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

physical properties phenols are polar and can hydrogen bond phenols are water insoluble phenols are stronger acids than water and

will dissolve in 5% NaOH

phenols are weaker acids than carbonic acid and do not dissolve in 5% NaHCO3

Intramolecular hydrogen bonding is possible in some ortho-substituted phenols. This intramolecular hydrogen bonding reduces water solubility and increases volatility. Thus, o-nitrophenol is steam distillable while the isomeric p-nitrophenol is not.
OH O N O H O NO2 p-nitrophenol bp decomposes 1.69 g / 100 mL water non-volatile with steam

o-nitrophenol bp 100oC at 100 mm 0.2 g / 100 mL water volatile with steam

phenols, syntheses: 1. From diazonium salts

N2 H2O,H+ OH

2. Alkali fusion of sulfonates

ONa

SO3 Na

NaOH,H2O 300o

H+

OH

Reactions: alcohols phenols

1. HX
2. PX3 3. dehydration 4. as acids 5. ester formation

NR
NR NR phenols are more acidic similar

6. oxidation

NR

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

CH4 < NH3 < HCCH < ROH < H2O < phenols < H2CO3 < RCOOH < HF

OH + NaOH SA water insoluble OH + NaHCO3 SB

ONa + H2O WB water soluble WA

NR

phenol < H2CO3

CH4 < NH3 < HCCH < ROH < H2O < phenols < H2CO3 < RCOOH < HF

water

5% NaOH

5% NaHCO3

phenols

insoluble

soluble

insoluble

carboxylic acids

insoluble

soluble

soluble

We use the ionization of acids in water to measure acid strength (Ka): HBase + H2O H3O+ + Base-

Ka = [H3O+ ][ Base ] / [ HBase] ROH Ka ~ 10-16 - 10-18 ArOH Ka ~ 10-10

Why are phenols more acidic than alcohols?

ROH + H2O

H3O+ + ROH3O+ + ArOO O O O O

ArOH + H2O
OH OH

Resonance stabilization of the phenoxide ion, lowers the PE of the products of the ionization, decreases the H, shifts the equil farther to the right, makes phenol more acidic than an alcohol

effect of substituent groups on acid strength?

OH G + H2O O G + H3O

Electron withdrawing groups will decrease the negative charge in the phenoxide, lowering the PE, decreasing the H, shifting the equil farther to the right, stronger acid. Electron donating groups will increase the negative charge in the phenoxide, increasing the PE, increasing the H, shifting the equilibrium to the left, weaker acid.

Number the following acids in decreasing order of acid strength (let # 1 = most acidic, etc.)

OH

OH

OH

OH

OH

NO2

CH3

Br

SO3H

COOH

OH

CH2OH

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

O H3C C

O COOH

analgesic anti-inflamatory antipyrretic anticoagulant Reye's syndrome not to be used by children with high fevers!

aspirin

OH aspirin substitute Tylenol H3C C NH O acetaminophen Kidney damage!

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

i) Reimer-Tiemann reaction

OH CHCl3, aq. NaOH 70oC H+

OH CHO

salicylaldehyde

The salicylaldehyde can be easily oxidized to salicylic acid

Spectroscopy of phenols:

Infrared: OH stretching, strong, broad 3200-3600 cm-1 CO stretch, strong, broad ~1230 cm-1

(alcohols ~ 1050 1200)

nmr: OH 4-7 ppm (6-12 ppm if intramolecular hydrogen bonding)

o-cresol

C--O

O--H

o-cresol
OH b CH3 c a

ethyl salicylate (intramolecular hydrogen bonding)

d OH O C

O CH2CH3 b a