtn 5 cnh:
O C + C O OC H5 2 CH2 - COOC2 H5 CH 2 OC2 H 5 CH - COOC2 H5
C2H5ONa

O =C - CH - COOC H5 2 CH2 O =C - CH - COOC H5 2

O C

OC2 H5 + C

CH2R O =C - CHR C =O CH2R


C2H5ONa

C-O O =C - CHR

OC H5 2

S ngng t ca 2 phn t este xuxinat s to thnh hp cht vng 6 cnh:

55

O O C CH2 H2 C C O OC H5 2 O C OC H5 2 O O + CH2 OC H5 H5C O - C 2 2 CH2


C H ONa 2
5

O C

OC H5 2 O CH - C CH2 C - CH C OC2 H 5

H2 C

Phng php ankyl ho trc tip cng c th thc hin bng phn ng ng vng cc hp cht hyrcacbon c 5 nguyn t cacbon vi xc tc Platin nhit 3000C.
CH3 CH3 - C - CH2 - CH - CH3 CH3 CH3
P(300 C)
0

CH2 - CH2 H3 C - C - CH2 CH 2 CH - CH3 + H2

i vi cc khung hyr cacbon c ln hn 5 nguyn t cacbon th bc u s to thnh vng 6 cnh nhng tip sau c th b hyr ho thnh vng benzen nu nh vng khng c mt nguyn t cacbon bc 40.
CH3 H2 C CH3 - CH2 - CH2 - CH - CH2 - CH3 H2 C CH2 CH2 CH2 + 3H2

S c mt ca nguyn t cacbon bc bn s cn tr qu trnh thm ho :


H3C C H3 C H2 C CH 2 CH2 CH2 + H2 CH - CH3

CH3 CH3 - C - CH2 - CH2 - CH CH3

CH 3 Pt CH3

56

Phn ng ankyl ho thu nhn hp cht vng c quan st thy s chuyn ho ln nhau ca cc hp cht vng. Phn ng m rng vng c thc hin bng s tn cng ca mt nguyn t cacbon mch nhnh ca vng vo khung cacbon ca vng (s chuyn v): V d:
CH2 H H2C - CH2 H2 C - CH - CH2 OH CH - CH2OH H2SO4
H2 SO4

H2C - CH H 2C - CH CH2

+ H2O + H2 O

H2C H2 C

CH2

Phn ng cng c th xy ra theo hng ngc li km theo s hp vng:


OH H
+

CH - CH2OH

C ch chuyn ho ca qu trnh chuyn v trn y xy ra theo s sau: S m vng:


CH2 (CH2 )n- C - C OH O H R
H2SO -HOH
+

CH2 (CH2 ) - C - C n O H

CH2 (CH2 ) - C - C n

R R

C +H O

+H

S hp vng:
OH CH3 OH CH 3
+ +

+ H -HOH

CH3 OH CH 3

- CH3 C =O CH3

Cc phn ng ankyl ho khng nhng ch dng iu ch cc hp cht n vng m cc hp cht a vng khc nhau. V d s to thnh cc hp cht hai vng c th c thc hin theo cc phn ng sau: a. Tng hp vuyc:

57

- CH2 Cl + 2 Na

- CH2 - CH 2

b. Tng hp bng s h tr ging ca tc nhn c magi:


-Br + Mg - MgBr

OH =O + - MgBr

c.Ngng t cc vng anhyt hoc xtn vi nhau:


=O O + - MgBr O Mg - Hg OH OH

d.Kh ho cc vng xtn:


2 =O

e. Phn ng to thnh cc hp cht spiran:


CH2 CH2 COOC H5 2 CH2 COOC H5 2 COOC2 H5 O

NaOH

OH

OH

OH

OH

3.2. PHN NG CNG HP:

58

3.2.1. PHN NG CNG HP INX AN Cc hp cht cacbonyl , khng no tham gia mt phn ng rt quan trng vi cc ien lin hp c gi l phn ng inx An. Sn phm ca phn ng ny l mt vng 6 cnh c hnh thnh do kt qu cc mi lin kt gia nguyn t cacbon ca ni i trong hp cht cacbonyl khng no. Duwowis y l mt s v d v phn ng cng hp inx An:
O CH2 + CH CH2 Buta -1,3 ien H C C An cis -1,2,3,6 -tetra ehyt hy rphatalic O H C O C
20 C benzer
0

O O

CH

O Anhy m rit aleic

59

H CH2 + CH CH2 Buta -1,3 ien CH2 + CH CH2 Buta -1,3 ien O p - Benzoquinon O O 5,8,9,10 -Tetrahy - 1,4 -naphtquinon r O
20 C beyzen
0

C =O HC HC H Arclin An cis -1,2,3,6 -tetra hyt hy rbenzan hyt O


But -1,3, 100 C in
0

CH

100 C

CHO

CH

O O H C + H Xyclohecxa -1,3 ien O C C O O C-O C


Benzen t C
0

C =O

Thc nghim chng minh rng phn ng cng hp xy ra d dng nu Anken (thng gi l phn ienophin) c th bi mt hoc nhiu nhm ko electron mnh, th
- C - R, - C N...

d nh COOH, O

60

Trong bng sau y l mt s ienophin c kh nng phn ng cao.

MT S CHT IENPHIN HOT NG TN CNG THC

61

Ttraxiantylen Crlonanhyt Axitxinamic (els v trans) Anhirit malic

(CN)2 C = C(CN)2 CH3 CH =CH - CHO C6 H5 CH =CH - COOH

O H HC O HC C O

H C

COOCH 3

Dimtyl malic
H

C COOCH 3 CH3CH - CH - NO2 CH2 - CH - CN CH2- CH - CNO CH2- CH - COOC2 H 5 O C HC N - C6 H5 C O H C C COOCH3 H C6 H5- CH =CHNO2 COOCH3

1- Nitrpropen Acrilnitrin Acrlin tyl acrital

N phnylmalimit

HC

imtyl fumaral
62

-Nitrositren
Mt trong nhng u im ca phng php inx An l n xy ra rt c th v mt lp th. ien phn ng cu dng s-eis ca cc ni i ca n, bi v ni i sn phm (mt vng su) phi c cu hnh cis.
CH2 C C CH2 H CH 2 H CH2 C C H CH2 = CH2 CH2 C C CH2 H H H CH2 C CH2 H C CH2 H

CH2 CH2

CH2

Mt im ng ch na l cu hnh ca ien v ca cht ienphin vn gi nguyn sn phm. iu ddod c ngha l hai cht ny cng hp cis vi nhau. Chng hn butaien phn ng vi imtyleste ca axit fumaric hoc axit malic trong tluen v 0 nhit 155 C cho imtyleste ca cc axit trans - hoc cis xyclhexen - 1 icacbxylic -4,5.

63

H CH3OOC

- COOCH3 CH3OOC

H COOCH3 H H H COOCH 3 COOCH 3

im tyleste ca axit trans -xiclhexen -1- icacbxylic -4,5 H CH3OOC - COOCH3 CH3OOC H H COOCH3 COOCH3 H H COOCH3

COOCH3

cc th d ny ta thy cu hnh ca cht ienphin c gi nguyn . Ta cng cn k n mt c im na ca phn ng ix An l trong nhiu trng hp cc cht phn ng b nh hng v mt ho lp th. Th d phn ng cng anhirit vo xyclpentaien c th i theo hai con ng dn ti hai sn phm khc nhau.
O O O O O Sn phmca en O O O

im tyleste ca axit trans -xiclhexen -1- icacbxylic -1,5

64

O O O O O S phm ca ex n

Trong thc t thng hnh thnh ng phn en l sn phm ch yu duy nht. Phn ng ix An c l xy ra theo mt c ch nhiu trung tm, trong hai lin kt mi gia ien v cht ienphin hnh thnh ng thi (Hoc hu nh ng thi). Mt tin trnh phn ng ng thi nh vt c nhng yu cu rt cao v mt lp th, cc i tng phn ng phi c sp xp sao cho hai lin kt c th hnh thnh cng mt lc, ph hp vi iu ny cc phn ng ix An thng c entropi hot ho m mnh (t -20 n -25 cal/. Mol). Sn phm phn ng ca cc tng hp ien thng l cc cht trung gian cho nhiu tng hp hu c. Bixicl -[2,2,1] heptaien (2.5) (I) c tng hp t xyclpentaien v axtien vi hiu sut khong 65%. Cht ny phn ng vi hecxaclozxiclpentaien mt cch hu nh ton lng trong mt tng hp ien th hai thnh cht anrin II l mt loi thuc tr su c hiu lc:
H C H C Cl Cl Cl Cl Cl Cl (I )

(I ) Cl Cl 9 Cl

11 Cl Cl 8 H H 6 5 4

1 10 Cl

2 ( II )

12 3

Trong s cc sn phm cng hp ix An ca hecxaclopentaien cn c nhiu loi thuc tr su khc v mt s plime chu nhit. Cc phn ng ix An l thun nghch. Ta c th s dng tnh cht ca phn ng vo trong tng hp v sau khi thc hin cc bin i cc sn phm cng hp ix An ta li c th tch chng ra thnh cc hp phn. Chng hn cht tianhirit ca axit

65

malic cng hp vi butalien, sau sn phm c chuyn thnh dn xut ion III ri tch ra thnh cc hp phn.
O O
Na Sx 2
HCl

O (I )

O ( II )

O ( III ) ( IV )

Mc du ni chung cc ien lin hp tc dng vi cc cht ienphin v tr 1,1 cho cc hp cht vng su, ngi ta cng bit c mt s phn ng cng 1,2 cho cc hp cht vng 4. Rt c th bn cht ca cht ienphin l yu t qut nh vic cng hp theo 1,4 hoc 1,2. Chng hn mc du tylen cng hp 1,4 vi butadien, ttraflotyln li cng hp 1,2:
CH2 =CH - CH =CH2 + F2C =CF 2 100 C
0

CH2 =CH CH - CH2 F C CF 2 2

Trong khi ttrafltylen cng vo xyclpentaien cho mt hn hp cc sn phm cng hp ng vng 1,2 v 1,4.

+ F2C = CF2

190 C

F 2 + F
2

3.2.2. PHN NG CNG HP CA CACBEN V NITREN VO ANKEN L nhng hp cht ho hc hot ng rt mnh v trong cc phn ng vi cc hp cht anken chng s dng nhm mtylen: CH2 to thnh cc hp cht vng. Mtylen v dn xut mtylen tham gia phn ng cng hp vo ni i (- C = C -) theo s sau:

66

CH C =C + : CH2 C

Cl C =C Cl + : CH2 Cl2C

CCl2 C Cl2

: CCl 2

CCl2

Loi phn ng ny cng c iaknp s dng iu chnh mt s dn xut ca axit cacbxylic:


H H C C3H7 - C = C - C H7 3 COOC H 5 2
+

COOC H5 2 C

H COOC H5 2

N =N =C

H7C - C - C - C H7 3 3 C COOC H5 H 2

Phn ng cng c th dng tng hp xyclbutan t Anken:


CH2 = C = O + CH2 = N = N H2C - C = O + CH2 = N = N CH2 H2C H2C C =O + N2 CH2 H2O C =O + N2

CH2

Mtylen v dn xut ca n c th tham gia phn ng cng hp vo h ni i ca bn:

67

:CH

CH
noc - caradien xycloheptatrien

Tng t nh vy clocacben tc dng vi benzen to thnh ion tripili theo s sau:


Cl + :CH CH noc - caradien xycloheptatrien Cl + Cl -

Cc hp cht cacben v iazmtan cng c th tham gia phn ng cng hp vo ni ba (Ch c phn ng vi dn xut ca axetylen, nhng khng phn ng vi axtylen) to thnh vng khng no. V d:
CH2 CH3- C C + CH3 + : CH 2 C6H5 CH3 - C = C - CH3 + : CH2 Br C H5 6 C H5 6 + Br C H5 6 CH3 C = C - CH 3 CH2 CH3 C = C - C H5 6

Mtylen cng c th cng hp vo cc hp cht vng ete v m rng vng hn:


O + : CH2 O O - CH2

3.3. PHNG PHP TO VNG THM V D VNG 3.3.1. TNG HP BENZEN V DN XUT CA BENZEN Benzen c th c tng hp bng phn ng trime ho hp cht axtylen:

68

HC HC + HC HC CH CH

Phn ng ny c nhiu nh ho hc nghin cu vi cc xc tc v iu kin phn ng khc nhau. thu c benzen Zelinxki tin hnh phn ng trn than hot tnh nhit 450 5000C. Trong khi Repe s dng xc tc l icabony itriphenylphotphin Niken [ (C6H5)3P]2 Ni (Co)2 v thu c dn xut th 1, 3, 4 ca Benzen. Bng vic s dng xc tc l [ Al(C2H5)3 + TiCl4] Xigler thu nhn c cc dn xut th 1, 3, 5 ca benzen. Vi xc tc l CrCl3 Xeis iu ch c hp cht hecxaphnylbenzen t iphnylxtylen:
C H5 6 C C + C C H5 6 C C H5 6 C - C H5 6 C - C H5 6 H5C6 C H5 6 C6H5

C H5 6

H5C6

C H5 6

C H5 6

b. Hp cht axtn di tc dng ca axit sunfuric m c s to thnh 1, 3, 5

trimtylbenzen (mzitilen).
CH3 C O CH3 C H3C O CH3 + C - CH3 CH3 H3C O + 3H2O CH3 CH3

Phn ng cng xy ra tng t i vi cc xtn loi R-CO-CH3. V d t axtphenon C6H5COCH3 c th iu ch 1, 3, 5 triphnylbenzen.


69

Loi phn ng ny cng c th s dng iu ch cc dn xut bn t cc hp cht anhyt c nhm mtyl linh ng:
COOH CHO CH2 HOOC + CH2 OHC COOH CH2 CHO COOH COOH COOH

c. Mt trong nhng phn ng c s dng rng ri iu ch benzen l phn ng

thm ho cc hp cht parafin bng xc tc platin nhit ~3000C:


CH3 - CH2 - CH2 - CH2 - CH2- CH3 Pt + 4H2 Pt CH3 + 4H 2

CH3 - CH2 - CH2 - CH2 - CH2- CH3 - CH 3

Phn ng ny c th thc hin bng xc tc [ Al2O3 + Cr2O3 ] nhit trn 4000C. d. Cc hp cht benzen cng c th c iu ch bng phn ng ehyr ho xyclhecxan v xyclohecxaien vi xc tc platin nhit cao.
Pt

Pt

+2

Pt

3.3.1.2. Tng hp cc d vng 5 cnh: a. Phng php quan trng v chung nht dng tng hp cc hp cht d vng thm, 5 cnh c bt u bng 1,4 - dicacbonyl.

70

PO 2 5

HC - CH R C O
PS 2
5

CH2 - CH2 R C OO C R R

HC - CH C C

PO 2 5

HC - CH R C S HC - CH R C NH C R C R

OH OH
NH3

Cc hp cht d vng 5 cnh c th c thu nhn bng phn ng nhit phn (cacbonxyl ho) axit muxic nh sau:
tC HO - CH - CH - OH HO - CH O =C OH CH - OH C =O OH NH3 , t0C NH + 2 CO + 4 H2O 2
O
0

+ 2CO2 + 3 H2O

Phn ng ny khng s dng iu ch tiphen c nhng tiphen c th c iu ch bng phn ng ca axit vi P2S3
CH2 - CH2 HOOC COOH NH3 ,t C O c. chuyn ho ln nhau gia cc d vng thm v khng thm 5 cnh lurep s
0

dng xc tc Al2O3 4000C cho cc phn ng xy ra theo s sau:

71

Hth m H2S HOH O

NH 3 HOH

H2S HOH

Hkhng th m

NH 3

HOH O

NH3 S H2S NH S

NH3 H2S NH

d. Phn ng cng hp 1, 3 vo h ni i v ni ba ca tc nhn loi iazo, axit nit, axit, oxit nitril, hp cht nitron... cho php thu nhn mt s lng rt ln cc hp cht d vng 5 cnh khc nhau di y l mt s v d:

72

1. R - C
+

C-R

R - C =C - R : N CH 2 N ..

R -C-C-R :N C NH R - C - CH - R : N CH 2 NH

N.=. . - CH2 . N

2. R - CH
+

CH - R

R - CH =CH - R : N CH 2 N ..

N. =N - CH2 . ..

3. R - C
+ -

C-R

R - C =N - R :N N - R N .. R - C =N :N N - R N ..

N =N - . . - R N .. .. 4. R - C N

N . . =N - N - R
+

5. H - C =N - OH Cl H-C C-R

R - C =N - O

R - C =N - O xit nitril

H - C =C - R R-C ' RI,HO


-

.. + R - C =N - O

O N
+ + -

6. H - C =N - OH

R - CH =N - O R

R - CH =N - O nitrol

H -C

C-R

H2 - CH - R'' C R - CH O N .. ' R

.. + R - C =N - O ' R

73

e. Cc hp cht d vng 5 cnh cng c th c iu ch bng phn ng ca Shulte nh sau:


H2O,C2H5O
-

HC

C-C

HC

NH3 ,CuCl 150 C


0

NH

e. Ngoi cc phng php chung iu ch cc hp cht d vng 5 cnh trn y, ngi ta cn s dng nhng phng php tng hp cc hp cht ring bit. V d: 1. Phn ng iu ch furan v dn xut furan:
HO - CH - CH - OH CH2 CH - CHO
-3H O 2

CHO O

OH OH HO - CH2 - CH2 - CH2 - CH2 - OH O

1. Phn ng iu ch tiphen:
Ar CHCl C =O Ar + OC2 H5 C =O CH C N
-

Ar
+

COOC H5 Ar 2 = NH Ar O

COOC H5 2

Na

Ar

NH2

2. Phn ng iu ch diophen:

74

CH3CH2CH2CH3 CH + CH H2 S CH CH

+ 4S

700 C + S

+ S H2

3 H2 S

Al2O 3

400 - 500C

H5 C6 un 2C H5 - CH =CH - C H5 + S nng 6 6 H5 C6 R ' R O

C6 H5 C6 H5 S

_ R - CH - CH2 - C = CH C R'

CH3 S

3. Phn ng iu ch pirol:
R - CH2 C R' + O O = C - R'' CH NOH ' R R '' R

NH

4. Phn ng iu ch indol:

75

CH = CH - Cl + C H5 ONa 2 NH2 NH + NaCl + C H5 OH 2

+ NH2

CH CH - H2 NH

CH2 - CH3 CH N - N H C - CH3 CH 2 CH NH2


- NH3

CH - CH3 CH N - N H H

CH3 NH

3.3.2. TNG HP CC HP CHT D VNG 6 CNH: a. Tng hp piriin: Piriin c th thu nhn bng phn ng ca axetylen vi axianhyric (phn ng Betlo):
CH CH + CH N CH N CH

b. Cc dn xut ca Piriin c th iu ch bng phn ng ca anehyt RCH2CHO vi amniac khi c mt xc tc Al2O3 4000C nh sau:

76

CH2 - R CH O R - CH2 CH O O CH R - CH2 + R - CH2 CH O CH RCH3 N CH2 + NH3 O R R R + H2O + H2 H2O - R H2C - R CH CH2R R R + 3H2O + H2 N

O . NH3

Dn xut Piridin cng c th c iu ch bng phn ng ca cc ien vi ankylinitril:


CH CH CH2 CH2 + N C - R N R

3.4. PHN NG M VNG: Phn ng m vng ca cc hp cht vng xy ra di tc dng ca cc tc nhn khc nhau theo nhng c ch khc nhau tu thuc vo cu trc ca vng. Di y l mt s phn ng m vng c bn thng gp. 3.4.1. M VNG BNG PHNG PHP KH HO Do qu trnh to thnh hp cht vng, cc nguyn t cacbon b bin dng khi trng thi lai to tng ng cu mnh nn trong cc hp cht vng tn ti mt sc cng (Sc cng Baye, sc cng Fitze...). iu ny dn n cc hp cht vng tham gia mt s phn ng kh ho tng t nh cc hp cht hyrcacbon khng no. V d: Xyclpropan tham gia phn ng hr ho vi s ph v vng lin kt cacbon cacbon nhit 800C.
77

CH2 H2 C H2 - CH2 C H2C - CH2 CH2

H2 /Ni

CH3 - CH2 - CH3

Trong khi phn ng vi xiclbutan xy ra 1200C.


H2 /Ni

CH3 - CH2 - CH2- CH3

Phn ng cng xy ra tng t i vi cc dn xut ca Xyclpropan v xiclbutan nhnh tu thuc vo s c mt ca cc nhm chc khc nhau s thu c cc sn phm khc nhau. V d phn ng hyr ho izpropyl - xiclpropan v izpropenyl xiclpropan s to thnh cc sn phm khc nhau nh sau:
CH3 H2C H2C CH - CH - CH3
H2

CH3 CH - CH CH3

CH3

CH3 CH

CH3 H2C H2C CH - CH - CH 3


H2

CH 3- CH2 - CH2- CH CH

3.4.2. PHN NG CNG HP THEO C CH ELECTROPHIN: Cc hp cht vng c th tham gia cc phn ng cng hp vi cc tc nhn electrophin vi s ph vng. Phn ng thng xy ra di tc dng ca cc hyrhalogenua. V d: phn ng ca xiclpropan v xiclbutan vi HBr xy ra nh sau:
H2C CH2 HBr (CH2)n CH3 - (CH2) - CH2 Br n

Phn ng cng xy ra tng t khi s dng tc nhn electrophin l H2SO4 hoc Brm.
H2C CH2
H SO 4
2

(CH2)n
Br2

CH3 - (CH2 ) - CH2OSO3 H n Br CH2 - (CH2 ) - CH2 Br 2 n

Kt qu nghin cu cc phn ng m vng cho thy rng s c mt ca cc nhm th i in t ca vng nh COOH, - CHO... s lm cho phn ng ph vng xy ra kh
78

khn. V d cc dn xut ankyl ho ca xiclpropan rt d dng phn ng vi axetat thu ngn:


CH2 R - CH - CH - R + Hg(OCOCH3 )2 R - CH CH3O CO CH 2 CH - HgOCOCH2 R

c bit cc phn ng ca h lin hp vng vi ni i thng xy ra theo quy tc phn Macopnhicop:


CH2 H2C - CH - C - C H5 + HBr 6 O CH2 - CH2 - CH 2 - C - C6 H5 Br O

3.4.3. PHN NG CNG HP THEO C CH NUCLEPHIN: Phn ng cng hp dn n p v vng theo c ch nuclonphin xy ra ch yu cc vng xtn, lactn... V d phn ng cng hp ca xianat Kali vo vng lactn xy ra theo s sau:
H2 C - CH 2 O + KCN H2 C - C O CH2 - C - OK O CH2 - CH2 - CN

y l phn ng rt quan trng dng iu ch axit cacboxylic. Phn ng Buton vi tc nhn Grinha to thnh cc hp cht xtancol:
H2C - CH2 H2 C - CH2 O +RMgCl H2 C - C O R - C - CH2 - CH2 - CH2 OH + Mg Cl O R MgCl OH
HOH

H2 C - C =O O

3.4.4. PHN NG M VNG BNG MT S TC NHN KHC: Cc hp cht vng khng no hoc xtn c th tham gia phn ng oxy ho dn n s ph vng. V d hp cht xiclohexen b ph v bi phn ng oxy ho bng zn theo s sau:

79

O3 O

O - O

HOH Zn

O = CH - (CH2)4 - CHO

Phn ng xy ho cng xy ra tng t i vi hp cht Xibtn nh sau:


HC HC (CH2 ) 7 (CH2)7 C =O HOOC - (CH2 ) - COOH + HOOC - (CH2 ) - COOH 6 7

Mt s loi hp cht vng c th b ph v bi phn ng thu phn. V d hp cht caprolactam b thu phn thnh axit aminocapric nh sau:
CH2 H2C H2C CH2 C =O
H2O,H
+ -

CH - (CH ) - COO 24
+

H2C - NH

NH

Phn ng thu phn dn n s ph vng ca cc hp cht xtn cng c th xy ra di tc dng ca nh sng.


CH3 O
Hv,H2O

CH5 - (CH2)5 - COOH

80

CHNG 4 BO V NHM CHC TRONG TNG HP HU C CHIN LC CHUNG: Trong tng hp hu c nhiu trng hp ngi ta phi tin hnh bo v mt s nhm chc m nhng nhm nu trng thi t do th n c th tham gia vo mt s phn ng ho hc theo nhng hng khng cn thit. Phng php ny ngy cng c ng dng rng ri trong cng nghip sn xut ho cht nhm to ra nhiu loi sn phm cn thit vi cht lng tt. Trong lch s pht trin ca nghnh ho hc hu c trc y, ngi ta s dng kh nhiu phng php bo v nhm chc khc nhau. c bit l trong nhng nm gn y, khi m cc phn ng tng hp hu c c thc hin vi cc hp cht c nhiu nhm chc khc nhau th phng php bo v cc nhm chc li cng c pht trin ht sc nhanh chng. Mt trong nhng thnh cng ln nht ca vic s dng phng php ny l s bo v cc nhm chc trong cc phn ng tng hp cc cht Peptt (v d vic tng hp cc protit nh Inxulin, Ribonuclazas). V vy vic nghin cu mt cch c h thng cc phng php bo v cc nhm chc tr nn ht sc quan trng v cn thit cho ngnh ho hc ni chung v ngnh ho hc hu c ni ring. BO V CC LIN KT C H: BO V LIN KT C H AXTILEN: Lin kt C H trong cc hp cht axtilen loi RC CH thng cn c bo v trong cc phn ng iu ch cc hp cht c kim loi v nguyn t Hyro y rt linh ng - c tnh axit. V d:
C6 H5L i + RC C2 H5MgBr + RC CH CH RC RC CLi + C6 H 6 C - MgBr + C2 H 6

V vy, khi ta mun thu nhn mt ho cht Grinha n LiC 6H4C MgBr (V d t n Bromphnylaxtilen) (1) v magi) m nu ta khng tin hnh bo v lin kt C H bng mt tc nhn Grinha v sau cho tc dng vi hp cht c Liti th s thu c hp cht cn thit (hng b).

81

n - BrC6 H4 C (1)

CH

Mg

n - BrMgC H4 C 6

CH LiC6 H5

n- C H C 6 5

CMgBr

n - BrC H4 C 6 n - BrC6 H4 C CMgBr

CMgBr (b)

Trong phng th nghim v trong cng nghip thng hay s dng nhm Triankylsilyl lm nhm bo v cho lin kt C H. V d c th a nhm Trimtylsililclorua vo phn t hp cht Broma (2) sau cho tc dng vi hp cht Grinha v cui cng ti to li lin kt C H bng phn ng thu phn trong mi trng kim.
n - BrC H C 6 4 (2) n - R MC H4C 6 HO n - R3MC H4C 6 CH
3 CMgBr Me SiCl

n - BrMgC6H4C

CSiMe3 Mg, THF

CSiMe R MH L n - BrMgC H 4C 6

CSiMe3 CO2 , H3 O
+

n - HOOC C6H 4C

CSiMe3 HO, H3 O
+

n - HOOC C6 H4C

CH

Ngoi ra, ngi ta cng thng hay chn cc nhm nh cacboxyl, -OH... bo v lin kt C H cc axtilen. V d:
RC R (C CH + BrC C)3 COOH CCOOH R (C R(C C)3H C)2 COOH R(C C)2H

Hoc l;
RC R (C CH + BrC C) CHO
2

CCH2 OH R (C C) H
2

R(C

C)2 CH2 OH

R(C

C)2 H

BO V LIN KT C H CA HP CHT THM Phn ng th electrophin l mt trong nhng phn ng rt c bn dng tng hp cc dn xut ca cc hp cht thm khc nhau. Phn ng th xy ra theo hng
82

u tin vo nhng v tr giu in t ca vng thm. V vy, hng phn ng vo nhng v tr cn thit ...(v d v tr c mt in t thp) th cn phi bo v nguyn t hyr ca v tr c mt in t cao. V d phn ng brm ho cht tecbutylbenzen s cho sn phm ch yu l p bromtecbutylbenzen. V vy thu nhn sn phm th octo th cn phi bo v lin kt C H ca v tr Para nh sau:
C H9- tec 4 HNO3 H2SO4 NO 2 C H9- tec 4 Br HNO2 H3 PO2 NH2 C H9- tec 4 Br C H9 - tec 4 Br /H2 SO4 2 AgSO 4 NO2 C H9 - tec 4 Br Fe/HCl

a, nh hng oct v Para thng ngi ta s dng cc nhm bo v nh: cacboxyl, Nitr, Sunf. V d thu nhn hp cht 2,6 diclophenol ngi ta thc hin nh sau:
OH OH Cl OH Cl t0C xt Cl OH Cl

COOH

COOH

Cc phn ng cng tin hnh tng t nh vy khi s dng nhm bo v l sunf:


OH OH OH Y X SO H 3 SO3H OH Y X

X = CH3 X = CH3 X = Cl Y = NO2 Y = Br Y = NO2 b, nh hng mta thng ngi ta s dng cc nhm bo v nh: amin, halogen, tite... V d iu ch cc ng phn mtaca cc hp cht ankylbenzen c th tin hnh nh sau:

83

X NH2 NH2

R = CH3, Iz C3H7 R = C6H3, C2HG5, Iz C3H7, tec C4H9 X = NO2 X = Br c bit vic s dng nhm bo v l halogen c rt nhiu thun li v sau khi phn ng kt thc, chng ta d dng b kh i bng nhng tc nhn chn lc thch hp. V d:
I
0

I CH2CN

HCO3 OCH3 OCH2C6H5

tC xt OCH3 OCH3 H3CO HCO3 OCH2C H5 OCH2C6H5 6 LiAlH4

CH2CN H3CO OCH 3 OCH2C6H5

BO V LIN KT C H HP CHT BO: Mc ch chnh ca cc phng php ny l nhm bo v cc lin kt C H ca nguyn t Hyr nm v tr so vi nhm cacbonyl. t c iu ny ngi ta s dng cc phng php bo v trc tip v khng trc tip. a, Phng php bo v trc tip: CH2 > C = CH C6H5 V d: Qa trnh bo v nguyn t H mtyl ho hp cht decalon -1 cacbon C3 nh sau:

84

O
2 9

O CHC H5 6 Metyl ho O O

O CH3

CHC H5 6

CH3 Cl2

CHClC H5 6 C H5ONa 2 Cl

CH3

OC H5 2 C H5 6

H3O

O CH3

H COC H5 6

HO

CH3

Bo v bng phng php trc tuyn cng c th thc hin qua phn ng chuyn ho thnh hp cht anhyt: > CH2 > CH CHO
O O CHO O R CHO R O

b, Phng php bo v khng trc tip y l phng php bo v cc nhm mtylen hot ng bng cch kh cc nhm cacbonyl bn cnh v sau khi phn ng kt thc th khi phc li nhm cacbonyl bng phn ng oxi ho. V d: Phn ng mty ho cacbon C2 ca vng A tetrahyromanon nh sau:
O CH3 A B
NaBH 4

CH3

OH Metyl ho O

OH CH3

O O CH3 O

CH3

BO V NHM AMIN: BO V CC NHM AMIN BC MT V BC HAI:


85

Cc amin bc 10 v bc 20 l nhng hp cht rt d tham gia cc phn ng oxy ho v phn ng th. V vy bo v cc nhm ny thng ngi ta thc hin bng cch bo v cc lin kt N H ca cc amin. Di y l mt s phng php bo v c bn: Phng php Protn ho: y l phng php bo v cc nhm amin n gin nht. Phn ng xy ra trong mi trng axit v khi nhm nhm amin chuyn ho thnh Protn v ngn cm cc phn ng th khng cn thit
NH2 H
+ +

NH3 ho c

NH

NH

Tuy nhin, phn ng ny khng ngn cn c cc phn ng oxy ho. Phng php selat ho y l phng php bo v cc nhm chc amin rt c hiu qu bng s tham gia ca cp electron t do ca nguyn t Nit to thnh mt ni phc (selat) vi cc kim lai chuyn tip. V d c th tin hnh phn ng Benzol ho nhm Hyrxi ca hp cht tirozin sau khi bo v nhm amin bng phc vi ng:
O CH2 - CH - C H2N HO HO HO O CH2 - CH - C H2N Cu O CH2 - CH - C H2N C H2COO 6 Cu O O

Phc cht c to thnh sau phn ng c th thu phn bng H2S ti to li hp cht amin axit ban u. 4.3.1.3. Phng php axyl ho y l phng php nhm bo v da vo kh nng d to thnh cc hp cht axyl ca cc nhm amio. Thng thng trong phng php ny hay s dng cc nhm bo v nh focmyl axtyl v benzoyl. V d: a, Phn ng s dng phng php bo v focmyl ho iu ch cc amin axit:

86

CH2 (COOR) 2

NaNO , AcOH 2

Zn, HCOOH HON = C(COOR) 2 R' HONH - C(COOR) 2

HONH - CH(COOR) 2 ' R H2N - CH COOH R' = CH3, C H5 2

b, Phn ng tng hp synfanilamit t anilin:


NH2 HCOOH, toc NHCHO

CHCHO H2NO2 S

NH2 CHO

ClO2 S

c, Phn ng dng phng php bo v nhm chc axyl ho (COCF3) tng hp cc hp cht glycozit:
CH2OH
OH

OH NH2 CH2OH

CH2OAc
OAc

OAc

CH2OAc Br
OAc

HO

Aco NHCOCF3 O N H N

NHCOCF3 CH2OH O N HO NH 2 N H O CH 3

AcO

NHCOCF3

CH3

d, Phn ng tng hp ete ca dn xut piperidin bng phng php bo v benzoyl ho nhm amin bc 20:

87

CH2 Br

CH2 Br

CH2 CH2 COOC H5 2

N H

N COC H5 6 CH2 CH2 COOC H5 2

N COC H5 6

N COC H5 6

e, Phn ng bo v bng to ra hp cht diaxyl:


O
NK

O RX O COOH RN H3 + COOH
+

N-R

H, H2O

4.3.1.4. Phng php azmtyl ho: y l phng php da vo phn ng to thnh cc nhm azmtin (cc baz ship) bng phn ng ca cc nhm amin bc 10 vi cc anehyt v xtn. V d: Phn ng chuyn ho amin bc 10 thnh amin bc 20
O O O O
+

CH2 CH2 NH2

C H5 CHO 6

O O O O

CH2CH2N =CH - H 6H5 (CH)2 SO4

CH2 CH2NHCH3

CH2 CH2 - N =CH - C6H5 t C 0 CH3

88

4.3.1.5. Phng php: Nitroz v nitr ho: Phng php nitroz ho c thc hin ch yu vi cc amin bc 20. Sau khi kt thc phn ng nhm amin c phc hi bng phn ng kh c xc tc kim loi hoc trong mi trng axit. V d:
H3 CN NH H3 C N NH - NO O H3 C - N CH2 C H5 6 H2 / Ni H C - ON CH2 C6 H5 NH N - NO

Phn ng nitr ho to lin kt N N nhm bo v nhm amin, ch c ngha i vi hp cht arginin. O y, ngi ta s dng phng php ny tng hp Poly Li arginin. 4.3.1.6. Phng php to thnh cc lin kt N P v N S Cc ete ca - aminoaxit tc dng vi ibenzylclphtphat c s dng bo v nhm amin trong phn ng tng hp peptit.
R '' CH O O P O R NH - CH - CO - Peptit HO O R O HO NH - CH - CO - Peptit

H , HOH pH =4

H3PO4 +H2 N - CH - CO - Peptit

Ngi ta cng s dng nhiu hp cht ca lu hunh lm nhm bo v cc hp cht amin: a. Phn ng ca sunfenylclorua vi cc amin
R - NH2 C H5 SCl 6 C6 H5S C6 H5S N-R RNH3 Cl
+ -

b. Phn ng ca fenanxylsynfonyclorua vi cc amin:

89

R - NH2 + C H5 COCH2 SO Cl 2 6 R' R


NO 2

RNHSO CH2 COC H5 2 6

R' X

NSO2 CH2 COC H5 6

' Zn/CH3 COOH R R

NH

c. Phn ng bo v bng s to thnh hp cht N surfaxit:


NO2 NH 2 + N

NH2

NHSO3 H N =N - Ar

NHSO H 3

NHSO3 H

NHSO H 3 4.3.2. BO V NHM N NH2 CA NHM HYRAZIN:

bo v nhm chc N NH2 ca Hyrazin trong tng hp hu c, ngi ta s dng nhiu loi hp cht khc nhau. a. S dng nhm tec Butoxicacbonyl lm nhm bo v tng hp 1 Benzoyl 1Benzythyrazin.
H2 N - NH2 tec-Bu-OCONHNH2 tec-Bu-OCONHN =CHC H 6 5 tec-Bu-OCONH-N-CH2 C H 6 5 H NNH2 COC H 6 5 tec-Bu-OCONHNHCH2 C H5 6 C H5 CH2 6 C6 H5 CO

b. S dng phn ng bo v focmyl ho iu chhp cht 1 aminobenzimirazol t 0 Nitrophenyl hyrazin:

90

NHNH2 NO 2
N

NHNHCHO NO 2 NHCHO CH3


N

NHNHCHO

NH2 NH2
N

CH3
N

d. Bo v nhm N NH2 bng anhyt - tng hp 1 amintetrazol. H2 N - NH2 +C H5 - CHO C H5 - CH =N - NH2 C H5 - CH =N - N =CH =O - C H 6 6 2 5 6 C H5 - CH =N 6 N N N N N N H2N N N

4.3.3. BO V NHM O NH2 CA HYRXYLAMIN:

thu nhn cc hp cht O axyl v O ankyl ca Hyrxylamin th cn phi bo v lin kt N H. iu ny c th t c bng nhiu phng php khc nhau. V d c th dng cc hp cht cacsonyl nh sau:
CH3 CH3 C =O +H2 N - OH CH3 C =N - OH CH3 C H5 CH2 Cl 6

CH3 CH3 C =N - CH2 C6 H 5 HCl H 3N - OCH 2- C6 H 5


+

Phng php bo v trn y tuy rng c s dng rt rng ri nhng trong mt s trng hp khi dng phn ng thu phn hp cht thu c sau phn ng ti to li nhm amin th ph hu lung lin kt O- Axyl hoc O- Ankyl. khc phc nhc im ny ngi ta thng s dng nhm Tec Butoxi cacbonyl lm nhm bo v.

91

Cl NO2 tec - BuOCON NH2 OH tec - OCONHOH ; KOH NO2

ONHCOO - Bu - tec NO 2 CF COOH 3

ONH2

NO 2

NO2

NO2

III.4. BO V NHM AMIN BC 30 NR3 bo v cc nhm amin bc 30 ngi ta tm cch chuyn ho chung thnh mui amni bc 40 hoc thnh cc hp cht nictin thnh mui ca Pirdin nh sau:
N N CH3 HI N N
+

CH3 I N
+

CH3 H

CH3 H

CH3 N N
+

CH3

CH3

bo v nhm amin bc 30 ca Piniin, trong cc phn ng chuyn ho, ngi ta dng phng php to hp cht N oxit. V d:

92

NH2

C H5 2 H3C

NH2

C H5 2 H3C

CN C2 H5 N O

H3C

N O COOCH3

COOCH3

C2 H5 H3C N+

C H5 2

H3C

N+ O

4.4.

BO V NHM CHC ANCOL Ancol tham gia d dng vo cc phn ng ankyl ho, axyl ho, xy ho, hyrt ho... V vy trong rt nhiu cc phn ng tng hp thu c nhng sn phm cn thit th phi bo v nhm ancol c s dng rt rng ri trong cc phn ng tng hp sterit, cc loi ng, glyxerit... Cc phng php c bn thng c s dng bo v nhm chc ancol thng l ete ho, axtal ho v ketal ho. 4.4.1. PHNG PHP ETE HO: Nhm Hyrxy ca cc hp cht ancol rt d dng tham gia phn ngd to thnh cc hp cht ete khc nhau. Di y l mt s ete thng c s dng bo v nhm chc ancol. a. Ete metylic: Cc nhm chc hyrxyl trong hyrcacbon v trong ancol rt d dng mtyl ho bi imtylsunfat trong mi trng kim hoc bi metylioua vi xc tc oxit bc. y chnh l c s ca phn ng dng bo v cc nhm chc ancol bng phng phng php ete mtylic. b. Ete Tec Butylic: Nhm tec Butylic thng c s dng bo v cc nhm chc ancol trong cc phn ng tng hp peptit steroit. Ete tec Butylic c th c iu ch vi mt hiu sut kh cao bng phn ng ca ancol v izbutylen vi Metylen clorua c xc tc bng axit:
ROH +(CH 3)C =CH2 H
+

ROC(CH3)3

Sau phn ng c th tch nhm bo v tec Butyl bng phn ng vi trifloaxtic axit khan. c. Ete alylic:

93

Trong rt nhiu trng hp c bit l trong mi trng axit yu th c th s dng ete allylic bo v nhm chc ancol.
ROH +CH2 = CH - CH2 Br NaOH ROCH2CH = CH 2

d. Ete Benzylic: Nhm bo v benzyl c ng dng rt rng ri bo v cc nhm chc ancol trong cc tng hp ng, nucleozit, glyxrit, aminaxit. Phn ng bo v c thc hin bng s un nng ancol vi benzyl clorua d trong dung mi khng phn cc. V d phn ng chuyn D- glucoza thnh L sorboza c bo v bi Ete benzylic nh sau:
CH2 OH O OH OH OH HO C6 H5 CH2 Cl OCH2C H5 6 O OH OCH2 C6 H5 CH2OH HCOCH2C6 H5 C6 H5CH2CH HCOCH2 C6 H5 HCOH HO O OH OH CH2OH CH2OCH2 C6 H5

C6 H5 CH2O

e. Ete triarylmtylic: Ete triarymtylic c s dng rt rng ri bo v nhm ancol bc 1 0 trong cc phn ng tng hp ng, nucleozit, glyxerit v steroit. Hp cht bo v c to thnhf khi cho ancol tc dng vi triphenylclomtan. V d:

H3 CO

Cl +ROH

H3 CO

OR

Nhm bo v sau phn ng c tc i bng phn ng thu phn trong mi trng axit. f. Ete trimtysilic: Nhm trimtyl silyl c ng dng rng ri bo v cc nhm chc ancol trong cacbon hyrat, steroit. u im ln ca phng php ny l nhm bo v rt d dng b y i trong nhng iu kin phn ng khng khc nghit lm. Hp cht bo v thng c thu nhn bng phn ng ca ancol vi trimtylclosilan.

94

ROH +(CH3)3 SiCl

ROSi(CH3) 3

4.4.2. PHNG PHP EXETAL V KETAL HO: a. Ete tetrahyrfiranylic: Phn ng ca 2, 3 ihyr 4H- piran tc dng vi ancol trong mi trng axit to thnh ete tetrahyrpiranylic l c s ca phng php bo v axtal:
+HOR O H
+

OR

Phn ng ny c s dng rng ri bo v cc nhm chc ancol trong cc phng php tng hp steroit, nucleotit. Ete tetrahyrpiranylic rt bn vng trong mi trng kim, nhng d dng b thu phn trong mi trng axit cho li hp cht ancol ban u. b. Cc hp cht axetal. Cho n nay trong ho hc tc dng hu c ch yu vn s dng Tuy nhin, trong mt s trng hp ngi ta c s dng mt s axetal Ete tetrahyrpiranylic bo v nhm ancol theo phng php axetal. Tuy nhin, trong mt s trng hp ngi ta c s dng mt s axeta khc nh dn xut ca uridin, tetrahyrtifuran, tetrahyrtipiran.
O HN O N

CH3 COOCH2 C

OR

OR

O P - O OOCHOC2 H5 3 CH3

c. Cc hp cht ketal: Vic s dng nhm bo v tetrahyrpiranyl cho cc nhm chc ancol quang hot dn n mt kh khn l to thnh hn hp ng phn khc nhau. khc phc vn ny trong nhiu trng hp ngi ta thay nhm tetrahyrpiranyl bng mt hp cht axetal i xng (ketal). Nhng ketal thng c s dng bo v nhm chc ancol trong cc phn ng tng hp nh ketal axtn, ketal uridin, ketal ca dn xut tetrahyr 4H piranon 4.

95

CH3 O C CH 3

OR

CH 3O

O - Ur

CH3O O

OR

CH 3

4.4.3. PHNG PHP ESTE HO; Mt trong nhng phong php c s dng rng ri nht bo v cc nhm chc ancolca cc phn ng xy ra trong mi trng axit hoc l trung tnh l phng php este ho - to thnh cc hp cht axetat, hoc l cc hp cht cacboxylat. Cc phn ng axyl ho ny thng xy ra nhit thng bi phn ng ca ancol vi anhyrit hoc cloranhyrit ca cc axit cacboxylic trong piridin. a. Cc hp cht axetat: y l phng php c s dng tng i rng ri bo v nhm chc ancol trong cc hp cht steroit, cacbonhyrat, nuclozit... Hp cht bo v c to thnh bi phn ng ca anhyrit axetic vi ancol cn bo v trong piridin. Sau khi phn ng kt thc th nhm bo v c tch ra bng phn ng thu phn trong mi trng axit. b. Cc hp cht Benzoat v p notrobenzoat: bo v cc nhm chc ancol c bit l trong cc hp cht ng thng s dng rng ri phng php benzoat ho. Phn ng to thnh hp cht bo v xy ra gia nhm ancol vi hp cht Benzoyl clorua trong piridin. So vi phng php axetat ho th phng php ny xy ra trong nhng iu kin chn lc tt hn v t c cc phn ng chuyn v hn. c. Phng php focmiat ho: Phng php ny c u im ln l d b thu phn phc hi li ancol ban u m khng lm nh hng n cc nhm bo v ca cc loi este khc. Hp cht bo v c to thnh by phn ng ca nhm ancol vi axit focmic v sau khi kt thc phn ng nhm ancol c ti to li bi phn ng thu phn ca bicacbonat Kali trong ru metylic. V d phng php focmiat ho c s dng bo v nhm ancol trong phn ng chuyn ho cht hyrizoanrosteron thnh testosterron.

96

OCOCH3

HO

HCOO OCOCH3

HCOO

4.4.4. PHNG PHP BO V CC IOL: Cc nhm chc 1, 2 v 1, 3 glycol thng c bo v bng cc axtal v ktal vng hoc cc este vng. 4.4.4.1. Cc axtal v ktal vng Phng php bo v cc hp cht glycol bng cc axtal v ktal vng c ng dng rng ri trong ho hc steroit, glyxerit, cacbon hyrt. Cc nhm bo v thng c hnh thnh bng phn ng ca hp cht glycol vi cc hp cht cacbonyl tng ng trong mi trng axit. Phn ng c th tin hnh trong cc dung mi nh ixan ete, benzen, tetrametylfocmamit hoc khng c dung mi. Cc nhm bo v loi ny bn trong mi trng trung tnh v mi trng kim, d b thu phn bi axit. Sau y l mt vi phng php hay c s dng. 1. Mtylenaxetal: Hp cht ny thu nhn c bng phn ng ca glycol vi focmanhyt trong mi trng axit. Nu phn ng tin hnh vi cc ancol a chc th thng to ra mt hn hp nhiu sn phm. V d nu cho focmanhyt tc dng vi D Glucoxit trong HCl th s thu c mt hn hp sn phm iaxetal v triaxetal.
HO - CH2 OH OH OH OH CH2OH HCHO O O OH CH2OH + O - CH2 O O - CH2 O O O O CH2 - O

2. Etylien axetal:

97

Hp cht ny c ng dng ch yu trong tng hp cc loi ng. Nhm bo v c hnh thnh bng phn ng glycol vi axetanhyt, 1, 1 imetxyetanol vi s xc tc ca axit. V d hp cht metyl 4,6 O etylien - - D Glucopiranozit c to thnh bng phn ng trao i gia mtyl - - D Glucopiranozit vi 1,1 imetxietan vi xc tc H2SO4.
HOCH2
O OH

OCH3 OCH3
3

O - CH2 CH3CH
O OH

+ CH3 - CH OCH3

OCH3

O HO OH

HO

OH

Etylienaxetal l hp cht bn trong mi trng kim nhng d b thu phn trong mi trng axit ti to li hp cht ban u. 3. Benzylien axetal: Hp cht bo v ny c ng dng rng ri trong tng hp ng v glyxrit. Benzylien axetal c to thnh bng phn ng ca cc glycol vi benzanhyt vi xc tc axit. V d phn ng to thnh dn xut benzylien axetal 1,2 v 1,3 ca glyxrin xy ra nh sau:
CH2 - OH CH - OH + C6H5 - CHO CH2 - OH H+ CH2 - O CH - O CH2OH CH2 - O + CHOH CH2 - O CHC6H5

Benzylien axetal rt bn trong cc iu kin phn ng khc nhau (tr axit). Mt khc mi lin kt bo v ca hp cht cng d b ph v bng phn ng kh c xc tc. V d:
O - CH2 C6H5 - CH O O
O

HOCH2 H2, Pd/c HO


O O

OCH3

Ngoi ra bo v cc iol theo phng php ny ngi ta cn s dng nhiu cc hp cht khc nhau nh dn xut ca benzelien axetal, izopropy lien ketal, xyclohecxylien ketal. V dphn ng to thnh hp cht bo v xyclohecxylie axettal gia D Kxiclofuranoza vi xc tc H2SO4 xy ra nh sau:
HOCH2 O OH OH OH + = O H
+

HOCH2

O OH O O

4.4.4.2. Cc este vng;

98

bo v cc iol theo phng php ny, thng ngi ta hay phenyborat vng. Phng php ny c ng dng rt rng ri trong cc tng hp ng, nuclofit, glyxerit. Cc hp cht cacbonat c hnh thnh bng phn ng ca glycol vi focgen trong piriin. V d cc nhm glycol ca D glucza c bo v bng hp cht cacbonat vng nh sau:
HOCH 2 O OH OH OH

COCl2/Piridin

O - CH O= O O OH O O

u im ln nht ca cc hp cht bo v cacbonat l kh bn trong mi trng axit v ch b ph v trong mi trng kim. Cc hp cht bo v phenolborat vng c to thnh khi cho glycol tc dng vi axit phenylbonic trong cc dung mi nh benzen axtn, ixan y l nhng hp cht bn trong khng kh nhng rt b ph v bi 1,3 propanion. V d phn ng chuyn ho - D - Kxylopiranozit thnh dn xut 3 0 axtyl bng phng php phenolborat vng xy ra nh sau:
OH
O OCH3

OH C6H5(OH)2 O O

OCH3 1.(CH3CO)2O 2.HOCH2CH2CH2OH

OH

OH

B C6H5 OCH3 OH

OH CH3COO

4.5 BO V NHM CHC CACBOXYL Trong tng hp rt nhiu khe cn thit phi bo v nhm chc cacboxyl tin hnh phn ng ti cc v tr khc v sau khi phn ng kt thc th tm cachs phn hu nhm bo v khi phc li nhm chc cc boxyl ban u. V d nhm chc cacboxyl c bo v trong phn ng tng hp penyxylin nh sau:

99

O COOH S N-CH O NH CH3 CH3 COOH

O COO(CH3)3 S N-CH O NH CH3 CH3 COOCH2C6H5

COO(CH3)3 S (C6H5)3C-NH-CH NH

CH3 CH3 COOCH2C6H5 CH3 CH3 COOCH2C6H5

COOH S (C6H5)3C-NH-CH NH

CH3 CH3 COOCH2C6H5

(C6H5)3C-NH-CH N O
S

S 1.H2/pd 2.H3O
+

CH3 CH3 COOH

H2N -CH N O

CH3 CH3 COOH

CH O O

CH N

Phng php ch yu l phng php este ho.

100

4.5.1. PHNG PHP ESTE HO BNG ANCOL: bo v nhm chc cacbonyl ngi ta tin hnh este ho cc axit caboxyl hoc l cc dn xut ca n bng cc ancol khc nhau. Sau y l mt s phng php c bn: a. Phng php este ho trc tip cc axit c th thu nhn c cacboxylat cuar mtyl, tyl, benzyl, cc dn xut benzylbng phng phn ng ca axit v ancol tng ng. Cc phn ng ny thng c xc tc bng axit v c hoc mt s axit kim khc nhau. b. Phng php este ho bng phn ng ca halogenanhyrit axit vi ancol c thc hin trong mi trng kim. Phn ng ny thng dng iu ch tec-butyl cacboxylat. c. Phn ng este ho ca cc anhyrit axit vi cc ancol c th c xc tc bi axit hoc baz. Mt trong nhng u im ln ca phn ng ny l n to thnh mn este khi cho ancol tc dng vi c anhyrit vng ca cc hp cht iaxit. V d: Ngi ta ng dng u im tng hp glutamic nh sau:
COOH COO + NH3 C C O O C6H5OH COOH COOCH2C6H5 NHCOCH2C6H5 CONH2 COO + NH3

O NHCOCH2C6H5

d. Phng php este ho bng phn ng ca cc dn xut halogen vi cc mui ca axit cacboxylic c s dng iu ch mtyl, tyl, benzyl cacboxylat. e. Ngoi ra, iu ch este ngi ta cn s dng cc phng php nh trao i este, phn ng ca axit cacboxylic vi olefin, vi iafoankan, v nhng phng php khc. 4.5.2. NG DNG V PHNG PHP TCH CC NHM BO V CA ESTE: a. Mtyl v tyl este: y l cc nhm bo v c ng dng rng ri trong nhng phn ng anlyl ho v ngng t. Cc nhm bo v ny c th c tch ra bng phn ng thu phn bi axit hoc baz. b. Tec Butyl este: Hp cht ny rt bn trong cc phn ng thu phn bi baz nhng rt b thu phn bi axit. V vy, n thng c s dng bo v cc nhm caboxyl trong cc phn ng tng hp xy ra trong mi trng kim, c bit l iu ch cc xtn. V d: C6H5CH2 CH(COO tec Bu)2 + P O2N C6H4COCl
P O2N C6H4 CO CH2 CH2 C6H5

d. Benzyl v cc dn xut benyl este:

101

Cc nhm bo v ny rt d dng tch i bng phng php thu phn. Nhm benzyl c th b tch i bng phng php thu phn trong mi trng kim hoc l trong mi trng axit vi iu kin khc nghit. Tc thu phn ca cc este ny ph thuc vo nng ca axit, nhit , thi gian, phn ng u im v bn ca cc nhm bo v ny trong mi trng axit yu c p dng tng hp nhiu hp cht m khng th iu ch c trong mi trng kim. Ngoi ra, bo v nhm chc caboxyl trong tng hp hu c ngi ta cn s dng nhiu nhm bo v khc nhau: 2,4 initr benzensunfophenyl, O nitrbenzhyryl, benzilienyl, phenylaxtylSau phn ng nhng nhm chc ny cng c tch ra bng phn ng thu phn trong mi trng axit hoc baz. 4.6 . BO V CC NHM CHC ANHYT V XTN Nhm cacbonyl trong cc hp cht anhyt v xtn l nhm chc rt linh ng, tham gia nhiu phn ng khc nhau trong tng hp hu c. V vy, vic bo v n tin hnh mt phn ng theo mun c ngha rt ln. Di y l mt s phng php quan trng thng c s dng. 4.6.1. AXTAL V KTAL HO 4.6.1.1. Cc phng php bo v bng Axtal v Ktal: a, Phng php 1,3 ixlan Nhm ixlan:
R' C=O R R R' C O O CH2 CH2

c s dng bo v cc nhm anhyt v xtn trong mi trng kim v trung tnh. Kh nng to thnh hp cht ixlan c sp xp theo dy sau: Cc anhyt > Cc xtn mch h v xycl-hecxannon > xyclopentanon > , - xtn khng no > cc dn xut xut -mn v ixtn > Cc xtn thm. Di y l mt vi phng php iu ch cc ixlan t anhyt v xtn: * Phng php trc tip: Trong phng php ny ixlan c iu ch bng phn ng ca cc hp cht cacbonyl vi tylenglycol trong mi trng axit. Phn ng c tin hnh vi s tham gia ca octeste, l tc nhn tch loi nc. Ngoi xc tc bng axit thng ngi ta s dng cc xc tc nh sunfoaxit, pirinin clohyrat. i vi cc xtn hot ng mnh th c th s dng cc xc tc nh xyt selen, axit malnic * Phng php trao i: C s ca phng php ny l phn ng trao i gia cc nhm chc cabonyl vi cc hp cht ixolan ca cc xtn c nhit rt thp. Thng hay s dng cc hp cht ixlan ca butanon 2, axtn. Phng php ny c th dng bo v cho cc ixtn c kh nng phn ng tng t nh nhau. * Mt s phng php khc: iu ch cc ixolan trong tng hp hu c, ngi ta cn s dng mt s hp cht nh etylenxyt vi xc tc clorua thic, sunfit glycol b, Cc phng php axetal v ketal vng: S to thnh cc hp cht axetal v ketal vng c thc hin bi phn ng ca cc anhyt v xtn vi ancaiol. Cc kt qu
102

nghin cu cho thy rng kh nng to thnh cc ketal bin i theo dy: 2,2 imtyprpaiol 1,3 > etylenglycol > propaiol 1,3. c. Phng php iankylaxetal v ianxylxtal:
R' C=O R R R' C OR''' OR"

S to thnh cc iankylaxetal v ianxylxtal ch yu ch xy ra vi cc anhyt v cc xtn hot ng mnh. Phn ng xy ra vi xc tc axit gia cc hp cht cacbonxyl vi cc ancol. y l cc hp cht tng i bn trong mi trng trung tnh v mi trng kim. 4.6.1.2. Phng php phn hu axtal v ktal: Cc axtal v ktal thng c phn hu phc hi li cc nhm chc cacbonyl di tc dng ca axit. Tuy nhin tu thuc vo cc hp cht axtal v ktal, c th n ngi ta s dng axits thch hp. Thng th s to thnh cc axtal v ktal cng d dng bao nhiu th s phn hu bng axit cng nh nhng by nhiu. Mt khc, s phn hu ca cc ketal quang hot thng xy ra trong iu kin khc nghit vi cc tc nhn l nhng axt v c. 4.6.2. POLYTI V I AXTAL V KTAL: 4.6.2.1. 1,3 Ocxatiolan (Polytioketal):
R' C=O R R R' C S CH2 O CH2

Cc hp cht ny c to thnh khi cho xtn tc dng vi 2-mcaptoetanol trong mi trng axit. Trong mt s trng hp cng c th chuyn ha cc anhyt bng phn ng ny. Ngoi ra cc polytiketal cng c th thu nhn bng phng php ny t cc dn xut ca mcaptoetanol v mcaptpropanol. So vi etylen glycol th cc phn ng ca cc anhyt v xtn xy ra vi mcaptoetanol d dng hn. Mt khc, cng tng t nh ixalan, cc polytiktal rt bn vng trong mi trng trung tnh v baz nhng khng bn trong mi trng axit. Cc polytiktal thng b phn hu bi cc axit v c trong ancol hoc ixan. Nhc im c bn nht ca phng php ny l vic to thnh hp cht polytiktal dn n s xut hin trung tm bt i v do c th to thnh sn phm l nhng ng phn quang hc khng i quang. 4.6.2.2. itiaketal v itiktal: Cc hp cht ny c th thu nhn bng phn ng ca cc hp cht cacbonyl. Vi ankylmcaptan hoc imcaptan trong mi trng axit. Thng hay s dng cc tc nhn phn ng nh: 1,2 imcaptotan, tylmcaptan. Cc itiaketal v itiktal u bn trong mi trng trung tnh v baz nhng khng bn trong mi trng axit. phn hu cc hp cht ny tt nht l s dng khng phi axit m cc mui ca thu ngn (II) trong cc dung mi khc nhau. 4.6.3. CC DN XUT ENOL V NAMIN
103

y l phng php bo v c s dng rng ri trong ho hc sterit, c bit l i vi cc , - xtn cha no. V vy cc hp cht c ngha ch yu l cc ienol v ienamin. 4.6.3.1. Cc ete enol v tienol:
R H R' C C =O C R' R C O(S) R''

Phn ng chuyn ho cc , - xtn cha no thnh cc ete ienol thng xy ra di tc dng ca este octfocmiat hoc 2,2 imtxypropan trong ancol vi xc tc axit. thu nhn ete ienol thng s dng cc iol hot ng mnh, v d nh benzylmcaptan. Cc ete enol v ienol cng nh cc dn xut ca chng rt bn trong mi trng kim nhng rt d b phn hu bi cc axit. Ngoi ra, phc hi li cc nhm chc cacbony cng c th phn hu cc ienol bng mui thu phn (II). 4.6.3.2. Enanin v cc mui ca enamin:
R' C =O R' C H R C R' C N

Cc hp cht enamin thng c dng bo v cc nhm anehyt v , - xtn cha no trong cc hp cht sterit. ti to li cc nhm cacbonyl ban u, c th thu phn cc enamin bng cc dung dch axit hoc bng kim long. 4.6.4. SEMICACBAZON, OXIM V CC DN XUT HYRAZON; 4.6.4.1. Semicacbazon:
C=O C=N NH CONH2

Trong nhng trng hp, c bit l trong ho hc sterit cc hp cht semicacbazon c iu ch rt d dng. Hp cht semicacbazon rt bn di tc dng ca NaBH4, LiBH4 v trong mi trng kim. Trong ho hc hyrat cacbon, hp cht semicacbazon c s dng bo v nhm anhyt ca cc hp cht mch h khi tin hnh phn ng ankyl ho cc nhm ancol. phn hu cc semicacbazon ti to li cc nhm cacbonyl thng tin hnh phn ng thu phn trong axit mnh. 4.6.4.2. Oxim
C=O C = NOH

Hp cht bo v lai ny c bn vng tng ng vi semicacbszon nhng phn ng phn hu n xy ra kh khn hn. Phn ng thu phn hp cht xim ti to li
104

nhm cacbonyl ban u cng c tin hnh trong mi trng axit nhng phi c thm mt s cht xc tc khc. Trong mt s trng hp c th s dng phng php xi ho trong mi trng axit. 4.6.4.3. Dn xut hyrazon:
O2N C=O C = N - NH NO2 va C=N-N CH3 CH3

Hp cht 2,4 initrphenyl hyrazon c s dng ch yu nh tnh anhyt v xtn cn bo v nhm chc th t hn v phn ng phn hu n xy ra rt kho khn. Tuy vy, trong cc phn ng tng hp v chyn ho cc hp cht steroit hp cht ny nhiu khi cng c s dng. Nhm bo v thng c tch ra bng phng php kh vi cc tc nhn nh clorua thic (II), clorua thic (III), Liti nhm hyrua.. Hp cht N, N imtylhyrazon l mt trong nhng hp cht kh l tng dng bo v cc nhm anhyt v xtn v rng vic ti to li cc hp cht cacbonyl sau phn ng c thc hin trong nhng iu kin rt nh nhng trong mi trng trung tnh.

105

CHNG 5 S XI HO - KH S xi ho v s kh l hai hin tng c lin quan mt thit vi nhau v khng th tch ri nhau c, khng c s xi ho no m li khng c s kh ng thi vi n. Hai qu trnh c coi l mt: S xy ho - kh. Trong thc t ta ni mt phn ng no l xy hohy l kh ch l quy c nhn mnh tng mt. S xy kho - kh l mt khi nim tng i phc tp. V vy, trc khi xt n c ch phn ng ny ta cn cp n vn ny. 5.1. S XI HO - KH V C CH PHN NG. 5.1.1. Quan nim v s xy ho - kh trong ho hu c: Trc kia ngi ta cho rng s xy ho l qu trnh cng thm xy, cn s kh l qu trnh tch bt xy, hoc tng hm lng tng i ca hyr trong phn t. nh ngha khng c tnh tng qut, tuy rng do s thun tin v thi quen ngi ta vn dng n trong vic phn chia cc phn ng ca hp cht hu c. Trong ho v c, phn ng xy ho- kh thng c trng bng s thay i ho tr hoc s chuyn dch mt s electron. Trong ho hu c quan nim khng c dng v nguyn t cacbon trong phn t hu c lun lun c ho tr 4, cn nhng phn ng c s chuyn dch hn cc electron th t gp. V nhng l trn, hin nay ngi ta thng nh ngha s xy ho - kh da trn c s bin i ca nhng i lng c tnh cht quy c gi l s xy ho hoc bc xy ho. S xy ho l s in tch quy c ca nguyn t, tnh c khi gi thit rng phn t gm ton nhng in n gin tri du kt hp li. Ni mt cch khc, s xy ho l s in tch xut hin nguyn t trong phn t nu nh xy ra s dch chuyn hon ton tt c cc cp electron lin kt v pha nguyn t no c m in tng i ln hn. (Nu hai nguyn t ng nht lin kt vi nhau th khng c s chuyn ch , v nh vy khng lm xut hin in tich). S xy ho c k hiu bng ch n (t ting Anh oxidation number) v biu th bng s Ar rp cng vi du in tch v ghi pha trn k hiu ca nguyn t. Th d:
0 H +1 -2 H - O 0 H +1 H +1 H +1 -4 +1 H - C - H +1 H +1 H +1 -2 -1 H - C - H +1 H

S xy ho l mt khi nim c tnh hnh thc, v tt c cc lin kt cng ho tr gia hai nguyn t thuc hai nguyn t khc nhau u c coi nh l nhng lin kt ion in

106

hnh, m thc ra khng phi nh vy: phn ln cc lin kt ch phn cc t nhiu m thi. Mt nguyn t c th c nhiu s xy ho khc nhau, tu theo bn cht v s lng cc nguyn t lin kt vi nguyn t ca nguyn t trong phn t. Th d: cacbon c s xy ho (k hiu nC) t -4 n +4 trong dy cc hp cht sau: Hp cht: CH4 CH3OH C CO CO2 nC : -4 -2 0 +2 +4 Ta c th tnh s oxy ho cho mt nguyn t nht nh trong phn t bng cch ly tng cng cc in tch xut hin nguyn t khi cho ion ho tt c cc lin kt. Th d:
+1 H -1 +1 H+1 -1C H -1 -1 +1 H nc = 4 H+1 -1 +1 -1 +1 -1 -1 +1 H C O H -1 +1 H nc = -2 H+1 H+1 -1 +1 -1 -1 +1 +1 -1 H C C O H -1 +1 +1 H H nc(CH3) = -3; nc(CH2OH) = -1

Cng c th xc nh s xy ho trung bnh cho cc nguyn t ca mt nguyn t nht nh trong phn t. Khi y ta phi tun theo mt s quy tc sau: a. Tng i s cc xy ho trong phn t lun lun bng o, trong ion bng s in tch ca ion. b. S xy ho ca mt nguyn t dng n cht u bng 0. c. Trong cc hp cht, hydr c s oxi ho +1 ( tr trng hp cc hydrua kim loi, trong nH = -1), xy c s oxi ho -2 ( tr trng hp cc peoxyt v mt s hp cht khc), kim loi c s oxy ho dng v bng ho tr ca n. Th d tnh s oxy ho trung bnh: CH4 nC + 4nH = 0 NC + 4(+1) = 0 nC = -4 CH3OH nO + 4nH + nO = 0 nC + 4(+1) + (-2) = 0 nC = -2 CH3CH2OH 2nC + 6nH + nO= 0 nC + 6(+1) + (-2) = 0 nC = -2 CH3COOH 2nC + 4nH + 2nO = 0 2nC + 4(+1) + 2(-2) = 0 nC = -2

107

Ta nhn thy rng s oxy ho trung bnh ca cacbon chng hn s trng vi s oxy ho tnh cho tng nguyn t cacbon khi trong phn t ch cha mt nguyn t cacbon ( th d CH4, CH3OH,.) hoc cha 2 nguyn t C ging ht nhau: Th d: CH3 CH3, CHO CHO, .. Trong cc thnh phn khc, s oxy ho tnh cho tng nguyn t bao gi cng l mt s nguyn hoc 0, th s oxy ho trung bnh c th l mt s thp phn, th d s xy ho trung bnh ca cacbon trong phn t prpan bng 2,67, trong phn t butan bng -2,5. Bn cnh khi nim s oxy ho, trong ho hu c cn mt khi nim tng ng gi l bc xy ho. Theo nh ngha, bc xy ho ca nguyn t cacbon l s nhm hydrxy c th xut hin nguyn t cacbon, nu gi thuyt l phn t b thu phn hon ton.

C
C

Cl C

H2O H2O

C
C H

OH C OH

bc xy ho:1

Cl

H2O

C
OH

OH

bc xy ho:2
OH

H2O
C O

C
OH

Theo quan nim ny th cacbon trong phn t hu c c th c 5 bc oxy ho khc nhau: 0, 1, 2, 3, v 4. (Xem bng trang sau). Khi nim oxy ho ( v khi nim bc oxy ho cng vy) cho php hnh dung mc tng i kh nng oxy ho hay kh ca mt cht. S oxy ho cng ln th kh nng oxy ho ( hay l b kh ) cng tng, v kh nng kh ( hay b oxi ho) cng gim. T y ta c th nh ngha: Qu trnh oxy ho l qu trnh lm tng s oxy ho cht phn ng vag lm gim s oxy ho tc nhn phn ng, cn qu trnh kh l qu trnh ngc li. Ni chung, oxy ho - kh l qu trnh bin i s oxy ho (hay bc oxy ho)

108

nh ngha trn v s oxy ho - kh c tnh cch tng qut v bao hm c tt c cc nh ngha c. Trong ho hu c, ngoi nhng phn ng oxy ho - kh bng cc tc nhn oxy ho hay cc tc nhn kh. Bng phn loi cc nhm nguyn t theo bc oxy ho ca cacbon.

109

Bc xy ho ca cacbon

Nhm nguyn t c tr ng C

Thd

CH 4 ; M C Li

RCH

MgBr

Hal ;

O;

S,

C =C X C X 2 C =Y

CH2 = CH ; RR' C = CRR' Hal C Hal C =O ; ; C OH C =S ; OH ; C S C =N ; S

C =C C =C - CX - C =Z -C-X 3 Y C = CX2 CX4 Y =CX 4 Y =C =Y Z =C - X

C =C - Hal ; C =CH - CHal ; C =N - C - Hal Y C = CX2 CHal : :

C = C - OH RC =CR -C(OR) - C - OH O C =C(OH)


2

C(OR) 4 S =C(OR)

O =CCl S =C =S

N = - OH C

= - Cl C

110

S xy ho ca cacbon trong mt s phn t hu c v qu trnh xy ho - kh


-4 CH4 -3 -2 CH -3 OH -1 0 HCHO R - CH OH 2 R - CHO 1 2 HCOOH R - COOR 3 4 CO
2

R - CH3

CH3- CH3 CH2 CH2 CH =CH = S xy ho S kh

Thng thng nh xy, hyro, pemanganat kali, axit crmit cn nhiu phn ng khc cng c coi l phn ng xy ha - kh. Th d cc phn ng halgen ho ho v nitro ho hyrocacbon, phn ng dhalgen ho dn xut ihalgen, phn ng cacbxyl ho axit cacbxylic.v.v. Trong khi nhng phn ng nh thu phn dn xut halogen v hp cht c kim, este ho v thu phn este khng thuc loi phn ng xy ho kh. Khi cn bng phng trnh phn ng xy ho kh trong ho hu c ngi ta cng p dng nguyn tc thng bng s xy ho nh trong ho v c. Th d c s phn ng:
CH3CH2OH + KMnO4 + H2SO4
-1
+7

CH3COOH + MnSO4 + K2SO4 + H2O

+3

+2

Trong tanol l cht kh v s xy ho ca cacbon tng 4 n v (t -1 tanol n +3 axit axtic) cn pemanganat kali l cht xy ho, v s xy ho ca mangan gim 5 n v (t +7 KmnO4 n +2 MnSO4). m bo nguyn tc thng bng s xy ho ta phi ly 5 phn t tanol v 4 phn t pemanganat kali, cn s phn t H2SO4 c ly sao cho tng ng vi s ion Mn2+ v K2+ sinh ra trong phn ng. Do ta c th vit: 5CH3CH2OH + 4KmnO4 + 6H2SO4 5CH3COOH + 4MnSO4 + 2K2SO4 + 11H2O Nh vy quan nim v xy ho kh da theo s bin i s xy ho c th trong c ho v c ln ho hu c. 5.1.2. C ch phn ng xy ho - kh nh ngha trnh by trn v xy ho - kh khng ni ln iu g v c ch cc phn ng c. Ta bit rng phn ng xy ho - kh c th xy ra theo kiu ng ly hay d ly. Tuy vy c ch xy ho - kh l mt vn rt phc tp, v c ch rt a dng v thng bin i nhiu tu theo bn cht ca tc nhn xy ho - kh c dng. Nhiu ngi c gng h thng ho cc c ch xy ho - kh vo mt s loi nht nh. C ch ca cc phn ng xy ho - kh c tp trung ni n 5.2 v 5.3. Di y l mt s loi c ch xy ho - kh ph bin. 5.1.2.1. Chuyn dch trc tip electron: S tng qut:
111

A+e B hoc Be A Th d: Kh hp cht cacbnyl bng halri kim loi:


R2C = O + e R2C - O ...

Chuyn ho gi ion v gc t do:


R
(+)

ee
-

ee-

(- )

5.1.2.2. Chuyn dch nguyn t hyr: S tng qut:


A + H Z A - H + Z

Th d:
R H + Cl HCl + R
RH + CR'3

...

hoc:
R + H - CR'3 ...

5.1.2.3. Chuyn dch ion hyrua S tng qut:


(- )

A + H

AH

+ Z

(+)

Th d:
R + H - R'
(+)

RH + R'

(+)

hoc:
R2C = O + LiAlH4 R2CH - O Li + AlH3
(- )

(+)

...

5.1.2.4. Chuyn dch cp electron S tng qut:


A: + Z A -> Z

Th d:
C + Br - Br C Br C Br - Br C C (+)Br + C

hoc:

112

R3N: + O - O - H H

(+) (-) R3N - O - H + HO

R3 N

(+)

(-) O + H2O

5.1.2.5. To este trung gian: Cht phn ng v tc nhn tc dng vi nhau to thnh este trung gian (thng l este v c), sau este b phn tch:
...
(+) (-) A - C - B -> A - C - B + Z + H

OZ

O H

Z thng l CrO3H, MnO3, SeO2HTh d:


RCH = O + HMnO4 R - C - OH OMnO3
B

R - O = O + MnO OH

(+)

5.2. Cc phn ng xy ho: 5.2.1. xy ho lin kt ca Hyrcacbon Ta bit rng nng lng phn ly cc lin kt trong phn t alkanthngf khng khc nhau nhiu, cho nn t c phng php xy ho lm dt mt cch chn la hoc lin kt C C hoc lin kt C H m khng ng n phn t ni chung. Tuy vy, nng lng phn ly ca cc lin kt C H bc ba hay cc v tr alyl v benzyl yu hn cc lin kt khc mt cch r rt, do ta c th ch xy ho cc lin kt m phn cn li ca phn t vn c nguyn vn. Th d:
CH2 = CHCH3
O2

CuCl2

CH2 = CHCHO

Prpen
(CH3)2C - H C6H5
O2

Acrlin
(CH3)2C - OOH C6H5 (CH3)2CO + C6H5OH

Cumen
C6H5CH3 C6H5CH3
(CH3CH)2O CrO3

Hypcxylcumyl
C6H5CHO C6H5COOH

KMnO4

Phn ng xy ho cc arylalkan bng Cr(VI) c nghin cu tng i nhiu. Tluen b xy ho thnh axit benzic, iphnylmtan to ra benzphnon cn triphnylmtan to ra triphnylcacbinol. Tc xy ho ph thuc nhiu cu to ca

113

hyrcacbon. Trong trng hp xy ho, nhm p mtyl lm tng tc , cn nhm p nitr lm gim tc , hiu ng n c t hp tuyn tnh vi +, = -1,4. Nu hai nguyn t hyr tham gia phn ng c thay bng teri, tc phn ng s gim 6,4 ln, iu chng t rng tc phn ng xy ra s phn cch lin kt C H. Tuy vy c ch ca giai on ny ni ring cng nh ton b phn ng ni chung cn cha r rng. Phn ng xy ho nhm alkyl nhn thm bng pemaganat kali cng thng to ra axit. Cc dn xut th nhn ca toluen b xy ho to thnh axit benzic tng ng. So vi CrIV th MnVII thng xy ho mnh hn. Chng hn 2-5 ibrm-p-xylen b xy ho c hai nhm mtyl bi penmanganat Kali, nhng ch xy ho mt nhm myl bi axit crmic. Bt k cht xy ho l CrVI hay MnVII, phn ng xy ho nhm alkyl vi vng benzen thng xy ra v tr (to ra cc axit benzic tng ng). Tuy vy, cn lu rng nhm alkyl bc 3 th d t- butyl rt kh b xy ho v khng cn nguyn t hyr. 5.2.2.1. XY HO LIN KT CA HYRCACBON 5.2.2.2. zn phn
C = C
O3

O O C O C

Zn AcOH

C = O + O = C

Hp cht c ni i C = C tc dng vi zn sinh ra znit. C th phn lp c znit, nhng ngi ta thng em phn hu n bng cch kh thnh hai phn t hp cht cacbnyl. Cng c th kh znit thnh hai phn t alcol (tc dng ca LiAlH 4) hoc xy ho thnh xton v cacbxylic (tc dng ca H2O2). C ch ca giai on to thnh znit c th nh sau:
C = C Alken O C = C O O znit
O3

C O

C - C O O (+) O (-)

O3

(+)

O = C O
(-)

O (III)

(IV)

Nu qu thc c to ra sn phm trung gian III v Iv nh nu s trn th III c th ime ho

114

(+)

O +

(-)

O O
(-)

O
(+)

C O O

C O C (V)

(III)

hoc chuyn ho thnh hyrpexyt. Trong mt s trng hp, th d zn ho (CH3)2C=C(CH3)2, ngi ta tch c sn phm V, v nu c zn ho trong mtanol c th phn lp c hyrpexyt:
(CH3)2C - OCH3 O - OH

Mt dn chng na v c ch zn ho trn l s to thnh cc sn phm cho: theo c ch nu xut pht t mt alken khng i xng RCH = CHR ta phi c 3 znit khc nhau:
O RCH O O CHR RCH O O O CHR' R'CH O O CHR' O

Trong thc t, khi zn ho nhng hp cht nh penten-2, hexen-2, lat mtyl ngi ta phn lp c c ba loi znit trn cc dng ng phn cis-trans tng ng. Cc hp cht c ni ba C C v hp cht thm b zn ho kh hn alken. 5.2.2.2. ihyrxy ho:
C = C C C

OH OH

Mun cng hai nhm OH vo ni i (ihyrxy ho) c th dng OsO4 hoc KmnO4 trong mi trng kim. l nhng phn ng cng theo kiu cis. Khi dng cht xy ho l OsO4 c ch phn ng nh sau:
C ==C C O C O OsO2 (I)
HOH

C OH

C OH

Ngi ta phn lp c este vng trung gian I.


115

Khi dng KmnO4 trong mi trng kim, ta c c ch:


C C (MnVII) H2MnO4
(-)

(-) MnO4

C C

O O

(-) H O MnO4 2

C C

OH OH

+ MnO4 (MnVII)

(-)

(MnVII)
MnO4
(-)

MnO42(MnV)

C = C

MnO2 (MnV)

(MnV)

Hin nay, tuy cha phn lp c este vng MnV nhng c chng c khc v c ch
H18 O - C - C - 18OH

trn, c th l khi dng Mn18O(-)4 ngi ta thu c: . Ngoi ra, chng minh rng phn ng chy theo kiu cis, ngi ta ihyrxy ho axit d,l-tactric, ng nh d on theo c ch trn. Mun trans-ihyrxy ho ni i C=C ngi ta dng H2O2 v axit fomic. Trong trng hp ny, axit pefomic sinh ra t H 2O2 v axit fomic pxy ho ni i theo kiu cng cis, sau pxit sinh ra s b thu phn theo c ch S N2 vi s quay cu hnh, kt qu xt ton b th phn ng chy theo kiu trans:
H - C - OH + H2O2 O H - C - O - OH + H2O O O C C O H C O H C O + C HO O C H

Epxy ho:

Thu phn:
OH2 H
(+)

OH C -H (+) HO C

C O - H C

C
H2O

O C

C HO

Do c tnh cng trans ca phn ng, khi cho H 2O2 v HCOOH tc dng vi xyclohexen ta c trans-1,2-xyclohexandiol
116

HCOOH H2O2

H2O (+) H

OH

OH

5.2.2.3. Oxy ho ct mch:


- C = C H H - C = C H - C = C - C = O + O = C OH OH - C = O + O = C OH - C = O + O = C -

Ni i C=C c th b oxy ho ct mch theo cc s trn nh tc dng ca nhiu cht oxy ho khc nhau, ph bin l cc cht oxy ho pemanganat v bicromat trng mi trng axit. C ch phn ng cn cha c r rng. Cng c th trong phn ng sinh ra nhng sn phm trung gian l glycol hoc este ca n. Ni ba CC thng kh b oxy ho hn ni i. Axtylen b oxy ho bng pemanganat kali to thnh mt hn hp sn phm trong c axit xalic. Vng thm cng c th b oxy ho t mch bi cc cht oxy ho mnh. Khi oxy ho benzen v naphtalen bng V2O5 ta c ln lt anhydrit malic v anhydrit phtalic. 5.2.3. XY HO ALCOL: 5.2.3.3. xy ho mnalcol thnh hp cht cacbnyl
CHOH C = O

S oxy ho cc alcol bc mt v bc hai bng pemngnat kali xy ra rt chm trong dung dch trung tnh, nhng thng li rt nhanh trong dung dch baz v axit mnh. Kho st phn ng xy ho benzhydrol (C6H5)2CHOH trong dung dch trung tnh v baz, ngi ta thy: V = k [alcol][MnO4-][OH-] hiu ng ng v 250C khi oxy ho (C6H5)2CDOH c gi tr bng 6,6; benzphnn sinh ra khng cha oxy t pemngnat kali. T cc d kin ngi ta ngh c ch phn ng nh sau:
(C6H5)2CHOH (C6H5)2CHO HMnO4
2(-)

+ HO

(-) (-) (-)

(C6H5)2CHO chm nhanh

(-)

+ H2O + HMnO4
2-

+ MnO4
(-)

(C6H5)2C = O 2MnO4
2-

+ MnO4 + HO

+ H2O

Kho st phn ng oxy ho alcol izppylic bng axit cromic ngi ta thy tc phn ng trong dung dch axit axetic ln hn trong dung dch axit v c vi cng gi tr v H0; khi thay th nguyn t -hydro bng teri 250C tc gim 6,6 ln, trong khi thay th cc nguyn t - hydro bng teri hu nh khng lm thay i tc phn ng:
(CH3)2 CH - OH (CH3)2 CDOH (CD3)2 CHOH

117

Tc :

1,0

0,16

1,0

T cc d kin ngi ta ngh c ch phn ng nh sau:


(CH3)2 CHOH + HCrO4 + 2H (Cr ) CH3 C CH3 H :B
(+)

(-)

(+)

(CH3)2CHOCrO3H2 + H2O CH3 C = O + BH CH3


(+)

(+)

VL

O - CrO3H2

(+)

+ HCrO3 (CrIV)

(+)

Sau : Hoc:

3Cr

IV

H
IV

Cr

IV

+ 2Cr

III

3Cr + Cr Cr
V

IV

+ 2CrV -H
(+)

+ (CH3)2CHOH

Cr

III

+ (CH3)2 C = O

5.2.3.2. xy ho ct mch 1,2 iol Cc 1,2 iol c c tnh khc v mnalcol ch chng b xy ho bi axit peiic v ttraxtat ch lm t lin kt
- COH - COH - C - OH C - OH HIO4 hoc Pb(CH3COO)4 - C - OH + C - OH

Khi xy ho bng HIO4 phn ng i qua mt este vng trung gian:


- C - OH C - OH + HIO4 - C - O C- O IO3H - C - OH C - OH + HIO3

118

Nhng th nghim dng 18O cho thy rng nguyn t xy cacbnyl sn phm cng chnh l nguyn t xy glycol. C ch to este vng trung gian ca phn ng trn c xc nhn bng cc d kin ng hc v quang ph, dn chng c bit l cc glycol vi hai nhm trans-OH th d trans-9,10-calindiol khng phn ng vi axit peiic.
OH + OH HIO4

Khi xy ho 1,2 -ddioolbng Pb (CH3COO)4 ngi ta cng c nhiu d kin cho thy phn ng xy ra theo c ch vng. Th d phn ng c bc mt ni i vi mi cht phn ng gim i, cis-ddiolb xy ho nhanh hn trans-iol tng ngC ch vng nh sau:
- C - OH C - OH - C - O + Pb ( CH3COO)4
-2CH3COOH

C- O

Pb(CH3COO)2

Pb(CH3COO)2

- C - OH + C - OH

Tuy nhin, c mt s trans-1,2-ddiol li d phn ng hn dng cis tng ng. V d trng hp 9,10 ihyrphnantren-9,10 -ddiol dng trans phn ng nhanh hn dng cis 9,4 ln, trans 9,10 ecaliniol khng phn ng vi HIO 4 nhng li b xy ho bi Pb(CH3COO)4. Nh vy, c th y phn ng xy ra theo c ch khng vng.
OH
Pb(CH3COO)2 -CH3COOH

O
-2CH3COOH

O + Pb(CH3COO)2

OH

O Pb(CH3COO)2

1,2-iol cng c th b xy ho ct mch bi axit crmic v phn ng cng chy theo c ch este vng trung gian. 5.2.4. XY HO ALEHYT V XTN

119

5.2.4.1. xy ho bng tc nhn v c: Cc hp cht cacbnyl, nht l alhyl c th b xy ho bi cc hp cht xy ho khc nhau nh MnVII, CrVI, Cu'', AgI, CeIV Nghin cu phn ng xy ho alhyt thm bng KmnO4 trong dung dch trung tnh ngi ta thy rng phn ng c bc mt i vi alhyt cng nh i vi pemanganat, hiu ng ng v teri bng 7, nu dng KMn18O4, 18O s xut hin trong thnh phn phn t ca axit thm sinh ra, cc nhm th vng thm ch c nh hng yu n tc phn ng ( = -0,25). Ta c th m t c ch phn ng xy ho bng s sau:
O ArC H + MnO4
(-)

OH + H
(+)

Ar - C OMnO3 H

OH Ar - C - O - MnO3 H :B chm ArCOOH + BH + MnO3


(+) (+)

Phn ng xy ho alhyt bng axit crmic c nhiu nt tng t phn ng xy ho alcol cng bng tc nhn . C ch phn ng nh sau:
O RC - H + HCrO4
(-)

OH +H
(+)

OH RC - H
:OH2

RC + HCrO3 + H3O O

(+)

O - CrO3H

Trong trng hp dng C6H5CDO ngi ta thy hiu ng ng v bng 4,3, iu chng t giai on phn ct lin kt cacbon-hyr quyt nh tc chung ca phn ng. Gia hai phn ng xy ho alhyt v xy ho alcol bng axit crmic c hai im khc nhau ng k. Mt l, cc nhm th ht electron xc tin s xy ho alhyt ( = +1,02) nhng li lm gim nh tc xy ho alcol ( = -1,0). Hai l thay th dung mi

120

nc bng axit axetic khng lm tng mnh tc xy ho alhyt nh thy khi xy ho alcol. Khc vi anhyt, xtn tng i kh b xy ho bi pemangant kali v axit crmic. Tuy vy cc xtn vng d dng b xy ho thnh axit icacbxylic. Th d:
O COOH COOH

CrO3
Hoc HNO3

Axitaipic

C th cc xtn tc dng di dng enol to ra este v c trung gian, sau este ny b thu phn:

- C -CO H

- C = C OH

H2CrO4

- C - C OH OCrO3 H2 -H
(+) (+)

(+)

xy ho tip

- C - C - thu phn O OH

- C - C O OCrO3 H2
(-)

ng ch l nhm -metylen ca xtn cng nh aldhyt c th b xy ho thnh cacbnyl th hai nh tc dng ca xyt selen:
- C - CH2 - + SeO2 O AeOH -H2O - C - C - + Se +H2O O O

Trong phn ng trn, tc nhn xy ho trc tip c l l axit selen: axit ny tc dng vi lin kt ca dng enol theo s :

121

- C - CH2 O

- C = CH OH

H2SeO3 - C = CH -H2O O - SeO2H

- C - C O O

- Se - C - CH - H2 O O O - SeOH

5.2.4.2. xy ho bng tc nhn hu c: Nhng phn ng xy ho alhyt bng cht hu c cn c th c coi l phn ng kh i vi cht hu c . Nhng phn ng ny thng chy theo c ch chuyn dch in hyrua, m tiu biu hn c l phn ng Cannizar v phn ng Tissenc. a. Khi c tc dng ca mt baz mnh nh NaOH chng hn cc alhyt thm v alhyt bo khng c nguyn t -hyr s tham gia phn ng Cannizar, trong mt phn t alhyt b xy ho thnh cacbxylic tng ng, cn phn t alhyt b xy ho thnh alcol tng ng. Trong phn ng ny, thot tin aion HO(-) tc dng vo nguyn t cacbon-cacbnyl ca mt phn t alhyt:
OH R - C - H + HO O
(-)

O HO
(-)

(-)

R - C - H O
(-)

R - C - H O
(-)

Sau aion sinh ra s chuyn in hyrua sang nhm cacbnyl ca phn t alhyt th hai:
OH R OH R
(-)

O H2 O

(-)

R-C -H +C=O O
(-)

R-C + H-C-O O H

R - C + H - C - OH O H

hoc

122

(-)

(-)

R
(-)

O H2O

(-)

R-C -H +C=O O
(-)

R-C + H-C-O O H

R - C + H - C - OH O H

Phn ng trn c bc mt i vi b v bc hai i vi anhyt, phn ng ca RCHO trong D2O - kim to ra alcol khng cha eteri, iu c s chuyn dch trc tip hyr t phn t anhyt th nht sang phn t anhyt th hai. Phn ng Cannizar c th xy ra gia hai nhm C = O ca mt phn t (Th d: C6H5CO CHO) hoc gia hai nhm C = O ca hai phn t khc hn nhau(th d: (CH3O)2C6H3CHO v HCHO2. b. Tt c cc alhyt khng c hoc c -hyr ni chung u tc dng c vi alkxyt nhm, khi y mt phn t alhyt b xy ho to ra axit cacbxylic, cn phn t khc b kh to ra alcol, hai sn phm ny dng este (Phn ng Tisenco):
RCHO + RCHO Al(OR')3 RCOOCH2R

Khi dng hn hp hai alhyt khc nhau ta c th thu c ti bn este RCOOCH2R', R'COOCH2R, RCOOCH2R v R'COOCH2R'. Tng t phn ng Cannizar, phn ng Tisenc chy theo c ch chuyn dch in hyrua:
O RC H
Al(OR')2

O Al(OR')3 RC H
O = CHR

(-)

O Al(OR')3 RC - O - CHR H
Al(OR')3

(-)

O RC - O - CH2R

5.3. CC PHN NG KH 5.3.1. KH LIN KT B CACBON CACBON 5.3.1.1. Kh bng hyr trn b mt cht xc tc kim loi Bt k c nhm th l y electron cc lin kt bi cacbon-cacbon u c th b hyr ho trn b mt cht xc tc kim loi. Nhng cht xc tc hay dng l Ni, Pt, Rd, Ru v CuCr2O4. Kh ho v hyr ho l nhng qu trnh thun nghch i vi nhau. Qa trnh hyr ho pht nhit (28-33kcal/mowl), cn qu trnh hyr ho thu nhit. C ch ca phn ng hyr ho trn b mt cht xc tc kim loi l mt vn phc tp cn cha c gii quyt trn vn. Phn ng hyr ho lun lun xy ra theo kiu cis. Vy cc alkyn b hyr ho to thnh cis-alken.

123

RCH2 RCH2 - C C - CH2R H2,Pd quinlin H C=C

CH2R

Cc axit imtylmalic v imtylfumaric khi b xy ho to ra nhng ng phn khc nhau ca axit imtylsucxinic:
CH3 CH3 COOH H2/Ni CH3 COOH H H COOH COOH Mz-

CH3

Axit dimtylfumaric

CH3

COOH H2/Ni

HOOC H

H CH3 + HOOC H

COOH CH3

CH3

COOH

CH3

COOH D, L -

CH3

V kh nng phn ng, alkyn d b hyr ho hn alken. Nu so snh kh nng phn ng hyr ho ca cc lin kt bi cacbon-cacbon vi cc lin kt b khc ta c th t gn ng nh sau:
RC = O > RNO2 > RC Cl CR > RC = O > RCH = CHR >RC = O > H H

> dn xut ca naphtalen > RC = O > O dn xut ca benzen


OR'

Vng benzen khi b hyr ho thng khng dng li giai on cng mt phn t hyr, v anken d b hyr ho hn vng benzen rt nhiu. Th d mt mol benzen tc dng vi mt mol hyr khng cho xycllexaien hay xyclhexen m cho 1/3 mol xyclhexan. Trong iu kin nh vy naphtalen b kh cho ta ttrahyrnaphtalen (ttralin). Tuy vy, i vi nhng hp cht thm nhiu vng ngng t hn nh antraxen, phnantren ta li d dng cho phn ng dng giai on cng hyr vo hai nguyn t 9, 10 v nhng v tr ny hot ng hn c:

124

H2 xt Benzen H2 xt Napncaten Tetralin Phenantren Xyclhexan Antraxen H2 xt

H2 xt 9,10- Dihydrantraxen

9,10- Dihydrantraxen

5.3.1.2. Kh bng cc tc nhn khc: Cc alken -1 d dng b kh bi hyrua nhm to thnh alken:
RCH = CH2 + AlH3 Benzen (RCH2CH2)3Al H3O
(+)

RCH2CH3

iboran cng kh c alken tng t nh vy


RCH = CH2 + B2H6 (RCH2CH2)3B H
(+)

RCH2CH3

Tc cng iboran vo anken s gim khi s nhm alkyl ni i tng ln. Khi dng iboran kh alkyl ta c cis.alken.
RCH2C CC2R B2H6 RCH2CH = C - B RCH2 H3O
(+)

RCH2 C=C

CH2R

Tri li nu dng cht kh l natri trong amniac lng ta s c trans-Anken:


RCH2 Na
(+)
(-)

RCH C = CCH R
2 2

2Na

C=C

(-)

Na

(+)

RCH2 2NH -2NaNH C=C H


2

H CH R
2

CH R
2

Dng natri-amniac kh vng thm ta c sn phm cng 1,4 l xyclhexaien khng lin hp:

125

H Na H

Na

(+)

H NH 3 H

H H Na H

H NH3 H Nd

Cc nhm th y electron (th d OCH3) trong vng benzen nh hng phn ng to ra dn xut 2,5 ihir, trong khi cc nhm th ht electron (th d COOH) li nh hng to ra dn xut 1,4-ihyr:
OCH3 H H OCH 3 H H H H COOH H COOH

Naphtalen b hyr ho bi natri-tanol trc tin cho ta 1,4-ihyrnaphtalen nhng cht ny khng bn, n chuyn ho ngay thnh 1,2- ihyrnaphtalen (c hai phn ng u to nhit)
Na C HOH 6 5 Naptalen 1,4- ihy rNaptalen 1,2 - ihi r Naptalen

5.3.2 KH ALEHYT V XTN: 5.3.2.1. Kh thnh alcol: Alhyt v xtn ni chung d b kh thnh alcol bc mt v bc hai. Cc cht kh c th l: natri trong ru, hyr trn niken Rany, hyrua litinhm, hyrua natribo a. Kh bng LiAlH4 v NaBH4: V thc cht cc phn ng ny l phn ng cng nucleophin vo nhm cacbnyl:
R' R - C = O H - AlH3
(-)

R' R - C = OAlH3 H
(-)

R'
RR'C = O

R'
(-) H O 2

R - C = O Al H
4

R - C = OH H

Cc hyrua kim loi nh LiAlH4 thng khng kh lin kt bi cacbon cacbon v th chng c th kh chn lc nhm C = O ca hp cht cacbnyl cha no. Th d:
C6H5CH = CH - CH = O C H CH = CH - CH2OH ete -100C 6 5
LiAlH4

Tuy vy iu kin nhit phng phn ng kh trn to ra alcol no C6H5CH2CH2CH2OH.

126

Dng NaBH4 lm cht kh c u im l tnh chn la cao v c th thc hin phn ng trong mi trng nc. NaBH4 khng kh cc nhm C = C, COOH, COOR 9v tnh kh chn la, xem bng XV-3) b. Kh bng izproopylat nhm: Mt s alcolat kim loi, c bit l izprpylat nhm c kh nng kh alhyt v xtn thnh alcol tng ng theo mt qu trnh thun nghch.
R C = O + (CH3)2CHOH R' R
(i-C3H7O)3Al

CH - OH + (CH3)2C = O

R'

Qa trnh thun, dng kh hp cht cacbny, c gi l phn ng MecvaiPondoo-Vecly, cn qu trnh nghch, dng xy ho alcol, c gi l phn ng Openao. Bn cht ca cc phn ng trn l qu trnh chuyn dch ion hyrua t alcolat nhm sang nhm cacbnyl qua mt trng thi chuyn tip vng:
CH3 C O
(i - C3H7O)2Al

CH3 H + C O R' R

CH3 C O
(i - C3H7O)2Al

CH3 H R C O

CH3 C O
(i - C3H7O)2Al

CH3

+ HHR C O R'

R'

Dn chng v s chuyn dch ion hyrua l khi dng izprpylat nhm c cha teri RRCDOH. Khi kh bng izprpylat nhm ngi ta chng ct cho axtn thot ra khi mi trng phn ng v cn bng v bn phi. Tri li khi mun xy ho alcol ngi ta dng d axtn v dng t-butylat nhm lm xc tc, v cht ny khng cn - hyr c th kh axtn m ch c th chuyn alcol cn oxy ho thnh alcolat tng ng. 5.3.2.2. Kh thnh hyrcacbon no:
RCR' O RCH2R'

C mt s phng php kh nhm C = O thnh nhm CH 2, quan trng nht l phng php Kizne Vnf v phng php clemmenxen. Trong phng php clemmenxen ngi ta un nng alhyt hoc xtn hn hp km trong axit clohyric m c. C ch ca phn ng cn cha r rng, ch bit rng sn phm trung gian khng phi l mt alcol v cht ny khng b kh thnh hyrcacbon trong iu kin ni trn. Nu trong phn t anhyt v xtn c nhng nhm th khng bn trong mi trng axit, th tt nht nn dng phng php Kizne Vnf. Theo phng php ny

127

hp cht cacbonyl c chuyn thnh hyraz tng ng, ri un hyrazon vi kim c hoc tylat natri:
R C = O + NH2 - NH2 R R
-H2O

R C = N - NH2
C2H5ONa
2000C

CH2 + N2 R

C ch ca giai on chuyn ho hyrazon thnh hyrcacbon c th c m t bng s sau:


R C = NNH2 R' R CH2 R' R
C2H5O
(-)

R C = NNH2 R' R CH
(-) (-)

C - N = NH

R' R
C2H5O
(-)

-N2

CH - N = N

(-)

R'

R'

Phng php Kizne Vnf c Hong Minh Long ci tin bng cch un trc tip hp cht cacbnyl vi hyrazin v kim trong tylenglycol di p sut thng (v th c tn gi phng php Hong Minh Long). Cram li ci tin thm bng cch dng ibutoxyt kali lm baz v imtylsunfxyt lm tng dung mi, do c th thc hin phn ng ngay nhit phng m hiu sut t c vn cao. 5.3.3. KH AXIT CACBOXYLIC V CC DN XUT CA CHNG: Axit cacbxylic RCOOH khng b kh bng cc ch kh thng thng, nhng li d b kh bi LiAlH4, v mt vi cht khc to thnh alcol bc nht:
RCOOH
LiAlH4

RCH2OH

C ch ca phn ng c th nh sau:

128

RCOOH + LiAlH4

H2 + AlH3 + RCOO Li

(-)

(+)

LiAlH4 H RCH2OH
1.LiAlH4

2.H2O

(+)

R - CH = O

Li2O

R - C - OLi O
(-)

(-)

(+)

Li

(-)

Este d b kh hn axit cacbonxylic, phn ng kh este bng LiAlH 4, xy ra tng t phn ng kh alhyt v xtn.
R' R - C = O H - Al H2
(-)

R' R - C - O H
(-)

- RO

(-)

R- C = O H

1.LiAlH 2.H2O

R - CH2OH

Ngoi LiAlH4, este cn c th b kh bi mt s cht khc nh hyr trn cromit ng, natri trong tanol Phng php kh este thnh alcol bng natri trong tanol c gi l phng php Buv-Blng. Trc khi tm ra LiAlH4, phng php Buv-Blng c dng rt ph bin. Clorua v anhyrit axit cng d b kh bi LiAlH4, thnh alcol bc nht:
RCOOCOR RCOCl
LiAlH4

2RCH2OH RCH2OH

LiAlH4

Clorua axit c th b kh bi hyr trn cht xc tc Pd to thnh alcol, qua cht trung gian l alhyt:
RCOCl
H2

xt

RCHO

H2

xt

RCH2OH

ngn cn giai on chuyn alhyt thnh alcol ngi ta dng BaSO 4 lm cht c i vi Pd (phng php kh Rzenmun):
RCOCl
H2

Pd-BaSO4

RCHO

Mun kh clorua axit thnh alhyt ta cn c th dng cc cht kh l liti hyrua hoc tri-t-butxy nhm hyrua. Trong trng hp dng cht kh l hn hp natri trong te ta s c este ca eniol:
R 4RCOCl + 4Na RCOO 129 C = C OCOR R + 4NaCl

Kh nng phn ng ca mt s nhm chc i vi cc cht kh khc nhau:

Phn ng

RCH = CHR RCH2CH2R TCHO RCH2OH RCOR RCHOHR RCHO RCOCl + RCH2OH RCOOR RCH2OH + + ROH RCOOH RCH2OH (-) RCOO RCH2OH

Hyr ho c xc tc + + +

LiAlH4 trong te + + + + + +

B2H6 trong THF + + + +

NaBH4 trong etanol + + + -

NaBH4 + AlCl3 trong iglime + + + + + + +

THF: ttrahyrfuran, iglime: (CH3OCH2CH2)2O 5.3.4. KH CC HP CHT CHA NIT: S kh cc hp cht cha nhm C N, - C = N v CONH2 ni chung tng t s kh hp cht cacbnyl, sn phm sinh ra thng l amin. Th d cc xim b kh bng LiAlH4 thnh amin bc nht:
R C = NOH R'
LiAlH4

R CHNH2 R'

Phn ng kh xim chy chm hn phn ng kh xtn. Amit b kh bi LiAlH4(NaBH4 khng c tc dng) tng t este. C ch phn ng kh nh sau:

130

R - C - NH2 O RCH2 - NH2

AlH4

(-)

RC - NH O

(-)

AlH4

(-)

R - CH - NH O
(-)

(-)

H2O

RCH2 - NH

(-)

AlH4

(-)

R - CH = NH

Amit, xim cng nh nitrin u c th b kh bng hyr nh cht xc tc kim loi. Cc hp cht nitr v nhng dn xut th ca chng rt d b kh bng nhiu tc nhn khc nhau. S kh trong mi trng axit hoc kh bng hyr trn cht xc tc kim loi thng cho ta hp cht amin:
RNO2 Cht kh, axit H2, Pt, Pd hoc Ni RNH2

S kh nhm nitr trong mi trng kim phc tp hn nhiu v c nhng phn ng ngng t gia cc sn phm kh khc nhau:
RNO Cht kh, ki m
2

RNO H p cht nitrz

RNHOH H p cht hy rxyamino RNO RN - NR OH OH


- H2O

RNH2
Amin RNO RN - NHR OH
- H2O

H p cht nitr

RN = NR

RN = NR H p cht az

O H p cht azxy

RNHNHR H p cht Hy rz

Tuy s kh hp cht nitr phc tp nh vy, nhng nu chn cc cht kh thch hp ngi ta c th cho phn ng u tin dng li mt giai on nht nh no .

131

CHNG 6 S CHUYN V Trong nhng chng trc, chng ta thng kho st cc phn ng ca hp cht hu c trn c s ca nguyn tc bin i cc tiu cu to, ngha l tha nhn rng trong phn ng trong phn ng ho hc ch cc nhm chc thay i, cn phn gc hyrcacbon vn c bo ton. Nguyn tc t ra ng n trong rt nhiu trng hp, v rt b ch trong vic xc nh cu trc phn t bng con ng ho hc. Tuy vy, ta bit c nhng trng hp khng theo nguyn tc bin i cc tiu. Chng hn, c nhng phn ng th, trong nhm th i vo phn t li khng vo ch vn c nhm th i ra trc y, m li vo nguyn t khc thng l cnh . Hin tng ny c gi l chuyn v. Hin tng chuyn v rt a dng v phong ph. Ta phn bit ba loi chuyn v ch yu. a. Chuyn v 1,2 l loi chuyn v t v tr 1 n v tr 2 trong phn t hp cht thuc dy tr. b. Chuyn v 1,3 t v tr 1 n v tr 3 trong phn t hp cht thuc dy cha no. c. Chuyn v t nhm chc vo vng thm trong dy thm. Chng ny s ni v s chuyn v 1,2 v chuyn v t nhm chc vo vng thm. 6.1. S CHUYN V 1,2 NUCLPHIN Nhng qu trnh chuyn v, trong nguyn t (hay nhm nguyn t) chuyn dch ti mt trung gian ang thiu ht electron, mang theo c cp electron lin kt, c gi l chuyn v nuclphin.
R A B A R B

R: Nhm chuyn dch: A: v tr chuyn i

B: V tr chuyn n

Hp cht hu c tham gia chuyn v c th l ion hay phn t. Thng thng v tr chuyn i (A) l nguyn t cacbon, cn v tr chuyn n (B) c th l cacbon, xy, nit

132

R C C
(+) (+)

CR

R C O
(+)

(+)

OR

R C .. N C NR

Nu R l nguyn t c cha cp electron cha s dng (Z) nh halgen, xy, lu hunh, nit s chuyn v 1,2 c th i qua bc trung gian to thnh vng ni ba cnh khng bn:
Z
(+)

C Thi du: CH3 Br


Ag
(+)

CH3
AgBr

CH3
H2O

CH3 - C - CH - CH3 CH3O:

CH3 - C - CH - CH3
(+)

CH3 - C - CH - CH3 OH OCH3

O CH3

Nu R l nguyn t cacbon hoc hyr, c bit khi R l nguyn t cacbon thm th sn phm trung gian c th l mt ion cu ni:

133

Z
(+)

C Thi du: H CH3 - CH - CH2


(+)

H
(+)

H CH3 - CH - CH2
(+)

CH3 - CH - CH2

V vy, trong qu trnh chuyn v thng xy ra s quay cu hnh ca nguyn t cacbon v tr chuyn n cng nh v tr chuyn i. a s cc qu trnh chuyn v 1,2 nuclphin u l chuyn v ni phn t, nhm R khng tch ra trng thi t do m lun lun gn vi cc phn t cht phn ng theo mt cch no . iu ny c chng minh bng cc th nghim cho v bng cch xc nhn s bo ton cu hnh ca cc nhm R quang hot. 6.1.1 S CHUYN V N NGUYN T CACBON 6.1.1.1. Chuyn v Vanhe Mecvai: Trong cc qu trnh th v tch nucleophin n phn t cng nh trong qu trnh cng electrphin vo lin kt bi cacbon cacbon u sinh ra cacbcation. Nhng cacbcation c th tham gia chuyn v, lm cho mt nguyn t hyr hoc nhm alkyl hay aryl v tr i vi C(+) chuyn dch C(+) n . Th d:
CH3 CH3 - C -CH2 - OH CH3 Alcol nepentylic
HCl -H2O

CH3
(+) CH3 - C -CH2 chuyn v CH3 - C -CH2 - CH3 (+)

CH3 Cl CH3 CH3 - C -CH2 - Cl CH3 Clorua nepentyl


(-)

CH3 Cl Cl CH3 - C -CH2 - CH3 CH3 Clorua t-amyl


(-)

chng minh s chuyn dch cacbcation sinh ra t alcol nepentylic ngi ta dng ph hng ngoi v ph CTN xc nh cu to ca cc alken sinh ra t (CH3)3CCD2OH. Kt qu cho thy phn ng sinh ra alken ph hp vi s to thnh cacbcation trung gian nh sau:

134

H (CH3)2C - CD2OH -H O (CH3)2C - CD2


2

(+)

(+)

(CH3)2C - CD2OH

-H

(+)

CH2 = CCD2CH3 CH3

(+)

CH3

CH3 -D
(+)

(CH3)2C = CDCH3

Loi phn ng lm thay i b khung cacbon nh kiu trn c gi l chuyn v Vanhe-Mecval. S chuyn v c th xy ra khng nhng alcol m cn nhiu loi hp cht khc nh dn xut halgen, amin, hyrcacbon Th d:
CH3 (CH3)2C - CH2Br CH3 (CH3)2C - CH2
(+)

(CH3)2C - CH2 - CH3

(+)

-H

(+)

(CH3)2C = CH3 OH

H2O

-H

(+)

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

(CH3)2C - CH = CH2 H CH3

(+)

(CH3)2C - CH - CH3 CH3

(+)

(CH3)2C - CH(CH3)

(+)

-H

(+)

S chuyn v Vanhe-Macvai c tnh c th lp th r rt: iu cho thy rng cacbcation trung gian khng phi l cacbcation cu ni. Th d khi cho tsylat ca cc 3 phnylbutanol -2 tc dng vi axit axtic ta s c cc axtat tng ng, vi cu hnh lp th khc nhau, tu theo cu hnh ca tsytal ban u:
CH3 C6H5 CH3 C6H5 H H
-OTs
(-)
(+)

H OAc C 6 H5 CH3 H

AcOH

OTs CH3 H

CH3 CH3

-H

(+)

CH3

H CH3 OAc

Tsylat rytr

Ion phnni

Axtat rytr (quang hot) 135

CH3 C6 H 5 H C6H5 H CH3


-OTs
(-)
(+)

H OAc

AcOH

CH3 C6 H 5

OTs CH3 H

H CH3

CH3 -H

(+)

H CH3 OAc

H CH3

Tsylat rytr

Ion phnni

Axtat rytr (quang hot)

6.1.1.2. Chuyn v pinacol pinacolon: Th d c tnh cch kinh in nht v chuyn v pinacol pinaclon l chuyn ho 2,3 imtylbutaniol -2,3 (pinacol) trong mi trng axit thnh 3,3 imtyl butanon -2 (pinaclon):
CH3 CH3 CH3 - C - C - CH3 OH OH
(+)

CH3 CH3 CH3 - C - C - CH3 OH OH2


(+)

CH3
-H2O

CH3 - C - C - CH3 OH CH3 (I) CH3

(+)

CH3 CH3 CH3 - C - C - CH3 O CH3 Pinaclon


(+)

-H

(+)

CH3 - C - C - CH3 OH CH3 (II)

S chuyn v cacbocation I II c th xy ra i vi bt k hp cht no c kh nng to ra cacbocation tng t I. Th d:

136

CH3 CH3 CH3 - C - C - CH3 OH Br


Ag
(+)

CH3
-AgBr

CH3
(+)

CH3 - C - C - CH3 OH CH3 -N2 CH3 CH3

CH3 - C - C - CH3 OH CH3 -H


(+)

(+)

CH3 CH3 CH3 - C - C - CH3 OH Br


NaNO2-HCl

CH3 CH3 - C - C - CH3 O CH3

CH3 - C - C - CH3 OH N2
(+)

Tng t nh trong s chuyn v Vanhe-Mecval, cation I sinh ra ttrong s chuyn v pinacal-Pinacolon khng phi l mt cabotion t do vi cu trc phng, v xut pht t hp cht quang hot vi C quay cu hnh (quang hot). Th d:
H C6H5 OH C6H5 CH3
(+)

C6H5 H
-N2
(+)

C6H5 H O CH3

N2

CH3
-H
(-)

C6H5

OH

C6H5

Nh vy, nhm phnyl b chuyn dch tin cng nguyn t C t pha i lp vi pha c nhm N2(+) (sinh ra t nhm NH2). Trong trng hp to ra cacboncation kinh in vi cu trc phng th nhm C6H5 t phi tin cng C t hai pha vi xc sut nh nhau v to ra sn phm raxemic. V nhm b chuyn v mang theo c cp electron lin kt nh mt tc nhn nuclphin, cho nn khi c hai nhm th, nhm d b chuyn dch hn chnh l nhm c tnh y electron mnh hn. Th d trong phn ng di y hu nh ch nhm ptlyl chuyn dch:
p-CH3C6H4 C6H4 CH3 - p C6H5 - C - C - C6H5 OH OH C6H4 CH3 - p C6H4CH3 - p

C6H5 - C - C - C6H4CH3 - P + CH3C6H4 - C - C - C6H5 O C6H5 94% O C6H5 6%

137

Trong cc pinacol khng i xng hng chuyn v thng c quyt nh bi kh nng tch nhm OH, tc l bi n nh tng i ca cacbocation trung gian, v vy trong phn ng di y khng phi nhm p-anyzyl m chnh nhm phnyl chuyn v l ch yu:
(p-CH3OC6H4)2C - C(C6H5)2 OH OH 28% (p-CH3OC6H4)2C - C(C6H5)2 OH C6H4 CH3 - p (p-CH3OC6H4)2C - C(C6H5)2 O
(+)

72% (p-CH3OC6H4)2C - C(C6H5)2 OH C6H5 (p-CH3OC6H4)2C - C(C6H5)2 O


(+)

Ngoi ra, hng chuyn v cn ph thuc vo cc yu t khng gian. Chng hn kh nng chuyn dch ca o anazyl km p anizyl hn 1500 ln. 6.1.1.3. Chuyn v Vnf: Khi c mt Ag2O cc - iazxtn chuyn v thnh xten l cht c kh nng phn ng rt cao v d dng tc dng vi nc (hoc alcol) trong mi trng, to thnh axit cacbxylic (hoc este):

R - C - CH - N O

(+)

(+)

Ag2O

-N2

R - C - CH .. O Cacben

O = C = CH - R xeten

H2O

O = C - CH2 - R OH

Khc vi cc phn ng chuyn v pinacol pinacolon v Vanhe-Macvai, trong s chuyn v Vnf nhm th R khng chuyn dch n nguyn t cacbon mang in dng ca cacbcation, m chuyn n nguyn t cacbon trung ho vi lp v electron cha ca mt cacbon. S chuyn v Vnf c dng trong tng hp Acn Aixt chuyn ho mt axit cacbxylic thnh ng ng cao k tip, theo s sau:
RCOOH
SOCl2

RCOCl

CH2N2

-HCl

RCOCHN2

Ag2O, H2O

Vonfo

RCH2COOH

138

Cng c th dng s chuyn v vnf vo vic chuyn ho mt xtn thnh ng ng cao hn hoc m rng vng xyclalkann. Th d:
CH2N2

O X XyclhexaNn

(-)

CH2 - N

N O Xyclheptanon

Trong nhng phn ng , hng cnh tranh ng k l ng vng to thnh xyt tylen. 6.1.1.4. Chuyn v benzilic: Chuyn v benzilic hay cn gi l chuyn v benzil axit benzilic l phn ng chuyn ho - ixtn trong mi trng baz thnh - hyrxyaxit. n gin v tiu biu nht l trng hp chuyn v benzyl thnh axit benzilic (v th c tn gi trn). Phn ng bt u bng tng tc gia baz v mt nhm cacbnyl, sau nhm aryl chuyn dch n nhm cacbnyl th hai mang theo c cp electron lin kt:
Ar Ar - C - C - Ar O - ixetn Ar Ar - C - C - OH OH O - Hyrxyaxit
H3O
(+)

Ar Ar - C - C - OH
(-)

HO

(-)

Ar - C - C - OH O O

O O Ar

Ar - C - C - O OH O

(-)

Nu thay NaOH bng CH3Ona ta s thu c este mtylic ca - Hyrxyaxit:


ArCO - COAr + CH3O
(-)

ArC - COOCH3 OH

Ch rng khng th dng cc alcolat nh C2H5ONa v i-C3H7Ona thay cho CH3Ona c, v nhng alcolat kh ArCOCOAr thnh ArCHOH COAr. Mt khc phn ng khng xy ra khi dng C6H5Ona, c l v phnolat c tnh baz yu. S chuyn benzilic thng ch xy ra cc - i xtn thm, bao gm c cc ixtn ni vng nh 9, 10 phnantrenquinn. Khi trong vng bn c nhm th ht electron kh nng chuyn dch nhm cha vng gim i.

139

Ngoi cc ixtn thm, mt s ixtn bo v xtaxit cng tham gia chuyn v benzilic. Th d:
OH HOOC - CH2 - C - C - CH2COOH O O Axit xtpinic
1.KOH

HOOC - CH2 - C - CH2COOH COOH Axit xitric

6.1.2. S CHUYN V N NGUYN T NIT 6.1.2.1. Cc phn ng chuyn v Hpman, Cuatiut, Ltxen, Smit c im chung ca cc phn ng chuyn v ny l to ra mt cacbenit trung gian v nhm alkyl hoc aryl trong cacbenit chuuyn dch ni phn t n nguyn t nit thiu ht electron. Trong s chuyn v Hpman mt amit khng c nhm th chu tc dng ca hypbromit kim (hoc kim v brm cng vy) chuyn thnh izxyanat l cht c kh nng phn ng cao, nn b hu phn ngay thnh amin bc nht km amit mt nguyn t cacbon.
R - C - NH2 O Amit
BrO
(-)

R - C - NH - Br O N - Brmamit

HO

(-)

R - C - N - Br O

(-)

R - C - NH : O

CO2 + H2NR

O = C - NH - R OH

O = C = N - R

Amin

Axit cacbomic

Izxyanot

Trong nhng iu kin thch hp, ngi ta tch ring c cc sn phm trung gian N- brmamit, izxyanant Giai on quyt nh tc phn ng trong s trn l tch Br(+) ra khi anion brmamit, tuy nhin rt c th l s chuyn dch nhm R xy ra gn nh ng thi vi s tch Br(-), tng t mt phn ng th SN2 ni phn t. Nh vy, ta c th d on rng tc phn ng s cng ln nu tnh cht nhng electron ca R cng mnh. iu d on ny c cc kt qu thc nghim xc nhn, khi o tc phn ng ca cc benzamit c cha nhng nhm th khc nhau trong vng benzen. S chuyn v Hpman c th p dng tt cho amit ca cc axit bo cng nh axit thm. Th d:

140

(CH3)3CCH2CONH2 CONH2
Br2KOH

NaOBr
94%

(CH3)3CCH2NH2 O C NH
NaOCl

NH2

NH3 COOH

Br

Br

C O

S chuyn v Cuatiut xy ra khi phn tch bng nhit azit ca axit cacbxylic to ra izxyanat, ri izxyanat li chuyn ho thnh sn phm bn.
R - C - N3 O Azit
-N2

R - C - N: O

O = C = N - R

Izxyanat

Cht azit khi u c th iu ch t clorua axit v aziua natri, hoc bng cch cho axit nit tc dng vi hyazit ca axit. Nu s chuyn v c tin hnh trong dung mi tr (Th d: benzen) ta c th cho phn ng dng sn phm Izxyanat, nhng nu thc hin trong dung mi c hyr linh ng ta s c sn phm chuyn ho Izxyanat (thng l amin). Th d:
(CH3)2CHCH2COCl
NaN3

(CH3)2CHCH2CON3 -N2

Clorua izvalryl
(CH3)2CHCH2NH2
H2O

(CH3)2CHCH2N = C = O

Izbutylamin 70% p-CH3OC6H4COOC2H5


H2NNH2

p-CH3OC6H4CONHNH2 HONO

p-CH3OC6H4COOC2H5 85%

C2H5OH

p-CH3OC6H4CON3

-N2

p-CH3OC6H4 = C = O 86%

Trong s chuyn v Ltxen mui ca axit hyrxamict hoc hp cht tng t b phn tch trong mi trng kim thnh izxyanat, tng t nh trong phn ng Hpman:
R - C - NH - OH -N
2

OH -H2O

(-)

R - C - N - OH O

(-)

R - C - N: O

O = C = N - R

141

Axit hyrxamic

Izxyanat

Trong thc t ngi ta thng khng tc hin s chuyn v Ltxen vi cc axit hyrxamit t do, m vi cc dn xut O-axyl ca chng (RCNHAc), v nh vy t c hiu sut cao hn. C ch phn ng trong trng hp vn khng thay i, ch khc ch gion b tch khng phi l HO(-) m l ArO(-). Cng nh phn ng Hpman, phn ng Ltxen c xc tin khi nhm th trong gc phnyl chuyn dch c tnh y electron, tri li cc nhm th ht electron lm cho phn ng chm li. Ngoi ra, tc ca phn ng Ltxen cn ph thuc vo bn cht nhm th trong vng benzen nhm b tch Oac theo mt quy lut ngc li: nhm th ht electron lm tng tc , cn nhm y electron lm gim. Nhng d kin l bng chng xc nhn thm rng giai on quyt nh tc phn ng l tch nhm Oac dng AcO(-). S chuyn v Smit l mt bin dng ca cc chuyn v Hpman v Cuatiut. l phn ng gia axit cacbxylic vi axit hyrazic khi c mt H2SO4 to ra azydua axyl, sau azydua axyl tham gia chuyn v: C ch phn ng vi axit cacbxylic nh sau:
R - C - OH O
H
(+)

R - C

(+)

HN3

R - C - N-N O Axylazit
-N2

(-)

(+)

O Cation axyli

CO2

+ RNH3

(+)

(+)

O = C = N - R Izxyanat

R - C - N: O

Giai on quyt nh tc phn ng l to ra ion axyli. Cc axit bo tham gia phn ng vi hiu sut tt nht khi R mch di. Nu R l aryl, hiu sut phn ng bin ng, tt nht l khi aryl c nhm th n ng khng gian (th d trng hp axit mzitic). Ngoi axit cacbxylic, ta cn thy phn ng Smit vi xtn to ra amit. Trong trng hp , c ch phn ng tng t phn ng Becman (Xem di). Ta c th m t c ch nh sau:

142

R - C - OH O

(+)

R - C-R
(+)

(+)

HN3

R - C - N-N OH R

(-)

(+)

OH

R - C - NH - R O

R - C = N - R OH

R - C - N: O

Trong phn ng trn mt hoc c hai nhm R c th l alkyl hoc aryl. Ni chung cc ialkylxtn v xtn vng d tham gia phn ng hn alkyl aryl, xtn v iarylxtn. i vi alkyl arylxtn, nhm chuyn dch thng l aryl, Th d:
C6H5 - CO - CH3
HN3

(+)

CH3 - CO - NH - C6H5 77%

6.1.2.2. S chuuyn v Becman: Chuyn v becman l qu trnh chuyn ho xtxim hoc cc dn xut O-axyl ca chng to thnh amit th:
R - C - R N - OH R - C - NHR' O

hoc

R' - C - NHR O

Phn ng trn c xc tin nh cc tc nhn axit nh H2SO4, PCl5, SO3, RSO2Cl BF3, P2O5 Trong nhng iu kin thng thng ch c mt s t alxim tham gia phn ng, nhng nu dng ng axit plyphtphoric lm cht xc tc ta c th m rng din tch cc aloxim tham gia chuyn v. Trong s chuyn v becman khng c s trao i trc tip gia nhm R v OH (nhm OH t dung mi i vo sn phm). iu ny c chng minh bng cch cho benzphnxim chuyn v trong H218O.
(C6H5)2C = NOH C6H5CO - NHC6H5 Ta bit rng xim cng nh anilit sinh ra khng c kh nng trao i oxi vi 18O trong

H218O cho nn s trao i ni phn t cc nhm R v OH khng th dn n anilit cha 18 O c. Song, trong th nghim trn ngi ta li thy anilit cha 18O nhm cacbnyl vi t l 18O/16O nh nc dng lc u. R rng s chuyn v xy ra theo cch tch nhm OH v cng nc. Ta c th m t c ch ca s chuyn v Becman bng s sau:

143

R C N

R'
H
(+)

R C N

R'
(+)

R' C N R R' C N Ox
H2 O

H2 O C N R

R'

OH C
-H
(+)

R'

-H2O

N R

OH R X-Cl -HCl

OH2

O -Ox
(-)

R' C NH R

x = R''CO

R''SO2 ...

Theo s trn th s chuyn v Becman trong mi trng axit mnh bt u qu trnh prtn ho oxim, cn khi c mt clorua axit X-Cl th to ra dn xut axit RR C = NOX. xc minh s to thnh dn xut axyl ngi ta iu ch n v thm ch cho dn xut tham gia chuyn v trong mi trng trung tnh khng c tnh cht xc tc. Ngoi ra, ngi ta cn thy rng nu axit X-OH cng mnh, tc l nu XO(-) cng bn th anion ny cng d tch ra khi phn t v tc phn ng cng tng nh sau: CH3COCl < ClCH2COCl < C6H5SO2Cl. Khi tng cc phn ca dung mi tc chuyn v cng tng ln C6H6 < C6H5Cl < (CH3)2CO < CH3NO2. iu chng t ion ho (to ra RC (+) = NR quyt nh tc ca phn ng. Hin nay, n cn kh m khng nh rng trong s chuyn v Becman s phn ct lin kt N-O v s chuyn dch nhm R c xy ra ng thi hay khng. D cho hai qu trinhg khng ng thi th s chuyn dch nhm R cng phi din ra ngay tc khc sau khi lin kt N-O b t. Chng c l nhm R tin cng nguyn t nit t pha i lp vi nhm OH b tch, tc l s chuyn v xy ra u tin vi nhm R no v tr anti vi nhm OH. chng minh quy lut trn v ho lp th ca phn ng ngi ta xc nh cu hnh ca sn phm chuyn v xut pht t hai ng phn hnh hc ca mt xtxim khng i xng. Kt qu cho thy rng ch nhm R no anti i vi nhm OH mi b chuyn dch:

144

C6H5 C = N p-CH3OC6H4 C6 H 5 C = N p-CH3OC6H4 OH OH


PCl5 PCl5

O ete C = N p-CH3OC6H4 C6 H 5 ete C = N O

C6 H 5

p-CH3OC6H4

chng minh c tnh ni phn t ca s chuyn v ngi ta tin hnh chuyn v ng thi hn hp hai xim c nhm th khc nhau v thy khng to ra sn phm chuyn v cho. S chuyn v Becman c dng trong tng hp hu c, c bit trong vic tng -caprlactam sn xut plycaprlactam (capron hay peclon): hp
H2NOH
-HOH

(+)

Becman

NH

O Xyclohexanon

NOH Xyclhexanxim

Caprlactom

6.1.3. S CHUYN V N NGUYN T XY: 6.1.3.1. Chuyn v Bai- Viligi: Trong phn ng Bai-Viligi, xtn chu tc dng ca peaxit chuyn thnh este:
RCR + R'C - O - OH O Xtn O RC - OR + R'C - OH O Este O

Ta c th m t c ch phn ng nh sau:

145

R R - C - R O Xtn R - C - R OH R - C - O - O - C - R'
-(+)

OH R

OH

R - C - OR O Este

-H

(+)

R - C - OR OH
(+)

R - C - O - R' - C - OH' OH O

(+)

chng minh rng nguyn t xy cacbnyl ca este chnh l nguyn t xy ca xtn ban u, ngi ta cho benzphnol cha C = 18O tc dng vi axit pebenzic, kt qu l thu c benzat phnyl cng cha nhm C = 18O
O

C6H5 - C - C6H5
18

C6H5COOH

C6H5C - OC6H5
18

Khi dng -phnyltyl cng quang hot:


CH5CHCCH3 CH3 O C6H5CH - O - CCH3 CH3 O

Quang hot

Quang hot

iu chng t nhm C 6H5CHCH3 b chuyn dch vn gi nguyn cu hnh v phn ng chuyn v c c tnh ni phn t. D kin trn cng cho thy rng nhm phnyltyl d chuyn dch hn nhm mtyl. Ni chung i vi cc xtn khng i xng kh nng chuyn v ca cc gc R tng theo th t: mtyl < alkyl bc I < alkyl bc II < alkyl bc III. Cc -ixtn c kh nng enol ho khng th b xy ho theo Bai-Viligi c, nhng -ixtn c th b xy ho thnh anhyrit axit:

146

RC - CR R'COOOH
Baz-Viligi

RC - O - CR O O

6.1.3.2. Chuyn v Hyrpexit: Khi phn hy nhiu hp cht pexyt khc nhau ngi ta thy c hin tng chuyn v tng t chuyn v Bai-Viligi.
R R - C - O - OH R'
H
(+)

R - C = O + ROH R

Th d c ngha thc tin l phn hy hyrpexyt cumyl (iu ch t izprpylbenzen bng cch xy ha bi xy). C ch phn ng nh sau:
C6H5 CH3 - C - O - OH CH3 Hyrpexyt cumyl
(+)

C6H5
H
(+)

C6H5
(+)

CH3 - C - O - OH2 CH

H2O

CH3 - C - O CH3

(+)

OH CH3 - C = O + HOC6H5 CH3


(+)

CH3 - C - OOC6H5 CH3

H2O

(+)

CH3 - C - OC6H5 CH3

Giai on cui cng s trn l giai on thy phn smiaxtal. Phn ng xy ha mt dn xut hyrxy hoc dn xut amin ca benzal-hyt nh pcxyt hyr thay th nhm CHO bng nhm OH cng l mt trng hp ca chuyn v pxyt. 6.2. CC KIU CHUYN V 1,2 ELECTRPHIN V NG LY 6.2.1. S chuyn v 1,2 electrphin: Ta gi chuyn v electrphin l nhng qu trnh chuyn v trong , nhm chuyn dch (R) dng electrphin, khng mang theo cp electron lin kt. Nhm chuyn dch s to nn lin kt mi bng cch phi tr vi cp electron cha s dng trung tm chuyn n (B), trong khi cp electron li trung tm chuyn i (A) s kt hp vi prton. Thng thng phn ng bt u bng mt qu trnh tch prton ra khi trung tm B nh tc dng ca baz.

147

R A - B H
-H

R
(+)

A - B:

(+)

R A - B H

S chuyn v 1,2 electrphin c th to ra sn phm bn hoc t bn, ri li chuyn ha tip thnh sn phm bn hn. Di y s trnh by mt vi phn ng chuyn v electrphin quan trng. 6.2.1.1. Chuyn v Xtven: S chuyn v nhm alkyl hoc aryl t nguyn t nit (hoc lu hunh) ca nhm amni (hoc sunfni) sang nguyn t cacbon bn cnh gi l s chuyn v Xtven:
(+)

Z - CH2 - N(CH3)2 R

OH

(-)

Z - CH - N(CH3)2 + H2O R

Nhm th Z thng l nhng nhm ht electron nh R'CO, R'OOC cn nhm chuyn dch R thng l alyl, benzyl, 9-fluorenyl, 3-phnylprpacgyl, Ta c th hnh dung c ch ca s chuyn v Xtven qua th d sau:
C6H5C - CH2 - N(CH3)2 O CH2C6H5
(+)

OH

(-)

C6H5C - CH - N(CH3)2 O CH2C6H5

(-)

(+)

C6H5C - CH - N(CH3)2 O CH2C6H5

Nh vy l trong phn ng sinh ra mt ylit trung gian. c tnh ni phn t ca s chuyn v Xtven c xc nhn bng php th nghim cho (khng thy c s chuyn v cho) v dng nguyn t nh du 14C. Th d khi thc hin chuyn v ring r hai cht:
p - Br - C6H4COCH2 - N(CH3)2
14 CH C H 2 6 5
(+)

(+)

C6H5COCH2 - N(CH3)2 CH2C6H5

Ta ln lt c hai sn phm
p - Br - C6H4COCH - N(CH3)2
14 CH C H 2 6 5
(+)

C6H5COCH - N(CH3)2 CH2C6H5

(+)

Nu cho chuyn v hn hp hai hp cht amni trn ta cng ch c hai sn phm ch khng c sn phm chuyn v cho:
p - Br - C6H4COCH - N(CH3)2 CH2C6H5

C6H5COCH - N(CH3)2
14 CH
2C6H5

148

Cc nhm th v tr mta v para trong nhm benzyl c nh hng nht nh n tc chuyn v: nhm ht electron xc tin phn ng, cn nhm y electron th km hm.
CH3 < H,CH3 < Cl, Br, I < NO2

nh hng ca cc nhm th gc phnaxyl ArCOCH2 c phn yu hn: ng c l nhng nhm th ht electron li lm gim tc phn ng. V phng din ha lp th ca s chuyn v Xtven, ngi ta thy rng nhm chuyn dch vn giu nguyn cu hnh sau phn ng. Th d:
C6H5COCH2 - N(CH3)2 CH3 - CH - C6H5
(+)

HO

(-)

C6H5COCH2 - N(CH3)2 CH3 - CH - C6H5

Quang hot

Cc ng phn ia

6.1.2.1.2. Chuyn v Vittic S chuyn mt t lm t lin kt C-O v hnh thnh lin kt C-C c gi l chuyn v Vittic. thc hin qu trnh ny, ngi ta phi dng nhng baz mnh nh phnyl liti, amiua natri Th d:
O - CHC6H5 CH3
C6H5Li C 6H 6

O - CHC6H5

O - CHC6H5 CH3

(-)

HO - CHC6H5 CH3

CH3

Kho st kh nng chuyn dch ca gc R trong cc 9 fluorenyl te khc nhau, ngi ta thy c trt t sau: alyl, benzyl > mtyl, tyl > phnyl.
H OR
C6H5Li C 6 H6

OH

ng ch l khi nhm chuyn dch c trung tm bt i nh trong trng hp di y, th sau phn ng ngi ta thy c s razmic ha mt phn cng vi s gi nguyn cu hnh:
CH2C6H5 O CH CH3 C2H5
C4H9Li 2H2O
(+)

HO - CH - C6H5 CH CH3 C2H5

Quang hot

Mt phn raxmic ho: Mt phn gia nguyn cu hnh 149

S raxmic ha mt phn cho thy rng c th cn c mt c ch chuyn v khc na xy ra song song vi c ch nu trn. 6.2.2. S CHUYN V 1,2 NG LY S chuyn v 1,2 ng ly km ph bin rt nhiu so vi nhng s chuyn v 1,2 d ly. Tng t nh s chuyn v mt cacbcation, ta c th khi qut ha s chuyn v mt gc t do bng s :
R A - B A - B R

Gc t do mi sinh ra phi t bn vng ha bng cc phn ng tip theo. Hng chuyn v l to ra gc t do tng i bn hn nh nu. 6.2.2.1. Chuyn v aryl 1,2: Loi chuyn v gc t do tng i ph bin hn c l chuyn v nhm aryl t v tr 1 sang v tr 2. Th d: khi c mt cht khi mo pxyt i-t-butyl alhyt phnyllizvalric trong clobenzen s b phn hu ng thi lm chuyn dch nhm phnyl: Khi mo:
(CH3)3C - O - O - C(CH3)3 Phn ng: C6H5 CH3 - C - CH2 - C - H + RO' CH3 O C6H5 CH3 - C - CH2 - CH + ROH CH3 C6H5 CH3 - C - CH2 + CO CH3 O (CH3)3C - O + (RO:)

Chuyn v:

150

C6H5 CH3 - C - CH2 CH3 (A) Bn vng ho: C6H5 + CH3 - C - CH2C - H CH3 O CH3 - C - CH2C6H5 CH3 (B) C6H5 CH3 - C - CH2C6H5 H CH3 + CH3 - C - CH2 - C C6H5 O (C)

CH3 - C - CH2C6H5 CH3

hoc: C6H5 C6H5 C6H5

C6H5

CH3 - C - CH2 + CH3 - C - CH2C - H CH3 CH3 O

CH3 - C .. CH3 + CH3 - C - CH2 - C CH3 (D) CH3 O

Thc nghim cho thy rng trong phn ng trn sinh ra hai sn phm (C) v (D) vi t l 1:1, t hiu sut chung ~70%. Ta nhn thy giai on chuyn v nhm phnyl chuyn dch ch khng phi nhm mtyl. iu ny cho php ngh rng trong phn ng to ra mt gc trung gian cu ni, tng t nh cacbcation cu ni.

C - C

151

C l gc trung gian ny c hnh thnh sau khi to ra gc (A) v nh trn thy trong phn ng sinh ra sn phm tng ng vi (A) l (D), v trong mt s trng hp cn thu c c sn phm ime ha gc (A) . 6.2.2.2. Chuyn v halgen 1,2: Gn y s chuyn v nguyn t halgen t v tr 1 sang v tr 2 bn cnh cng c ch . Th d khi clo ha brmua izprpyl bng t-C4H9Ocl ngi ta c mt hn hp sn phm gm CH3CClCH2Br v (CH3)2CClBr:
Cl CH3 - CH - CH3 Br
t-C4H9OCl
-78 C
0

CH3CH - CH2Br + CH3 - C - CH3 Cl (15%) Br (60%)

S to thnh CH3CClCH2Br cho thy s chuyn v gc t do trung gian theo s :


CH3 - CH - CH3 Br + Cl (T - C4H9OCl) -HCl CH3 - C - CH2 Br

CH3 - CH - CH2Br Cl (15%)

(T - C4H9OCl)

CH3 - CH - CH2Br

L tt nhin, hng chnh ca phn ng l to ra gc t do nguyn t cacbon bc hai (CH3)2CBr, v gc ny bn hp gc bc nht tham gia chuyn v trn. Do 2brom-2-cloprpan chim t l cao hn 1-brom-2-cloprpan:
Cl CH3 - CH - CH3
-HCl

CH3 - C - CH3 Br

T - C4H9OCl

CH3 - C - CH3 Br (60%)

Br (T - C4H9OCl)

6.3. S CHUYN V T NHM TH VO VNG THM: Phn ln nhng phn ng chuyn v vo vng thm l nhng phn ng lm chuyn dch mt nhm X t d nguyn t Z vo v tr oct hoc para ca vng:

152

X Z Z

H x + x Z

y Z = O khi X = alkyl, aryl; Z = N khi X = alkyl, halgen, hyrxy, nitr, nitrz, az, sunf Hu ht cc phn ng chuyn v trn c xc tc bng axit v s tn cng ca nhm X vo vng thm c tnh cch mt phn ng th electrphin. Ta gi l phn ng chuyn v electrphin vo vng thm. Nhng phn ng chuyn v nuclphin vo vng thm (th d chuyn v nhm OH phnylhyrxylamin) tng i t gp. 6.3.4. S CHUYN V T NGUYN T XY VO VNG THM: 6.3.1.1. Chuyn v Frai: Khi c tc dng ca axit Liuyt (AlCl3, ZnCl2, FeCl3.) nhm axyl trong este ca phnyl chuyn dch vo cc v tr oct v para ca vng:
O C O R
1.AlCl3

2.H3O

(+)

OH O C R +

OH

C O R

R l alkyl hoc alyl. Cc kt qu th nghim cho cho thy rng chuyn v Frai c tnh cch lin phn t. Tuy vy, c ch ca s chuyn v ny cha c xc nh hon ton y , ngi ta cho rng qu trnh chuyn v Frai tng t qu trnh axyl ha theo Friden-Crap. Di tc dng ca cht xc tc, este to ra cation axyli RC(-) = 0, cation ny s tin cng cc v tr oct v para ca vng thm:

153

Cl2AlO O C O R
AlCl3
(-)
(+)

O C R
H3 O
(+)

O OH C R

O Cl3AlO CR -HCl Cl2AlO


H3O
(+)

OH

C O R O

C R

Do tnh cht electrphin ca qu trnh chuyn v nn khi trong vng c nhm th y electron, phn ng s tr nn d dng hn. Phn ng Frai lun lun to ra mt hn hp hai sn phm ng phn, nhit thp l iu kin thun li cho s to thnh ng phn para. Th d:
OH
AlCl3,25 C
0

OCOCH3
80 C
0

AlCl3,165 C

0 CH3CO

OH CH3

CH3 COCH3 OCOCH3

CH3

95 C

L tt nhin khi v tr para b chim th ch to thnh sn phm oct. Th d:


OH
AlCl3

CH3CO

Nitrobenzen

CH3

CH3

6.3.1.2. Chuyn v Claizen: Khi un nng alyl aryl te s chuyn thnh oct-alylphnol theo mt phn ng gi l chuyn v claizen. Th d:
OCH2CH = CH2
0 200 C

OH

CH2CH = CH2 CH3

CH3

90%

Nghin cu s chuyn v alylphnyl te c nh du bng 14C hoc c nhm th v tr para, ngi ta ngh mt c ch ni phn t nh sau:

154

CH2 CH O C CH2 O CH CH2 H

CH C OH CH2

chng minh rng trong phn ng c hnh thnh ienn trung gian I ngi ta cho thm anhyrit malic vo mi trng phn ng v thy c xy ra phn ng ix-o gia ienn v anhyrit . Hn na, trong mt s trng hp ngi ta cn iu ch c ienn vi hiu sut nh lng. Th d:
H3 C O
(-)

CH3 + CH2 = CHCH2Br


-Br
(-)

H3 C
C6H6 15 C
0

CH2CH = H2 CH3

chng minh c ch ni phn t ca s chuyn v ngi ta tin hnh phn ng cho vi hn hp hai te I v II. Nu phn ng xy ra theo c ch ni phn t th ch sinh ra hai sn phm III v IV; tri li nu phn ng xy ra qua giai on to thnh th ngoi cc sn phm III v IV cn to ra V v VI. Thc t khng tm thy V v VI.
OCH2CH = CH2 + D (I) OH CH2CH = CH2 + D (III) D (II) C6H5OH OHC6H5 OH CHCH = CH2 CH2CH = CH2 CH2CH = CH2 + + D D (V) (VI) OCH2CH = CHC6H5

(IV)

Trong trng hp cc v tr oct b chim nhm alyl ca t s chuyn dch n v tr para. Ngi ta gi l s chuyn v para-Claizen. Nu tt c cc v tr oct v para u b chim th khi un nng khng xy ra s chuyn v no c. Rt c th s chuyn v para-Claizen cng phi qua bc chuyn v oct, sau mi xy ra s chuyn v tip n v tr para:

155

OCH2CH = CH2 R

O R R CH2 CH CH2 H R

O R R

OH

CH2CH = CH2

CH2CH = CH2

chng minh c ch chuyn v hai ln ni trn, ngi ta dng alyl 2,6ddialyl-phnyl t c nh du bng 14C v tr ca mt nhm oct-alyl; sau khi chuyn v ngi ta c 2,4,6-trialylphnol trong nguyn t 14C phm hoc v tr ca nhm p-alyl hoc v tr ca nhm o-alyl.
CH2CH = CH2 OCH2CH = CH2 14 CH2CH = CH2

14

CH2CH = CH2

CH2CH = CH2

CH2CH = CH2

OH CH2 =CHCH2
14

OH CH2 =CHCH2 +
14

CH2CH = CH2

CH2CH = CH2

CH2 =CHCH2

CH2 =CHCH2

Nu nh nhm alyl chuyn dch trc tip t nguyn t xy n v tr para th khng sinh ra sn phm c 14C p-alyl. 6.3.2. S CHUYN V T NGUYN T NIT VO VNG THM. 6.3.2.1. Chuyn v nhm alkyl: Khi un nng cc mui halgenhyrat ca alkyl s chuyn dch n v tr oct hoc para ca nhn thm. Th d:
C6H5NR2 C6H5NHR
HHal

o- hoc o- hoc

p-RC6H4NHR p-RC6H4NH2

HHal

C l phn ng bt u bng mt qu trnh th nuclephin tch dn xut halgen Rhal ra khi mui halgenhyrat, sau Rhal s tc dng vi nhn thm theo c ch th electrphin. Th d:
156

C6H5 NH2R + Hal

(+)

(-)

RHal + C6H4NHR RC6H4NH3Hal


(+)
(-)

C6H5NH2R + RHal

(-)

Ph hp vi c ch trn, trong mt s trng hp ngi ta tch c Rhal trung gian, v khi thay i Hal(-) t l cc sn phm o/p cng thay i. ng ch l phn t chuyn v nhm alkyl nh trn c th xy ra khi un amin t do vi CoCl2. Khi y phn ng mang tn Ryli-Hickinbttm. C ch ca s chuyn v Ryli-Hickibttm cha r rng. 6.3.2.2. Chuyn v nguyn t Halogen S chuyn v nguyn t Halogen t nguyn t Nit vo vng Benzen gi l chuyn v Octn. Th d: Khi un N-Cloaxtanilit trong axit axtic hoc nc c clorua hyr ta c o- v p- cloaxtanilit.
C6H5 - N - COCH3 Cl
HCl

Cl - C6H4 - NH - COCH3

Ngi ta cho rng trong phn ng trn clorua hyr tc dng vi cloaxtanilit sinh ra axtanilit v clo, sau clo tc dng vi vng thm ca axtanilit theo c ch electrphin:
C6H5N - COCH3 + HCl Cl C6H5NH - COCH3 + Cl2 ClC6H4NH - COCH3 + HCl

Tc ca phn ng trn tun theo phng trnh: v~ [cloaxtanilit] [H(+)] [Cl(+)]. Nu thay HCl bng HBr ta s thu c o- v p- brmaxtanilit. Nhng d kin ch c th gii thch c da trn c ch nu c th l theo s sau:
C6H5N - COCH3 + HBr Cl C6H5NH - COCH3 + Br - Cl BrC6H4NH - COCH3 + HCl

Nh vy s chuyn v Octn thuc loi chuyn v lin phn t 6.3.2.3. Chuyn v nhm arrylaz: Th d tiu biu v chuyn v nhm arrylaz l phn ng chuyn ha iazaminbenzen thnh p-aminazbenzen:
C6H5N = N - NHC6H5
HCl
hoac C6H5NH2 + HCl

p- NH2C6H4N = NHC6H5

Trong trng hp v tr para b chim nhm arylaz s chuyn dch n v tr oct. Th d:

157

CH3 p- CH3C6H4N = N - NH CH3


p-CH3C6H5NH2

HCl

p- CH3C6H4N = N NH2

Nu thay p-CH3C6H4NH2 bng C6H5NH2 trong phn ng trn ta s c 4-mtyl-4'aminazbenzen. iu ny cho thy phn ng chuyn v nhm arylaz thuc loi chuyn v lin phn t. Nghin cu ng hc ca phn ng ngi ta xc nh c tc chuyn ha ca iazaminbenzen t l vi nng ca anilinclohyrat; nu ly mui ca amin vi axit khc thay cho anilinclohyrat th tc phn ng ph thuc lc ca axit . iu ny cho php ta gi thit rng chnh axit t do tham gia vo qu trnh chuyn v. ng ch na l phn ng ca clorua phnyliazni vi anilin c th xy ra theo hai hng khc nhau ty theo pH ca mi trng:
pH ln hn
C6H5N2Cl
(+)
(-)

C6H5N = N - NHC6H5 C6H5N = N - C6H4NH2

H2NC6H5

pH nh hn

Da trn cc d kin thc nghim trn ngi ta cho rng s chuyn v nhm arylaz xy ra qua hai giai on to thnh ion aryliazni v amin t do, sau ion aryiazni s tc dng vo nhn thm ca amin theo c ch electrophin:
C6H5 = N - NHC6H5
HCl

C6H5N2 + C6H5NH2

(+)

C6H5N = NC6H4 - NH2 - p

6.3.2.4. Chuyn v nhm nitrz (Chuyn v Fis Hep) Khi c mt axit clohyric, nhm nitrz ca nitrzamin thm s chuyn dch vo nhn thm. Th d:
C6H5N - N - CH3 NO
HCl

o-

p- NOC6H4 - NH - CH3

C ch chuyn v Fis-Hep tng t c ch chuyn v Octn. Di tc dng ca axit, nitrzamin b phn tch thnh amin v clcorua nitrozyl (NOCl) hoc ion nitrzni; sau l qu trnh nitrz ho nhn thm theo c ch electrphin:

158

CH3 C6H5N + NO H
(+)

CH3 C6H5N H + NO
(+)

O = N - C6H4NHCH3 + H

(+)

C nhiu d kin thc nghim xc nhn c ch chuyn v gia cc phn t va nu. Chng hn, khi cho vo hn hp phn ng mui nitri natri 9mui ny s to ra NO hoc NOCl). Hiu sut phn ng chuyn v s tng; tri li nu cho thm r (cht ny d kt hp vi NO v NOCl) ta s khng thu c dn xut nitrz m ch c amin bc hai. 6.3.2.5. Chuyn v benziin: Khi cho axit mnh tc dng ln hyrazbenzen s xy ra s chuyn v lm t lin kt nit nit v hnh thnh ln kt cacbon cacbon to ra benziin (4,4 iaminbiphnyl):
NH - NH
H
(+)

H2N

NH2

Hyrzbenzen

Benziin

Trong phn ng chuyn v ca hyabenzen ngoi benziin l sn phm ca s t hp o,p (chim ~ 30%) v lng rt nh cc sn phm t hp khc.
NH2 NH2 iphenylin 0-Benziin H2N NH2 NH NH2 p-Xemidin NH2 -NH o-Xemidin

Nu c hai v tr para trong phn t hyrazobenzen ban u u b chim c bi cc nhm th. Cn nu ch c mt v tr para b chim th phn ng c th to ra cc dn xut th ca iphnylin, p-xemiin v o-xmiin.

159

Vn c ch ca s chuyn v benziin l vn phc tp c nhiu ngi quan tm t u th k ny. Khi cho hn hp hai hyrazbezen cng chuyn v ngi ta khng thu c sn phm cho, iu cho thy s chuyn v xy ra theo kiu ni phn t. Kho st ng hc cho thy rng phn ng chuyn v thng c bc hai i vi H (+), v khi thay hyr v tr para ca hyrazobenzen bng tri, tc ni chung khng thay i. Nh vy giai on phn ct lin kt C H khng quyt nh tc chung ca phn ng v tiu phn
(+) (+)

trc tip tham gia phn ng l hyrazbenzen prton ho hai ln ArNH3 - NH2Ar. Rt c th c ch chuyn v benziin nh sau:
D NH2 NH - NH
(+) (+)

2H

NH2 - NH2

(+)

(+)

NH2

+
+

H2N............NH2 ................. D D

2D

(+)

NH2

(+)

NH2

Theo c ch trn th phn ng bt u bng qu trnh prton ho hai nguyn t nit ca hyrazbenzen to thnh ication. iu ny c mi ngi tha nhn. Tuy vy, cc chi tit v nhng giai on tip theo, nht l v cu to ca trng thi chuyn tip cn cha c tr li y v thng nht. iu ny chc chn l trong mi trng phn ng phi sinh ra ication ca benziin nh mt sn phm trung gian.

160

MC LC Chng 1: Cch a nhm chc vo phn t cht hu c v s chuyn ho gia chngTrang 1 Chng 2: S phn ct v to thnh lin kt Cacbon CacbonTrang 28 Chng 3: Phng php ng v m vngTrang 52 Chng 4: Bo v nhm chc trong tng hp hu c...Trang 80 Chng 5: S xy ho - khTrang 105 Chng 6: S chuyn vTrang 131

161

You might also like