MANUFACTURE OF CERTAIN DYE MATTERS
Year: 1887

page_text: I, GEORGE THOMAS of the firm of George Thomas and Company of 28 Deansgate
Manchester in the County of Lancaster Engineer do hereby declare the nature of said
Invention for THE MANUFACTURE OF CERTAIN DYE MATTERS which Invention has been
communicated to me from abroad by Dr. H. Schulz of Berlin Germany Chemist to
be as follows:-
to
This invention consists in the manufacture of blue dye matters :-
1. By the condensation of Paranitroso compounds of tertiary Monamines that is
say those Monamines in which two Alcohol Radicals replace the two equivalents
of Hydrogen which are in connection with the Nitrogen examples of such tertiary
Monamines being Paranitroso-dimethylaniline, Paranitroso-methylethylaniline, etcetera
with Monamines viz., Aniline Orthotoluidine etcetera and their secondary and tertiary
Alkyl derivatives in diluted Acid solutions in the presence of Sulphuretted Hydrogen
in statu nascendi by means of Chloride of Zinc and by oxidising the product of
condensation (after removing the free Sulphuretted Hydrogen) by suitable oxidising
agents such as Chloride of Iron Chromic Acid etcetera.
2. By condensing the Paranitroso compounds of tertiary Monamines such as
Paranitroso-dimethylaniline, Paranitroso-diethylaniline, Paranitroso-methylethylaniline
in the presence of Sulphuretted Hydrogen in statu nascendi by means of Chloride of
Zine and oxidising the product of the condensation after removing the free
Sulphuretted Hydrogen by oxidising agents like Chloride of Iron Chromic Acid
etcetera.
The manner of carrying out this said Invention will be readily understood from the
following examples
1. I dissolve 12 K° (Kilogrammes) Dimethylaniline in 50 K° concentrated
Hydrochloric Acid and mix it in the cold state with a concentrated solution of 7.25 K°
of Nitrite of Soda. After some time the Hydrochloric Nitrosodimethylaniline
separates and is pressed to remove the excess of liquor. I then mix it with four times
its weight of water into a thin paste and add it together with Sulphide of Iron (or
any other Sulpho compound giving Sulphuretted Hydrogen in Acid solution) to a
warm solution of 60 Ko Chloride of Zinc and 12 K Dimethylaniline in a mixture of
200 K concentrated Hydrochloric Acid and 2500 K° of water.

page_text: After gently heating, say by a waterbath, for from half an hour to one hour the
solution which is at first dark yellow becomes pale yellow or nearly colourless I now
remove the excess of Sulphide of Iron by filtration, heat till all the Sulphuretted
Hydrogen contained in the solution has disappeared and till the usual tests with Lead
Salts etcetera fail to show any re-action in the Acid solution. In case any Sulphur
should have been separated I remove it by filtration and then oxidise the Leucobase
contained in the solution by oxidising agents such as Chloride of Iron Chromic Acids
its Salts etcetera. A blue dye is thus formed which can by adding common salt be
separated out as a dark blue powder. This dye is soluble in water.
2. 12 Ko Dimethylaniline are dissolved in 50 K° concentrated Hydrochloric Acid.
This solution is mixed in the cold state with a concentrated solution of 7-25 K° Nitrite
of Soda. The Hydrochloric Nitroso-dimethylaniline which separates after some
time is collected and pressed to remove excess of liquor and then dissolved in a
solution of 60 K Chloride of Zinc in 200 K° Hydrochloric Acid and 2500 K° of
water.
I gently heat this solution and add slowly Sulphide of Iron till the solution is
nearly colourless, remove the excess of Sulphide of "Iron by filtering, heat the solution
till the last traces of Sulphnretted Hydrogen have disappeared and the usual tests with
Lead Salts etcetera fail to give the slightest re-action. Any Sulphur, that should
happen to be separated, is filtered off and the Leucobase in solution is oxidised by
suitable oxidising agents such as Chloride of Iron Chromic Acid its Salts etcetera.
A blue dye is formed which can be precipitated by Common Salt. This dye is soluble
in water.

page_text: The Manufacture of Certain Dye Matters.
1 GEORGE THOMAS of the firm of George Thomas and Company of 28 Deansgate
Manchester in the County of Lancaster Engineer do hereby declare the nature of said
Invention for THE MANUFACTURE OF CERTAIN DYE MATTERS which Invention has been
communicated to me from abroad by Dr. H. Schulz of Berlin Germany Chemist
and in what manner the same is to be performed, to be particularly described and
ascertained in and by the following statement:-
:-
This invention consists in the manufacture of blue dye matters:―
1. By the condensation of Paranitroso compounds of tertiary Monamines, that is
to say those Monamines in which two Alcohol Radicals replace the two equivalents of
Hydrogen which are in connection with the Nitrogen, examples of such compounds
being Paranitroso-dimethylaniline, Paranitroso-diethylaniline, Paranitroso-methylethyl-
aniline Paranitroso-dimethylorthotoluidine, Paranitroso-diethylorthotoluidine, Para-
nitroso-methylethylorthotoluidine with Monamines, viz. Aniline or Orthotoluidine and
their secondary and tertiary Alkyl derivatives in weak Acid solutions in the presence
of Sulphuretted Hydrogen "in statu nascendi" by means of Chloride of Zine and by
oxidising the product of condensation (after removing the free Sulphuretted Hydrogen)
by suitable oxidising agents such as Chloride of Iron Chromic Acid etc.
2. By condensing the Paranitroso compounds of tertiary Monamines such as
Paranitroso-dimethylaniline, Paranitroso-diethylaniline, Paranitroso-methylethylani-
line or Paranitroso-dimethylorthotoluidine, Paranitroso-diethylothotoluidine, Para-
nitroso-methylethylorthotoluidine in the presence of Sulphuretted Hydrogen "in
statu nascendi" by means of Chloride of Zinc and oxidising the product of the
condensation (after removing the free Sulphuretted Hydrogen) by suitable oxidising
agents like Chloride of Iron Chromic Acid etc.
The manner of carrying out this said Invention will be readily understood from the
following examples:-
1. I dissolve 12 K° (Kilogrammes) Dimethylaniline in 50 K° concentrated
Hydrochloric Acid and mix it in the cold state with a concentrated solution of 7.25
Ko of Nitrite of Soda. After some time the Hydrochloric Nitroso-dimethylaniline
separates and is pressed to remove the excess of liquor I then mix it with four times
its weight of water into a thin paste and add it together with Sulphide of Iron (or
any other Sulpho compound giving Sulphuretted Hydrogen in Acid solution) to a
warm solution of 60 K Chloride of Zinc and 12 K° Dimethylaniline in a mixture of
200 K concentrated Hydrochloric Acid and 2500 K° of water.
After gently beating, say by a water bath, for from half an hour to an hour the
solution which is at first dark yellow becomes pale yellow or nearly colourless. I now
remove the excess of Sulphide of Iron by filtration, heat till all the Sulphretted
Hydrogen contained in the solution has disappeared and till the usual tests with Lead
Salts etc. fail to show any re-action in the Acid solution. In case any Sulphur should
have been separated I remove it by filtration and then oxidise the Leucobase contained
in the solution by suitable oxidising agents such as Chloride of Iron Chromic Acid
its Salts etc. A blue dye is thus formed which can by adding Common Salt, be
separated out as a dark blue powder. This dye is soluble in water.

page_text: 2.-12 K Dimethylaniline are dissolved in 50 K° concentrated Hydrochloric Acid.
This solution is mixed in the cold state with a concentrated solution of 7.25 K° Nitrite
of Soda. The Hydrochloric Nitroso-dimethylaniline which separates after some time
is collected and pressed to remove excess of liquor and then dissolved in a solution of
60 K° Chloride of Zinc in 200 K° Hydrochloric Acid and 2500 K° of water.
I gently heat this solution and add slowly Sulphide of Iron (or any other Sulpho
compound giving Sulphuretted Hydrogen in Acid solution) till the solution is nearly
colourless remove the excess of Sulphide of Iron by filtering, heat the solution till
the last traces of Sulphuretted Hydrogen have disappeared and the usual tests with
Lead Salts etc. fail to give any material re-action. Any Sulphur that should happen
to be separated, is filtered off and the Leucobase in solution is oxidised by suitable
oxidising agents such as Chloride of Iron Chromic Acid its Salts etc. A blue dye is
thus formed which can be precipitated by Common Salt. This dye is soluble in
water.
Having now particularly described and ascertained the nature of this said Invention
and in what manner the same is to be performed I wish it to be clearly understood
that I do not tie myself absolutely to the exact quantities details or course of
procedure hereinbefore specified as the same may be varied or modified as found
desirable or advantageous without departing from the nature of this said Invention
I declare that what I claim is―
1.- The process of preparing a blue dye matter by condensing Hydrochloric-
Dimethylaniline with Hydrochloric Paranitroso Dimethylaniline by means of a
solution of Chloride of Zinc in dilute Hydrochloric Acid in the presence of
Sulphuretted Hydrogen "in statu nascendi" and, after the free Sulphuretted
Hydrogen has been removed by oxidising the product of condensation by suitable
oxidising agents such as Chloride of Iron Chromic Acid etc. substantially as herein
described.
2. The process for preparing a blue dye matter by replacing in the process
described and claimed in Claim 1 the Paranitroso-dimethylaniline by Paranitroso-
diethylaniline or Paranitroso-methylethylaniline or Paranitroso-dimethylorthotoluidine
or Paranitroso-diethylorthotoluidine or Paranitroso-methylethylorthotoluidine and
replacing the Hydrochloric-dimethylaniline by Hydrochloric Salts of Aniline or
Orthotoluidine and their derivatives in which the Hydrogen equivalents in connection
with the Nitrogen have been totally or partially replaced by ethyl or methyl or both
of them.
«
3.-The herein described process for preparing a blue dye matter by condensing
Hydrochloric Paranitroso-dimethylaniline in the presence of Sulphuretted Hydrogen
in statu nascendi " by means of a solution of Chloride of Zinc in dilute Hydro-
chloric Acid and after removing the free Sulphuretted Hydrogen by oxidising the
product of the condensation by suitable oxidising agents like Chloride of Iron
Chromic Acid etc. and separating the dye thus formed by means of Common Salt.
4. The process for preparing a blue dye matter by replacing in the process herein
described and claimed under Claim 3 the Paranitroso-dimethylaniline by Paranitroso-
diethylaniline or Paranitroso-methylethylaniline or Paranitroso-dimethylorthotoluidine
or Paranitroso-diethylorthotoluidine or Paranitroso-methylethylorthotoluidine.
5. The blue dye matter manufactured by either of the processes herein described
or any mere equivalent therefor.
Dated 1: 391 Damhan 1007