Year: 1888

page_text: Date of Application, 26th July, 1888
Complete Specification Left, 12th Mar., 1889
Complete Specification Accepted, 25th May, 1889
a
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:-
My invention consists in the production of new diazo and tetrazo dye stuffs from
the sulpho acids of the amidophenols and amidocresols.
I found
•
1.) That the diazo compounds of the above named sulpho acids combine with
naphtylamine to form diazo dye stuffs of the general formula.

page_text: "
can be
2) That these diazo bodies, which I call "intermediate compounds
diazotated once more and then combined with a and ẞ naphtolsulpho acids to form
the new tetrazo dye stuffs.
All the dye stuffs of this class are distinguished by great fastness against the action
of ann libt
1) Dye stuff of amidoparaphenolsulpho,-acid a naphtylamine & R salt (German
Patent No. 3229).
A solution of 21.5 lbs. of amidoparaphenolsulphate of soda and 7 lbs. of nitrite
of soda is poured slowly into an excess of muriatic acid at the ordinary temperature.
The diazo combination formed gives to the liquid a yellow brown colour; the
reaction finished a solution of 20 lbs. of hydrochlorate of a naphtylamine is added.
The mixture is at the beginning clear and becomes troubled after a while by the
separation of the dye stuff acid.
At the ordinary temperature and in a diluted solution the reaction goes on slowly
for several days; by heating the mass to 40-50° the formation of the intermediate
compound is accelerated. The reaction is considered to be completed when a
sample filtered off gives no more precipitate after being a little heated or standing
for some time.
The precipitate forms dark green crystals, dissolving in ammonium with brown-
orange and in concentrated sulphuric acid with violet colour. Being insoluble
in water, it can be washed and is then dissolved in a humid state in 10 lbs. of
ammonium of 17%; add 7 lbs. of nitrite of soda and pour the whole solution in
muriatic acid cooled with ice to 0°.
The intermediate compounds precipitates first in the shape of blackish flakes, which
change colour with the progressing diazotation and appear finally pure brown.
Arrived at this point of the process the last step is begun by pouring the diazotated
compound into an alkaline solution of 38 lbs. of R salt cooled with ice.
The dye stuff is formed at once in the shape of a black precipitate, which is
filtered, pressed and dried and then crystallized in water for purification. The
dissolution in concentrated sulphuric acid is blue. This colouring matter dyes wool
from violet to violet-black according to its strength.
2 and 3. The production of dye stuffs of amidoparaphenolsulpho acid-azo-a naphty-
lamine and Schaeffers ẞ naphtolsulphoacid or a naphtolsulphoucid, (the latter
prepared from naphtionacid by following Neville and Winthers method).
Proceed exactly as in example 1. with the exception of taking for the final
reaction 28 lbs. of Schaeffers ẞ naphtolsulphate of soda or an equal quantity of
naphtolsulphate of soda instead of 38 lbs. of R. Salt.
a
The dye stuff with Schaeffers salt forms a bronze lustred powder; it is soluble in
water with violet colour; an addition of ammonium changes the solution into blue
violet; the solution in concentrated sulphuric acid is green. The second dye stuff
with R salt is similar in its reactions.

page_text: orthocresolsulphoacid and the same naphtolsulphoacids are employed.
The properties of the intermediate compounds belonging to this class are the
following.
The potassic salt of the nitrosulphoacid obtained by the nitrification of paracresol-
sulphoacid which has probably already been prepared by Armstrong and Field, see
Berichte der deutschen chemischen Gesellschaft 6 page 974) crystallizes in bright
yellow needles.
The amidoparacresolsulphoacid forms large colourless needles, and is with difficulty
soluble in cold water; a diluted aqueous solution becomes of a light greenish hue
by the addition of sesquichloride of iron. Its diazocombination is more easily
soluble in water than the acid itself. The intermediate compound appears in the
shape of small dark green crystals which dissolve in concentrated sulphuric acid
with a violet colour; its ammonium salt crystallizes in small bright brown leaves.
The diazo-combination of the intermediate compound is of a brown red colour
and forms a greenish solution in ammoninm which soon burns into red.

page_text: COMPLETE SPECIFICATION.
'
Improvements in and relating to the Manufacture of Coloring
Matters.
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 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 production of new diazo and tetrazo dye stuffs from
the sulpho acids of the amidophenols and amidocresols.
The communicator has found :-
:-
1) That the diazo compounds of the above named sulpho-acids combine with
a naphtylamine to form diazo dye stuffs of the general formula.
Cx H, x, OH SO, HN=NC₁。 H, NH,.
10
2) That these diazo bodies, which I call intermediate compounds can be diazotated
once more and then combined with a and ẞ naphtolsulphoacids to form the new
tetrazo dye stuffs.
All the dye stuffs of this class are distinguished by great fastness against the action
of sunlight.
A. DYE STUFFS OF THE AMIDOPHENOLSULPHOACIDS.
1) Dye stuff of amidoparaphenolsulphoacid, a naphtylamine and R salt (German
Patent No. 3229.)
A solution of 21.5 lbs of amidoparaphenolsulphonate of soda and 7 lbs. of nitrite of
soda is poured slowly into an excess of muriatic acid at the ordinary temperature.
The diazo combination formed gives to the liquid a yellow brown color; the
reaction finished, a solution of 20 lbs of hydrochlorate of a naphtylamine is added.
The mixture is at the beginning clear and becomes troubled after a while by the
separation of the dye stuff acid."
At the ordinary temperature and in a diluted solution the reaction goes on slowly
for several days; by heating the mass to 40-50° the formation of the intermediate
compound is accelerated.
The reaction is considered to be completed, when a sample filtered off gives no more
precipitate after being a little .heated or standing for some time.
The precipitate forms dark green crystals, dissolving in ammonia with brown-
orange and in concentrated sulphuric acid with violet color. Being insoluble in
water, it can be washed and is then dissolved in a humid state in 10 lbs. of ammonia
of 17%; add 7 lbs. of nitrite of soda and pour the whole solution in muriatic acid
cooled with ice to 0°. The intermediate compound precipitates first in the shape of

page_text: blackish flakes, which change color with the progressing diazotation and appear finally
pure brown. Arrived at this point of the process the last step is begun by pouring
the diazotated compound into an alkaline solution of 38 lbs. of R salt cooled with ice.
The dye stuff is formed at once in the shape of a black precipitate, which is filtered,
pressed and dried and then crystallized in water for purification. The dissolution in
concentrated sulphuric acid is blue. This coloring matter dyes wool from violet to
violet-black according to its strength.
2 and 3. The production of dye stuffs of amidoparaphenolsulpho-acid-azo
a naphtylamine and Schaeffers ẞ naphtolsulphoacid or a_n phtolsulphocid,
(the latter prepared from naphtionacid by following Neville and Winther's method.
Proceed exactly as in example 1, with the exception of taking for the final reaction
28 lbs. of Schaeffer's ẞ naphtolsulphonate of soda or an equal quantity of a naphtol-
sulphonate of soda instead of 38 lbs. of R salt.
The dye stuff with Schaeffers salt forms a bronze lustred powder; it is soluble in
water with violet colour; an addition of ammonia changes the solution into bluo
violet; the solution in concentrated sulphuric acid is green. The second dye stuff
with a naphtholsulphonate is similar in its reactions.
B. DYE STUFFS OF THE AMIDORTHOCRESOLSULPHOACIDS.
1) Dye stuff of amidoorthocresolparasulphoacid.
a) Intermediate compound.
If orthocresol is sulphurated in the heat, one obtains orthocresolparasulphoacid (see
Handke, Berichte der deutschen chemischen Gesellschaft 1887 p. 3209). With this
acid it is possible to make by means of Kolbe's method of the nitrification of
paraphenolsulphoacid (Beilstein's Handbuch 2nd. Edit. vol. II page 540) a nitro-
orthocresolparasulphoacid. The potassic salt of it crystallizes in needles united to
lumps of a dark flesh colour soluble in cold water with difficulty.
Reducing agents such as for example, iron and muriatic acid or sulphide of soda
transform the nitrosulphoacid into an amidosulpho acid which is with difficulty
soluble in cold water and crystallizes in big needles. A diluted aqueous solution is
colored for an instant violet red by the addition of sesqui chloride of iron.
For the production of amidoorthocresol parasulphoacid-azo a naphtylamine I
proceed exactly as described in example A 1. for the production of amidopara-
phenolsulphoacid-azo a naphtylamine with this difference that instead of 21.5 lbs.
amidoparaphenolsulphonate of soda I use 23 lbs. of amidoorthocresolsulphonate of
soda. The intermediate compound thus obtained forms dark green crystals which
are soluble in ammonia forming a brownish yellow red, and in concentrated sulphuric
acid forming a violet colour.
b) Dye stuffs with the hereinbefore described intermediate body and Schaefforsẞ
naphtholsulphoacid or R salt or a naphtholsulphoacid.
In order to diazotate the intermediate compound dissolve 36 lbs. of it in 10 lbs. of
ammonia of 17 % and 1000 lbs. of water; add 7 lbs. of nitrite of soda and pour the
whole in diluted acid (21 lbs. of muriatic acid of 22.50B in 500 lbs. of water) cooled
with ice. After standing for 4 hours, the reaction will be finished and the final
combination is proceeded with. For this purpose use 28 lbs. of Schaeffers B
naphtolsulphonate of soda or an equal quantity of a naphtolsulphonate of soda or
38 lbs. of R salt.

page_text: The properties of the intermediate compounds belonging to this class are the following.
The potassic salt of the nitrosulphoacid obtained by the nitrification of paracresol-
sulphoacid (which has probably already been prepared by Armstrong and Field, see
Berichte der deutschen chemischen Gesellschaft 6 p. 974) crystallizes in bright yellow
needles.
The amidoparacresolsulphoacid forms large colourless needles and is with difficulty
soluble in cold water; a diluted aqueous solution becomes of a light greenish hue by
the addition of sesquichloride of iron. Its diazocombination is more easily soluble
in water than the acid itself. The intermediate compound appears in the shape of small
dark green crystals which dissolve in concentrated sulphuric acid with a violet colour ;
its ammonium salt crystallizes in small bright brown leaves.
The diazocombination of the intermediate compound is of a brown red colour and
forms a greenish solution in ammonia which soon turns into red.
TABLE OF THE PROPERTIES OF THE DYE STUFFS NAMED IN SUB D AND U.
Dye stuffs of amidoorthocresol-
parasulphoacid.
and
Dye stuffs of amidoparacresol-
sulphoacid.
and
Schaeffers
ẞ naphtol-
mono-
sulphoacid
a naphtol- Schaeffers
sulphoacid 3 naphtol-
R Salt
of Neville
& Winther
mono-
sulphoacid
R Salt
a
naphtol-
sulphoacid
of Neville
& Winther

page_text: 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
correspondent I declare that what I claim is :-
First The method of producing new diazo-dye stuffs called intermediate compounds
by the reaction of the diazo-compounds of the amidoparaphenol-amidoorthocresol
and amidoparacresolsulphoacids upon a naphtylamine.
Second-The method of producing new tetrazo-dye stuffs by the combination of
the intermediate compounds mentioned in the first claim with the Schaeffer ẞ naphtol-
sulphoacid, with R Salt or with a naphtolsulphoacid.
A
1 1000
HASELTINE, LAKE & Co.,
45, Southampton Buildings, London.
Agents for the Applicant.