Improvements in the Manufacture of Nitroso Compounds and of Colouring Matters therefrom Suitable for Dyeing and Printing.
Year: 1888

page_text: Improvements in the Manufacture of Nitroso Compounds and of
Colouring Matters therefrom Suitable for Dyeing and Printing.
JAMES YATE JOHNSON of 47 Lincolns Inn Fields in the County of Middlesex
Gentleman do hereby declare the nature of this Invention which has been communi-
cated to me from abroad by the Badische Anilin and Soda Fabrik of Ludwigshafen
on-the-Rhine in the Empire of Germany to be as follows:-
This Invention relates to the manufacture of a new series of blue colouring matters
resulting from the condensation of Alpha-naphthylamine and its secondary and
tertiary alkyl-derivatives with the hitherto unknown mononitroso-compounds of
dimethyl-meta-amido-phenol and of diethyl-meta-amidophenol.
The said mononitroso-compounds are produced by the reaction of nitrous acid
upon the said alkyl-derivatives of meta-amidophenol equal molecules of the reagents
being employed. Nitrous acid may be used either in its free or in its combined
state according to the known methods of producing aromatic nitroso compounds
(such for instance as nitrosodimethylaniline).
The process of preparing the new blue colouring matters therefore consists of two
consecutive steps vist. of the preparation of the above said mononitroso-compounds
followed by the condensation thereof with alpha-naphthylamine and its derivatives
and I shall now proceed to illustrate the practical manner of carrying out the said
steps by the following examples:
1. PREPARATION OF THE MONONITROSOCOMPOUNDS.
0
In order to prepare the mononitroso compound of diethyl-meta amido-phenol about
10 parts by weight of diethyl-meta-amido phenol are dissolved in about thirty parts
by weight of strong hydrochloric acid-The solution thus obtained is cooled down
to zero by the addition of ice and then (whilst constantly stirring) an equally cooled
solution of about four parts and four tenths of a part by weight of commercial
Nitrite of Soda (containing about ninety six per cent. of the pure Nitrite) in about
гр

page_text: nine parts by weight of water is added thereto. Throughout this operation the
temperature of the mixture should be kept at zero-The mononitroso-compound
thus produced separates out in a crystalline condition and may then be filtered
pressed and dried at an ordinary temperature."
In an analogous manner the mononitroso-compound of dimethyl-meta-amidophenol
may be prepared by allowing the equivalent proportion of nitrous acid (say about
53 parts by weight of commercial. Nitrite of Soda of 96%)-to react upon about
ten parts by weight of dimethyl-meta-amidophenol substantially in the manner
hereinbefore described.
.
The mononitroso-compounds thus obtained in the state of their respective hydro-
chlorates are yellow-coloured crystalline bodies soluble in water with an intense
yellow or yellow-orange colour-From these-aqueous solutions the free nitroso-
compounds may be isolated by careful addition of the requisite amount of a caustic
or carbonated alkali- and by subsequent extraction with a suitable solvent say with
Benzene or Chloriform. The Nitroso-compounds likewise combine with salifiable
bases forming partly well defined and crystallized salts.
2. CONDENSATION OF THE MONONITROSOCOMPOUNDS WITH ALPHANAPHTHYLAMINE
AND ITS SECONDARY AND TERTIARY ALKYL-DERIVATIVES.
1. As an example of the manner in which a blue coloring matter may be produced
by the condensation of the before described diethyl-meta-amidophenol with Alpha-
naphthylamine I give the following description
About ten parts by weight of hydrochlorate of Alpha-naphthylamine are intimately
mixed with about forty parts by weight of glacial Acetic Acid and with about twenty
parts by weight of water. The mixture thus produced is heated up to about sixty
degrees Centigrade in an enamelled pan and then under constant agitation about
ten parts by weight of the above named hydrochlorate of nitroso-diethyl meta-
amidophenol are aided by degrees. This operation being completed the temperature
of the mixture is raised to about one hundred degrees Centigrade and maintained
thereat for say about three hours or until the blue colour thus gradually developed,
does no longer appear to increase in intensity. The contents of the vessel are then
allowed to cool down to about thirty degrees Centigrade and are afterwards intimately
mixed with about twenty parts by weight of water. The colouring matter will then
become precipitated and may be separated by filtration. A further purification is
effected by boiling the colouring matter thus obtained with about one hundred
parts by weight of water allowing the mixture to cool down to about sixty degrees
Centigrade filtering pressing and drying the product thus obtained.
The
In the manner hereinbefore described the coloring matter is obtained in the state
of a hydrochlorate possessing a crystalline bronze-like appearance on account of its
deficient solubility in water which may interfere with its convenient application in
dyeing and printing, it will be advisable to convert the said hydrochlorate into its
corresponding soluble Sulphate by dissolving the dry colouring matter in about eight
times its own weight of concentrated and gently warmed Sulphuric Acid.
solution thus obtained is then allowed to cool and poured into about from seven
to eight times its own weight of cold water. The mixture is to be kept agitated until
the precipitated Sulphate of the coloring matter has assumed a Crystalline condition
and the product thus obtained is then filtered washed with a solution of glauber-
salt in order to remove the acid mother-liquor pressed, and dried.
By employing naphthylamine-base in lieu of its hydrochlorate as hereinbefore
described less satisfactory results are obtained.
2. As an example of a secondary alkyl-derivative of alpha-naphthylamine the
mono-ethyl-alphanaphthylamine is selected and I will describe its condensation with
mono-nitroso-diethylmeta-amidophenol.
About ten parts by weight of the said monoethyl-alphanaphthylamine are put into
an enamelled pan and carefully mixed therein with about thirteen and a half parts by
weight of hydrochlorate of mononitroso-diethylmeta-amidophenol and with about

page_text: fifty parts by weight of glacial acetic acid. The mixture is then heated (whilst
constantly stirred) to a temperature of about one hundred degrees Centigrade until
it has assumed a blue colour and afterwards the reaction is completed by maintaining
the said temperature during say about half an hour. The melt thus produced is then
dissolved in about three hundred and fifty parts of hot water and the filtered solution
is precipitated with common salt and chloride of zinc say with about fourteen parts
by weight of a solution of chloride of zinc to about 19 specific gravity. A further
purification of the precipitate of the colouring matter thus obtained may then be
effected by redissolving the same in hot water and reprecipitating the filtered solution
by means of common salt and chloride of zinc. In its dry state the coloring matter
has the appearance of a dark amorphous powder exhibiting a bright coppery lustre
upon its surface and endowed with a sufficient degree of solubility in order to be
employed in dyeing and printing.
3. In a similar. manner nitrosodiethyl-meta-amidophenol may be condensed with
dimethyl-alplanaphthylamine the representative of the tertiary alkyl-derivatives of
alpha-naphthylamine-In this instance the same weights and proportions of the
materials can be employed as in the last preceding example.
In lieu of the free bases of the alkyl derivatives of alpha-naphthylamine as herein-
before described their respective hydrochlorates may be employed.
The blue colouring matters produced in the manner herein before described
possesses a basic character and accordingly dye animal fibres in a neutral or in a
slightly acidulated dye-bath without the aid of a mordant, whilst they require a
tannin-mordant, in order to become fixed upon vegetable fibres. The shades which
they are able to produce in dyeing and printing are similar to those of methylene-
blue.
Dated thi 52-1 dav of Mura 1888
J. H. JOHNSON & Co.,
47, Lincoln's Inn Fields, London,
Agents.

page_text: COMIT LIN ST MULTICATION.
Improvements in the Manufacture of Nitroso Compounds and of
Colouring Matters therefrom Suitable for Dyeing and Printing.
I JAMES YATE JOHNSON of 47 Lincolns Inn Fields in the County of Middlesex
Gentleman do hereby declare the nature of this invention.which has been communi-
cated to me from abroad by the Badische Anilin and Soda Fabrik of Ludwigshafen
on the Rhine in the Empire of Germany and in what manner the same is to be
performed to be particularly described and ascertained in and by tlie following
statement:-
This Invention relates to the manufacture of a new series of blue colouring matters
resulting from the condensation of alpha-naphthylamine and its secondary and tertiary
alkyl derivatives with the hitherto unknown mononitroso-compounds of dimethyl-
meta-amido-phenol and of diethyl-meta-amido-phenol.
The said mononitroso-compounds are produced by the reaction of nitrous acid upon
the said dimethyl and diethyl derivatives of meta-amidophenol, equal molecules of the
reagents being employed. Nitrous acid may be used either in its free or in its
confbined state according to the known methods of producing aromatic nitroso-
compounds (such for instance as nitrosodimethylaniline).
The process of preparing the new blue colouring matters therefore consists of
two consecutive steps, viz. of the preparation of the above said mononitroso
compounds followed by the condensation thereof with alpha-naphthylamine and its
derivatives and I shall now proceed to illustrate the practical manner of carrying out
the said steps by the following examples.
EXAMPLE I. PREPARATION OF THE MONONITROSOCOMPOUNDS.
In order to prepare the mononitrosocompound of diethyl-meta-amido-phenol about
ten parts by weight of diethyl-meta-amido-phenol are dissolved in about thirty parts
by weight of strong hydrochloric acid. The solution thus obtained is cooled down to
zero by the addition of ice and then (whilst constantly stirring) an equally cooled
solution of about four parts and four tenths of a part by weight of commercial nitrite
of soda (containing about ninety six per cent. of the pure nitrite) in about nine parts
by weight of water is added thereto. Throughout this operation the temperature of
the mixture should be kept at zero. The mononitrosocompound thus produced
separates out in a crystalline condition and may then be filtered pressed and dried at
an ordinary temperature.
In an analogous manner the mononitrosocompound of dimethyl-meta-amidophenol
may be prepared by allowing the equivalent proportion of nitrous acid (say about
5.3 parts by weight of commercial nitrite of soda of 96 %) to react upon about
ten parts by weight of dimethyl-meta amidophenol substantially in the manner herein-
before described.

page_text: The mononitrosocompounds thus obtained in the state of their respective hydro-
chlorates are yellow coloured crystalline bodies soluble in water with an intense
yellow or yellow orange-colour. From those aqueous solutions the free nitroso-
compounds may be isolated by careful addition of the requisite amount of a caustic or
carbonated alkali and by subsequent extraction with a suitable solvent, say with.
benzene or chloroform. The nitrosocompounds likewise combine with salifiable bases
forming partly well defined and crystallized salts.
EXAMPLE II. CONDENSATION OF THE MONONITROSOCOMPOUNDS WITH ALPHA-
NAPHTHYLAMINE AND ITS SECONDARY AND TERTIARY ALKYL DERIVATIVES.
1. As an example of the manner in which a blue colouring matier may be
produced by the condensation. of the before described mononitrosocompounds of
dimethyl or diethyl-meta-amidophenol with alpha naphthylamine I give the following
description.
About ten parts by weight of hydrochlorate of alpha-naphthylamine are intimately
mixed with about forty parts by weight of glacial acetic acid and with about
twenty parts by weight of water. The mixture thus produced is heated up to about
sixty degrees centigrade in an enamelled pan, and then under constant agitation
about ten parts by weight of the above named hydrochlorate of nitroso-diethyl-meta-
amidophenol are added by degrees. This operation being completed the temperature
of the mixture is raised to about one hundred degrees centigrade and maintained
thereat for say about three hours or until the blue colour thus gradually developed,
does no longer appear to increase in intensity. The contents of the vessel are then
allowed to cool down to about thirty degrees centigrade and are afterwards intimately
mixed with about twenty parts by weight of water. The colouring matter will then
become precipitated and may be separated by filtration. A further purification is
effected by boiling the colouring matter thus obtained with about one hundred parts
by weight of water allowing the mixture to cool down to about sixty degrees centigrade,
filtering pressing and drying the product thus obtained.
In the manner hereinbefore described the colouring matter is obtained in the state
of a hydrochlorate, possessing a crystalline bronze-like appearance. On account of
its deficient solubility in water which may interfere with its convenient application in
dyeing and printing it will be advisable to convert the said hydrochlorate into its
corresponding soluble sulphate by dissolving the dry colouring matter in about
eight times its own weight of concentrated and gently warmed sulphuric acid. The
solution thus obtained is then allowed to cool and poured into about from seven to
eight times its own weight of cold water. The mixture should be kept agitated until
the precipitated sulphate of the colouring matter has assumed a crystalline condition
and the product thus obtained is then filtered, washed with a solution of glauber-salt
in order to remove the acid mother-liquor pressed and dried.
By employing a naphthylamine base in lieu of its hydrochlorate as hereinbefore
described less satisfactory results are obtained.
2. As an example of secondary alkyl-derivative of alphanaphthylamine the mono-
ethyl-alphanaphthylamine is selected, and I will describe its condensation with mono-
nitroso-diethylmeta-amidophenol.
About ten parts by weight of the said mono-ethyl-alphanaphthylamine are put into
an enamelled pan and carefully mixed therein with about thirteen and a half parts by
weight of hydrochlorate of mono-nitroso-diethylmeta-amidophenol and with about
fifty parts by weight of glacial acetic acid. The mixture is then heated (whilst
constantly stirred) to a temperature of about one hundred degrees centigrade, until it
has assumed a blue colour and afterwards the re-action is completed by maintaining
the said temperature during say about half an hour. The melt thus produced is then
dissolved in about three hundred and fifty parts of hot water and the filtered solution
is precipitated with common salt and chloride of zinc, say with about fourteen parts
by weight of a solution of chloride of zine of about 1.9 specific gravity. A further
purification of the precipitate of the colouring matter thus obtained may then be

page_text: effected by redissolving the same in hot water and reciprocating the filtered solution
by means of common salt and chloride of zinc. In its dry state the colouring matter
has the appearance of a dark amorphous powder exhibiting a bright coppery lustre
upon its surface and endowed with a sufficient degree of solubility in order to be
employed in dyeing and printing.
3. In a similar manner nitrosodiethyl-meta-amidophenol may be condensed with
dimethyl alphanaphthylamine the representative of the tertiary alkyl-derivatives of
alphanaphthylamine. In this instance the same weights and proportions of the
materials can be employed as in the last preceding example.
In lieu of the free bases of the alkyl derivatives of alpha-naphthylamine as herein-
before described their respective hydrochlorates may be employed.
The blue colouring matters produced in the manner herein before described possess
a basic character and accordingly dye animal fibres in a neutral or in a slightly
acidulated dyebath without the aid of a mordant, whilst they require a tannin mordant
in order to become fixed upon vegetable fibres. The shades which they are able to
produce in dyeing and printing are similar to those of methylene blue.
.
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:
Ist. The manufacture or production of mononitroso-compounds of dimethyl-meta-
amidophenol and of diethyl-meta-amidophenol by the action of nitrous acid upon
dimethyl- or diethyl-meta-amidophenol substantially as hereinbefore described.
2nd. The manufacture or production of mononitroso-compounds of dimethyl or
diethyl-meta amidophenol as hereinbefore described under Example I.
3rd. The manufacture or production of colouring matters by the condensation of
the mononitroso-compounds of dimethyl or diethyl meta amido-phenol with alpha-
naphthylamine or its secondary or tertiary alkyl derivatives substantially as herein-
before described.
4th. The condensation of the mononitroso compounds of dimethyl or diethylmeta
amidophenol with alpha naphthylamine or its secondary or tertiary alkyl-derivatives
in the manners hereinbefore described under Example II.
5th. The manufacture or production of colouring matters by acting upon dimethyl
or diethyl meta amidophenol with nitrous acid and then condensing the mono-
nitroso compounds so produced with alphanaphthylamine or its secondary or tertiary
alkyl derivatives substantially as hereinbefore described.
Dated this 24th day of Doma 1900