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CHEM1102 Lecture Notes 10

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56 views17 pages

CHEM1102 Lecture Notes 10

greag

Uploaded by

Callum Biggs
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Chemistry 1102

Charlie Bond
MCS Rm 4.16/4.27
[email protected]
What is Organic Chemistry?
Organic Reactions I II
Alkanes (Ch 21)
Conformational Analysis (Ch 21)
Stereochemistry I II III (Ch 22)
Alkyl Halides I II (Ch 24)
Alcohols and Ether I II (Ch 24)

Substitution & Elimination


Alkyl halides are used to demonstrate 2 types of reaction
nucleophilic substitution
-elimination
asanucleophile,
ethoxideionattacks
thiscarbon

nucleophilic
substitution

Br
-

+ EtO Na
H anucleophile
andabase
asabase,ethoxideion
attacksthishydrogen

ethanol
elimination
ethanol

OEt

+ Na Br

+ EtOH + Na+Br-

-Elimination

-Elimination:
-Elimination removal of atoms or
groups of atoms from adjacent carbons to
form a carbon-carbon double bond
we study a type of -elimination called
dehydrohalogenation (the elimination of HX)

C C
H X
Analkyl
halide

CH3 CH2 O-Na+

CH3 CH2 OH

Base
C

CH3 CH2 OH

Na+X 3

Analkene

-Elimination
Zaitsev rule: the major product of a elimination is the more stable (the more
highly substituted) alkene
Br
2Bromo2
methylbutane

CH3 CH2 O-Na+


CH3 CH2 OH

Br

+
2Methyl2butene
(majorproduct)

CH3 O-Na+

CH3 OH
1Bromo1methyl
cyclopentane

2Methyl1
butene

1Methyl
cyclopentene
(majorproduct)

Methylene
cyclopentane
4

-Elimination
Zaitsev rule: the major product of a elimination is the more stable alkene
Note: Trans alkenes are more stable than
cis.

-Elimination
There are two limiting mechanisms for elimination reactions
E1 mechanism: at one extreme, breaking of
the C-X bond is complete before reaction with
base breaks the C-H bond
only R-X is involved in the rate-determining step

E2 mechanism: at the other extreme, breaking


of the C-X and C-H bonds is concerted
both R-X and base are involved in the ratedetermining step
6

E1 Mechanism
Step 1: ionization of C-X gives a carbocation
intermediate
CH3
CH2 -C-CH3

slow,rate
determining

Br

CH3
CH3 -C-CH3 +
+
(Acarbocation
intermediate)

Br

Step 2: proton transfer from the carbocation


intermediate to a base (in this case, the solvent) gives
the alkene
H

O
H3 C

CH3
+ H-CH2 -C-CH3
+

fast

CH3
H +
O H + CH2 =C-CH3
H3 C

E2 Mechanism
A one-step mechanism; all bond-breaking
and bond-forming steps are concerted

CH3 CH2 O

CH3
+ H-CH-CH2 -Br
CH3 CH2 O-H + CH3 CH=CH2 + Br

10

Elimination Reactions
Summary of E1 versus E2 Reactions for
Haloalkanes
Haloalkane
Primary
RCH2 X

E1
E1doesnotoccur.
Primarycarbocationsare
sounstablethattheyare
neverobservedinsolution.

E2
E2isfavored.

Secondary Mainreactionwithweak
Mainreactionwithstrong
R2 CHX basessuchasH2 OandROH. basessuchasOHandOR.
Tertiary
R3 CX

Mainreactionwithweak
Mainreactionwithstrong
basessuchasH2 OandROH. basessuchasOHandOR.
11

Substitution vs Elimination
Many nucleophiles are also strong bases
(OH- and RO-) and SN and E reactions
often compete
the ratio of SN/E products depends on the
relative rates of the two reactions

H C

C X + Nu

nucleophilic
substitution H C
elimination

C Nu + X

C C

+ HNu + X
12

SN1 versus E1
Reactions of 2 and 3 haloalkanes in
polar protic solvents give mixtures of
substitution and elimination products
E1
CH3
CH3 C I
CH3

-I-

or

CH3
CH3 C Cl
CH3

-Cl

CH3
CH3 C +
CH3

SN1
H2O

CH3
CH2 C
+ H+
CH3
CH3
CH3 C OH + H+
CH3

CH3
SN1
+
CH3 C OCH3 + 13
H
CH3 OH
CH3

SN2 versus E2
It is considerably easier to predict the ratio
of SN2 to E2 products
Attackofbaseonahydrogenby
E2isonlyslightlyaffectedby
branchingatthecarbon;alkene
formationisaccelerated

R R
H

C
C leavinggroup

SN 2attackofanucleophileis R
R
impededbybranchingatthe
andcarbons

14

Summary of S vs E for Haloalkanes


for methyl and 1haloalkanes
Methyl
CH3X

SN2

Primary
RCH2 X

SN2

ThemainreactionwithstrongbasessuchasOHand
EtO .Also,themainreactionwithgood
nucleophiles/weakbases,suchasIandCH3 COO.

E2

Themainreactionwithstrong,bulkybases,suchas
potassiumtertbutoxide.

SN1

SN1/ E1

Theonlysubstitutionreactionsobserved
SN1reactionsofmethylhalidesareneverobserved.
Themethylcationissounstablethatitisnever
formedinsolution.

Primarycationsareneverformedinsolution;therefore,
S N1andE1reactionsofprimaryhalidesareneverobserved.
15

Summary of S vs E for Haloalkanes


for 2 and 3 haloalkanes
Secondary SN2
R2CHX

Tertiary
R3CX

Themainreactionwithweakbases/goodnucleophiles,
suchasIandCH3COO.

E2

Themainreactionwithstrongbases/goodnucleophiles
suchasOH andCH3CH2O.

SN1/ E1

Commoninreactionswithweaknucleophilesinpolar
proticsolvents,suchaswater,methanol,andethanol.

SN2

SN 2reactionsoftertiaryhalidesareneverobserved
becauseoftheextremecrowdingaroundthe3carbon.
Mainreactionwithstrongbases,suchasHOandRO.

E2
SN1/ E1

Mainreactionswithpoornucleophiles/weakbases.
16

Summary of S vs E for Haloalkanes


Examples: predict the major product and the
mechanism for each reaction
1.

Cl

2.

3.

Br
Br

+ (C2 H5) 3N

+ -

+ Na I

30C
CH2 Cl2

+ CH3O Na
Cl

4.

80C
H2O

+ NaOH

methanol

acetone

17

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