Improvements in the Manufacture of Colouring Matters.
Year: 1890

page_text: Date of Application, 20th Dec., 1890
Complete Specification Left, 25th Aug., 1891-Accepted, 26th Sept.,
1891
PROVISIONAL SPECIFICATION.
[Communicated from abroad by Messrs. WIRTH & Co., of Frankfort-on-the-Main,
in the Empire of Germany, acting as Agents of Kalle & Co., of Biebrich-on-
the-Rhine, in the Empire of Germany, Manufacturers.]
Improvements in the Manufacture of Colouring Matters.
1, HENRY HARRIS LAKE, of the firm of Haseltine, Lake & Co., Patent
Agents, 45 Southampton Buildings, in the County of Middlesex, do hereby declare
the nature of this invention to be as follows:-
In the Specification of British Letters Patent No. 15259, dated 23rd October
1888 and United States Patents No. 430,975, dated June 24th 1890 and
No. 431,404 dated July 1st 1890, are described two sulpho-acids of the basic
colouring matter, which are termed rosinduline (Berichte der Deutsch. Chem.
Ges. 21. 2621), and the discovery of which was due to the researches made by the
communicators during a long series of years in collaboration with Professor
Otto Fischer in regard to the "indulin group." The communicators have now
found that the rosinduline belongs to a new class of basic colouring matters of the
general formula C2H4NR and of yellowish to reddish violet shades, and that all
thesc basic substances can be easily converted into sulpho-acids of very suitable
properties for dyeing purposes. The simplest examples of these new basic products
having the formula C₂HN, may be obtained by treating a salt of benzol-azo-
a-naphthylamine under pressure with aniline in presence of alcohol. The others are
prepared by substituting benzol-azo-a-naphthylamine by the azo-compounds
obtained from diazo-benzol and substituted naphthylamines. Very valuable dye-
stuff's of the formulas C22H,,N. CH, and C2H₁N. CH, are in particular produced
by treating a salt of benzol-azo-tolyl-naphthylamine or of benzol-azo-di-a-naphthyl-
amine with aniline in presence of alcohol or by melting these compounds with
aniline in the well known manner of the so called "induline melts."
14
22 143
I. In preparing the rosinduline C22H₁, N2, I proceed as follows:-1 part of
chlorhydrate of benzol-azo-a-naphthylamine is treated for about 6 hours under
pressure with 2 parts of aniline and 4 parts of alcohol. The alcohol and the
aniline are then driven off by steam and the residue is boiled with water acidulated
by sulphuric acid until the whole basic dye-stuff has dissolved. The base pre-
cipitated by an alkali from the filtered solution can be directly sulphurated, or it
is purified by means of the salts which are crystallized from a hot solution to
which is added common salt. The residue consists of rosindone having the
formula CHN₂O. The base crystallizes in reddish brown leaves and melts
at 198-190° C., the alcoholic solutions absorbing quickly the carbonic acid from
the air, like the basis of safranines. The alcoholic solutions of the base show a
yellowish red fluorescence, the alcoholic solutions of the salts a fiery red
fluorescence. The salts are very easily soluble in water and when dyeing mordanted
cotton, they yield more yellowish shades than the rosinduline C.,H,,N. In strong
sulphuric acid, the dye dissolves with a green colour which turns red when diluted
with water.
25
3
32
19
II. The rosindulines C, H, N, and C2H2N, may be obtained in the same way
as the rosinduline C.HN, or by melting 1 part of chlorhydrate of benzol-azo-
ortho-tolyl-a-naphthylamine or of benzol-azoparatolyl a naphtylamine or 1 part of
chlorhydrate of benzolazodi a naphtylamine for about 5 hours at 130-150° C.
with 2 parts of aniline and by treating the "melt" in the above described
manner.
21
The basis CH,N, obtained from benzolazoorthotolyl a naphtylamine and
benzolazoparatolyl a naphtylamine crystallizes in reddish brown brilliant leaves

page_text: melting at 228° or at 231-233° C. The salts are very slightly soluble in cold
the rosin-
water and dye mordanted cotton" perhaps the same shades as
duline CH,N
10
The base C32N3 obtained by means of benzolazodi a naphtylamine crystallises
in the form of small leaves with a metallic lustre giving; when pulverized, a dark
violet powder and melting at 256° C. The salts dye mordanted cotton reddish
violet shades. In strong sulphuric acid the dye dissolves with a blue colour.. As
a secondary product appears an isomeric rosinduline melting at 247° C. and dis-
solving in strong-sulphuric acid- with a green colour. To convert the-rosin-
duline CHN into the corresponding sulpho acid one part of the base is
dissolved in 5 parts of fuming sulphuric acid containing 23% free anhydride, the
mixture being first well cooled and then heated for some time on a water bath
until a sample diluted with water dissolves completely in caustic ammonia. The
solution is then poured into water the sulpho acid being in this way precipitated
and the filtered precipitate directly used for dyeing purposes.
N
3
In order to prepare the sulpho acids of the rosinduline OHN and CH
32
I part of the base is dissolved in 4 parts of funing sulphuric acid containing 24
free anhydride and the mixture is heated for about 4-5 hours at 70-80°
The solution is then poured into water, the filtered precipitate dissolved in caustic"
ammonia and the solution' evaporated to dryness...
Dated this 20th day of December 1890:
COMITETE SPECIFICATION.
Improvements in the Manufacture of Colouring Matters.
1, HENRY HARRIS LAKE of the firm of Haseltine Lake & Co. Patent Agents,,"
45 Southampton Buildings in the 'County of Middlesex, do hereby declare the
nature of this invention and in what manner the-same-is to be performed,
to be particularly described and ascertained in and-by the following.statement:
•
"
In the Specification of British Letters Patent No. 15259 dated 23rd October 3
1888 and United States Patents No: 4301975, dated 24th June 1890; and
No. 431,404 dated 1st July 1890, are described two sulpho-acids of the basic
colouring matter which the communicators terméd rosinduline (Berichte der
Deutsch: Chem. Ges. 21. 2621), and the discovery of which was due to the
researches made by them during a long series of years in collaboration with Pro-
fessor Otto Fischer in regard to the indulin group." The communicators haver
now found that the rosinduline belongs to a 'new class of basic colouring matters
of the general formula C22H,NR and of yellowish to reddish violet shades; and
that all these basic substances can be easily converted into sulpho-acids of very
suitable properties for dyeing" purposes. The less complicated body belonging to
the said class of products and having the forinula CN may be obtained by
treating'a salt of benzol-azo-a-naphthylamine under pressure with aniline in the
presence of alcohol. The others are prepared by substituting benzol-azó
a-naphthylamine by the azo compounds obtained from diazo-benzol and substituted
naphthylamines. Very valuable dye-stuffs of the formulas CHN,CH,.and
CNC, are in particular produced by heating a salt of benzol-azo-tolyl-
a-naphthylamine or of benzol-azo-di-u-naphthylamine with aniline in-presence of
alcohol or by melting these compounds with aniline in the well 'known'manner
of the so called induline melts.
.
-
3
1. In preparing the rosinduline CH, I proceed as follows: 1 part of"
chlorhydrate of benzol-azo-a-naphthylamine is heated for about 6-hours under.
pressure with 2 parts of aniline and 4 parts of alcohol: The alcohol and the
aniline are then driven off by steam and the residue is boiled with water acidulated
2

page_text: by sulphuric acid until the whole basic dye-stuff has dissolved. The base pre-
cipitated by an alkali from the filtered solution can be directly sulphurated, or it
is purified by means of the salts which are crystallized from a hot solution to
which is added common salt. The residue consists of rosindone having the
formula C₂HN,₂O. The base crystallizes in reddish brown leaves and melts at
22 14
198–1993 C. The alcoholic solutions absorbing quickly the carbonic acid from
the air, like the basis of safranines. The alcoholic solutions of the base show a
yellowish red fluorescence, the alcoholic solutions of the salts a fiery red
fluorescence. The salts are very easily soluble in water and when dyed on mor-
danted cotton, they yield more yellowish shades than the rosinduline C‚‚N¸
In strong sulphuric acid, the dye dissolves with a green colour which turns red
when diluted with water.
21 3
32 21 3
28 193
2. To prepare the rosindulines C2H2N and CH2N, I prefer to melt 1 part
of chlorhydrate of benzol-azo-ortho-tolyl-a-naphthylamine or of benzol-azo-para-
tolyl-a-naphthylamine or 1 part of chlorhydrate of benzol-azo-di-a-naphthylamine
for about five hours at 130-150° C. with 2 parts of aniline and to treat the melt
in the above described manner.
29
3
The two basis C, H, N, obtained from benzol-azo-orthotolyl-a-naphtylamine
and benzol-azo-para-tolyl-a-naphthylamine crystallize in reddish brown brilliant
leaves the first melting at 228° and the other at 231-233° C. The salts are very
slightly soluble in cold water and dye mordanted cotton perhaps the same shades
as the rosinduline C, H,,N,
28 19
21
The base C₂HN, obtained by means of benzol-azo-di-a-naphthylamine
crystallizes in the form of small leaves with a metallic lustre giving when
pulverized, a dark violet powder and' melting at 256° C. The salts dye mordanted
cotton reddish violet shades. In strong sulphuric acid the dye dissolves with a
blue colour. As a secondary product appears an isomeric rosinduline melting
at 247° C. and dissolving in strong sulphuric acid with a green colour. To convert
the rosinduline C22HN3 into the corresponding sulpho acid one part of the base is
dissolved in 5 parts of fuming sulphuric acid containing 23% free anhydride, the
mixture being first well cooled and then heated for some time on a water bath
until a sample diluted with water dissolves completely in caustic ammonia. The
solution is then poured into water the sulpho acid being in this way precipitated
and the filtered precipitate directly used for dyeing purposes.
3
-21
In order to prepare the sulpho-acids of the rosinduline CH2N, and C₁₂H Nз.
One part of the base is dissolved in 4 parts of fuming sulphuric acid con-
taining 24% free anhydride and the mixture is treated for about 4-5 hours
at 70-80° C. The solution is then poured into water, the filtered precipitate
dissolved in caustic ammonia and the solution evaporated to dryness.
I am well aware that three sulpho acids of the red basic naphthaline dye-
stuff CHN have been described in the British Letters Patent No. 15259 and I
therefore lay no claim to these special sulpho acids.
Having now particularly described and ascertained the nature of the said inven-
tion and in what manner the same is to be performed as communicated to me by
my foreign correspondents I declare that what I claim is,
The production of sulpho acids of the rosindulines C₂H₁N, C₂HN, and
CH, by means of fuming sulphuric acid as above specified."
Dated this 25th dox of Avec 1901
HASELTINE, LAKE & Co.,
45, Southampton Buildings, London, Agents for the Applicant.