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Y:–
Br
Elimination involves removing the halide and an adjacent hydrogen atom to yield an alkene:
B:–
Br
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106
Chemistry S-20ab Week 2
CN– + Br
• What would be the rate law of this reaction? (Do you remember rate laws?)
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107
Chemistry S-20ab Week 2
H H3C
O + C Br
H
(CH2)5CH3
100% (R)-2-bromooctane
• Can you explain why that stereochemical result is observed for all SN2 reactions?
• Let’s take a look at the transition state for the SN2 reaction:
Nucleophile
approaches along
"proper" trajectory a
Nuc C LGp
c
b
Nucleophile
begins to bond a
Leaving group – carbon
Nuc C LGp bond begins to break
c
b
sp2 C
Transition state - a
Nucleophile – Transition state - Leaving
carbon bond
"halfway made" Nuc C LGp group – carbon bond
"halfway broken"
c
b
a
Past the Past the transition
transition state - Nuc C LGp state - Leaving
Nucleophile – group – carbon bond
carbon bond c b "almost broken"
"almost complete"
a
Nucleophile – carbon Leaving group
bond "complete" the Nuc C LGp
nucleophile's electron has left with its
c electron pair
pair now forms the new b
bond
Reading: Section 9.4
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108
Chemistry S-20ab Week 2
H
Br
HH
methyl bromide
rapid SN2
H3C
Br
H3C H
isopropyl bromide
slow SN2
H3C
Br
H3C
CH3
tert-butyl bromide
noSN2
H3C
CH3
H3C
Br
HH
neopentyl bromide
VERY slow SN2
Reading: Section 9.4
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109
Chemistry S-20ab Week 2
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110
Chemistry S-20ab Week 2
• Can you explain the relative leaving group ability of the following leaving groups?
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Chemistry S-20ab Week 2
• Stereochemistry:
Steric Effects:
Nucleophilicity:
Leaving-Group Ability:
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Chemistry S-20ab Week 2
H3C Br H3C H
Ph
C2H5O Na + + C2H5OH + Na Br
H
sodium H Ph Ph Ph
ethoxide
• Examine the stereochemistry of the above reaction. Why is this an example of anti-
elimination?
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Chemistry S-20ab Week 2
H3C Br
Ph
H
H Ph
FMO considerations
donor orbital - ! C–H acceptor orbital - !* C–Br
anti transiton state syn transiton state
H3C Br H Br
Ph
H H3C H
H Ph Ph
Ph
donor acceptor donor acceptor
best overlap poor overlap
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114
Chemistry S-20ab Week 2
KOEt
+ +
EtOH
Br 41% 14% 25%
• You may notice that the above percentages do not add to 100%. What do you suppose is
the other product that emerges from the above reaction?
• The choice of base can affect the distribution of products. For example:
Br KOEt
+
EtOH
71% 29%
Br KOtBu
+
tBuOH
28% 72%
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Chemistry S-20ab Week 2
CH3I + OH–
CH3I +
O–
Br + OH–
Br + CN–
Br +
O–
Br + OH–
Br + CN–
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Chemistry S-20ab Week 2
Br EtOH O
+
25°C
81% 19%
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Chemistry S-20ab Week 2
H 2O
+
S S R
• In fact, the products are: 33% S and 67% R. How can we explain this observation?
• Can we make any generalizations about the stereochemical outcome of SN1 reactions?
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Chemistry S-20ab Week 2
• It is often the case that higher temperatures favor elimination. For instance:
Br EtOH O
+
• One can ensure elimination by starting with an alcohol, instead of an alkyl halide, and
treating it with concentrated sulfuric acid. Can you propose a mechanism for this
reaction? Does this mechanism resemble any mechanism you have seen before?
conc.
OH H2SO4
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Chemistry S-20ab Week 2
(Note that SN1 and E1 reactions almost always occur together, although you can ensure
elimination by treating an alcohol with concentrated H2SO4.)
• Use the hierarchy to determine the primary product (and identify possible secondary
products) for each of the following reactions:
Br + CN–
Br + OH–
Br + H 2O
+ OH–
Br
+ CH3OH
Br
+ H2SO4
OH
Reading: Section 9.7
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