The Manufacture and Production of New Substantive Dyestuffs.
Year: 1890

page_text: Date of Application, 16th Sept., 1890
Complete Specification Left. 25th May, 1891-Accepted, 11th July, 1891
PROVISIONAL SPECIFICATION.
The Manufacture and Production of New Substantive Dyestuffs.
I, JAMES YATE JOHNSON of 47 Lincoln's Inn Fields, in the County of Middlesex,
Gentleman, do hereby declare the nature of this invention (which has been com-
municated to me from abroad by Badische Anilin and Soda Fabrik of Ludwig-
shafen-on-Rhine in the Empire of Germany) to be as follows:-
In the Provisional Specification accompanying the application for Letters
Patent No. 12550 of the year 1890 I have described the manufacture of a new
base or amido-acid called diamido-di-phenoxy-acetic acid. The said amido-acid
is prepared as follows:-
(1.) Nitro-phenoxy-acetic acid is dissolved in diluted caustic soda solution, the
solution is boiled and alternately zinc dust and further quantities of caustic soda
solution are added until the solution is colourless. The whole mass is added to a
large excess of strong hydrochloric acid and further heated till all the zinc is
dissolved. Throughout the above operations the air is excluded as far as possible.
An anhydride of the amido-acid separates out and is collected after cooling,
washed and pressed, and is further treated as hereinafter described.
(2.) Another method of preparing this anhydride consists in reducing the azo-
or azoxy-compound of phenoxy-acetic acid, in a hot solution of stannous chloride
in strong-hydrochloric acid, until, on heating a filtered portion of the liquid, no
more precipitate separates-out. At this point the mixture is diluted with cold
water, filtered, washed, and pressed.
-
(3.) The amido-acid or base is prepared from the anhydride obtained by either
of the above methods by dissolving it in a hot solution of caustic soda and boiling
the solution, until the addition of hydrochloric acid to a cold test-portion gives no
precipitate of the anhydride. After cooling, the sodium salt of the amido-acid is
precipitated with common salt, filtered and pressed. To purify it, it can be
recrystallized from aqueous solution containing caustic soda and common salt.
The present invention relates to the manufacture of new substantive dyestuffs
from this amido-acid. The said dyestuffs belong to the class of disazo compounds,
and in their manufacture the amido acid (the hereinbefore described di-amido di-
phenoxy-acetic acid) is converted into a new tetrazo-compound by the action of
nitrous acid and then this tetrazo-compound is caused to combine with amines,
phenols or their sulpho or carboxylic acids. The dyestuffs may be symmetrical or
asymmetrical, that is to say to form symmetrical compounds one molecular pro-
portion of the new tetrazo-compound may be combined either with two molecular
proportions of one amido or phenolic body or a sulpho or carboxylic acid thereof,
or to form asymmetrical compounds, one molecular proportion of the tetrazo-com-
pound may be combined with one molecular proportion of one amido or phenolic
body or a sulpho or carboxylic acid thereof and then with one molecular pro-
portion of another amido or phenolic body or a sulpho or carboxylic acid thereof.
Many of these new compounds dye cotton from the alkaline bath yielding very
beautiful clear colours, ranging from yellowish-brown through red and violet to
bluish green.
The colourings obtained by means of some of these dyestuffs
undergo a very beautiful change on subjecting the dyed material to the action of
copper salts, thus red sometimes becomes blue and blue turns green and these new
colours so obtained are characterized by a very high degree of fastness to light and
to alkalies.
The new tetrazo-compound combines with all the phenolic and amido-bodies
known to be capable of combination with diazo or tetrazo compounds in the

page_text: manufacture of dyestuffs. The following table contains a few instances of such
combinations and shews the range of colour attainable and the changes under
treatment with copper sulphate.
I give the following examples to illustrate the operations constituting the
process for the manufacture of the new dyes, without confining myself to details
or to the use of the 18 dihydroxynaphthalene taken below, for as hereinbefore
explained a large number of second components can be used. The parts are by
weight.
EXAMPLE 1. PREPARATION OF THE NEW TETRAZO-COMPOUND.
Dissolve about eighteen parts of the sodium salt of the diamido-di-phenoxy-
acetic acid (obtained as hereinbefore described or in any other way) in about three
hundred parts of water and cool the mixture with about one hundred and fifty
parts of ice, add about thirty six parts of hydrochloric acid containing about
thirty eight per cent. of real hydrochloric acid (HCI). Next diazotize by running
in a solution of about seven parts of sodium nitrite in about twenty parts of water, 1
and allow the mixture to stand for a short time, when a clear yellowish solution of

page_text: the new tetrazo-compound is obtained. This is at once used in the production of
dyestuffs.
EXAMPLE 2. PREPARATION OF A SYMMETRICAL PURPLE-BLUE SUBSTANTIVE
DYESTUFF.
Dissolve about 18 parts of 11 dihydroxynaphthalene (Journal of Chemical
Society 56, 157) in a mixture containing, about four thousand parts of water,
about fourteen parts of soda-lye containing about thirty. five per cent., caustic
soda (NaOH), about seventy parts of crystallized sodium acetate and about one
thousand-
d parts of ice, then add just enough-acetic acid-to-make the solution weakly
acid. In this way the dihydroxynaphthalene is obtained partly dissolved and
partly in a state of fine suspension in the liquid: Now run in the solution of the
new tetrazo-compound, obtained as hereinbefore described from' about' eighteen
parts of the sodium salt of the di-amido-di-phenoxy-acetic acid and stir till the
formation of dyestuff is complete, which usually takes about twelve hours. Add
soda till alkaline, boil, precipitate the dyestuff with salt, press and dry.
J. H: JOHNSON & Co.,
A mento
COMPLETE SPECIFICATION:
The Manufacture and Production of New Substantive Dyestuffs.
I JAMES YATE JOHNSON of 47 Lincoln's Inn Fields in the County of
Middlesex Gentleman do hereby declare the nature of this invention which has
been communicated to me from abroad by The Badische Anilin and Soda Fabrik
of Ludwigshafen on Rhine in the Empire of Germany 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 the manufacture of new substantive dyestuff's from
diamido-di-phenoxy-acetic acid, a new amido acid or base described in the appli-
cation for Patent No. 12550 of 1890. The said dyestuff's belong to the class of
disazo-compounds and in their manufacture the amido acid is converted into a new
tetrazo-compound by the action of nitrous acid and then this tetrazo-compound, is
caused to combine with amines, phenols or their sulpho or carboxylic acids. The
dyestuffs may be symmetrical or asymmetrical, that is to say to form symmetrical
compounds one molecular proportion of the new tetrazo-compound may be com-
bined with two molecular proportions of one amido or phenolic body or a-sulpho-or
carboxylic acid thereof or to form asymmetrical compounds one molecular pro-
portion of the tetrazo compound may be combined with one molecular proportion
of one amido or phenolic body or a sulpho or carboxylic acid thereof and then
with one molecular proportion of another amido or phenolic body or a sulpho or
carboxylic acid thereof.
Many of these new compounds dye cotton from the alkaline bath, yielding very
beautiful clear colours, ranging. from yellowish brown through red and violet to
bluish green. The colourings obtained by means of some of these dyestuffs
undergo a very beautiful change on subjecting the dyed material to the action of
copper salts thus red sometimes becomes blue and blue turns green and these new
colours so obtained are characterized by a very high degree of fastness to light and
to alkalies.
The new tetrazo-compound combines with all the phenolic and amido-bodies
known to be capable of combination with diazo or tetrazo compounds in the manu-
facture of dyestuffs. The following table contains a few instances of such com-
binations and shows the range of colour attainable and the changes under treatment
with copper sulphate..

page_text: I give the following examples to illustrate the operations constituting the
process for the manufacture of the new dyes without confining myself to details
or to the use of the 11' dihydroxynaphthalene taken below, for as has been
above explained, a large number of second components can be used. The parts
are by weight.
EXAMPLE 1. PREPARATION OF THE NEW TETRAZO COMPOUND.
Dissolve about nineteen parts of the sodium salt of the diamido-diphenoxy
acetic acid (obtained as described in the Specification of the aforesaid application
for Patent No. 12550 of 1890 or in any other way) in about three hundred parts
of water, cool the mixture with about one hundred and fifty parts of ice and add
about thirty six parts of hydrochloric acid containing about thirty eight per cent.
of real hydrochloric acid (HCI) next diazotize by running in a solution of about
7 parts of sodium nitrite in about twenty parts of water and allow the mixture to
stand for a short time when a clear yellow solution of the new tetrazo compound
is obtained. This is at once used in the production of dyestuffs.

page_text: EXAMPLE 2. PREPARATION OF A SYMMETRICAL PURPLE BLUE SUBSTANTIVE
DYESTUFF.
Dissolve about eighteen parts of 1.1' dihydroxynaphthalene (Journal of Chemical
Society 56, 157) in a mixture containing about four thousand parts of water,
about fourteen parts of soda lye containing about thirty five per cent. caustic
soda (NaOH) about seventy parts of crystallized sodium acetate and about one
thousand parts of ice then add just enough acetic acid to make the solution weakly
acid. In this way the dihydroxynaphthalene is obtained partly dissolved and
partly in a state of fine suspension in the liquid. Now run in the solution of the
new tetrazo compound obtained as hereinbefore described from about nineteen
parts of the sodium salt of the di-amido-diphenoxy acetic acid and stir till the
formation of the dyestuff is complete, which usually takes less than about twelve
hours. Add soda till alkaline, boil, precipitate the dyestuff with salt press and
dry. In preparing the asymmetrical, or mixed, disazo dyes one molecular pro-
portion of the tetrazo compound is first combined with one molecular proportion
of the one component and then the intermediate compound so obtained is combined
with one molecular proportion of the other as will be readily understood by
chemists. In combining the tetrazo compound with amido-derivatives it is best to
work with neutral, or acetic acid, solutions and with alkaline solutions when
phenolic bodies are to be combined.
Having now particularly described and ascertained the nature of the said inven-
tion and in what manner the same is to be performed 1 declare that what I
claim is :--
1. The manufacture of substantive dyes from di-amido-di-phenoxy-acetic acid, by
first converting it into a new tetrazo-compound by the action of nitrous acid then
combining this (to form symmetrical or asymmetrical compounds) with amido- or
phenolic bodies or sulpho- or carboxylic acids thereof all substantially as herein-
before described.
2. In the manufacture of substantive dyes the preparation of a new tetrazo-
compound by the action of nitrous acid on di-amido-di-phenoxy-acetic acid.
3. The manufacture of the dyestuffs herein before mentioned in the table sub-
stantially as hereinbefore described.
4. As new articles of manufacture the bodies such as are obtained as herein-
before described and claimed in the preceding claiming clauses.
Dated this 25th day of May 1891.
J. H. JOHNSON & Co.,
Agents.