CHEM1102 Lecture Notes 10
CHEM1102 Lecture Notes 10
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)
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 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
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
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
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
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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.
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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
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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.
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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.
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Cl
2.
3.
Br
Br
+ (C2 H5) 3N
+ -
+ Na I
30C
CH2 Cl2
+ CH3O Na
Cl
4.
80C
H2O
+ NaOH
methanol
acetone
17