CHEM191

Organic Chemistry part one

Organic Chemistry
• Chemistry of carbon compounds

• Carbon has the ability to exist in a number of geometries and to bond

to any atom type

• Without this property, large biomolecules such as proteins, lipids,

carbohydrates, and nucleic acids could not form.
Structure of carbon compounds
• C can form four bonds
• There are three hybridisation states and geometries found in organic
compounds:
➢ All single bonds - sp3 Tetrahedral
➢ One double bond - sp2 Trigonal planar
➢ One triple bond - sp Linear
• C forms stable bonds with many elements, including C, H, O, N, and
halogens
• Groups of atoms that determine how an organic molecule reacts are
called functional groups
Hydrocarbons
• Consist of ONLY carbon and hydrogen
• Four basic types:
➢ Alkanes - contain single bond
➢ Alkenes - contain double bond
➢ Alkynes - contain triple bond
➢ Aromatic hydrocarbons - contain aromatic system
Alkanes

• Contain only single bonds.

• sp3 hybridised, tetrahedral, and have 109.5° bond angles
• Saturated hydrocarbons
➢“Saturated” with hydrogens.
• Called aliphaticalkanes
• Can be straight chained, branched or cyclic.
• Have general formula:
➢CnH2n+2
Organic Nomenclature
Name Molecular formula Condensed structural formula Boiling point
(°C)
Methane CH4 CH4 -161
Ethane C2H6 CH3CH3 -89
Propane C3H8 CH3CH2CH3 -44
Butane C4H10 CH3CH2CH2CH3 -0.5
Pentane C5H12 CH3CH2CH2CH2CH3 36
Hexane C6H14 CH3CH2CH2CH2CH2CH3 68
Heptane C7H16 CH3CH2CH2CH2CH2CH2CH3 98
Octane C8H18 CH3CH2CH2CH2CH2CH2CH2CH3 125
Nonane C9H20 CH3CH2CH2CH2CH2CH2CH2CH2CH3 151
Decane C10H22 CH3CH2CH2CH2CH2CH2CH2CH2CH2CH3 174
Methods for writing formulas
• Structural formulas show how atoms are bonded to each other

• Condensed structural formulas don’t show all C-H, they condense

them to groupings, like CH3
Line - angle formula
Structural isomers
• Compounds with the same molecular formula but different
connections of atoms are called structural isomers
Naming substituents
Nomenclature
• Rules for naming organic compounds:
➢ Determine the longest continuous chain of C atoms
➢ Number the chain from the end nearest to the first substituent and name each substituent
➢ Begin the name with the number on the C atom to which each substituent is bonded
➢ If two or more substituents are present, list them alphabetically (ignoring the prefix when
alphabetising)
Example 1
Example 1 solution
Example 2
Example 2 solution
Classes of carbons
• Primary carbon (1°) – carbon bonded to one carbon
• Secondary carbon (2°) - carbon bonded to two carbons
• Tertiary carbon (3°) - carbon bonded to three carbons
• Quaternary carbon (4°) - carbon bonded to four carbons
Cycloalkanes
• Alkanes that form rings or cycles
• Possible with at least three C atoms, but sp3 hybridisation requires
109.5° angles – not a very stable molecule
• Four C ring is also not very stable
• Five C and more have room for proper bond angle
• Naming cycloalkanes:
➢Add cyclo- as a prefix to alkane name
Conformers
• The 3-D shape or conformation of a molecule changes as a result of
rotation about a C-C single bond
• Conformational isomers, or conformers, are formed as the result of
rotation about a C-C single bond
• Newman projections are useful ways of viewing molecules and
gaining
an idea of the relative energies of all conformers
• Two conformations about a C-C single bond are likely: eclipsed and
staggered conformations
conformers
Saturated vs unsaturated
• Saturated hydrocarbons
➢ only single bonds, are the alkanes

• Unsaturated hydrocarbons
➢ have fewer hydrogen atoms than alkanes with the same number of carbon atoms, alkenes,
alkynes, and aromatic hydrocarbons

• Unsaturated hydrocarbons are more reactive than saturated

hydrocarbons
Bond lengths and enthalpies
• C-C triple bonds and double bonds are stronger than single bonds:
➢ But not proportionately so
➢ π-bonds are weaker than sigma-bonds
➢ This leads to the increased reactivity of alkenes and alkynes
Alkenes
• Contain at least one C=C bond (σ and π bond)
• CnH2n
• No free rotation about the double bond
• Naming:
➢ Longest C chain must include both carbons that share the double bond
➢ Name end in “-ene”
➢ Lowest number possible given to double bond carbon atoms
➢ Isomers also indicated
Geometric isomers
• Since there is no free rotation around the double bond, the direction
of the longest chain can differ for four or more C atoms.
• Compounds that have all atoms connected to the same atoms but
differ in 3-D arrangement are geometric isomers.
• Alkenes have cis (same side of the double bond) or trans (opposite
side of the double bond) isomers.
E,Z - notation
• While cis/trans nomenclature is useful for simple alkenes, it fails to
describe more complex isomers accurately

• The E,Z system removes ambiguity:

➢ E – indicates opposite
➢ Z – indicates same side
Example
Example - solution
Alkynes
• Contain at least one triple bond (σ and 2 π bonds)

• Unsaturated

• CnH2n-2

• Naming:
➢longest continuous chain containing both carbon atoms in the triple bond
➢name ends in –yne
➢give C atoms in triple bond lowest number.
Aromatic hydrocarbons
• Aromatic hydrocarbons have six-membered rings containing localised
and delocalised electrons
• π-ring is much more stable than a π-bond, so, aromatic hydrocarbons
are much less reactive than alkenes and alkynes
Aromatic nomenclature
• Many aromatic hydrocarbons are known by their common names
• Others are named as derivatives of benzene
• Substitution positions for two substituents:
➢ 1,2 – ortho-, 1,3 – meta-, 1,4 – para-
Functional groups
• The chemistry of an organic molecule is largely determined by the functional groups it contains.
• R represents the alkyl portion (C,H) of an organic molecule; for example, R-OH is an alcohol.
Functional Groups
Alcohols
• Alcohols contain one or more —OH group (the alcohol group or the hydroxyl group).
• They are named from the parent hydrocarbon; the suffix is changed to -ol and a number
designates the carbon to which the
—OH group is attached.
Alcohol classification
• Primary (1°) alcohol
➢ The carbon atom bearing the OH group is also bonded to two hydrogen atoms

• Secondary (2°) alcohol

➢ The carbon atom bearing the OH group is only bonded to one hydrogen atom

• Tertiary (3°) alcohol

➢ The carbon atom bearing the OH group is not bonded to a hydrogen atom
Alcohol classification
Alcohol properties
• The difference in electronegativity between oxygen and hydrogen
allows alcohols to hydrogen bond

• Compared to alkanes they:

➢ Are more soluble in water
➢ Have higher boiling and melting points
ethers
• R—O—R
• Formed by dehydration between alcohol molecules
• Not very reactive (except combustion)
• Used as solvents for organic reactions
Aldehydes
• Aldehydes have at least one hydrogen atom attached to the carbonyl
carbon atom
• Name the longest chain containing the carbonyl group and replace –
ane with –al
• Must, by definition, occur at one of the ends of a molecule
• Remember that aldehyde group takes priority over both methyl and
hydroxyl groups
Ketones
• Ketones have two R groups attached to the carbonyl carbon atom
• Longest chain containing the carbonyl group, replace –ane with –one
• Constitutional isomers occur
Carboxylic acids
• Structure:
➢ hydroxyl group bonded to the carbonyl group
• H on the hydroxyl group is weakly acidic.
• Important in manufacturing polymers for films, fibers, and paints
• Oxidation product of alcohols (some make aldehydes)
esters
• Esters are the products of reactions between carboxylic acids and
alcohols.
• They are found in many fruits and perfumes.
• Naming: name the alcohol part as an alkyl name; separate word is the
acid part as an -ate anion.
Nitrogen-Containing Organic Compounds
• Amines are organic derivatives of ammonia (NH3). One, two, or all
three H atoms can be replaced by R groups (the same or different R
groups).

• If H in NH3 or an amine is replaced by a carbonyl group (N directly

attached to C=O), an amide is formed.
chirality
• Carbons with four different groups attached to them are chiral.
• These are optical isomers, or enantiomers.
• Enantiomers have the same physical and chemical properties when they react with nonchiral
reagents.
• Enantiomers rotate plane-polarized light in opposite directions.
Amides
Nomenclature priority