Alcohols

General properties
OH

Contain hydroxyl groups Hybrid C :

Geometry :
High bp relative to hydrocarbons Branching will lower bp

alcohol

Alcohols

alcohols is weak bases and weak acids alkyl substituents decrease acidity by preventing solvation of alkoxide ions electron withdrawing substituents increase acidity by delocalization of the negative charge Similar acidity to water much less acidic than mineral acids or carboxylic acids do not react with weak bases (amines, bicarbonates) can react with alkali metals (Na, K) react with strong bases (NaH, NaNH2 and RMgX)

Alcohols
CH3 CH3 C CH3 tert-butyl alcohol OH CH3

2K

CH3

C CH3

O K

H2

potassium tert-butoxide

CH3OH methanol

NaH

CH3O

Na

H2

sodium methoxide NaNH2 CH3CH2O Na

+

CH3CH2OH ethanol

NH3

sodium methoxide

OH

CH3MgBr

MgBr

CH4

bromomagnesium cyclohexoxide

Alcohols

Preparation of alcohols
(A) From alkenes (hydration)

i) Hydroboration (oxidation)

- anti-Markovnikovs rule

ii) Oxymercuration (reduction) - Markovnikovs rule

(B) From carbonyl compounds

i) Reduction of carbonyl compounds

ii) Reaction of carbonyl compounds with Grignard reagents

NaBH4 - mild reducing agent LiAlH4 - strong reducing agent

Alcohols

Reactions of alcohols
(A) Dehydration of alcohols to yield alkenes i) Acid catalysed (E1 mech)
H C C OH
H2SO4

H2O

Zaitsevs rule 3 alcohols are readily dehydrated 2 alcohols need severe conditions (75% H2SO4, 100oC) 1 need even harsher conditions (95% H2SO4, 150oC)

Alcohols

ii)

Under milder and basic conditions (E2 mech) 2 and 1 alcohols

Uses POCl3 in pyridines (act as base and solvent)

(B) Conversion to alkyl halides i) Reaction of 3 alcohols with HX (SN1 mech) ii) Reaction of 1 and 2 alcohols with SOCl2 and PBr3 (SN2 mech)

Alcohols

(C) Oxidation of alcohols Strong oxidizing agents : KMnO4, CrO3, Na2Cr2O7 - oxidizes alcohols to ketones and carboxylic acid Mild oxidizing agent : Pyridinium chlorochromate (C5H6NCrO3Cl or PCC) - used to oxidize primary alcohol to the aldehyde only - also used on sensitive alcohols

Alcohols
OH C H H [O] R O C H R [O] O C O H

aldehyde primary alcohol

OH C H [O] R O C R'

carboxylic acid

R R'

secondary alcohol

ketone

OH C R"

[O]

No reaction

R R'

Tertiary alcohol

Alcohols

Exercises
CH3 CH2CH2C=CH2 BH3, THF H2O2, HO CH3

CH2CH2CHCH

OH CH3CH2CH C(CH3)2 i) Hg(OAc)2, H2O ii) NaBH4

O CH3CH2CH2CH
O C i) NaBH4, ethanol ii) H3O
+

CH3CH2CH2C(CH3)2

i) NaBH4, ethanol ii) H3O

+

OH CH3CH2CH2CH H
H C OH

Alcohols
i) CH3CH2MgBr, ether O ii) H3O+

OH CH2CH3

O CH3CH2CH2CH2COCH2CH3 i) 2CH3MgBr, ether ii) H3O

+

OH CH3CH2CH2CH2CCH3 CH3

CH3CH2OH

O CH3(CH2)7CH CH(CH2)7COH

i) LiAlH4, ether ii) H3O

+

CH3(CH2)7CH

CH(C

O CH3(CH2)7CH CH(CH2)7COCH3

i) LiAlH4, ether ii) H3O

+

CH3(CH2)7CH

CH(CH2

Alcohols
MgBr CH2OH O i) mix ii) H3O+

+ H C H

CH3 CH3 CH CH3 CH2 O C H MgBr CH i) ether ii) H3O

+

CH3

CH

CH3(CH2)8CH2OH

CrO3 H3O+, acetone

O CH3(CH2)8COH

CH3(CH2)8CH2OH

PCC CH2Cl2

O CH3(CH2)8CH

Alcohols

CH3 CH3 C CH3 OH

NaCr2O7 H2O, CH3COOH, heat CH3

CH3 C CH3

CH2OH

PCC CH2Cl2

1. 2.

How could you use the addition of a Grignard reagent to a carbonyl compound to synthesize 2-methyl-2-pentanol ? How could you use the addition of a Grignard reagent to a ketone to synthesize 2-phenyl-2-propanol ?