CH203

Lecture 8
September 19

Review and clarifications
3
Functional Groups
Functional group: An atom or group of atoms within a
molecule that shows a characteristic set of chemical
reactivities.
Functional groups are:
1. The units by which we divide organic compounds into
classes.
2. The sites of characteristic chemical reactions.
3. The basis for naming organic compounds.
4
Alcohols
An alcohol contains an -OH (hydroxyl) group bonded to
a carbon atom with four single bonds.





Ethanol may also be written as a condensed structural
formula.
CH
3
-CH
2
-OH CH
3
CH
2
OH
or
5
Alcohols
Alcohols are classified as primary (1), secondary (2), or
tertiary (3) depending on the number of carbon atoms
bonded to the carbon bearing the -OH group.
6
Alcohols
There are two alcohols with the molecular formula C
3
H
8
O.
7
Amines
Contain an amino group; a nitrogen atom bonded to
one, two, or three carbon atoms by single bonds.
An amine are classified as 1, 2, or 3.
8
Aldehydes and Ketones
Contain a carbonyl (C=O) group.
9
Carboxylic Acids
Contain a carboxyl (-COOH) group.
10
Carboxylic Esters
Ester: A derivative of a carboxylic acid in which the
carboxyl hydrogen is replaced by a carbon group.
11
Carboxylic Amides
Amide: A derivative of a carboxylic acid in which the
-OH of a -COOH group is replaced by an amine.




12
Valence-Shell Electron Pair Repulsion (VSEPR) is based on
twin concepts
Atoms are surrounded by regions of electron density.
Regions of electron density repel each other.
Bond Angles and Shapes of Molecules
13
VSEPR
What is the hybridization of N in the structure above?

(Is this what an amide actually looks like?)
14
The Electronic Structure of an Amide
Amides have structural characteristics that are unique among carboxylic acid derivatives.
Had you been asked in Chapter 1 to describe the geometry of an amide bond, you
probably would have predicted bond angles of 120 about the carbonyl carbon and
109.5 about a tetrahedral amide nitrogen. In the late 1930s, one of Linus Paulings most
important discoveries was that the geometry of the nitrogen atom of an amide bond in
proteins is actually trigonal planar (sp2), not tetrahedral (sp3). A large number of
subsequent experiments have verified that amides should be thought of as being best
represented as the resonance hybrid of three resonance contributing structures, not two
like other carbonyl species. In the unique third contributing structure of an amide, the
lone pair on nitrogen donates electron density to create a pi bond between carbon and
nitrogen. (http://iverson.cm.utexas.edu/courses/310N/POTDSp06/POTD2-17-12.html)
15
VSEPR and the amide group
It is estimated from computer models that acetamide
may be described as 62% A and 28% B.

Kemnitz, Carl R.; Loewen, Mark J. (2007). ""Amide Resonance" Correlates with a
Breadth of CN Rotation Barriers". Journal of the American Chemical Society 129 (9):
25218
A B
16
Real picture of an amide group
Inclusion of the third resonance contributing structure explains why the
amide nitrogen is sp2 hybridized and therefore trigonal planar. The
presence of a partial double bond (pi bond) in the resonance hybrid
indicates the presence of a restricted bond rotation about the C-N bond.
In fact, the measured C-N bond rotation barrier is on the order of 63-84
kJ/mol in amides, enough so that the bond does not rotate appreciably
at room temperature. (iverson)
17
pi-like character of the C-N amide bond
Bond Barrier to rotation (kJ/mol)

C-C ethane 12.5

C-C butane 19

N-C amide 62-84

C=C 272
18
Cahn-Ingold-Prelog Rules (simple version)
19
Cahn-Ingold-Prelog Rules (simple version)
20
Cahn-Ingold-Prelog Rules (simple version)
21
Multiple Stereocenters
22
Multiple Stereocenters
23
Multiple Stereocenters
24
Meso Compounds
25
Meso Compounds
The best way to identify a meso compound is to prove that it is superimposable with its mirror
image. However, a quick test is to see if it contains a plane of symmetry:
Compounds containing a plane
of symmetry are achiral!
No plane of symmetry