Guide to Solving Spectroscopy Problems

by Jessica Reel, Fall 2016

Shown below are the MS, IR, 1H NMR, and 13C NMR spectra of an unknown compound.
What is the structure of this compound?
These types of problems are common in undergraduate organic chemistry. The easiest way to go about
solving these is to make a list of all the information that you can glean from the provided spectra, and
then solve the structure bit by bit, similar to a jigsaw puzzle.

1. MS: gives molecular weight, presence of halogens

The mass spec molecular ion peak, designated as M or M+, gives the molecular weight.

An M+2 peak roughly the same height as the M peak indicates Br; an M+2 peak that is 1/3 the
height of the M peak indicates Cl.

If the molecular (or empirical) formula is not given, use the molecular weight to make a list of
possible formulas. C has a mass of 12, H = 1, O = 16. Use other spectra to refine the list.

2. Molecular (or empirical) formula: degree of unsaturation

If the compound has only C, H, and (optionally) O atoms, its fully saturated if the formula fits
the pattern

Cn H2n+2 O(any)

If its not fully saturated, you can calculate the degree of unsaturation (DoU) as follows:
+
= + = 1 + (
)
2
where C = number of carbons, H = number of hydrogens, X = number of halogens, and N =
number of nitrogens. (Note that oxygen has no effect on degree of unsaturation.)

An alternate method for determining DoU: Draw any structure that contains the same number
of C, N, O, X, etc. atoms as the molecular formula, disregarding Hs. Do not include any rings or
-bonds in your drawing, and use as many hydrogens as needed to complete the octet for each
atom. Count the number of Hs in your structure and subtract the number of Hs in the actual
molecular formula. The difference, divided by two, equals the degree of unsaturation.

If the degree of unsaturation is at least 4, its reasonable to assume a benzene

sub-structure (1 ring + 3 bonds)

3. IR: what functional groups are present or absent?

Dont try to assign every peak in the spectrum. Look for the presence or absence of a few key
peaks; use the DoU to rule out possible functional groups (such as C=O and C=C) beforehand.
The table below lists the most informative IR peaks from left-to-right; the most important peaks to
check for first are highlighted in blue.

Guide to Solving Spectroscopy Problems

Stretch
OH

4.

Approx. cm-1
35003100
33002500

NH

35003300

CH
=CH
CH
O=CH
CC, CN
aromatic
C=O
C=C

3300
31003010
29502850
28302700
22602100
20001600
18001650
16801600

13

Appearance
Very broad, smooth hump.
Very broad but jagged. May overlap
with CH stretches.
Two somewhat broad peaks.
One somewhat broad peak.
Strong, sharp peak.
Medium intensity.
Medium to strong intensity.
Small sharp peak.
Relatively weak, but easy to spot.
A group of fairly weak peaks.
Very strong, sharp peak.
Intensity may vary.

J. Reel, Fall 2016

Indicates
Alcohol
Carboxylic acid
(if C=O also present)

1 amine/amide
2 amine/amide
Terminal alkyne
Alkene/aromatic
Alkyl groups
Aldehyde
Triple bond
Aromatic
Carbonyl
Alkene

C NMR: how many, and what types, of carbons?

Number of peaks = number of chemically inequivalent carbons. These are carbons that cannot
be exchanged or interconverted via symmetry or bond rotation.

Peak height (integration) is not useful information in 13C NMR.

The chemical shift (ppm) gives information about the functional group containing the carbon.
Carbons near electronegative atoms (O, N, F, etc.) are more deshielded (higher ppm).
Approx. ppm
< 0 ppm (rarely seen)
040 ppm
3080 ppm
65100 ppm
77 ppm, 1:1:1 triplet
100150 ppm
160210 ppm

Type of carbon
carbon attached to a metal
sp3 carbon NOT attached to an electronegative heteroatom.
sp3 carbon attached to an electronegative atom (O, N, X, etc.)
alkyne sp carbons ( CC )
signal for CDCl3 solvent; not part of the structure youre solving
sp2 carbons (alkenes and aromatics)
carbonyl (C=O) carbons

13

DEPT-135 spectra will show CH and CH3 peaks above the baseline, CH2 below the baseline, and
omit quaternary carbons (including C=O). DEPT-90 will show only CH peaks (above the baseline).
These can be useful for determining sub-structures (puzzle pieces).

C NMR spectra are often acquired in proton decoupled mode. However, if you are given a
proton coupled spectrum, you can use it to determine how many Hs are attached to each C, via
the splitting patterns: a carbon with N attached hydrogens will be split into N+1 peaks.

5. 1H NMR: how many, and what types, of hydrogens?

Number of peaks =number of chemically inequivalent hydrogens.

H NMR spectra tend to take the most time to analyze, so you may want to do that last.

Guide to Solving Spectroscopy Problems

J. Reel, Fall 2016

Peak height (integration) gives a ratio of how many Hs produced each signal. Divide all
integrations by the smallest integration to give the ratio of protons for each peak.

As with 13C NMR, the chemical shift gives information about the functional group:
Approx. ppm
02 ppm
23 ppm
35 ppm
56 ppm
68 ppm
910 ppm
1012 ppm

Type of proton
sp3 CH attached to another sp3 C
sp3 CH attached to C=O, C=C, or C=N,
OR terminal alkyne CCH (singlet)
sp3 CH attached to O, N, or halogen
alkene sp2 C=CH
aromatic sp2 C=CH
aldehyde O=CH
carboxylic acid COOH

The splitting pattern tells how many non-equivalent protons are on the same carbon or adjacent
carbons. A signal will be split into N+1 peaks by N non-equivalent neighboring protons. (Each
non-equivalent neighboring H adds 1 to the multiplicity.) A signal which is not split (a singlet)
means the proton has no adjacent non-equivalent H atoms, indicating that the carbon which
bears the proton is likely connected to a heteroatom (O, N, etc.) or a 4 carbon (including C=O).
Some common splitting patterns are provided in the table below:
Common 1H NMR patterns
3H singlet between 04 ppm
2H quartet with a 3H triplet
1H sextet with a 6H doublet
9H singlet between 03 ppm
two 1H doublets around 6 ppm
three 1H doublet of doublets

Indicates this
( indicates a heteroatom or 4 C)
methyl group
CH3
ethyl group
CH2CH3
isopropyl group
CH(CH3)2
tert-butyl group
C(CH3)3
alkene with 2 different
CH=CH
substituents (see below)
C=CH2
vinyl group
CH=CH2

(may be hard to distinguish)

two 2H doublets around 7 ppm

one 1H s, two 1H d, one 1H dd
two 1H d, two 1H dd

para-disubstituted benzene
meta-disubstituted benzene
ortho-disubstituted benzene

(these may be difficult

to discern; may appear
as a multiplet)

When comparing two H atoms on a ring or double bond, the two protons are equivalent only if
they are cis and trans to the same groups; see the examples below.

These dichloroethenes each produce one singlet

in the 1H NMR spectrum.

These bromochloroethenes each produce two doublets

in the 1H NMR spectrum.

Chlorocyclopropane gives rise to 3 separate 1H NMR signals.

Guide to Solving Spectroscopy Problems

J. Reel, Fall 2016

A special note about OH and NH proton signals: They may not be visible on the spectrum, may
appear over a wide ppm range, may be broad, tend not to split, and may not integrate to the
expected ratio. They will also exchange with D2O, which will cause them to no longer show up
on the spectrum.

6. Put the pieces together!

Draw all the known sub-structures or functional groups; dont worry about connecting them yet.

Double-check that all the pieces add up to the molecular formula (or molecular weight).

Account for degree(s) of unsaturation. If the DoU > 0 and none of the spectra indicate bonds,
you probably have a cyclic compound.

Try to connect pieces, based on 1H NMR splitting patterns (neighboring Hs)

Chemical shift can tell you if a C or H is next to an O, F, Cl, Br, N, C=O, etc.

The mass spec fragmentation pattern (if provided) can give clues. A series of high-intensity
peaks all separated by 14 (corresponding to CH2) is characteristic of long-chain hydrocarbons.

Assemble the pieces into an educated guess for the complete structure.

Once you make a complete structure, double-check! Does this structure make sense? Would
this structure have produced exactly these spectra?