Manufacture of Yellow Azo-dyestuffs Fast to Washing and Light.
Year: 1897

page_text: Date of Application, 22nd July, 1897
Complete Specification Left. 22nd Apr., 1898-Accepted, 11th June, 1898
Date of Application, 22nd July, 1897
Complete Specification Left. 22nd Apr., 1898-Accepted, 11th June, 1898
PROVISIONAL SPECIFICATION.
Manufacture of Yellow Azo-dyestuffs Fast to Washing and Light.
I, OLIVER IMRAY, of No. 28, Southampton Buildings, Chancery Lane, in the
County of London, Chartered Patent Agent, do hereby declare the nature of
this invention (which has been communicated to me from abroad by The
Farbwerke vormals Meister Lucius and Bruning, of Hoechst a/Main, in the
Empire of Germany, Chemical Manufacturers), to be as follows:-
It is known, that when diazobenzene reacts upon ethyl aceto acetate ethyl
benzeneazoaceto acetate is formed (see Meyer B. 10, 2075) and when it reacts
upon malonic acid ester benzeneazomalonic acid is formed (see Meyer, Berichte
21, 118; 24, 1241).
These and some similarly formed mixed azobodies have been several times the
subject of experiments, particularly with regard to their constitution. (Compare
Zublin, Berichte 11, 1417; Richter & Munzer, Berichte 17, 1920; Beyer & Claisen
Berichte 21, 1697.)
The aptitude of aliphatic bodies to form azo-bodies with diazo-compounds has
hitherto not been utilised.
According to the experiments of my foreign correspondents diazotised amido-
sulphonic acids produce, as a rule, respectively with the diketones, ketoneal-
dehydes and ketone acids, azo-compounds or hydrazones which mostly, however,
are deficient in tinctorial power and are consequently useless as dyestuffs.
They have found that, in a different way, very beautiful and useful, mostly
strong greenish-yellow, dyestuffs may be obtained from the diazo-compounds of
dehydrothio-toluidine (or xylidine) sulphonic acid, primuline sulphonic acid,
amido-azobenzoicsulphonic acid and from the tetrazo-compounds of sulphonated
diamido-diphenyl and diamidostilbene-derivatives.
The dyestuffs are chiefly for wool, some of them, however dye also vegetable
fibre, particularly the derivatives of sulphonated thio-bases and benzidene mono-
sulphonic acid, in neutral or alkaline solution on unmordanted cotton.
Their manufacture does not differ from that used for simple azo-dyestuffs.
The diketones are, wherever possible and before combining, brought into solution
with 1 molecule of caustic soda or are merely well mixed with the soda solution.
The latter method is advisable, for instance, in the case of malonic ester which
easily reacts in presence of free caustic alkali, as vide Pechmann Berichte 25, 3175,
and Bamberger Berichte 25, 3205, have shown.
The same dyestuffs containing sulphonic groups may likewise be obtained in
another way. For this purpose, the process starts from those bodies which form
the base of the above mentioned sulphonic acids. Benzidine for instance is tetrazo-
tised and combined with the diketone in a soda alcoholic solution and the yellow
body, insoluble in water, is sulphonated in the usual way with sulphuric acid
containing sulphuric anhydride. According to the degree of sulphonation,
products may be obtained which are identical with dyestuffs from a mono or
disulphonic acid.

page_text: This method is specially described in Example III.
EXAMPLE I.
343 kilos. of dehydrothiotoluidine sulphonate of sodium are diazotised in the
usual way. The suspended diazo-compound is while stirring run into a solution
of 13 kilos. of ethyl aceto acetate in 12 kilos. of soda-lye of 40° Bé and 500 litres
water, to which is added as much soda or sodium acetate as is requisite for
neutralizing the excess of hydrochloric acid and the formation of the sodium
salt.
The dyestuff thus formed dissolves with a greenish-yellow colour. The solution
is salted out after some stirring.
EXAMPLE II.
388 kilos. of benzidine disulphonate of sodium are dissolved with 14 kilos. of
nitrite of sodium in 500 litres of water. This solution is slowly run while stirring
into a mixture of 84 kilos. of hydrochloric acid of 19° Bé. and about 200 litres of
water at 10°--15° C.
After an hour and a half the emulsion thus obtained from the tetrazosulphonic
acid is run while rapidly stirring into an emulsion of 21 kilos. of acetylacetone
in a solution of 55 kilos. of soda in about 500 litres of water. The dyestuff thus
formed dissolves at first with a light yellow tint and then partly crystallises. On
addition of common salt, a complete separation is effected.
EXAMPLE III.
31 kilos. of ethyl aceto acetate are stirred together with a solution of 40 kilos.
of soda in about 600 litres of water in a cold state until the ethyl aceto acetate
has dissolved. Into this is run while rapidly stirring the tetrazodiphenyl
solution made from 184 kilos. of benzidine, prepared as usual. At once a body
separates out in fine yellow flakes, insoluble in soda solution and water, which is
identical with dibutanon acid ester-2-phenylhydrazone, described by Widekind
(Annalen 295, 333).
For the sulphonation 20 kilos. (or parts by weight) of this body are introduced
while rapidly stirring into 100 kilos. (or parts by weight) of fuming sulphuric
acid of 10 per cent. and finally heated up to 30° C. The mixture is poured on
ice salted out with common salt and the separated dyestuff is transformed as usual
into its sodium salt.
Dated this 22nd day of July 1897
COMPLETE SPECIFICATION.
Manufacture of Yellow Azo-dyestuffs Fast to Washing and Light.
I, OLIVER IMRAY, formerly of No. 28, Southampton Buildings, but now of
Birkbeck Bank Chambers, Southampton Buildings, Chancery Lane, in the County
of London, Chartered Patent Agent, do hereby declare the nature of this invention
(which has been communicated to me from abroad by The Farbwerke vormals
Meister Lucius and Bruning, of Hoechst a/Main, in the Empire of Germany,
Chemical Manufacturers), and in what manner the same is to be performed to be
particularly described and ascertained in and by the following statement:-
-
It is known, that when diazobenzene reacts upon aceto-acetic-acid ether
benzeneazo-aceto-acetic-acid-ether is formed (see Meyer B. 10, 2075) and when it

page_text: reacts upon malonic acid ether, benzeneazomalonic acid is formed (see Meyer,
B. 21, 118; 24, 1241).
These and some similarly formed mixed azo bodies have been several times the
subject of experiments, particularly with regard to their constitution. (Compare
Zublin Berichte 11, 1417; Richter & Munzer, Berichte 17, 1920; Beyer & Claisen,
Berichte 21, 1697.)
The aptitude of aliphatic bodies to form azo-bodies with diazo-compounds has
hitherto not been utilised.
According to the experiments of my foreign correspondents diazotised amido-
sulphonic acids produce, as a rule, respectively with the B-diketones, B-ketoneal-
dehydes and the ethers and anilides of ẞ-ketone acids, azo-compounds or hydra-
zones which mostly, however, are deficient in tinctorial power and are consequently
useless as dyestuffs.
They have found that, in a different way, very beautiful and useful, mostly.
strong greenish yellow, dyestuffs may be obtained from the diazo compounds of
dehydrothio-toluidine (or xylidine) sulphonic acid, primuline sulphonic acid,
amido-azo-benzene sulphonic acids and from the tetrazo compounds of sulphonated
diamido-diphenyl and diamido-stilbene derivatives.
The dyestuffs are chiefly for wool, some of them, particularly the derivatives of
sulphonated thio-bases and benzidine monosulphonic acid dyeing also in neutral
or alkaline solution unmordanted cotton.
Their manufacture does not differ from that used for simple azo-dyestuffs.
The diketones are, wherever possible, before combining brought into solution
with 1 molecule of caustic soda or are merely well mixed with the soda solution.
The latter method is advisable, for instance, in the case of malonic ether which
easily reacts in presence of free caustic alkali, as Pechmann Ber. 25, 3175, and
Bamberger Ber. 25, 3205, have shewn.
The same dyestuffs containing sulphonic groups may likewise be obtained in
another way. For this purpose, the process starts from those bodies which form
the base of the above mentioned sulphonic acids.
Benzidine, for instance, is tetrazotised and combined with the diketone in
a soda solution and the yellow body, insoluble in water, is sulphonated in
the usual way with sulphuric acid containing sulphuric anhydride. According to
the degree of sulphonation, products may be obtained which are identical with dye-
stuffs from a mono- or disulphonic acid. This method is specially described in
Example III.
EXAMPLE I.
343 kilos. of dehydrothiotoluidine-sulphonate of sodium are diazotised in the
usual way. The suspended diazo-compound is, while stirring, run into a solution
of 13 kilos. of aceto-acetic acid ether in 12 kilos. of caustic soda lye of 40° Bé. and
500 litres of water, to which is added as much soda or sodium acetate as is requisite
for neutralising the excess of hydrochloric acid and for the formation of the sodium
salt.
The dyestuff thus formed dissolves with a greenish yellow colour. The solution
is salted out after some stirring.
EXAMPLE II.
388 kilos. of benzidine disulphonate of sodium are dissolved with 14 kilos. of
sodium nitrite in 500 litres of water. This solution is slowly run, while stirring,
into a mixture of 84 kilos. of hydrochloric acid of 19° Bé. and about 200 litres of
water at 10-15° C.
After an hour and a half, the emulsion thus obtained from the tetrazosulphonic
acid is run, while rapidly stirring, into an emulsion of 21 kilos. of acetylacetone
in a solution of 55 kilos. of soda in about 500 litres of water. The dyestuff thus
formed dissolves at first with a light yellow tint and then partly crystallises. On
addition of common salt, a complete separation is effected.

page_text: EXAMPLE III.
31 kilos. of aceto-acetic-acid-ether are stirred together with a solution of 40 kilos.
of soda in about 600 litres of water in a cold state, until the aceto-acetic-acid-ether
has dissolved. Into this is run, while rapidly stirring, the tetrazodiphenyl
solution made from 184 kilos. of benzidine, prepared as usual. At once a body
separates out in fine yellow flakes, insoluble in soda solution and water, which is
identical with dibutanon acid ether-2-phenylhydrazone, described by Widekind
(Annalen 295, 333).
For the sulphonation, 20 kilos. (or parts by weight) of this body are introduced,
while rapidly stirring, into 100 kilos. (or parts by weight) of fuming sulphuric
acid of 10 per cent. and finally heated up to 30° C. The mixture is poured on
ice salted out with common salt and the separated dyestuff is transformed as usual
into its sodium salt.
Having now particularly described and ascertained the nature of this in-
vention and in what manner the same is to be performed I declare that what I
claim is:
1. The manufacture of yellow-greenish dyestuffs by diazotising the sulphonic
acids of dehydrothiotoluidine, dehydrothioxylidine, primuline, amidoazobenzene,
benzidine, tolidine, ethoxybenzidine, benzidinesulphone, diamidostilbene and com-
bining the products with B-diketones, ẞ-ketonealdehydes, ẞ-ketone-acid-ethers
and B-ketone-acid-anilides.
2. The modified manufacture of the dyestuffs by sulphonating the products
obtained by the reaction of diazotised dehydrothiotoluidine, dehydrothioxylidine,
primuline, amido-azobenzene benzidine, tolidine, ethoxybenzidine, benzidine-
sulphone, diamidostilbene upon B-diketones, ẞ-ketonealdehydes, B-ketone-acid-
ethers.
3. The colouring matters manufactured as above set forth.