NMR Practice Problems

1) Tell precisely how you would use the proton NMR spectra to distinguish between the following pairs of
compounds:
By
a. I-bromopropaneand2-br?m~propane
E(~
~/v.)jl\
shDtv' OVt(j "2. Fe~k.~
b. prop anal and propanone
D.

4~

c. ethyl acetate (MeC02Et)

d. I-butyne and 2-butyne~

11--=---..

JL~,.... . ...':-...
(~fer @te+ '2(IH~
t: ..

~('H

~V1a

c--- .!j-,o~ tc>.

~v..

::.\"\1). t:.--'\.

and methyl propanoate (EtC02Me)

cLnt b l-e:f ( b H 10)

J.
(1('"'1

PF

.,

J- /'

SiVI..c1e-+
(b\\"')3lo~@~~~ifr(l

0 I.ZPf""

tt~c.--=-c.J\6.
i'\.eCO'2-e+
-.~ ~auk-f- ~ 'V3ISp~r(\
'rr"2) ~ach of the following compounds exhibits a single IH NMR peak. Approximately where would you expect
each compound to absorb?
t-\
a. cyciohexane
tV I, I f' P fY\
~
o
b. acetone tt3C.;~H3>(
tl.')
/V
r 2~~F-rY'
G? -v IffM

~ 3"~

c. benzene
d. glyoxal (ethandial)
e. dichloromethane
f.

lri
ctt dz
l-\

trimethylamine ((CH3)3N)fj

ti-torpvV'

@'" S ff ('(".
c,- I/J /'vM3>
/'v ~Ff'~'

~
Lrt3
3) Draw structures for compounds that meet these descriptions:
a. C2H60; one singlet

~c..-O-c..tt3

b. C3H7Cl; one doublet and one septet

/cH3~)

e-\

-c--t:!.(~t1 'b

c,
0 ~Gf
'
d. C4H802; one singlet, one triplet, and one quartet S
c. C4H8Cl20; two triplets

If)

Ci.-

/\o~

1;-

4) The two spectra below are of phenol and benzaldehyde. Assign them.

lfl\",
-krP

Af

100
L-J

5.43

L........J
,..,...,....,

515
L-.-I

100
I....-...J

5) For each spectrum below, chose between the alternative compounds. Give your reasons.

c..

0
~

~OH

or

OHCL

Courbo'#.~ t\ cII

0.86
I

12.5

I
11.5

12.0

11

"''-

J"....

5.0

'.5

'.0

Gt~J

III

3.5

30

207
I

3 00

I..............
I

25

1.5

2.0

1.0

0.5

0.0

C(H
Ih-

~h,

J..

kr

.b

vOH~

or

tA\c.ohc \

8.0

ii,

7.5

7.0

6.5

6.0

5,5

5,0

4.5

4.0

3.5

3.0

2.5

2.0

1.5

Iii

1.0

0.5

0.0

b ',

./

./'-...
~
"V",

./

0r

"-./"

ot'
<&dM\f\Ae..~

C~I

3s~~V\q\~
~'~'~'~'~'~'~'~'~'

,~',~'~'~

J~

OH

4 SIa-v'C\ ~s
l

~
I

5.0

c-

1,
I

'.5

'.0

3.5

3.0

2.5

2.0

1.5

1
I

1.0

j
I

0.5

0.0

or

OHc

q~~

3s;~G\k

C-~

c.1

;y-{

el

,,2-d~~\efVe-~~

l,\,2-*v-,&

",/

ZZ-&.~~'f.j

'f'OfOM-t.

ero~\\e

6) The spectra below are of acetone, 1,2-dichloroethane,

bromopropane and 2-bromopropane. Assign them.

1,1,2-trichloroethane,

a)

b)

GIl

C!)"'~

~
r~
..,

0;;e.b

C.

e-

2,2-dimethoxypropane,

1-

b
<:-1

lit

1.0

0.5

0.0

6.0

5.5

5.0

4.5

4.0

d)

6~O

5~5

5~O

4~5

4~O

2.0

c.~ ~v(

e)

1.5

T
1.0

0.5

3.0

5.0

t
4.5

,.,.,...".,...

4.0

3.5

0.0

Hk

,.,.,...".,...

3.0

0.5

C-

5.5

1.0

:...!,

@)

1.5

t\,,~.~b
C\

6.0

0.0

2.5

2.0

T
0.0

T
6.0

T
5.5

T
5.0

4.5

4.0

2.0

1.5

r
1.0

0.5

0.0

bjjV
I

~\

~'0

~~\

I~

0.

_=-tC

1\

I'OM

.....
C
A

~'

IS

7) Assign the following spectra to one of the compounds listed: 1,4-dimethylbenzene, 1,4-dimethoxybenzene,
phenylethyne, 3-methyl-3-hydroxy-l-butyne, 2-bromobutane, 1,2-dibromo-2-methylpropane.

C.

' E

c. b

'1,,11,,11'1,,111""1""111,11,11,11"'1,,"111"1,,111111'1,11'1,,111""1,1"1,1111,11'1,1111""1"'

~5

~o

~5

~o

~o

~5

~5

4~

15

10

25

jll"I'''II,'I'I'IIII''''I"IIIII''I''''II,,'I''

2~

1~

1.0

~5

~O

1.0

0.5

'lii1llili"""""'!""I""j""!""I"""""""ji"'I"""""""""""""",!,"""""""""i'iii""'j""j""j""j""I""j""j"

7.5

7.0

6.5

6.0

5.5

5.0

4.5

4.0

3.5.:}.0

2.5

2.0

1.5

0.0

iii

iii j "

7.5

'I i "

7.0

Ij " i

'I "

6.5

I Ij Iii

i i i

6.0

Ij i Ii iii

Ii

5.5

Ii i

i"

5.0

i ij

j "

I' "

4.5

I I , II

I'

j "

4.0

I Ii

'I ii,

3.5

II '

j ~

I' "

.~3.0

I Ii I I i

I"

2.5

Ii

I " , iii

" I I I II ,

2.0

I' i "

1.5

Ii, ..

i"

1.0

i " iii

0.5

iii"

iii.

0.0

1.00

6.00

3.00

'===!

2.012.00
bdbd

bd

3.00
Id

50

7.5

7.0

6.5

6.0

5.5

5.0

4.5

H4' 5("

Cg

4.0

3.5

3.0

2.5

2.0

1.5

d)

1.00
bd

bd

T
2.5

3.5

3.0

T
2.0

603
bd
T
1.5

T
1.0

501
"===d
,
Iii
n
n

0.0

.b

-::: 4

=: ~

(j,~

V'\'\.O'

~tf) ~(

~t\.l

2.002.00

W'===!

--

2-

Ii,

iii"

s- @

1-1, ~'f'~

Cqt\r2-

-<;~-C!> t1.,

L~t-)

\~~fn>~ ~~

C~4'(d-+~

.b
5.00

i"i"],'"".,.""'"",]""""""""""",,,,,"1111"",11""""'11""""1""""'1""""'11li'I""j""""'fi""""]""""']""'"

7.5

7.0

6.5

6.0

5.5

5.0

4.5

4.0 'I

3.5

1.00

6.04

Ld

3.0

2.5

~O

Cg tt"l
- cb t(r
Cz. rI\{ tv-

9) Compound H,C9H12, gives a proton NMR spectrum as shown below. Assign a structure.

'J:t\b

0.5

(ST\@ 7t'~a

Ar

2.01

~T\lJ = I~-~O<;'f(~"'~)

~rt(Io,f.:~

1.0

2.0

1.5

1.0

0.5

0.0

iii

10) Two spectra are given below along with their moleclJlar formulas. Propose a structure that corresponds to
each spectrum.
:r.t\b::: g -;.Jl";" 0 (s.a..fu..q-oJ-ed)
.
C3H7Cl

lA Y\~d'M\Mt2.J~CQ\,

3 'i>\<Q""-c:?\C:

3 ca.N~c;.,

b
Ir
JJMlJ
2.00

2.01

302

bd

1.97

2.00

=:J

303

bd

Id

"I"ii!""I""""'i""""'j""!""!""""'i'ii'i""I""""'I""I""i""!"'' !' ' !' ' ' ' '!'1I'I""""'I""""'j""!""I""I""I"".""1II

~o
~s
~o
as
aD
~s

~o

~o

~s

3.01

bJ
1S

10

2.S

~O

1~

1.0

os

00

11) The integrated 1H NMR spectrum of a compound of formula C4H 100 is shown. Propose a structure
consistent with the data. /.
f-u,tI'qJeJ '6 /.f ~
Cq
4- Ce:urfoOk ~, z!". it; tot'tl ~ ).

C~l-hoO

"It\l>=

104o/z =-0 (.&ev

205
T
3.5

3.00

bd
T
4.0

l'

1 I:)

bdT
3.0

T
2.0

1~5

1~o

~~

hr'F~

;)...~.(

~tI\.l)tJF

12) The compound whose proton NMR spectrum is shown below has the molecular formula C3H6Br2. Propose
a plausible structure.
c~rt,,&('2.
.:I:rtb ~ a--R(7.- 'f:.. 0 ~~.J,
~~~(
(3
IS, 2..

c.

Sl~~~(~

~,-

4.00

bd

i4~Oi

iii

i3~5i

iii

2.01
i

'3~O' ,

ii,

'2~5' , , ,

'2~O' ,

i1~5'

iii

'1~O'

Iii

jO~5' , ,

'O~O'

13)A compound (CIOH1202), whose spectJiUmappears below was isolated from a reaction mixture containing
2-phenylethnaol and acetic acid. Propose a structure for this comppund.
brh
r~ -r
C1011
Ll 0
:rtl
h
2."- ::-12
.
.
p. ~C~
V)""'-i
+' bull/~
~d.
~I.<I
,'2 ~
k
. (J

W ~

-C,\i~

tr

o
V~dt~-c.tt~-o-c.

L..:::::.---U

c.

tt3

a-.

Jif"

5.00

2.00

2.00

bd

ld

ld

'i'ii"""""""""""""""""""""""'""1""1"1'1""",1"""1""1,1"1",'111"1,,,111ii'i""""'j""""']"""""""""""
~5
~O
&5
&0
~5

~O

~5

~o

15

10

302

2.5

~O

1~

1~

Q5

QO

14) The compound whose proton NMR spectrum is shown has the molecular formula C4H702Cl and shows an
infrared absorption peak at 1740 cm/\-l. Propose a plausible structure.
tt,Oz.. c( .:i1"\ ~ -= 10 -'i'~~bl:-

e;

c...

KJ

c\

--~~
\\

0?

".2~

~V~ ~

C?

301

2
b:j

.[,11""1.,,,
4.5

4.0

Ii,

"I,i

3.5

I"

iii

'i'

3.0

I,ii"

"I

",.,11"1"

2.5

2.0

,.11'1.,11

bd

11

1.5

",,11

1.0

11,11,

".",1'1
0.5

Ii
0.0

b '~

bo>td ;

15) A small plant was adding bromine across the double bond of 2-butene to make 2,3-dibromobutane. A
controller malfunction and allowed the reaction temperature to rise beyond safe limits. A careful
distallation of the product showed that several impurities had formed, including the one whose NMR is
shown below. Determine the structure.

d
t\

b
~.

____

~
1.00
i

~J~~

2.01

bd

I;
4.5

I
4.0

bd
"I"
3.5

-.

2.00
i ( ,

3~O...

bd
j

'2~5'

'--

3.00

bd

i2~O

iii

'1

~5.

iii

iii

'1

~ci

Iii

'o~5

'O~Oi

16) When 2-chloro-2-methylbutane is treated with a variety of strong bases, the products always seem contain
two isomers (A and B) of formula C5HIO:When sodium hydroxide is used as the base isomer B
predominates. Determine the structures of A and B and explain the experimental results.
>
Col
t>q s.-e

t13 c

..,...

~ tt?>

-r

E>
c.

-re(~t

w)

S'MCl.tle.v bq~e

A.

17) A new chemist moved into an industrial lab where work was being done on oxygenated gasoline additives.
Among the additives that had been tested she found an old bottle containing a clear, pleasant smelling liquid
but missing its label. She took a quick NMR and was able to determine the identity of the compound
without additional information. Can you? The proton NMR is shown below.

i4~O'

iii

ii,

~IO
~1
.",

'3~5i

iii

i3~Oi

'2~5'

iii

Ii'

'2~O'

'1~5

ii"

'1~O'

iii

llW~4 .'..

'O~5'

'o~o'

18) An allylic halide A of formula C5H9Cl undergoes Snl reaction with water to yield a mixture of two
isomeric products, Band C. The proton. ~:~1Rspectra ofB and Care Sh0(t). . Suggest structures for A, B,
and C.
~./">
IOU
C

\\C\

t\~

B)

~.

-':~

.~~ ~~\" t

OH1P~l~~~

'fz,

~H

,., .~

~
,

'2.ti

tho \

11-1

~~

\Y -

'\

114

,\~

ift/ott,.

"1'

6.0

'.;"1

0.52

0.56

3.00

bd

bd

5.5

1'

1 '.11','1","',"1".11',,'j"",II".I"'IIII"I"'I""'I""II"II"'I""'1
5.0
4.5
4.0

3.5 . .,

3,0:'

2.5

2.0

trtJ 1
1.5

1.0

1".,1.'.111,"1.'
0.5

0.0

~5

~o

C)

3.00
"'1"11111"1,1111,1111"",.1"1""""'1""""'1""1""1""1.1"1'
~o
~5
~o

bd

4~

4~

15

10

.. ,11"'1",,,,1"1,,111,1"1,.1'1'1,11"'ljll"I,1
~5
~o
1~

1~

\$L-,

lIZ.