Structure and Nomenclature. Developing Lewis Structures For Organic Compounds 1. Draw the full structure of the molecules with the connectivity suggested.

Structure and Nomenclature

ethaneethene

(ethylene)ethyne

(acetylene)

C C

H

H H

H

C CH HC C

H

H

H

H

H

H

Three bonds to nitrogen...

N

H

HH

ammonia

N

H

C

H

aminomethane(methylamine)

H

H

H

CC

H

H

H

N

acetonitrile

Stable carbon-containing compounds have four bonds to carbon.

Two bonds to oxygen...

HO

HH

O C

H

H

H

C

O

HHwater

methanol f ormaldehyde

One bond to H, F, Cl, Br, I...

C C

H

H H

ClC

H

BrH

H

bromomethanechloroethene(vinyl chloride)

Developing Lewis Structures For Organic Compounds1. Draw the full structure of the molecules with the connectivity suggested by the formula such that all valences are met (octets for C, N, O, F, Cl, Br, I - ALWAYS).

2. Always show all valence electrons (bonds and lone pairs).

a) Count the number of valence electrons in the entire molecule (each atom has the same number of valence electrons as its group number in the periodic table).

b) From the number in a, subtract the number of bonding electrons (2x the number of lines in your structure). Any electrons that are unplaced are added to atoms that lack a full octet (usually heteroatoms) as lone pairs.

c) Atoms still lacking octets are satisfied by using lone pairs from adjacent atoms to form multiple bonds.

3. Always show formal charges according to the following formula:

FC = # of valence electrons – (# of bonds to that atom) – (# of lone pair electrons)

4. Formal charges of 0 is always better than charge separation.

5. No charges on carbon if the molecule is neutral.

Developing Lewis Structures For Organic Compounds

6. Never draw structures with adjacent like charges.

7. Do not place multiple charges on 1st and 2nd row atoms (-1 and +1 only).

8. When placing charges, - charges should be placed on the more electronegative atoms and + charges should be placed on the less electronegative atoms.

9. In general, H only needs 2 electrons, B and Al need only 6 electrons, and atoms below the second row may have more than 8 electrons.

10. Avoid the formation of O-O bonds when possible and the formation of Halogen-Heteroatom bonds. A heteroatom is any atom other than Carbon or Hydrogen.

Drawing Organic molecules - Condensed and Line Structures.

Name Expanded form Condensed form

methyl

methylene

methine

C

H

H

H

C

H

H

C H

CH3

CH2

CH

Hydrocarbon fragments.

Full Structure (expanded form)

H C

H

H

C

H

H

C

H

H

C

O

O H

Writing condensed structures…

The condensed form of most functional groups is written backwards if the group is found on the left hand side of the structure...

H O CH2 CH3 HOCH2CH3 not OHCH2CH3

Writing line structures…

H C

H

H

C

H

H

C

H

H

C

O

C

H

H

H

Expanded Structure

When drawing line structures:

•use lines to represent carbon-carbon bonds.

•ignore carbon-hydrogen bonds in hydrocarbon units.

•always draw heteroatoms and hydrogen atoms attached to heteroatoms.

•draw all the atoms for functional groups (for the most part).

H CN

O

SH

Line structures are very useful for cyclic molecules.

C C

CC

C

H HO

H

HHH

H

H

H

H

C N

O

O

CC

C

C C

HH

H

H H

OH

NO2

These examples demonstrate how ‘clean’ line structures look compared to expanded or even condensed structures.

Practice!

C

C

CC

C

O

C

H

H

H

H

HHH

H

H

H

N C

H

H

H

H

C

Cl

H

C

H

H

H

Practice!

CN

NH

C CH3

O

Warnings: •The end of a line represents a methyl group not a hydrogen atom. •If you draw ‘C’, you must draw all atoms attached to it.

Warnings: •The end of a line represents a methyl group not a hydrogen atom. •If you draw ‘C’, you must draw all atoms attached to it.

Ultimately, organic molecules are usually drawn as a mixture of expanded, condensed, and line structures. Be careful however, molecules can be drawn many different ways and look completely different...

H3C CH2 CH2 C

O

CH2 C H

O

H2C

CH2H3C

C

O

CH2

CO H

CHO

O

CH3CH2CH2COCH2CHO

H

CH

H

C

H

H

C

H

H

C

O

C

H

H

C

O

HO

CCH3CH2CH2 CH2 C

O

H

H

O OO

OH

(CH2)2 C

O

CH2 C H

O

H3C

For most (neutral) organic compounds, Lewis structures can be determined simply by taking the implied connectivity and ensuring that each atom has an octet of electrons (except H of course). Remember, 4 bonds to carbon, 3 bonds to nitrogen, 2 bonds to oxygen, and 1 bond to hydrogen.

O

CCC

H

HH C

H

HH

CH N

C

H

H

HH

C C C

Cl

HH

H

For most (neutral) organic compounds, Lewis structures can be determined simply by taking the implied connectivity and ensuring that each atom has an octet of electrons (except H of course). Remember, 4 bonds to carbon, 3 bonds to nitrogen, 2 bonds to oxygen, and 1 bond to hydrogen.

C C

C

S

CHH

H H

(CH3O)2CH+

Drawing Organic Molecules in Chem2500

•Remember your bond angles

•You must use dashes and wedges to depict 3-dimensionality

•Always draw lone pairs

In Chem2500, your structures will be graded so practice!

Rules for Drawing and Interpreting Resonance Structures

Resonance structures show how electrons are delocalized within a species. When drawing and evaluating resonance structures, it is important to keep track of any and all lone pairs (unshared electron pairs).

1. Only lone pair electrons and multiple-bond electrons (pi-electrons) move from one resonance structure to another. Atoms never move.

H2CC

H

O

H2CC

H

O

H2CC

H

OH

H3CC

H

O

2. From structure to structure, electron pairs move in the following ways:

lone pair to form adjacent bond:

bond to form a lone pair:

bond to form a new bond:

C O

H

H H

C O

H

H H

H2CC

CH2

H

CH2

CH2C

H

H3CS

CH3

O

H3CS

CH3

O

3. Electrons move only to adjacent positions, but more than one pair of electrons can move from one structure to another:

4. Always check to see what happens to the formal charges on specific atoms. The net charge on each structure must be the same.

5. Structures that are identical in form are said to be degenerate. Such structures contribute equally to the overall structure. Resonance ‘hybrids’ are often drawn of such strucutres.

N N O N N O

H2CC

CH2

H

CH2

CH2C

H

CH2

CH2C

H

=

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

i) resonance structures in which second row atoms (B, C, N, O, F) all have octets are favoured over those with electron deficient atoms – resonance structures (and Lewis structures for that matter) in which these atoms have more than 8 electrons are not valid.

ii) when comparing resonance structures with the same number of bonds, structures with fewer formal charges contribute more to the character of a species.

C O

H

H H

C O

H

H H

NC

H

HH

O

NC

H

HH

O

N N O N N O

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.

a) structures with more than 8 electrons on a second row element.

Invalid Resonance Structures

N N O N N O N N OXb) structures with less than 8 electrons on N or O (or similarly electronegative elements).

OC

CH2

H

CH2C

O

HX

NCO O C N O C N2-

X

c) structures with more than two atoms bearing formal charges (excepting polynitros and a few others).

d) structures containing atoms with formal charges greater than +/-1 (excepting S).

OC

O

H

OC

O

H

OC

O

H

X

CH3NO2

H2CN2

HCONH2

HCO2-

For the following molecules, draw the Lewis Structure and all valid Resonance Structures.

Isomerism

CH4 C2H6 C3H8

C4H10 C5H12

C3H8O

Constitutional Isomers:

How many constitutional isomers are there for the formula C4H8O?

Carbon atoms are often classified as primary (1°), secondary (2°), tertiary (3°), and quaternary (4°)...

CH H

H

H

CH R

H

H

CH R

H

R

CR R

H

R

CR R

R

Rmethane 1° 2° 3° 4°

H3C C

CH3

CH2

H

CH3

Label the carbon atoms in the following molecule as 1°, 2°, 3°, or 4°.

Remember, these labels only pertain to carbon atoms with four single bonds.

C

H

C

H

H

alkenyl protons

alkenyl carbons

aryl protons and carbons

CH3C

CH2CCH

H3C

H3C

alkynyl carbons

alkynyl hydrogen

1°

1°

1° 4°

2°

Unsaturated Carbon Classification...

For more examples, see the text, page 23.

This terminology also applies to amines...

NH H

H

NH R

H

NH R

R

NR R

R

NR R

R

R

ammonia 1° 2° 3° 4°

and amides...

H3CC

N

O

CH3

H