Improvements in the Process of Combining certain Diazo Compounds with Phenol, Cresol, Naphthol, and the Sulpho-
Year: 1884

page_text: Improvements in the Process of Combining certain Diazo
Compounds with Phenol, Cresol, Naphthol, and the Sulpho-
PROVISIONAL SPECIFICATION.
1, ALEXANDER MELVILLE CLARK, of the firm of A. M. and Win. Clark, of
53, Chancery Lane, in the County of Middlesex, Fellow of the Institute of Patent
Agents, do hereby declare the nature of the said Invention for IMPROVEMENTS
IN THE PROCESS OF COMBINING CERTAIN DIAZO COMPOUNDS WITH PHENOL CRESOL
NAPHTHOL AND THE SULPHOACIDS" OF THESE BODIES FOR THE PRODUCTION OF
COLORING MATTERS a communication to me from abroad by Wirth and Co acting
as Agents for Rudolph Krügeuer and the Farbfabrik vorm Brönner all of Frankfort
on-the-Main in the Empire of Germany to be as follows:-
The process hitherto used for combining Diazo compounds with Phenols and
their Sulphoncids is as follows :— The Diazo compounds are allowed to flow into a
solution of the Oxy-bodies kept cool with ice and also alkaline up to the close of
the operation.
In complete contradistinction to this method, it has been observed that those
diazo compounds that withstand decomposition for some time at the ordinary
temperature, as for instance the Diazonaphthalin Sulphoacid (from Naphthoic
acid) and the Diazobenzol monosulphoncid, have the remarkable property of uniting
with both the naphthols, and even with Phenol, if the last mentioned bodies are
dissolved in acetic acid by addition of acetate of soda; and this takes place with
good results as regards the output. One can obtain for instance from Betanaphthol
with both diazo compounds a large output of coloring matter which moreover
dyes purer than the same body obtained by the ordinary method. The reaction
is applicable to many other less stable diazo compounds. In most cases however
the technical value is doubtful owing to bad results due to the unstable property
of the diazo compounds. Therefore by this process the formation of the coloring
matter stands in direct proportion to the stable property of the particular diazo
compound. One great advantage of this improved process is the doing away with
the use of ice, the work being performed at a raised temperature otherwise the
reaction in the acetic acid solution does not take place.
The molecules of the coloring matter obtained by this method seem to be
differently linked to those obtained by the known method. For instance, the
coloring matters made from diazonaphthalinesulphoacid (from naphthoic acid) and
from Beta-naphthol, show deviations from those made in the cold and in alkaline

page_text: solutions and made from the same components. The first possesses a somewhat
more yellow tinge and the great advantage over the other of setting on the wool
much slower.
The following is a description of a few of the methods by which the coloring
matters, named as under, are obtained :-
Method 1. 10 kilogrammes Naphthoic acid are diazotised in the usual way, the
somewhat insoluble diazo compound separated by filtration and freed from water
as much as possible.
Further 6.5 kilogrammes Betanaphthol and 6 kilogrammes acctate of soda
are dissolved in about 100 litres acetic acid of 20 to 30 % at a temperature of
70° to 90° C. and the diazo compound which has been separated by filtration is
added gradually, at the same time stirring. The temperature thereby rises to
.70° to 90° C. When the reaction is finished a little common salt is added and the
whole is allowed to cool whereby the coloring matter separates out in a crystalline
form. It is then filtered and the filtrate distilled in a suitable apparatus. The
distilled acetic acid may be used at once for a second operation. The acetic acid
being with difficulty volatilised the losses are scarcely worth mentioning.
well pressed coloring matter is purified by known methods.
The
Method 2. The same quantity of diazo compound as given in Method I is added
under stirring to a solution of 16 kilogrammes of Betanaphtholsodasulphonate and
6 kilogrammes acetate of soda in 50 or 60 litres of acetic acid from 20 to 30% at
a temperature of 70° to 90° C. It is then allowed to cool, salted out, and filtered
whereby the acetic acid is recovered. In both methods a stronger acetic acid may
be used whereby proportionately less must be taken. For instance naphthol
dissolves easily in double the quantity of acetic acid of 50% by warming. In
both methods amidoazobenzol monosulphoacid or the diazoazobenzolmonosulphoacid
can be taken instead of Naphthoic acid. The reaction taking place by this method
is expressed by the following formula

page_text: I, ALEXANDER MELVILLE CLARK, of the firm of A. M. and Win. Clark, of
53, Chancery Lane, in the County of Middlesex, Fellow of the Institute of Patent
Agents, do hereby declare the nature of the said Invention for
THE
IN
PROCESS
CRESOL, NAPIITHOL,
COMBINING
OF
AND
THE
IMPROVEMENTS
DIAZO
OF
COMPOUNDS WITH
BODIES
THESE
CERTAIN
SULPHO-ACIDS
PHENOL,
FOR THE
PRODUCTION OF COLORING MATTERS," (a communication to me from abroad by
Wirth and Co acting as Agents for Rudolph Krügener and The Farbfabrick Vorm.
Brönner, all of Frankfort-on-the-Main, Germany,) and in what manner the same
is to be performed, to be particularly described and ascertained in and by the
following statement :—
The process hitherto used for combining Diazo compounds with Phenols and
their Sulphoacids, is as follows:-The Diazo compounds are allowe i to flow into a
solution of the Oxy-bodies kept cool with ico and also alkaline up to the close of
the operation.
In complete contradistinction to this method it has been observed that those
diazo compounds that withstand decomposition for some time at the ordinary
temperature, as for instance the diazonaphthalin sulpho-acid (from naphthionic
acid) and the diazobenzol monosulphoacid, have the remarkable property of uniting
with both the naphthols and even with phenol, if the last mentioned bodies are
dissolved in acetic acid by addition of acetate of soda; and this takes place with
good results as regards the output. One can obtain for instance from betanaphthol
with both dinzo compounds a large output of coloring matter which moreover dyes
The reaction is
purer than the same body obtained by the ordinary method.
applicable to many other less stible diazo compounds. In most cases however the
technical value is doubtful owing to bad results due to the unstable property of
the diazo compounds. Therefore by this process the formation of the coloring
matter stands in direct proportion to the stat le property of the particular diazo
compound. One great advantage of this improved process is the doing away with
the use of ice, the work being performed at a raised temperaturo, otherwise tho
reaction in the acetic acid solution does not take place.
The molecules of the coloring matter obtained by this method seem to bo
differently linked to those obtained by the known method. For instance, tho
coloring matters made fron diaz naphthalinesulphoacid (from naphthoic acid) and
from Betanaphthol, show deviations from those made in the cold, and in alkaline
solutions and made from the same components. The first possesses a somewhat
more yellow tinge and the great advantage over the other of setting on the wool
much slower.

page_text: The following is a description of a few of the methods by which the coloring
matters, named as under, are obtained.
Method 1. 10 kilogrammes naphthionic acid are diazotised in the usual way, the
somewhat insoluble diazo compound separated by filtration and freed from water
as much as possible.
Further, 6.5 kilogrammes letanaphthol and 6 kilogrammes acetate of soda are
dissolved in about 100 litres acetic acid of 20 to 30 per cent at a temperature of
70° to 90° C. and the diazo compound which has been separated by filtration is
added gradually, at the same time stirring. The temperature thereby rises to
70° to 90° C. When the reaction is finished, a little common salt is added and the
whole is allowed to cool, whereby the coloring matter separates out in a crystalline
form. It is then filtered and the filtrate distilled in a suitable apparatus. The
distilled acetic acid may be used at once for a second operation. The acetic acid
being with difficulty volatilised, the losses are scarcely worth mentioning. The
well pressed coloring matter is purified by known methods.
Method 2. The same quantity of diazo compound as given in Method 1 is added
under stirring to a solution of 16 kilogrammes of betanaphtholsodasulphonate
and 6 kilogrammes acetate of soda in 50 or 60 litres of acetic acid from 20 to
30 per cent at a temperature of 70° to 90° C. It is then allowed to cool, salted
out, and filtered, whereby the acetic acid is recovered. In both methods a stronger
acetic acid may be used, whereby proportionately less must be taken.
instance, naphthol dissolves easily in double the quantity of acetic acid of 50 per
cent by warming. In both methods amidoazobenzolmonosulphoacid or the
diazoazobenzosulphoacid can be taken instead of naphthionic acid. The
reaction taking place by this method is expressed by the following formula:—
For
Oxynaphthalinazonaphthalinsodasulphonate + acetic acid.
Those bodies best suited for the preparation of azodyes by these methods are as
follows:-
I. Diazonaphthalinsulphoacid (from naphthionic acid) acts upon phenol, cresol,
betanaphthol, alphanaphthol, betanaphtholsodadisulphonate, or mixtures of both
salts, betanaphtholsodatrisulphonate and alphanaphtholalphasodasulphonate (from
diazonaphthalinsulphoacid by boiling).
II. Diazobenzolmonosulphoacid acts upon betanaphthol, betanaphtholsodadi-
sulphonate, and betanaphtholsodatrisulphonate. Instead of dissolving the naphthol
in acetic acid and adding acetate of soda to this solution, the following course may
be taken-Betanaphtholsodium is mixed with so much acetic acid so as on the
one hand to form acetate of soda, and on the other hand that acetic acid in excess
is still present; the betanaphthol separating out of the solution in a very fine state
of division. To this mixture of finely divided betanaphthols, acetic acid and
acetate of soda, the diazo compound separated by filtration is added at the common
temperature and intimately mixed. It is then heated to about 50° C. whereupon
both components unite to a crystalline coloring matter.
Having now particularly described and ascertained the nature of the said
Invention and in what manner the same is to be performed, I declare that what
I claim is
1st The herein described process of combining alphadiazonaphthalinsulphoacid,
diazoazobenzolmonosulphoacid and similar stable diazo compounds with phenol,
cresol, naphthol, and their sulpho acids in a solution of acetic acid by the addition
of an acetate at a raised temperature.

page_text: 2nd The herein described process of combining the same substances by mixing
the diazo compounds with very finely divided naphthol in the presence of acetate
of soda and an excess of acetic acid, at the same time warming the mixture.
A. M. CLARK.
By A. M. & W Clark,
53, Chaucery Lane, London.