Year: 1887

page_text: Date of Application, 16th Mar., 1887
Complete Left, 8th Dec., 1887
Complete Accepted, 13th Jan., 1888
1 HENRY HARRIS LAKE of the firm of Haseltine Lake & Co., Patent Agents,
Southampton Buildings, in the County of Middlesex do hereby declare the nature of
this invention to be as follows :-
This invention relates to a process of preparing fast colouring matters by chlorinating
brominating, nitrating, or alkylating other colouring matters.
Certain colouring matter combinations of tetrazosulpho acids with phenols have
the defect that the fibre dyed therewith, especially cotton, shows a change of colour
when being soaped or treated with weak alkalies.
As such I mention by way of example:
(a) The colouring matter obtained from tetrazostilbenedisulpho-acid with phenol
or cresol.
(b) The colouring matter obtained from tetrazodiphenyldisulpho-acid with phenol
or cresol.
(c) In like manner the yellow dying product of condensation, which is obtained
from paranitrotoluolsulpho-acid by treatment with alkaline lye and converted by
reduction into diamidostilbenedisulpho-acid shows when dyed on cotton, and treated
with soap or weak alkalies a change of the yellow colour to red.
It is found that this property of the said colouring matters is based upon their
capability of forming basic salts, which are produced during the treatment of the dyed
cotton, that is to say, of the fibre itself with soap or alkalies.
If such colouring matters are deprived of the capacity of forming basic salts, new
colouring matters are produced which are now sufficiently fast for use in dying.
The agents to be employed for this purpose are prescribed by the chemical nature
of the colouring matter to be acted upon.
J

page_text: .
With the colouring matters named under (a) (b) the object is attained by alkylating
the phenol constituent thereof; whereas with the product of condensation (c) a treat-
ment with chlorine, bromine or nitric acid has to be effected.
As examples for this process I give the following directions:
1st. 62 Kilograms of the colouring matter obtained from tetrazostilbenedisulpho-
acid and phenol are, together with 2.5. kilograms of lye of 30%; 3 kilograms of
benzylchloride, and 10 litres of spirit, heated for several hours on the reflux cooler.
The spirit is then distilled, and unchanged phenol colouring matter is removed with
hot alkaline water. The benzylated colouring matter formed remains upon the filter,
the said colouring matter being indifferent to soap and alkali.
and
2nd. 6 Kilograms of the colouring matter from tetrazodiphenylisulpho-acid
phenol, together with 30 litres of water, 2.5 kilograms of lye of 30%, and 6 kilograms
of ethyl bromide, are heated in iron autoclaves for eight hours to from 70 degrees to
80 degrees. After the cooling and opening of the autoclave, the ethylated colouring
matter is filtered and freed from the unchanged phenol colouring matter by washing
with alkaline dilute salt-water.
The ethylation can also be effected by means of ethylic sulphate of soda in a
spirituous solution at 140 to 150 degrees. The isolation of the ethylated colouring
matter is for the rest quite analogous.
3rd. 10 Kilograms of the red product of condensation obtained from paranitro-
toluolsulpho-acid by means of soda-lye are, together with 100 litres of water and
9 kilograms of nitric acid of 40 degrees Baumè, heated for several hours on the
reflux cooler.
The liquid is then neutralized and the nitrated colouring matter sulted out.
I wish it to be understood that I do not adhere particularly in the above direction
to the proportions before mentioned as regards quantity and concentration, and would
especially state that, when making use of more nitric acid, substantially the same
result is obtained.
After
4th. 10 Kilograms of the product of condensation mentioned in clause 3 are
dissolved hot in 200 litres of water, and to the cooled liquid are added, first
25 kilograins of lye of 30 per cent, then gradually 8 kilograms of bromine.
standing for some time, acidification is caused with diluted sulphuric acid until
an odour of bromine is perceived, alkalization is again effected, and the brominated
colouring matter is salted out.
·ה
101 1
M1 1007
HASELTINE, LAKE & Co.,
45, Southampton Buildings, London, W.C.,
Agents for the Applicant.

page_text: COMPLETE SPECIFICATION.
Improvements in the Manufacture of Colouring Matters:
1, HENRY HARRIS LAKE, of the firm of Haseltine Lake & Co., Patent Agents,
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 :-
This invention relates to a process of preparing fast colouring matters by chlorinating,
brominating, nitrating, or alkylating other colouring matters.
Certain colouring matter combinations of tetrazosulpho-acids with phenols have
the defect that the fibre dyed therewith, especially cotton, shows a change of colour
when being soaped or treated with weak alkalies.
As such I mention by way of example,
(a) The colouring matter obtained from tetrazo-stilbene-disulpho-acid with phenol,
cresol or their homologues.
b) The colouring matter obtained from tetrazodiphenyldisulpho-acid with phenol
cresol or their homologues.
c) In like manner the yellow dyeing product of condensation, which is obtained
from paranitrotoluolsulpho-acid by treatment with alkaline lye and converted by
reduction into diamidostilbenedisulpho-acid shows when dyed on cotton, and treated
with soap or weak alkalies a change of the yellow colour to red.
I have found that this property of the said colouring matters is based upon their
capability of forming basic salts, which are produced during the treatment of the
dyed cotton, that is to say, of the fibre itself with soap or akalies.
If such colouring matters are deprived of the capacity of forming basic salts, new
colouring matters are produced which are sufficiently fast for use in dyeing.
The agents to be employed for this purpose are prescribed by the chemical nature
of the colouring matter to be acted upon.
With the colouring matters named under a) b) the object is attained by alkylating
the phenol constituent thereof; whereas with the product of condensation c) a treatment
with chlorine, bromine or nitric acid has to be effected.
As examples for this process I give the following directions.
1st. 6.2 kilograms of the colouring matter obtained from tetrazostilbenedisulpho-acid
and phenol are together with 2.5 kilograms of lye of 30%, 3 kilograms of benzyl-
chloride, and 10 litres of spirit heated for several hours on the reflux cooler.
The spirit is then distilled and unchanged phenol colouring matter is removed with
hot akaline water. The benzylated colouring matter formed remains upon the filter,
the said colouring matter being indifferent to soap and alkali.
2nd. 6 kilograms of the colouring matter from tetrazodiphenyldisulpho-acid and
phenol together with 30 litres of water, 2.5 kilograms of lye of 30%, and 6 kilograms
of ethyl bromide, are heated in iron autoclaves for about eight hours to from
70 degrees to about 100 degrees Celsius. After the cooling and opening of the

page_text: autoclave, the ethylated colouring matter is filtered and freed from the unchanged
phenol colouring matter by washing with akaline dilute salt water.
The alkylation can also be effected by any other alkylating means as for instance
by means of ethylic sulphate of soda in a spirituous solution at 140 to 150° Celsius.
The isolation of the ethylated colouring matter is for the rest quite analogous.
3rd. 10 Kilograms of the red product of condensation obtained from paranitro-
toluolsulpho-acid by means of soda-lye are, together with 100 litres of water and
9 Kilograms of nitric acid of 40 degrees Baumé, heated for several hours on the
reflux cooler. The liquid is then neutralized and the nitrated colouring matter
salted out.
4th. 10 Kilograms of the product of condensation mentioned in clause 3 are
dissolved hot in 200 litres of water, and to the cooled liquid are added, first
25 kilograms of lye of 30 per cent, then gradually 8 kilograms of bromine.
After standing for some time, acidification is caused with diluted sulphuric acid
until an odour of bromine is perceived, alkalization is again effected, and the
brominated colouring matter is salted out."
I wish it understood that I do not adhere particularly in the above direction to the
proportions before mentioned as regards quantity and concentration, and as regards
the 3rd example I would especially state that when making use of more nitric acid,
substantially the same result is obtained.
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 1 declare that what I claim is :-
The process of converting colouring matters, which possess the property of forming
basic salts of another tint into fast colouring matters, which do not show this property,
this process consisting in alkylation or treatment with chlorine, bromine or nitric
acid (according to the nature of the substance to be acted upon) and being applied
to the following substances.
1.) Combination of {tetrazodiphenyldisilph-naid } with phenol, cresol or their
homologues.
2.) Product of condensation from paranitrotoluolsulpho-acid with caustic lye.