SPECTRA PROBLEMS

HINTS for PROBLEM #1

Find the molecular weight from molecular ion in the mass spectrum
What functional groups are present from the IR ?
Count the number of types of C in the 13 C-nmr
Look at the integration in the H-nmr
Use the above to get the molecular formula (make sure it matches the MW)

SPECTRA PROBLEM #1 SOLUTION

In the MS, the molecular ion occurs at m/z = 72 indicating the MW = 72 g /

mol.
The IR shows a carbonyl C=O (1720 cm-1), no -OH or -NH (above 3200 cm1
), no C=C (1600 cm-1)
13 C-nmr shows 4 types of C, including a C=O (210 ppm), and 3
hydrocarbon C (37, 29 and 8 ppm)
H-nmr
/ppm
2.4

multiplicity

integration

quartet

CH2 coupled to 3H

2.1

singlet

isolated CH3

1.1

triplet

CH3 coupled to 2H

assignment

The following pieces can be deduced from the H-NMR spectra : an isolated
-CH3, and a -CH2CH3.

Summary....

The MS indicated MW = 72 g/mol.

The IR showed the presence of a C=O bond.
13C peak at 210 ppm suggests that the C=O is an aldehyde or ketone.
H nmr gives an uncoupled -CH3 and an -CH2-CH3
Note we can rule out it being an aldehyde (no peak at 9-10 ppm in the HNMR)
Use what we have to check the molecular formula : C4H8O = 4 x 12 + 8 x 1
+ 1 x 16 = 72 g/mol
This has an IHD = 1, and is consistent with the bond of the C=O.

Altogether....
With the pieces we have : C=O, -CH2-CH3, and -CH3.
IR and 13C is consistent with a ketone.
Given these pieces, there is only one way they can fit
together:

2-butanone
or

ethyl methyl ketone

PROBLEM #2

HINTS for PROBLEM #2

Find the molecular weight from molecular ion in the mass spectrum
What functional groups are present from the IR ?
Count the number of types of C in the 13 C-nmr
Look at the integration in the H-nmr
Use the above to get the molecular formula (make sure it matches the MW)
Use the coupling patterns in the H-nmr to identify the hydrocarbon "pieces"
What is the 1H, singlet in the H-nmr ? (what did the IR show ?)

SPECTRA PROBLEM #2 SOLUTION

In the MS, the molecular ion occurs at m/z = 60 indicating the MW = 60 g /

mol.
The IR shows an -OH (3350 cm-1) and C-O (1075 cm-1) but no C=O
(around 1700 cm-1), or C=C (around 1600 cm-1)
13 C-nmr shows 3 types of C, including a deshielded C (69 ppm), and 2
other hydrocarbon C (27 and 10 ppm)
H-nmr
/ppm
3.6

multiplicity

integration

assignment

triplet

CH2 coupled to 2H, deshielded

2.3

singlet

isolated H (-OH ?)

1.6

multiplet

CH2 coupled to many H

0.9

triplet

CH3 coupled to 2H

The H-NMR gives us the following pieces -OH (helped by the IR) CH3, and 2 different -CH2-.
We can start to fit them together based on the coupling patterns
as: CH3CH2CH2-

Summary....

The MS indicated MW = 60 g/mol.

The IR showed the presence of an O-H and C-O bonds.
H nmr gives a CH3CH2CH2- group
From the data, we can get a molecular formula of C3H8O = 3 x 12 + 8 x 1 +
1 x 16 = 60 g/mol
This has an IHD = 0, so no bonds or rings.

Altogether....
With the pieces we have : CH3CH2CH2- and -OH
IR an consistent with an alcohol.
Given these pieces, there is only one way they can fit
together.

1-propanol
Checking the H-nmr, the middle -CH2- is actually six lines
since it has a total of 5 similar neighbours. The -OH deshields
the other -CH2- but does not couple to it.

HINTS for PROBLEM #3

Find the molecular weight from molecular ion in the mass spectrum
What functional groups are present from the IR ?
Count the number of types of C in the 13 C-nmr
Look at the integration in the H-nmr
Use the above to get the molecular formula (make sure it matches the MW)
Use the coupling patterns in the H-nmr to identify the hydrocarbon "pieces"

SPECTRA PROBLEM #3 SOLUTION

In the MS, the molecular ion occurs at m/z = 86 indicating the MW = 86 g /

mol.
The IR shows an C=O (1715 cm-1) and but no -OH or -NH (around 3500
cm-1) or C-O (1250-1000 cm-1)
13 C-nmr shows 5 types of C, including a C=O (210 ppm), and 4 other
hydrocarbon C (55, 34, 22 and 18 ppm)
H-nmr
/ppm
2.4

multiplicity

integration

assignment

triplet

CH2 coupled to 2H, slightly deshielded

2.1

singlet

isolated CH3

1.7

hextet

CH2 coupled to 5 H

0.9

triplet

CH3 coupled to 2H

The following pieces can be deduced from the H-NMR spectra 2 different CH3, and 2 different -CH2-.
Given these pieces, we can start to fit them together based on the coupling
patterns: an uncoupled CH3- and a CH3-CH2-CH2- group.

Summary....

The MS indicated MW = 86 g/mol.

The IR showed the presence of a C=O bond.
13C peak at 210 ppm suggests that the C=O is an aldehyde or ketone.
H nmr gives an uncoupled -CH3 and a -CH2-CH2-CH3 group.
Note we can rule out it being an aldehyde (no peak at 9-10 ppm in the HNMR).
Use what we have to check the molecular formula : C5H10O = 5 x 12 + 10 x
1 + 1 x 16 = 86 g/mol
This has an IHD = 1, and is consistent with the bond of the C=O.

Altogether....
With the pieces we have : C=O, -CH2-CH2-CH3, and CH3.
IR and 13C is consistent with a ketone.
Given these pieces, there is only one way they can fit
together:
With the H-NMR chemical shifts we can see the CH3C=O
Checking the H-NMR, the middle -CH2- is actually six
lines since it has a total of 5 similar neighbours. The C=O
slightly deshields the other adjacent groups.

2-pentanone
or
propyl methyl ketone

HINTS for PROBLEM #4

Find the molecular weight from molecular ion in the mass spectrum

What functional groups are present from the IR ?

Count the number of types of C in the 13 C-nmr
Look at the integration in the H-nmr
Use the above to get the molecular formula (make sure it matches the MW)
Use the coupling patterns and chemical shifts in the H-nmr to identify the
"pieces"

SPECTRA PROBLEM #4 SOLUTION

In the MS, the molecular ion occurs at m/z = 88 indicating the MW = 88

g/mol (even, no isotope pattern for Cl or Br)
The IR shows a carbonyl C=O (1740 cm-1), and possible C-O (between
1250-1000 cm-1). No -OH or -NH (above 3200 cm-1).
13 C-nmr shows 4 peaks indicating 6 types of C, a C=O (171 ppm, probably
an acid derivative), a C-O at 60 ppm and 2 hydrocarbon C (21 and 14 ppm)
H-nmr
/ppm
4.1

multiplicity

integration

quartet

CH2 coupled to 3H, deshielded by O ?

2.0

singlet

CH3 with no adjacent H, slightly deshielded

1.3

triplet

CH3 coupled to 2H

assignment

The most significant structural information in the H nmr data is that we have
an ethyl group : -CH2-CH3 most likely as an ethoxy group: -O-CH2-CH3 and
an isolated methyl group : -CH3

Summary....

The MS indicated MW = 88 g/mol.

The IR showed the presence of C=O and C-O bonds, possibly an ester
13C peak at 171 ppm suggests that the C=O is a carboxylic acid derivative,
an ester ?
H nmr also gives a -O-CH2-CH3 and an uncoupled -CH3.
Use this to check the molecular formula : C4H8O2 = 4 x 12 + 8 x 1 + 2 x 16
= 88 g/mol
So with all this information we have the following pieces: C=O, -O-CH2CH3, and -CH3.

Altogether....
With the pieces we have : C=O, -O-CH2-CH3, and -CH3.
IR and 13C suggest an ester so we have : CO2CH2-CH3
This only leaves the -CH3 group.
Therefore, it must be CH3-CO2CH2-CH3

ethyl ethanoate
or
ethyl acetate

HINTS for PROBLEM #5

Find the molecular weight from molecular ion in the mass spectrum
What is the significance of the two peaks at 122 and 124 m/z in the MS ?
What functional groups are present from the IR ?
How many types of C in the C nmr ?
How many H in the H nmr (look at the integration) ?
Use the above to get the molecular formula (make sure it matches the MW)
What hydrocarbon chain does the H-nmr indicate ?

SPECTRA PROBLEM #5 SOLUTION

In the MS, the pair of peaks of about 1:1 ratio at 122 and 124 suggest Br due
to the isotopes79Br and 81Br
The molecular ion occurs at m/z = 122 indicating the MW = 122 g / mol
(based on 79Br)
The IR shows has no absorbtions for the main functional groups, looks like
C-H and C-C only.
13 C-nmr shows 3 types of C, including a slightly deshielded C (35 ppm)
plus 2 other hydrocarbon C (26 and 13 ppm)
H-nmr
/ppm
3.4

multiplicity

integration

assignment

triplet

CH2 deshielded, coupled to 2H

1.8

sextet

CH2 coupled to 5H

1.0

triplet

CH3 coupled to 2H

Summary....

The MS indicated MW = 122 g/mol.

The H nmr gives a total of 7 H, C nmr 3 C
Use this to check the molecular formula : C3H7Br = 3 x 12 + 7 x 1 + 1 x 79
= 122 g/mol
This confirms that we have the molecular formula

Altogether....
The coupling patterns in the H nmr are the critical
information
The patterns give a CH3 next to a CH2 and a CH2 next to
another CH2
Since we only have 3C, this means we have a CH3CH2CH2With the pieces we have : CH3CH2CH2- and -Br
This can only be put together to give CH3CH2CH2-Br

1-bromopropane

HINTS for PROBLEM #6

Find the molecular weight from molecular ion in the mass spectrum

What functional groups are present from the IR ?

What do the peaks at 7-8 ppm in the H-nmr and at 125-145 ppm in the 13Cnmr reveal ?
Look at the integration in the H-nmr...
Use the above to get the molecular formula (make sure it matches the MW)
What does "exchanges with D2O" tell you in the H-nmr ?

SPECTRA PROBLEM #6 SOLUTION

In the MS, the molecular ion occurs at m/z = 108 indicating the MW = 108
g/mol (even, no isotope pattern for Cl or Br)
The IR shows an O-H (broad 3330 cm-1) and a C-O at 1020 cm-1. There is
no carbonyl C=O (around 1715 cm-1)
13 C-nmr shows 5 types of C, including 4 ArC between 125-145 ppm and a
deshielded C (65 ppm)
H-nmr
/ppm
7.2-7.4

multiplicity

integration

"singlet"

5 ArH = monosubstituted

4.6

singlet

deshielded CH2 no coupling

2.3

singlet

H no coupling (-OH ?)

assignment

The H-NMR gives us a monosubstituted benzene ring, C6H5-, a -CH2- and a

peak that could match the -OH seen in the IR.

Summary....

The MS indicated MW = 108 g/mol.

The IR gave us an -OH but no C=O, so looks like some type of alcohol.
The 13C and H NMR show a benzene system C6H5-.
The H NMR gives another -CH2Use this to check the molecular formula : C7H8O = 7 x 12 + 8 x 1 + 1 x 16 =
108 g/mol
This confirms that we have the molecular formula

Altogether....

With the pieces we have : C6H5-, -CH2- and -OH

These can actually only be put together in one way....
benzyl alcohol
or
phenylmethanol

HINTS for PROBLEM #7

Find the molecular weight from molecular ion in the mass spectrum

What functional groups are present from the IR ?

What do the peaks at 7-8 ppm in the H-nmr and at 120-180 ppm in the 13Cnmr reveal ?
Look at the integration in the H-nmr
Use the above to get the molecular formula (make sure it matches the MW)
Count the number of types of C in the 13 C-nmr. What does this tell you ?
(particularly those between 120-180ppm)

What hydrocarbon pieces the H-nmr indicate ?

Using the chemical shifts how are these pieces connected together ?
Symmetry ?

SPECTRA PROBLEM #7 SOLUTION

In the MS, the molecular ion occurs at 164 indicating the MW = 164 g/mol
(even, no isotope pattern for Cl or Br)
In the IR there are significant absorptions at 1720cm-1 due to a C=O and at
1600cm-1 due to aC=C, C-O possible due to bands at 1275 and 1100cm-1.
There is no OH (about 3500cm-1).
13 C-nmr shows 8 types of C. By analysis of the chemical shifts, we have a
C=O (probably an acid derivative) at 167 ppm, 4 types in the region 125145 ppm is typical of aromatic C, 61 ppm is typical of a C-O and those at 22
and 14 ppm most likely from hydrocarbon.
H-nmr

/ppm
7.8

multiplicity

integration

"doublet"

7.3

"doublet"

Ar-H, must be disubstituted, most likely

para

4.3

quartet

CH2 coupled to 3H, deshielded by O ?

2.4

singlet

CH3 with no adjacent H, slightly

deshielded

1.4

triplet

CH3 coupled to 2H

assignment

The most significant structural information in the H nmr data is that we have
a disubstituted phenyl group, an ethyl group : -CH2-CH3 most likely as an
ethoxy group: -O-CH2-CH3 and an isolated methyl group : -CH3

Summary....

The MS indicated MW = 164 g/mol.

The IR gave us the C=O and the C-Owhich the C nmr suggests is an acid
derviative, such as an ester rather than a ketone (typically > 200ppm).
13C peak at 167 ppm suggests that the C=O is a carboxylic acid derivative,
an ester ?
Together the IR and 13C NMR suggests it is an acid derviative, such as an
ester rather than a ketone (typically > 200ppm).
The H nmr gives us -O-CH2-CH3 , -CH3 and C6H4Use all the pieces to check the molecular formula = C10H12O2 = 10 x 12 + 12
x 1 + 1 x 16 = 164 g/mol
The molecular formula of C10H12O2 implies an IHD = 5.

Altogether....
So with this information we have the following pieces: C=O, -OCH2-CH3, -CH3 and C6H4-.
IR and 13C suggest an ester so we have : CO2CH2-CH3
The -CH2- in the ethyl group is deshielded by O and coupled to the CH3, while the other -CH3 is isolated and only slightly deshielded
by the phenyl ring. The number of types of ArC (4) and the coupling
in the Ar region of the H nmr (7-8ppm) suggests the para
substitution pattern.

ethyl p-toluate
or
ethyl 4-methylbenzoate

HINTS for PROBLEM #8

Find the molecular weight from molecular ion in the mass spectrum
What functional groups are present from the IR ?
What type of C=O does the peak at 171 ppm in the 13C-nmr suggest ?
What do the peaks at 4.5-7 ppm in the H-nmr, at 95-150 ppm in the 13Cnmrand at 1650cm-1 in the IR reveal ?
Look at the integration and coupling patterns in the H-nmr to make sure
Use the above to get the molecular formula (make sure it matches the MW)
What hydrocarbon pieces the H-nmr indicate ?
Use the H nmr chemical shifts to decide which part is next to the C=O

SPECTRA PROBLEM #8 SOLUTION

In the MS, the molecular ion occurs at m/z = 114 indicating the MW = 114 g
/ mol (even, no isotope pattern for Cl or Br)
The IR shows a carbonyl C=O (1770 cm-1), C=C (1650 cm-1) and possible
C-O (between 1200-1000 cm-1). No -OH or -NH (above 3200 cm-1).
13 C-nmr shows 6 peaks indicating 6 types of C, a C=O (171 ppm, probably
an acid derivative), 2 types in the region of for C=C, one at 141 ppm the
other at 97 ppm plus 3 other hydrocarbon C (61, 18 and 14 ppm)
H-nmr
/ppm

multiplicity

integration

assignment

7.4

doublet of
doublets

=CH coupled to 2 different H

4.9

doublet

=CH coupled to H

4.6

doublet

=CH coupled to H

2.4

triplet

CH2 coupled to 2H, slightly

deshielded

1.7

sextet

CH2 coupled to 5H

1.0

triplet

CH3 coupled to 2H

The most significant structural information in the H nmr data is that we have
an monosubstituted alkene HC=CH2 (not a benzene system), a propyl group
: -CH2-CH2-CH3

Summary....

The MS indicated MW = 114 g/mol.

The IR showed the presence of C=O, C=C and C-O bonds.
13C peak at 171 ppm suggests that the C=O is a carboxylic acid derivative,
probably an ester : RCO2R'
H nmr gives a monosubstituted alkene HC=CH2, and -CH2-CH2-CH3.
Use these pieces to check the molecular formula : C6H10O2 = 6 x 12 + 10 x 1
+ 2 x 16 = 114 g/mol
So with all this information we have the following pieces: -CO2-, -CH2CH2-CH3, and HC=CH2.

Altogether....
We have : -CO2-, -CH2-CH2-CH3, and HC=CH2.
IR and 13C suggest an ester so we have : RCO2R'
The key is to sort out which group is connected to the
carbonyl C=O and which is connected to the -O- of the
ester....
The -CH2- at 2.4 ppm is not deshielded enough to be OCH2- (nearer to 4 ppm), so we must have CH3-CH2CH2-C=O and O-HC=CH2 these connect to give the
answer.

vinyl butanoate
or
ethenyl butanoate

HINTS for PROBLEM #9

Find the molecular weight from molecular ion in the mass spectrum

What functional groups are present from the IR ?

What do the peaks at 7-8 ppm in the H-nmr and at 120-180 ppm in the 13Cnmr reveal ?
Look at the integration in the H-nmr
Use the above to get the molecular formula (make sure it matches the MW)
Count the number of types of C in the 13 C-nmr. What does this tell you ?
(particularly those between 120-180ppm)

What hydrocarbon pieces the H-nmr indicate ?

Using the chemical shifts how are these pieces connected together ?
Symmetry ?

SPECTRA PROBLEM #9 SOLUTION

In the MS, the molecular ion occurs at m/z = 150 indicating the MW = 150 g
/ mol.
The IR shows an C=O (1680 cm-1) and possible C-O (1250-1000 cm-1) but
no -OH or -NH (around 3500 cm-1)
13 C-nmr shows 7 types of C, including a C=O (196 ppm), and 3 ArC (163,
131, 130 and 114 ppm) plus 2 other hydrocarbon C (55 and 26 ppm)
H-nmr
/ppm

multiplicity

integration

8.0

doublet

2 x ArH

7.0

doublet

2 x ArH

3.9

singlet

isolated CH3 deshielded, possibly by O

2.6

singlet

isolated CH3 slightly deshielded

assignment

The lack of a peak at about 9 ppm rules out an aldehyde and therefore
suggests a ketone.
The peaks at 7-8 ppm in the H-nmr and the 4 peaks in the aromatic region of
the 13C-nmr suggests a para-disubstituted benzene
This gives the following pieces C6H4, C=O, and 2 different -CH3

Summary....

The MS indicated MW = 150 g/mol.

The IR showed the presence of C=O and maybe C-O bonds.
The 13C C=O at 196 ppm is a little high for an ester, and is more indicative
of an aldehyde or a ketone.
H nmr gave the following pieces C6H4, C=O, and 2 different -CH3

Leads to a suggested molecular formula of C9H10O = 9 x 12 + 10 x 1 + 1 x

16 = 134 g/mol.
This is 16 short, suggesting an extra O, which if we look at the H-NMR is
probably as part of -OCH3 (peak at 3.9 ppm).
So with all this information we have the following pieces: C6H4, C=O, CH3 and -OCH3

Altogether....
With the pieces we have : C6H4, C=O, -CH3 and -OCH3
IR and 13C suggest a ketone rather than an ester.
H-nmr and 13C-nmr suggest a para-disubstituted benzene
Checking the H-nmr, we can see the two uncoupled methyl groups,
one deshielded by O, the other slightly deshielded by the C=O and the
para-disubstituted benzene.

p-methoxyacetophenone

HINTS for PROBLEM #10

Find the molecular weight from molecular ion in the mass spectrum
What functional groups are present from the IR ?
What type of C=O does the peak at 167 ppm in the 13C-nmr suggest ?
What do the peaks at 4.5-7 ppm in the H-nmr, at 120-140 ppm in the 13Cnmrand at 1650cm-1 in the IR reveal ?
Look at the integration in the H-nmr to make sure
Use the above to get the molecular formula (make sure it matches the MW)
What hydrocarbon pieces the H-nmr indicate ?
Use the H nmr chemical shifts to decide which part is next to the C=O

SPECTRA PROBLEM #10 SOLUTION

In the MS, the molecular ion occurs at m/z = 114 indicating the MW = 114
g/mol (even, no isotope pattern for Cl or Br)
The IR shows a carbonyl C=O (1720 cm-1), C=C (1640 cm-1) and possible
C-O (between 1200-1000 cm-1). No -OH or -NH (above 3200 cm-1).
13 C-nmr shows 6 peaks indicating 6 types of C, a C=O (167 ppm, probably
an acid derivative), 2 types in the region of 125-140ppm for C=C, a C-O at
61ppm and 2 hydrocarbon C (18 and 14 ppm)
H-nmr
/ppm
6.1

multiplicity

integration

"multiplet"

C=C-H

5.5

"multiplet"

C=C-H

4.2

quartet

CH2 coupled to 3H, deshielded by O ?

1.9

singlet

CH3 with no adjacent H, slightly deshielded

1.3

triplet

CH3 coupled to 2H

assignment

The most significant structural information in the H nmr data is that we have
an disubstituted alkene (not a benzene system), an ethyl group : -CH2CH3 most likely as an ethoxy group: -O-CH2-CH3 and an isolated methyl
group : -CH3

Summary....

The MS indicated MW = 114 g/mol.

The IR showed the presence of C=O, C=C and C-O bonds.
13C peak at 167 ppm suggests that the C=O is a carboxylic acid derivative
H nmr also gives a disubstituted alkene, a -O-CH2-CH3 and an uncoupled CH3.
Use this to check the molecular formula : C6H10O2 = 6 x 12 + 10 x 1 + 2 x
16 = 114 g/mol

So with all this information we have the following pieces: C=O, -O-CH2CH3, -CH3 and H-C=C-H or H2C=C.

Altogether....
With the pieces we have : C=O, -O-CH2-CH3, -CH3 and H-C=C-H or
H2C=C.
IR and 13C suggest an ester so we have : CO2CH2-CH3
This means the two substituents on the alkene C=C are the ester group
and the -CH3
There are three possible arrangements: 1,1- , cis-1,2- or trans-1,2If it were 1,2- then the methyl group would have to have an H
neighbour and therefore appear as a doublet (i.e. in a CH3-CH=
system).
Therefore, it must be the 1,1-isomer where is has no adjacent H.....

ethyl methacrylate
or
ethyl 2-methylpropenoate

http://orgchem.colorado.edu/Spectroscopy/Problems/Problems.html

Show Unsaturation answer

C5H10O
Rule 2, omit O, gives C5H10
5 - 10/2 + 1 = 1 degree of unsaturation.
Look for 1 pi bond or aliphatic ring.
Show IR answer
The band at 1716 indicates a carbonyl, probably a ketone. The bands at
3000-2850 indicate C-H alkane stretches.

Show Structure answer

This is the structure. See if you can assign the peaks on your own.
Show NMR answer

Problems list Next Problem

Show Unsaturation answer

C7H14O
Rule 2, omit O, gives C7H14
7 - 14/2 + 1 = 1 degree of unsaturation.
Look for 1 pi bond or aliphatic ring.
Show IR answer
The band at 1718 indicates a carbonyl, probably a ketone. The bands at
3000-2850 indicate C-H alkane stretches.
Show Structure answer

This is the structure. See if you can assign the peaks on your own.
Show NMR answer

Note that D and E are chemically similar enough that their peaks overlap.

Problem 3
Formula: C4H10O
Spectroscopy Reference

Show Unsaturation answer

C4H10O
Rule 2, omit O, gives C4H10
4 - 10/2 + 1 = 0 degrees of unsaturation.
No pi bonds or rings.
Show IR answer
The broad band at 3339 indicates an O-H stretch, probably an alcohol.
The bands at 3000-2850 indicate C-H alkane stretches. The band at 1041
is C-O stretch, consistent with an alcohol.
Show Structure answer

This is the structure. See if you can assign the peaks on your own.
Show NMR answer

A and B do not couple because of A's ability to H-bond.

Problem 4
Formula: C6H14O
Spectroscopy Reference

Show Unsaturation answer

C6H14O
Rule 2, omit O, gives C6H14
6 - 14/2 + 1 = 0 degrees of unsaturation.
No pi bonds or rings.
Show IR answer
The broad band at 3350 indicates O-H stretch, probably an alcohol. The
bands at 3000-2850 indicate C-H alkane stretches. The bands from 13201000 indicate C-O stretch, consistent with an alcohol.
Show Structure answer

This is the structure. See if you can assign the peaks on your own.
Show NMR answer

As noted, C and D are not equivalent even though they're on the same
carbon.

Problem 5
Formula: C4H8O2
Spectroscopy Reference

Show Unsaturation answer

C4H8O2
Rule 2, omit O, gives C4H8

4 - 8/2 + 1 = 1 degree of unsaturation.

Look for 1 pi bond or aliphatic ring.
Show IR answer
The band at 1743 indicates a carbonyl, probably a saturated aliphatic
ester. The bands at 3000-2850 indicate C-H alkane stretches. The bands
in the region 1320-1000 could be due to C-O stretch, consistent with an
ester.
Show Structure answer

This is the structure. See if you can assign the peaks on your own.
Show NMR answer

Previous Problem Problems list Next Problem

Problem 6
Formula: C5H10O2
Spectroscopy Reference

Show Unsaturation answer

C5H10O2
Rule 2, omit O, gives C5H10

5 - 10/2 + 1 = 1 degree of unsaturation.

Look for 1 pi bond or aliphatic ring.
Show IR answer
The band at 1740 indicates a carbonyl, probably a saturated aliphatic
ester. The bands at 3000-2850 indicate C-H alkane stretches. The bands
in the region 1320-1000 could be due to C-O stretch, consistent with an
ester.
Show Structure answer

This is the structure. See if you can assign the peaks on your own.
Show NMR answer

C has a higher chemical shift than D because it's closer to a more

electron-withdrawing functional group.

Problem 7
Formula: C8H14O3
Spectroscopy Reference

Show Unsaturation answer

C8H14O3
Rule 2, omit O, gives C8H14
8 - 14/2 + 1 = 2 degrees of unsaturation.
Look for 2 pi bonds or aliphatic rings, or 1 of each.
Show IR answer
The bands at 1745 and 1716 indicate that there are two carbonyls,
probably an aliphatic ester and an aliphatic ketone. The bands at 30002850 indicate C-H alkane stretches.
Show Structure answer

This is the structure. See if you can assign the peaks on your own.

Show NMR answer

Even though A, B, C and D are all 2H peaks, they can be distinguished by

chemical shift and splitting. B is outside the normal range for protons next
to carbonyls, because it's adjacent to both carbonyls and the combined
deshielding is higher than normal.

Problem 8
Formula: C5H10O
Spectroscopy Reference

Show Unsaturation answer

C5H10O
Rule 2, omit O, gives C5H10
5 - 10/2 + 1 = 1 degree of unsaturation.
Look for 1 pi bond or aliphatic ring.
Show IR answer
The band at 1727 indicates a carbonyl, probably an aldehyde; an
aldehyde is also suggested by the band at 2719 which is likely the C-H
stretch of the H-C=O group. The bands at 3000-2850 indicate C-H alkane
stretches.
Show Structure answer

This is the structure. See if you can assign the peaks on your own.
Show NMR answer

Previous Problem Problems list Next Problem

Problem 9
Formula: C11H14O2
Spectroscopy Reference

Show Unsaturation answer

C11H14O2
Rule 2, omit O, gives C11H14
11 - 14/2 + 1 = 5 degrees of unsaturation.
Look for an aromatic ring, plus 1 other pi bond or aliphatic ring.
Show IR answer
The band at 1603 or 1894 might indicate a carbonyl outside the normal
range; the small peak around 1800 indicates it may be an aldehyde. The
band at 1510 is an aromatic ring. The bands at 3000-2850 indicate C-H
alkane stretches.
Show Structure answer

This is the structure. See if you can assign the peaks on your own.
Show NMR answer

Based on what is covered, you shouldn't need to distinguish between B

and C, but you should be able to tell that the ring is para-substituted.

Problem 10
Formula: C3H6O2
Spectroscopy Reference

Show Unsaturation answer

C3H6O2
Rule 2, omit O, gives C6H6

3 - 6/2 + 1 = 1 degree of unsaturation.

Look for 1 pi bond or aliphatic ring.
Show IR answer
The band at 1716 indicates a carbonyl. The wide band from 3300-2500 is
characteristic of the O-H stretch of carboxylic acids. The bands at 30002850 indicate C-H alkane stretches. The bands in the region 1320-1000
indicate the C-O stretch of carboxylic acids.
Show Structure answer

This is the structure. See if you can assign the peaks on your own.
Show NMR answer

Previous Problem Problems list Next Problem

Problem 11
Formula: C8H8O2
Spectroscopy Reference

Show Unsaturation answer

C8H8O2
Rule 2, omit O, gives C8H8

8 - 8/2 + 1 = 5 degrees of unsaturation.

Look for an aromatic ring, plus another pi bond or aliphatic ring.
Show IR answer
The band at 1689 indicates a carbonyl, probably an acid. The broad dip at
2924 indicates the OH group of the acid. The band at 1589 indicates an
aromatic ring.
Show Structure answer

This is the structure. See if you can assign the peaks on your own.
Show NMR answer

You are not expected to tell the aromatic Hs apart from each other, but
you should be able to tell that the ring is not para-substituted.

Problem 12
Formula: C7H9N
Spectroscopy Reference

Show Unsaturation answer

C7H9N
Rule 3, omit the N and one H, gives C7H8

7 - 8/2 + 1 = 4 degrees of unsaturation.

Look for an aromatic ring, plus another pi bond or aliphatic ring.
Show IR answer
The two bands at 3433 and 3354 indicate a primary amine (-NH2). The
bands at 3000-2850 indicate C-H alkane stretches. The band at 3034
indicates aromatic C-H stretch; aromatics also show bands in the regions
1600-1585 and 1500-1400 (C-C in-ring stretch), and 900-675 (C-H outof-plane). C-N stretch of aromatic amines would show up at 1335-1250
(there is a band in that region).
Show Structure answer

This is the structure. See if you can assign the peaks on your own.
Show NMR answer

You are not expected to tell the aromatic Hs apart from each other, but
you are expected to know that the ring is not para-substituted.
Previous Problem Problems list Next Problem

Problem 13
Formula: C5H13N
Spectroscopy Reference

Show Unsaturation answer

C5H13N
Rule 3, omit the N and one H, gives C5H12
5 - 12/2 + 1 = 0 degrees of unsaturation.
No pi bonds or rings.
Show IR answer
The two bands at 3388 and 3292 indicate a primary amine (-NH2). The
bands at 3000-2850 indicate C-H alkane stretches.
Show Structure answer

This is the structure. See if you can assign the peaks on your own.

Show NMR answer

Note that C is showing as 2 2H peaks, instead of a 4H peak. This may be

caused by a similar effect as in Problem 4 - on each carbon C, the H
closer to the N will be in a slightly different environment. If the rotation of
this carbon is hindered, these Hs may have a different chemical shift.

Problem 14
Formula: C8H14O
Spectroscopy Reference

Show Unsaturation answer

C8H14O
Rule 2, omit O, gives C8H14
8 - 14/2 + 1 = 2 degrees of unsaturation.
Look for any 2 of pi bonds or aliphatic rings.
Show IR answer
The band at 1718 indicates a carbonyl, probably a ketone. The bands at
3000-2850 indicate C-H alkane stretches. Since the compound is an
alkene, one would expect to see C=C stretch at 1680-1640; these weak
bands are not seen in this IR (according to Silverstein, "the C=C
stretching mode of unconjugated alkenes usually shows moderate to
weka absorption at 1667-1640"). Since the compound is an alkene, C-H

stretch should appear above 3000 (not seen: the absorption for this
single hydrogen must be too weak).
Show Structure answer

This is the structure. See if you can assign the peaks on your own.
Show NMR answer

Here, the two E methyl groups have different chemical shifts because
they are permanently locked into different positions with respect to the
alkene.

Problem 15
Formula: C4H9Br
Spectroscopy Reference

Show Unsaturation answer

C4H9Br
Rule 1, replace halogens with hydrogens, gives C4H10

4 - 10/2 + 1 = 0 degrees of unsaturation.

No pi bonds and no rings.
Show IR answer
The bands at 3000-2850 indicate C-H alkane stretches. The bands in the
region 1300-1150 could indicate C-H wag (-CH2Br) of an alkyl halide.
Show Structure answer

This is the structure. See if you can assign the peaks on your own.
Show NMR answer

Previous Problem Problems list Next Problem

Problem 16
Formula: C10H14O
Spectroscopy Reference

Show Unsaturation answer

C10H14O
Rule 2, omit O, gives C10H14
10 - 14/2 + 1 = 4 degrees of unsaturation.
Look for an aromatic ring.
Show IR answer
The broad dip at 3250 indicates an OH group. The peak at 2963 indicates
an alipahtic group. The peaks at 1599 and 1514 indicate an aromatic ring.
Show Structure answer

This is the structure. See if you can assign the peaks on your own.
Show NMR answer

You are not expected to tell the aromatic Hs apart from each other, but
you should be able to tell that the ring is para-substituted.
Previous Problem Problems list Next Problem

Problem 17
Formula: C13H10O3
Spectroscopy Reference

Show Unsaturation answer

C13H10O3
Rule 2, omit O, gives C13H10
13 - 10/2 + 1 = 9 degrees of unsaturation.
Look for 2 aromatic rings plus another pi bond or aliphatic ring.
Show IR answer
The band at 1682 indicates a carbonyl, probably an ester. The band at
3192 indicates C-H aromatic stretch; aromatics also show bands in the
regions 1600-1585 and 1500-1400 (C-C in-ring stretch), and 900-675 (CH out-of-plane). The wide band just to the left of the 3192 band indicates
O-H stretch (alcohols and phenols).
Show Structure answer

This is the structure. See if you can assign the peaks on your own.
Show NMR answer

You're not expected to be able to tell all the aromatic Hs apart. In fact,
there are several structures that could match this pattern, as far as you
can tell from the information on this site:

Previous Problem Problems list Next Problem

Problem 18
Formula: C8H14
Spectroscopy Reference

Show Unsaturation answer

C8H14
8 - 14/2 + 1 = 2 degrees of unsaturation.
Look for any 2 of pi bonds or aliphatic rings.
Show IR answer
The bands at 3000-2850 indicate C-H alkane stretches. There really aren't
many other bands in the spectrum to indicate functional groups. The
compound is an alkyne; we would expect to see a carbon-carbon triple
bond stretch at 2260-2100, however, this is a weak band at best and
often does not show up on IR.
Show Structure answer

This is the structure. See if you can assign the peaks on your own.
Show NMR answer

The integral values for A, B, and C need to be multiplied by 2 to get a

total of 14 protons in the molecule. By convention, integral values on an
NMR spectrum are reported as the lowest common multiple.

Problem 19
Formula: C9H13N
Spectroscopy Reference

Show Unsaturation answer

C9H13N
Rule 3, omit the N and one H, gives C9H12
9 - 12/2 + 1 = 4 degrees of unsaturation.
Look for an aromatic ring.
Show IR answer
The bands at 3000-2850 indicate C-H alkane stretches. The band at 3028
indicates C-H aromatic stretch; aromatics also show bands in the regions
1600-1585 and 1500-1400 (C-C in-ring stretch), and 900-675 (C-H outof-plane). The bands in the region 1250-1020 could be due to C-N
stretch. The weak, broad banc at about 3500 could be amine N-H stretch
or it could be a slight contamination of an impurity (water) in the sample.
Show Structure answer

This is the structure. See if you can assign the peaks on your own.
Show NMR answer

Previous Problem Problems list Next Problem

Problem 20
Formula: C9H10
Spectroscopy Reference

Show Unsaturation answer

C9H10
Rule 2, omit O, gives C7H14
9 - 10/2 + 1 = 5 degrees of unsaturation.
Look for an aromatic ring, plus another pi bond or aliphatic ring.
Show IR answer
The bands at 3000-2850 indicate C-H alkane stretches. The band at 3060
indicates C-H aromatic stretch; aromatics also show bands in the regions
1600-1585 and 1500-1400 (C-C in-ring stretch), and 900-675 (C-H outof-plane).
Show Structure answer

This is the structure. See if you can assign the peaks on your own.
Show NMR answer

Again, the integral values need to be multiplied by two to give the right
number of Hs.
http://orgchem.colorado.edu/Spectroscopy/Spectroscopy.html

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CHEM 39
Answers to Combined Spectral Problems:

Unknown Structure

Alternative
structure

Study questions

How do you know that we

have para disubstituted benzene?
How can you recognize presence of the
ethyl group?
Can the carbonyl groups of an ester and
amide be easily distinguished?

Unknown Structure

Alternative
structure

Study questions

Unknown Structure

Alternative
structure

Study questions

Does the presence of the two carbonyl

peaks in IR mean that we have two
nonequivalent carbonyl groups?
Does the MS allows one to distinguish the
two possibilities?
Could you propose a structure just on the
basis of the molecular formula and 13C
NMR spectrum?

What kinds of carbons are present based on the

proton and carbon NMR spectra?
If the clue about carbon connectivity was not given,
could you distinguished between the two structures?
What is the spectral evidence for the presence of
chlorine?

Unknown Structure

Alternative
structure

Study questions

What is the evidence for the presence of bromine?

How do you know that that there is a CH2 group
present?
Could you decide the position of the Br on the
double bond based on the 1H NMR spectrum?
Could you tell the E and Z isomers apart for the
alternative structure?

Unknown

Structure

Alternative
structure

Study questions

What does the 13C spectrum tell you about symmetry

in this molecule?
What type of functional group is present based on the
1735 cm-1 band in the IR spectrum?
Both the 1H and off-resonance decoupled 13C spectra
indicate the presence of a -CH2- group. How do they
do that?
How can you distinguish between the alternative
structures based on 1H spectrum?

Unknown

Structure

Alternative
structure

Study questions

Unknown Structure

none

Alternative
structure

Study questions

The molecule has 9 carbons. Why there are only

three 13C resonances?
Show how this substitution pattern is consistent
with 1H spectrum.
Is there another way to arrange three methyls on
an aromatic ring to give a compound that will
have only three carbon resonances?

How can you tell the difference between the phenyl

and alkenyl carbons?
How can you tell the difference between the phenyl
and alkenyl protons?
How do you know that the phenyl ring is
monosubstituted?
If the alternative structure were right, could you
distinguish between the E and Z isomers?

Unknown Structure

Alternative
structure

Study questions

What MS pattern tell you about the presence of two

bromine atoms?
How can you tell that the phenyl ring
is para disubstituted (and not ortho, as suggested in
the alternative structure)?
List all the spectral evidence that is inconsistent with
the alternative structure.

Unknown Structure

Alternative
structure

Study questions

Can the presence of the nitro group be deduced from

the IR spectrum?
Can you deduce presence of the propyl group
from 1H spectrum alone?
Would an isopropyl group produce the same 1H
spectrum?
Do you know a way to distinguish between the
alternative structures for the functional group (NO2 vs. -ONO)?

Unknown Structure

Alternative
structure

Study questions

What would the 13C spectrum for the alternative

structure look like?
What would the 1H spectrum for the alternative
structure look like?
What condition would have to be satisfied for both
compounds to show identical 13C and 1H spectra?

Solving Spectral Problems

November 21, 1997

The following is an example of the typical sort of approach that one uses to solve
spectral problems. What you should learn from it is a sense of the logic that's
involved, not the order in which you consider the data (especially that in the nmr
spectrum). It is most important that you work on developing your
own general approach to solving a problem - as usual, this can only be
accomplished through practice. There are lots of opportunities for this between the
problems in Chapter 11 of Ege, Problem Set 9, and Assignment 3.
First, qualitatively examine all the data given, and extract any information that
"jumps out" at you. Then proceed to a more detailed inspection of the data.
The infrared and 1H nmr spectra of a compound with molecular formula
C10H12O2 are shown below. Deduce the structure of the compound from these data.
Note that in the nmr spectrum, the integration has been done for you; the number
of protons responsible for each of the "signals" is indicated right above it in the
spectrum.

C10H12O2 -> 5 sites of unsaturation. For a molecule this size, (i.e., only ten
1.
Molecular carbons), such a large number of sites of unsaturation is usually due to the
Formula presence of a phenyl ring (which provides 4 sites on its own). For a quick proof,
take a quick glance at the 1H nmr spectrum, and look for signals in the 7-8 ppm
(aromatic proton) region. No question, they're there! This leaves only one
site unaccounted for.
- strong peak at ~1700 cm-1 -> C=O (this accounts for the other site of
2.
Infrared unsaturation!)
Spectrum
- nothing at ~3500 cm-1 -> no OH, so a carboxylic acid or alcohol can be ruled
out.
- weak absorption in the 3000-3100 cm-1 region indicative of sp2 C-H stretches,
in addition to prominent bands in the 2800-3000 cm-1 range due to sp3 C-H.
There is lots more information here, but this is the easiest to pull out, and all we
need for the present.
1

H NMR
spectrum

- 6 types of H's:
- singlet at 9.8 ppm (1H) -> aldehyde or carboxylic acid proton. The ir spectrum
rules out a carboxylic acid, so this must be an aldehyde. The absence of coupling
indicates that the -CHO group is bonded to an atom with no protons attached to
it.
- two doublets at ~6.9 and ~7.7 ppm (4H) -> aromatic protons; symmetrical
pattern of two doublets suggests a 1,4-disubstituted benzene. Each doublet
corresponds to 2 equivalent protons, each of which has one nearest neighbour:

Note that the two doublets are skewed towards one another and that the
magnitude of the splitting is the same for both - this verifies that the two
doublets "belong together"; i.e., they represent a pair of protons coupled to each
other.
We've accomplished alot; check the molecular formula to see what's left! We've
accounted for a -CHO group and a -C6H4-. All that's left is three carbons
bearing 7 hydrogens and an oxygen. Since all sites of unsaturation are
accounted for, the seven H's must all be bound to sp3 carbons.
- triplet at ~4 ppm (2H) -> two equivalent protons with 2 nearest neighbours.
With only 3 carbons left, this must be due to a CH2 attached to a CH2!
- triplet at 1 ppm (3H) -> three equivalent protons with 2 nearest neighbours.
This must be due to a methyl group attached to a CH2.
The last two bits of information, coupled with the fact that we have only
C3H7 left, are only consistent with one structure - CH2CH2CH3!
- sextet at ~1.8 ppm (2H) -> two equivalent protons with 5 nearest neighbours.
This is the middle CH2 in the -CH2CH2CH3 chain.

Let's take stock of what we have:

There are only TWO possible ways that these fragments can be put together:

To choose between the two, we need to take a closer look at the nmr spectrum and
ask "how will the spectra of these two compounds differ?" One set of protons will
have a significantly different chemical shift in the two structures. (Sometimes,
more than one set can be identified as being significantly different; sometimes
none can, in which case we would need more data). This is the terminal
CH2 group in the CH2CH2CH3chain. In A, it's attached to oxygen and should
come at around 4 ppm (look at the table of "representative chemical shifts" in Ege).
In B, it's attached to an sp2 carbon and should come at 2-2.5 ppm. Clearly,
structure A is the one that fits the spectrum the best.

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