24.

11 Preparation of Aryl Ethers

Typical Preparation is by Williamson Synthesis

ONa + RX

SN2

NaX OR + NaX

Typical Preparation is by Williamson Synthesis

ONa + RX

SN2

NaX OR + NaX

but the other combination X + RONa fails because aryl halides are normally unreactive toward nucleophilic substitution

Example

acetone

ONa + CH3I

heat

OCH3 (95%)

Example + H2 C CHCH2Br

OH

K2CO3

acetone, heat

(86%)

OCH2CH

CH2

Aryl Ethers from Aryl Halides F CH3OH 25 25C NO2 (93%) nucleophilic aromatic substitution is effective with nitro-substituted (ortho and/or para) aryl nitrohalides OCH3 + KOCH3 NO2 + KF

24.12 Cleavage of Aryl Ethers by Hydrogen Halides

Cleavage of Alkyl Aryl Ethers Ar

O + H

Ar Br
Br +

+O R

Cleavage of Alkyl Aryl Ethers Ar

O + H

Ar Br
Br +

+O R

An alkyl halide is formed; never an aryl halide! R

Ar Br

Example

OCH3 OH

HBr heat

OH + CH3Br OH (85(85-87%) (57(57-72%)

24.13 Claisen Rearrangement of Allyl Aryl Ethers

Allyl Aryl Ethers Rearrange on Heating OCH2CH CH2

200 200C OH CH2CH (73%)

allyl group migrates to ortho position

CH2

Mechanism OCH2CH CH2

rewrite as

OH

keto-toketo-to-enol isomerization

Sigmatropic Rearrangement Claisen rearrangement is an example of a sigmatropic rearrangement. A W bond migrates from one end of a conjugated T electron system to the other.
this W bond breaks

conjugated T electron system is the allyl group

H
this W bond forms

24.14 Oxidation of Phenols: Quinones

Quinones The most common examples of phenol oxidations are the oxidations of 1,2- and 1,4-benzenediols 1,21,4to give quinones. OH Na2Cr2O7, H2SO4 H2 O OH O O

(76(76-81%)

Quinones The most common examples of phenol oxidations are the oxidations of 1,2- and 1,4-benzenediols 1,21,4to give quinones. OH OH Ag2O diethyl ether CH3 CH3 O O

(68%)

Some quinones are dyes

OH OH

O Alizarin (red pigment)

Some quinones are important biomolecules O CH3O CH3O O Ubiquinone (Coenzyme Q) n = 6-10 6involved in biological electron transport CH3 n

Some quinones are important biomolecules

O CH3 CH3 O CH3 CH3 CH3 CH3

Vitamin K (blood(blood-clotting factor)