Organic Chemistry 101

Problems #14

Spectroscopy

Answers

1.

For each of the following 7 1H-NMR spectra (300 MHz) of compounds A-G, analyze each by constructing a table that
contains
a) Chemical shift () for each set of equivalent Hs b) integral (in some unit of measure, usually mm)
c) relative number of hydrogens
d) multiplicity for each different signal.
e) assign to likely groups
Propose a structure using this data and label each H in your structure.

A.

C4H8O2 (1 unsaturation)
integral

8.1
5.9
a
4.2
12.0
b
1.7
12.0
c
0.95
17.7
d
47.6/8

B.

C.

D.

E.

F.

C4H8O2 (1 unsaturation)
integral

3.75
18.0
a
2.33
11.3
b
1.2
16.7
c
46.0/8

# Hs
1
2
2
3
5.95//H

Mult.
s
t
sextet
t

O
H

C C CH 3
H2 H2
d
c
b

# Hs
3
2
3
5.75/H

Mult./J
s
quart.
t

C4H8O2 (1 unsaturation)
integral

4.15
11.5
a
2.05
18.0
b
1.30
17.0
c
46.5/8

# Hs
2
3
3
5.8/H

Mult./J
quart.
s
t

C7H12 (2 unsaturations)
integral

4.60
6.0
a
2.15
12.0
b
1.6
18.0
c
36/12H

# Hs
2
4
6
3/H

Mult./J
s
br. s
br. s

C6H12 (1 unsaturation)
integral

5.75
3.2
a
5.00
b
6.5
4.98
c
1.90
6.4
d
1.7
3.4
e
0.90
19.0
f
38.5/12H

# Hs
1
1
1
2
1
6
3.2//H

Mult.
ddt
d
d
t
nonet
d

C6H12 (1 unsaturation)
integral

5.15
3.1
a
2.0
7.0
b
1.70
9.0
c
1.60
9.5
d
0.95
8.7
e
37.3/12H

# Hs
1
2
3
3
3
3.1//H

Mult.
t
quintet
s
s
t

H 3C

C CH 3
H2
c
b

C CH 3
H2
c
a

O
H 3C

c
H 2C

H2
C

H2
C

H
C a

b C
C
H2

C
H2

H a

c H
C
b H

f
C C
H2 H
CH 3
d
e

c
H 3C

H a
C

H 3C
d

CH 3

C
C CH 3
H2
e
b
1

G.

3.

C6H12 (1 unsaturation)
integral

5.7
3.0
a
4.97
b
6.0
4.94
c
2.05
3.2
d
1.35
6.2
e
0.98
8.8
f
0.85
10.2
g
37.4/12H

c)

H a

c H
C
b H

H2 e
C

C
H
f H 3C
d

CH 3

C3H5Cl3 (0 unsat.)
a triplet,
45.3
b doublet, 59.0

Cl
a b
Cl C C
H2 H

C3H5Br (1 unsat.)
a triplet, 32.6
b triplet, 118.8
c doublet, 134.2

b
H 2C

b) C4H8Br2(0 unsat.)
a quartet, 10.9
b triplet, 29.0
c triplet, 35.5
d doublet, 54.3

a
C Cl
H2

c
C
H

a
C
H2

dH
C

Br

Br
c
H 2C

or

b
C
H2

b
C
H2

Hd a
C
CH 3

Br

Br

a
CH 3

c
C
H2

(best )

Br

Give a structure or structures consistent with each of the following sets of 1H-NMR data. Assign the signals to
hydrogens in your structures.
a)

C3H3Cl5
a triplet,
b doublet,

(0 unsat.)
4.52, 1H
6.07

Cl

Cl

b HC

C
H
a

Cl

c)

d)

4.

Mult.
ddd
d
d
septet
quintet
d
t

Give a structure or structures consistent with each of the following sets of 13C-NMR data. Assign the signals to the
carbons in your structures.
a)

2.

# Hs
1
1
1
1
2
3
3
3.1//H

C9H11Br
a quintet,
b triplet,
c triplet,
d singlet,

C6H12O2 (1 unsat.)
a singlet, 1.50, 9
b singlet, 2.01, 3

Cl
CH b
Cl
H
C

(4 unsat.)
2.15, 2H
2.75, 2H
3.38, 2H
7.22, 5H

C4H8Cl2 (0 unsat.)
a doublet, 1.60, 3H
b multiplet, 2.15, 2H
c triplet,
3.72, 2H
d multiplet, 4.27, 1H

HC
d

e)
Cl

b H2 d
C H CH 3
C
C
a
c H2
Cl

CH

H3C

CH3
C

O
O

CH3

b
CH3

H2 c
C

b H
2
C

HC

C
H2
a

Br

C
H

C3H5ClF2 (0 unsat.)
a triplet, 1.75, 3H
b triplet, 3.63, 2H
(remember that F can couple with H)

F
Cl

C
b H2

CH 3
a

Propose a structure or structures consistent with the 13C-NMR spectrum shown for compound H. Assign the signals to
the carbons in your structure(s).
Carbon
H(C6H12O)

22
-CH3
a
a
O
24
-CH
b
c
30
-CH3
c
b
52
-CH2
d
e
d
208
C=O
e

5.

Compound J, molecular formula C5H10O, readily decolorized Br2 in CCl4, and is converted by H2/Ni into compound K,
molecular formula C5H12O. Following is the 1H-NMR spectrum of compound J. The 13C-NMR spectrum of J shows
signals at 146.12, 110.75, 71.05, and 29.38. Deduce the structural formulas of compounds J and K and assign all proton
and carbon signals to the appropriate atoms in your proposed J structure..
111
Reaction of Br2 indicates the one unsaturation in J is a C=C.
146
c
C5H10O
a
H
H
d
integral
# Hs
Mult.

J
C C
OH
6.0
4.0
1
dd
a
bH
C CH 3
5.25
4.0
1
d
b
e
5.0
4.2
1
d
c
71 CH 3
1.95
4.0
1
s
d
OH
29
1.33
25.0
6
s
e
K
41.2/10H
4.1//H