Roldan M.

de Guia
Department of Biochemistry

Faculty of Pharmacy
University of
Santo Tomas
Physical Properties of Organic
Compounds
• Alkanes
– Melting and boiling points increase with increasing
molecular weight within a homologous series.

Compound Formula MW mp (ºC) bp (ºC)

(g/mol)

Methane CH4 16 –182 –164

Pentane CH3(CH2)3CH3 72 –130 36

Decane CH3(CH2)8CH3 142 –30 174

Pentadecane CH3(CH2)13CH3 212 10 271

Eicosane CH3(CH2)18CH3 282 37 343

Physical Properties of Organic
Compounds
Physical Properties of Organic
Compounds
Physical Properties of Organic
Compounds
• Alkanes
– Boiling points decrease with chain branching.

mp bp
Compound
(oC) (oC)
CH3
CH3 −57 127
octane
CH3
−121 118
CH3 4-methylheptane
CH3
CH3 CH3
−107 99
CH3 CH3
CH3
2,2,4-trimethylpentane
Physical Properties of Organic
Compounds

• Alkanes
– Solubility – “Like dissolves like”
– Alkanes are nonpolar, hydrophobic
– They are soluble in nonpolar solvents
and insoluble in water.
Physical Properties of Organic
Compounds
bp H2O
Compound MW
(oC) solubility
CH3
CH3 86.18 69 insoluble
hexane

Cl 98.96 83 0.8%
Cl
1,2-dichloroethane

O
CH3 86.09 88 20%
CH3
O
2,3-butanedione
Physical Properties of Organic
Compounds
bp H2O
Compound MW
(oC) solubility
O CH3 90.12
CH3 O 83 ∞
dimethoxyethane
OH 90.12 230 ∞
HO
1,4-butanediol

NH2 88.15
H2N 158 ∞
putrescine
H
N CH3 88.15 119 ∞
CH3 N
H
N,N'-dimethylethylenediamine
Physical Properties of Organic
Compounds
Which of the following has the highest
boiling point?

CH3CH2 CH CH3 CH3CH2 CH CH3 CH3CH2 CH CH3

1. CH3 2. NH2 3. OH

4. CH3CH2 CH CH3 5. CH3CH2 CH CH3

Cl CH2CH3
Physical Properties of Organic
Compounds
 Isomerism
• Isomerism – The phenomenon
whereby certain chemical compounds
have structures that are different
although the compounds possess the
same elemental composition.
• Isomers – Two or more chemical
substances having the same elementary
composition and molecular weight but
differing in structure.
 Isomerism
• Consider C4H10
H
H H H H H H
H C H
H C C C C H
H C C C H
H H H H
H H H
Normal Butane Isobutane
 ISOMERS

STRUCTURAL CONFORMATIONAL
OPTICAL CONFIGURATIONAL

Skeletal Compounds w/ same Enantiomers – chiral, Same

Functional molecular formula but non-superimposable stereochemical
Positional w/ structures that are mirror images configuration but
Tautomers mirror image of the Diastereomers – non- differing in 3D
other superimposable, non- conformation
Rotate plane of mirror images
polarized light equally Anomers
but in opposite direction Epimers - different in
geometry
Constitutional Isomers-skeletal

C 4H10

C 5H12
Constitutional Isomers-skeletal
C 6H14 ?
Constitutional Isomers-skeletal
Constitutional Isomers-skeletal
O O

H H

OH OH

O O
Constitutional Isomers-
positional
OH
OH

HO OH HO

OH

O
Constitutional Isomers-
functional
OH O

O O

H
Conformational Isomers
Conformational Isomers
H
θ
H H
= Staggered
θ = 60o
H H
H

H
H
Eclipsed
= θ = 0o
H
HH H
Conformational Isomers
 Conformational Isomers

o o o o
θ 60 120 180 0
Erel 0.9 kcal/mol 3.4 kcal/mol 0 kcal/mol 6.1 kcal/mol
Which is the most stable conformation for 1-
chloropropane about the C1-C2 bond?
CH3 CH3 CH3

H Cl H H Cl H
1. 2. 3.
H H H H H
H Cl H
H
Cl
H
CH3
CH3
4. 5.
Cl H H
H H H
H H
Ring Conformers
Ring Conformers
 Ring Conformers

H H
H H
H H

H H

H H
H H

Cyclohexane
Cyclohexane Ring Conformers
Cyclohexane Ring Conformers
BOAT

H H
H H H H
H H
H H
H H
Cyclohexane Ring Conformers
BOAT

H H
H H H H Steric
H H interactions
H H
H H
Cyclohexane Ring Conformers
BOAT

H H
H H H H Eclipsing
H H
H H
H H
Cyclohexane Ring Conformers
CHAIR

H H
H
H
H H
H H
H
H
H H
Cyclohexane Ring Conformers
CHAIR

H H
H
H
H H Equatorial
H H hydrogens
H
H
H H
Cyclohexane Ring Conformers
CHAIR

H H
H
H
H H Axial
H H hydrogens
H
H
H H
Cyclohexane Ring Conformers
Cyclohexane Ring Conformers
Cyclohexane Ring Conformers
Cyclohexane Ring Conformers
tert-Butylcyclohexane

severe steric
interactions

much more stable

 Geometric Isomerisms in
•
Cycloalkanes
Geometric isomers have the same molecular
formula and the same order of attachment but
a different orientation in space that cannot be
overcome by rotation around a s bond.
1,2-Dimethylcyclopentane:

H3C CH3
1,2-dimethylcyclopentane

H H H CH3

H3C CH3 H3C H

cis-1,2-dimethylcyclopentane trans-1,2-dimethylcyclopentane
Geometric Isomerisms in
Cycloalkanes
H
C
CH3
H H C
C
H
H3C
trans-1,2-dimethylcyclopropane

H H H3C CH3
H3C C CH3
H H
H H
H H
H H
cis-1-tert-butyl-4-methylcyclohexane
Geometric Isomerisms in
CH
Cycloalkanes
3
H H H3C H

H3C CH3 H CH3

CH3
Geometric Isomerisms in
Cycloalkanes
Geometric Isomerisms in
Cycloalkanes