Putting together organic molecules: death taxes and

Practice this in Exercise 1.

The following species are not stable, but are reaction intermediates...
CH3
Carbanion

CH3

Loss of H+

Carbocation

Loss of H

H
Loss of H

CH3
Free radical

C
H

H
H

Loss of H2
CH2
Carbene

The other elements of row 2...

H

H
N

Loss of H+

Gain of H+

N
H

Replacement of one or more hydrogen atoms with a carbon-based group gives

an amine: an organic derivative of ammonia.

O
H

Loss of H+

Gain of H+

O
H

Replacement of a hydrogen atom with a carbon-based group gives an alcohol:

an organic derivative of water.
Exercise 2

CH3OH Methanol

H
H

Isomerism
CH4

C2H6

C4H10

C5H12
Constitutional isomers ...

C3H8

C3H8O

Positional isomers ...

Functional isomers...

Ex. 14

Drawing molecules showing their proper shape:

Condensed Structures - for saturated carbons i.e. having four single bonds
Hydrocarbon Fragments
Name

Structure

Condensed Form

Methyl

CH3

HS

CH3

H
H

Methylene

CH2

Cl CH2 Cl

OCH3

Methine

CH

H3CO

CH
CH3

Exercise 5

Condensed structure

Line Structures

When drawing line structures:

use lines to represent carbon-carbon bonds
CH bonds are not usually shown, nor are the atom labels
heteroatoms and H atoms attached to them are always shown
show all the atoms in functional groups (usually condensed)

Beware
The same molecule can be drawn in many different ways and in many different
orientations.

Full

O
H3C CH2 CH2 C

H3C CH2 CH2 C

CH3

CH3
H3C

C CH2 CH2 CH3

O

CH3CH2CH2COCH3

CH3(CH2)2COCH3

For most (neutral) organic compounds, Lewis structures can be determined simply by
taking the connectivity implied, remembering that there are 4 bonds to carbon, 3 to
nitrogen, 2 to oxygen and 1 to hydrogen and by filling octets.

CH2O

H3CSOCH3

HCONH2

H2COH+

CH3OCONH2

H2CN-

[H2CCHO]-

[H2NCHNH2]+

This is an extremely important case. Whenever you have a structure in which

there is an atom with a lone pair adjacent to a multiple bond, you can ALWAYS
draw an additional resonance structure.

6) When resonance structures are not degenerate, use the following rules
to judge which structures contribute more to the character of the species:

iii) In cases where there are resonance structures with the same number of formal
charges, the favoured structure will be that in which the negative charge is on the more
electronegative atom or positive charge is on the more electropositive element.
N

Invalid Resonance Structures

i) have more than eight electrons on a second
row element

N

ii) have less than eight electrons on O or N (or similarly

electronegative element)

O
C
H

CH2

O
C
H

CH2

iii) have more than two atoms bearing formal charges (excepting polynitros and a few
special cases).

X
O

C
O

iv) have any atom with a formal charge greater than +/-1. Beyond the second
row of the periodic table this rule may not apply.

2O

Practice

C
H3C

NH2

O
1

C
H3C

NH2

O
2

C
H3C

NH2

O
3

C
H3C

NH2

O
4

Given a structure, you should be able to deduce all reasonable resonance structures

Where can we get information about species that display resonance?

Spectroscopy, diffractometry, calculation.
C=N: 1.28
C-N: 1.48
C=O: 1.20
Amide:
CO: 1.22
CN: 1.39
IR, NMR, Structure

SO2: 1.44
SOH: 1.715
DMSO: 1.557

What do resonance structures tell us?

Resonance structures are a simple way to describe electron delocalization.
They give us information about structure, reactivity/stability and pi MO structure (i.e.
no of pi MOs).

Where does protonation occur? NMR? Geometry around N?

Carbon atoms are classified based on the number of carbons attached to them.
Primary (1), secondary (2), tertiary (3), quaternary (4), alkenyl, aryl, alkynyl
Alkenyl protons

1
CH3
1
H3C

3
H

1
CH3

2
CH2

H
C

Alkenyl carbons

Aryl carbons and aryl protons

Alkynyl carbons

2
CH2
C

See text page 23.

CH3 1

H3C
CH3 1
Alkynyl proton 1
Until you hear otherwise, the terms primary, secondary, tertiary and quaternary shall apply to saturated
carbons. So, in the exercise where I ask you to come up with a molecule that contains only 3 carbons,
benzene would not be a correct answer.

This terminology is also applied to amines...

H

N
H

and amides...
O
C
H3C

N
H

CH3

N
R

R
R

N
R

R R

N
R

Alcohols and alkyl halides are classified based on the type of carbon to
which the OH or X group is attached: