Example 14

C
4
H
6
O
MW 70
Calculate the degree of unsaturation: the answer is 2. The molecule has 2 double bonds and/or
rings.
IR Spectrum
Since the molecule has an oxygen and two double bonds, look for a carbonyl band. There is one
at 1693, and the compound is probably an aldehyde because of the C-H stretch bands from 2830-
2695. Also look for a C=C stretch at 1680-1640: there is a band there, at 1641, indicating an
alkene.

NMR Spectrum
From the IR and degree of unsaturation, we suspect both an aldehyde and a carbon-carbon
double bond. The peak of one proton at 9.9 ppm supports the presence of an aldehyde. The peak
at 2 ppm is a methyl group next to a carbon that has one hydrogen.

There are only 4 carbons in the molecule - these groups "tie up" 3 of them. One of two ways the
molecule can be put together is shown below (the molecule is drawn trans, the other way would
be the cis isomer).


The discussion above does not cover coupling constants or the explanation for the number and
type of peaks seen in the NMR spectrum; knowledge of these details allow you to designate
whether the molecule is cis or trans. If you want to learn more about this, ask your TA or
instructor or consult one of the references.
Summary
Example 14 is trans-2-butenal:


Example 15
C
6
H
10

MW 82
Calculate the degree of unsaturation: the answer is 2. The molecule has two double bonds and/or
rings.
IR Spectrum
The IR spectrum below doesn't show much of interest. We would expect two carbon-carbon
double bonds (1680-1640), or one carbon-carbon triple bond (2260-2100). Could it be a ring, or
two rings? The C-H stretching vibrations are all under 3000, indicating that there are no
hydrogens on a carbon-carbon double bond or on a carbon-carbon triple bond - it is possible that
the compound is a internal alkyne.




NMR Spectrum

The above spectrum indicates two identical -CH2CH3 groups. The degree of unsaturation of 2
both hints at an alkyne, although the carbon-carbon triple bond stretch 2260-2100 is not seen.
This does not rule out the compound being an alkyne, because the normally weak carbon-carbon
triple bond stretch is not observed in a symmetrically substituted alkynes. If we put the carbon-
carbon triple bond in the middle of a straight carbon chain molecule, we get this:

This compound has two equivalent ethyl groups and a symmetrically substituted carbon-carbon
triple bond. The C-H stretch is not seen in the IR because it is not a terminal alkyne (and
therefore does not have a C-H on the triple-bonded carbon. This is how it correlates with the
NMR spectrum:


Summary
Example 15 is 3-hexyne:


Example 16
C
3
H
5
O
2
Br
MW 153
Calculate the degree of unsaturation: the answer is 1. The molecule has one double bonds or
rings.
IR Spectrum
Since the molecule has an oxygen and one degree of unsaturation, look for a carbonyl band -
there is one at about 1700. There is also a wide O-H stretch band centering about 3000; this is
characteristic of a carboxylic acid.

NMR Spectrum

The singlet at 11.6 ppm supports the IR suggestion that the compound is a carboxylic aci, R-
CO
2
H. The triplets of two hyrogens each at 3 and 3.6 ppm indicate two different methylene
groups, both adjacent to a carbon that has two hydrogens. Since the molecule only has 3 carbons,
these must be next to each other. A methylene group which has a bromine on the same molecule
will be from about 2.5-4 ppm and a methylene group adjacent to a carboxylic acid will be from
about 2-2.7 ppm. The following molecule satisfies these criteria:


Summary
Example 16 is 3-bromopropionic acid:


Example 17
C
7
H
8
O
MW 108
Calculate the degree of unsaturation: the answer is 4. The molecule probably has an aromatic
ring.
IR Spectrum
The most prominent band is the O-H stretch at 3335. Also look for aromatic bands from 1600-
1585 and 1500-1400: they are present.

NMR Spectrum

The 4 protons from 6.6-7.2 ppm indicate an ortho- or meta-disubstituted aromatic ring. The
phenol proton, -OH, shows up anywhere from 4-12 ppm; the singlet at 5.2 ppm indicates this
proton. Since the ring is disubstituted, the singlet at 2.3 ppm of 3 hydrogens must indicate a
methyl group on the ring.


Summary
Example 15 is 3-methylphenol:


Example 18
C
4
H
9
NO
MW 87
Calculate the degree of unsaturation: the answer is 1. The molecule has one double bonds or one
ring.
IR Spectrum
Look for C=C (1680-1640) or C=O (1760-1665) stretching vibrations - there are none. Since the
molecule has a nitrogen, look for a band in the region 3400-3250 - there is a band at 3335, which
probably indicates the N-H stretch of a primary or secondary amine. Since the molecule has an
oxygen, look for O-H stretch: the band in this region more resembles N-H stretch than O-H
stretch. (See examples 3, 11, and 12). This compound is a good candidate for containing a non-
aromatic ring.

NMR Spectrum

The singlet at 1.6 is in the region 0.5-3.0 ppm, indicating a single amine proton. The NMR shows
2 sets of equivalent methylene (-CH
2
-) groups, each of which is next to a carbon with 2
hydrogens.
You can try drawing different structures for this compound. When you are done trying, the
correct structure is drawn below. Hydrogens on a carbon which is adjacent to a nitrogen show up
from 1.5-2.0 (see Amines); while hydrogens on a carbon adjacent to an oxygen show up from
3.3-4.0 ppm (see Ethers).


Summary
Example 18 is morpholine: