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Ha Hc Hu C

TS Phan Thanh Sn Nam


B mn K Thut Hu C Khoa K Thut Ha Hc Trng i Hc Bch Khoa TP. HCM in thoi: 8647256 ext. 5681 Email: ptsnam@hcmut.edu.vn
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Chng 3: C CH PHN NG CA HP

CHT HU C
I. Phn ng th i nhn nguyn t carbon no I.1. Khi nim chung Phn ng th: 1 nguyn t hay nhm nguyn t ca cht ban u b thay th bi 1 nguyn t hay nhm nguyn t khc CH3-CH2-Cl + OHCH3-CH2-OH + Cl-

Tc nhn i nhn: cc tc nhn mang in tch m (hay phn t trung ha cha cp in t t 2 do) tn cng vo trung tm tch in +

Phn ng th i nhn (SN) y- + R-X R-y + Xy-: RO-, OH-, RCOO-, NH3, NH2R, H2O, ROH R: gc hydrocarbon X: Cl, Br, OH, OR, OSO2R V d: CH3-CH2-Cl + OHCH3-CH2-Br + CH3OCH3-CH2-Br + NH3 CH3-CH2-OH + ClCH3-CH2-O-CH3 + BrCH3-CH2-NH2 + HBr
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I.2. Phn ng th i nhn lng phn t (SN2)


Lng phn t: giai on chm, c s tham gia ca 2 tiu phn

y + R-X

cham

a.C ch:

[y-... R ... X-]

nhanh

R-y + X-

trang thai chuyen tiep


Lin kt gia C & y hnh thnh ng thi vi s yu i & t ca C & X 2 tiu phn tham gia vo giai on chm Nu y- khng d nhiu: r = k[y-].[R-X] phn ng 4 bc 2

Gin nng lng:

R-OH: phn ng th ch xy ra trong mi trng acid v C-O bn Dn xut ca carbon bc 1 ch cho SN2 SN2: carbon bc 1 (ch cho SN2) > carbon bc 2 > carbon bc 3 (ch cho SN1) SN2: CH3-CH2-Cl + OHCH3-CH2-OH + Cl6

b. Tnh lp th ca SN2 Phn t c cha C*: s c s thay i cu hnh (R S & ngc li) (nghch o Walden)
R1 R1 C* R2 X R1 X R2

y- +

cham

y H

C*

nhanh

C*

H R2

(R)-

(S)-

y- tn cng ngc hng so vi X sn phm c 7 cu hnh ngc vi tc cht

I.3. Phn ng th i nhn n phn t (SN1) n phn t: giai on chm ch c s tham gia ca 1 tiu phn a. C ch

R-X R+

cham

R+ +

X-

+ y

nhanh

R-y

giai on chm: y- khng tham gia SN1 thng c bc 1 r = k[R-X]


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Gin nng lng:

Dn xut ca carbon bc 3 ch cho SN1 SN1: carbon bc 3 (ch cho SN1) > carbon bc 2 > carbon bc 1 (ch cho SN2) V d SN1:

CH3 H3C C CH3 Br

CH3

+ OH-

H3C

C CH3

OH

+ Br-

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Tnh lp th ca SN1
R1 y R1 R2 R3 C* X C* R2 R3

cham -XR2

C*

nh an h h an nh
R2

R1

R3

R1 C* R3 y

(R1 R2 R3)

Sn phm c th l hn hp racemic Carbocation c cu trc phng kh nng tn cng ca y- 2 pha l nh nhau 50% S + 50% 11 R

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I.4. Cc yu t nh hng ln phn ng th i nhn


a. nh hng ca gc R kh nng SN1 tng & SN2 gim SN1: carbon bc 3 (ch cho SN1) > carbon bc 2 > carbon bc 1 (ch cho SN2) Do SN1 ph thuc vo bn ca carbocation to thnh:
CH3+ < H H C CH2 H < H H H HH C H + < H C C H C C+ HH C H HH C H H 13 H

Gc R bc cng cao:

Bc ca R cng cao y- cng kh tn cng do in tch (+) C gim & do hiu ng khng gian ca gc alkyl SN2 cng kh xy ra

SN2: carbon bc 1 (ch cho SN2) > carbon bc 2 > carbon bc 3 (ch cho SN1)

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b. nh hng ca tc nhn i nhn y SN1: khng ph thuc y SN2: ph thuc nhiu vo y- do giai on chm c y- tham gia Tc nhn c tnh i nhn cng cao th cng d cho SN2 Thng thng, tnh i nhn ng bin vi tnh base NH2- > (CH3)3CO- > (CH3)2CHO- > C2H5O- > CH3O> OH- > C6H5O- > HCO3- > CH3COO15

Trong cng 1 phn nhm chnh ca bng HTTH: tnh i nhn nghch bin vi tnh base (phn ng thc hin trong H2O, ROH): Tnh base: F- > Cl- > Br- > ITnh i nhn: F- < Cl- < Br- < ITnh i nhn: HS- > OHTnh i nhn: C2H5S- > C2H5OTuy nhin trong pha kh, tnh i nhn: F- > Cl- > Br- > I-

Phn bit tnh base & tnh i nhn: Tnh base tr cn bng, tnh i nhn tc !!!

v
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c. nh hng ca nhm b th -X Cc nhm th c tnh base cao rt kh b tch ra, v d: -OH, -OR, -NH2, -F V d: R-OH + HBr R-Br + H2O cn xc tc H2SO4 R-OH khng phn ng vi KBr

Halogen, kh nng tch nhm: F- < Cl- < Br- < I(Do I c bn knh ln C-I d phn cc hn Nng lng t lin kt: C-I < C-Br < C-Cl < C-F)
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d. nh hng ca dung mi Dung mi phn cc c proton nh H2O, ROH, HCOOH c kh nng solvate ha cao c anion & cation thun li cho SN1

R1 H R1 cham + R2 C X - C+ O -X R3 R2 R3 H

X- H O H

Dung mi phn cc khng c proton nh (CH3)2SO, (CH3)2NCHO khng c kh nng solvate ha anion thun li cho SN2 18

II. Phn ng tch loi


L phn ng trong c s tch 1nguyn t hay nhm nguyn t ra khi cht ban u
R CH2 CH2 Br

ROto H+ to HOt
o

CH

CH2 +

HBr HOH HOH + NR3

CH2

CH2

OH

CH

CH2 +

CH2

CH2 N+R3

CH

CH2 +

Nhm b tch cng H: -OH, -OR, -X, -O+(R)2, -N+(R)3, -OSO2R 19 Base s dng: cc base mnh nh OH-, RO-, NH2-

II. 1. Phn ng tch loi lng phn t (E2) a. C ch


y + R CH2 CH2 X
-

cham

R y

C CH2

nhanh

H trang thai chuyen tiep H-y + R CH CH2 + X-

giai on chm, c s tham gia ca 2 tiu phn lng phn t Tc phn ng r = k[R-X].[y-] R-CH2-CH2-OH: ch tch loi trong mi trng acid 20 o cao (thng l sulfuric acid, acid rn) t

b.Tnh lp th ca E2 Cc hydrocarbon khng no tch loi d khi cc nhm b tch v tr trans vi nhau
(1)
HOOC Cl COOH

(2) OH-HCl

HOOC

Cl

OH-HCl

COOH COOH

HOOC

chlorofumaric acid

chloromaleic acid

Tc (1) ln hn (2) 30 ln

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Cc hydrocarbon no hay vng no tch loi d khi cc nhm b tch v tr trans, anti vi nhau Lu : dn xut ca cyclohexane ch tch c khi nhm b tch v tr trans & phi kiu lin kt axial (trc)!!!
Br CH3 H H CH3

+
CH3

san pham chnh


Br

kho
H H CH3 CH3

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II.2. Phn ng tch loi n phn t (E1) C ch:

H C C X

cham

H C C+

X-

H C C

nhanh

H+

Thng cc dn xut ca hydrocarbon carbon bc 3 bao gi cng cho E1 Carbocation cng bn, cng d cho E1 Tc r = k [R-X] Nhng yu t lm thun li SN1 cng lm thun li 23 cho E1

V d:

CH3 H3C C Br CH3 H HH C H H C C+ HH C H H

cham

H HH C H H C C+ HH C H H
nhanh

+ Br-

+ C2H5O-

CH3 + H2C C CH3

C2H5OH

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II.3. Hng ca phn ng tch loi


a. Quy tc Zaitsev Dn xut bc 1 thng ch cho 1 sn phm duy nht khi tch loi CH3-CH2-CH2-Br ch cho CH3-CH=CH2 Dn xut bc 2, bc 3: cho nhiu hn 1 sn phm
H H H H3C C C C H H Br H OHH3C CH CH CH3 (Zaitsev)

H3C CH2 CH CH2

(Hofmann)

Sn phm Zaitsev : bn hn (do +H) thng thng, phn ng tch loi cho sn phm Zaitsev Quy tc: phn ng tch loi s cho sn phm m 25 carbon ca ni i lkt vi nhiu nhm alkyl nht

b. Quy tc Hofmann Khi gc R (bc 1 & 2) ca R-X cha nhiu nhm th kch thc ln, tc nhn base c kch thc ln (vd (CH3)3CO-) hoc X l nhm th mang in tch dng c kch thc ln (vd N+R3, S+R2, SO2R) sn phm Hofmann chim ch yu (E2)
CH3 H2C C CH2 CH3 (CH3)3COCH3 H3C C CH CH3 28% 72%

CH3 H3C C CH2 CH3 Br

26 Nu base l C2H5O- th sn phm chnh l Zaitsev!!!

H H3C C CH2 CH3 N+(CH3)3

OH(E2)

CH2=CH-CH2-CH3

CH3CHCH2CH2CH3 SO2CH3

OH(E2)

CH2=CH-CH2-CH2-CH3

Lu : Nu trong phn t c sn 1 ni i (C=C, C=O), sn phm lin hp thng l sn phm chnh (bn hn) 27

II. 4. Quan h gia phn ng th i nhn & tch loi


Nhit phn ng cng cao phn ng tch loi cng chim u th

<140oC CH3-CH2-OH H2SO4 >170oC

C2H5-O-C2H5

CH2=CH2 + H2O
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Gc R c bc cng cao, hay base cng mnh th tch loi cng chim u th

CH3-CH2-CH2-Br

+ C 2 H5 O -

to thng

CH3-CH2-CH2-O-C2H5

CH3 H3C C Br CH3

C2H5Oto cao

CH3 H2C C CH3


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III. Phn ng cng hp


III. 1. Phn ng cng hp i in t (AE) Phn ng cng hp vo ni i ca hydrocarbon khng no nh alkene, alkyne vi cc hp cht nh X2 (halogen), HX, H2O, HOX, H2SO4

C C

+ X-Y

X C C Y
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a. C ch: Giai on 1:
C C + X+-Y dung moi xuc tac nhanh cham C C X+ Y phc khong ben C+ C X ben hoa C C X+

Giai on chm: X+ tn cng vo C=C

i in t

Giai on 2:

Y-

C C X+

nhanh

Y C C X
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Y-

tn cng vo pha i lp vi X

Chng minh AE c 2 giai on: Phn ng cng hp ca CH2=CH2 vi Br2 vi s c mt ca NaCl, NaNO3, sn phm thu c l 1 hn hp: Br-CH2-CH2-Br + Br-CH2-CH2-Cl + Br-CH2-CH2-ONO2 Nu phn ng thc hin trong dung mi l CH3OH, sn phm chnh l Br-CH2-CH2-OCH3 !!!
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H2C CH2 + Br2

CCl4

H2C CH2 Br Br

H2C CH2 + Br2

CH3OH

H2C CH2 Br OCH3

H2C CH2 + Br2

H2O

H2C CH2 Br OH
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b. Quy lut cng hp Quy tc Markonikov (dnh cho C=C khng i xng): H+ s tn cng vo C cha nhiu H CH3-CH=CH2 + H+ CH3-CH2-C+H2 CH3-C+H-CH3 (bn hn) +

Quy tc Zaitsev-Wagner: H+ s tn cng vo pha to thnh carbocation trung gian bn nht


HBr

CH3-CH=CH-CH2-CH3

CH3-CH-CH-CH2-CH3 34 Br

c. Ha lp th ca phn ng AE Phn ng cng hp AE xy ra theo kiu trans ph thuc vo tc cht ban u m c cc ng phn lp th khc nhau ng phn cis sn phm threo (nhm th tng ng khc pha)
C2H5 Br C2H5 H CH3 H Br2 C2H5 Br+ CH3 H BrC2H5 H Br CH3 Br H CH3 H Br Br H C2H5 threoH Br H CH3 CH3 Br H H Br C2H5

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ng phn trans sn phm erythro (nhm th tng ng cng pha)

C2H5 H

H CH3

Br2

CH3 Br H Br H C2H5

CH3 H Br H Br C2H5 erythro

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d. nh hng ca nhm th lin kt vi ni i Nhm th y in t tng mt in t ca C=C tng kh nng phn ng AE Nhm th ht in t gim kh nng AE

Cc nhm th nh phenyl nu c kh nng cho +C vi carbocation bn ha cation thun li cho AE


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Kh nng AE:
O2N H H HOOC < H H Cl < H H H H H3C < H H H H3C < H CH3 H H3C < H CH3 H3C < CH3 H3C CH3 CH3

Phenyl gy nh hng mnh hn 1 nhm methyl nhng yu hn 2 nhm methyl CH3CH=CH2 < C6H5CH=CH2 < (CH3)2 C=CH2
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III.2. Phn ng cng hp i nhn vo C=O (AN)

C O + X -Y

OX C Y

X-Y c th l H-OH, H-OR, H-CN, H-SO3Na, Li-R, BrMg-R

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a. C ch: 2 giai on, lng phn t Giai on 1:

+ Y

cham

C OY carbanion
i nhn
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Giai on chm: Y- tn cng vo C+

Giai on 2:
-

C OX C O Y Y Phn ng AN c th khng cn xc tc. Tuy nhin, pH c nh hng V d: Trong acid yu (pH 4) + X+

nhanh

C O

H+

C+ OH

in tch (+) ca carbon c tng cng AN cng thun li R-N+ H3 Tuy nhin, acid qu mnh: R-NH2 + H+ 41 Kh nng phn ng vi C=O gim

b. nh hng ca nhm th lin kt vi C=O Nguyn t C trong C=O c in tch dng cng ln AN cng thun li Nhm th y in t (+C, +I, +H) lm gim kh nng phn ng Nhm th ht in t (-C, -I) lm tng kh nng phn ng
NO2 CH2 C O H > Cl CH2 C O H > CH3 C O H > H3C C CH3 o

> H3C C OR o

> H3C C NH2 o

> H3C C Oo

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IV. Phn ng th i in t vo nhn thm (SE)


X + X+ acid + H+

Xc tc: cc acid v c: H2SO4, H3PO4, HF hay Lewis acid: FeCl3, AlCl3, ZnCl2 V d: C6H6 + (CH3)3C-Br /AlBr3 HBr C6H5-C(CH3)3 +
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C ch phn ng: 2 giai on, lng phn t Giai on 1: to phc ( benzonium cation)
xt nhanh
H + + + X H

+ X -Y

X+-Y

phc

X cham

H +

phc

Trong phc : X khng lin kt trc tip vi C no c Phc : X c lin kt trc tip vi 1 C ca benzene
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Giai on 2: tch proton

X +

H nhanh

X + HY

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+++ Nhm th y in t (+C, +H, +I) SE tng V d: * alkyl +I, +H *-NR2 (R: H hay gc alkyl), -OH, -OCH3, -NH-CO-CH3 (+C > -I) Anion: -O- : +C, +I mnh +++ Nhm th ht in t (-C, -I) SE gim V d: -N+N, -NO2, -CN, -CHO, -COR, -COCl, -COOH, -CO-NH2 (-I, -C) Cation: -N+R3 (-I mnh) * halogen (-I > +C)
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