20-11-2014

SN1 vs. SN2 vs. E1 vs. E2

• Factors affecting the type of reaction an alkyl

halide undergoes include:

– Type of alkyl halide

• methyl, 1o, 2o, 3o, allylic or benzylic

– Strength of nucleophile or base

SN1 vs. SN2 vs. E1 vs. E2

• Guidelines for Predicting Products of Substitution and Elimination

Reactions:
– The strength of the nucleophile or base determines the order of
the reaction.
• SN2 and E2 reactions require strong nucleophiles (or bases)

• SN1 and E1 reactions generally use weak nucleophiles (or bases)

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SN1 vs. SN2 vs. E1 vs. E2

• Nucleophilicity (nucleophile strength):

– a measure of the rate at which a nucleophile attacks an
electrophilic carbon of a standard substrate

• A species with a negative charge is a stronger nucleophile than a

similar neutral species:
– nucleophilicity of base > conjugate acid
• CH3O- > CH3OH

SN1 vs. SN2 vs. E1 vs. E2

• Nucleophilicity decreases from left to right in the

periodic table
– look at the element with lone pair of e-
– more electronegative elements hold on to electrons
more tightly

• OH- > F-

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SN1 vs. SN2 vs. E1 vs. E2

• Nucleophilicity increases from top to bottom

– size increases
• electrons held more loosely
– polarizability increases
» bond can begin forming when atoms are farther apart
– I- > Br-

• Polarizable: having electrons that can move more freely

toward a positive charge

SN1 vs. SN2 vs. E1 vs. E2

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SN1 vs. SN2 vs. E1 vs. E2

Example: Identify the stronger nucleophile in each pair.

Explain why.

NH3 or NH2-
H2O or NH3
HS- or Cl-
PH3 or NH3

SN1 vs. SN2 vs. E1 vs. E2

• Base Strength:
– Weaker acids produce stronger conjugate bases.

CH3CH2OH CH3CH2O-
strong base
weak acid strong nucleophile
– Strong acids produce weak conjugate bases.
HBr Br-

Weak base
Strong acid
good nucleophile

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SN1 vs. SN2 vs. E1 vs. E2

• The presence of bulky groups on the nucleophile makes

CH3
it less nucleophilic but a stronger base.
– hinders approach to the electrophilic carbonCH3 C O
CH3

CH3
-
CH3 C O CH3CH2O -
CH3
t-butoxide ion ethoxide ion
hindered unhindered
strong base weaker base
weak nucleophile stronger nucleophile

SN1 vs. SN2 vs. E1 vs. E2

Example: Identify the stronger base in each pair.

OH- or H2O
CH3OH or CH3O-
(CH3)3CO- or CH3O-

Water and alcohols are amphoteric. They can serve as either an

acid or a base. Water and alcohols are weak acids and weak bases.

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SN1 vs. SN2 vs. E1 vs. E2

• Guidelines for Predicting Products of Substitution and

Elimination Reactions:
– The type of alkyl halide is important in determining the
type of reaction:
• Methyl halide: SN2 exclusively
• 1o halide:
– SN2 with a strong nucleophile (favored)

– E2 with strong base (sometimes)

– SN1 or E1 are sometimes observed at high temperatures if

rearrangement produces more stable carbocation.

SN1 vs. SN2 vs. E1 vs. E2

• Guidelines for Predicting Products of Substitution and

Elimination Reactions:
– The type of alkyl halide is important in determining the
type of reaction:
• 3o Halides:
– E2 with a strong base

– SN1 and E1 with weak nucleophile or weak base

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SN1 vs. SN2 vs. E1 vs. E2

• Guidelines for Predicting Products of Substitution and

Elimination Reactions:
– The type of alkyl halide is important in determining
the type of reaction:
• 2o Halides:
– Mixtures of products are common

– Strong base/nucleophile gives SN2 and E2

– Weak base/nucleophile gives SN1 and E1

SN1 vs. SN2 vs. E1 vs. E2

• Guidelines for Predicting Products of Substitution

and Elimination Reactions:
– Strong bulky bases favor E2 reactions.
• t-butoxide ion

– Good nucleophiles with limited basicity favor SN2

reactions.
• Br-
• I-

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CH CH2OH
CH
3 CH
3
OH 2 SN1 vs. SN2 vs. E1 vs. E2

Example:
CHCH CH Predict
CH OCH3the product(s) and mechanism of the
OCH
3 3 22
following reaction. If more than one product or mechanism
CH2 CH
is possible,
CH CH
explain
2
which is/are most likely.
2 2

CH3CH2OCH3
CH3CH2Br CH CH2OH
+ NaOCH
3
CH3CH2Br + NaOCH3 3
CH3CH2OCH3 + CH2 CH2
CH3OH major minor
CH3CH2OCH3
NaOCH3 = strong base and strong nucleophileCH3CH2Br + NaOCH3
CH2 CHS2N2 or E2
2nd order kinetics
CH3CH2Br + NaOCH3
1o Halide favors SN2 over E2

CH3CH2Br + NaOCH3

SN1 vs. SN2 vs. E1 vs. E2

Example: Predict the product(s) and mechanism of the following

reaction. If more CH3productCH
than2one
NaOCH CH CH2
or 3mechanism is possible, explain
which is/are most likely.
CH CH OH3 2

CH CHCH
NaOCH CH CHCHCH CH3 CH
CH
CHCH CH2 2
CH3CHCH3 NaOCH
3 CH
22 3 33
3 33 + CH3CH CH2
NaOCH2CH3
Br CH Br
CH3CHCH2OH
OH OCH 2
CH 3
3 2
CH3CH2OH

NaOCH2CH3 = strong base/nucleophile

CH3CHCH
CHCH3 3
CH CHCH3 3 CH
CH3CHCH 3
CH3CHCH3
3
CH CHCH3
2nd order kinetics
Br
Br S N 2 3
OCH
OCH or E2
CHCH
Br 2 2 3 3 OCH2CH3
Relative amounts of SN2 vs E2 depends on temperature.

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SN1 vs. SN2 vs. E1 vs. E2

CH3OH
CH3OH
D
Example: Predict the product(s) and mechanism ofDthe following
reaction. If more than one product or mechanism is possible,
CH3 explain CH3
CH3
CH3OH CH3
which is/are
CHmost
OH likely. Br OCH3
3
D Br OCH3
D

CH3 CHCH
3
OHOHCH3
CH 3
CH3
+ CH3 +
CH2
CH2
3 CH3
 Br OCH3
Br  OCH3
major major trace
CH3 CH 2
CH3
CH3
CH3OH = weak CHBr CH3 or weak
nucleophile OCH base CH3
2
CH
1st
3 order kinetics SN1 or E1
3

Br OCH3
Saytzeff ’s orientation favored for elimination product.
CH2
CH3
CH2
CH3