4: Alcohols and Ethers / - 2102/1102 2nd semester

Alcohols are usually classified as primary, secondary and tertiary.

H R H primary OH R

H OH R secondary R

R OH R tertiary phenol OH

Physical Properties:

The polar nature of the O-H bond (due to the electonegativity difference of the atoms ) results in the formation of hydrogen bonds with other alcohol molecules or other Hbonding systems (e.g. water). The implications of this are: high melting and boiling points compared to analogous alkanes high solubility in aqueous media

Acidity of Alcohols and Phenols

Just like water, the hydroxyl groups in alcohols are weakly acidic strong bases can generate alkoxide ions. R-O-H + B- R-O- + B-H
Acidity of Phenols
Cyclohexanol and phenol are similar in structure, yet their acidities are very different. (Phenol is 108 more acidic).

Preparation of Alcohols

1 Addition of Sulfuric Acid followed by Hydrolysis nucleophile sub.

+ H2SO4 H alkene H2O OSO3H H OH

alkyl hydrogen sulfate

alcohol

Markovnikov addition

2- Oxymercuration-demercuration

+ Hg(OAc)2 alkene

H2O

NaBH4 OH HgOAc OHH alcohol

3 - Hydroboration-oxidation (anti-Markovnikov) Hydroboration of Alken

H3C H3C CH3 1. "BH3" H 2. [O] CH3 CH3 H3C OH H H anti-Markovnikov alcohol

4 Permanganate Hydroxylation

O O Mn O O-

O O HO Mn O O-

OH + MnO2 OH

5- Osmium Tetroxide Hydroxylation

OsO4, H2O2 or KMnO4,
-

OH

OH OH syn diol

H3C H BH3,THF _ H2O2, OH H Trans-2 -Methylcyclohexaneol H3C CH3

OH

Hg(OAc)2 NaHSO3

OH

1-Methylcyclohexanol 1-Methylcyclohexene H3C OH OsO4 NaHSO3 H 1-Methyl-Cis-1,2 cyclohexanediol OH

OH CH3 RCOOOH + CH2Cl2 , H3O H 1-Methyl- Trans-1,2 -cyclohexanediol

OH

7-Reduction of ester and carboxylic acids

Sodium borohydride will not reduce esters or acids, whereas lithium aluminum hydride reduces esters and acids to primary alcohols. Note that : Sodium borohydride will reduce carbonyl group beside reducing unsaturated double bond whereas lithium aluminum hydride reduces carbonyl group without reducing unsaturated double bond .
H OH

NaBH4, Ethanol, H2O O Cyclohexanol

2-Cyclohexanone

OH

LiAlH4, ether , H2O

2-Cyclohexenol

8- Catalytic Hydrogenation

H O

H2, Ni OH

Alcohol reaction
OH [O] R H H primary alcohol O R H [O] O R acid OH aldehyde

1- Oxidation of Alcohols
OH O Na 2CrO7, H2SO4 R H R R R ketone secondary alcohol

A common reagent that selectively oxidizes a primary alcohol to an aldehyde (and no further) is pyridinium chlorochromate, PCC. Tertiary Alcohols

H OH PCC O aldehyde

These are resistant to oxidation because they have no hydrogen atoms attached to the oxygen bearing carbon (carbinol carbon).

2-Reduction of Alcohols
H OH H H

LiAlH4

3-Dehydration Reactions of Alcohols

H OH + H2O

4- Esterification of Alcohols
O R OH + R' alcohol C OH acid H
+

O R O C R' + H2O ester