Molecular Representations, Nomenclature, and Isomers

O O

HO H

Isobutyric acid 2-((R)-3-diisopropylamine-1 -phenylpropyl)-4-(hydroxymethyl) phenyl ester Fesoterodine

Molecular Representations
Several ways to represent structure of organic molecules....
H H C H H C H H C H H C H H C H H C H H C H H C H H H

Lewis dot structure

C H H

Cumbersome

Kekul structure Bonding pairs become Condensed structure

C H

Still cumbersome

CH3CH2CH2CH2CH3
H3C

Often unclear
CH3

Bond-line structure Carbon framework = zigzag lines End of each line = carbon H omitted (unless carbon shown as C)

Nomenclature
Different people = different names Different molecules need different names Names can be simple or complex Most molecules have several names
H H C H Cl
HO H O

Hey you

Hey you
O

Hey you

Nomenclature: Naming scheme that describes structure

Chloromethane Methyl chloride

Isobutyric acid 2-((R)-3-diisopropylamine-1 -phenylpropyl)-4-(hydroxymethyl) phenyl ester Fesoterodine

Nomenclature Rules
Lets start with alkanes... What is the rule for these names? CH3CH2CH2CH2CH3 CH3CH2CH2CH2CH2CH3 Answer: Number of carbons + ane Structure CH4 CH3CH3 CH3CH2CH3 CH3CH2CH2CH3 CH3CH2CH2CH2CH3 CH3CH2CH2CH2CH2CH3 Formula CH4 C2H6 C3H8 C4H10 C5H12 C6H14 Name Methane Ethane Propane Butane Pentane Hexane Structure CH3(CH2)5CH3 CH3(CH2)6CH3 CH3(CH2)7CH3 CH3(CH2)8CH3 CH3(CH2)9CH3 CH3(CH2)10CH3 Formula C7H16 C8H18 C9H20 C10H22 C11H24 C12H26 Name Heptane Octane Nonane Decane Undecane Dodecane Pentane Hexane C5H12 C6H14 C8H18

CH3CH2CH2CH2CH2CH2CH2CH3 Octane

Isomers
More than one way to connect the atoms of a certain formula? CH4, C2H6, C3H8: Only one sequence to arrange the atoms Verify with models C4H10: Two possible atom sequences
H H C H H C H H C H H C H H
H H C H CH3 H C H C H H

C4H10 Butane

C4H10 Name = ?

Isomers: Molecules with same chemical formula but different structure Constitutional isomers: Isomers that differ in sequence of atom connectivity Example: Pentane isomers

Substituents
Substituent: An atom or group other than hydrogen on a molecule.
H H C H CH3 H C H C H H

Name?

How to name alkanes with substituents? What is the rule for these names? Methylpropane Answer: Substituent name = parent alkane ane + yl
H H C H H H H C H
H H C H CH3 H C H C H H

Methylbutane

Ethylpentane

Methane

Methyl group

Substituent Names
Substituent name = parent alkane ane + yl
Parent alkane Methane
H

Substituent structure
H C H
H C H H

Substituent name Methyl

Parent alkane Butane

Substituent structure
CH2CH2CH2CH3
H

Substituent name Butyl Sec-butyl (1-methylpropyl)

Ethane
H

C H

Ethyl

Butane

H3C

CH2CH3

H C H H C

H C H H C H H H

CH3

Propane

C H H

Propyl

Butane

H3C

C H

CH2

Isobutyl (2-methylpropyl) Tert-butyl (2-methyl-2-propyl)

Propane

C H

Isopropyl

Butane

C(CH3)3

Locants
What happens when substituents can be at different positions on the parent chain? What is the rule for these names?
CH3
CH3

CH2CH3

2-Methylpropane

3-Methylpentane

4-Ethylheptane

Answer: Write locant number before substituent name Locant: Number which indicates position of atom or group within a molecule Number chain so substituent is on lowest number carbon
CH3 2 1 3 4

2-Methylpentane
5

CH3 4 5 3 2

4-Methylpentane
1

Multiple Substituents
What happens when the parent chain has multiple substituents? What is the rule for these names?
CH3 CH3

H3C

CH3

H3C

CH3

H3C

CH3

2,2-Dimethylpropane Answer:

2,3,4-Trimethylhexane

CH3

2,2,6,6-Tetramethyloctane

Di = two of same substituent Tri = three of same substituent Tetra = four of same substituent When one substituent, mono not included: 2-Methylbutane Correct 2-Monomethylbutane Incorrect

Multiple Substituents: Alphabetizing

Multiple substituents may lead to multiple names:
CH3
H3C CH3

CH2CH3

CH2CH3

3-Ethyl-4-methylheptane Correct 4-Methyl-3-ethylheptane Incorrect

4,4-Dimethyl-3-ethylheptane Incorrect 3-Ethyl-4,4-dimethylheptane Correct

What rule is operating in this case? Answer: Ethyl beats methyl Ethyl beats dimethyl Number prefixes ignored Ignore sec and tert
CH3

3-Tert-butyl-2-methylhexane Correct 2-Methyl-3-tert-butylhexane Incorrect

C(CH3)3

Multiple Substituents: Locant Numbering

When there are multiple substituents, number chain to give lowest locant total:
H3C 2 1 CH2CH3 3 4 5 CH3 6 7 7 CH2CH3 6 H3C 5 4 3 CH3 2 1

4,4-Dimethyl-3-ethylheptane

4,4-Dimethyl-5-ethylheptane

Cycloalkanes
Alkanes can also form rings; called cycloalkanes. Examples:

Cyclopropane

Cyclopentane

Cyclohexane

What naming rule is operating for these cycloalkanes? Answer:

Propane - acyclic Three carbons

Cyclopropane cyclic Three carbons

5 6 1 3 2 CH3CH2 4 CH3 CH3

Naming rules otherwise same as acyclic alkanes. Example:

1,1-Dimethyl-4-ethylcyclohexane

Other Substituents
Nomenclature applies to more than just alkanes and cycloalkanes. Many other substituent rules exist. Example: Halogens: F = fluoro; Cl = chloro; Br = bromo, and I = iodo In simple cases, write halide name followed by substituent name
H H C H Cl

H3C C H3C

CH3 Br

Chloromethane Methyl chloride

2-Bromo-2-methylpropane Tert-butyl bromide

Many other rules Many other substituents

More details More examples

Klein and Brown & Foote