Year: 1886

page_text: Date of Application, 11th Nov., 1886.
Complete Left, 10th Aug., 1887.
Complete Accepted, 16th Sept:, 1887.
I JOHN HENRY JOHNSON of 47 Lincolns Inn Fields in the County of Middlesex
Gentleman do hereby declare the nature of this Invention which has been
communicated 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 preparation of a series of yellow red and purple
coloring matters belonging to the class of the so-called Azo-dyes and chiefly remark-
able on account of their property to dye vegetable fibre without the aid of a mordaunt,
a property which they share with certain already known Azo-dyes-derivatives of
Benzidine and its homologues.
According to this Invention the said coloring matters are produced by the combina-
tion of certain aromatic amines and phenolic bodies hereafter to be defined with the
Tetrazo-compound of Alpha-diamidonaphthalene.
The said Alpha-diamidonaphthalene which may also be called "Alphanaphthylene
diamine" is a known reduction-compound of the Alpha-dinitronaphthalene fusing at a
temperature of 216 degrees Centigrade. Its Tetrazo-compound which forms the
starting point of the present Invention, has hitherto remained unknown several attempts
to obtain well defined products of the reaction of nitrous acid upon the said 'diamine
having failed (Comp. Ber. Deutsche Chem. Ges. VII page 306. 319).
Now my Foreign Correspondents have discovered that by the employment of very
strongly acidified solutions of Alpha-diainidonaphthalene (as will hereafter be exemplified)
the said Tetrazo-compound may be easily prepared without any appreciable formation
of bye-products and that by its action upon the before mentioned aromatic bodies a
valuable series of coloring matters may be obtained. The coloring matters the
preparation of which constitutes the object of the present Invention are produced by
the combination of one molecule of the before named Tetrazo-compound with two
molecules of any of the following bodies vizt. the Sulpho-acids of Alphanaphthylamine
of Betanaphthylamine of Alphanaphthol of Betanaphthol or Salicylic Acid. The
combination or reaction is effected in the manner generally practised in the preparation
of Azo dyes and requires a considerable length of time in order to complete. It
1D.c

page_text: therefore becomes necessary to apply the tests, hereafter described in the subjoined
example in order to ascertain the point in which the reaction is complete or nearly so.
The following is an example of the manner in which this Invention may be carried
into effect.
About twenty three parts by weight of the Hydrochlorate of Alpha-Naphthylene-
diamine about one hundred and twenty five parts by weight of Hydrochloric Acid
containing about thirty five per cent of H Cl about two hundred and fifty parts by
weight of water and an equal quantity of ice are intimately mixed and then about
fourteen parts by weight of Nitrite of Sodium previously dissolved in three times their
weight of water are gradually added. By the employment of the very large excess of
Hydrochloric Acid as above prescribed the conversion of the Diamine into its corre-
sponding Tetrazo compound proceeds in the before mentioned regular manner.
The solution of the Tetrazo compound thus obtained is then added to a solution of
about seventy parts by weight of Naphthionate of Sodium and about two hundred
parts by weight of crystallized Acetate of Soda in about three thousand parts by
weight of water. Immediately a red precipitate begins to form. The mixture is to be
kept well agitated until by the application of the following tests the end of the roaction
will be indicated. From time to time a sample of the mixture is withdrawn and is
rendered strongly alkaline by the addition of Carbonate of Soda and is heated to
ebullition when the end of the operation will be indicated by the absence of any
evolution of Nitrogen.
Another sample of the mixture is to be tested by dyeing therein some cotton. It
will then be noticed that the clearness and purity of the color gradually increases until
the close of the reaction which generally requires several days to be thoroughly
completed.
The formation of the coloring matter being thus finished the mixture is rendered
strongly alkaline by the addition of Carbonate of Soda heated to ebullition and then
allowed to get cool and crystallized. The coloring matter thus obtained in a crystalline
condition is then separated from the mother liquor pressed and dried.
In an analogous manner coloring matters, dyeing reds of various shades upon cotton
and similar vegetable fibre in an alkaline dye bath may be obtained by the employment
of suitable Sulpho-acids of Alpha- or Betanaphthylamine.
With Salicylic Acid a yellow dye stuff is produced whilst the azo-dyes obtained from
the Sulpho-acids of the isomeric Napthols are capable of dyeing various shades of
purple upon vegetable fibre.
Dated this 11th day of November 1886.

page_text: Improvements in the Preparation of Red Coloring Matters.
I JOHN HENRY JOHNSON of 47 Lincolns Inn Fields in the County of Middlesex
Gentleman do hereby declare the nature of this Invention which has been
communicated to me from abroad by The Badische Aniline and Soda Fabrik of
Ludwigshafen on 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 the following
statement :-
This Invention relates to the preparation of red coloring matters belonging to the
class of the so called "Azo-dyes" and chiefly remarkable on account of their property
to dye vegetable fibre without the aid of a mordant a property which they share with
certain already known Azo dyes, Derivatives of Benzidine and its homologues.
According to this Invention the said coloring matters are produced by the
combination of certain aromatic Amines and phenolic bodies hereafter to be defined
with the Tetrazo-compound of Alpha-diamidonaphthalene.
The said Alpha-diainidonaphthalene (which may also be called "Alphanaphthylene-
diamine") is a known reduction compound of the Alpha-dinitronaphthalene fusing at
a temperature of 216° Centigrade. Its Tetrazo-compound which forms tho starting
point of the present Invention has hitherto remained unknown several attempts to
obtain well defined products of the reaction of Nitrous Acid upon the said diamine
having failed (Compare Berichte der Deutschen Chemischen Gesellschaft VII
page 306-319.
Now my foreign Correspondents have discovered that by the employment of very
strongly acidified solutions of Alphadiamido-naphthalene (as will hereafter be
exemplified) the said Tetrazo compound may be easily prepared without any
appreciable forination of bye products and that by the combination of one molecule of
the Tetrazo compound with two molecules of Salicylic Acid or of the monosulpho acids
of either Alpha or Beta-naphthylamine or of the monosulpho acids of either Alpha or
Betannphthol a series of coloring matters may be prepared. Although amongst these
are yellow and purple coloring matters as well as red coloring matters yet since the
date of the application for the Patent for this Invention my Correspondents have
submitted the single members of the said series of coloring matters to comparative dye
trials upon a somewhat larger scale in order to ascertain (as far as possible) which
coloring matters would be likely to enter into successful competition-as far as regards
price or quality-with similar coloring matters produced by different processes and
the result of their enquiry has been that they restrict their claim under this present
Specification to the preparation of red coloring matters resulting from the combination
of one molecule of the above named. Tetrazo-compound of Alphanaphthylene-diamine
with two molecules of either Naphthionic Acid or of any of the three modifications of
tho Monosulpho Acid of Betanaphthylamine hereafter to be defined.

page_text: In general it may be remarked that the combination or reaction of the said
Tetrazo-compound is effected in the manner generally practised in the preparation of
Azodyes but that it requires a considerable length of time in order to become
completed. It therefore becomes necessary to apply the test hereafter described for
the purpose of ascertaining the point in which the reaction is complete or nearly so.
The following is an example of the manner in which this Invention may be carried
into effect:-
About twenty three (23) parts by weight of the hydrochlorate of the before named
Alpha-Naphthylenediamine in a state of fine division about One hundred and twenty
five (125) parts by weight of hydrochloric Acid containing about Thirty five (35) per
cent. of the dry Acid (HCl) about Two hundred and fifty (250) parts by weight of
water and an equal quantity of ice are intimately mixed and then about Fourteen (14)
parts by weight of Nitrite of Sodium previously dissolved in three times their weight
of water are gradually added. By the employment of the very large excess of
hydrochloric Acid as above prescribed the conversion of the diamine into its
corresponding Tetrazo-compound proceeds in the before mentioned regular manner.
The solution of the Tetrazo-compound thus obtained is then added to a solution
obtained by dissolving about seventy (70) parts by weight of Naphthionate of Sodium
(prepared from Alpha-naphthylamine) and about Two hundred (200) parts by weight
of Crystallized acetate of soda in about Three thousand (3000) parts by weight of
water. Immediately (after the said ingredients are mixed a red precipitate begins to
form.
The mixture is to be kept well agitated during several days until by the application
of the following tests the end of the reaction will be indicated From time to time a
sample of the mixture is withdrawn rendered strongly Alkaline by the addition of
Carbonate of Soda and heated to ebullition. The operation will then have to be
considered at an end when no longer any evolution of Nitrogen can be observed.
Another sample of the mixture may be tested from time to time by dyeing therein
some cotton. It will then be noticed that the clearness and purity of the dyed shades
gradually increases until the close of the reaction. The formation of the coloring
matter being thus finished the mixture is rendered strongly Alkaline by the addition
of Carbonate of Soda heated to ebullition and then allowed to get cool. The coloring
matter thus obtained in a crystalline condition is then separated from the mother
liquor pressed and dried.
The coloring matter or dye stuff prepared as herein before described dyes a full and
bright red upon vegetable fibre in an Alkalino dye bath without the aid of a Mordant
and in the manner practised by dyers for dying with the so called "Congored." The
shades thus obtained resist very well the action of light air and moderate soaping but
they are turned by Acetic Acid into a purple and by strong hydrochloric Acid into a
dingy green.
In an analogous manner isomeric coloring matters dyeing bright reds of various
shades upon Cotton and similar vegetable fibre in an Alkaline dye bath without the
aid of a Mordant are obtained by employing in lieu of Naphthionic Acid in the above
described process the same proportions of the isomeric inonosulpho-acids or Beta-
Naphthylamine.
The best results have been obtained by employing the following modifications of the
said monosulpho acids of Beta-Naphthylamine vizt. 1. the modification corresponding
in its molecular structure to the so called Schaeffer's monosulpho-acid of Beta-naphthol
and which as is well known may be prepared by the action of ammonia upon the said
beta naphthol compound.
2. The modification known under the name of Dahl's Acid produced by the direct
sulphonization of Betanaphthylamine at about 100 degrees Centigrade difficultly
soluble in water and forming a sodium-salt easily soluble in Alcohol.
3. The modification known as Delta-monosulpho acid of Betanaphthylamine
produced by the direct sulphonization of Betanaphthylamine at a temperature
exceeding 150° Centigrade.
The red coloring matters resulting from the combination of the Tetrazo compound

page_text: of Alpha-naphthylenediamine with the monosulpho acids of Beta-naphthylamine as
aboyo defined produce shades upon vegetable fibre which besides being sufficiently fast
against the action of light air and soap are not affected by Acetic Acid but are turned
by concentrated hydrochloric Acid into a dingy yellow shade.
Having now particularly described and ascertained the nature of this Invention and
in what manner the same is to be performed I declare that what I claim is :-
The preparation of red coloring matters by the combination of one molecule of the
Tetrazo-compound of Alpha-naphthylene-diamine with two molecules of Naphthionic
Acid or with two molecules of any of the hereinbefore defined modifications of
monosulpho acid of Beta-naphthylamine substantially as hereinbefore described.
Dated this 10th day of August 1887.