P. 1
Lecture 13

Lecture 13

4.0

|Views: 1,242|Likes:
Published by vipulugale

More info:

Categories:Types, School Work
Published by: vipulugale on Feb 22, 2009
Copyright:Attribution Non-commercial

Availability:

Read on Scribd mobile: iPhone, iPad and Android.
download as PDF or read online from Scribd
See more
See less

11/14/2012

Lecture 13 ELIMINATION REACTIONS

1

E1
ALKYL HALIDES + WEAK BASE (SOLVOLYSIS)
The removal of a β -hydrogen becomes difficult without a strong base and a different mechanism (ionization) begins to take place ….. if the substrate is capable.

2

Mechanisms of Elimination—E1 An E1 reaction exhibits first-order kinetics: rate = k[(CH3)3CI] The E1 reaction proceed via a two-step mechanism. The bond to the leaving group breaks first before the π bond is formed. The slow step is unimolecular, involving only the alkyl halide.
3

The E1 Elimination Reaction (two steps)
B: H C C X C C + Weak base carbocation
fast slow

H
+

:X

unimolecular

rate = k [RX]

C C
4

5

Mechanisms of Elimination—E1
The rate of an E1 reaction increases as the number of R groups on the carbon with the leaving group increases.

6

REGIOSELECTIVITY

7

Mechanisms of Elimination—E1
• E1 reactions are regioselective, favoring formation of the more substituted, more stable alkene. • Zaitsev’s rule applies to E1 reactions also.

8

THE E1cB MECHANISM
Elimination, unimolecular, of the conjugate base. Carbanion mechanism
B: H C C X

proton first

halogen second
C C X C C

carbanion

Regioselective and stereselective reaction
A regioselective reaction forms more of one constitutional isomer than the other. A B + C more ‘B’ is formed than ‘C’, where B and C are constitutional isomers. A stereoselective reaction forms more of one stereoisomer than the other. A B+ C more ‘B’ is formed than ‘C’, where B and C are stereoisomers.
10

Stereospecific reaction
In a stereospecific reaction, each stereoisomeric reactant forms a different stereoisomeric product or a different set of stereoisomeric products. A C B D

‘A’ AND ‘C’ ARE STEREOISOMERS ‘B’ AND ‘D’ ARE STEREOISOMERS
11

Alkene synthesis by elimination reactions

12

Acid Catalyzed Dehydration of Alcohols

Typical acids used in dehydration are sulfuric acid and phosphoric acid Primary alcohols are most difficult to dehydrate, tertiary are the easiest. Rearrangements of the carbon skeleton can occur
13

Acid Catalyzed Dehydration of Alcohols
The temperature and concentration of acid required to dehydrate depends on the structure of the alcohol

14

Mechanism for Dehydration of Secondary and Tertiary Alcohols: An E1 Reaction Only a catalytic amount of acid is required since it is regenerated in the final step of the reaction The second step of the E1 mechanism in which the carbocation forms is rate determining Tertiary alcohols react the fastest because they have the most stable tertiary carbocation - like transition state in the second step
15

E1 Mechanism

16

Carbocation Stability and the Transition State Recall the stability of carbocations is:

17

The relative heights of ΔG‡ for the second step of E1 dehydration indicate that primary alcohols have a prohibitively large energy barrier

18

A Mechanism for Dehydration of Primary Alcohols: An E2 Reaction Primary alcohols cannot undergo E1 dehydration because of the instability of the carbocation-like transition state in the 2nd step. In the E2 dehydration the first step is again protonation of the hydroxyl to yield the good leaving group water
19

20

E2: Vicinal Dibromides
• Remove Br2 from adjacent carbons. • Bromines must be anti-coplanar (E2). • Use NaI in acetone, or Zn in acetic acid.

21

E2: Vicinal Dibromides

22

Dehydrohalogenation of alkyl halides Removing HX via E1
• • • • • Secondary or tertiary halides Formation of carbocation intermediate May get rearrangement Weak nucleophile Usually have substitution products too.

23

24

Removing HX via E2
• Strong base abstracts H+ as X- leaves from the adjacent carbon. • Tertiary and hindered secondary alkyl halides give good yields. • Use a bulky base if the alkyl halide usually forms substitution products.

25

Removing HX via E2
Bromocyclohexane, a secondary alkyl halide, can undergo both substitution and elimination E2 is favored over substitution using bulky base diisopropylamine
H Br (iPr)2NH, heat H H H + [(CH3)2CH]2NH2Br H

bromocyclohexane

Cyclohexene (93%)

26

Formation of Hofmann Product
• Bulky bases abstract the least hindered H+ • Least substituted alkene is major product.

27

Hofmann Elimination
• A quaternary ammonium salt has a good leaving group - a neutral amine. • Heating the hydroxide salt produces the least substituted alkene.

28

29

Hofmann Elimination

30

E2 Mechanism

31

E2 Mechanism

32

Cope Elimination
Amine oxides undergo elimination to form the least substituted alkene under milder conditions than the Hofmann reaction.

33

DIFFERENCES BETWEEN E1 AND E2

34

Structure of substrate
R H H R-C-X R-C-X R-C-X primary secondary tertiary R R H E1 formation of carbocation intermediate rate :tertiary > secondary > primary > methyl But this same order holds for E2 also. tertiary has more β -hydrogens
H H H H H C H C C C H H

EtO-

more opportunites Br for reaction
35

H

ALKYL HALIDE + BASE strong base weak base or solvolysis E2 mechanism
anti-coplanar requirement

E1 mechanism must be able to make “good” carbocation not stereospecific regioselective
36

stereospecific regioselective

E1 or
• Tertiary > Secondary • Weak base • Good ionizing solvent • Rate = k[halide] • Zaitsev product • No required geometry • Rearranged products

E2?

• Tertiary > Secondary • Strong base required • Solvent polarity not important • Rate = k[halide][base] • Zaitsev product • Coplanar leaving groups (usually anti) • No rearrangements
37

Elimination vs. Substitution
SN2 and E2 favored over SN1 and E1 by a strong base/Nu SN2 is slowed by steric hindrance, but E2 is not Stronger bases favor E2 over SN2 higher temperatures favor elimination
38

Elimination vs. Substitution
S N2 weaker bases less steric hindrance lower temperature E2 stronger bases more steric hindrance higher temperature

39

Elimination vs. Substitution
Benzylic halides undergo substitution reactions without competition from elimination. 10 benzyl halides react via SN2 pathway.

CH2Cl SN2 condition + CH3O

CH2OCH3 + Cl-

40

20 and 30 benzyl halides react via SN1 pathway, without benzylic rearrangement
CH2Cl CH2+ + Cl-

SN1 condition

CH3OH CH2OCH3 + H+
41

Rearranged products are possible from Allyl halides
H2O Na2CO3

Cl

HO

42

Vinyl halides and aryl halides do not undergo SN2 reaction because the nucleophile approaches the backside of sp2 carbon and is repelled by the π electron cloud of the double bond or the aromatic ring
Br

X
R CH CHCl

+ Br-

X

R C

CHCl + Cl-43

Aryl and vinyl halides do not undergo SN1 reactions, two reasons: 1. Vinylic and aryl carbocations are very unstable due to positive charge on sp carbon atom. 2. sp2 carbon atom makes stronger bond than sp3.
H H C H C H + 464 kJ
44

H C H + 372 kJ

An exceptionally stable cation triphenylmethyl cation used to form ether with a primary alcohol by an SN1 reaction.
Ph Ph Ph Cl slow -Cl
-

Ph Ph Ph HO

Ph fast Ph Ph R Py Ph Ph Ph O R O H fast R

PhH2C-X kSN1 1

Ph2HC-X 1000108

Ph3C-X
45

Apocamphyl chloride is inert to hydroxide ion Steric hindrance from backside of the C-Cl prohibits SN2 reaction. Carbenium ion produced by SN1 is not planar, therefore is unstable. Larger bicyclic system undergo slow SN1 at bridged head position.
Cl SbF6

Apocamphyl chloride

1-bicyclo 46 [3.2.2]nonyl cation

Substitution or Elimination?
• Strength of the nucleophile determines order: Strong nucleophile, bimolecular, SN2 or E2. • Primary halide usually SN2. • Tertiary halide mixture of SN1, E1 or E2 • High temperature favors elimination. • Bulky bases favor elimination. • Good nucleophiles, but weak bases, favor substitution.
47

You're Reading a Free Preview

Download
scribd
/*********** DO NOT ALTER ANYTHING BELOW THIS LINE ! ************/ var s_code=s.t();if(s_code)document.write(s_code)//-->