Aliphatic Amide Groups

Chemical Properties

Amides have quite high boiling points because they are capable of
strong intermolecular interactions.

In the laboratory, amides are made by the reaction of ammonia with

acid chlorides or acid anhydrides. Industrially, they are often prepared
by heating the ammonium salts of carboxylic acids.

Spectral Interpretation

NH stretching
Primary Near 3350 - 3180 cm-1
Secondary 3320 - 3070 cm-1(trans and cis)
CO (amide I)
Primary Near 1650 cm-1
Secondary 1680 - 1630 cm-1
Tertiary 1670 - 1630 cm-1
NH2 def. (amide II)
Primary 1650 - 1620 cm-1
Secondary 1570 - 1515 cm-1
Amide III
Secondary Near 1270 cm-1
Aliphatic Alkyne Groups

Chemical Properties

Alkynes have the general formula CnH<SUB<2< sub>n-2. Then

simplest member of the alkyne family is acetylene which has the
formula:

H:C:::C:H m.p. -82 / b.p. -75

The IUPAC naming is based on the closest triply bonded carbon.

CH3-C:::C-CH(CH3)2 chain = Five carbons; 4-Methyl-2-pentyne

Acetylene is the family member of chief industrial importance and is
prepared by the action of water on calcium carbide.

Spectral Interpretation

R-C:::C-R'

The infared spectroscopic detection of the alkyne triple bond depends

on the substitution. The mono-substituted acetylenes can easily be
identified by the strong -C:::C-H (carbon hydrogen) stretching
absorption around 3300 cm-1. In the di-substituted alkyne there are no
hydrogens on the triply bonded carbons and this band is absent. If the
substitution is asymmetric the -C:::C- (carbon carbon) stretching
absorption around 2100 cm-1 may be used as an indicator. If the
substitutions is symmetric about the alkyne bond, this absorption will
be weak or non-existent.
1-octyne is asymmetric with a hydrogen on the triply bonded carbon.
Therefore the bands around 3300cm-1 and 2100cm-1 are present. 4-
octyne is symmetric with regard to the triple bond with no hydrogen
atoms on the triply bonded carbon. In this case there the characteristic
absorptions are absent.

Aliphatic Groups
Aliphatic Functional Groups
Aliphatic groups are found in many compounds that the
infrared spectroscopist is likely to encounter. The most
important vibrational modes are the C-H stretching around
3000 cm-1 and the -CH deformation modes around 1460 cm-1
and 1380 cm-1. The atoms directly attached to the alphatic
groups may result in significant shifts from the standard
frequencies. In particular adjacent atoms with high electro
negativity will shift the band locations to higher frequencies.

-CH3 and –CH2 Stretching Absorptions

The CH3 asymmetric stretching vibration occurs at 2975-2950
cm-1 while the CH2 absorption occurs at about 2930 cm-1. The
symmetric CH3 vibration occurs at 2885-2865 cm-1 while the
CH2 absorption occurs at about 2870-2840 cm-1.

-CH3 Deformation Absorptions

The CH3 asymmetric deformation vibration occurs at 1470-
1440 cm-1. This band is overlapped with the CH2 scissor
vibration which occurs at 1 490-1440 cm-1. The symmetric
CH3 vibration occurs at 1390-1370 cm-1. The relative
intensities of the asymmetric CH3 and the CH2 scissor bands
can be used as an indicator of their proportions in the
molecule.

-CH3 Deformation Absorption Band Splitting

When there are more than one methyl group on a single
carbon the symmetric CH3 vibration which occurs at 1390-
1370 cm-1 becomes split into two bands. When three methyl
groups are on a single carbon (t-butyl) a band appears near
1365 cm-1 and a weaker band appears near 1390 cm-1. When
two methyl groups are on a single carbon (isoproply) bands of
approximately equal intensity occur at near 1390 and 1365
cm-1. The presence of the t-butyl group can be confirmed by
the presence of bands around 1255 and 1210 cm-1 while the
isopropyl group shows bands near 1170 and 1145 cm-1.

-(CH2)n -Rocking Absorption

When there are four or more CH2 in a row, a rocking
absorption is found centered at 720 cm-1. This absorption
splits into two bands when the number of adjacent methylene
groups reaches about ten methylene groups.

©2001, 2008 Thermo Fisher Scientific Inc.

Alcohol Functional Groups
Alcohol Chemical Properties
Alcohols are compounds which contain the hydroxyl (-OH)
group. These compounds are classified as primary, secondary
or tertiary according to the number of other carbon atoms
attached to the oxygen bound carbon.
Alcohols contain the very polar -OH group. This allows
hydrogen bonding between molecules in the condensed phase.
Due to this hydrogen bonding the boiling points of alcohols
are much higher than the corresponding alkane with the same
number of carbon atoms.

-C-O stretching and -OH deformation vibrations

Primary alcohols 1050 cm-1
Secondary alcohols 1100 cm-1
Tertiary alcohols 1150 cm-1
Phenols 1200 cm-1
-OH stretching frequencies Free -OH form
Primary alcohols 3643 - 3630 cm-1
Secondary alcohols 3635 - 3620 cm-1
Tertiary alcohols 3620 - 3600 cm-1
Phenols 3612 - 3593 cm-1