CHAPTER 7—STRUCTURE AND SYNTHESIS OF ALKENES; ELIMINATION

7-1 The number of elements of unsaturation in a hydrocarbon formula is given by:

2(#C) + 2 – (#H)
2
(a) Solve this equation for #H. Three double bonds
#H = 10
plus one ring makes 4 elements of unsaturation.

C8H10 has 4 elements of unsaturation.

(b) C5H10 ⇒ 2(5) + 2 – (10)

= 1 element of unsaturation
2
(c) Many examples are possible. Yours may not match these structures, but all possible answers must have
either one double bond or one ring, that is, one element of unsaturation.

2(3) + 2 – (4)
7-2 C3H4 ⇒ = 2 elements of unsaturation
2

Of the three structures, one has 1 triple bond, one has 2 double bonds, one has 1 ring plus 1
double bond.

7-3 Hundreds of examples of C4H6NOCl are possible. Yours may not match these, although all must
contain two elements of unsaturation. H Cl O
O Cl C N Cl N O
Cl NH2 N C C Cl
N
OH
OH H
7-4 Many examples (sometimes thousands) of these formulas are possible. Yours may not match these,
but correct answers must have the same number of elements of unsaturation. Check your answers in your
study group.
(a) C4H4Cl2 ⇒ C4H6 = hydrocarbon equivalent Cl Cl
Cl
C4H10 = saturated formula
a 4H deficiency = Cl
2 elements of unsaturation Cl
Cl
O OH
(b) C4H8O ⇒ C4H8 = hydrocarbon equivalent
C4H10 = saturated formula
O
a 2H deficiency =
1 element of unsaturation O O
(c) C6H8O2 ⇒ C6H8 = hydrocarbon equivalent O
O
C6H14 = saturated formula H C C C C OCH CH O
3 2 3
a 6H deficiency = 158
3 elements of unsaturation Copyright © 2017 Pearson Education, Ltd.
7-4 continued
O O
O N N C O O
(d) C5H5NO2 —using the formula: C C NH2
2(5) + 2 + (1) – (5) O
= 4
2
C N
Br N C CH2 Cl
(e) C6H3NClBr —using the formula:
Br NH
2(6) + 2 + (1) – (3 + 2)
= 5
2 Cl HC C C C C CH Br Cl

Note to the student: The IUPAC system of nomenclature is undergoing many changes, most notably
in the placement of position numbers. The new system places the position number close to the
functional group designation, which is what this Solutions Manual will attempt to follow; however,
you should be able to use and recognize names in either the old or the new style. Ask your instructor
which system to use.
7-5 The E/Z system is unambiguous and is generally preferred for designating stereochemistry around a
double bond. However, cis and trans are still used for geometric isomers from substituents on a ring.
(a) 4-methylpent-1-ene (b) 2-ethylhex-1-ene (Number the longest chain containing the double bond.)
(c) penta-1,4-diene (d) penta-1,2,4-triene
(e) 2,5-dimethylcyclopenta-1,3-diene (f) 3-methylene-4-vinylcyclohex-1-ene ("1" is optional)
(g) 3-phenylprop-1-ene ("1" is optional)
For comparison, these are the old IUPAC names for problem 7-5. The old names will not be used in this
Solutions Manual.
(a) 4-methyl-1-pentene (b) 2-ethyl-1-hexene
(c) 1,4-pentadiene (d) 1,2,4-pentatriene
(e) 2,5-dimethyl-1,3-cyclopentadiene (f) 3-methylene-4-vinyl-1-cyclohexene ("1" is optional)
(g) 3-phenyl-1-propene ("1" is optional)
Note to the student: How to tell whether a double bond has geometric isomers? Look at the four
groups bonded to the two carbons of the double bond: w, x, y, and z.

w y If w ≠ x AND y ≠ z, it will have geometric isomers.

C C If w = y (or x = z), it is the cis isomer.
x z If w = z (or x = y), it is the trans isomer.

7-6 Parts (b) and (e) do not show cis,trans isomerism.

(a)

(Z)-hex-3-ene (E)-hex-3-ene
(cis-hex-3-ene) (trans-hex-3-ene)
(c)

(2Z,4Z)-hexa-2,4-diene (2Z,4E)-hexa-2,4-diene (2E,4E)-hexa-2,4-diene

cis,cis-hexa-2,4-diene cis,trans-hexa-2,4-diene trans,trans-hexa-2,4-diene
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7-6 continued
(d) "Cis" and "trans" are not clear for this example;
"E" and "Z" are unambiguous.

(Z)-3-methylpent-2-ene (E)-3-methylpent-2-ene

1 H 1 Br In this example, cis and trans refer

(f) H H
2 4 2 4
to the relative positions of the Br
atoms, not the double bond. All
3 Br 3 H double bonds in rings of 7 or fewer
Br Br atoms must be cis.
cis-3,4-dibromocyclopent-1-ene trans-3,4-dibromocyclopent-1-ene
(Both Br atoms could also be (Both Br atoms could also
up, the enantiomer.) be inverted, the enantiomer.)
4
3 2
7-7 2
6
3 4 5
(a) 5 (b) (c) 3
2 1 1
1
4 5
trans-3-ethylhexa-1,4-diene 1-methylcyclopentene
cis-3,4-dimethylpent-2-ene (Whether cis or trans is not
(The only positions to attach two specified in the problem; the vinyl
methyl groups to make the double group is part of the main chain.
bond cis are at C-3 and C-4.) This could also be named as the E
isomer. The cis (Z) isomer is
equally good.)
4
Cl 5 2
Br
3 1 4
(d) (e) 3 (f) 5
2 1 2 3
1 4 Br
5-chlorocyclohexa-1,3-diene
(Positions of double bonds need 1,4-dimethylcyclohexene (E)-2,5-dibromo-3-ethylpent-2-ene
to be specified.) (The cis designation does not apply—
four different groups on the double
7-8 bond.)
Cl Cl Br
(a)
Br
(E)-3-bromo-2-chloropent-2-ene (Z)-3-bromo-2-chloropent-2-ene

(b)

(2E,4E)-3-ethylhexa-2,4-diene (2Z,4E)- (2E,4Z)- (2Z,4Z)-

H
(c)

H
Br (E)-3-bromo-2-methylhex-3-ene
(Z)-3-bromo-2-methylhex-3-ene Br

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7-8 continued
(d) (e)

(Z)-penta-1,3-diene (E)-penta-1,3-diene
no geometric isomer
(f)

Cl Cl Cl Cl
(2Z,5E)-3,7-dichloroocta-2,5-diene (2E,5E)-3,7-dichloroocta-2,5-diene
Cl Cl

Cl Cl
(2Z,5Z)-3,7-dichloroocta-2,5-diene (2E,5Z)-3,7-dichloroocta-2,5-diene
(g) no geometric isomers (An E double bond would be too highly strained.)

(h)

(Z)-cyclodecene (E)-cyclodecene

(i)

(1E,5E)-cyclodeca-1,5-diene (1Z,5E)-cyclodeca-1,5-diene (1Z,5Z)-cyclodeca-1,5-diene

7-9 NOT stereogenic: two H on end C preclude geometric isomers.

(a) Stereogenic: unequal groups on each side.
C C C C C C C C
* * * * *Each of the four stereocenters is marked with *.

trans,trans-octa-1,3,5-triene
trans,cis-octa-1,3,5-triene

cis,cis-octa-1,3,5-triene

cis,trans-octa-1,3,5-triene
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7-9 continued
(b) C C C C C C C C Whereas octa-2,4,6-triene has three stereogenic double bonds,
because of symmetry, the middle one has two equal and
indistinguishable ends, reducing the total number of
stereoisomers very much like a meso form with chiral
stereocenters.
isomers with trans in the middle isomers with cis in the middle

trans,trans,trans-octa-2,4,6-triene cis,cis,cis-octa-2,4,6-triene

trans,trans,cis-octa-2,4,6-triene cis,cis,trans-octa-2,4,6-triene
(same as cis,trans,trans- if numbered (same as trans,cis,cis- if numbered
in the reverse direction) in the reverse direction)

cis,trans,cis-octa-2,4,6-triene trans,cis,trans-octa-2,4,6-triene

7-10
The rate-limiting step in oxidation is abstraction of an atom A by atmospheric O2 to form A–OO• and a
carbon free radical. The energies of bond breaking and bond forming in this step determine whether it
will be successful, that is, whether the oxidation will occur.
It is important to note that atmospheric oxygen exists in a diradical form (•O–O•), so there is no
energy required to disrupt any bond in O2.

polyethylene
H

C + O2 C + H—OO• ∆H = –(192) + (400) =

+208 kJ/mole—endothermic—
H H 192 kJ/mole requires high temperature
400 kJ/mole

Teflon
F

C + O2 C + F—OO• ∆H = –(63) + (460) =

+397 kJ/mole—almost twice
F F 63 kJ/mole as endothermic—requires
460 kJ/mole very high temperature
Because the C-F bond is particularly strong, and the O-F bond is particularly weak, the energy required
for O2 to abstract an F atom is huge, almost twice as large as the energy required for O2 to abstract an H
from polyethylene. Both require high temperature to get over the energy barrier, but Teflon will
decompose at a much higher temperature because the rate-limiting step has a higher energy barrier.
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7-11
(a) The dibromo compound should boil at a higher temperature because of its much larger molecular weight.
(b) The cis should boil at a higher temperature than the trans as the trans has a zero dipole moment and
therefore no dipole-dipole interactions.
(c) 1,2-Dichlorocyclohexene should boil at a higher temperature because of its much larger molecular weight
and larger dipole moment than cyclohexene.
7-12 From Table 7-2, approximate heats of hydrogenation can be determined for similarly substituted
alkenes. The energy difference is approximately 6 kJ/mole (1.4 kcal/mole), the more substituted alkene
being more stable.
gem-disubstituted tetrasubstituted
116.3 kJ/mole 110.4 kJ/mole
(27.8 kcal/mole) (26.4 kcal/mole)

7-13 Use the values in Table 7-2. Alternatively, the relative values in Figure 7-8 could be used to reach the
same conclusions. Minor discrepancies between kcal and kJ are due to rounding.

(a) 2 x (cis-disubstituted − trans-disubstituted) =

2 x (118.5 − 114.6) = 7.8 kJ/mole more stable for trans, trans trans,trans cis,cis
(2 x (28.3 − 27.4) = 1.8 kcal/mole) more stable

(b) monosubstituted − gem-disubstituted = 126.3 − 118.2 = 8.1 kJ/mole

(30.2 − 28.3 = 1.9 kcal/mole)
2-methylbut-1-ene is more stable
disubst. monosubst.
more stable

(c) gem-disubstituted − trisubstituted = 118.2 − 111.6 = 6.6 kJ/mole

(28.3 − 26.7 = 1.6 kcal/mole)
2-methylbut-2-ene is more stable
trisubst. disubst.
more stable

(d) cis-disubstituted − trisubstituted = 117.7 − 111.6 = 6.1 kJ/mole

(28.1 − 26.7 = 1.4 kcal/mole)
2-methylpent-2-ene is more stable
trisubst. cis-disubst.
more stable

7-14
CH3
(a) Slightly strained but stable (b) Could not exist as the ring size must be 8
with C=C in a 5-membered atoms or greater to include trans double
CH3 ring. bond—see answer to part (e).

(c) CH3
The trans refers to the two methyls since this compound can exist, rather than the
trans referring to the alkene, a molecule that could not exist because the ring
CH3 would have too much strain. A ring must have 8 or more atoms before a trans
double bond can exist in the ring.

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7-14 continued
(d) CH3

stable—trans in 10-membered ring

CH3

(e) Unstable at room temperature—it cannot have trans alkene in 7-membered ring (possibly isolable at
very low temperature—this type of experiment is one of the challenges chemists attack with gusto).
(f) Stable—the alkene is not at a bridgehead.
(g) Unstable—violates Bredt's Rule (alkene at bridgehead in 6-membered ring).
(h) Stable—alkene is at bridgehead in 8-membered ring.
(i) Unstable—violates Bredt's Rule (alkene at bridgehead in 7-membered ring).
7-15
(a)

aromatic and not aromatic, not aromatic, aromatic but

conjugated; fully conjugated partially conjugated; not conjugated
MOST STABLE LEAST STABLE
O O O
(b)

only 2 pi bonds conjugated all 3 pi bonds conjugated; all 3 pi bonds isolated;

MOST STABLE LEAST STABLE

(c)

all 3 pi bonds isolated; all 3 pi bonds conjugated aromatic; only 2 pi bonds

LEAST STABLE MOST STABLE conjugated
7-16
If the CH3OH acts as a nucleophile, the product will be a substitution; the overall mechanism will be SN1.
H CH3 H CH3
H
C O O O O
H CH3 H CH3
H HH H
H H H
+ CH3OH2
7-17 H3C
(a)
Br Br– O H O CH3
C
H3C O H H3C O H + CH3OH2

The SN1 mechanism begins with ionization to form a carbocation, attack of a nucleophile, and in
the case of ROH nucleophiles, removal of a proton by a base to form a neutral product.
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7-17 continued
(b) In the E1 reaction, the solvent (methanol, in this case) serves two functions: it aids the ionization
process by solvating both the leaving group (bromide) and the carbocation; and second, it serves as a base
to remove the proton from a carbon adjacent to the carbocation in order to form the carbon–carbon double
bond. The SN1 mechanism adds a third function to the solvent: the first step is the same as in E1,
ionization to form the carbocation; the second step has the solvent acting as a nucleophile—this step is
different from E1; third, the solvent acts like a base and removes a proton, although from an oxygen (SN1)
and not a carbon (E1). Solvents are versatile!
7-18 H H H H
H
C H CH2 H H
O CH3 O CH3
C C C C
H H
E1 C E1 C

H H
H2C H
C
C H
C
SN1

O CH3
O CH3 S N1
H
H
H H H H
CH3 CH3 H H
C C
C O CH3 C OCH3 C CH3 C CH3
O O
O CH3
H OCH3
H
H
H

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7-19 This solution does not show CH3
complete mechanisms. Rather, it Br
shows the general sequence of all H3C 2-bromo-3-methylbutane
four pathways leading to five CH3
different products. H
Ethanol is the solvent shown here H
in the substitution products; it is
often used in solvolysis reactions. ionization

CH3 CH3
hydride shift H
unrearranged H3C H3C C rearranged
2° carbocation C CH3 CH3 3° carbocation
H
H H
E1 E1
S N1 S N1

CH3CH2 CH3 CH3 CH3 CH3

O H H
H3C H2C H3C H3C
CH3 CH3 CH3 CH2
H H O
H H H CH2CH3 H

Five unique products CH3 CH3

shown in the boxes.
One alkene can be H3C H3C
produced from either the CH3 same CH3
2° or the 3° carbocation. compound
H H
two possible E1 products two possible
E1 products

7-20 Substitution products are shown first, then elimination products.

Ph
(b) Ph
OCH2CH3
(a) +
+ Ph = phenyl
OCH3

OH
OH
(c) CH3 CH3 CH3 CH2
+ CH3 +

SN1 product without SN1 product with major E1 product with or

rearrangement rearrangement without rearrangement minor

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 without rearrangement with rearrangement
7-21
CH3 OCH2CH3
CH3 C CH CH3 CH3 C CH CH3
CH3 OCH2CH3 CH3 CH3
7-22
Br
CH CH2 Rearrangement by ring expansion is
H rearrangement theoretically possible but very
C unlikely because the ring size is
CH3OH hydride shift
already at the optimum six-
∆ membered.
ionization
unrearranged rearranged

SN1 reactions: CH3 CH3

O O
CH H
H 1
O O
H CH3 H CH3

CH3 CH3

O O
C O H O 2
H CH3 H CH3

E1 reactions: H
H
C H2C
CH CH H CH CH
H
O O
H CH3 3 H CH3 4
and

H SAME
C H CH
H
C O 3 C H O C 5
H CH3 H CH3 CH
and

5 is the major elimination product: trisubstituted and endocyclic (in the ring), the more stable position.
3 is trisubstituted but is exocyclic, a less stable position.
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7-23

NaOCH2CH3
OCH2CH3
E2—minor E2—major SN2—probably
product—less product—more very small
Br substituted alkene substituted alkene amount because
(monosubstituted) (trisubstituted) of steric hindrance

7-24 Br OCH3
NaOCH3
(a)
minor alkene— major alkene— SN2 product—some
monosubstituted disubstituted will be formed on a
NaOCH3 (cis + trans) 2° carbon
Br
(b)
No SN2 product will be
formed; SN2 cannot
major alkene— minor alkene— occur at a 3° carbon.
trisubstituted disubstituted
(cis + trans)
Br OH
NaOH
(c)

minor alkene— major alkene— SN2 product—very

monosubstituted trisubstituted small amount because
2° carbon is hindered
7-25 H3C Br
3°
(a) NaOH Strong base (hydroxide) will give second
+ order reactions; a 3° alkyl halide precludes
acetone SN2, so E2 is the only option.
major minor
E2 E2

H3C Br
3° E2 is only option; hindered base gives less
(b) (CH3CH2)3N
+ substituted double bond as major isomer.

minor major
E2 E2
Cl OCH3
(c) 2° NaOCH3
+ Major product is difficult to predict
CH3OH for unhindered 2° halides and strong,
unhindered bases/nucleophiles; both
Cl SN2 E2 SN2 and E2.
(d) 2° NaOC(CH3)3 NaOC(CH3)3 is a bulky base and a poor
nucleophile, minimizing SN2.
(CH3)3COH
E2 168
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7-26 Base:
Ph
H H
S Ph
Br H H3C H
= C C C C
S Ph
H3C H H3C Ph
Ph Br cis
Ph

7-27 CF3 H HBr CF3

CH3 H
(a) H
H Br rotate
H and Br
CH3CH2 180°
H CH3 CH3CH2 CF3 CH3 Br
CH2CH3 HO–
HO–
H OH CH3CH2 CF3
C C
CH3 H
E2 elimination
CH3CH2
CH3 HCF3
Since hydroxide is a strong base, the reaction
SN2 product will be second order: on a 2° alkyl bromide,
both substitution and elimination will occur.
(b) Ph hindered base
H H Ph Ph
(CH3CH2)3N
C C
Ph Note that these products are
Br H geometric isomers. If a reaction
Br Br
only alkene isomer starts with stereoisomers and
meso E2 produces stereoisomers, that is
Ph hindered base the definition of a stereospecific
(c) H H Ph reaction.
(CH3CH2)3N Br
C C
Br H
Ph Br Ph
one enantiomer only alkene isomer
of the d,l pair E2

H Cl HO H
(d) SN2 is the only mechanism possible because
NaOH no H can get coplanar with Cl; an elimination
acetone product would violate Bredt's Rule.

1
2 Cl (CH3)3CO
(e) H
3 D
H H
H
Models show that the H on C-3 cannot be anti-coplanar with the Cl on C-2. Thus, this E2 elimination must
occur with a syn-coplanar orientation: the D must be removed as the Cl leaves.
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7-27 continued π bond
(f) CH3 rotate H
H CF3 back H CF3 O
carbon CH3CH2 CH3
H CF3
hindered base:
H CH2CH3 CH3CH2 CH3 E2 only
Br Br
H and Br must be 180°. H CH2CH3 only E2
product
F3C CH3

7-28 As shown in Solved Problem 7-5, the H and the Br must have trans-diaxial orientation for the E2
reaction to occur. In part (a), the cis isomer has the methyl in the equatorial position, the NaOCH3 can
remove a hydrogen from either C-2 or C-6, giving a mixture of alkenes where the most highly
substituted isomer is the major product (Zaitsev). In part (b), the trans isomer has the methyl in the axial
position at C-2, so no elimination can occur at C-2. The only possible elimination orientation is toward
C-6. Br CH3 CH3
H3C
1 NaOCH3
(a)
Zaitsev orientation
6 CH3OH
H
Either H H major minor
can be removed.

(b) Br CH3
H
1
NaOCH3
Only alkene formed; stereochemistry of E2
6 CH3OH precludes other isomer from forming.
H3C
Only this H H
can be removed.

CH3 no hydrogens trans diaxial to the Br

7-29 E2 elimination requires that the H and the
leaving group be anti-coplanar; in a chair cyclohexane, CH3
this requires that the two groups be trans diaxial. H
However, when the bromine atom is in an axial
position, there are no hydrogens in axial positions on H
adjacent carbons, so no elimination can occur. H
Br axial

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7-30 H
H H H
(a) H

Br H
H KOH
H Br axial + H
H H

Br
Br equatorial H
H H
Showing the chair form of the decalins makes the answer clear. The top isomer locks the H and the Br that
eliminate into a trans-diaxial conformation—optimum for E2 elimination. The bottom isomer has Br
equatorial where it is exceedingly slow to eliminate.
(b) Br
KOH

In this cis isomer, the Br is in the optimum axial position

Br for elimination while the large isopropyl group is in the
Br must be axial to eliminate by E2, energetically preferred equatorial position; this will be
forcing the large isopropyl group axial, a the reactive conformer.
very unstable conformer; this trans isomer
will be exceedingly slow to react as the
preferred conformer will be diequatorial.

7-31 Models are a big help for this problem. CH3

(a) Br
CH3 CH3
NaOCH3 H
H
=
H H
H CH CH3 H CH3
3

the only H the only elimination

trans diaxial product
H H H
(b) Br
NaOCH3
= H
H H
H H D
H D D H
(from elimination of H and Br)
+
both trans diaxial—
gives two products H H

=
H H
H H H
H
(from elimination of D and Br)
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7-32
The base NaOEt is strong and not hindered, so this
(a) + reaction will follow the E2 mechanism. The product
ratio will follow Zaitsev's Rule: trisubstituted double
MAJOR MINOR bond is major, and monosubstituted double bond is minor.

(b) This E1 reaction is complicated because the carbocation intermediate in two possible ways, and each
carbocation can give two possible alkene products.
unrearranged carbocation rearranged carbocation 1 rearranged carbocation 2
H H H
H
C C C
C

SAME +
+ +

Five different alkene products are possible in this E1 reaction. The ratio of products is difficult to
predict because it depends on the rate of rearrangement and the relative amounts of the two different
rearrangements. The safest prediction is that the most stable alkene is most likely the major product: of
these five alkenes, the trisubstituted double bond in the six-membered ring is the most stable (the one in
the box), so it is likely to be the major product.
Br δ
–
Follow-up question to Solved Problem 7-6(a):
In the E2 transition state, the C—H bond
and the C—Br bond are stretched as the CH3
O—H bond is being formed. H

H H trans diaxial to Br

δ– O
CH3

Follow-up question to Solved Problem 7-6(b):

CH3 rearrangement
CH3 CH3
CH3OH by hydride shift C All of the products
H shown below are derived
∆ C C from one of these two
I ionization H H carbocations.
I H
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Follow-up question to Solved Problem 7-6(b), continued
SN1 on unrearranged carbocation
CH3 CH3 CH3
CH3 CH3
C O O O O
H H CH3 H CH3
H H H
E1 on unrearranged carbocation
CH3
CH3 CH3 CH3
H
O H CH3
C H CH3 C O
H H H H
major H H minor
H

SN1 on rearranged carbocation CH3 CH3

CH3 CH3
CH3
C C O C O
O H O
H CH3 H CH3

E1 on rearranged carbocation H H
H
CH3 CH3 C C
C C H C H
C O O
H H CH3 H H CH3
H major minor

7-33
(a) Ethoxide is a strong base/nucleophile—second-order conditions. The 1° bromide favors substitution
over elimination, so SN2 will predominate over E2.
O
substitution—major elimination—minor
(b) Methoxide is a strong base/nucleophile—second-order conditions. The 2° chloride will undergo SN2 by
backside attack as well as E2 to make a mixture of alkenes.
OCH3

elimination— elimination—
substitution minor alkene major alkene
(cis + trans)
(c) Ethoxide is a strong base/nucleophile—second-order conditions. The 3° chloride is hindered and cannot
undergo SN2 by backside attack. E2 is the only route possible.
CH3 C CHCH3 CH2 C CH2CH3
major minor
CH3 CH3
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7-33 continued
(d) Heating in ethanol are conditions for solvolysis, an SN1 reaction. Heat also promotes elimination.
OCH2CH3

CH3 C CH2CH3 CH3 C CHCH3 Substitution and

elimination are possible.
CH3 SN1 CH3 E1
major elimination product
(e) Hydroxide is a strong base/nucleophile—second-order conditions. The 1° iodide is more likely to
undergo SN2 than E2, but both products will be observed.
CH3 CHCH2OH CH3 C CH2
CH3 CH3
substitution—major elimination—minor
(f) Silver nitrate in ethanol/water are ionizing conditions for 1° alkyl halides that will lead to
rearrangement followed by substitution on the 3° carbocation. (No heat, so E1 is unlikely.)
OCH2CH3 from ethanol as OH from water as
nucleophile nucleophile
CH3 C CH3 CH3 C CH3

CH3 CH3
(g) Ethoxide in ethanol on a 3° halide will lead to E2 elimination; there will be no substitution.
CH3 CH2

major alkene minor alkene

trisubstituted disubstituted
(h) Heating a 3° halide in methanol is quintessential first-order conditions, either E1 or SN1 (solvolysis).
CH3 CH2
CH3 OCH3

substitution elimination (E1): (trace)

(SN1)

Solved Problem 7-7(b): removal of protons from carbocation intermediates:

unrearranged rearranged
H H H
H2
C H C H C C
C C C C CH3 C CH3
H H H H H
H H C
H
H2O H2O H2O H2O
H H H
H2
C H C H C C
C C C C CH3 C CH3
H
H H C
H
SAME
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7-34 In these mechanisms, the base removing the final proton is shown as water. Other alcohols are
just as likely to serve as the base.
(a) H

OH O H H H
H OSO3H ∆ C H2O
H as base

H H
H H
(b) OH O H
H OSO3H ∆ C

H H

H2O
as base H2O as base

cis + trans minor isomer

major isomer

H
(c) 2° H
OH O H H rearrange— H
H OSO3H ∆ C hydride shift

C
CH3 CH3 H CH3
CH3 3°

from unrearranged 2° carbocation H from rearranged 3° carbocation

H
H
H H H H2O
H2O
H H as base CH3
H
C as base greatest amount
CH3
C
H CH2
H2O H
CH3
H H
as base H
H2O
as base
CH2
CH3
least amount
greatest amount

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7-34 continued
H OSO3H ∆
(d) C
C
OH O H
H
H
When proposing mechanisms, always look for what bonds are broken and what H2O
new bonds must be formed. In this problem, the new ring must come from the as base
pi electrons forming a new sigma bond at a 3° carbon, which must have been a
carbocation.

7-35 H—A is the generic symbol for an acid.

(a) Only one elimination product is possible.
H H
OH O H H

C H C H
H A ∆ H2O
C C
–H2O H
H H

benzylic—
resonance-stabilized
(b) Three elimination products are possible: two from an unrearranged carbocation, and two from a
rearranged carbocation, one product of which is the same to both pathways.
CH3 CH3 CH3
H H3C H
H
C C
OH H A O ∆ H
C C
H –H O H
2

unrearranged rearranged
from unrearranged carbocation

H2O CH3
H3C H H3C H
C C C
H H H
C AND C + C
C C
H H2O
H H
from rearranged carbocation SAME
H
H H H H
C H2O CH3 C
H H
C C C
H +
C AND C C
H H
H2O
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7-35 continued
(c) Three elimination products are possible: the intermediate carbocation is allylic, with positive charge
shared by two different carbons. An H can be removed from any of three carbons adjacent to positively-
charged carbons.

H A ∆
H C C C
H3C OH H3C O –H2O H H

H
Although the two resonance forms do not represent real structures, each can be treated separately to
determine the alkenes that could be produced. Resonance braces omitted for space reasons.
H
H
C C
H H2O
C C
H H

H H
H2O H
C C C
H H
+
H C C H C C H C C
C H C H C H
H H
H H2O H H

7-36
(a) ∆G° = ∆H° − T∆S°
= + 116,000 J/mol − 298 °K (117 J/°K•mol) = + 116,000 J/mol – 34,866 J/mol
= + 81,134 J/mol = + 81.1 kJ/mol (+19.3 kcal/mole)
∆G° is positive, the reaction is disfavored at 25°C.
(b) ∆G1000 = + 116,000 J/mol − 1273 °K (117 J/°K•mol) = + 116,000 J/mol – 148,941 J/mol
= − 32,941 J/mol = − 32.9 kJ/mol (– 8.0 kcal/mole)
∆G is negative, the reaction is favored at 1000°C.

7-37
(a) Basic and nucleophilic mechanism: Ba(OH)2 is a strong base.
(b) Acidic and electrophilic mechanism: the catalyst is H+.
(c) Free radical chain reaction: the catalyst is a peroxide that initiates free radical reactions.
(d) Acidic and electrophilic mechanism: the catalyst BF3 is a strong Lewis acid.

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7-38 H H H H H H H
(a) H OSO3H
CH3 C C C OH CH3 C C C OH OSO3H

H H H H H H
∆
H H H H H hydride H H H
shift
CH3 C C CH3 CH3 C C C H CH3 C C C + H2O
E+Z H2O
H H H H H
but-2-ene
major product This 1° carbocation would be
H2O very unstable.
H H H

CH3 C C C H but-1-ene
minor product
H

(b) Br H
S N2
+ NaBr
H Na+ OCH3
O CH3
as a nucleophile
Br
E2 H
H + NaBr + CH3OH
Na+ O CH3
H as a base H
H
"B"
(c)
H OSO3H ∆ H H
H2O +
C
OH O H "A"
Pi electrons
H form sigma
bond at carbo- H2O "A"
cation.
"B"
H
H
H2O

C
new bond

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7-39
H H H
(a) H H
OH H OPO3H2 OH ∆ C

H
H2O H
H
+ H2O
H

(b) CH2 OH CH2 OH CH2

H OSO3H ∆ This 1° carbocation would be

− H2O very unstable.

Two possible rearrangements

1. Hydride shift H

CH2 H C H CH2 CH3

H C H
H2O
H

2. Alkyl shift—ring expansion

CH2 H H
H
H C C H
C H2O
H

(c) carbocation formation

HO H O H H

H OSO3H ∆ C
+ H2O
H H

continued on next page

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7-39 (c) continued
without rearrangement
H H
H H
C H H2O H

H
H H

H H
H
C H H2O H
H H
H H
E+Z

with hydride shift

H H H
H
C H H2O
C
H H H
H H H
H2O H H
H
(d)

∆
H OSO3H C
H E1 product from
H OH H O H H unrearranged
H carbocation
+ H2O
rearrangement by alkyl shift
3°
C
C
2° H

E1 on rearranged carbocation

H H2O

H3O
C
H2O
H H H

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7-40 (a) (b) (c) (d)
Cl
Cl alternate name: cyclopentadiene
(e) (f) (g) Br (h) (i)

7-41 (a) neither—two hydrogen on one carbon (b) Z (c) E (d) Z

7-42 Parts (a) and (d) have no geometric isomers.

(b) (c)

trans-pent-2-ene cis-pent-2-ene trans-hex-3-ene cis-hex-3-ene

(E)-pent-2-ene (Z)-pent-2-ene (E)-hex-3-ene (Z)-hex-3-ene
Br
(e) trans-1,2-dibromopropene Br cis-1,2-dibromopropene
(E)-1,2-dibromopropene (Z)-1,2-dibromopropene
Br
Br
(f) Cis and trans do not apply to the C=C at C-1, only the one at C-3. The E/Z system is unambiguous.
Br Cl Br Cl
trans trans Z Z
Cl Z E Br E E Cl Z Br E
cis cis

7-43 These names follow the modern IUPAC system of placement of position numbers.
(a) 2-ethylhex-1-ene (Number the longest chain containing the double bond.)
(b) 3-ethylhex-2-ene
(c) (3E,5E)-2,6-dimethylnona-1,3,5-triene
(d) (Z)-4-ethylhept-3-ene
(e) 1-cyclopentylcyclohexa-1,3-diene
(f) (3Z,5Z)-6-bromo-3-(chloromethyl)nona-1,3,5-triene
7-44
F
(a)
F F
F F
(Z)-1-fluoro- (E)-1-fluoro- 2-fluoro- 3-fluoro- fluorocyclopropane
prop-1-ene prop-1-ene prop-1-ene prop-1-ene

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7-44 continued
(b) C4H7Br has one element of unsaturation, but no rings are permitted in the problem, so all the isomers
must have one double bond. Only four isomers are possible with four carbons and one double bond, so
the 12 answers must have these four skeletons with a Br substituted in all possible positions.

trans cis
enantiomers
Br Br H Br
Br
H Br
Br
Br
Br Br
Br
Br
Br

(c) Cholesterol, C27H46O, has five elements of unsaturation. If only one of those is a pi bond, the other
four must be rings. (The structure of cholesterol can be found in text section 25-6.)
7-45 (a) Neither cis nor trans is defined for the double bond beginning at C-2 because none of the four
groups are the same.
(b) All are 3-methylhepta-2,4-diene.The E/Z nomenclature is unambiguous and is preferred for all four
of these isomers.

7-46
H Cl F F F CH3
(a) Cl Cl (b)
Cl H CH3 F
H H H H
dipole moment = 0 dipole moment = 0

F F F F larger dipole moment

(c) (no bromines opposing the
Br Br H H dipole of the fluorines)

7-47
more stable than by 4 kJ/mole

more stable than by 16 kJ/mole

Steric crowding by the tert-butyl group is responsible for the energy difference. In cis-but-2-ene, the two
methyl groups have only slight interaction. However, in the 4,4-dimethylpent-2-enes, the larger size of the
tert-butyl group crowds the methyl group in the cis isomer, increasing its strain and therefore its energy.
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7-48

endocyclic exocyclic endocyclic exocyclic

trisubstituted disubstituted trisubstituted trisubstituted

9 kJ/mole 5 kJ/mole
A standard principle of science is to compare experiments that differ by only one variable. Changing more
than one variable clouds the interpretation, possibly to the point of invalidating the experiment.

The first set of structures compares endo and exocyclic double bonds, but the degree of substitution on the
alkene is also different, so this comparison is not valid—we are not isolating simply the exo or endocyclic
effect. The second pair is a much better measure of endo versus exocyclic stability because both alkenes are
trisubstituted, so the degree of substitution plays no part in the energy values. Thus, 5 kJ/mole is a better
value.

7-49
The carbocation produced in this E1 elimination is
(a) + + 3° and will not rearrange. The product ratio follows
the Zaitsev rule.
major minor trace amount

(b) The carbocation produced in this E1

+ + elimination is 2° and can either eliminate to
give the first two alkenes, or can rearrange by
trace—from from either from rearranged a hydride shift to a 3° carbocation which
unrearranged unrearranged 3° carbocation would produce the last two products. The
2° carbocation 2° carbocation amounts of the last two products are not
or rearranged predictable as they are both trisubstituted, but
3° carbocation the first product will certainly be the least.
The carbocation produced in this E1
elimination is 2° and can either eliminate to
(c) + + give the first alkene, or can rearrange by a
methyl shift to a 3° carbocation which would
produce the last two products. The middle
trace—from major minor product is major as it is tetrasubstituted
unrearranged versus disubstituted for the last structure and
2° carbocation from rearranged from rearranged
3° carbocation 3° carbocation monosubstituted for the first structure.

7-50
(a) (b) + +
only product minor
major
CH3 CH3
(c) + (d) (e) Br NaOH
+

major minor The E2 mechanism requires anti-

coplanar orientation of H and Br.
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7-51 The bromides are shown here. Chlorides or iodides would also work.

(a) Br (b) Br (c) (d) (e)

or
Br Br Br
Br

7-52
CH3 CH3
(a) (b) (c) (d)
disubstituted
trisubstituted disubstituted
trisubstituted
7-53 CH3 CH3
(a) (b) (c)
major minor
major minor minor

7-54

(a)

(b)

(c)

(d)

7-55
(a) + (b) +

major minor
major minor
CH3 Only product from E2—anti-
coplanar is possible only
(c) + (d) from carbon without CH3 by
removing H and Cl.
major minor D
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7-55 continued
ax
(e) (CH3)3C Cl (CH3)3C
1 KOH
3 4 ∆
Cl (CH3)3C Cl
eq
Cl Cl
The conformation must be considered because the leaving
group must be in an axial position. The tert-butyl group is so (CH3)3C
large that it must be equatorial, locking the conformation into
the chair shown. As a result, only the Cl at position 4 is axial,
so that is the one that must leave, not the one at position 3.
Two isomers are possible but it is difficult to say which would
be formed in greater amount. Cl
(f) H H
H Br
Only one of the two Br atoms is in KOH
the required axial position for E2
elimination. There are axial H Br ∆
atoms at the two adjacent carbons, Br Br
H H H
so two alkene products can be
formed. Predicting major and minor
would be difficult.
7-56 S N2
Br2 Br Br KOH Br NaOEt OEt
(a) (b) (c)
hν ∆ cold to
avoid E2
all positions from (a) from (a)
equivalent or KO-t-Bu
or SN1: EtOH, ∆
Br Br
S N2
Br NaOH OH
NBS KOH
(d) (e) (f)
hν ∆ cold to
avoid E2
from (b) or low conc. from (d) or KO-t-Bu from (a)
or SN1: H2O, ∆
of Br2 , hν

7-57
OH H2SO4
(a)
heat

Br NaOC(CH3)3 Other bases could also be used. The hindered bases would
(b)
heat minimize the amount of substitution that would occur.

(c) Br2 , hν Br NaOC(CH3)3

heat

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7-58 "Ph" is the abbreviation for the phenyl substituent.
Br OCH2CH3 solvolysis conditions—SN1
If the reaction mixture got too
Br2 CH3CH2OH warm, some E1 elimination might
Ph hν Ph ∆ Ph occur.
(NBS can also be used for
benzylic bromination) Using a hindered base like tert-
Benzylic bromination is very butoxide will give exclusively the
NaOC(CH3)3
selective; dibromination might E2 product, with no competing SN2
∆ Ph
occur if an excess of Br2 is used. as KOH or NaOCH3 might give.
7-59 H H H
– H2O H H
OH H OSO3H OH ∆ C H2O

H
H
H2O H

OSO3H E1 works well because only one carbocation and

only one alkene are possible. Substitution is not a
H problem here. The only nucleophiles are water,
C H which would simply form starting material by a
+ HSO4− reverse of the dehydration, and bisulfate anion.
H Bisulfate anion is an extremely weak base and poor
nucleophile; if it did attack the carbocation, the
H unstable product would quickly re-ionize, with no
net change, back to the carbocation.

7-60 δ–
(a) H O CH3 H O CH3 HOCH3

Br
δ– Br
Br
Methoxide is a strong base and nucleophile so the reaction is second order. The Br is on a 3° carbon so SN2
is not possible, only E2. The transition state shows bond-forming and bond-breaking with dashed bonds.

transition state
The reaction-energy diagram for a one-step activation
mechanism like E2 has one peak. energy
energy

reactants products

reaction coordinate

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7-60 continued
(b) H H O CH3
H O CH3 Br
HOCH3 H H
C
∆
Br slow
3° carbocation
intermediate intermediate carbocation

The reaction-energy diagram for a two-step

mechanism like E1 has two peaks, with the

energy
first step as the slow step with higher
activation energy.

reaction coordinate

7-61
(a) HOCH3
∆ C O CH3 O CH3
– Br–
Br 3° carbocation; H O H
no rearrangement H3C H

H O CH3
S N1
C H C O
E1 H3C
C C

E1
C C
C O CH3 C
H H H H

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7-61 continued
This 1° carbocation would be very unstable.

H
(b) H OSO3H ∆ CH2
OH O H + H2O
H
alkyl shift
hydride ring expansion
shift
H2 H
C
C C H
H H2O
H2O H
H H2O

H
This alkene could be produced from the unrearranged
carbocation, but the 1° carbocation has such a short lifetime
that it is more reasonable to propose the pathway through the H
rearranged 3° carbocation.

(c) EtOH
H OEt
∆ H OEt
C
H H OEt H OEt
Br H
H
H H OEt

Et H
H OEt O OEt
H H OEt

7-62
(a) The first step in this first-order solvolysis is ionization, followed by rearrangement.
H
H H
hydride C
Br CH2 CH3OH H CH2 shift CH2
Br – C
H ∆
allylic!

continued on next page

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7-62(a) continued H H
E1
H C H
CH2 CH2
CH3OH CH3OH2
H

S N1 H3C
H OCH3
H O H
C CH3OH CH3OH
CH2 CH2 CH2

CH3OH2

H3C H
H H
O OCH3

CH2 CH3OH CH2 CH3OH CH2

CH3OH2

(b) The first step in this first-order solvolysis is ionization, followed by rearrangement.
CH3OH

∆ CH3OH CH3OH
C
H Br H H O H H OCH3
Br –
H3C SN1 product from
unrearranged
rearrangement by alkyl shift carbocation

C E1 on rearranged carbocation

C
H CH3OH2
C CH3OH

H H H

SN1 on rearranged carbocation

CH3OH2
C CH3OH CH3OH
O OCH3
H3C H

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7-63 All five products (boxed) come from rearranged carbocations. Rearrangement, which may occur
simultaneously with ionization, can occur by hydride shift to the 3° methylcyclopentyl cation, or by ring
expansion to the cyclohexyl cation.
This 1° carbocation would be very unstable.
H CH2 Br H CH2

Br – +

hydride shift
H
H CH2 CH2 CH3 CH2
C H H
HOCH3
H

H
CH3 CH3 O CH3 CH3 OCH3
C
HOCH3 HOCH3

alkyl shift (ring expansion)

H CH2 H H
H
C H
HOCH3
H

H
H
H O CH3 H OCH3
C HOCH3 HOCH3

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7-64 H H H
H
(a) H Br − H2O C
Br
SN1 OH OH Br
H
H H H
H Br Br
SN2 OH OH Br + H2O
H
(b)
H OSO3H ∆ C

C H2O
OH O H H
H
7-65 The symmetry of this molecule is crucial.
(a) Ph H Ph
Regardless of which adjacent H is removed by tert-butoxide, the
CH3 C C C CH3 product will be 2,4-diphenylpent-2-ene.
H Br H
(b) Here are a Newman projection, a three-dimensional representation, and a Fischer projection of the
required diastereomer. On both carbons 2 and 4, the H has to be anti-coplanar with the bromine while
leaving the other groups to give the same product. Not coincidentally, the correct diastereomer is a meso
structure.
π bond
Ph H Br H CH3
Ph
H 2
H3C H3C H H H Ph H
2 H3C Ph 3
Ph 2 Ph Br 3
H
H3C Ph
H3C CH3 Ph H
Br
H and Br are anti-coplanar CH3
7-66 H Ph Ph Ph
CHCH3
NaOEt CH 3 Ph
H + +
CH3 Ph CH CH
Br 2 3
Ph Ph Ph
2S,3R B A = E,Z mixture
H CHCH3
H Ph Ph Ph
NaOEt CH 3 CH 2 CH 3
+ +
CH3 Ph Ph
Ph Br Ph Ph
2S,3S C A = E,Z mixture
E2 dehydrohalogenation requires anti-coplanar arrangement of H and Br, so specific cis-trans isomers (B or
C) are generated depending on the stereochemistry of the starting material. Removing a hydrogen from C-4
(achiral) will give about the same mixture of E and Z (A) from either diastereomer.
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7-67 Begin with a structure of (S)-2-bromo-2-fluorobutane. Since there is no H on C-2, the lowest
priority group must be the CH3 . The Br has highest priority, then F, then CH2CH3, and CH3 is fourth.
Sodium methoxide is a strong base and nucleophile, so the reaction must be second order, E2 or SN2.
(a) π bond
Br Br
H CH3 NaOCH3 H CH3 H3C H NaOCH3 H C H
3
H3C F H3C F
H3C F H3C F
H H
rotate back carbon 120° π bond

In regular structural formulas, the reaction would give three products including the stereoisomers shown
above.
H3C H H3C CH3 H2C H
NaOCH3

Br F F CH3 F H F CH3
(S) trans cis minor product from E2

(b) 4 3 4 3
NaOCH3
2 In these structures, the numbers 1 to 4 indicate the group's
1 2 S N2 1
Br F F OCH3 priority in the Cahn-Ingold-Prelog system.
(S) (S)
A cursory analysis of the designation of configuration would suggest to the uncritical mind that this
reaction proceeded with retention of configuration—but that would be wrong! You know by now
that a careful analysis is required. In the Cahn-Ingold-Prelog system, the F in the starting material
was priority group 2, but in the product, because Br has left, F is now the first priority group. So
even though the designation of configuration suggests retention of configuration, the molecule has
actually undergone inversion as would be expected with an SN2 reaction. (See the solution to
problem 6-21 for a similar example.)

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7-68 substitution CH3 CH3

H Br Br H
+
Br H H Br

CH3 CH3 Regardless of which bromine is substituted

2S,3S 2R,3R on each molecule, the same mixture of
racemic mixture products results.

Each of the substitution products has one

KOH chiral center inverted from the starting
material. The mechanism that accounts for
inversion is SN2. If an SN1 process were
CH3 CH3 occurring, the product mixture would also
contain 2R,3R and 2S,3S diastereomers.
HO H H OH Their absence argues against an SN1
+ process occurring here.
Br H H Br

CH3 CH3
2R,3S 2S,3R
racemic mixture
elimination
H Br Br CH3
Br H HO
Br H CH3
rotate
C C
H CH3 Br
CH3 CH3 CH3 H trans
H and Br
anti-coplanar
The other enantiomer gives the same product (you should prove this to yourself).

The absence of cis product is evidence that only the E2 elimination is occurring in one step through an
anti-coplanar transition state with no chance of rotation. If E1 had been occurring, rotation around the
carbocation intermediate would have been possible, leading to both the cis and trans products.
7-69 "Ph" = phenyl
(a) Ph Ph Ph
NaOCH3
+
E2
major minor
Br Z,E mixture

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7-69 continued
(b) H and Br must be anti-coplanar in the transition state.
H
H δ−
CH3 H OCH3

Ph H H CH3
CH3 Br H CH3 CH3
2R,3R H
Ph CH3
NaOCH3 Ph CH3 Ph CH3
Br
Ph H −
C C Br δ
CH3 CH3 transition state
methyls cis
(c) H
CH3 H Ph CH3
CH3 H
Ph CH3 C C
Ph CH3 CH3 H
Br 2S,3R methyls trans

(d) The 2S,3S is the mirror image of 2R,3R; it would give the mirror image of the alkene that 2R,3R
produced (with two methyl groups cis). The alkene product is planar, not chiral, so its mirror image is the
same: the 2S,3S and the 2R,3R give the same alkene.

7-70
A pi bond is formed from two parallel p orbitals. Rotating around a double bond breaks the pi bond by
forcing the p orbitals to be perpendicular. If anything can stabilize the transition state, the rotational energy
barrier will be lower.
H H rotate right sp2 H
carbon by 90°
H
Each radical is on a 2° carbon, not particularly
C C C C stable. Two radicals on adjacent carbons are
H3C CH3 particularly unstable.
CH3
H3C

H H rotate right sp2 H

carbon by 90°
H
Each radical is on a benzylic carbon; each is
C C C C stabilized by resonance. Review the
Ph Ph solution to 4-45(b) or 6-51 for benzylic
resonance forms.

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7-70 continued

H3CO
H O O O
sp2
rotate right H H
C C carbon by 90° OCH3 OCH3
N O C C C C
OCH3 OCH3
H3CO N N
O O

An unequal distribution of electrons between the

two sp2 carbons gives resonance forms
O
maximizing the number of pi bonds, all atoms
H
with full octets, and negative charge on the more
OCH3
electronegative atoms! This large degree of C C
stabilization explains the lowest rotational OCH3
energy barrier: this transition state is the easiest N
to form. O

7-71 In E2, the two groups to be eliminated must be coplanar. In conformationally mobile systems like
acyclic molecules, or in cyclohexanes, anti-coplanar is the preferred orientation where the H and leaving
group are 180° apart. In rigid systems like norbornanes, however, SYN-coplanar (angle 0°) is the only
possible orientation and E2 will occur, although at a slower rate than anti-coplanar.
The structure having the H and the Br syn-coplanar is the trans, which undergoes the E2 elimination.
(It is possible that the other H and Br eliminate from the trans isomer; the results from this reaction
cannot distinguish between these two possibilities.)

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7-72 It is interesting to note that even though three-membered rings are more strained than four-membered
rings, three-membered rings are far more common in nature than four-membered rings. Rearrangement
from a four-membered ring to something else, especially a larger ring, will happen quickly.
H

OH O H
H+ – H2O This 1° carbocation
CH2 would be very unstable.
∆

without rearrangement

H This alkene could be produced from the unrearranged

carbocation, but the 1° carbocation has such a short
H2O lifetime that it is more reasonable to propose the
CH2 CH2 minor pathway through the rearranged 3° carbocation.

with rearrangement—hydride shift

H H
H2O
CH2 C CH2 CH2 minor

3° carbocation, but
still in a strained
4-membered ring
H
H H

H2O
C CH3 CH3 minor

with rearrangement—alkyl shift—ring expansion

H
CH2 C H H MAJOR
H2O
C H2C C H
H2
H H
2° carbocation on
5-membered ring—
HOORAY!

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7-73
H
CH2OH CH2 OH CH2 1° carbocation—terrible!—will
H+ ∆ rearrange; can't do hydride shift, must
do alkyl shift = ring expansion.
− H2O

This is an unstable carbocation even

though it is 3°; bridgehead carbons
H C H cannot be sp2 (planar—try to make
H2O a model), so this carbocation does a
H
hydride shift to a 2°, more stable
carbocation.
Abstraction of adjacent
H gives bridgehead
alkene—violates hydride shift
Bredt's Rule.

H This 2° carbocation loses an

H adjacent H to form an alkene; can't
H C form at bridgehead (Bredt's Rule)—
H H only one other choice.
H2O H
H

7-74 CH3 CH3 CH3 CH3 CH3 CH3

− H2O
CH3 C C CH3 CH3 C C CH3 CH3 C C CH3
H OSO3H ∆
HO OH HO OH2 HO
methyl shift

CH3 CH3 CH3

CH3 C C CH3 CH3 C C CH3 CH3 C C CH3

H2O
O CH3 O CH3 OH CH3
H

The driving force for this rearrangement is the great stability of the resonance-stabilized, protonated
carbonyl group.

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7-75 Br

(a) E2— H2C CH CH3 H2C CH CH3 + H2O + Br –

one step
H
OH

Br OH
SN2— CH3 CH CH3 CH3 CH CH3 + Br –
one step
OH

(b) In the E2 reaction, a C—H bond is broken. When D is substituted for H, a C—D bond is broken,
slowing the reaction. In the SN2 reaction, no C—H (C—D) bond is broken, so the rate is unchanged.

(c) These are first-order reactions. The slow, rate-determining step is the first step in each mechanism.
Br H
slow fast
E1 H2C CH CH3 H2O H2C CH CH3 H2C CH CH3

H H H
SN1 Br O OH
slow H2O H2O
H3C CH CH3 H3C CH CH3 H3C CH CH3 H3C CH CH3
fast fast
+ Br –

The only mechanism of these two involving C—H bond cleavage is the E1, but the C—H cleavage does NOT
occur in the slow, rate-determining step. Kinetic isotope effects are observed only when C—H (C—D) bond
cleavage occurs in the rate-determining step. Thus, we would expect to observe no change in rate for the
deuterium-substituted molecules in the E1 or SN1 mechanisms. (In fact, this technique of measuring isotope
effects is one of the most useful tools chemists have for determining what mechanism a reaction follows.)

7-76 Both products are formed through E2 reactions. The difference is whether a D or an H is removed
by the base. As explained in Problem 7-75, C—D cleavage can be up to 7 times slower than C—H
cleavage, so the product from C—H cleavage should be formed about 7 times as fast. This rate preference
is reflected in the 7 : 1 product mixture. ("Ph" is the abbreviation for a benzene ring.)
D H H H H H D H
H − D, Br H − H, Br
C C C C C C C C
H Ph
Ph Br Ph H D Br Ph H
requires C—D bond cleavage; requires C—H bond cleavage;
slow; minor product 7 times faster; major product

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 HOW TO PREDICT SN vs. E MECHANISMS
Is the base/nucleophile strong or weak?
(like HO– or RO–) STRONG WEAK (like H2O or ROH)
Second order: SN2, E2 First order: SN1, E1
Type of carbon with leaving group Type of carbon with leaving group
1°, CH3
1°, CH3, esp. 2° 3° or 2°, 3°,
benzylic and hindered allylic, no appreciable
allylic benzylic reaction, very slow
E2
SN2 > E2
(SN2
easy for nucleophile

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extremely
to attack electrophilic SN1 and E1
slow)
colleagues, Dr. Hima Joshi, who has permitted its use here.

carbon; higher temperature

higher temperature SN2 and E2
higher temperature and hindered base
and hindered base favor elimination
and hindered base

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favor elimination
favor elimination
Note: a methyl halide
cannot undergo elimination.
I know whether a reaction will follow an SN1, SN2, E1, or E2 mechanism? The answer is not always

Here are some generalizations that can provide guidelines about how to make reasonable predictions.
Most instructors have their own version of this "concept map"; this one was modified from one of my
Note to the student: The most common question from students studying Chapter 7 material is: How do

simple even for experienced chemists, and mixtures of substitution and elimination products are typical.
Students: use this space for notes or to solve problems.

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