Production of New Colouring Matters or Dyes from Paradinitrodi- benzyldisulpho Acid.
Year: 1897

page_text: Date of Application, 17th Aug., 1897
Complete Specification Left, 16th May, 1898-Accepted, 17th Aug., 1898
PROVISIONAL SPECIFICATION.
Production of New Colouring Matters or Dyes from Paradinitrodi-
benzyldisulpho Acid.
I, THOMAS RICHARD SHILLITO, of 89, Chancery Lane, London, W.C., Engineer
and Patent Agent, do hereby declare the nature of this invention, a communication
to me from abroad by Messieurs John Rudolph Geigy & Co., of Basle, Switzer-
land, Colour Manufacturers, to be as follows
This invention relates to the production of new colouring matters from p-dinitro-
dibenzyldisulpho acid.
If paranitrotoluolsulpho acid is treated with oxidizing agents in presence of
caustic alkalies, such for instance as hypochlorites, hypobromites or persulphates,
a salt of the paradinitrodibenzyldisulpho acid is formed which separates as a white
or scarcely yellow coloured precipitate.
EXAMPLE I.
12 kilos. of paranitrotoluol sulphonate of sodium is dissolved in 50 liters of hot
water to which is then added 100 liters of a solution containing 3 per cent. of
hypochlorite of sodium and 60 kilos. of caustic soda lye of 40° Beaumé. The
mass is then heated to from 70° to 75° Celsius whilst stirring for a short time and
then mixed with ice in order to bring the temperature down to about 40° Celsius.
The paradinitrodibenzyl disulphonate of sodium separates as a firm crystalline
powder which is filtered, pressed, and dried.
Yellow to orange colouring matters may be obtained by treating the paradinitro-
dibenzyldisulpho acid with caustic soda alone or under simultaneous addition of
reducing agents such as powder of zinc, sulphide of alkali, ethylalcohol, methyl-
alcohol, glycerine, formaldehyde, glucose, or with hydrazines such as phenyl-
hydrazine, diamide. The reduction may likewise be carried out with ammonia and
powder of zinc.
EXAMPLE II.
A solution of 24 kilos. of dinitrodibenzyldisulphonate of sodium in 300 liters of
hot water has added to it 50 kilos. of caustic soda lye of 40° Beaumé and treated
for about half an hour at a temperature of 80° Celsius, then the mass is nearly
neutralised by hydrochloric acid and the colouring matter filtered off; it dyes un-
mordanted cotton in greenish yellow shades. By addition of alcohol the above
reaction is accelerated.
The colouring matter turns to orange by addition of a reducing agent. The
reduction may also be carried out with the yellow colouring matter of this example
as described in the following example.
EXAMPLE III.

page_text: Example II. is dissolved in 300 liters of boiling water, then is added 80 kilos. of
ammonia of 22 per cent. and 12 kilos. of powder of zinc. The filtered solution is
precipitated by hydrochloric acid and the colouring matter filtered, washed,
dissolved with carbonate of soda and evaporated.
New colouring matters are obtained if paradinitrodibenzyldisulpho acid or the
colouring matter of Example II. are brought into reaction with the following
substances in presence of caustic soda lye :-Ortho, meta, or paraphenylendiamine,
ortho, meta, or paratoluylendiamine, benzidine, methylbenzidine, tolidine, ethoxy-
benzidine, diamisidine, diamidostilbene, diamidostilbendisulpho acid, 1·4 naphtyl-
endiamine, ortho, meta, or paraamidophenol or amidocresols, paraamidosalicylic
acid, dehydrothioparatoluidinesulpho acid, primuline, dehydrothiometaxylidinesulpho
acid, dehydrothio pseudocumidinesulpho acid, the sulpho acids of the thiobenzenylic
bases which are obtained by reaction of sulphur upon mixtures of aniline, para-
toluidine, metaxylidine, or pseudocumidine, the sulpho acid of amidobenzenylortho-
amidothiophenol and finally aniline and its homologues as ortho, meta, and
paratoluidine, xylidine, cumidine and their nitro compounds.
The colouring matters thus obtained yield upon unmordanted cotton, yellow,
orange, or brown shades. By a further oxidation in alkaline solution with, for
instance, hypochlorites, hypobromites or persulphates, they can be transformed
into colouring matters of more yellowish or greenish yellow shade. A similar
result is obtained by alkaline oxidation of the colouring'matter of Example II.

page_text: EXAMPLE VIII.
36 kilos. of the colouring matter obtained from 24 kilos. of paranitrotoluolsulphonate
of sodium and 12 kilos. of dehydrothioparatoluidinesulphonate of sodium with
caustic soda lye at the temperature of boiling water is treated for a short time
with 300 liters of a solution containing 3 per cent. of hypochlorite of sodium, and
the colouring matter thus obtained is filtered and dried. It dyes unmordanted
cotton in yellow shades.
D
181 .
1007
THOMAS R. SHILLITO,
89, Chancery Lane, London, W.C.
Production of New Colouring Matters or Dyes from Paradinitrodi-
benzyldisulpho Acid.
I, THOMAS RICHARD SHILLITO, of 89, Chancery Lane, London, W.C., Engineer and
Patent Agent, do hereby declare the nature of this invention and in what
manner the same is to be performed, a communication to me from abroad by
Messieurs John Rudolph Geigy & Co., of Basle, Switzerland, Colour Manufacturers,
to be particularly described and ascertained in and by the following statement :--
This invention refers to the production of new colouring matters from para-
dinitrodibenzyldisulpho acid.
New colouring matters are obtained if paradinitrodibenzyldisulpho acid, or the
colouring matter obtained by heating dinitrodibenzyldisulphonate of sodium in
watery solution with caustic soda lye for half an hour at a temperature of
80 C., are brought into reaction with the following substances in presence
of caustic soda lye -Ortho, meta, or paraphenylenediamine, ortho, meta,
or paratoluylenediamine, benzidine, methylbenzidine, tolidine, ethoxybenzidine,
dianisidine, diamidostilbene, diamidostilbendisulpho acid, 14 naphtyleu-
diamine, ortho, meta, or paraamidophenol or amidocresols, paraamidosalicylic
acid, dehydrothioparatoluidinesulpho acid, primuline, dehydrothiometaxyli-
dinesulpho acid, dehydrothiopseudocumidinesulpho acid, the sulpho acids of
the thiobenzenylic bases which are obtained by reaction of sulphur upon
mixtures of aniline, paratoluidine, metaxylidine, or pseudocumidine, the sulpho
acid of amidobenzenylorthoamidothiophenol and finally aniline and its homologues
as ortho, meta, and paratoluidine, xylidine, cumidine and their nitro compounds.
The colouring matters thus obtained yield upon unmordanted cotton, yellow,
orange or brown shades. By a further oxidation in alkaline solution with, for
instance, hypochlorites, hypobromites or persulphates, they can be transformed
into colouring matters of more yellowish or greenish yellow shade. A similar
result is obtained by alkaline oxidation of the colouring matter obtained by
heating dinitrodibenzyldisulphonate of sodium in watery solution with caustic
soda lye for half an hour at a temperature of 80° C.

page_text: EXAMPLE II.
24 kilos. of the colouring matter obtained by heating dinitrodibenzyldisulphonate
of sodium in watery solution with caustic soda lye for half an hour at a temperature
at 80° C., are dissolved in 300 liters of boiling water, then 14 kilos. of sulphate
of benzidine in paste and 50 kilos. of caustic soda lye are added and the procedure 5
is then the same as that described in Example I.

page_text: 2. The process for the production of new colouring matters by alkylation or
benzylation of the colouring matters referred to in Claim 1, which are produced by
means of p-amidophenol, substantially as described.
3. The new colouring matters obtained according to the preceding Claims 1
and 2, substantially as described.
1
1000