A New or Improved Manufacture of Para Amido Phenol Ethers.
Year: 1889

page_text: Date of Application, 31st Jan., 1889
Complete Specification Left, 29th Oct., 1889-Accepted, 4th Jan., 1890
PROVISIONAL SPECIFICATION.
A New or Improved Manufacture of Para Amido Phenol Ethers.
I, BENJAMIN WILLCOX of 47 Lincolns Inn Fields, in the County of Middlesex,
Patent Agent, do hereby declare the nature of this invention, which has been communi
cated to me from abroad by Farbenfabriken vormals Friedrich Bayer & Co. of
Elberfeld in the Empire of Germany, to be as follows :-
This Invention relates to the production of para amnido phenol- methyl- ethyl- or
amyl ethers by decomposing Para phenol methyl ether-azo phenol methyl ether-
Para phenol ethyl ether-azo phenol ethyl ether-Para phenol amyl ether-azo phenol
amyl ether into 2 molecules of para amido phenol methyl- ether-amyl and benzyl
ethers by reduction as hereinafter described.
The manufacture of para amido phenol ether is attended with considerable difficulty
in practice this being especially the case in the manufacture of the ethyl ether or the
monacetyl combination of para phenetidine being the raw material from which the
antipyreticum and antineuralgicum commercially known as phenacitine are directly
obtained. The nitriting of the phenol always proceeds in such a manner that only
50 per cent. of the para combination is obtained.
My foreign correspondents have now discovered that by conducting the process as
hereinafter described phenol can be smoothly and quantitatively converted into the
para amido phenol ether without the formation of any bye products whatever. The
para amido phenol ether is converted in an acid solution with sodium nitrite into its
diazo compound and the latter is caused to produce the azo reaction on phenol in the
usual manner. The resulting yellow dye stuff, para amido phenol ether azo phenol,
is converted into the ether with alkyl halogens and split up into two molecules of
para phenetidine by the reduction of this azo substance. As the diazotising of the
para phenetidine, the combining to form the dyestuff, alkylising the same and the
reduction proceed smoothly this process of converting phenol into para amnido phenol
ether decidedly presents a great advantage over the process heretofore employed
consisting in the nitriting of the phenol, alkylising the same and reducing the nitro
ether, especially as one half of the phenol employed in the ordinary process goes
to form the ortho combination and is thereby rendered useless for the purposes of
this invention.
The following may be taken as an example of the proportions to be employed-
about fifty parts by weight of para amido phenol ether (phenetidine) are diazotised
in the known manner and the clear solution thereof is poured into an alkaline solution
of about thirty two parts by weight of phenol. The yellow dyestuff para amido
phenol ether azo phenol is immediately formed and is separated by salting out and filtra-
tion. About thirty parts by weight of this dyestuff are alkylised by dissolving them
in about three hundred parts by weight of spirit with the addition of about six and
a half parts by weight of caustic soda and about fifteen parts by weight of bromo
ethyl are added thereto. The alkylising is completed in about twelve hours in a closed
vessel at the temperature of a water bath. The alcohol is distilled off and the ether
(insoluble in alkali) is then obtained being separated from the non alkylised dyestuff
by washing out with dilute soda lye.
To reduce this alkylised azo substance for the conversion into two molecules of
phenetidine about thirty parts thereof by weight are elutriated with about one hundred
and twenty parts by weight of water with the addition of about seventy parts of hydro-
chloric acid at about 20 degrees Beaumé and about twenty parts by weight of iron
are slowly added to the materials. Under gradual heating of the mixture the
reduction now proceeds and the azo body smoothly and with loss of colour splits
up into two molecules of phenetidine hydrochlorate. On lime being added to

page_text: the hydrochlorate solution the phenetidine is set free and is driven over with
steam.
By employing chloro or bromo methyl or amyl in place of the bromo ethyl
mentioned in this example the methyl or ethyl ether of the para amido phenol are
obtained.
In place of the iron, zinc, tin or chloride of tin may be employed for the
reduction process or the reduction may be effected by other known methods of reducing
dyestuffs.
When these ethers are melted with dry acetate of soda and some free acetic acid
the mono acetyl compounds or combinations thereof are obtained. These combinations
are capable of being employed in pharmacy.
COMPLETE SPECIFICATION.
A New or Improved Manufacture of Para Amido Phenol Ethers.
I BENJAMIN WILLCOX, of 47 Lincolns Inn Fields in the County of Middlesex
Patent Agent do hereby declare the nature of this Invention (which has been
communicated to me from abroad by the Farbenfabriken vormals Friedrich Bayer
& Co. of Elberfeld in the Empire of Germany) and in what manner the same is to
be performed to be particularly described and ascertained in and by the following
statement:-
The manufacture of para amido phenol ethers is attended with considerable diffi-
culty in practice, this being especially the case in the manufacture of the ethyl ether
or the monacetyl combination of para phenetidine being the raw material from which
are directly obtained the antipyreticuin and antineuralgicum commercially known as
phenacitine. The nitriting of the phenol proceeds in such a manner that only about
50 per cent. of the para combination is obtained.
My foreign Correspondents have discovered that by conducting the process as
hereinafter described, phenol can be smoothly and quantitatively converted into the
para- amido- phenol- ether, without the formation of any bye products whatever.
Para amido phenol ether or phenetidine is converted in an acid solution with
sodium nitrite into its diazo compound and the latter is caused to react on phenol in
the usual manner. The resulting yellow dye stuff-para phenol ether azo phenol-
is converted into the para amido Azo phenol ether with alkyl halogens and splits up
into two molecules of para phenetidine by the reduction of this azo substance. As the
diazotising of the para phenetidine, the combining to form the dyestuff, the alkylising
of the same and the reduction, proceed smoothly, this process of converting phenol
into para amnido phenol ether presents a great advantage over the process heretofore
employed-consisting in nitriting the phenol, alkylising the same and reducing the
nitro ether-especially as one half of the phenol employed in the ordinary process
goes to form the ortho combination and is thereby rendered useless.
The following may be taken as an example of the molecular proportions to be
employed.
About fifty parts by weight (50 kilos.) of para amido phenol ether hydrochlorate
(phenetidine) are diazotised in the known manner and the clear solution thereof is
poured into an alkaline solution of about thirty two parts by weight (32 kilos.) of
phenol. The yellow dyestuff-para phenol ether azo phenol-is immediately formed
and is separated by salting out and filtration. About thirty parts by weight (30 kilos.)
of this dyestuff or colouring matter are alkylised by dissolving them in about three
hundred parts by weight (300 litres) of alcohol with the addition of about six and a
half parts by weight (6.5 kilos.) of caustic alkali, and about fifteen parts by weight
(15 kilos.) of bromo (or chloro) ethyl are added thereto. The alkylising is completed
in about twelve hours in a closed vessel at the temperature of a water bath (or about

page_text: 100 degrees Centigrade). The alcohol is distilled off and a para amido phenol ether
insoluble in alkali is then obtained, being separated from the non alkylised colouring
matter by washing out with weak or diluted soda lye.
To reduce this alkylised azo substance with a view to its conversion into two mole-
cules of phenetidine about thirty parts thereof by weight (30 kilos.) are given or
added to about one hundred and twenty parts by weight of water (120 litres) with
the addition of about seventy parts (70 kilos.) of hydrochloric acid of 20 degrees
Baumé, and about twenty parts by weight (20 kilos.) of iron filings are slowly added to
the materials. Under gradual heating of the mixture the reduction now proceeds
and the azo body smoothly and with loss of colour splits up into two molecules of
phenetidine hydrochlorate. On adding lime to the hydrochlorate solution the
phenetidine is set free and is driven over with steam.
By employing chloro or bromo- methyl or amyl in place of the bromo-ethyl
mentioned in this example the corresponding methyl or amyl ethers of the para amido
phenol are obtained. In place of the iron filings zinc, tin, or chloride of tin may be
employed for the reduction process or the reduction may be effected by other known
methods of reducing such dyestuffs. When these ethers are melted with dry acetate
of soda, and some free acetic acid, the mono acetyl compounds or combinations
thereof are obtained. These combinations are capable of being employed in
pharmacy.
Having now particularly described and ascertained the nature of the said Inven-
tion and in what manner the same is to be performed I declare that what I claim
is_
Manufacturing para amido phenol-methyl or ethyl or amyl ethers by decomposing
para phenol methyl ether-azo phenol methyl ether, or para-phenol ethyl ether--azo
phenol-ethyl ether or para phenol-amyl ether-azo phenol-amyl ether into 2 molecules
of para amido phenol methyl or ethyl or amyl ethers by reduction substantially as
herein before described.
Dated this 20th day of 3000