Year: 1887

page_text: Date of Application, 25th Mar., 1887
Complete Left, 18th Aug., 1887
Complete Accepted, 22nd Nov.. 1887.
[Communicated from abroad by Messrs. WIRTH & Co., of Frankfort on the Main,
Germany, acting as Agents of K. Oehler, of Offenbach on the Main, in the
Empire of Germany.]
I, 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:-
The chief object of this invention is the production of new azo dye stuffs by the
combination of tetrazo-diphenyl, tetrazoditolyl and their sulpho-acids with aromatic
metadioxy-metadiamido-and metaamidooxy compounds and their sulpho-acids.
A series of new dye stuffs is obtained by treating a neutral or slightly alkaline
solution of an aromatic metadioxy-metaamido-or metaamidooxy compound or one
of their sulpho-acids with a solution of tetrazo diphenyl, tetrazo-ditolyl or one of
their sulpho-acids.
The dye stuffs thus obtained show a striking affinity to raw cotton fibres without
any mordant.
The dye stuffs produced with the aromatic dioxy compounds (such as orcine
resorcine resorcylacid) and metaoxyamido compounds (metaoxydiphenylamin)
are soluble in alkali and dye cotton fast even in a cold alkaline solution. The
shades vary from yellow to blueish red and stand soaping or milling. As examples
I name the combination of tetrazo-diphenyl and resorcine which gives a bright
yellow whereas the combination of tetrazo-ditoly with resorcine gives a saffranine
like bluesh red shade.
The colouring matters obtained by treating aromatic metadiamines (as metaphenylen-
diamin, metatoluylendiamin, metaxylylendiamin and their alkylderivatives) with the
tetrazo combinations of benziden and tolidin-sulpho-acids resulting from the
sulphuration of benzidin and tolidin are also soluble in alkali; whereas the
combination products of the before named diamines with tetrazo-diphenyl and

page_text: ditolyl are not soluble in alkali, but can easily be made soluble by treating with
concentrated sulphuric acid in the well known manner. The colouring properties
of the compounds are the same as those of the above oxy-combinations.
By treating tetrazodiphenyl and tetrazoditolyl with metaphenylendiamin sulpho-
acid (made from meta-nitranilin-sulpho acid or phenylen-diamin, see Post Annalen
der chemic tome 205 page 102 etc.) and metatoluylendiamin sulpho-acid (from
meta-toluylen-diamin, see Wissinger Berichte der deuteschen chemischen gessell-
schaft VII., 464) or metaxylylendiaminsulphoacid (Limpricht. Berichte der
deutschen chemischen gesellschaft XVIII 2190) one obtains orange red azo dye
stuffs, which differ from the other by having a yellower shade and greater fastness
against acids; but for the rest, they are of the same colouring properties.
All the above named dye stuffs are made after well known methods. I proceed
especially as follows.
I. Example. 1 dilute 31 pounds sulphate of tolidin, made of orthonitrotoluol in
500 pounds water and then add 25 lbs muriatic acid of 200 Beaume. This mixture is kept
cold and a solution of 14 lbs nitrite of soda in 50 lbs water is poured in tetrazo-
ditolylchlorid is thus formed in the solution, which is continually agitated and
allowed to run slowly into a cold solution of 22 lbs resorcin and 26 lbs calcined
soda in 500 lhs water. The colouring matter is formed at once and precipitated in
the shape of brown-red crystalline flakes, which are filtered off, pressed and dried.
II. Example. a) Take 28,, lbs sulphate of Benzidin and prepare a solution of
tetrazo-diphenyl-chlorid as described in Example I. To this solution add, whilst
continually agitating a cold solution of 21,6 lbs metaphenylendiamin and 16 lbs
calcined soda in 2000 lbs water. The dye stuff is at once precipitated as black-
brown flakes which are filtered off pressed and dried.
b) This dye stuff not being soluble in alkali, 50 lbs of it are slowly brought in
150 lbs fuming sulphuric acid of 20% anhydrous SO, and agitated at a moderate
temperature as long as the sulphuration is not completed; the colour which is at the
beginning red-violet assumes a blue-violet hue. The sulpho acid thus obtained is not
easily soluble in water and falls out when sufficiently diluted; it is then filtered off
and treated with caustic or common soda to transform into soluble natron salts.
III. Example. Take 34.4 lbs benzidinsulpho-acid, (see Berichte der deutschen
chemischen gasellschaft XIV. 300) dilute it in 500 lbs water, add 25 lbs muriatic
acid of 20° Be. and then transform them into the tetrazo combination by further
treating with a solution of 14 lbs nitrite of soda in 50 lbs water. Then let this
tetrazo combination run slowly into a solution of 21,, lbs metaphenylendiamin and
26 lbs calcined soda in 2000 lbs water, the dye stuff thus formed is precipitated in
the shape of brown-red flakes which are filtered off, pressed and dried.
IV. Example. Dilute 28,, lbs sulphate of benzidin in 500 lbs water mixed with
25 lbs muriatic acid of 20° "Be. and 14 lbs nitrite of soda to be diazotated in the
known way.
Then pour the mixture into a slightly alcaline solution of 42 lbs
metaphanylendiamin sulphate of natron in 1000 lbs water; after having agitated
for some time, the dye stuff must be precipitated by an addition of common salt,
filtered off, pressed and dried. This colouring matter dyes cotton orange-red in an
alkaline bath without mordant.
If 31 lbs sulphate of tolidin are taken instead of sulphate of benzidin and worked in
the same manner as above described the dye stuff obtained is of a yellower shade.
V. Example. Prepare a solution of tetrazodiphenylchlorid as indicated in example I
and pour it whilst agitating into an alkaline solution of 44,, lbs metatoluylendiamin
sulphate of natron in 1000 lbs water. The colouring matier formed is precipitated by
common salt, filtered off, pressed and dried; its shade is of a yellow orange.
If you take instead of tetrazo-diphenyl an equivalent quantity of tetrazo-ditolyl, the
dye stuff gets a redder shade.
In all the above named processes the formation of azo dye stuffs is the result of two
distinct reactions. When adding for instance tetrazodiphenyl- or ditolyl-chlorid to a
solution of the before mentioned diamines or their sulpho-acids dark brown precipi-
tates are formed immediately resulting from the combination of one molecule of

page_text: tetrazodiphenyl or ditolylchlorid with one molecule of said diamines or their sulpho-
acids, this combination still contains one uncombined diazogroup which slowly unites
in presence of an alkali with a second molecule of said substances forming normal
azo-dyestuffs.
This well known (G. Schultz Berliner Berichte der deutschen chemischen
Gessellschaft XVII 461). behaviour of tetrazo-diphenyl or ditolylchlorid allows the
production of so called mixed azocolours by first combining one molecule of tetrazo-
diphenyl or ditolylchlorid with one molecule of a diamine or of its sulphoacid then
adding one molecule of any other aromatic amine phenol or their sulpho- or carbon
derivatives and completing the formation of the mixed azodyestuff by allowing the
mixture to stand for some time in presence of an alkali.
As an example of the production of these mixed azocolours I describe the formation
of an orange dyestuff deriving from tetrazo-ditolyl or metatoluylendiamin-sulphoacid
and salicylic acid.
I first prepare a solution of the hydro-chlorate of tetrazoditolyl by mixing 31 pounds
of sulphate of tolidine, 25 pounds of muriatic acid (20° Be.) and 500 pounds of water
and adding to this mixture a solution of 14 pounds of nitrite of soda in 50 pounds of
water.
Care must be taken to keep the mixture cool during the operation, the end of which
is indicated by the dissolving of the suiphate of tolidine.
The so prepared solution of the hydrochloride of tetrazoditolyl is then allowed to
run slowly into a cold solution of 20 pounds of metatoluylendiaminsulphoacid and
21,2 pounds of dry soda in 1000 pounds of water. To this liquid, which contains a
brown insoluble precipitate are added 16 pounds of the soda salt of salicylic acid in
500 pounds of water whereupon the whole mixture is allowed to stand at a temperature
of 30-40° until the precipitate disappears and a clear orange solution results.
The colouring matter is then precipitated by adding a sufficient quantity of salt,
filtered, pressed and dried.
In the above process the employed quantity of metatoluylendiamine sulphoacid may
be substituted by an equivalent quantity of the before named metadioxy, metadiamido
metaamido-oxy compounds or their derivatives, while instead of salicylic acid other
amido bases, phenols or their sulpho and carbon acids may be used in quantities
corresponding to their respective molecular weights.
1
L
1 1902
HASELTINE, LAKE & Co.,
45, Southampton Buildings, London,
Agents for the Applicant.

page_text: COMPLETE SPECIFICATION.
Improvements in the Manufacture of Colouring Matters.
I, HENRY HARRIS LAKE, of the firm of Haseltine, Lake and 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 he performed to be particularly
described and ascertained in and by the following statement:—
The chief object of this invention is the production of new azo dye stuffs by the
combination of tetrazodiphenyl, tetrazoditolyl and their sulpho acids with aromatic
metadioxy meta-diamido and metaamidooxy compounds and their sulpho acids.
A series of new dye stuffs is obtained by treating a neutral or slightly alkaline solu-
tion of an aromatic metadioxy-metaamido- or metaamidooxy compound or one of their
sulphoacids with a solution of tetrazodiphenyl, tetrazoditolyl or one of their sulpho-
acids.
The dye stuffs thus obtained show a striking affinity to raw cotton fibres without
any mordant.
The dye stuffs produced with the aromatic dioxy compounds (such as orcine
resorcine resorcyl-acid) and metaoxyamido compounds (metaoxydiphenylamin) are
soluble in alkali and dye cotton, fast even in a cold alkaline solution. The shades vary
from yellow to bluish red and stand soaping or milling; as examples I name the
combination of tetrazodiphenyl and resorcine which gives a bright yellow whereas
the combination of tetrazoditolyl with resorcine gives a saffranine like blueish red
shade.
The colouring matters obtained by treating aromatic metadiamines (as metaphenyl-
endiamin, metatoluylendiamin, metaxylylendiamin and their alkyl derivatives) with
the tetrazo combinations of benzidin and tolidin sulphoacids resulting from the sulphura-
tion of benzidin and tolidin are also soluble in alkali; whereas the combination products
of the before named diamines with tetrazo-diphenyl and ditolyl are not soluble in
alkali, but can easily be made soluble by treating with concentrated sulphuric acid
in the well known manner. The colouring properties of the compounds are the same
as those of the above oxy-combinations.
By treating tetrazodiphenyl and tetrazoditolyl with metaphenylendiamin sulphoacid
(made from meta-nitranilin-sulphoacid or phenylendiamin, see Post Annalen der
Chemic tome 205 page 102 etc.) and metatoluylendiamin sulphoacid (from meta-
toluylendiamin see Wissinger Berichte der Deutschen Chemischen Gesellschaft. VII.464)
or metaxylylendiamin sulphoacid (Limpricht, Berichte der Deutschen Chemischen
Gesellschaft XVIII. 2190) one obtains orange red azo dye stuffs which differ from the
other by having a yellower shade and greater fastness against acids but for the rest
they are of the same colouring properties.

page_text: All the above named dye stuffs are made after well known methods: I proceed
especially as follows.
1. Example. I dilute 31 pounds sulphate of tolidin made of orthonitrotoluol, in
500 pounds water and then add 25 pounds muriatic acid of 20° Beaumé. This
mixture is kept cold and a solution of 14 lbs. nitrite of soda in 50 lbs. water is
poured in, tetrazoditolyl chlorid is thus formed in the solution, which is continually
agitated and allowed to run slowly into a cold solution of 22 lbs. resorcin and 26 lbs.
calcined soda in 500 lbs. water. The colouring matter is formed at once and precipi-
tated in the shape of brown-red crystalline flakes which are filtered off, pressed and dried.
II. Example. (a) take 28, lhs. sulphate of benzidin and prepare a solution of
tetrazodiphenylchlorid as described in Example I. To this solution add while con-
tinually agitating a cold solution of 21.6 lbs. inetaphenylendiamin and 16 lbs. calcined
soda in 2000 lbs. water. The dye stuff is at once precipitated as black brown flakes
which are filtered off pressed and dried.
() This dye stuff not being soluble in alkali, 50 lbs. of it are slowly brought
in 150 lbs. fuming sulphuric acid of 20% anhydrous SO, and agitated at a moderate
temperature as long as the sulphuration is not completed the colour which is at
the beginning red-violet assumes 21 blue-violet hue. The sulpho-acid thus
obtained is not easily soluble in water and falls out when not sufficiently diluted;
it is then filtered off and treated with caustic or common soda to transform it into
soluble natron salts.
III. Example. Take 34.4 lbs. benzidin sulphoacid (see Berichte der Deutschen
Chemischen Gesellschaft XIV. 300) dilute it in 500 lbs. water, add 25 lbs. muriatic
acid of 20° Beaumé and then transform them into the tetrazo combination by
further treating with a solution of 14 lbs. nitrite of soda in 50 lbs. water. Then
let this tetrazo combination run slowly into a solution of 21.6 lbs. metaphenyl-
endiamin and 26 lbs. calcined soda in 2000 lbs. water; the dye stuff thus formed
is precipitated in the shape of brown-red flakes, which are filtered off pressed
and dried.
IV. Example. Dilute 28.2 lbs. sulphate of benzidin in 500 lbs. water mixed
with 25 lbs. muriatic acid of 20° Beaumé and 14 lbs. nitrite of soda to be diazotated
in the known way. Then pour the mixture into a slightly alkaline solution of
42 lbs. metaphenylendiamin sulphonate of natron in 1000 lbs. water; after having
agitated for some time the dye stuff must be precipitated by an addition of common salt,
filtered off, pressed and dried. This colouring matter dyes cotton orange-red in an
alkaline bath without mordant.
If 31 lbs. sulphate of tolidin are taken instead of sulphate of benzidin and
worked in the same manner as above described, the dye stuff obtained is of a
yellower shade.
V. Example. Prepare a solution of tetrazodiphenyl chlorid as indicated in Example 1
and pour it, whilst agitating, into an alkaline solution of 44.8 lbs. metatoluylen-
diamin sulphonate of natron in 1000 lbs. water. The colouring matter formed is
precipitated by common salt filtered off, pressed and dried; its shade is of a
yellow orange.
If you take instead of tetrazodiphenyl an equivalent quantity of tetrazoditoly!, the
dye stuff gets a redder shade.
In all the above named processes the formation of azo dye stuffs is the result of
two distinct reactions when adding for instance tetrazodiphenyl- or- ditolyl chlorid to
a solution of the before mentioned diamines or their sulpho acids, dark brown
precipitates are formed immediately resulting from the combination of one molecule
of tetrazodiphenyl or ditolyl chlorid with one molecule of said diamines or their sulpho-
acids, this combination still contains one uncombined diazo-group which slowly unites
in presence of an alkali, with a second molecule of said substances forming normal azo
dye-stuffs.
This well known (J. Schultz, Berliner Berichte der Deutscher Chemischen Gesell-
schaft XVII. 461) behaviour of tetrazodiphenyl or ditolyl chlorid allows the production

page_text: of so called mixed azo colours by first combining one molecule of tetrazodiphenyl
or ditolyl chlorid with one molecule of a diamine or of its sulpho acid, then adding
one molecule of any other aromatic aminephenol or their sulpho or carbon derivatives
and completing the formation of the mixed azo dye stuff by allowing the mixture to
stand some time in presence of an alkali.
As an example of the production of these mixed azo colours I describe the formation
of an orange dye stuff derived from tetrazoditolyl and metatoluylendiamin-sulpho-
acid and salicylic acid.
I first prepare a solution of the hydrochlorate of tetrazoditolyl by mixing 31 pounds
of sulphate of tolidine 25 pounds of muriatic acid (20° Beaume) and 500 pounds of
water and adding to this mixture a solution of 14 pounds of nitrite of soda in
50 pounds of water.
Care must be taken to keep the mixture cool during the operation the end of
which is indicated by the dissolving of the sulphate of tolidine.
The so prepared solution of hydrochloride or tetrazoditolyl is then allowed to
run slowly into a cold solution of 20.2 pounds of metatoluylendiamin-sulpho-acid
and 21.2 pounds of dry soda in 1000 pounds of water. To this liquid which contains
a brown insoluble precipitate, are added 16 pounds of the soda salt of sylicylic acid
in 500 pounds of water whereupon the whole mixture is allowed to stand at a
temperature of 30-40° C until the precipitate disappears and a clear orange solution
results.
The colouring matter is then precipitated by adding a sufficient quantity of salt filtered,
pressed and dried.
It is evident that the process can be inverted by first treating the diazo chloride
with the salicylic acid and then adding the diamido sulphoacid and the result will be the
same.
In this case a good way of proceeding is as follows;
I prepare two solutions one of tetrazoditolyl chlorid by treating 10 pounds of
tolidin 25 pounds of muriatic acid (20° Beaume) 250 pounds of water and 6.5 pounds
of nitrite of soda at a temperature of 0° C. and the other of 6.5 pounds of salicylic
acid 3.3 pounds of dry soda in 80 pounds of water. These two solutions are poured
together quickly and a third solution of 12.5 pounds of dry soda in 10 pounds of
water is added. When the formation of the first compound is finished, I add a solution
of 10 pounds of metatoluylendiamin sulphoacid and three pounds of dry soda in
200 pounds of water. The combination can be considered as finished when a sample
of the precipitate formed and suspended in the solution dissolves clearly in hot water
and without developing gaseous products. The dye stuff is then precipitated by common
salt, filtered off, pressed and dried.
In the above processes the employed quantity of motatoluylendiamine, sulphoacid
may be substituted by an equivalent quantity of the before named metadioxy-meta-
diamido, metaamidooxy compounds or their derivatives while instead of salicylic acid
other amido bases, phenols or their sulpho and carbon acids may be used in quantities
corresponding to their respective molecular weights.
I wish it to be understood that I do not confine myself to the exact formule herein-
before mentioned in my description as mere examples and which may be varied within
certain limits.
Having now particularly described and ascertained the nature of the said inven-
tion and in what manner the same is to be performed, as communicated to me by
my foreign correspondent I declare that what I claim is.
First. The method of producing dye stuffs by the treatment of tetrazodiphenyl,
tetrazoditolyl and their sulphoacids with aromatic metadioxy and metaoxyamido
compounds, substantially as set forth.
Second. The method of producing dye stuffs by the treatment of tetrazodiphenyl
and tetrazoditolyl with aromatic metadiamines and their alkyl derivatives and
transformation of these dye stuffs in sulphoacids by sulphuration substantially as
set forth.
Third. The method of producing dye stuffs by the treatment of tetrazodiphenyl

page_text: and ditolyl sulphoacids with aromatic metadiamines: and their alkyl derivatives sub-
stantially as set forth.
Fourth. The method of producing azo dye stuffs by the combination of tetrazo-
diphenyl and ditolyl salts with metaphenylendiamin sulphoacid, metatoluylendiamin
sulphoacid and metaxylylendiamin sulphoacid, substantially as set forth.
Fifth. The method of producing azo dye stuffs by first combining one molecule
of tetrazodiphenyl or ditolylchlorid, with one molecule metadioxy metadiamido,
metaoxyamido compounds and their sulpho-derivatives and with another molecule of
an aromatic amin or phenol or their sulpho or carbon acids in presence of an alkali
in one of the two ways, hereinbefore set forth.