CHAPTER 7

ALCOHOLS, THIOLS, PHENOLS, ETHERS

Several of the following functional groups are based on oxygen and sulfur in the sp2
hybridization state. Containing two pairs of nonbonding electrons and are the cornerstone
of many organic processes.

7.1 Alcohols

7.1a Nomenclature

Priorities in nomenclature.

The priority list is as follows: carboxylic acids > aldehydes> ketones> alcohols > amines
> alkene > alkyne > alkyl, halogen, nitro

A compound containing hydroxyl , alkenes and ketones functions would be named as a

ketone and substituents are numbered accordingly and named in alphabetical order. Then
the compound on the left is called as an alcohol , but the right one is named as a ketone
although both compounds have seven carbon skeleton .

Alcohol Nomenclature
The IUPAC system names the longest chain hydrocarbon as the parent and adds a new
ending of -ol. The alcohol has a higher priority in nomenclature than alkenes, alkynes,
alkyl groups and halogen and is given a number lower than any of those groups.
Examples:

When more than one hydroxyl group is present, the IUPAC system uses numbers to
designate the location of the hydroxyl with a prefix di-, tri- , denote hydroxyl number.
The aliphatic alcohols are classified as primary, secondary or tertiary. If the carbon takes
attached an alkyl group, the alcohol is primary. With two alkyl groups attached to the
alcohol carbon is secondary, and three alkyl groups attached is tertiary alcohol.

7.1b Physical Properties of Alcohols.

In pure alcohol systems, additional energy is added to boiling the sample dea therefore
high boiling points are observed. Furthermore, the alcohols form hydrogen bonds with
water and as a result are very soluble in water unless more than six carbon atoms are
present. The difference in boiling points is as much as 153 or due to hydrogen bonding.

7.1c Naturally Occurring Alcohols.

citronellol and geraniol are both found in plants and trees and belong to a family called
terpenes. Are used as spice and perfume mixtures . Citronellol used candles to help repel
mosquitoes. Meso inisotol , a carbohydrate present in foods and is important in the healthy
metabolism. Theaflavine found in black tea contains both aliphatic and aromatic hydroxyl
functions and features ether.

7.1d Preparation of Alcohol

Several low molecular weight alcohols are prepared on an industrial scale and are used
throughout the chemical and academia commercially as solvents , medicinal repairs , and
alcohol (ethanol) Methanol is produced by the catalytic hydrogenation of carbon
monoxide carbon is extremely toxic and cause blindness if swallowed.

Grignard Reactions with Carbonyl Compounds, their use is so valuable and general
in organic chemistry. The following example can have many variations by changing the
halide and the carbonyl compound

Hydration of Alkenes
Oxymercuration - demercuration provides alcohols from alkenes under mild conditions
without rearrangement. Acetate reacts with the mercury to form a cyclic alkene
mercurinium ion with a positive charge. Water attacks the intermediate from the carbon
with the highest positive charge , here the tertiary carbon , and from the back of the
mercury atom .

Reactions of Haloalkanes
Reactions of primary alkyl halides react by SN2 reactions and E2 , while the secondary
and tertiary reactions substrates mainly react by SN1 , E1 and E2 . The results are shown
for the reactions of primary and tertiary halides hydroxide , which is a good nucleophile
strong base.
Reactions with water ( or water in a solvent ), which is non-nucleophilic and non-basic ,
SN1 and E1 show only tertiary halide processes .

Reduction of Acids, Esters, Aldehydes and Ketones

Oxidation of Alkenes to Vicinal Diols

Compounds with hydroxyl groups on adjacent carbons are called vicinal diols. Oxidation
of alkenes with cold KMnO4 or OsO4 provides occurs with syn addition and provides cis
vicinal diols. Trans vicinal diols can be prepared by ring opening of an oxirane, a three-
membered ring containing oxygen.

7.1e Reactions of Alcohols Acidic properties of alcohols

The high electronegativity causes oxygen takes away electrons from the hydrogen atom .
The OH bond is polarized and is able to give up a proton, H + . Alcohols are weak acids
, but may become stronger acids depending on the types of organic substituents present .

The ionization constant for the above equilibrium is given by Ka = [RO-][H+] / [ROH].
Acidity is often expressed as pKa which is the negative logarithm of the Ka. Thus, pKa
= -log Ka .

The acidic property of the alcohols allowing the formation of alkoxide salts , alkoxides
called . Alkoxides are useful both as strong bases and good nucleophiles for SN2
reactions.
Conversion of Alcohols to Alkyl Halides Reaction with Hydrogen Halide

The +OH2 group is an excellent leaving group as it forms a neutral molecule of water.
Primary alcohols react by the SN2 - E2 mechanism while secondary and tertiary alcohols
follow SN1 - E1 carbocation paths. The cation reacts with Br - to give mostly the
substitution product accompanied by some alkene elimination product.

Reaction of 3 -methyl- 2 -butanol with HCl oxonium ion passes through the carbocation.
But the secondary cation rearranges the more stable tertiary cation, chloride attack
occurring in the tertiary cation.

The following example illustrates the formation of a stable allylic carbocation.