Manufacture of Phenolether and Oxydiphenyl, their Homologues and Analogues.
Year: 1890

page_text: Date of Application, 12th June, 1890
Complete Specification Left, 12th Mar., 1891-Accepted, 18th Apr., 1891
PROVISIONAL SPECIFICATION.
Manufacture of Phenolether and Oxydiphenyl, their Homologues
and Analogues.
We, JOHN DAWSON, of Kirkheaton Color Works, Kirkheaton, near Hudders-
field, and ROBERT HIRSCH, Ph. D., of Huddersfield, do hereby declare the nature
of this invention to be as follows:-
If the aqueous solutions of diazobenzene, diazotoluene, diazonapthalene & other
aromatic diazo compounds are mixed with phenol, the diazosalts dissolve in the
phenol. The solutions thus obtained are fairly stable & may be kept for several
days almost unchanged at a low temperature, but at a higher temperature they
rapidly decompose giving off nitrogene gas. Apparently these solutions contain a
loose combination between the diazo-molecules & the phenol as shown by the
following formula C,H,N=N-O-CH. If the mixture thus obtained is separated
by fractional distillation the excess of phenol used is recovered & at the same
time, with the diazo benzene for instance, the isomeric combinations phenol-
ether CH-O-CH, & oxydiphenyl C.H-CH, OH are obtained, besides
small quantities of the mixed ether CH-O-CH, CH.
The homologues of the aniline are throughout similar, but in this instance the
homologues of the oxydiphenyl occur in two modifications derived from the para
& the ortho-oxydiphenyl, the boiling point of the latter being about 20° lower than
that of the former.
Instead of separating the products by fractionated distillation it is advisable to
use their different action against caustic solutions for their separation.
We proceed as follows:-
Ten kilo of aniline are dissolved in 100 litres of water & 30 kilo hydrochloric
acid, the solutions mixed with 7.5 kilo of nitrite of soda dissolved in 15 litres of
water, & the diazo solution thus obtained agitated with 30 kilo of phenol. The
solution of phenol is then drawn off & the treatment, repeated three times with ten
kilo of phenol.
The solutions of phenol are mixed and heated in small quantities in a capacious
vessel provided with a condenser. The water formed by the reaction is drawn off &
the phenol solution is distilled. At 200° the phenol not acted upon is recovered.
At 200°-350° the products of the reaction distil, about 14 kilo in weight. These
are mixed with 30 kilo of toluene & the warm toluene solution is repeatedly shaken
with a warm solution of caustic containing about 5% Na.O.H., till all compounds
soluble in the caustic are removed. The addition of the toluene renders the
separation of the layers less difficult.
In the following distillation the toluene is first recovered, then between 240°
& 290° about 2,5 kilo phenolether, which after repeated rectification boils at
about 255°-258°. The parts soluble in caustic are precipitated with hydrochloric
acid & purified by distillation or crystalization with glacial acetic acid.
About 12 kilos of paraoxydiphenyl with its well known qualities are obtained
In the same way are prepared:
Phenyl phenylether
Phenyl o tolylether
F.P. 25°
Boiling point 257°
Liquid
263°
"
33

page_text: p Oxyphenyl a napthyl
o Oxyphenyl o tolyl
o Oxyphenyl p tolyl
Syrupy
liquid
"
Boiling point 370°
"
280°
12
280°
COMPLETE SPECIFICATION.
Manufacture of Phenolether and Oxydiphenyl, their Homologues
and Analogues.
We, Jonx DAWSON, Kirkheaton Color Works, near Huddersfield, and
ROBERT HIRSCir, Ph. D. of Huddersfield, do hereby declare the nature of this inven-
tion, and in what manner the same is to be performed, to be particularly described
and ascertained in and by the following statement :-
If the aqueous solutions of diazobenzene, diazotoluene, diazonaphthalene and
other aromatic diazocompounds are mixed with phenol, the diazosalts dissolve in
the phenol.
The solutions thus obtained are fairly stable and may be kept for several days
with scarcely any decomposition at a low temperature, but at a higher temperature
they rapidly decompose giving off nitrogen gas.
Apparently these solutions contain a loose combination between the diazomolecules
and the phenol as shewn by the following formula CH¸N=N-O-C₂H.
If the mixture thus obtained is separated by fractionated distillation, the excess
of phenol used is recovered and at the same time, with the diazobenzene for instance,
the isomeric combinations phenolether C,HOCH, and o. and p. oxydiphenyl
CH-CH, OH are obtained besides small quantities of the mixed ether
CH-O-CHCH.
The homologues of the aniline are throughout similar in their behaviour.
Instead of separating the products by fractionated distillation it is advisable to
use their different action against caustic solutions for their separation.
We proceed as follows:
Ten kilos of aniline are dissolved in 10 litres of water and 30 kilos of
hydrochloric acid, the solutions mixed with 75 kilos of nitrite of soda dissolved in
15 litres of water and the diazo solution thus obtained agitated with 30 kilos of
phenol. The solution of phenol is then drawn off and the treatment repeated three
times with 10 kilos of phenol.
The solutions are mixed and decomposed by heating in small quantities in
a capacious vessel provided with a condenser. The water formed by the
reaction is drawn off and the phenol solution is distilled. At 200° the phenol not
acted on is recovered. At 200° to 350° the products of the reaction distil, about
14 kilos in weight. These are mixed with 30 kilos of toluene and the warm toluene
solution is repeatedly shaken with a warm solution of caustic soda containing
about 5% NaOEL, till all compounds soluble in caustic soda are removed. The
addition of the toluene renders the separation of the layers less difficult. In the
following distillation the toluene is first recovered, then between 240° and 200°
about 2,5 kilos phenolether which after repeated rectification boils at about
255°-258°. The parts soluble in caustic are precipitated with hydrochloric acid
and purified by distillation or crystallization with glacial acetic acid. About 12
kilos of o. and p. oxydiphenyl are obtained which may be separated by crystalliza-
ion or fractional distillation.
In the same way are prepared:

page_text: p. Oxyphenyi o. tolyl
p. Oxyphenyl p. tolyl
p. Oxyphenyl a. napthyl
liquid
F.P. 155°
syrupy
liquid
Boiling point 300°
330°
22
29
370°
33
22
280°
"
22
280°
::
o. Oxyphenyl o. tolyl
o. Oxyphenyl p. tolyl
23
We are aware that phenylether has been obtained by a similar process by
Hofmeister (Berichte III 747, Annalen 159, 196) but his process admits no
utilization for industrial purposes, as the employment of dry diazo compounds is
obviously impossible, and the second way used by him gives only very small yields,
the sulphuric acid under those conditions giving phenolsulpho acid and benzol-
sulpho acid.
Having now particularly described and ascertained the nature of our said
invention, and in what manner the same is to be performed, we declare that what
we claim is-
The manufacture of phenolether o. and p. oxydiphenyl and their homologues and
analogues by the decomposition of a solution of diazo benzol, its homologues and
analogues, in phenol, substantially as herein before described.
n
1001
JOHN DAWSON.
ROBERT HIRSCH.