Name:____________________________ ID:_____________________

AVERAGE
Standard deviation

110/150 (corresponds to lowest B(-)

25

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signature

CHEMISTRY 140B
10/19/2015
st
1 Midterm Exam
Instructions:
1: This exam consists of 5 pages, including this page. (Page 5 is blank). At the beginning of
the examination period, put your name at the top of each page.
2. This exam accounts for 25% of the final grade (300 points total).
3. You can use the backside of each page, or page 5 as a scratch paper. However your
final answers must be clearly written within the designated box that follows after each
question. At the end cross out all unused space.
4. You may use pen or pencil. However exams completed with pencil will not be regraded.
5. Last day for regrades: 10/23/15.
6. All exams will be available to you on Friday 3/20/2015 (from 5224B Pacific Hall, 5th floor)
10:00am -5:00 pm.
7. Read carefully the instructions for each problem.
8. Keep your eyes in your own exam!!!
GOOD LUCK

Problem

Points

Score

1.

50

________

2.

50

________

3.

50

________

TOTAL

300

_______

Name:____________________________ ID:_____________________

Problem 1 (50 points)

A

Predict the 1H NMR spectrum of compound A.

Cl

a. Show the integration, chemical shift and proposed splitting

1

patterns of each peak. Indicate the identity of each peak using the

carbon numbering shown in the structure.

b. Add the chemical shift of TMS and CHCl3 (reference peaks).

50 points total
subtract 5 points per mistake

(C1,3)
6H

(C6)

(C4)

(C5)

(C2)

1H

1H

2H

1H
TMS

CHCl3

10 ppm

c. Explain your predictions on chemical shift and splitting patterns using 1-2 sentences for each family of
protons (e.g. Cx proton integrates as 1 and has a chemical shift of Y because of the effect of Z. It has 2 nonidentical neighbors thus it should be a www with relative peak intensity xxxx).
C1 proton(s): C1 and C3 protons are identical (the same family) and integrate as 6 protons at ca 1ppm.
They have one neighbor at C2, thus they resonate as a doublet of relative intensity 1:1.

C2 proton(s): The C2 proton should resonalte at ca 2ppm since it is in a more substituted carbon than the
C1. It has 6 identical neighbors (at C1, C3) and 1 other neighbor at C4.
If the J value between these two families is identical, then we have 7 identical neighbors, thus an
octet (7+1=8 peaks) of relative intensity 1 : 7 : 21 : 35 : 35 : 21 : 7 : 1.
If the J value between these two families is not identical, then we have a doublet of septets
2x(6+1)=14 peaks of relative intensity 1:1 : 6:6 : 15:15 : 20:20 : 15:15 : 6:6 : 1:1
C3 proton(s): C1 and C3 protons are identical (see above)

C4 proton(s): The C4 proton should be around 3.5 due to the effect of Cl and the substitution. It has one
neighbor at C2 and 2 identical neighbors at C5.
If the J value between these two familes is identical, then we have 3 identical neighbors, thus a
quartet (3+1=4 peaks) of relative intensity 1:3 :3 :1.
If the J value is not the same, then we have a doublet of triplets with a relative intensity: 1:1:2:2:1:1

C5 proton(s): The C5 protons should integrate for 2 and be around 2.2 due to the effect of allylic carbonyl +
the substitution.
They have one neighbor (at C4) and 1 neighbor (at C6). Due to the restricted rotation of the sp2
system, it is highly unlikely to have similar J values of these neighbors. Thus, they should look like
a doublet of doublets.
C6 proton(s): The C6 proton should be around 9ppm due to the carbonyl deshielding effect. It has
two neighbors (at C5), so it should look like at triplet with relative intensity 1 : 3 : 1

Name:____________________________ ID:_____________________

50 points total
10 points per correct answer in box
3 points partial credit if appropriate

Problem 2 (50 points)

The reaction between compound 1 and NaOCHMe2 in Me2CHOH as a solvent produces a mixture of
two products 2 and 3, all with identical molecular formula and with a relative yield of 50% and 50%
respectively. The 1NMR of these compounds with relative integrations of signals is shown below.
What are the structures of compounds 2 and 3?

CH3

H3C

Na O

Br

stereochemistry

HO
(solvent)

stereochemistry
3 (yield: 50%)

2 (yield: 50%)
3

compound 2

CH3

H3C

CH3

H3C

compound 3

10

PPM

PPM

b. With what reagent and solvent would you treat compound 1 if you want to obtain higher
yield of compound 2? Explain your answer with 1-2 sentences

Use of a less bulky base, such as NaOMe in MeOH, will produce

higher yield of the thermodynamically more stable and more
sterically hindered alkene 2
c. With what reagent and solvent would you treat compound 1 if you want to obtain higher
yield of compound 3? Explain your answer with 1-2 sentences

Use of a more bulky base, such as KOtBu in tBuOH, will

produce higher yield of the kinetically faster and sterically
more accessible akene 3
d. What product(s) and in what relative ratio(s) would you obtain by treating compound 4 with
NaOCHMe2 in Me2CHOH as the solvent? Explain your answer with 1-2 sentences.

CH3 Na O

H3C
4

Br

HO

H3C

CH3

Only alkene 2 will be formed

since the E2 elimination can
proceed only from the C1 center

Name:____________________________ ID:_____________________