(CHE 325) Organic Chemistry II

Spring 2011

EXAM #3
Name:

KEY

ID#:

Check your exam to be sure it is complete. There are seven questions in this exam. It
is worth 100 points. To receive full credit for your submissions, make sure you do
your own work. Read each question carefully, and answer in clearly legible and
coherent English. Use the back of the page for additional space if needed. Partial
credit will be given, so show your work. Don't fall in love with individual problems. Do
the ones first which you can do easily. Pace yourself. Good luck!
N. Totah

1.

(of 11)

2.

(of 8)

3.

(of 10)

4.

(of 8)

5.

(of 38)

6.

(of 10)

7.

(of 15)

Total:

(100)

Name:
1. (11 points) Give IUPAC names for the following compounds:
a.
Cl

4-chl orobutane nitrile

C N

b.

O
OCH2CH3
ethyl benzoate

c.
O

pentanoic anhydride

d.
O
OH
OH

2-hydroxyheptanoic aci d

e.
O
N
H

CH3

CH3

N,N-dimethylprop-2-ynamide

Name:
2a. (4 points) Rank the following compounds in order of decreasing acidity. Rank the
most acidic compound 1, and the least acidic compound 4. Place the number
corresponding to the relative acidity of each compound in the blank below it.

CO2H
OMe

CH3
Me3N

CO2H

CO2H
OH
OMe

2b. (4 points) Rank the following compounds in order of decreasing reactivity to

nucleophilic acyl substitution. Rank the most reactive compound 1, and the least
reactive compound 4. Place the number corresponding to the relative reactivity of
each compound in the blank below it.

O
1

O
OCH3

O
NHCH3

OCH3
2

Name:
3. Write a complete, stepwise mechanism to account for each of the following
transformations. Use curved arrows to denote electron flow.
a. (3 points)
O
R

NaSCH3
OCH3

SCH3 +

NaOCH3

mechanism:
O
R

O
O CH3

O CH3
SCH3

SCH3

OCH3

SCH3

b. (7 points)

O
HO

CH3OH
catalyst

H+

OCH3

H2O

mechanism:

H+

O
HO

H
H

HO

proton

OH

transfer

HOCH3

H
O

OH
H

- H 2O

OCH3
H

- H+

H
O

OCH3

Name:
4. (8 points) Clearly explain how you could distinguish between each set of
compounds using the spectral technique indicated. For full credit, identify what
distinguishing features you would expect to see for each compound. Be specific. Cite
numerical values/ranges and identify relevant functional groups to support your
claims.
a. Distinguish between A and B using

C NMR spectroscopy

13

O
NH2

vs.

The compounds can be distinguishe d easily be the chemical shift of

the carbonyl carbon atom in each functi onal group:
A: the amide will have a shift between 160 - 180
B: the aldehyde will have a shift between 190 - 220

b. Distinguish between C and D using Mass Spectrometry

O

vs.

D: will show a fragment due to a McLafferty rearrangment

so will see a peak at m/z = 58; or will see a loss of 28amu
H O

(CH 2 =CH 2 )
C: will not
Note: Both C and D will show the sa me alpha cleavage products
so these fragments don't distinguish the two
5

Name:
5. (38 points) Predict the major product(s) for the following reactions. Assume
reagents are present in excess amounts unless otherwise indicated. Clearly depict any
stereochemistry. "No Reaction" is a possible answer. CAUTION! Don't confuse
reactions that will occur slowly with those that will not occur!
a.
O

O
1. NaH
O
2.

OH

O
O

Cl

b.

OH

CrO3
H2SO4

OH

(step 1)

product(s)
of step 1

1. NaH
Br
2.

(step 2)

c.
O

Ph3P CHCH2CH3

H
H

Name:
d.
O

CO2H

Cl

SOCl2

e.
CH3O

OCH3
H3O+

f.
O
N

1. LiAlH4
2. H2O

g.
O

OH
H

KCN
HCN

CN

(step 1)

product(s)
of step 1

OH

1. DIBAH

2. H2O
O

(step 2)

Name:
h.
O

OH

(1 equiv)

Cl

Et3N

HO

i.
O

O
(CH3CH2)2CuLi
(step 1)

product(s)
of step 1

H2NNH2
KOH
(step 2)

j.
O
SOCl2

CN

NH2

k.
Ph

1. LiAlH4
2. H3O+

OH

OH
OH

Ph

Name:
l.
O

N
H
pH = 4.5

m.
O

H3O+

H2N

HO

heat
(step 1)

product(s)
of step 1

CH3CH2OH
HCl (cat)

CH3CH2O

(step 2)

n.
O

O
1. BH3
2. H3O+

OH

CH3O
O

OH

CH3O

o.
O

NH2

NH

OH
O

Name:
6. (10 points) A neutral compound A (C7H14O) has the 1H NMR spectrum shown on
the following page. Compound A reacts with 2,4-dinitrophenylhydrazine to give a
positive 2,4-DNP test. Compound A also reacts with phenylmagnesium bromide (1.
PhMgBr, 2. H3O+) to give a new compound B (C13H20O). Upon treatment with
concentrated HBr Compound B reacts to give compound C (C13H19Br). Compound C is
carried through a sequence of reactions (1. Mg, 2. CO2, 3. H3O+) to give a final
product D that shows two strong absorptions (3200 [broad], 1710 cm-1) in the IR.
Identify the lettered compounds A - D by drawing structural formulas for each. Show
your reasoning, including a complete interpretation of the NMR data provided for
compound A (e.g. show how every resonance in the NMR corresponds to the
structure you propose for compound A; label each peak).
O
A

HO

Br

HO2C

positive 2,4-DNP test says A is an aldehyde or ketone

IR data indicates that compound D is a carboxylic acid
C=O
OH

1710 cm-1
3200 cm-1

H NMR assignments for A are shown on the following page

10

Name:
H NMR spectrum for Compound A:

(integral values are provided above each resonance)

a
6H

e
3H
c
2H
b
1H

Compound A:
O

c
a

11

d
2H

Name:
7. (15 points) Show how you would carry out the following transformations, avoiding
product mixtures if possible. Use any organic or inorganic reagents that you need.
Show all reagents and intermediate products.
a.

OH
O
Ph3P=CH2

SOCl2

Cl

(CH3CH2)2CuLi

b.
H
N

Br

O
O
NaCN

O
O

Cl

Et3N
CN

NH2

1. LiAlH4
2. H2O

c.
HO

CH3

1. PhMgBr (2 equiv)
2. H3O+

KMnO4

O
OH

OCH3

MeOH
HCl (cat)

12

or