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 5: ALKENE I. Gii thiu chung Alkene: hydrocarbon mch h, cha 1 lin kt i C=C (CnH2n, n2) Trong C=C: 1 & 1, hnh thnh do lin kt ca orbital sp2

 Lin kt vung gc vi mt phng phn t Alkene n gin nht l ethylene CH2=CH2

121.7o 116.6o 1.08 1.33
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II. H danh php

II.1. Tn thng thng Tn alkane tng ng, i ane ylene

t dng, tr 3 alkene thng dng: CH2=CH2 ethylene CH2=CH-CH2 propylene (CH3)2C=CH2 isobutylene
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II.2. Danh php IUPAC Tn alkane tng ng, i ane ene

Chn mch carbon di nht & cha C=C lm mch chnh nh s sao cho C=C c ch s nh nht Ch s ca C=C chn theo v tr C gn C1 nht, vit cch tn mch chnh 1 gch ngang
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CH3-CH-CH=CH2 CH3
CH3 CH3-C-CH=CH-CH3 H

3-methyl-1-butene

4-methyl-2-pentene (c cis & trans)

II.3. Tn gc ca alkene Alkenyl CH2=CH- 1-ethenyl (vinyl) CH2=CH-CH2- 2-propenyl (allyl) CH3-CH=CH- 1-propenyl
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III. Cc phng php iu ch

III.1. Tch nc t alcohol Phn ng c th pha lng (xc tc acid H2SO4, H3PO4, 100-170oC) hay pha kh (xc tc Al2O3, zeolite, 350-400oC)

C C H OH

to xt

C C

+ H 2O

 Kh nng tch nc: alcohol bc 3 > bc 2 > bc 1

CH3CH2CH2CH2-OH

H2SO4 75% 140 oC

CH3CH=CHCH3

CH3-CH-CH2-CH3 H2SO4 50-60% CH3-CH=CH-CH3 o 100 C OH (CH3)3C-OH H2SO4 20% 80 oC CH2=C(CH3)2

III.2. Tch HX t dn xut ca halogen

C C H X to KOH/ethanol C C + H2O + KX

Kh nng tch HX: RX bc 3 > bc 2 > bc 1

to CH3CH2CH=CH2 CH3CH2CH2CH2Cl KOH/ethanol CH3CH2CHCH3 Cl to KOH/ethanol CH3CH2CH=CH2 20% CH3CH=CHCH3 80%

Lu : tch R-X bc 1 khng c chuyn v R-OH bc 1

CH3CH2CH2CH2-OH

H2SO4 75% 140 C

o

CH3CH=CHCH3

III.3. Kh dn xut 2 ln th ca halogen

C C X X
H H H3C C C CH3 Br Br

Zn to
Zn to

C C

+ ZnX2

CH3CH=CHCH3 + ZnX2

III.4. Hydro ha alkyne

t , x ar H 2 dl Lin ) (Pd

R H

R' H

R C C R'
Na ,N H
3

R H

H R'
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III.5. Nhit phn ester CnH2n+1-O-COR CnH2n + RCOOH

Nhit phn ester ca ru bc 1 < bc 2 < bc 3 Ester bc 1 1 sn phm, bc 2 & bc 3 nhiu sn phm IV. Tnh cht vt l (t c)
Ch tan trong dung mi khng phn cc hay t phn cc

V. Tnh cht ha hc Lin kt (E phn ly = 60 kcal/mol) yu hn lin kt (E = 80 kcal/mol) 11 o... Xc tc, t lin kt d b t

V.1. Phn ng cng hp i in t V.1.1. C ch: Giai on 1:

dung moi xuc tac nhanh

C C

+ X+-Y

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
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 Giai on 2:

Y-

C C X+

nhanh

Y C C X

Y- tn cng vo pha i lp vi X Nhm th y in t (+C, +I, +H) tng mt in t ca C=C tng kh nng phn ng AE
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V.1.2. Phn ng cng hp halogen 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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***Lp th ca phn ng cng X2: Cng hp trans (anti) cis sn phm l hn hp racemic (1 i i quang) trans sn phm c th l meso (1 sn phm)
H H C C CH3 CH3 Br2 CH3 H C Br Br C H CH3 CH3 H C Br H C Br CH3 meso CH3 Br C H H C Br CH3 rac-

H3C H

C C

H CH3

Br2

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V.1.3. Phn ng cng HX a. Quy tc Markonikov (dnh cho C=C khng i xng): H+ s tn cng vo carbon cha nhiu H
CH3-CH=CH2 + HBr CH3-CH-CH3 Br Br CH3-C-CH3 CH3

CH3-C=CH2 + HBr CH3

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

CH3-CH=CH-CH2-CH3 HBr CH3-CH-CH-CH2-CH3 Br
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c. Quy tc Kharasch: khi c mt peroxide, phn ng s i theo hng ngc vi Markonikov & theo c ch cng hp gc t do CH3-CH=CH2 + HBr CH3-CH2-CH2-Br

Cc peroxide: H2O2, acetyl peroxide CH3CO-O-OCO-CH3, benzoylperoxide C6H5CO-O-O-COC6H5

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 C ch: Theo hng to gc t do bn

CH3-C-O-O-C-CH3 O O CH3-CO-O + HBr Br to CH3 + CH3-CO-O + CO2

Br

+ CH3COOH + CH3-CH-CH2Br

CH3-CH=CH2

CH3-CH-CH2 Br

CH3-CH-CH2Br

HBr

CH3-CH2-CH2Br + Br

Lu : HI & HCl khng tham gia phn ng cng 19 gc t do nh HBr!!!

V.1.4. Phn ng cng hp nc Cn xc tc acid: H2SO4, H3PO4 (khng dng HX)

CH3-CH=CH2 + H2O H2SO4 CH3-CH-CH3 OH

Tun theo quy tc Markonikov C ch:

CH3-CH=CH2 + H+ -H
+

+ CH3-CH-CH3

+ H2O -H2O

H H3 C C O CH3

H H

-H+ + H+

CH3-CH-CH3 OH

Nu dng nhiu H2SO4: CH3-CH=CH2 + H2SO4 (CH3)2CH-OSO3H (CH3)2CH-OSO3H + H2O (CH3)2CH-OH + H2SO4

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V.1.5. Phn ng cng hp B2H6 Phn ng quan trng iu ch alcohol bc 1 & 2 t alkene, ngc vi sn phm Markonikov
CH3-CH=CH2 1. B2H6 2. H2O2 / NaOH CH3-CH2-CH2-OH

C ch: B2H6
CH3-CH=CH2 BH3 (Lewis acid) H + CH3-CH-CH2-B H H H-

BH3
CH3-CH2-CH2-BH2

[CH3-CH2-CH2]3B

H2O2

OH[CH3-CH2-CH2-O]3B
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CH3-CH2-CH2-OH

V.2. Phn ng hydro ha V.2.1. C ch:

C C + H2 Ni C C H H

Xc tc thng dng: Ni, Pd, Pt C ch: gc t do (AR), 2 H gn vo cng pha ni i (khc phn ng +X2) cng hp cis
C C C C H H
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H H + H2

H H

V.2.2. Tnh lp th Phn ng cng hp cis (syn) ng phn cis c th thu sn phm meso (1 sn phm) ng phn trans sn phm l hn hp racemic (1 i i quang)
H H C C COOH COOH D2 Ni COOH H C D H C D COOH meso COOH H C D D C H COOH COOH D C H H C D COOH rac-

maleic acid H HOOC COOH H D2 Ni

C C

fumaric acid

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V.3. Phn ng oxy ha V.3.1. Tc nhn oxy ha peracid

C C O C C

R-C-O-O-H O

O C C

+ RCOOH

OH H2O C C (H+, OH-) OH

Cng hp trans, to -diol Phn ng khng gy ct mch C=C

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V.3.2. Oxy ha bng ddch KMnO4 long (pH 7, 0oC ) Cng hp cis, to diol
OH0 oC pH 7 C O O C O OH2O H
+

C C

MnO4

Mn

C C OH OH

+ MnO3-

Phn ng khng ct mch C=C

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V.3.3. Oxy ha bng ddch KMnO4 m c, to cao Phn ng gy ct mch C=C Sn phm l carboxylic acid CH3-CH=CH-CH3 + KMnO4 / to 2 CH3COOH

(CH3)2CH=CH-CH3 + K2Cr2O7 /H2SO4/to (CH3)2C=O + CH3COOH

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V.3.4. Oxy ha bng ozone Phn ng gy ct mch C=C Sn phm l carbonyl (khc KMnO4 )
C O C O
3 /CH Zn H2/Pt

OH CO

C O + H2O C O + H2O C O + H2O2

C C

O3

O molozonide

C C O O ozonide

2O

(H + )

CH3-C=CH-CH2-CH3 CH3

1. O3 2. H2O

CH2-C-CH3 + O

CH3-CH2-CHO + H2O2

Lu : H2O2 d dng oxy ha carbonyl thnh 27 carboxylic acid sn phm cui l acid!!!

V.4. Phn ng polymer ha Phn ng to polymer di tc dng ca nh sng, to cao, xc tc C th xy ra theo c ch gc t do (xc tc peroxide), c ch cation (xc tc H2SO4, AlCl3, BF3) hay anion (xc tc LiNH2)
CH3 H2C C CH3
nCH2=CH Cl

H+

CH3 H3C C CH2 CH3

Cl

CH3 C CH2 CH3

CH3 C CH3

peroxide

--CH2-CH- CH2-CH- CH2-CH-Cl Cl polyvinyl chloride

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