Phenols Ar-OH

Phenols are compounds with an OH group attached to an aromatic carbon. Although they share the same functional group with alcohols, where the OH group is attached to an aliphatic carbon, the chemistry of phenols is very different from that of alcohols.

Nomenclature.
Phenols are usually named as substituted phenols. The methylphenols are given the special name, cresols. Some other phenols are named as hydroxy compounds.
OH OH CH3 OH Br phenol m-bromophenol OH OH OH OH catechol resorcinol hydroquinone OH p-hydroxybenzoic acid o-cresol OH salicylic acid COOH OH COOH

OH

phenols, syntheses: 1. From diazonium salts

N2 H2O,H+ OH

2. Alkali fusion of sulfonates

ONa

SO3 Na

NaOH,H2O 300o

H+

OH

phenols, reactions:
1. as acids 2. ester formation

3. ether formation
4. EAS a) nitration b) sulfonation c) halogenation f) nitrosation g) coupling with diaz. salts h) Kolbe

d) Friedel-Crafts alkylation
e) Friedel-Crafts acylation

i) Reimer-Tiemann

as acids: with active metals:

OH Na + H2(g) sodium phenoxide ONa

with bases:
CH4 < NH3 < HCCH < ROH < H2O < phenols < H2CO3 < RCOOH < HF
OH + NaOH SA SB WB ONa + H2O WA

2. ester formation (similar to alcohols)

OH CH3 + CH3CH2C O OH H+ CH3CH2C O O + H2O

H3C O H3C C COOH + (CH3CO)2O

OH

O COOH

salicyclic acid

aspirin

3. ether formation (Williamson Synthesis)

Ar-O-Na+ + R-X Ar-O-R + NaX note: R-X must be 1o or CH3

Because phenols are more acidic than water, it is possible to generate the phenoxide in situ using NaOH.
OH + CH3CH2Br, NaOH CH3 CH3 OCH2CH3

4. Electrophilic Aromatic Substitution

The OH group is a powerful activating group in EAS and an ortho/para director. a) nitration
OH HNO3 O2N OH NO2

polynitration!
OH

NO2 OH dilute HNO3 OH NO2 + NO2

b) halogenation

OH Br2 (aq.) Br

OH Br no catalyst required use polar solvent Br

polyhalogenation!
OH Br + Br

OH Br2, CCl4 non-polar solvent

OH

c) sulfonation
OH H2SO4, 15-20oC OH SO3H

OH H2SO4, 100oC SO3H

At low temperature the reaction is non-reversible and the lower Eact orthoproduct is formed (rate control).
At high temperature the reaction is reversible and the more stable paraproduct is formed (kinetic control).

d) Friedel-Crafts alkylation.

OH + CH3 H3C C CH3 Cl AlCl3

OH

H3C C CH3 CH3

e) Friedel-Crafts acylation
OH O + CH3CH2CH2C Cl O AlCl3 OH

Do not confuse FC acylation with esterification: OH O + CH3CH2CH2C Cl O O

Fries rearrangement of phenolic esters.

OH O + CH3CH2CH2C Cl O

AlCl3 OH

f) nitrosation
OH HONO p-nitrosophenol NO OH

EAS with very weak electrophile NO+ OH CH3 NaNO2, HCl

OH CH3

NO

g) coupling with diazonium salts

(EAS with the weak electrophile diazonium)
OH CH3 + benzenediazonium chloride an azo dye N N N2 Cl OH CH3

h) Kolbe reaction (carbonation)

ONa + CO2 125oC, 4-7 atm. OH COONa

sodium salicylate EAS by the weakly electrophilic CO2 H+

O C O

OH COOH

salicylic acid