IMPROVEMENTS IN THE PRODUCTION OF ANILINE DYES
Year: 1876

page_text: LETTERS PATENT to Justus Wolff, of Wyke, near Bradford, Consulting and
Engineering Chemist, and Ralph Betley, of Wigan, Analytical and Consulting
Chemist, for the Invention of "IMPROVEMENTS IN THE PRODUCTION OF ANILINE
DYES."
Sealed the 4th April 1876, and dated the 26th January 1876.
PROVISIONAL SPECIFICATION left by the said Justus Wolff and Ralph Betley
at the Office of the Commissioners of Patents on the 26th January 1876..
JUSTUS WOLFF, of Wyke, near Bradford, Consulting and Engineering Chemist,
and RALPH BETLEY, of Wigan, Analytical and Consulting Chemist. "IMPROVE
MENTS IN THE PRODUCTION OF ANILINE DYES."
Our Invention relates to the production of a series of dyes from aniline with
or without toluidine in the manner herein-after described.
According to one mode of carrying out our Invention we mix, say about 3
equivalents of aniline (with or without toluidine) with, say from about 2 to 3
equivalents of any suitable acid, by preference hydrochloric acid, into this mixture
we introduce in a stream, say about one equivalent of chlorine gas, or we add about
one equivalent of bromine or iodine. The mixture thus obtained we heat to, say
from about 220° to 230° Celsius, until a sample drawn out and dropped into boiling
water communicates to the latter a brownish yellow tint. When it is ascertained
that this effect is produced the heating is continued at the temperature arrived at
until a sample drawn out is found to yield up its colouring matter by repeated
treatment with acidulated water at an elevated temperature. The source of heat is
then removed and from the melt thus obtained the dye is separated by repeated
extraction with water (preferably slightly acidulated with hydrochloric acid) at an
elevated temperature, such extraction being repeated so long as coloring matter is
dissolved. The coloring matter is precipitated from the filtered extraction liquids
by means of salt or soda or caustics filtered off, dried preferably with a little
hydrochloric acid, and is then ready for use.
According to another mode of carrying out our Invention we mix, say about 3
equivalents of anilino (with or without toluidine) with, say from about 2 to 3
equivalents of hydrochloric or other suitable acid, and we then add, say about one
equivalent of peroxyde of manganese or of peroxyde of lead, or of any other suitable
[Prins Ad

page_text: metallic oxide capable of producing an oxidising effect in the process. We heat
and treat this mixture until the reactions herein-before mentioned have taken place,
and extract and precipitate the coloring matter in the manner herein-before
described.
According to a further mode of carrying out our Invention we mix, say about 6
to 7 equivalents of aniline (with or without toluidine) with, say from 6 to 7
equivalents of hydrochloric or other suitable acid, and we then add, say about one
equivalent of commerical nitric acid, and subject this mixture to the treatment
herein-before described. Or we mix, say from about 6 to 7 equivalents of aniline
(with or without toluidine with, say from about 7 to 8 equivalents of hydrochloric or
other suitable acid, and add to the mixture, say one equivalent of nitrate of soda or
of any suitable nitric acid, salt, or oxidizing nitrous acid salt. The mixture thus
obtained is subjected to the subsequent treatment for the production and
precipitation of the coloring matter as herein-before described. Or we mix, say
from about 14 to 15 equivalents of aniline (with or without toluidine) with, say
from 14 to 15 equivalents of hydrochloric or other suitable acid, and add to the
mixture, say about one equivalent of chloric acid or bromic acid, or iodic acid, or
any suitable oxidising compound of chlorine, bromine, or the like with oxygen or
with one equivalent of the suitable salts of these acids and compounds, and these
mixtures we subsequently treat in the manner herein-before described.
According to another modification of our processes we mix, say from about 7 to 8
equivalents of aniline with or without toluidine) with, say from about 6 to 10
equivalents of hydrochloric or other suitable acid, and we then add slowly, say
about 2 equivalents of chromic acid in solution, or a quantity of a chromic acid salt
containing that amount of chromic acid or any other suitable metallic acid salt.
The mixture is subsequently treated in the manner herein-before described.
According to a further modification of our processes we mix, say about 3
equivalents of aniline (with or without toluidine) with, say from 2 to 3 equivalents
of hydrochloric or other suitable acid, and add to the mixture, say about 2
equivalents of copper, perchloride, or any other suitable reducible metallic per-
chloride. The mixture thus obtained we subsequently treat in the manner
herein-before described. Or we mix, say from about 5 to 6 equivalents of aniline
(with or without toluidine) with, say from 2 to 4 equivalents of hydrochloric or other
suitable acid, and we then add to the mixture, say about 2 equivalents of sulphate of
copper (or any other suitable oxidising metallic oxysalt), and we subsequently treat
the mixture thus obtained in the manner herein-before described. The coloring
matters produced according to this Invention are soluble in water and in acidulated
water, and are capable of dyeing wool, cotton, and other fibres in dark shades;
such for example, as bluish black and grey, violet black and grey, and in all the
different shades of black and grey.
SPECIFICATION in pursuance of the conditions of the Letters Patent filed by
the said Justus Wolff and Ralph Betley in the Great Seal Patent Office on the
6th July 1876.
JUSTUS WOLFF, of Wyke, near Bradford, Consulting and Engineering Chemist,
and RALPH BETLEY, of Wigan, Analytical and Consulting Chemist. " IMPROVE-
MENTS IN THE PRODUCTION OF ANILINE DYES."
Our said Invention relates to the production of a series of dyes from aniline with
or without toluidine in the manner herein-after described.
According to one mode of carrying out our Invention we mix, say about 3.
equivalents of aniline (with or without toluidine) with, say from about 2 to 3
equivalents of any suitable acid, by preference hydrochloric acid; into this mixture
we introduce in a stream, say about one equivalent of chlorine gas, we add about
one equivalent of bromine or iodine. The mixture thus obtained we heat to, say

page_text: from about 220° to 230° Celsius, until a sample drawn out and dropped into boiling
water communicates to the latter a brownish yellow tint. When it is ascertained
that this effect is produced the heating is continued at the temperature arrived at
until a sample drawn out is found to yield up its coloring matter by repeated
treatment with acidulated water at an elevated temperature. The source of
heat is then removed, and from the melt thus the dye is separated by repeated
extraction with water (preferably slightly acidulated with hydrochloric acid) at an
clevated temperature, such extraction being repeated so long as coloring matter is
dissolved. The coloring matter is precipitated from the filtered extraction liquids
by means of salt or of soda, or of caustic alkalies filtered off, dried preferably with
the addition of a little hydrochloric acid, and is then ready for use.
According to another mode of carrying out our Invention we mix, say about 3
equivalents of aniline (with or without toluidine) with, say from about 2 to 3
equivalents of hydrochloric or other suitable acid, and we then add, say about one
equivalent of peroxyde of manganese or of peroxyde of lead, or of any other suitable
metallic oxide capable of producing an oxydising effect in the process. We heat
and treat this mixture until the reactions herein-before mentioned have taken place,
and extract and precipitate the coloring matter in the manner herein-before
described.
According to a further mode of carrying out our Invention we mix, say from
about 6 to 7 equivalents of aniline with or without toluidine) with, say from 6 to 7
equivalents of hydrochloric or other suitable acid, and we then add, say about one
equivalent of nitric acid and subject this mixture to the treatinent herein-before
described. Or we mix, say from about 6 to 7 equivalents of aniline (with or
without toluidine) with, say from about 7 to 8 equivalents of hydrochloric or other
suitable acid and add to the mixture, say one equivalent of nitrate of soda or of
any suitable nitric acid salt or ozydising nitrous acid salt. The mixture thus
obtained is subjected to the subsequent treatment for the production and
precipitation of the coloring matter as herein-before described. Or we mix, say
from about 14 to 15 equivalents of aniline (with or without toluidine) with, say
from 14 to 15 equivalents of hydrochloric or other suitable acid, and add to the
mixture, say about one equivalent of chloric acid, or bromic acid, or iodic acid or any
suitable oxydising compound of chlorine, bromine, or the like with oxygen or with
one equivalent of the suitable salts of the acids and compounds, and these mixtures
we subsequently treat in the manner herein-before described.
According to another modification of our processes we mix, say from about 7 to 8
equivalents of aniline (with or without toluidine) with, say from about 6 to 10
equivalents of hydrochloric or other suitable acid, and we then add slowly, say
about 2 equivalents of chromic acid in solution or a quantity of a chronic acid salt
containing that amount of chromic acid or any other suitable metallic acid salt.
The mixture is subsequently treated in the manner herein-before described so as to
obtain the coloring matters therefrom.
According to a further modification of our processes we mnix, say about 3
equivalents of aniline (with or without toluidine) with, say from 2 to 3 equi-
valents of hydrochloric or other suitable acid, and add to the mixture, say about
2 equivalents of copper, perchloride, or any other suitable reducible metallic
perchloride. The mixture thus obtained we subsequently treat in the manner
Ierein-before described. Or we mix, say from about 5 to 6 equivalents of anilino
(with or without toluidine) with, say from 2 to 4 equivalents of hydrochloric or
other suitable acid, and we then add to the mixture, say about 2 equivalents of
sulphate of copper (or any other suitable oxydising metallic oxysalt), and we
subsequently treat the mixture thus obtained in the manner herein-before described.
The coloring matters produced according to this Invention are soluble in water or
in acidulated water and are capable of dyeing wool, cotton, and other fibres in dark
shades, such for example, as bluish black and grey, violet black and gray, and in
all the different shades of black and gray. The less toluidine there is contained in
the aniline used the bluer will be the black obtained, the more toluidine there is

page_text: contained in the aniline the more violet or brownish or yellowish are the black and
gray shades obtained, the shades thus varying according to the quantity of toluidine
contained in the mixture.
Having now described and particularly ascertained the nature of our said In-
vention, and the manner in which the same is or may be used or carried into, we
would observe in conclusion that what we consider to be novel and original, and
therefore claim as the Invention secured to us by the herein-before in part recited
Letters Patent is, the production from aniline partially or completely neutralized or
saturated by hydrochloric acid or by any other suitable acid, and treated in the
manner herein-before described, of coloring matters soluble in water or in acidulated
water at an elevated temperature, the same being capable of dyeing various shades
of black and gray on wool, cotton, and other fabrics.
In witness whereof, we, the said Justus Wolff and Ralph Betley, have to
this our Specification set our hands and seals, this Fifth day of July, One
thousand eight hundred and seventy-six
JUSTUS WOLFF. (L.S.)
RALPH BETLEY. (L.S.)
JUSTUS WOLFF. (L.S.)
RALPH BETLEY. (L.S.)