8.

Alkena: Pembuatan dan Reaksi

Based on McMurrys Organic Chemistry 6th edition

Pembuatan Alkena: Reaksi Eliminasi

Alkena biasanya dibuat dengan cara:

Dehydration
CH3 OH

Alkohol Tersier

H2SO4, H 2O

CH3
+ H 2O

McMurry Organic Chemistry 6th edition Chapter 7 (c) 2003

Pembuatan Alkena: Reaksi Eliminasi

Dehydrohalogenation

H H Br H H KOH + KBr + H2O H

McMurry Organic Chemistry 6th edition Chapter 7 (c) 2003

8.1 Preparation of Alkenes: A Preview of Elimination Reactions

Dehidrohalogenasi

McMurry Organic Chemistry 6th edition Chapter 6 (c) 2003

Reaksi-reaksi alkena

Alkena bereaksi dengan banyak elektrofil menghasilkan produk melalui reaksi adisi

Menghasilkan alkohol (bila mengadisi H-OH) Menghasilkan alkana (bila mengadisi H-H) Menghasilkan halohidrin (bila mengadisi HO-X) Menghasilkan dihalida (bila mengadisi X-X) Menghasilkan halida (bila mengadisi H-X) Menghasilkan diol (bila mengadisi HO-OH) Menghasilkan siklopropana (bila mengadisi :CH2)
McMurry Organic Chemistry 6th edition Chapter 6 (c) 2003 5

8.2 Adisi Halogen pada Alkena

CH3 CH= CH CH 3 2-Butene

+ Br2

CH2 Cl 2

Br Br CH3 CH- CHCH3 2,3-Dibromobutane Br

+ Br2

CH2 Cl 2

Cyclohexene

Br trans- 1,2-Dibromocyclohexane

McMurry Organic Chemistry 6th edition Chapter 6 (c) 2003

Mechanism Step 1: Pembentukan bridged bromonium ion intermediate

: Br : :Br : :Br : C C

: :
C C + : Br :

Step 2: Penyerangan ion halida dari arah yang berlawanan

(opposite side) dari cincin anggota tiga
: Br : + :Br : C C C :Br : Anti (coplanar) orientation 7 of added bromine atoms : Br : C

: :

: :

8.3 Pembentukan Halohidrin

Reagennya Br2 atau Cl2 )

HO CH3 CH= CH 2 Propene Cl 2 H2 O

Cl + HCl

CH3 CH- CH2 1-Ch loro-2-propanol (a chlorohydrin)

McMurry Organic Chemistry 6th edition Chapter 6 (c) 2003

Mekanisme pembentukan Bromohidrin

Step 1
: Br : :Br :

: :
H - Br H
-

:Br : C

:Br : H H R H minor contributin g structure C

H R

Step 2

C C H H R H bridge d bromonium ion

:Br : H O: H H R C C H H

H R C

:Br : C H H
9

+
H

McMurry Organic Chemistry 6th edition Chapter 6 (c) 2003

8.4 Adisi air pada alkena: Oksimerkurasi/Reduksi

OH CH 3 CHCH CH 3 Hg OA c An organome rcury compound OH N aBH4 Hg OA c CH 3 CHCH CH 3 + CH 3 COOH + Hg H 2-Butanol Ace tic acid + CH3 COOH Ace tic acid

CH 3 CH= CH CH 3 + Hg ( OAc ) 2 2-Butene Mercu ry(I I) acetate

H2 O

OH CH3 CHCH CH 3

McMurry Organic Chemistry 6th edition Chapter 6 (c) 2003

10

Addition of Hg(II) and oxygen is anti & stereoselective

Hg ( OAc ) 2 H2 O H Cyclope ntene H

OH

H Hg OA c (Anti addition of -OH and -HgOAc)

McMurry Organic Chemistry 6th edition Chapter 6 (c) 2003

11

Mechanism of Oxymercuration

1. Electrophilic addition of Hg(OAc)2 produces mercurinium ion. 2. Water acts as a nucleophile, attacks the more substituted carbon atom to form a C-O bond. Acetate ion removes hydrogen, forming a neutral product, but the HgOAc is still attached. NaBH4 reduces the HgOAc, replacing it with a hydrogen atom to form the alcohol product.
H 2O H 3C H 3C Hg OAc OAc Hg OAc

H3C

Hg OAc

H O

OAc

- H+ H C

OH

NaBH4 HgOAc

HO

H 3C

HgOAc

3 McMurry Organic Chemistry 6th edition Chapter 7 (c) 2003

H 3C

12

8.5 Adisi air pada alkena: Hidroborasi

Boran adalah asam Lewis yang mampu menerima elektron Boran diadisi alkena menghasilkan organoboran

McMurry Organic Chemistry 6th edition Chapter 6 (c) 2003

13

Orientasi dalam hidrasi melalui Hidroborasi

Regiokimianya berlawanan dengan orientasi Markovnikov

OH terikat pada karbon dengan atom H paling banyak

H and OH add with syn stereochemistry, to the same face of the alkene (opposite of anti addition)

McMurry Organic Chemistry 6th edition Chapter 6 (c) 2003

14

Hidroborasi, Efek Elektronik memberikan Non-Markovnikov

More stable carbocation is consistent with steric preferences

McMurry Organic Chemistry 6th edition Chapter 6 (c) 2003

15

Mekanisme Hidroborasi

McMurry Organic Chemistry 6th edition Chapter 7 (c) 2003

16

8.7 Reduksi Alkena: Hidrogenasi

Alkena bereaksi dengan H2dengan adanya katalis logam transisi menghasilkan alkana
+ H2 Cyclohexene Pd 25C, 3 atm Cyclohexane

commonly used catalysts are Pt, Pd, Ru, and Ni

Proses ini disebut reduksi katalitik (catalytic reduction) atau hidrogenasi katalitik (catalytic hydrogenation)
McMurry Organic Chemistry 6th edition Chapter 6 (c) 2003 17

Mechanism of Hydrogenation

McMurry Organic Chemistry 6th edition Chapter 7 (c) 2003

18

8.8 Oksidasi alkena: Hidroksilasi dan Pemutusan

Hidroksilasi mengadisi OH pada kedua karbon C=C Dikatalisis oleh osmium tetroksida Stereokimia adisi adalah syn Produknya adalah 1,2-dialkohol or diol (disebut juga glikol = glycol)

McMurry Organic Chemistry 6th edition Chapter 6 (c) 2003

19

Ozonolisis alkena

McMurry Organic Chemistry 6th edition Chapter 6 (c) 2003

20

Structure Elucidation With Ozone

Cleavage products reveal an alkenes structure

McMurry Organic Chemistry 6th edition Chapter 6 (c) 2003

21