Chemistry 233

Chapter 11 Problem Set – Pt. 2 (Elimination Reactions) Answer Key

1. The example below was given on the Ch. 9 Problem Set. Given what you now know, what product(s)
would you expect to isolate from this reaction?
+ Na O No Substitution Reaction
Br
This bulky base is a poor nucleophile
(NaOt-Bu)
Gives the Hofmann elimination product.
H
OtBu
Br
2. Specify how each of the following would affect the rate of an E2 reaction. E2 rate = k[RX][Base]
a. Increase changing the base from NaOCH3 to NaNH2.
Increased rate (H2N¯ is a stronger base than H3CO¯)
b. Increasing the concentration of base.
Increased rate
c. Decreasing the concentration of alkyl halide.
Decreased rate
d. Changing the alky halide from 2-bromo-2-ethylpentane to 2-bromopentane.
Decreased rate (in E2, 3º halide is more reactive than 2º halide)
e. Changing the alkyl halide from 2-bromopentane to 2-iodopentane.
Increased rate (I¯ is a better leaving group than Br¯)

3. Specify how each of the following would affect the rate of an E1 reaction. E1 rate = k[RX]
a. Changing the base from NaOH to H2O.
No change (in E1 the base has no effect on the rate)
b. Decreasing the concentration of base.
No change (in E1 the base has no effect on the rate)
c. Changing the solvent from acetone to methanol.
Increased rate (E1 reactions go faster in a polar protic solvent that stabilizes the LG and carbocation.
d. Changing the alky halide from 2-bromo-2-ethylpentane to 2-bromopentane.
Decreased rate (in E1, 3º halide is more reactive than 2º halide)

4. Predict the product(s) for each of the E2 elimination reactions below. Identify the major product for
each.
a.
O
(Zaitsev)
Br Heat

b. Cl Cl
NaOCH 3 Elim
(Zaitsev)
Ph Heat Ph Ph
H
H
orient H & Cl antiperiplanar
c. Br KOH
No Reaction (No β-hydrogen)
Heat

d. O
Br (Hofmann)

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 Chem. 233 – Chapter 11 – Pt. 2 Problem Set
5. Show the complete electron pushing mechanism for the reaction in question 4 part a.

H
βα O + Br + OH
Br Heat

6. Predict the product(s) for each of the E1 elimination reactions below. Identify the major product for
each.
a. H 2O
Br Heat

b.
I CH 3OH
Heat

c.
H 2SO 4
OH Heat

d. Br
CH 3OH
Heat

e. OH POCl 3
Pyridine

7. Show the complete electron pushing mechanism for the reaction in question 6 part c.
Here you are simply protonating the alcohol to make it a good leaving group, then using water or HSO4¯ as
a base to do the elimination step.

H HSO 4 H
+ H 2O
OH Heat OH2

carbocation
rearrangement

H 2O
+ H 3O H

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 Chem. 233 – Chapter 11 – Pt. 2 Problem Set
8. Circle the one in each of the following pairs that would be expected to give a higher yield of
elimination over substitution.

2° substrates tend to favor elimination over substitution

a. I
+ NaOH vs I + NaOH

Bulky base gives elimination only

b. Small base will give a
Cl + KO vs Cl + KO mix of elimination and
substitution products

c. Br Br Elimination is favored
+ CH 3O vs + CH 3O over substitution with
Low T High T heat

9. For each of the following reactions, predict the major mechanism (SN1, SN2, E1, or E2) and provide
the major product. Show correct stereochemistry where appropriate.

Strong bulky base

a. O E2 only
Cl E2
1° Cl: SN 2, E2

b. Strong base/strong Nu
Does not form because H
NaNH 2 E2, SN 2 and Br are not
antiperiplanar to give this
Br Heat product.
favors E1, E2 E2
2° Br: SN1, SN 2, E1, E2

c. Weak base/weak Nu
Br HOCH 3 E1, SN1 +
Heat E1
favors E1, E2 (both Zaitsev products)
You will also get the enantiomers if you
2° Br: SN1, SN 2, E1, E2 rearragne the carbocation to the other 3° position.
Strong Nu, but weak base
d. KSCH 3 favors SN 2
Cl SCH 3 SN2
acetone
1° Cl: SN 2, E2 polar aprotic
favors SN 2, E2

e. I Strong base/strong Nu
NaNH 2
E2, SN 2
E2
Heat
favors E1, E2
2° allylic I: SN1, SN 2, E1, E2

f. Cl Strong base/strong Nu Cl
NaNH 2 E2, SN 2
DMF Can get double elimination
Cl polar aprotic E2 to give the alkyne
2° Cl: SN1, SN 2, E1, E2 favors SN 2, E2 2° substrates, E2 typically favored over SN 2
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 Chem. 233 – Chapter 11 – Pt. 2 Problem Set
g. Weak base/weak Nu
Br
NH 3 E1, SN1
+
NH 2
2° Br: SN1, SN 2, E1, E2 E1 SN1
h. Strong Nu, but weak base
Br SCH 3
NaSCH 3 favors SN 2
SN2

2° Br: SN1, SN 2, E1, E2

i. I Strong bulky base

O E2 only
(bulky base gives
Hofmann Product)
E2
2° I: SN1, SN 2, E1, E2

j. Weak base/weak Nu
NH 3 E1, SN1
Br
Heat E1
favors E1, E2
3° Br: SN1, E1, E2
Weak base/weak Nu
k. CH 3OH E1, SN1
I H 3CO
+
3° I: SN1, E1, E2 E1 SN1
Strong base/strong Nu
l. KOH E2, SN 2 H
E2
Heat
Br
2° Br: SN1, SN 2, E1, E2 favors E1, E2
Weak base/weak Nu
m. H
H 2O E1, SN1
+
Br Heat E1 H
favors E1, E2
2° Br: SN1, SN 2, E1, E2
Cl- is a good Nu, but weak base
n.
HCl SN 2 (or SN1) Cl
OH
SN2

2° LG: SN1, SN 2, E1, E2

o. HSO 4- is a weak base, but non
H 2SO 4
OH nucleophilic. E1 only
Heat E1
favors E1, E2
2° LG: SN1, SN 2, E1, E2
10. Draw an energy diagram for reaction m in question 9.
loss of RDS
LG You are not expected to know
+ Br relative TS energies between I1 & I2
Br and I2 and P
Int. 1
SM
E
rearr.
Int. 1
Int. 2
elim.
SM
P Int. 2
Rxn Progress P

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 Chem. 233 – Chapter 11 – Pt. 2 Problem Set

11. Synthesis: Propose a synthesis for each of the following starting with 2-bromobutane.
a. 2-butene
Br NaOCH 3
Heat

b. 2-butyne
Br
Br NaOCH 3 Br 2 NaNH 2
Heat (2 equiv)
Br
c. 2-butanol
Br NaOCH 3 H OH
Heat H 2O

d. butane
Br NaOCH 3 H2
Heat Pd/C

e. 2-methoxybutane
Br NaOCH 3 H OCH3
Heat HOCH 3
Could also treat 2-bromopropane directly with NaOCH3 to give the substitution product, however
it would likely be minor wile the elimination product would be the major product.

12. Show three reactions that can be used to eliminate 2-butanol to give 2-butene. Show two reactions
that can be used to eliminate 2-butanol to give 1-butene.

OH 1. TsCl
OH POCl 3 Pyr
Pyridine 2. NaOtBu
Heat
OH H 2SO 4
Heat OH 1. HBr
2. NaOtBu
OH 1. TsCl Heat
Pyr
2. NaOH
Heat

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