Lecture Notes: Organic Chemistry I

CHM121 CHAPTER THREE

REVIEW OF CHAPTER TWO:
THINGS TO KNOW:
1) Valence bond view of molecules
2) Molecular orbitals including bonding (σ) and (σ*) antibonding orbitals
3) Classes of hydrocarbons: alkanes, alkenes, alkynes, arenes
4) Alkanes: methane through eicosane
5) Hybridization of atomic orbitals: sp3 methane and ethane (and NH3 and H2O) as examples
6) Hybridization of atomic orbitals: sp2 ethene and borane as examples
7) Formation of π bonds by parallel overlap of p orbitals
8) Hybridization of atomic orbitals: sp ethyne as example
9) Effect of hybridization on carbon electronegativity and hydrocarbon acidity
10) Isomers of butane, pentane etc.
11) IUPAC nomenclature: ALKANES
12) Alkyl groups
13) Classes of carbon: 0o(methane), 1o (methyl), 2o (methylene), 3o (methine), and 4o
14) IUPAC nomenclature: CYCLOALKANES
15) IUPAC nomenclature: SPIRANES
16) IUPAC (von Baeyer) nomenclature: BICYCLOALKANES
17) Introduction to functional groups
18) Physical Properties of alkanes: boiling point (linear vs. branched vs. cyclic)
19) Combustion (oxidation) of alkanes
20) Enthalpy of combustion as a measure of stability
21) Enthalpy of formation as a measure of stability
22) Oxidation state of carbon
ETHANE VS. METHANE
CONFORMATIONAL ANALYSIS OF ETHANE
TORSIONAL STRAIN
 CONFORMATIONAL ANALYSIS OF BUTANE

The basic idea with other groups is the same. This is the foundation for conformational analysis where
structures can be calculated based on molecular mechanics.
CONFORMATIONAL ANALYSIS: GENERAL PRINCIPLES
CYCLOPROPANE: AN EXAMPLE OF ANGLE STRAIN
CYCLOBUTANE and CYCLOPENTANE
CYCLOHEXANE
CYCLOHEXANE: the substituents
CYCLOHEXANE: NEWMAN PROJECTIONS
CYCLOHEXANE: RING FLIP
 CYCLOHEXANE: A VALUES

PROBLEMS
1) Explain the non-periodic trend for the halogens.
2) Explain why trimethylsilyl is so much smaller than tert-butyl
3) Draw to diagrams to explain why isopropyl > vinyl > alkynyl
CYCLOHEXANE: ORIGIN OF SUBSTITUENT STRAIN
 BICYCLIC CONFORMATIONS
The dots on the structures below indicate that an H is pointing up (out of the paper
or screen). Undotted H’s are trans to those.
STEROIDS
CYCLOHEXANE: THE BOAT CONFORMATION
 CONFORMATIONAL EFFECTS OF HETEROATOM
There are three critical considerations for evaluating the conformational effects of
non-carbon atoms in molecules.

1) BOND LENGTH: shorter bonds increase steric and torsional effects.

2) LONE PAIR ELECTRONS: lone pairs decrease steric and torsional effects
between atoms since the lone pair is localized at the heteroatom (which is the
same reason that bond angles are compressed by lone pairs)
3) NON-BONDED INTERACTIONS; some heteroatoms can participate in hydrogen
bonding or electrostatic attraction which can stabilize conformations that are
otherwise unstable.