Improvements in the Production of Diamidonaphtalene-sulpho Acid and Amidonaphtol Sulpho Acid, and Coloring Matters from the latter.
Year: 1893

page_text: Date of Application, 2nd Mar., 1893
Complete Specification Left, 1st Dec., 1893-Accepted, 6th Jan., 1894
PROVISIONAL SPECIFICATION.
Improvements in the Production of Diamidonaphtalene-sulpho Acid
and Amidonaphtol Sulpho Acid, and Coloring Matters from the
latter.
I, SYDNEY PITT, of Sutton, in the County of Surrey, Gentleman, (a communi-
cation to me from abroad by Leopold Cassella & Co., of Frankfort on Main, in the
Empire of Germany, Manufacturing Chemists,) do hereby declare the nature of
this invention to be as follows:-
In the British Specification 697201 it has been described, how the naplitalcue-
beta-monosulpho acid may be transformed into a 1. 8. diamido compound.
We have now applied the same process to the naphtalene-alpha-sulpho acid and
have obtained an acid, of the constitution:
Derore.
The formation of the mononitro acid precedes naturally the formation of the
dinitro acid. Whilst the naphtalene-beta-sulpho acid produces principally the
1. 6. mononitro compound, which is afterwards transformed into the 1. 8. 6. dinitro
acid, the mononitration of the naphtalene-alpha-sulpho acid principally yields
1. 8. mononitro acid, and only a small part of the 1. 5. mononitro acid, which latter
only however can be used for the formation of the 1. 8. 5. dinitro acid. Therefore
it is more advantageous to follow another process and to produce first the mono-
nitro compound of the naphtalene-alpha-sulpho acid according to Laurents process
(sulphonation of the nitronaphtalene) which, as is known, produces almost only the
1. 5. acid.
Example. 173 kilos. alpha-nitronaphtalene are transformed in the known manner
into monosulpho acid. After the sulphonation has been accomplished, allow to cool
to about 16° C. and slowly introduce 150 kilos. nitrosulphuric acid, containing
63 kilos. HNO,, keeping the temperature at 15° to 20° C.
Let stand for 24 hours
and let the finished product run into 3000 litres of salt water.
The greater part of the 1. 8. dinitronaph talene-alpha-sulpho acid is precipitated
from the cooled solution in the shape of a crystalline precipitate of a brown color;
it is filtered and then washed with salt water, until all the mineral acid is removed.
The dinitro acid is easily soluble in pure water, even in the cold, but in salt water
it is almost insoluble.
For the reduction it is preferable to dissolve the dinitro acid in 2000 litres of
water and then to heat this solution in the known manner with iron shavings and a
little acetic acid. After the very strong reaction terminated the dissolved iron
is precipitated with carbonate of sodium and then filtered. To the filtrate

page_text: 400 kilos. sulphuric acid are added. While cooling the sulphate of the diamido
acid crystallises completely in brilliant colorless needles.
The acid thus obtained is a derivative of the 1.8. naphtylenediamine. It
possesses, like the known analogous bodies, basic properties and combines with
mineral acids to form characteristic salts, of which besides the sulphate already
mentioned, the chlorhydrate stands foremost in its facile crystallisation. The acid
combines very easily with one as well as with two equivalents of diazo bodies. In
spite of the thus stated presence of two amido groups, the acid combines with only
one molecule of nitrous acid, forming a body not susceptible to reaction (azimido-
naphtalenesulpho acid). From this circumstance results for both the amido groups
the position 1. 8; consequently as the acid originates from the 1. 5 nitromonosulpho
acid, its constitution is 1. 8. 5.
The free acid is nearly insoluble in water; it is obtained by acidulating
cautiously the solution of soda salt. Its salts are without exception very easily
soluble.
The soda salt may be separated from its solutions with common salt.
By heating with mineral acids or with caustic alkalis 1. 8. amidonaphtolmono-
sulpho acid is obtained from the diamido acid.
Example. Heat 10 kilos. diamidonaphtalen-alpha-sulpho acid during 12 hours in
a covered vessel with 100 kilos. diluted sulphuric acid, containing 20 to 30% H₂SO.
The 1.8 amidonaphtolmonosulpho acid separates from the cold solution in the form
of colorless needles.
The acid is difficultly soluble in cold water.
Treated with nitrous acid it
The
dissolves with a yellow color, forming an unstable diazo derivative.
coloration thereof is changed into a violet red by the addition of carbonate of
sodium.
The salts of the new acid are very soluble, they show a violet fluorescence in
aqueous solution.
The acid combines very easily with one or two molecules of diazo bodies,
forming coloring matters which resemble much those deriving from the 1. 8. amido-
naphtol-beta-sulpho acid of the British Patent 6972º¹
If the acid is combined with diazo bodies two groups of dye-stuffs are obtained
according to the combination taking place in an acid or alkaline solution.
Example. The diazo compound of 22.5 kilos. naphtionic acid is stirred with
300 litres of water and then slowly entered into a solution of 26 kilos. 1. 8. 5. amido-
naphtolsulpho acid in 500 litres of water and 40 kilos. carbonate of sodium. The
dye-stuff is instantly formed. It remains, dissolved and has to be precipitated with
common salt. It dyes wool a blue violet. Or
The diazo compound of 22.5 kilos. naphtionic acid is added to a solution of
26 kilos. 1. 8. 5. amidonaphtolsulphonate and 30 kilos. acetate of sodium in
500 litres of water, acidulated with a little acetic acid. The dye-stuff is separated
to a large extent. It dyes wool a violet red. Instead of in acetic acid, the
combination may take place in a weak mineral acid solution.
In an analogous manner other dye-stuffs are obtained from simple diazo bodies
and the 1.8. 5. amidonaphtolsulpho acid. Quite analogous dye-stuffs are likewise
obtained by using diazoazo bodies for instance the diazo derivatives of amido-]
azobenzole, amidoazonaphtalene and their sulpho acids.
Example. The diazo compound which is obtained by diazotation of the product
from 31 kilos. alpha-naphtylaminedisulpho acid and 14.3 kilos. alphanaphtyl-
amine, is suspended in 300 litres of water and introduced into a solution
made alkaline with 40 kilos. soda, of 26 kilos. 1. 8. 5. amidonaphtolsulpho acid. A
deep black solution is produced, from which the dye-stuff, by the addition of little
common salt, is precipitated in small crystals in the shape of needles.
It dyes
wool a greenish black.
Analogous dye-stuffs are obtained from aniline, nitraniline, naphtylamine,
amidoazobenzene or their sulpho acids, amidobenzoic acid, amido-salicylic
acidite

page_text: If the new acid is combined in alkaline or acid solution with tetrazo bodies,
in this case also two groups of direct dyeing diazo dye-stuffs are obtained according
to the method of combination. The symmetrical derivatives of the new acid,
combined in an alkaline solution, shew deep blue black tints, whilst those combined
in an acid solution dye a red blue. With the mixed dye-stuffs, in which only one
side of the tetrazo body is combined with the new acid, the same dyeing properties
appear, with the deviations caused by other components.
The process of working is shown by the following examples.
I. 18.4 kilos. benzidine are diazotised in the known manner, the tetrazo compound
is allowed to flow at 0° to 5° C. into a solution of 52 kilos. amidonaphtolsulpho acid
and 80 kilos, soda. When the reaction has lasted a short time, a part of the dye-
stuff precipitates in crystals, the remainder is separated by a moderate addition of
salt. The dye-stuff dyes unmordanted cotton a blueish black.
II. Tetrazodiphenyl from 18.4 kilos. benzidine is introduced into a solution of
52 kilos. amidonaphtol-sulphonate, to which 50 kilos. acetate of sodium are added
and which is weakly acidulated with acetic acid. The intermediate body which is
first formed, is transformed after about twelve hours into the symmetrical dye-stuff,
which is precipitated in the shape of blue crystals of the form of needles. Then it
is heated to 50° C., made alkaline with soda and the dye-stuff precipitated with
common salt. It dyes unmordanted cotton a blackish red blue.
In the same way the dye-stuffs are obtained from the analogues of benzidine,
tolidine, diamidoethoxydiphenyle, p phenylenediamine, diamidodiphenol ether,
diamidoazobenzole, a₁ a diamidonapltalene ẞ, ẞ disulpho acid. They show the
same dyeing properties.
The unsymmetrical dye-stuffs may be produced in two different ways, as the
intermediate bodies may be obtained from the amidonaphtolsulpho acid or from
other components. The process is illustrated by the following example.
III. Tetrazoditolyl, obtained from 21.5 kilos. tolidine, is mixed with a neutral
solution of 25 kilos. ai a, naphtolsulphonate and the mixture is introduced into a
diluted solution of 80 kilos. soda. The red intermediate body is formed at once.
Then to this a solution of 26 kilos. amidonaphtolsulphonate is added. After 12 hours
the liquid is heated to the boil, and to the finished dye-stuff common salt is added.
It dyes unmordanted cotton a blackish blue.
Amongst the numerous possible combinations which in this way may be obtained
we mention the following as specially valuable.
Product from 1 molecule tetrazodiphenyle, 1 molecule a, a, amidonaphtol a, sulpho
acid and
If instead of benzidine its analogues as p phenylenediamine, tolidine, diamido-
ethoxydiphenyle, diamidodiphenol-ether are used, dye-stuffs are obtained which do
not deviate materially in shade from the above mentioned ones, and which with
0 regard to their dyeing properties behave in the same way.

page_text: Primary disazo dye-stuffs are obtained from 'the new amidonaphtolsulpho acid,
by reacting with two molecules of diazo bodies at once or successively on the said
acid.
The process for the production of these primary disazo dye-stuffs is illustrated by
the following-
Example. 31 kilos. beta naphtylamine-gamma-disulpho acid are diazotised and
the diazo compound is introduced into the solution of 26.3 kilos. of a, a amido-
naphtol as sulpho acid and 30 kilos. acetate of sodium. After the formation of the
dye-stuff it is made alkaline with 80 kilos. of soda, and then the diazo compound
from 10.8 kilos. p. nitraniline is added. The diazo dye-stuff is separated at once
in the shape of a finely distributed violet black precipitate. The dye-stuff is easily
soluble in warm water with a greenish black color. It dyes wool in an acid bath
a deep greenish black.
Instead of the diazo bodies mentioned, the derivatives of the following substances
may both as first or second component be applied to advantage: m nitraniline,
nitrotoluidine, aniline, anilsulpho acid and their homologues, alpha or beta naphtyl-
amine and their sulpho acids, amidoazobenzole and its sulpho acids, amidosalicylic
acid. By the use of these bodies dye-stuffs are obtained in all cases which dye
wool black in an acid bath.
Dated this 2nd day of March 1893.
CARPMAEL & Co.,
Agents for the Applicant.
COMPLETE SPECIFICATION.
Improvements in the Production of Diamidonaphtalene-sulpho Acid
and Amidonaphtol Sulpho Acid, and Coloring Matters from the
latter.
J, SYDNEY PITT, of Sutton, in the County of Surrey, Gentleman (a com-
munication to me from abroad by Leopold Cassella & Co., of Frankfort on Main,
in the Empire of Germany, Manufacturing Chemists,) do hereby declare the
nature of this invention and in what manner the same is to be performed to be
particularly described and ascertained in and by the following statement :-
In the British Specification 69721 it has been described how the naphtalene-beta-
monosulpho acid may be transformed into a 1.8. diamido compound.
We have now applied the same process to the naphtalene-alpha-sulpho acid and-
have obtained an acid, of the constitution :
The formation of the mononitro acid precedes naturally the formation of the
dinitro acid. Whilst the naphtalene-beta-sulpho acid produces principally the 4
1.6. mononitro compound, which is afterwards transformed into the 1.8. 6. dinitro
acid, the mononitration of the naphtalene-alpha-sulpho acid principally yields
1.8. mononitro acid, and only a small part of the 1. 5. mononitro acid, which latter
only however can be used for the formation of the 1. 8. 5. dinitro acid. Therefore

page_text: it is more advantageous to follow another process and to produce first the mononitro.
compound of the naphtalene-alpha-sulpho acid according to Laurents process
(sulphonation of the nitronaphtalene) which, as is known, produces almost only the
1.5. acid.
Example. 173 kilos. alpha-nitronaphtalene are transformed in the known manner
into mono-sulpho acid. After the sulphonation has been accomplished, allow to.
cool to about 10° C. and slowly introduce 150 kilos. nitrosulphuric acid, containing
63 kilos. HNO3, keeping the temperature at 15° to 20° C. Let stand for 24 hours.
and let the finished product run into 3000 litres of salt water.
The greater part of the 1. 8. dinitronaphtalene-alpha-sulpho acid is precipitated
from the cooled solution in the shape of a crystalline precipitate of a brown color;
it is filtered and then washed with salt water, until all the mineral acid is removed..
The dinitro acid is easily soluble in pure water, even in the cold, but in salt water
it is almost unsoluble.
For the reduction it is preferable to dissolve the dinitro acid in 2000 litres of
water and then to heat this solution in the known manner with iron shavings and a
little acetic acid. After the very strong reaction is terminated the dissolved iron
is precipitated with carbonate of sodium and then filtered. To the filtrate 400 kilos..
sulphuric acid are added. While cooling the sulphate of the diamido acid crystallises.
completely in brilliant colorless needles.
It
The acid thus obtained is a derivative of the 1. 8. naphtylenediamine.
possesses, like the known analogous bodies, basic properties and combines with
mineral acids to form characteristic salts, of which besides the sulphate already
mentioned, the chlorhydrate stands foremost in its facile crystallisation. The acid
combines very easily with one as well as with two equivalents of diazo bodies. In
spite of the thus stated presence of two amido groups, the acid combines with only
one molecule of nitrous acid, forming a body not susceptible to reaction (azimido-
naphtalenesulpho acid). From this circumstance results for both the amido groups
the position 1.8; consequently as the acid originates from the 1. 5 nitromonosulpho
acid, its constitution is 1.8. 5.
The free acid is nearly insoluble in water; it is obtained by acidulating.
cautiously the solution of soda salt. Its salts are without exception very easily
soluble.
The soda salt may be separated from its solutions with common salt.
By heating with mineral acids or with caustic alkalies 1. 8. amidonaphtolmono- .
sulpho acid is obtained from the diamido acid.
The best conditions are to heat with diluted sulphuric acid to about 100—110 C. ;
the caustic alkali method gives only small yields.
Example. Heat 10 kilos. diamidonaphtalene-alpha-sulpho acid during 12 hours.
in a covered vessel with 100 kilos. diluted sulphuric acid, containing 20 to.
30% H₂SO. The 1. 8. amidonaphtolmono-sulpho acid separates from the cold
solution in the form of colorless needles.
The acid is difficultly soluble in cold water. Treated with nitrous acid it dissolves
with a yellow color, forming an unstable diazo derivative. The coloration thereof
is changed into a violet red by the addition of carbonate of sodium.
The salts of the new acid are very soluble, they show a violet fluorescence in .
aqueous solution.
The acid combines very easily with one or two molecules of diazo bodies, forming
coloring matters which resemble much those deriving from the 1.8. amidonaphtol- .
beta-sulpho acid of the British Patent 6972º¹.
If the acid is combined with diazo bodies two groups of dye-stuffs are obtained
according to the combination taking place in an acid or alkaline solution.
Example. The diazo compound of 22.5 kilos. naphtionic acid is stirred with
300 litres of water and then slowly entered into a solution of 26 kilos. 1. 8. 5. amido--
naphtolsulpho acid in 500 litres of water and 40 kilos. carbonate of sodium. The.

page_text: dye-stuff is instantly formed. It remains, dissolved and has to be precipitated with
common salt. It dyes wool a blue violet. Or
The diazo compound of 22.5 kilos, naphtionic acid is added to a solution of
26 kilos. 1. 8. 5. amidonaphtolsulphonate and 30 kilos. acetate of sodium in
500 litres of water, acidulated with a little acetic acid. The dye-stuff is separated
to a large extent. It dyes wool a violet red. Instead of in acetic acid, the
combination may take place in a weak mineral acid solution.
In an analogous manner other dye-stuffs are obtained from simple diazo bodies
and the 1. 8. 5. amidonaphtolsulpho acid. Quite analogous dye-stuffs are likewise
obtained by using diazoazo bodies for instance the diažo derivatives of amidoazo-
benzole, amidoazona plitalene and their sulpho acids.
Example. The diazo compound which is obtained by diazotation of the product
from 31 kilos. alphanaphtylaminedisulpho acid and 14.3 kilos. alphanaphtylamine,
is suspended in 300 litres of water and introduced into a solution made alkaline
with 40 kilos. soda, of 26 kilos. 1. 8. 5. amidonaphtolsulpho acid. A deep black
solution is produced, from which the dye-stuff, by the addition of little common
salt, is precipitated in small crystals in the shape of needles. It dyes wool à
greenish black.
Analogous dye-stuffs are obtained from aniline, nitraniline, naphtylamine; amido-
azobenzene or their sulpho acids, amidobenzoic acid amido-salicylic acid, etc.
If the new acid is combined in alkaline or acid solution with tetrazo bodies, in
this case also two groups of direct dyeing diazo dye-stuffs are obtained according
to the method of combination. The symmetrical derivatives of the new acid,
combined in an alkaline solution, show deep blue black tints, whilst those combined
in an acid solution dye a red blue. With the mixed dye-stuffs, in which only one
side of the tetrazo body is combined with the new acid, the same dyeing properties
appear, with the deviations caused by other components.
The process of working is shown by the following examples.
I. 18.4 kilos. benzidine are diazotised in the known manner, the tetrazo
compound is allowed to flow at 0° to 5° C. into a solution of 52 kilos. amido-
naphtolsulpho acid and 80 kilos. soda. When the reaction has lasted a short time,
a part of the dye-stuff precipitates in crystals, the remainder is separated by a
moderate addition of salt. The dye-stuff dyes unmordanted cotton a blueish black.
II. Tetrazodiphenyl from 18.4 kilos. benzidine is introduced into a solution of
52 kilos. amidonaphtolsulphonate, to which 50 kilos. acetate of sodium are added
and which is weakly acidulated with acetic acid. The intermediate body which is
first formed, is transformed after about twelve hours into the symmetrical dye-stuff,
which is precipitated in the shape of blue crystals of the form of needles. Then it
is heated to 50° C., made alkaline with soda and the dye-stuff precipitated with
common salt. It dyes unmordanted cotton a blackish red blue.
In the same way the dye-stuffs are obtained from the analogues of benzidine,
tolidine, diamidoethoxydiphenyle, p phenylenediamine, diamidodiphenol ether,
diamidoazobenzole, a, a, diamidonaphtalene 2 ẞ, disulpho acid. They show the
same dyeing properties.
The unsymmetrical dye-stuffs may be produced in two different ways, as the
intermediate bodies may be obtained from the amidonaphtolsulpho acid or from
other components. The process is illustrated by the following example.
III. Tetrazoditolyl, obtained from 21.5 kilos. tolidine, is mixed with a neutral
solution of 25 kilos. a a, naphtolsulphonate and the mixture is introduced into a
diluted solution of 80 kilos. soda. The red intermediate body is formed at once.
Then to this a solution of 26 kilos. amidonaphtolsulphonate is added. After
12 hours the liquid is heated to the boil, and to the finished dye-stuff common salt
is added. It dyes unmordanted cotton a blackish blue.
Amongst the numerous possible combinations which in this way may be obtained
we mention the following as specially valuable.

page_text: If instead of benzidine its analogues as p. phenylenediamine, tolidine, diamido-
ethoxydiphenyle, diamidodiphenol- ether are used, dye-stuffs are obtained which
do not deviate materially in shade from the above mentioned ones, and which with
regard to their dyeing properties behave in the same way.
Primary disazo dye-stuffs are obtained from the new amidonaphtolsulpho acid
by reacting with two molecules of diazo bodies at once or successively on the said
acid.
The process for the production of these primary disazo dye-stuffs is illustrated
by the following.
Example. 31 kilos. beta naphtylamine-gamma-disulpho acid are diazotised and
the diazo compound is introduced into the solution of 26.3 kilos. of a₁ aş amido-
naphtol a, sulpho acid and 30 kilos. acetate of sodium. After the formation of
the dye-stuff it is made alkaline with 80 kilos. of soda and then the diazo compound
from 10.8 kilos. p. nitraniline is added. The diazo dye-stuff is separated at once
in the shape of a finely distributed violet black precipitate. The dye-stuff is easily
soluble in warm water with a greenish black color. It dyes wool in an acid bath
a deep greenish black.
Instead of the diazo bodies mentioned, the derivatives of the following
substances may both as first or second component be applied to advantage;
m nitraniline, nitrotoluidine, aniline, anilsulpho acid and their homologues, alpha
or beta naphtylamine and their sulpho acids, amidoazobenzole and its sulpho acids,
amidosalicylic acid. By the use of these bodies dye-stuffs are obtained in all cases
which dye wool black in an acid bath.
Having now particularly described and ascertained the nature of the said inven-
tion and in what manner the same is to be performed, I declare that what I
claim is :-
1st. The process of producing 1. 8. 5. naphtylenediaminesulpho acid by reducing
the dinitro-compound of a naphtalenesulpho acid substantially as described.
2nd. The process of producing 1. 8. 5 amidonaphtolsulpho acid by heating the
corresponding naphtylenediaminesulpho acid with diluted mineral acids, substantially
as described.
3rd. The process of producing azo-dyestuffs by combining the 1. 8. 5 amido-
naphtolsulpho acid with diazocompounds or tetrazocompounds in molecular
proportions substantially as described:
4th. The process of producing mixed azo-dyestuffs by combining one of the azo-
groups of a paradiamine with 1. 8. 5 amidonaphtolsulpho acid and the other one
with an amine or a phenol, or an amidophenol substantially as described.
5th. The process of producing primary disazo dyestuffs by combining two equal

page_text: or different molecules of diazo bodies with the 1. 8. 5. amidonaphtolsulpho acid
substantially as described.
6th. The new acids and the new dye stuffs produced from those acids herein-
before described.
Doted this 21st day of November 1893
SYDNEY PITT.