Improvements in the Manufacture and Production of Colouring Matters or Dyestuffs.
Year: 1889

page_text: Date of Application, 9th Sept., 1889
Complete Specification Left, 28th June, 1890-Accepted, 2nd Aug., 1890
PROVISIONAL DI
Improvements in the Manufacture and Production of Colouring
Matters or Dyestuffs.
We, THE CLAYTON ANILINE COMPANY LIMITED of Clayton near Manchester in the
County of Lancaster and Dr. PHILIP BRUNNER and JOHN HALL both of Clayton
aforesaid Chemists do hereby declare the nature of this Invention to be as
follows:-
By acting by sulphur on paratoluidine at a temperature of 170° to 250° Centigrade
two bases are formed dehydrothiotoluidine and primuline base as described in the
Berliner Berichte No. XXII pages 422, 330 and in the Journal of the Chemical
Society No. CCCXVIII page 227 in which publications several methods are described
for the separation and purification of the said two bases by means of different solvents
such as alcohol amylalcohol, toluole or solvent naptha and hydrochloric or sulphuric
acid. The proportion in which these two bases are formed by the action by sulphur
on paratoluidine varies according to the proportion between sulphur and paratoluidine
and the time and temperature used in the reaction. Thus a product can be obtained
containing these bases in varying proportions. As the colours which are described in
this Specification are all of, or nearly, of, the same shade and nature it is of no
We use for the
importance to make the said colours from the pure separated bases.
production of these colours the dehydrothiotoluidine and the primuline base as well as
their sulpho acids which are obtained by treating the said bases with fuming sulphuric
acid at 40 to 50° Centrigrade until the product gives a precipitate in water which
precipitate is soluble in alkalies.
The bases as well as their sulphonic acids form diazo compounds which give azo
colours by combining with phenoles, amines and their sulphonic acids. In conse-
quence of their characters as amido compounds the sulphonic acids of the two
sulphuretted bases also combine with diazo compounds and this Invention consists in
or comprises preparing azo colours by combining, either :-
(A.) The diazo compounds either of dehydrothiotoluidine or of the primuline base,
or of a mixture of both, with the sulphonic acids of dehydrothiotoluidine or of the
primuline base or of a mixture of both bases-or :-
(B) The diazo compounds of the sulphonic acid either of dehydrothiotoluidine, or
of the primuline base, or of a mixture of both bases, with the sulphonic acids
mentioned above under paragraph A.
In the following we give two examples illustrating the method of preparing the
colours mentioned above under paragraphs A and B.
EXAMPLE I.
i
+
100 parts of dehydrothiotoluidine are dissolved in 300 parts of sulphuric acid of
184 specific gravity at a temperature of 80° to 100° Centigrade and, after cooling
down to say 20° Centigrade, are mixed with cold solution of 25 parts of nitrite of
soda in 200 parts of sulphuric acid (monohydrate). The whole is thoroughly well
mixed for say a quarter to half an hour and is then thrown into 3000 parts of cold
water. The liquid is stirred constantly for say about half an hour and then it is run
into a cold solution containing 1200 parts of liquid caustic soda (of 1.34 specific
gravity) and 140 parts of the sodium salt of the dehydrothiotoluidine sulphonic acid
dissolved in 2000 parts of cold water. During this operation and for several hours
after the liquid is stirred constantly and after standing for some time (say for a
further 12 hours) is brought to boiling point. From the solution thus obtained the
colouring matter is precipitated (which may be done by adding common salt) filtered
off pressed and dried.

page_text: EXAMPLE II.
The cold liquid obtained by dissolving 100 parts of the sodium salt of the dehydro-
thiotoluidine sulphonic acid and 23 parts of nitrite of soda in 2000 parts of water is
run slowly into 500 parts of cold water containing 90 parts of hydrochloric acid of
1.18 specific gravity. During this operation, and for say an hour after the completion
of the mixing, the liquid is stirred and it is then run slowly into a cold solution
containing 100 parts of the sodium salt of the dehydrothiotoluidine sulphonic acid
and 60 parts of soda ash in 2000 parts of water. The whole is kept stirred for say
12 hours. From the clear yellow solution the colouring matter is precipitated by
adding common salt and is then filtered off pressed and dried.
The combinations herein before named under paragraph A as well as those named
under paragraph B are all soluble in water but the former less so than the latter and
they dye unmordanted cotton a fast yellow colour. From their solution the free
sulphonic acids are precipitated in a brown flocculent condition and again yield the
yellow solution on addition of diluted alkali. The said solution however turns deep
red on addition of excess of caustic soda. The yellow colour of the solution is not
altered on addition of a carbonate of an alkali.
Dated this 9th day of September 1889.
J. H. JOHNSON & Co.,
47, Lincoln's Inn Fields, London, W.C., Agents.
Improvements in the Manufacture and Production of Colouring
Matters or Dyestuffs.
We, THE CLAYTON ANILINE COMPANY LIMITED of Clayton near Manchester in the
County of Lancaster and Dr. PHILIP BRUNNER and JOHN HALL both of Clayton
aforesaid, Chemists, 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 :-
By acting by sulphur on paratoluidine at a temperature of 170° to 250° Centigrade
two bases are formed dehydrothioparatoluidine and primuline base as described in the
"Berliner Berichte" No. XXII pages 330 and 422 and in the Journal of the
Chemical Society No. CCCXVIII page 227 in which publications several methods
are described for the separation and purification of the said two bases by means of
different solvents such as alcohol amylalcohol carbon bisulphide toluole or solvent
naphtha and hydrochloric or sulphuric acid. The proportion in which these two bases
are formed varies according to the proportion between sulphur and paratoluidine and
the time and temperature used in the reaction. Thus a product can be obtained.
containing these bases in varying proportions. We use for the production of these
colours the dehydrothioparatoluidine and the primuline base as well as their sulpho
acids which are obtained by treating the said bases with fuming sulphuric acid at
40° to 50° Centrigrade until the product gives a precipitate in water which precipitate
is soluble in alkalies.
The bases as well as their sulphonic acids form diazo compounds which give azo
colours by combining with phenoles, amines and their sulphonic acids. In consequence
of their characters as amido compounds the bases and their sulphonic acids also
combine with diazo compounds and this invention consists in or comprises preparing
azo colours by combining either :-
A. The diazo compounds either of dehydrothioparatoluidine or of the primuline
base, or of a mixture of both, with dehydrothioparatoluidine and primuline base or the
sulphonic acids of debydrothioparatoluidine or of the primuline base or of a mixture of
both bases-or :—

page_text: B. The diazo compounds of the sulphonic acid either of dehydrothioparatoluidine,
or of the primuline base, or of a mixture of both bases with the bases or sulphonic
acids as mentioned above under paragraph A.
Those of the above mentioned colours which are insoluble are made soluble i.e. are
converted into sulphonic acid by treatment with two or three times their weight of
fuming sulphuric acid.
In the following we give two examples illustrating the method of preparing the
colours hereinbefore mentioned above under paragraphs A and B the parts being by
The cold liquid obtained by dissolving 100 parts of the sodium salt of the dehydro-
thioparatoluidine sulphonic acid and 23 parts of nitrite of soda in 2000 parts of
water is run slowly into 500 parts of cold water containing 90 parts of hydrochloric
acid of 118 specific gravity. During this operation, and for say an hour after the
completion of the mixing, the liquid is constantly stirred and it is then run slowly
into a cold solution containing 100 parts of the sodium salt of the dehydrothiopara-
toluidine sulphonic acid and 60 parts of soda ash in 2000 parts of water. The whole
is kept stirred for say 12 hours. From the clear yellow solution the colouring
matter is precipitated by adding common salt and is then filtered off pressed and
dried.
The combinations hereinbefore named under paragraphs A and B dye unmordanted
cotton a fast yellow colour. From their solution the free sulphonic acids are
precipitated in a brown flocculent condition and again yield the yellow solution on
addition of diluted alkali. The said solution however turns deep red on addition of
excess of caustic soda. The yellow colour of the solution is not altered on addition of
a carbonate of an alkali.
Having now particularly described and ascertained the nature of our said inven-
tion and in what manner the same is to be performed, we declare that what we
claim is:
1. The manufacture and production of dyestuffs by the action of the diazo
compounds of dehydrothioparatoluidine or of the so called primuline base or of the
two mixed as they are obtained by the action of sulphur on paratoluidine on an
alkaline solution of the sulphonic acids of dehydrothioparatoluidine or of primuline
base (primuline) or of the two mixed as they are obtained by the direct sulphonation
of the product of the action of sulphur on paratoluidine or on the two bases themselves
suspended in alkaline water.
2. The manufacture and production of dyestuffs by the action of the diazo
compounds of the sulphonic acids of dehydrothioparatoluidine or of primuline base or
of the two mixed on the alkaline solutions of dehydrothioparatoluidine sulphonic acid

page_text: or of primuline base sulphonic acid (primuline) or of the two mixed or on the two
bases themselves suspended in alkaline water.
3. The manufacture and production of colouring matters by proceeding as herein-
before described under Example I.
4. The manufacture and production of colouring matters by proceeding as herein-
before described under Example II.
1يمه
JT 1000
J. H. JOHNSON & Co.,
Agents.