Answers to Exam #3, Chemistry0225/0227, 2013

1. Addition of HBr to either methylenecyclopentene or 1-methylcyclopentene will give 1.

Each reaction must form the same tertiary carbocation, which will add bromide to give 1.
Each of these reactions is a garden-variety addition of HBr.
H

Br

CH2
Br
CH3

+
H

CH3

Br

Br
1

CH3

In addition, protonation, followed by hydride shift, can convert 3-methylcyclopentene

into the same cation, and thus to 1.
Br

+
CH3

HBr

CH3

CH3

Only hydroboration of methylenecyclopentane can give a molecule that satisfies the

spectral data:

split by one adajent C-H, thus a doublet

H
1. B2H6
2. HO/HOOH

H
H

these hydrogens are adjacent to an O, thus are

at about ! 3.6 ppm

OH
IR @ 3550 cm1 means alcohol

2. The formulae show you what to do to form X - add two carbons - how about two SN2
displacements on methyl iodide? The only tricky thing is to recognize the Hofmann
elimination to give Q (not Saytzeff) that follows.
1. 2 Equivalents of CH3I
2. HO, heat

N
H

CH3

+
N

H3C

HO

H
repeat
SN2

H
+
N

X C10H22N+ I

H3C

N
CH3

Note Hofmann
elimination!
C10H21N
Q

(CH3)2N

CH3

3.
(a) Just count carbons
H3C

CH3

4
=

1 2
(H3C)3C

5
5

CH3

8
CH3

4
=

1 2
(H3C)3C

7
CH3
6

C(CH3)3
H3C

6
CH3

10

6
5

C(CH3)3

CH3
9

(b) You could count Hydrogens. At 25 C the diethyl compound is flipping and averaging
some hydrogens. The tert-butyl compound cannot ring flip and one counts several more
hydrogens. You could not count carbons. They both have six different carbons at 25 C.
1
H
2

3
H

H
H3

(D3C)3C
D

C(CD3)3
D
1
H
1
H

1
H

H
4 H

H
2
2
H

CD2CD3

CD2CD3
H
H 3

D3CD2C
D3CD2C

H6

H
H
1
CD2CD3

H
H
H

D3CD2C
H

H
H

H
2 H
2

Note that the static diethyl compound is not distinguishable from the tert-butyl compound
by hydrogen counting..
1
H
1
H

2
H

3
H

H 3
H

CD2CD3

H6

D3CD2C
D3CD2C

2
CD2CD3

H
4 H
4

(c) The cis (0) coupling constant will be larger than the trans (ca. 120) coupling
constant.
(d) you can't, unless you think of using an optically active solvent in which the two
enantiotopic ring hydrogens of the cis compound will give different signals. The two ring
hydrogens of the trans compound are homotopic and will of course appear as one signal.

4. In dibromination, there is always a competition between the bromonium ion

mechanism and an open cation mechanism. Compound A is reacting through the
bromonium ion mechanism to give a single racemic trans dibromide. The open ion
formed from B is resonance stabilized and must be out competing the bromonium ion.
The open cation can add bromide from two sides to give both cis and trans dibromides.

Br2

Br
Cy

H
Br

Br2

Br

Br

Br

PhOCH3

H
Br

PhOCH3

OCH3

Here are the mechanisms:

Bromonium ion:

Br

+
Br

Br2

SN2

Cy

H
Br
A

Cy

Br

Open ion - note the resonance stabilization of the open cation:

Br
Br

Br
H
(+)

(+)
B

(+)

OCH3

Br adds to top
lobe

OCH3
(+)

Br adds to
bottom lobe

Br

Br
Br

PhOCH3

H
Br

PhOCH3

5.
(a) H2/Pd
(b) 1. HBr

2. Li

3. H2O

(c) Br2/H2O
(d) 1. B2H6

2. HO /HOOH 3 HBr

(e) (CH3)3COH/ catalytic H2SO4

6. Three dimensions are utterly essential here. In the trans starting material, there
is no CH bond in the proper position so that a 180 E2 is possible. Only the
SN2 is possible. Displacement from the rear gives the cis stereochemistry shown
H
Br
(CH3)3C

neither C-H bond

is properly aligned
for an E2

By contrast, in the cis compound, there are two CH bonds in the proper ideal
position for an E2 (arrows) and so there is lots of E2 reaction in competition with
the SN2.
Br
H
(CH3)3C

E2

H
H

both C-H bonds perfectly

aligned with the C-Br bond

(CH3)3C