Phenols

Phenols are molecules that have a hydroxyl group attached to the carbon atom of an aromatic ring.
Synthesis of Phenols
You can prepare phenols in large quantities by the pyrolysis of the sodium salt of benzene sulfonic acid, by
the Dow process, and by the air oxidation of cumene. Each of these processes is described below. You can
also prepare small amounts of phenol by the peroxide oxidation of phenylboronic acid and the hydrolysis of
diazonium salts.
Reactions of Phenolic Hydrogen
Phenols are acidic because of the ease with which the oxygen atom will release the hydrogen bonded to it.
This section describes typical reactions that occur as a result of the acidity of phenols.

Reactions of Phenolic Hydrogen
Phenols are acidic because of the ease with which the oxygen atom will release the hydrogen bonded to it.
This section describes typical reactions that occur as a result of the acidity of phenols.
Reactions with bases
Because phenol is acidic, it reacts with bases to form salts.



Esterification of phenol
Phenols form esters with acid anhydrides and acid chlorides.



Williamson ether synthesis
Ethers are produced from phenol by the Williamson method via an SN mechanism.



In organic chemistry
, phenols, sometimes called phenolics, are a class of chemical compound
s consisting of a hydroxyl
group
(-O
H
) bonded
directly to an aromatic hydrocarbon
group. The simplest of the class is phenol (C6H5OH).


Although similar to alcohol
s, phenols have unique properties and are not classified as alcohols (since the hydroxyl group is not bonded to a saturated carbon atom). They have
higher acid
ities due to the aromatic ring's tight coupling with the oxygen and a relatively loose bond between the oxygen
and hydrogen
. The acidity of the hydroxyl group in phenols is commonly intermediate between that of aliphatic alcohols and carboxylic acid
s (their pKa is usually between 10 and 12).

Loss of a positive hydrogen ion (H
+
) from the hydroxyl group of a phenol forms a corresponding negative phenolate ion or phenoxide ion, and the
corresponding salts are called phenolates or phenoxides, although the term aryloxides is preferred according to the IUPAC Gold Book.

Phenols can have two or more hydroxy groups bonded to the aromatic ring(s) in the same molecule. The simplest examples are the three benzenediol
s, each having two hydroxy groups on a benzene ring.

Some phenols are germicidal and are used in formulating disinfectants. Others possess estrogen
ic or endocrine disrupting
activity.
Synthesis of phenols

Several laboratory methods for the synthesis of phenols:
by an ester rearrangement in the Fries rearrangement

by a rearrangement of N-phenylhydroxylamines in the Bamberger rearrangement

by hydrolysis
of phenolic ester
s or ether
s
by reduction of quinone
s
by replacement of an aromatic amine by an hydroxyl group with water and sodium bisulfide in the Bucherer reaction

by hydrolysis
of diazonium salts
by oligomerisation with formaldehyde + base catalysed reaction with epichlorohydrine to epoxi resin components
by reaction with acetone/ketones to e.g. Bisphenol A
, an important monomer for resins, e.g. polycarbonate(PC), epoxi resins
by a rearrangement reaction
of dienones in the dienone phenol rearrangement :

by the oxidation of aryl silanes - an aromatic variation of the Fleming-Tamao oxidation

by the addition of benzene and propene in H3PO4 to form cumene then O2 is added with H2SO4 to form the Phenol (Hock
Process)

Reactions of phenols

Phenols react in a wide variety of ways.
Esterfication reactions and ether
formation
Electrophilic aromatic substitution
s as the hydroxyl group is activating
, for example synthesis of calixarenes
Reaction of naphtols and hydrazines and sodium bisulfite in the Bucherer carbazole synthesis

Oxidative cleavage, for instance cleavage of 1,2-dihydroxybenzene to the monomethylester of 2,4 hexadienedioic acid with oxygen, copper
chloride in pyridine
Oxidative de-aromatization to quinone
s also known as the Teuber reaction. Oxidizing reagents are Fremy's salt and oxone. In reaction depicted below 3,4,5-trimethylphenol
reacts with singlet oxygen
generated from oxone/sodium carbonate in an acetonitrile/water mixture to a para-peroxyquinole. This hydroperoxide is reduced to the
quinole with sodium thiosulfate.

Phenols are oxidized to phediols in the Elbs persulfate oxidation

Phenolate anions (deriving from phenols by the loss of H
+
) can act as ligands towards metal cations

Phenolic compounds
For a full list, see :Category:Phenols

Phenol
the parent compound, used as an disinfectant and for chemical
synthesis

Bisphenol A

and other bisphenols produced from ketones and phenol / cresol
BHT

(butylated hydroxytoluene) - a fat-soluble antioxidant
and food additive

Capsaicin the pungent compound of chilli peppers
Cresol found in coal tar
and creosote

Estradiol

estrogen
- hormones
Eugenol

the main constituent of the essential oil
of clove

Gallic acid found in galls
Guaiacol
(2-methoxyphenol) - has a smokey flavor
, and is found in roasted coffee
, whisky
, and smoke

4-Nonylphenol
a breakdown product of detergents and nonoxynol-9

Orthophenyl phenol
a fungicide
used for waxing citrus fruits
Picric acid

(trinitrophenol) - an explosive material

Phenolphthalein
pH indicator

Polyphenol

e.g. flavonoid
s and tannin
s
Propofol

an anesthetic
Raspberry ketone

a compound with an intense raspberry
smell
Serotonin
/ dopamine / adrenaline / noradrenaline
natural neurotransmitters
Thymol
(2-Isopropyl-5-methyl phenol) - an antiseptic
that is used in mouthwash
es
Tyrosine

an amino acid

Xylenol

-used in antiseptics & disinfecticides

Adverse health effects of some phenols

Some of the above substances are related to endocrine-disruptive chemicals.
GreenPeace report on Hazardous Chemicals in Consumer Products
Medicinals
Cannabinoids
the active constituents of cannabis

Diethylstilbestrol

a synthetic estrogen with a stilbene structure
L-DOPA a dopamine prodrug
Methyl salicylate

the major constituent of the essential oil of wintergreen

Propofol

a short-acting intravenous anesthetic
agent
Salicylic acid

a plant hormone
used for its analgesic
, antipyretic
, and anti-inflammatory
properties, also a precursor compound to Aspirin


Natural occurrence

Phenols are found in the natural world, especially in the plant kingdom. In some cases of natural phenol
s, they are present in vegetative foliage to discourage herbivory, such as in the case of Western poison oak.
Industrial processing

The class of phenols (or phenoles) is an important raw material and an additive for industrial purposes in:
laboratory processes
chemical industry
chemical engineering processes
wood processing
plastics processing
Ether
( /ir/) is a class of organic compounds that contain an ether group an oxygen atom connected to
two alkyl or aryl groups of general formula ROR'.
[1]
A typical example is the solvent and anesthetic
diethyl ether, commonly referred to simply as "ether" (CH
3
-CH
2
-O-CH
2
-CH
3
). Ethers are common in
organic chemistry and pervasive in biochemistry, as they are common linkages in carbohydrates and
lignin.


The general structure of an ether
Important ethers

Ethylene oxide The smallest cyclic ether.

Dimethyl ether
An aerosol spray propellant. A potential renewable
alternative fuel for diesel engines with a cetane rating
as high as 56-57.

Diethyl ether
A common low boiling solvent (b.p. 34.6C), and an
early anaesthetic. Used as starting fluid for diesel
engines.

Dimethoxyethane
(DME)
A high boiling solvent (b.p. 85C):

Dioxane A cyclic ether and high boiling solvent (b.p. 101.1C).

Tetrahydrofuran
(THF)
A cyclic ether, one of the most polar simple ethers that
is used as a solvent.

Anisole
(methoxybenzene)
An aryl ether and a major constituent of the essential
oil of anise seed.

Crown ethers
Cyclic polyethers that are used as phase transfer
catalysts.

Polyethylene glycol
(PEG)
A linear polyether, e.g. used in cosmetics and
pharmaceuticals.