IMPROVEMENTS IN THE MANUFACTURE OF COLOURING MATTERS SUITABLE FOR DYEING AND PRINTING, AND IN THE PREPARATION OF A NEW MONO- SULPHO ACID OF BETA NAPTHOL AND ITS SALTS AND DERIVATIVES
Year: 1881

page_text: LETTERS PATENT to Joseph Anthony Dixon, of No. 175, West George Street,
Glasgow, in the County of Lanark, North Britain, Solicitor, for an Invention
of "IMPROVEMENTS IN THE MANUFACTURE OF COLOURING MATTERS SUITABLE
FOR DYEING AND PRINTING, AND IN THE PREPARATION OF A NEW MONO-
SULPHO ACID OF BETA NAPTHOL AND ITS SALTS AND DERIVATIVES." A com-
munication from abroad by Carl Rumpff, of Elberfeld, in the Empire of
Germany, Manufacturing Chemist.
PROVISIONAL SPECIFICATION left by the said Joseph Anthony Dixon at
the Office of the Commissioners of Patents on the 21st March 1881.
JOSEPH ANTHONY DIXON, of No. 175, West George Street, Glasgow, in
the County of Lanark, North Britain, Solicitor. "IMPROVEMENTS IN THE
MANUFACTURE OF COLOURING MATTERS SUITABLE FOR DYEING AND PRINTING,
AND IN THE PREPARATION OF A NEW MONOSULPHO ACID OF BETA NAPTHOL AND
ITS SALTS AND DERIVATIVES." [A communication from abroad by Carl Rumpff,
of Elberfeld, in the Empire of Germany, Manufacturing Chemist.]
The preparation of colouring matters from the disulpho acids of beta napthol
has been patented in the Empire of Germany, under Letters Patent, No. 3220, of the
Patent Roll of the German Empire. The action of the only monosulpho acid of beta
napthol known up to the present time upon the diazo compounds gives only very
few colour-reactions of technical value. I have succeeded however in preparing a
new monosulpho-acid of beta napthol, and by means thereof in preparing, partly by
reaction upon the diazo compounds of the benzolic series and of napthalene and
partly by nitration, very valuable new colouring matters, the preparation whereof
is hereinafter described. The nature and object of the present Invention therefore
is the preparation and separation of the said new, monosulpho-acid of beta napthol
and of colouring matters therefrom by nitration or by causing the same to react on
diazo compounds as hereinafter described.

page_text: •
1
Beta-napthol-monosulpho-acid is formed (according to Schaefer, Ann. Chem. 152,
296) by heating beta napthol on the water bath with double its weight_of
commercial or English sulphuric acid till perfect solution has taken place. By
means of the lead salt the acid is obtained in a pure state. If however the process
of sulphonization is conducted in such a way that the duration of the reaction of
the excess of sulphuric acid upon the napthol-monosulpho-acid already formed is
as much as possible shortened, and the attainment of too high a temperature is
obviated, a second isomeric napthol-monosulpho-acid is formed, besides that
described by Schaefer, which is very essentially different in all its properties from
the above mentioned acid. It is especially in its different behaviour towards nitric
acid that the new sulpho acid is very sharply distinguished from the acid
described by Schaefer. For while no nitro-products can be isolated from Schaefer's
acid my new sulpho-acid when treated with nitric acid very readily gives nitro-
compounds, the potassium salts of which are crystallizable compounds, which dye
wool and silk of a beautiful yellow. Besides this the difference of the two isomeric
mono-sulpho-acids is proved by the different solubility of their respective neutral
soda salts in spirits of wine of 90%. The neutral soda salt of the beta-monosulpho-
"ONa
acid described by Schaefer C₁. H.
30.
SO, Na is nearly insoluble in boiling spirit
of 90°, while the neutral soda salt of the new acid on the contrary dissolves therein
with great facility, and settles in beautiful and extremely hygroscopic crystals as
the alcohol cools. The new acid and its neutral soda salt may be separated from
Schaefer's acid and, its neutral soda salt by this difference of solubility in
'alcohol.
In order to get a more copious yield of my new acid (which I shall designate
the alpha-monosulpho-acid of beta napthol) I proceed as follows:-
'
100 kilograms of finely powdered beta napthol freed from moisture are mixed as
quickly as possible with 200 kilograms of commercial sulphuric acid (66 per cent.)
The mixture heats spontaneously with great rapidity, but care must be taken that
the temperature does not exceed 50° to 60° centigrade, because if the temperature
is only a few degrees higher, and if sulphuric acid is at the same time present in
excess the new monosulpho-acid passes very quickly over into the common mono-
sulpho-acid. The napthol is very soon dissolved in the sulphuric acid.
As soon as
this point is reached (which generally requires no more time than 10 to 15 minutes,
and which can be most easily recognised by the fact that when it is reached a
sample of the melt saturated with ammonia gives a clear solution on the addition
of diazo benzol) the melt is poured into cold water. It then contains a mixture of
two different sulpho-acids of beta napthol.
The neutral soda salts of the monosulpho-acids thus formed are prepared and
dried in the usual manner. The crude mixture of these salts is treated with from
3 to 4 parts of boiling spirit of 90° and filtered hot. The soda salt of the mono-
sulpho-acid described by Schaefer remains nearly perfectly undissolved; the salt of
the new sulpho-acid on the contrary passes into solution and crystallizes as the
solution grows cool in fine large crystals containing spirit, which are freed from the
mother liquor by a mechanical method of separation.
This spirit-soluble salt gives in combination with the diazo compounds colouring
matters fast against soap and light, the shades of which are on the whole yellower
than those of the azo-dyestuffs prepared from the common beta napthol-
monosulpho-acid.
?
In order to obtain a scarlet-red dyestuff which dyes wool and cotton equally
well, and which I call crocëin-scarlet, I proceed in the following manner :-
50 kilograms of the monosulpho-acid of amidazobenzol are dissolved in
500 litres of water with addition of the necessary quantity of ammonia, and
cooled to about 5° centigrade, then 80 kilograms of muriatic acid and 13 kilograms
of pure nitrite of soda (of 100 per cent. strength) are added. After standing for
several hours the monosulpho-acid of diazo-azo-benzol which is formed is allowed
to run slowly into a solution of 75 kilograms of the crystallized alpha-monosulpho-

page_text: acid of beta napthol (prepared in the form of its soda salt, though other equivalent
salts may also be used), which salt has been dissolved in 500 litres of water
to which 140 kilograms of ammonia of 10 per cent. have been added.
By this operation the dye stuff is formed immediately according to the following
equation:-
=C₁ H₁
alpha-monosulpho-acid.
*SO, NH
N = NC
-
H
- N = NC H.
+ NH, CL
ONa
SO, Na
The colouring matter is precipitated by the addition of common salt and the
dyestuff purified by redissolving and reprecipitating.
If I use for azotising free amido-azo-benzol instead of its monosulpho-acid, I get
a dyestuff which possesses a somewhat more yellowish, but withal extremely clear
shade. The homologues of amido-azo-benzol and their monosulpho-acids give
correspondingly bluer shades; diazo-benzol and its homologues give with the new
alpha-mono-sulpho-acid reddish yellow tints or tones drawing to orange; alpha-
diazo-napthalin, a blueish red; betadiazonapthalin, a more brick red dyestuff.
Instead of the diazo compounds derived from benzol and its homologues toluol,
xylol, and so forth, the diazo compounds obtained from the other members of the
benzol series, which are not homologues in the ordinary sense of the term, may be
employed, as, for instance, the diazo compounds or derivatives of ethyl xylol, ethyl
benzol, ethyl methyl xylol, and other compounds of benzol and its homologues with
other alcoholic residues, as also the diazo derivatives of the said bodies which are
substituted with the sulpho-group, all of which I comprehend in the general
expression diazo compounds or derivatives of the benzol series, as well as the
diazo-azo derivatives of the benzoles and napthalin. The alphamonosulpho-acid of
beta napthol (in contrast to the monosulpho-acid described by Schaefer) gives
when treated in aqueous solution with nitric acid nitro-products, the alkali salts of
which are fine yellow dyestuffs or colouring matters easily soluble in water.
In order to prepare the dyestuff or colouring matter which I call crocëin yellow,
I work in the following manner:-
10 kilograms of crystallized alphamonosulpho-acid of beta napthol are dissolved
in 20 kilograms of water, and after having by boiling evaporated the spirit which
was present in the crystals of the monosulpho-acid, 15 kilograms of nitric acid of
about 50 per cent. are added at a temperature of 40° to 50° centigrade. After
standing for several days at a temperature of 30° to 40° the nitration is finished,
the liquid is neutralized with carbonate of potash, whereon the potassium salt of
the colouring matter precipitates as a yellow crystallized powder; it is obtained
pure by repeated crystallization,
I do not consider myself to be bound to the precise temperatures and quantities
of materials hereinbefore mentioned, as they are susceptible of considerable
variation without materially affecting the result.

page_text: SPECIFICATION in pursuance of the conditions of the Letters Patent filed by
the said Joseph Anthony Dixon in the Great Seal Patent Office on the 10th
September 1881..
JOSEPH ANTHONY DIXON, of 175, West George Street, Glasgow, in the County
of Lanark, North Britain, Solicitor. "IMPROVEMENTS IN THE MANUFACTURE OF
COLOURING MATTERS SUITABLE FOR DYEING AND PRINTING, AND IN THE
PREPARATION OF A NEW MONO-SULPHO ACID OF BETA NAPTHOL AND ITS SALTS
AND DERIVATIVES." A communication from abroad by Carl Rumpff, of Elberfeld,
in the Empire of Germany, Manufacturing Chemist.
The preparation of colouring matters from the disulpho acids of beta-napthol,
has been Patented in the Empire of Germany, under Letters Patent, No. 3220, of
the Patent Roll of the German Empire. The action of the only mono-sulpho-acid
of beta-napthol known up to the present time upon the diazo compounds gives
only very few colour reactions of technical value. I have succeeded however in
preparing a new mono-sulpho-acid of beta-napthol, and by means thereof, in pre-
paring partly by reaction upon the diazo compounds of the benzolic series and of
napthalene, and partly by nitration (that is by treating with nitric acid so as to
produce a nitro-substituted compound), very valuable new colouring matters, the
preparation whereof is hereinafter described. The nature and object of the present
Invention therefore is the preparation and separation of the said new mono-sulpho-
acid of beta-napthol, and of colouring matters therefrom by nitration, or by causing
the same to react on diazo compounds, as hereinafter described.
Beta-napthol-mono-sulpho-acid is formed (according to Schaefer, Ann. Chem.
152, 296) by heating beta-napthol on the water bath with double its weight of
commercial or English sulphuric acid, till perfect solution has taken place. By
means of the lead-salt the acid is obtained in a pure stato. If, however, the
process of sulphonization is conducted in such a way that the duration of the
reaction of the excess of sulphuric acid upon the napthol-mono-sulpho-acid already
formed is as much as possible shortened, and the attainment of too high a tempo-
rature is obviated, a second (isomeric) napthol-mono-sulpho-acid is formed, besides
that described by Schaefer, which is very essentially different in all its properties
from the above mentioned acid. It is especially in its different behaviour towards
nitric acid that the new sulpho acid is very sharply distinguished from the acid
described by Schaefer. For while no nitro-products can be isolated from Schaefer's
acid, my new sulpho-acid, when treated with nitric acid, very readily gives nitro-
compounds, the potassium salts of which are crystallizable compounds, which dye
wool and silk of a beautiful yellow. Besides this, the difference of the two isomeric
mono-sulpho-acids is proved by the different solubility of their respective neutral
soda salts in spirits of wine of 90°. The neutral soda salt of the beta-mono-sulpho-
ONa
_ acid described by Schaefer (CH₂-
(80%, Na) is nearly insoluble in boiling
spirit of 90°, while the neutral soda salt of the new acid, on the contrary, dissolves
therein with great facility, and settles in beautiful and extremely hygroscopic
crystals as the alcohol cools. The new acid and its neutral soda salt may be
separated from Schaefer's acid and its neutral soda salt by this difference of
solubility in alcohol.
In order to get a more copious yield of my new acid (which I shall designate the
alpha-mono-sulpho-acid of beta-napthol) I proceed as follows:-
100 kilograms of finely powdered beta-napthol, freed from moisture, are mixed
as quickly as possible with 200 kilograms of cold commercial sulphuric acid
(containing 66 per cent. of sulphuric anhydride). The mixture heats spontaneously
with great rapidity, but care must be taken that the temperature does not exceed

page_text: 50° to 60° centigrade, because if the temperature is only a few degrees higher, and
if sulphuric acid is at the same time present in excess, the new mono-sulpho-acid
passes very quickly over into the common mono-sulpho-acid. The napthol is very
soon dissolved in the sulphuric acid. As soon as this point is reached (which
generally requires no more time than 10 to 15 minutes, and which can be most
easily recognised by the fact that, when it is reached, a sample of the melt saturated.
with ammonia, gives a clear solution on the addition of diazo benzol), the melt is
poured into cold water. It then contains a mixture of two different sulpho-acids of
beta-napthol.
The neutral soda salts of the mono-sulpho-acids thus formed are prepared and
dried in the usual manner. The crude mixture of these salts is treated with from
3 to 4 parts of boiling spirit of 90°, and filtered hot. The soda salt of the mono-
sulpho-acid described by Schaefer, remains nearly perfectly undissolved; the salt of
the new sulpho-acid on the contrary passes into solution, and crystallizes as the
solution grows cool in fine large crystals containing spirit, which are freed from the
mother liquor by a mechanical method of separation.
This spirit-soluble salt gives, in combination with the diazo compounds, colouring.
matters fast against soap and light, the shades of which are on the whole yellower
than those of the azo-dyestuffs prepared from the common beta-napthol-mono-
sulpho-acid.
In order to obtain a scarlet-red dyestuff, which dyes wool and cotton equally
well, and which I call crocëin-scarlet, I proceed in the following manner:-
50 kilograms of the mono-sulpho-acid of amido-azo-benzol are dissolved in
500 litres of water, with addition of the necessary quantity of ammonia, and cooled
to about 5° centegrade; then 80 kilograms of muriatic acid and 13 kilograms of
pure nitrite of soda (of 100 per cent. strength) are added. After standing for
several hours the mono-sulpho-acid of diazo-azo-benzol which is formed is allowed
to run slowly into a solution of 75 kilograms of the crystallized alpha-mono-sulpho-
acid of beta-napthol, preferably in the form of its soda salt (though other equivalent
salts may also be used), which salt has been dissolved in 500 litres of water, to
which 140 kilograms of ammonia of 10 per cent. have been added.
By this operation the dyestuff is formed immediately according to the following
equation:-
SO, NH
N = NC E.
- N = NC. H
ONA
=C H
SO, Na + NH, Cl.
The colouring matter is precipitated by the addition of common salt, and the
dyestuff purified by redissolving and reprecipitating.
If I use for azotizing free amido-azo-benzol, instead of its mono-sulpho-acid, I
get a dyestuff which possesses a somewhat more yellowish, but withal extremely
clear shade. The homologues of amido-azo-benzol and their mono-sulpho-acids
give correspondingly bluer shades. Diazo-benzol and its homologues give with the
new alpha-mono-sulpho-acid reddish yellow tints or tones drawing to orange;
alphadiazo-napthalene, a blueish red; betadiazo-napthalene, a more brick red
dyestuff. Instead of the diazo compounds derived from benzol and its homologues,
toluol, xylol, and so forth, the diazo compounds obtained from the other members of
the benzol series, which are not homologues in the ordinary sense of the term, of
benzol, may be employed, as, for instance, the diazo compounds or derivatives of
ethyl-xylol, ethyl-benzol, ethyl-methyl-xylol, and other compounds of benzol and
its homologues, with other alcoholic residues, as also the diazo derivatives of the
said bodies (non-homologues with benzol) which are substituted once or oftener
with the sulpho group, all of which I comprehend in the general expression diazo
compounds or derivatives of the benzol series, as well as the diazo-azo derivatives
of the benzoles and napthaleno.

page_text: The alpha-mono-sulpho-acid of beta-napthol (in contrast to the mono-sulpho-acid
described by Schaefer) gives, when treated in aqueous solution with nitric acid,
nitro-products, the alkali salts of which are fine yellow dyestuffs or colouring
matters easily soluble in water.
In order to prepare the dyestuff or colouring matter which I call crocëin yellow,
I work in the following manner :-
10 kilograms of crystallized alpha-mono-sulpho-acid of beta-napthol are dissolved
in 20 kilograms of water, and after the spirit present in the crystals of the mono-
sulpho-acid has been evaporated or expelled by boiling, 15 kilograms of nitric acid
of about 50 per cent. are added at a temperature of 40° to 50° centegrade. After
standing for several days at a temperature of 30° to 40° the nitration is finished;
the liquid is neutralized with carbonate of potash, whereon the potassium salt of
the colouring matter precipitates as a yellow crystallized powder. It is obtained
pure by repeated crystallization.
I do not consider myself to be bound to the precise temperatures and quantities
of materials herein before mentioned, as they are susceptible of considerable variation,
without materially affecting the result.
Having now described and particularly ascertained the nature of my said
Invention, and the system, mode, or manner in or under which the same is or may
be used or practically carried into effect, I would observe in conclusion that what I
consider to be novel and original, and therefore claim as the Invention secured
to me by the hereinbefore in part recited Letters Patent is,―
First. The preparation, and also (separatim) the separation of the new isomeric
mono-sulpho-acid of beta-napthol, in manner herein before described, or in manner
substantially the same or similar.
Second. The preparation of the neutral soda salt of the said new isomeric acid
soluble in alcohol, herein before described.
Third. The preparation of colouring matters by the reaction of the said new
isomeric acid, or its said soda or other equivalent salt upon diazo or diazo-azo
derivatives or compounds of the benzol series, or of napthalene, or the sulpho
compounds thereof herein before mentioned, all in manner hereinbefore described:
Fourth. The preparation of nitro-products or derivatives of the said new isomerio
acid, as herein before described.
Fifth. The preparation of colouring matters from the said nitro products or
derivatives of the said new isomeric acid, as hereinbefore described.
In witness whereof, I, the said Joseph Anthony Dixon, have hereunto set
my hand and seal, this Eighteenth day of July, in the year of our Lord
One thousand eight hundred and eighty one.
JOSEPH ANTHONY DIXON. (L.S.)