Manufacture of Aldehydonaphtolsulphonic, Aldehydonaphtolcar- boxylic, and Aldehydonaphtolsulphocarboxylic Acids, and of New Blue and Green Colouring Matters or Dyes therefrom.
Year: 1897

page_text: Date of Application, 24th Aug., 1897
Complete Specification Left, 9th May, 1898-Accepted, 30th July, 1898
Manufacture of Aldehydonaphtolsulphonic, Aldehydonaphtolcar-
boxylic, and Aldehydonaphtolsulphocarboxylic Acids, and of
New Blue and Green Colouring Matters or Dyes therefrom.
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, Switzerland,
Colour Manufacturers, to be as follows:-
The only oxyaldehyde of the naphtaline series hitherto known has been the
B1 oxy a 1 naphtaldehyde obtained by G. Kaufmann after the method of obtaining
aldehydes invented by Reimer.
This aldehyde being obtainable only in very small quantity together with a large
number of bye products, it was not at all probable that Reimer's method would
be of any value for the naphtaline series, the inore so as Kaufmaun did not succeed
in obtaining an aldehyde deriving from a naphtol.
Reimer's method not having hitherto been used for obtaining aldehydes of
oxysulphonic acids, it could not be foreseen how the sulpho acids of the naphtols
would behave when boiled with chloroform and caustic soda. Quite unexpectedly
my correspondents have found that a whole series of sulpho acids of the a naphtol
and of the ẞ naphtol as well as the ẞ1 naphtol ẞ2 carboxylic acid and the
B1 naphtol ẞ2 carboxylic ẞ3 sulpho acid can be very easily transformed into the
corresponding aldehydonaphtolsulpho acids, aldehydonaphtolcarboxylic acid, and
aldehydonaphtolsulphocarboxylic acid, which can be separated as sodium or barium
salts or as free acids. All these acids distinguish themselves from the starting
materials by the property of furnishing with aromatic mono-amines and diamines
in acid solution intensely coloured yellow and red so-called benzylidene combina-
tions.
By condensation of these aldehydonaphtolsulpho acids, aldehydonaphtolcar-
boxylic acid and aldehydonaphtolsulphocarboxylic acid with mono and dialkylated
or benzylated aromatic amines and oxidation of the so obtained leukosulpho acids
in acidulated or alkaline solution, a large number of green and blue acid colouring
matters are obtained which are remarkable for their fastness against the action of
alkali and belong to the diphenylnaphtylmethane series.
EXAMPLE I.
17.5 kilos, of ẞ naphtolmonosulphonate of sodium (Schafer's salt) of 70 per
cent. is dissolved in 150 liters of boiling water and a sufficient quantity of chloride
of barium added in order to precipitate every trace of sulphuric acid.
The cooled
solution filtered off from the sulphate of barium has now added to it 25 kilos. of
caustic soda of 45° Bé, and 8 kilos. of chloroform and heated up to the boiling
point of the chloroform in a kettle fitted with a reversed refrigerating tube and
with a stirring apparatus in rapid motion. After two hours when the chloroform
has disappeared the temperature is raised to the boiling point of the alkaline
ונס..מ

page_text: same way as the other aldehydonaphtolsulphonic and carboxylic acids, but this one
is distinguished by a particularly bright shade.
EXAMPLE VII.
47 kilos. of ẞ1 oxy a naphtaldehyde B2 B3 disulphonate of barium finely
ground is heated in an enamelled kettle, fitted with a reversed refrigerating tube
and with a stirring apparatus, with 40 kilos. of diethylaniline, 40 kilos. of alcohol
and 15 kilos. of concentrated sulphuric acid during 30 hours. The mass is then
poured into diluted hydrochloric acid which dissolves the surplus diethylaniline;
the leukodisulphonic acid remains as barium salt insoluble and finely crystallised; it
is filtered, washed with diluted hydrochloric acid, and transformed into the easily
soluble sodium salt by boiling with a solution of carbonate of soda. The boiling
is only stopped when all emanations of diethylaniline have disappeared, then the
carbonate of barium is filtered off and the filtered solution diluted up to 1000 liters.
Into this solution containing the leukodisulphonate of sodium is poured at a
temperature of 10° C., whilst constantly stirring, a solution of permanganate
of potassium of 1 per cent. as long as the formation of the colouring matter is still
increasing. By an addition of salt to the solution filtered from the binoxide of
manganese, the colouring matter is completely precipitated as a crystalline powder
of copper coloured lustre.
It is easily soluble in water, with a blue shade not
changing by addition of ammonia or caustic soda but becoming green by acids and
dyeing wool in a green shade from an acid bath.
EXAMPLE VIII.
If in the preceding example the diethylaniline is replaced by the dimethyl-
aniline, the process is somewhat different. Instead of treating the product of
condensation first by hydrochloric acid, it is at once heated with a solution
of carbonate of soda and the surplus of dimethylaniline driven off by means
of steam. The cooled and filtered solution containing the leukodisulphonic acid is
diluted up to 1500 liters, acidulated with hydrochloric acid and oxidised, whilst
stirring, by means of 66 kilos. of peroxide of lead in 36.5 per cent. paste which is
rapidly added.
After two hours the sulphate of lead is filtered and the colouring
matter precipitated by addition of salt; it forms a violet powder of copper coloured
lustre and has the same properties as the ethylated product.
EXAMPLE 1X.
Exactly the same procedure obtains if the aldehydo-ẞ-naphtodisulphonic acid
The
is replaced by the 8 1-oxy-a 1-naphtaldehyde-ß 3-monosulphonic acid.
colouring matter thus obtained differs from that of the preceding Example VIII
only by a lower degree of solubility of the free acid, an alkaline solution of it being
precipitated in blue flocks upon acidulation.
Dated this 24th day of August 1897.
THOMAS K. SHILLITO,
89, Chancery Lane, London, W.C.

page_text: Manufacture of Aldehydonaphtolsulphonic, Aldehydonaphtolcar-
boxylic, and Aldehydonaphtolsulphocarboxylic Acids, and of
New Blue and Green Colouring Matters or Dyes therefrom.
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 Manu-
facturers, to be particularly described and ascertained in and by the following
statement :-
The only oxyaldehyde of the naphtaline series hitherto known has been the s 1
oxy a 1 naphtaldehyde obtained by G. Kauffmann after the method of obtaining
aldehydes invented by Reimer.
This aldehyde being obtainable only in a very small quantity together with a
large number of bye products, it was not at all probable that Reimer's method
would be of any value for the naphtaline series, the more so as Kauffmann did not
succeed in obtaining an aldehyde deriving from a naphtol.
Reimer's method not having hitherto been used for obtaining aldehydes of
oxysulphonic acids, it could not be foreseen how the sulpho acids of the naphtols
would behave when boiled with chloroform and caustic soda. Quite unexpectedly
my correspondents have found that a whole series of sulpho acids of the a naphtol
and of the s naphtol as well as the #1 naphtol s 2 carboxylic acid and the
8 1 naphtol s 2 carboxylic # 3 sulpho acid can be very easily transformed into the
corresponding aldehydonaphtolsulpho acids, aldehydonaphtolcarboxylic acid, and
aldehydonaphtolsulphocarboxylic acid, which can be separated as sodium or
barium salts or as free acids. All these acids distinguish themselves from the
starting materials by the property of furnishing with aromatic monoamines and
diamines in acid solution, intensely coloured yellow and red so called benzylidine
combinations.
By condensation of these aldehydonaphtolsulpho acids, aldehydonaphtolcarboxylic
acid and aldehydonaphtolsulphocarboxylic acid with mono and dialkylated or
benzylated aromatic amines and oxidation of the so obtained leukosulpho acids
in acidulated or alkaline solution, a large number of green and blue acid colouring
matters are obtained which are remarkable for their fastness against the action of
alkali and belonging to the diphenylnaphtylmethane series.
В
EXAMPLE I.
17.5 kilos. of B naphtolmonosulphonate of sodium (Schäfer's salt) of 70 per cent.
is dissolved is 150 litres of boiling water and a sufficient quantity of chloride of
barium added in order to precipitate every trace of sulphuric acid. The cooled
solution filtered off from the sulphate of barium has now added to it 25 kilos. of
caustic soda of 45° Bé. and 8 kilos. of chloroform, and heated up to the boiling
point of the chloroform in a kettle fitted with a reversed refrigerating tube and
with a stirring apparatus in rapid motion. After two hours when the
chloroform has disappeared, the temperature is raised to the boiling point
of the alkaline solution, which is then neutralised, while hot, with purified
hydrochloric acid and precipitated by means of a solution of 8 kilos. of
chloride of barium, a surplus of ammonia being finally added. The barium salt
of the 1 oxy a 1 naphtaldehyde 8 3 monosulphonic acid, which separates at once

page_text: В
this, a solution of common salt. The sodium salt of the oxynaphtoic sulphonic acid
which now is precipitated, is filtered off. By addition of hydrochloric acid to the
filtered solution the a 1 aldehydo g 1 g 2 oxynaphtoic 8 3 sulphonic acid is obtained
in the form of a yellow crystalline precipitate. A solution of this acid brought
together with chlorhydrate of paraphenylendiamine gives a blueish red precipitate
in the same way as the other aldehydonaphtolsulphonic and carboxylic acids, but
this one is distinguished by a particularly bright shade.
EXAMPLE VII.
В
47 kilos. of gl oxy a 1 naphtaldehyde 8 2 8 3 disulphonate of barium finely ground
is heated in an enamelled kettle, fitted with a reversed refrigerating tube and with
a stirring apparatus, with 40 kilos. of diethylaniline, 40 kilos. of alcohol and
15 kilos. of concentrated sulphuric acid during 30 hours. The mass is then poured
into diluted hydrochloric acid which dissolves the surplus of diethylaniline; the
leuko-disulphonic acid remains mixed with barium sulphate as an insoluble and
finely crystallised precipitate; it is filtered, washed with diluted hydrochloric acid,
and transformed into the easily soluble sodium salt by boiling with a solution of
carbonate of soda. The boiling is only stopped when all emanation of diethylaniline
has disappeared, then the carbonate of barium is filtered off and the filtered solution
diluted up to 1000 liters. Into this solution containing the leukodisulphonate of
sodium is poured at a temperature of 10° C. whilst constantly stirring, a solution of
permanganate of potassium of 1 per cent. as long as the formation of the colouring
matter is still increasing. By an addition of salt to the solution filtered from the
binoxide of manganese, the colouring matter is completely precipitated as a
crystalline powder of copper coloured lustre. It is easily soluble in water, with a
blue shade not changing by addition of ammonia or caustic soda but becoming
green by acids and dyeing wool in a green shade from an acid bath.
EXAMPLE VIII.
If in the preceding example the diethylaniline is replaced by the dimethylaniline
the process is somewhat different. Instead of treating the product of condensation
first by hydrochloric acid, it is at once heated with a solution of carbonate of soda
and the surplus of dimethylaniline driven off by means of steam. The cooled and
filtered solution containing the leukodisulphonic acid is diluted up to 1500 liters,
acidulated with hydrochloric acid and oxidised, whilst stirring, by means of 66 kilos.
of peroxide of lead in 36.5 per cent. paste which is rapidly added. After two hours
the sulphate of lead is filtered and the colouring matter precipitated by addition of
salt;
it forms a violet powder of copper coloured lustre and has the same properties
as the ethylated product.
EXAMPLE IX.
Exactly the same procedure is observed if the aldehyd s naphtoldisulphonic
acid is replaced by the s1 oxy a 1 naphtaldehyde 83 monosulphonic acid. The
colouring matter thus obtained differs from that of the preceding Example VIII
only by a lower degree of solubility of the free acid, an alkaline solution of it being
precipitated in blue flocks upon acidulation.
Having now particularly described and ascertained the nature of said in-
vention, and in what manner the same is to be performed, I declare that what I
claim is:
1. The production of aldehydonaphtolsulpho acids, aldehydonaphtolcarboxylic
acid and aldehydonaphtolsulphocarboxylic acid by by boiling of alpha or beta
naphtolmono, di, and trisulpho acids, a 1 naphtol s 2 carboxylic acid and s naphtol
83 sulphog 2 carboxylic acid in aqueous solution with chloroform in presence of

page_text: alkalies, and separation of the so formed aldehydo acids as sodium or barium salts
or as free acids, substantially as described.
2. The production of new green to blue acid colouring matters fast to alkalies
and belonging to the diphenylnaphtylmethane group, consisting in the con-
densation of the aldehydosulpho and carboxylic acids of the naphtols, obtainable in
the manner referred to in Claim 1, with mono and dialkylated or benzylated
aromatic amines and oxidation of the resulting leuco compounds in acidulated or
alkaline solution to the dye stuffs, substantially as described.
Dated this 9th day of May 1898
THOMAS R. SHILLITO,
89, Chancery Lane, London, W.C.