The Manufacture of Azodyestuffs and of Materials for their Production.
Year: 1890

page_text: Date of Application, 27th Sept., 1890
Complete Specification Left, 27th June, 1891-Accepted, 1st Aug., 1891
PROVISIONAL SPECIFICATION.
The Manufacture of Azodyestuffs and of Materials for their
Production.
I, SYDNEY PITT of Sutton in the County of Surrey, Gentleman, (a com-
munication from Leopold Cassella and Company of Frankfort-on-Main, Germany)
do hereby declare the nature of this invention to be follows:-
--
This invention relates to the manufacture of new azodyes and to the préparation
of materials suitable to be employed for this purpose. These materials are the
diamido a and ẞ naphtalene disulphonic acids. The following is a description of
the production of these acids. The naphtalenedisulphonic acids either in mixture
or isolated and prepared either by the method of Ebert and Merz (Ber. d. d. chem.
Ges. IX. 592) or by other methods are first transformed into dinitrocompounds.
The dinitrosulphonic acids are submitted to the action of reducing agents and are
thus transformed into the corresponding diamidocompounds. When starting from
the unseparated product of sulphonation either the dinitrocompounds or the diamido-
compounds can be isolated. The manner of proceeding is described in the following
examples:-
I. MANUFACTURE OF THE DIAMIDONAPHTALENEDISULPHONIC ACIDS.
Example I. To 256 kilos. of naphtalene, transformed by the action of 1280 kilos.
sulphuric acid into disulphoacids at a temperature of 0° C. is added 500 kilos. of
anhydrous sulphuric acid containing 60% SO, and a cooled mixture of 400 kilos.
nitric acid of 40° Bé. and 40 kilos. of monohydrated sulphuric acid. This mixture
is left for two or three days at 20-30° C. and is then poured into 5000 litres of
water, the hot solution is saturated with common salt up to 25° Bé. and the dinitro-
naphtalene a disulphonate of sodium which forms in colorless small crystals is
separated immediately and common salt added. to the filtered liquor up to
30-35° Bé.; a part of the dinitronaphtalene ẞ sulphonate of sodium precipitates
immediately in the form of small yellow crystals and the rest after cooling.
The thus separated dinitronaphtalenedisulphonic acids are transformed into
diamidonaphtalenedisulphonic acids by the action of iron and acetic acid or by
another of the usual methods for reducing nitrocompounds.
Or the unseparated dinitroacids are submitted to the reducing process and
muriatic acid is added to the solution of the diamidodisulphonic acids in 5000 litres
water. The acid precipitates and is separated by filtration, the filtered liquor is
saturated with common salt or with potassium chloride; the a acid separates nearly
completely after cooling.
Example II. 326 kilos. naphtalene ẞ disulphonate of lime are mixed at 0-10° C.
with 2000 kilos. monohydrated sulphuric acid; a cold mixture of 200 kilos. con-
centrated nitric acid and 200 kilos. of monohydrated sulphuric acid are then added;
after a lapse of three days this mixture is poured at a temperature of 20-30° C.
into 6000 litres water saturated with common salt. After cooling, the sodium salt
of the dinitro acid forming small yellow crystals, separated by filtration and washed
with salt water, is suspended in 4000 litres water and reduced with iron with
addition of acetic acid; when the reduction is performed the iron is precipitated
by carbonate of soda and to the filtered liquor is added 200 kilos. of hydrochloric
acid. The diamido 3 disulphonic acid separates immediately in form of colorless
microscopic crystals. In the mother lye remains an isomeric acid which can be
recovered by addition of a further quantity of 100 kilos. hydrochloric acid:
Example III. 376 kilos. mononitronaphtalene 3 disulphonate of sodium are

page_text: mixed with 3000 kilos. monohydrated sulphuric acid at 0° C. By addition of a
cold mixture of 100 kilos. of concentrated nitric acid and 100 kilos. mono-hydrated
sulphuric acid dinitronaphtalene ẞ disulphonic acid is formed which is transformed
into the amido-compound by the usual means.
The naphtalene ẞ disulphonate of lime mentioned in Example II can be replaced
by a salt of the naphtalene a disulphonic acid and in Example 3 the mononitro ẞ
disulphonate may be replaced by a salt of the corresponding a compounds and the
diamidonaphtalene a disulphonic acid obtained without altering the process.
The diamidonaphtalene ẞ disulphonic acid is almost insoluble in cold and hot water.
Its sodium salt is soluble in 21 parts of cold water and crystallizes free from water
of crystallization. The potassium salt is very soluble in cold water, the barium
salt is difficultly soluble in water.
The diamidonaphtalene a disulphonic acid has previously been prepared by a
different method by Alèn (Beilstein III, 1025); this is easily soluble in hot water
and crystallizes in long thin needles. Its sodium salt is soluble in 55 parts of cold
water and forms long pointed needles. The potassium salt is less soluble in water
than the corresponding ẞ salt.
When the diamido a acid is treated with nitrite of sodium in acid solution in the
usual manner no tetrazo compound is formed whilst the corresponding ẞ compound
submitted to this treatment forms a light yellow insoluble tetrazo compound, which
combines with phenoles and amines and the sulpho or carbo acids of which produce
azo-coloring matters.
With diazo and tetrazo compounds both acids form dyestuffs..
The way in which these special qualities of these acids is utilized may be
explained by the following examples.
II. APPLICATION OF THE DIAMIDONAPHTALENE
DISULPHONIC ACID.
Example 1. To 36-2 kilos. diamidonaphtalene ẞ disulphonate of sodium dissolved
in 400 litres of water are added 14 kilos. of sodiumnitrite and 60 kilos. hydrochloric
acid. The insoluble tetrazo compound of a light yellow colour is filtered and
introduced whilst stirring into a solution of 36 kilos. a naphtylamine chlorhydrate
in 1000 litres water or of 29 kilos. a naphtylamine in 600 litres alcohol. The
formation of the color sets in immediately and is terminated after addition of some
carbonate or acetate of sodium. The color thus obtained which dyes fibre in
neutral or alkaline bath a bright violet forms a brown powder which is difficultly
soluble in cold and easily soluble in hot water.
Example 2. The above described tetrazo compound is suspended in 200 kilos.
alcohol; a solution containing 28-6 kilos. ẞ naphtylamine and 40 kilos. soda acetate
in 300 litres alcohol is then added. The formation of the color begins immediately.
After 3 hours the undissolved new coloring matter is separated by filtration. It is
difficultly soluble in cold but soluble in hot water; it dyes unmordanted cotton a
corinth shade. By using naphtylaminesulpho acids instead of naphtylamine in the
above described process coloring matters varying from blueish to yellowish reds
very fast against acids are obtained.
III. APPLICATION OF THE DIAMIDONAPHTALENE a DISULPHONIC ACID.
Example 1. To the solution of 9.2 kilos. of benzidine in 200 litres water and
30 kilos. hydrochloric acid are added 7 kilos. sodium nitrite; the thus formed
tetrazo diphenyle is poured into a solution of 8 kilos. of diamidonaphtalene-
disulphonate of sodium in 500 litres water. At first a diazoamidocompound is
formed, which then settles into the real intermediate compound.
The formation of the latter is terminated, when a sample mixed with an excess
of muriatic acid no longer shews the formation of tetrazo diphenyle. The liquor
now containing the intermediate product in suspension is mixed with a solution of
7.2 kilos. of naphtylamine in 600 litres water with 6 kilos. of hydrochloric acid

page_text: nd 50 kilos. soda acetate. After 12 hours it is heated to 30° C. in order to
erminate the formation of the. coloring matter which is precipitated by common
alt. The new coloring matter forms an easily soluble brown powder and dyes
nmordanted cotton a blueish red color.
Example 2. In place of ẞ naphtylamine in the above example 25 kilos. of ẞ
aphtylaminemonosulphonic acid (Brönner) in 300 litres of water may be used.
The coloring-matter is easily soluble and dyes unmordanted cotton a brilliant red.
Dated this 27th day of Sentember 1890.
COMPLETE SPECIFICATION.
The Manufacture of Azodyestuffs and of Materials for their
Production.
I, SYDNEY PITT, of Sutton in the County of Surrey, Gentleman (a communi-
cation from Leopold Cassella and Company of Frankfort-on-Main Germany) 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 relates to the manufacture of new azodyes and to the preparation
of materials suitable to be employed for this purpose. These materials are the
diamido naphtalene a and ẞ disulphonic acids. The following is a description of
the production of these acids. The naphtalene disulphonic acids either in mixture
or isolated and prepared either by the method of Ebert and Merz (Ber. d. d. chem.
Ges. IX. 592) or by other methods are first transformed into dinitrocompounds.
The dinitrosulphonic acids are submitted to the action of reducing agents and are
thus transformed into the corresponding diamidocompounds. When starting from
the unseparated product of sulphonation either the dinitrocompounds or the
diamidocompounds can be isolated. The manner of proceeding is described in the
following examples
1. MANUFACTURE OF THE DIAMIDONAPHTALENEDISULPHONIC ACIDS.
Example I. 256 kilos of naphtalene, are transformed by the action of 1280 kilos.
sulphuric acid into disulphoacid. It is cooled down to about 20° C. and 350 kilos.
of a mixture of nitric and sulphuric acid containing 154 kilos HNO3 are slowly
added. The temperature is kept at 20-30° during the operation. This first reaction
leads to mononitroacids; the second nitration is performed by introducing 350 kilos.
of the same mixture of nitric and sulphuric acid. Either it may be cooled or the
temperature may rise to 120°-140° C.
After a short time the melt is diluted with 4000 litres of concentrated salt-
water of 20° Bé.
The dinitronaphtalene a disulphonate of sodium separates from the hot liquid in
form of small crystals, which are filtered off. The dinitronaphtalene ẞ sulphonate
of sodium is obtained from the filtered solution by addition of common salt and
cooling.
The thus separated dinitronaphtalene disulphonic acids are transformed into
diamidonaphtalenedisulphonic acids by the action of iron and acetic acid or by
another of the usual methods for reducing nitro compounds.
Or the dinitroacids are precipitated at once and the mixture of the same is
reduced for instance with iron and acetic acid. The iron is removed by means of
carbonate of soda and the solution (about 4000 litres) is saturated with common
salt which precipitates the diamidonaphtalene ẞ disulphonate of soda. The a acid
is obtained from the filtered solution by addition of 200 kilos. of muriatic acid.
Example II. 326 kilos. naphtalene ẞ disulphonate of lime are mixed at (-10° C.
with 2000 kilos. monohydrated sulphuric acid; a cold mixture of 200 kilos.

page_text: concentrated nitric acid and 200 kilos. of monohydrated sulphuric acid is then added;
after a lapse of three days this mixture is poured at a temperature of 20-30° C.
into 6000 litres water saturated with common salt. After cooling, the sodium salt
of the dinitro acid forming small yellow crystals, separated by filtration and washed
with salt water, is suspended in 4000 litres water and reduced with iron with
addition of acetic acid, when the reduction is performed the iron is precipitated
by carbonate of soda and to the filtered liquor is added 200 kilos. of hydrochloric
acid. The diamido ß disulphonic acid separates immediately in form of colorless
microscopic crystals. In the hot mother lye remains an isomeric acid which can
be recovered by addition of a further quantity of 100 kilos. hydrochloric acid.
Example III. 376 kilos. mononitronaphtalene B disulphonate of sodium are
mixed with 3000 kilos. monohydrated sulphuric acid at 0° C. By addition of a
cold mixture of 100 kilos. of concentrated nitric acid and 100 kilos. monohydrated
sulphuric acid dinitronaphtalene ẞ disulphonic acid is formed which is transformed
into the amido-compound by the usual means.
the
The naphtalene ẞ disulphonate of lime mentioned in Example II. can be replaced
by a salt of the naphtalene a disulphonic acid and in Example III. the mononitro
disulphonate may be replaced by a salt of the corresponding a compounds and
diamidonaphtalene a disulphonic acid obtained without altering the process.
The diamidonaphtalene ẞ disulphonic acid is almost insoluble in cold and hot
water. Its sodium salt is soluble in 21 parts of cold water and crystallizes free
from water of crystallization. The potassium salt is very soluble in cold water,
the barium salt is difficultly soluble in water.
The diamidonaphtalene a disulphonic acid has previously been prepared by a
different method by Alen (Beilstein III., 1025), this is easily soluble in hot
water and crystallizes in long thin needles. Its sodium salt is soluble in 55 parts
of cold water and forms long pointed needles. The potassium salt is less soluble
in water than the corresponding ẞ salt.
When the diamido a acid is treated with nitrite of sodium in acid solution in
the usual manner no tetrazo compound is formed, whilst the corresponding ẞ
compound submitted to this treatment forms a light yellow insoluble tetrazo
compound, which combines with phenoles and amines and the sulpho or carbo
acids of which produce azo-colouring matters.
With diazo and tetrazo compounds both acids form dyestuffs.
The way in which these special qualities of these acids are utilized may be
explained by the following examples.
2. APPLICATION OF THE DIAMIDONAPHTALENE 3 DISULPHONIC ACID.
Example I. To 36.2 kilos. diamidonaphtalene (3 disulphonate of sodium dissolved
in 400 litres of water are added 14 kilos. of sodium-nitrite and 60 kilo. hydrochloric
acid: The insoluble tetrazo compound of a light yellow colour is filtered and
introduced whilst stirring into a solution of 36 kilos. a naphtylaminechlorhydrate
in 1000 litres water or of 29 kilos. a naphtylamine in 600 litres alcohol. The
formation of the colour sets in immediately and terminates after the addition of
some carbonate or acetate of sodium. The colour thus obtained which dyes the
fibre in neutral or alkaline bath a bright violet forms a brown powder which is
difficultly soluble in cold and easily soluble in hot water.
Example II. The above described tetrazo compound is suspended in 200 kilos.
alcohol, a solution containing 286 kilos. ẞ naphtylamine and 40 kilos... soda
acetate in 300 litres alcohol is then added. The formation of the color begins
immediately. After 3 hours the undissolved new colouring matter is separated by
filtration. It is difficultly soluble in cold but soluble in hot water; it dyes
unmordanted cotton a corinth shade. By using naphtylaminesulpho acids instead
of naphtylamine in the above described process colouring matters varying from
blueish to yellowish reds very fast against acids are obtained.
Examples III. One equivalent of the said tetrazo compound is introduced into

page_text: the alkaline solution of two equivalents of phenol. The colouring matter produced
is easily soluble in water. It dyes unmordanted cotton a bright yellow. The
fastness of the colour may be improved in the known manner by etherifying the
hydroxyl groups. Instead of phenol, cresol or salicylic acid may be used.
Example IV. The tetrazo-compound of the ẞ acid is combined in weakly acid
solution with chrysoidine or Bismarck brown (Vesuvine). The resulting colouring
matters dye unmordanted cotton a deep brown of great fastness.
3. APPLICATION OF THE DIAMIDO-NAPHTALENE a DISULPHONIC ACID.
Example I. To the solution of 9-2 kilos. of benzidine in 200 litres water and
30 kilos. hydrochloric acid are added 7 kilos. sodium nitrite; the thus formed
tetrazodiphenyle is poured into a solution of 18 kilos. of diamidonaphtalenedi-
sulphonate of sodium in 500 litres water. At first a diazo amido compound is
formed, which then settles into the real intermediate compound.
The formation of the latter is terminated, when a sample mixed with an excess
of muriatic acid no longer shews the formation of tetrazo diphenyle. The liquor
now containing the intermediate product in suspension is mixed with a solution of
7-2 kilos. of ẞ naphtylamine in 600 litres water with 6 kilos. of hydrochloric acid
and 50 kilos. soda acetate. After. 12 hours it is heated to 30° C. in order to
terminate the formation of the colouring matter which is precipitated by common
salt. The new colouring matters forms an easily soluble brown powder and dyes
unmordanted cotton a blueish red colour.
Example II. In place of ẞ naphtylamine in the above example 25 kilos. of
ẞ naphtylaminemonosulphonic acid (Brönner) in 300 litres of water may be used.
The colouring matter is easily soluble and dyes unmordanted cotton a brilliant red.
Having now particularly described and ascertained the nature of my said inven-
tion and in what manner the same is to be performed I declare that what I
claim is :-
1. The process of preparing the dinitronaphtalene a disulpho acid and the
dinitronaphtalene ẞ disulpho acid by double nitration of the mixed or separated
naphtalene disulpho acids.
2. The process of preparing the diamido-naphtalene a disulpho acid and diamido
napltalene ẞ disulpho acid by reducing either the isolated dinitro acids or mixtures
of the same.
3. The process of separating the two dinitro acids from each other substantially
as herein described.
4. The process of separating the two diamido acids from each other substantially
as herein described.
5. The process of preparing new azo dyes by combining the tetrazo derivative of
the diamidonaphtalene ß disulpho acid with phenols or amines.
6. The process of preparing new azo-dyes by the action of diazo or tetrazo
compounds upon either diamidonaphtalene a or B disulpho acid.
7. The new products obtained according to Claims 1 to 6 both inclusive.
Dated this 27th day of June 1891.
CARI MAEL & Co.,
Agents for the Applicant.