chap 9

WWU -- ChemistryWWU -- Chemistry

ELIMINATION REACTIONS:ELIMINATION REACTIONS:ALKENES, ALKYNESALKENES, ALKYNES

Chapter 9


Chapter 9 Assigned ProblemsChapter 9 Assigned ProblemsIn-Text Problems1,2, 3 6, 7, 8, 10ab, 12abef 13ac14, 16, 17, 19, 21 23abceh

End of Chapter Problems24- 30 32, 33 36, 3740 - 42 44 49 - 50


Summer 2008Summer 2008

• Skip the following sections: 9.11, 9.12, 9.13, and 9.14

• Keep Sections 9.15 and 9.16!• Especially study: Volume 2, pp.

855 and 856 in section 9.16


Section 9.1: NomenclatureSection 9.1: Nomenclature• Review this on your own


Sect. 9.2 Elimination Sect. 9.2 Elimination ReactionsReactions

C C

X Y

C C + X Y

Dehydrohalogenation (-HX) and Dehydration (-H2O) are the main types of elimination reactions.


Dehydrohalogenation (-HX)Dehydrohalogenation (-HX)

strongbase

X = Cl, Br, I

+ " "C C

X

H XC C

H

See examples on pp. 770-771


Sect 9.3: the E2 mechanismSect 9.3: the E2 mechanism

..:..

__

+

+ Br_

..:

concerted mechanism

H O

C C

Br

H

H OH

C C

This reaction is done in strong base at high concentration, such as 1 M NaOH in water.

_


KineticsKinetics• The reaction in strong base at high

concentration is second order (bimolecular):

• Rate law: rate = k[OH-]1[R-Br]1


Sect 9.3: the E1 mechanismSect 9.3: the E1 mechanism

1)

++ Br

_slow

+

2)..

:

+fast

O.. +O

C C

Br

C C

H

C C

HC C

HH H

H

H

H

rate determining step

This reaction is done in strong base such as 0.01 M NaOH in water!! Actually, the base solution is weak!


KineticsKinetics• The reaction in weak base or under

neutral conditions will be first order (unimolecular):

• Rate law: rate = k [R-Br]1

• The first step (slow step) is rate determining!


Sect 9.4: the E2 mechanismSect 9.4: the E2 mechanism• mechanism• kinetics• isotope effects• stereochemistry of reactants• orientation of elimination (Zaitsev’s

rule)• stereochemistry of products• competing reactions


E2 mechanismE2 mechanism

..:..

__

+

+ Br_

..:

concerted mechanism

H O

C C

Br

H

H OH

C C

This reaction is done in strong base at high concentration, such as 1 M NaOH in water.


Kinetics of an E2 reactionKinetics of an E2 reaction• The reactions are second order

(bimolecular reactions).

• Rate = k [R-Br]1[Base]1

second order reaction (1 + 1 = 2)High powered math!!


energy

Reaction coordinate

C C

H OH

Br-

..:..

__H O

C C

Br

H

..:H O

C C

H

Br


Isotope EffectsIsotope Effects• Change in rate brought about by

replacing an hydrogen atom by its isotope, deuterium.C-D bond is stronger than a C-H bond!

• Usually expressed as kH/kD

• If kH/kD = about 7.0, this means that the isotopically-labeled bond is being broken in the rate-determining step, indicating that the reaction is E2.


Stereochemistry of reactantsStereochemistry of reactants• E2 reactions must go by an anti

elimination• This means that the hydrogen atom

and halogen atom must be 180o (coplanar) with respect to each other!!

• Draw a Newman projection formula and place the H and X on opposite sides.


Stereochemistry of E2 Stereochemistry of E2 ReactionReaction

KOH

AlcoholSolventH

Br

H

HH

CCH3

CH3

CH3

C

H

CH3

CH3

CH3H

H

This is the cis isomer. The trans isomer does not react by an E2 reaction.


(S,S)-diastereomer(S,S)-diastereomer

KOHethanolheat

(E)-isomer (Z)-isomer

??? ???

C C

Br

HCH3

CH3

H

C C

CH3 CH3

H t-butylC C

H CH3

CH3 t-butyl

t-butyl


(E)-isomer

C C

CH3 CH3

H T-butyl

This one is formed!


(R,S)(R,S)-diastereomer-diastereomer

KOHethanolheat

(E)-isomer (Z)-isomer

??? ???

C C

Br

HH

CH3

CH3

t-butyl

C C

CH3 CH3

H T-butylC C

H CH3

CH3 t-butyl


(Z)-isomer

C C

H CH3

CH3 t-butyl

This one is formed!


Orientation of elimination: Orientation of elimination: regiochemistry/ Zaitsev’s regiochemistry/ Zaitsev’s

RuleRule• In reactions of removal of hydrogen halides from alkyl halides or the removal of water from alcohols, the hydrogen which is lost will come from the more highly-branched -carbon.

A. N. Zaitsev -- 1875 C C C C

H

H

H H

X

H

H

HHCH3

Less branchedMore branched


Product formed from previous Product formed from previous slideslide

CC C

C

H

HH

H

HCH3

HH


Typical bases used in E2 Typical bases used in E2 reactionsreactions

High concentration of the following >1MIf the concentration isn’t given, assumethat it is high concentration!• Na+ -OH• K+ -OH• Na+ -OR• Na+ -NH2


Orientation of elimination: Orientation of elimination: regiochemistry/ Zaitsev’s regiochemistry/ Zaitsev’s

RuleRuleExplaination of Zaitsev’s rule:

When you remove a hydrogen atom from the more branched position, you are forming a more highly substituted alkene.


Stereochemistry of productsStereochemistry of products• The H and X must be anti with

respect to each other in an E2 reaction!

• You take what you get, especially with diastereomers! See the previous slides of the reaction of diastereomers.


Competing reactionsCompeting reactions• The substitution reaction (SN2)

competes with the elimination reaction (E2).

• Both reactions follow second order kinetics!


Sect 9.5: the E1 mechanismSect 9.5: the E1 mechanism• mechanism• kinetics• isotope effects• stereochemistry of reactants• orientation of elimination (Zaitsev’s

rule)• stereochemistry of products• competing reactions


E1 mechanismE1 mechanism

1)

++ Br

_slow

+

2)..

:

+fast

O..+O

C C

Br

C C

H

C C

HC C

H

H H

H

H

H

water helpsto stabilizecarbocation

This reaction is done in strong base at low concentration, such as 0.01 M NaOH in water)


E1 Reactions E1 Reactions • These reactions proceed under neutral

conditions where a polar solvent helps to stabilize the carbocation intermediate.

• This solvent also acts as a weak base and removes a proton in the fast step.

• These types of reactions are referred to as solvolysis reactions.


• tertiary substrates go by E1 in polar solvents, with little or no base present!

• typical polar solvents are water, ethanol, methanol and acetic acid

• These polar solvents help stabilize carbocations

• E1 reactions also occur in a low concentration of base (i.e. 0.01M NaOH).


•With strong base (i.e. >1M), goes by E2•Example reactions

However!!!!However!!!!


Structure of the Carbocation Structure of the Carbocation IntermediateIntermediate

C CH3

CH3

CH3


Carbocation stability orderCarbocation stability order

Tertiary (3o) > secondary (2o) > primary (1o)

It is hard (but not impossible) to get primary compounds to go by E1. The reason for this is that primary carbocations are not stable!


Kinetics of an E1 reactionKinetics of an E1 reaction• E1 reactions follow first order

(unimolecular) kinetics:

Rate = k [R-X]1

The solvent helps to stabilize the carbocation, but it doesn’t appear in the rate law!!


energy

Reaction coordinate

CH

CBr

CH

C

Br-

C C

H

C C

H

C C + H+

intermediate


Isotope effectsIsotope effects• E1 reactions do not show an isotope

effect: kH/kD = 1

• This tells us that the C-D or C-H bonds are not broken in the rate determining step (step 1). They are broken in the fast step (step 2) in the mechanism).


Stereochemistry of the Stereochemistry of the reactantsreactants

• E1 reactions do not require an anti coplanar orientation of H and X.

• Diastereomers give the same products with E1 reactions, including cis- and trans products.

• Remember, E2 reactions usually give different products with diastereomers.


Orientation of eliminationOrientation of elimination• E1 reactions faithfully follow

Zaitsev’s rule!• This means that the major product

should be the product that is the most highly substituted.


Stereochemistry of productsStereochemistry of productsE1 reactions usually give the thermodynamically most stable product as the major product. This usually means that the largest groups should be on opposite sides of the double bond. Usually this means that the trans product is obtained.


Some examples of E1 and E2 Some examples of E1 and E2 reactionsreactions


Competing reactionsCompeting reactionsSkip for Summer 07Skip for Summer 07

• The substitution reaction (SN1) competes with the elimination reaction (E1).

• Both reactions follow first order kinetics!


Whenever there are Whenever there are carbocations…carbocations…

• They can undergo elimination (E1)• They can undergo substitution

(SN1)• They can rearrange

– and then undergo elimination– or substituion


Sect 9.6: Dehydration of Sect 9.6: Dehydration of Alcohols (acid assisted E1)Alcohols (acid assisted E1)

strong acid+ H2OR C C R

R

OH

H

R

C C

R

R R

R

Acid assisted reactions are always E1


Which strong acids are used?Which strong acids are used?• H2SO4

• H3PO4


Mechanism of DehydrationMechanism of Dehydration1)

2)

3)

+ H+

+

+

slow

++ H2O

++ H

+

CH3 C CH3

CH3

OH

CH3 C CH3

CH3

OH2

CH3 C CH3

CH3

OH2

CH3 C CH3

CH3

CH3 C CH3

CH3

C CH2

CH3

CH3


85% H3PO4

80 °C

H H+

C

:

H

CH+

_

::H

secondary carbocation

CH3 C CH CH3

CH3

CH3

O

CH3 C

CH3

CH3

O

CH3

CH3 C

CH3

CH3

H2O

CH3

Sect 9.7: rearrangements in Sect 9.7: rearrangements in dehydration reactions dehydration reactions


+

+

major

minor

trace

CH3 C C CH3

CH3

CH3

H

CH3 C CH CH2

CH3

CH3

CH3 C C CH3

CH3

HCH3

CH2 C CH

CH3

CH3

CH3

C C

CH3

CH3 CH3

CH3

tertiary carbocationsecondary carbocation

Sect 9.7: rearrangements in Sect 9.7: rearrangements in dehydration reactionsdehydration reactions


RearrangementsRearrangements• Alkyl groups and hydrogen can

migrate in rearrangement reactions to give more stable intermediate carbocations.

• You shouldn’t assume that rearrangements always occur in all E1 reactions, otherwise paranoia will set in!!


Sect 9.8: comparison of E2 / Sect 9.8: comparison of E2 / E1E1

• E1 reactions occur under essentially neutral conditions with polar solvents, such as water, ethyl alcohol or acetic acid.

• E1 reactions can also occur with strong bases, but only at low concentration, about 0.01 to 0.1 M or below.

• E2 reactions require strong base in high concentration, about 1 M or above.


Sect 9.8: comparison of E2 / Sect 9.8: comparison of E2 / E1E1

• E1 is a stepwise mechanism (two or more);Carbocation intermediate!

• E2 is a concerted mechanism (one step)No intermediate!

• E1 reactions may give rearranged products

• E2 reactions don’t give rearrangement• Alcohol dehydration reactions are E1


Sect 9.9: bulky leaving Sect 9.9: bulky leaving groups -- Hofmann groups -- Hofmann

EliminationElimination

+OH

_

heat

+

6%

94%

CH3 CH2 CH2 CH CH3

N

CH3

CH3CH3

CH3 CH2 CH CH CH3

CH3 CH2 CH2 CH CH2

This give the anti-Zaitsev product (least substituted product is formed)!


Orientation of elimination: Orientation of elimination: regiochemistry/ Hofmann’s regiochemistry/ Hofmann’s

Rule Rule • In bimolecular elimination reactions in the presence of either a bulky leaving group or a bulky base, the hydrogen that is lost will come from the LEAST LEAST highly-branched -carbon.

C C C C

H

H

H H

X

H

H

HHCH3

Less branchedMore branched


Product from previous slideProduct from previous slide

CC

C

H

H

H

HCH3

HH

C

H


Sect 9.10 Elimination with Sect 9.10 Elimination with bulky basesbulky bases

• Non-bulky bases, such as hydroxide and ethoxide, give Zaitsev products.

• Bulky bases, such as potassium tert-butoxide, give larger amounts of the least substituted alkene (Hoffmann) than with simple bases.


Comparing Ordinary and Comparing Ordinary and Bulky BasesBulky Bases

CH3 C CH CH3

Br

NaOC2H5

C2H5OHheat

C CHCH3 CH3

CH3 C CH CH3

Br

KOC(CH3)3

(CH3)3COHheat

C CHCH3 CH2

Major

H

CH3 CH3

CH3

H

CH3

Major

H


1-butene: watch out for 1-butene: watch out for competing reactions!competing reactions!

H3C CH2 CH2 CH2 Br

KOCH3

Non-bulky

SN2

H3C CH2 CH2 CH2 O-CH3

H3C CH2 CH CH2

bulky baseKO-t-butyl

E2


Sect 9.11 the E1cb Sect 9.11 the E1cb mechanism: skip Summer mechanism: skip Summer

20062006.. _

.. :....

fast .._

1)

2)

.._

slow+ Br

_

C

O

C

O

C

O

C

O

C C

Br

C C

Br

H

H O

C C

Br

H O H

C C


Sect 9.13 alpha-Elimination Sect 9.13 alpha-Elimination Reactions: skip Summer Reactions: skip Summer

20062006• These unusual reactions occur with

one carbon compounds, only.• Examples include chloroform and

methylene chloride.• Cyclopropane compounds are

formed.


Sect 9.14: Dehalogenation: Sect 9.14: Dehalogenation: skip Summer 2006skip Summer 2006

+ ZnCH3COOH

+ ZnBr2CH3 C CH CH3

CH3

Br

Br

C C

CH3

CH3 H

CH3

This reaction requires the two Br’s to be anti.


Sect 9.15: Preparation of Sect 9.15: Preparation of Alkynes -- double Alkynes -- double

dehydrohalogenation dehydrohalogenation

KOH

ethanol

NaNH2

NaNH2

R C C R

Br

H

Br

H

C C

R

H R

Br

C CR R

R C C R

Br

H

Br

H

C CR R


Sect. 9.16: Multistep Sect. 9.16: Multistep reactions and Synthesis -- reactions and Synthesis --

Example 1 Synthesis: Example 1 Synthesis: Example 1Example 1

CH3 CH CH3

OH

CH3 CH2 CH2 Br


Multistep reactions and Multistep reactions and Synthesis Example 2Synthesis Example 2

Cl CH2 CH2 CH2 CH3 CH3 CH CH2 CH3

Cl



Br CH2 CH2 CH2 CH2 CH3 CH3 C CH2 CH2 CH3

Br

Br


Synthesis: Example 5Synthesis: Example 5

CH2 CH2 CH2 CH2 CH3 CH3 C CH2 CH2 CH2 CH3

O

CH2Br


Highlights of Chapter NineHighlights of Chapter Nine• Dehydrohalogenation -- E2 Mechanism• Zaitsev’s Rule• Isotope Effects• Dehydrohalogenation -- E1 Mechanism• Dehydration of Alcohols -- E1• Carbocation Rearrangements -- E1• Elimination with Bulky Leaving Groups

and Bulky Bases -- Hofmann Rule -- E2• Multistep Reactions and Synthesis

chap 9

Documents

c c c c wwu

step c c r c c r

c c c3

o h h c c c cwwu

h c h h h ha

carbocation c c r h

ch bond

e c c ch3 x c h hwwu