Improvements in the Manufacture of Colouring Matters.
Year: 1895

page_text: Date of Application, 29th May, 1895
Complete Specification Left, 2nd Mar., 1896-Accepted, 4th Apr., 1896
[Communicated from abroad by FARBWERK MUHLHEIM, of Muhlheim-on-the-
Main, in the Empire of Germany.]
Improvements in the Manufacture of Colouring Matters.
I, 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:-
This invention relates to the manufacture of colouring matters.
The communicators have found that derivatives of metaphenylendiamine or
metatoluylenediamine of the formula
where R signifies an acid radical such as acetyl can be easily combined with diazo
or tetrazo compounds yielding new and valuable colouring matters or raw materials
therefor, essentially differing from those obtained with unsubstituted meta-
diamines.
Moreover these new colouring matters or raw materials therefor can be further
diazotized (either directly or after a preceding sulphonation) and afterwards
combined with the known azodyestuff components. Such further diazotation and
combination may be effected on the textile fibre itself. Generally speaking, the
acid derivatives of metadiamines (the formula of which is given above and which
is hereinafter called A) "have proved to be a new species of the so called, middle
components" of the benzene series having advantages over the heretofore known
compounds of this class.
As representatives of such new colouring matters the following may be
mentioned as examples
1. Colouring matters produced by combining tetrazo stilbene disulpho acid with
2 molecules of A.
2. Colouring matter produced by combining tetrazodiphenyl with one molecule
of A and one molecule of another dyestuff component.
3. Colouring matter produced by combining tetrazo, diphenyl with one molecule
of A, further diazotizing and combining the new tetrazo compound with azo
dyestuff components.
4. Colouring matter produced by combining diazosulphanilic acid with A.
5. Colouring matter produced by combining diazonaphthalene disulpho acid
with A, further diazotizing and combining with a dyestuff component.
6. Colouring matter produced by combining diazotized paranitraniline with A,
reducing the obtained nitroamidoazo compound, further diazotizing one or two.

page_text: amido groups of the obtained diamidoazo derivative and finally combining with
azo dyestuff components.
The dyestuffs obtained in such a manner still contain the group NHR, R signifying
as above an acid radical. This acid radical can be split off by saponification. For
instance the colouring matter produced according to Example 5 the formula of 5
which is
which latter could not hitherto be produced, because the dyestuf
diazo naphthalene disulpho acid and metatoluylenediamine
Improvements in the Manufacture of Colouring Matters.
I, 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:-
I have found that the acid derivatives of metaphenylenediamine or meta-
toluylenediamine of the formula
where R signifies an acid radical can be combined with diazo or tetrazo compounds
yielding new and valuable colouring matters or raw materials for such, essentially
differing from those obtained with unsubstituted metadiamines.
These new colouring matters or raw materials for such can be further diazo-
tized and combined afterwards with the known azodyestuff components.
Such

page_text: "
further diazotation and combination may be effected on the fibre itself, generally
speaking the acid derivatives of metadiamines (the formula of which is given
above) have proved to be a new species of the so called "middle components
of the benzene series, having advantages over the compounds of this class hitherto
known.
The dyestuffs obtained in such a manner still contain the group NHR, R signifying
as above an acid radical. This acid radical can be split off by saponification. By
such a process it is possible to obtain azodyes containing aromatic metadiamines as
middle components and being characterized by the following group :
Such azodyes could not be produced hitherto and differ generally by a deeper
shade from the products non-saponified. To further illustrate the natures of this
invention and the manner, in which it is carried into practice I give the following
examples which have given good results, to which however I do not limit myself,
as the methods of operating can be largely varied without departing from the
nature of the invention which, generally speaking, consists in producing new
azocompounds containing acidylmetadiamines as end or middle components or
metadiamines as middle components.
The parts hereinafter civen
hu mainhe
COLOURING MATTER FROM DIAZOSULPHANILIC ACID AND ACETYLMETA-
TOLUYLENEDIAMINE.
A 1
buring
17-3 parts of sulphanilic acid are diazotized in the usual and the diazo-
compound is poured into a solution of 17 parts of acetylmetato!.. amine in
12 parts of hydrochloric acid (30%) and 500 parts of water.
,cipitate
of the free acid of the produced azodye is formed immediately. Aftanding,
heat up to about 50° C., then filter and press. The obtained acid of the
matter is transformed into its sodium salt, which can be salted out from the
watery solution.
It separates from the solution as an oil which solidifies after
some time. The dyestuff dyes wool in an acid bath a yellow shade.
The combination can also be effected in an alkaline solution.
In an analogous manner diazosulphanilic acid can be combined with acetyl-
/cn/NH,
metaphenylenediamine or metaphenylenediamine oxaminic acid (CH
COLOURING MATTERS DERIVING FROM
AND CONTAINING
COMPONENTS.
DIAZONAPHTHALENEDISULPHOACID
ACETYLMETATOLUYLENEDIAMINE
AS
MIDDLE
31 parts of alphanaphthylaminedisulphoacid are diazotized and the diazo-
compound is poured into a watery solution of 17 parts of acetylmetatoluylene-
diamine rendered alkaline by carbonate of soda. The obtained orange red dye is

page_text: violet shades.
further diazotized in an acid solution, whereby a brownish yellow solution is
obtained. By combining the new diazo-azocompound for instance with 35 parts of
betanaphtholdisulphoacid Ra dyestuff is obtained which dyes wool in an acid bath
Instead of betanaphtholdisulphoacid R, other dyestuff components
may be employed, for instance betanaphthol or alphanaphthol 4 sulphoacid.
Instead of alphanaphthylaminedisulphoacid, other diazotizable sulphoacids can be
employed, for instance betanaphthylamine 8 sulphoacid. Instead of acetylmeta-
toluylenediamine, acetylmetaphenylenediamine or the corresponding oxaminic acids
may be used.
COLOURING MATTERS DERIVING FROM DIAZONAPHTHALENEDISULPHOACID
AND CONTAINING METATOLUYLENEDIAMINE AS MIDDLE COMPONENT.
Diazotize one molecular proportion of betanaphthylaminedisulphoacid G in the
usual way, combine with one molecular proportion of acetylmetatoluylenediamine,
diazotize again and combine with one molecular proportion of betanaphthol in an
alkaline solution. The obtained dyestuff is salted out.
For the purpose of
saponification, dissolve one part of the dyestuff in 30 parts of water, add 15 parts
of soda lye of 33% and boil for about 2 hours until the solution has assumed a
blueish black colour. Neutralize the greater part of the alkali with hydrochloric
acid and precipitate the new dye with common salt.
Another mode of saponification is the following: Dissolve one part of the
dye-stuff derived from betanaphthylaminedisulphoacid, acetylinetatoluylenediamine
and betanaphtholdisulphoacid R in about 25 parts of water, add some hydro-
chloric acid (about 5 parts of an acid of 30%) and boil at the reflux cooler.
A violet fluid is obtained after a short time from which the saponified dyestuff
separates. It is trausformed into its sodium salt in the usual way. The saponified
colouring matter dyes wool in an acid bath in blueish black shades.
COLOURING MATTER DERIVING FROM DEHYDROTHIOTOLUIDINESULPHONIC
ACID AND ACETYLMETAPHENYLENEDIAMINE.
34.2 parts of the sodium salt of dehydrotbioparatoluidinesulphonic acid are
diazotized in the usual way with about 7 parts of sodium nitrite and the diazo-
compound is poured into a watery solution of 20.5 parts of the chlorhydrate of
acetylmetatoluylenediamine. The dyestuff is formed immediately. In order to
finish the formation the liquid after standing some time is heated up to 60° C. and
is then rendered alkaline and the dyestuff is isolated by salting out. It dyes cotton
in an alkaline bath with common salt in orange shades. In an analogous way a
dyestuff can be produced from benzoyl metaphenylenediamine.
COLOURING MATTERS FROM DEHYDROTHIOTOLUIDINESULPHONIC ACID AND
AS MIDDLE COMPONENT AND PRO-
ACETYLMETAPHENYLENEDIAMINE
DUCED ON THE FIBRE.
The dyestuff derived from acetylmetaphenylenediamine and produced according
to Example 4 is dyed on cotton and the dyed goods and treated in a dilute cold
solution of sodium nitrite acidulated with hydrochloric acid for about hour.
The diazocompound is thus formed on the fibre. When brought into an alkaline
solution of betanaphthol a brown colour is obtained; when brought into a
slightly acidulated solution of alphanaphthylamine a black colour is obtained;
and when brought into a solution of metaphenylenediamine a brown colour is
obtained.

page_text: COLOURING MATTER OBTAINED
FROM
METADIAZOBENZOIC
METAPHENYLENEDIAMINEOXAMINIC ACID.
ACID AND
The diazocompound from 14 parts of metaamidobenzoic acid is poured into an
aqueous solution of 19 parts of metaphenylenediamine oxaminic acid rendered
alkaline by carbonate of soda. A yellow solution is formed from which the dye-
stuff is precipitated by means of common salt after standing for 12 hours. It
dyes wool yellow on chrome mordant.
DYESTUFF FROM TETRAZODIPHENYL AND TWO MOLECULAR QUANTITIES OF
METAPHENYLENEDIAMINE OXAMINIC ACID.
1.8 parts of benzidine are diazotized in the usual way with 14 parts of nitrite
of sodium. Any free mineralic acid is removed from the solution by means of
acetate of sodium and 2 parts of acetic acid of 50 % are added to the fluid, the
quantity of which should be about 180 parts. On the other hand, 3.6 parts of
metaphenylenediamineoxaminic acid are dissolved in 40 parts of water and 1-2 parts
of carbonate of soda and this solution while stirring well is added to the solution
of tetrazodiphenyl. A dark brown precipitate is formed which after standing for
about 24 hours assumes an orange colour. When a sample boiled with water and
some carbonate of soda is nearly soluble, the whole is heated to boiling, the
precipitate is filtered, transformed into the sodium salt and salted out.
In the like manner the operation can be carried out by employing, instead of
tetrazodiphenyl, other tetrazocompounds used for the production of tetrazod yes, or

page_text: DYESTUFF
AND
FROM TETRAZOSTILBENEDISULPHOACID
TWO MOLECULAR
QUANTITIES OF ACETYLMETATOLUYLENEDIAMINE.
The tetrazoderivative from 38 parts of diamidostilbenedisulphoacid is poured
into an aqueous solution of 34 parts of acetylmetatoluylenediamine kept alkaline
by carbonate of soda. The formation of the colouring matter is finished after a
short time; it is isolated by salting out and dyes unmordanted cotton in an alkaline
bath in deep red shades.
In an analogous manner dyestuffs are produced by employing other tetrazo-
sulphoacids for instance tetrazonaphthalenebetadisulphoacid of British Patent
No. 1534600, or by employing acetylmetaphenylenediamine or metaphenylene-
diamineoxaminic acid or metatoluylenediamineoxaminic acid instead of acetylmeta-
toluylenediamine.
DYESTUFFS FROM
ACETYL-
TETRAZOSTILBENEDISULPHOACID CONTAINING
METATOLUYLENEDIAMINE AS MIDDLE COMPONENT AND PRODUCED ON
THE FIBRE.
When
The cotton dyed with the dyestuff as produced under the 10th example, is
treated in a dilute cold solution of nitrite of soda acidulated by hydrochloric acid for
about one half hour. The new tetrazocompound is produced on the fibre.
developed in the usual way with hetanaphthol, a violet black colour is obtained;
when with alphanaphthylamine, a black colour is obtained; and when with meta-
phenylenediamine, a brownish black colour is obtained.
MIXED
TETRAZODYES
FROM TETRAZODIPHENYL
TOLUYLENEDIAMINE.
AND ACETYLMETA-
1-8 kilos. of benzidine are diazotized in the known manner and the solution of
the tetrazocompound which should be about 500 litres is added to an aqueous
solution of 17 kilos. of acetylmeta toluylenediamine. The solution first assumes
a red tint, which turns to brown after about 12 hours. The solution, which, if
necessary, may be filtered, contains an intermediate product, which reacts with
the known dyestuff components. For instance in order to produce the dyestuff
with 1.8 amidonaphthol 4 sulphoacid, the solution of the intermediate product is
poured into an aqueous solution of 2.5 kilos. of this acid rendered alkaline by
carbonate of soda. The thus obtained dyestuff dyes unmordanted cotton in violet
shades.
Instead of benzidine, other diamines used for the production of tetrazodyes may
be used. The shades of the colouring matters produced in such a way vary from
grey or brown to red or violet.
MIXED TETRAZODYES CONTAINING METATOLUYLENEDIAMINE OXAMINIC ACID 4
OR METATOLUYLENEDIAMINE AS MIDDLE COMPONENT.
1.8 parts of benzidine are diazotized and the solution of the tetrazocompound
from which any free mineralic acid has been removed by sodium acetate is poured

page_text: into a dilute solution of 1.9 parts of metatoluylenediamine oxaminic acid in
0-6 parts of carbonate of soda, to which solution about 2 parts of acetic acid of
50% have previously been added. The intermediate product separates in the form
of a dark brown precipitate. After 12 hours standing, this product is filtered,
suspended in water and diazotized again with hydrochloric acid and about 0.7 parts
of sodium nitrite. The new diazocompound which has a light brown colour reacts
easily with azodyestuff components yielding dyestuffs the shades of which inay be
defined as varying from red or brown to violet or blackish. For instance, if the
final diazocompound mentioned above is combined with 7 parts of alphanaphthol
4.8 disulphoacid in an alkaline solution, a violet dye is formed which can be easily
salted out. This dyestuff can be saponified by dissolving it in about 20 parts of
water, adding 5 parts of hydrochloric acid of 30 % and boiling until a sample does
not show any more change of shade. The saponified dyestuff is transformed into
its sodium salt and dyes unmordanted cotton in blueish violet shades.
Having now particularly described and ascertained the nature of the said
invention 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 :-
1. The manufacture of new azocompounds containing aromatic acidylmeta-
diamines (such as acetylmetaphenylenediamine, acetylmetatoluylenediamine,
benzoylmetaphenylenediamine, metaphenylenediamineoxaminic acid, metatoluy-

page_text: lenediamineoxaminic acid) as end components, substantially as hereinbefore
described.
2. The process of producing new azocompounds containing aromatic acidylmeta-
diamines (such as mentioned in the first claim) as middle components, which process
consists in further diazotizing azocompounds containing aromatic acidylmeta-
diamines as end components, and combining the new diazo or tetrazocompounds
with azodyestuffcomponents, substantially as herein before described.
3. The process of producing new azocompounds containing aromatic meta-
diamines (such as metaphenylenediamine or metatoluylenediamine) as middle
components, which process consists in saponifying the azocompounds mentioned in
the 2nd claim, and containing aromatic acidylmetadiamines as middle components,
substantially as hereinbefore described.
4. As new articles of manufacture the azocompounds such as can be obtained
substantially in the manner claimed in the foregoing claiming clauses.
Dated this 2nd day of March 1896.
HASELTINE, LAKE & Co.,
45 Southampton Buildings, London, W.C., Agents for the Applicant.