Production of Amidonaphtholsulpho Acids and of Dye-stuff's therefrom.
Year: 1891

page_text: Date of Application, 22nd Apr., 1891
Complete Specification Left, 18th Jan., 1892-Accepted, 5th Mar., 1892
Production of Amidonaphtholsulpho Acids and of Dye-stuff's
therefrom.
I, SYDNEY PITT, of Sutton, in the County of Surrey, Gentleman, (a communi-
ation 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
his invention to be as follows:—
The objects of this Specification are certain additions or improvements referring
o the inventions described in Patents No. 16,69989, 19,3300 and 1742". The said
nventions relate to the manufacture of azo-dyes deriving from amido-naphthol-
ulpho acids. In connection therewith there has since been found some new
(isomeric) amido-naphtholsulpho acids and new colouring matters from those acids
and from the analogous compounds described in the above named Patents.
Production of Amidonaphtholsulpho Acids and of Dye-stuffs
therefrom.
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:-
The objects of this Specification are certain additions or improvements referring
o the inventions described in Patents No. 16,69989, 19,3300 and 1742". The said
nventions relate to the manufacture of azo-dyes deriving from amido-naphthol-
ulpho acids. In connection therewith there has since been found some new
(isomeric) amido-naphtholsulpho acids and new colouring matters from those acids
and from the analogous compounds described in the above named Patents.
I. NEW AMIDONAPHTHOLSULPHO ACIDS.
a. The naphtylamenetrisulphonic acid which is obtained by nitration and reduc-
tion of the naphtalenetrisulpho acid described in Patent No. 15,7168, is heated
at about 170-190 Centigrade with caustic alkalies in open or closed vessels. From
the acidulated solution of the smelt the acid separates in the form of a colourless
crystalline powder. Its neutral salts are easily soluble. By nitrous acid it is
transformed into a yellow crystallised diazo-compound.
b. A new naphtalenetrisulpho acid is produced by further sulphonation of
naphtalene ẞ disulpho acid. A mononitro-derivative is obtained by nitration,
which, treated with reducing agents yields a new naphtylamenetrisulpho acid. The
neutral sodium salt of the latter is easily soluble in water with a green fluorescence.
The acid salt is difficultly soluble. The diazo-acid is difficultly soluble and is
entirely precipitated by common salt. If, for instance, 20 kg. of the said
naphty lamenetrisulpho acid are heated for 6 hours up to 180° C. together with
25 kg. of caustic soda and 35 litros water in an autoclave, the formation of a new.
amidonaphtholdisulpho acid takes place, which can be isolated by acidulating the
cold solution of the resulting smelt. The free acid is somewhat soluble in water.
Its diazo-derivative, precipitable by common salt, shows a characteristic orange
colour, changing by alkalies into blue.
c. The naphtalene ẞ monosulpho acid subjected to a strong action of nitric acid
is substituted by two nitro groups. The dinitronaphtalene B-monosulpho acid is
reduced in the known manner, for instance with iron and acetic acid. The resulting
diamidonaphtalene ẞ sulpho acid, which in the form of the free acid is nearly.
insoluble in cold water, can easily be isolated. Heated under pressure with diluted
mineral acid to 120° C. the diamido-acid is decomposed. One of the amido groups
is split off and an hydroxyl group enters into the molecule. The new amido-
naphthol sulpho acid thus obtained is nearly insoluble in cold water.
d. The naphtylamene y disulpho acid is not the only product of the
disulphonation of ẞ naphtylamene. There are always formed larger or smaller
quantities of isomeric acids, varying according to the conditions of the process.
If therefore, instead of the pure ẞ naphtylamene y-disulpho acid the crude material
is used, which results from the said sulphonation, the amido-naphtholsulpho acid as
well as the colouring matters deriving from the latter are altered in a certain
degree. The diamine-black (the benzidine-derivative) for instance gets a more
violet shade. The general properties of the dye-stuffs, however, remain unchanged.

page_text: II. NEW COLOURING MATTERS.
e. Both the acids described under a and b combine in the well-known manner,
described in the Specifications of the former Patents, with diazo and tetrazo
compounds, forming colouring matters which in their shades resemble those deriving
from the amidonaphtholdisulpho acid H.
Tetrazodiphenyle and its analogues produce pure blue colours if one molecule of
the same is combined in alkaline solution with two molecules of the said amido-
naphtholdisulpho acids. With only one molecule of these acids the tetrazodiphenyle
(or the like) forms intermediate compounds which react with one molecule of
another amine or phenol. Of great technical value are the mixed combinations
containing a naphtol-a sulpho acid or y amidonaphtholsulpho acid.
f. The colouring matters which are obtained from tetrazo-compounds and the
amidonaphthol- monosulpho acid (described under c.) are of blue black shades,
not as deep as those of the y acid compounds, but also not as clear as the derivatives
of the acid H. The process of their preparation resembles that described in our
Patent No. 16,69989
9. The Bamidonaphtholdisulpho acid which (according to Patent No. 15,1758) is
obtained by heating the ẞ naphtylamene trisulpho acid (corresponding to the known
ẞnaphtholtrisulpho acid) with caustic alkalies, can also be used for the purpose of
this invention.
By the action of tetrazodiphenyle or its analogues upon the equivalents of the
said acid in alkaline solution, black colouring matters are formed which, however,
on account of their great solubility are not sufficiently resistant against washing.
But as it is known by Patent No. 16,6998 that the bodies of this kind possess a free
amido group which can be diazotised again, it is possible to fix the dye-stuff by
diazotizing it on the fibre and combining with naphthol or similar compounds. The
intermediate compounds which are prepared from one equivalent tetrazodiphenyle
or its analogues and one equivalent of the 3 amidonaphtholdisulpho acid can be
used for making mixed colours. The combinations with y amidonaphtholsulpho
acid show remarkable properties.
h. The blue colouring matters of Patent No. 1742" which result from the action
of tetrazodiphenyle and its analogues upon the amidonaphtholdisulpho acid H can
be diazotized with one or two molecules of nitrite and the diazo compounds can be
further combined with phenols or amines.
Example. 92 kg. of the colouring matter are dissolved in water and 7 kg. nitrite
are added to the solution which hereafter is acidulated. The greenish blue diazo
compound is brought into the alkaline solution of 11 kg. resorcine. The thus
obtained colouring matter dyes unmordanted cotton a deep green. Or the same
quantity of the blue dye-stuffs is transformed by 14 kg. nitrite into the green
tetrazo compound and the latter combined with 29 kg. a naphtylamene. The
resulting dye-stuff can be fixed on unmordanted cotton. It gives a blueish black
shade. Instead of a naphtylamene or resorcine, m. phenylenediamine, m. toluylene-
diamine ẞ naphthol or phenol can be used.
The process described in the above example is also applicable for those substances
which contain only one equivalent of H acid and which are produced by the action
of one molecule tetrazodiphenyle or a homologue thereof upon one molecule of
acid H and one molecule of an other amine or phenol such as y amidonaphthol-
sulphonic acid, salicylic acid, phenol, a naphtylamene, m. phenylenediamine.
i. By the presence of two reactive groups (NH, and OH) the amidonaphthol-
sulpho acids are enabled to absorb two molecules of diazo compounds. In this
manner there is obtained by the process described in the respective former Patents,
either in alkaline or acid solutions a large series of new azo-dyes from aniline and
its homologues, the naphtylamenes and their amido azo-compounds and the sulpho
acids of all these bodies.

page_text: With these same bodies or other diazo-derivatives, the amidonaphtholsulpho acids
can likewise be combined first in acid and then in alkaline solution or inversely.
Example. The amidonaphtholdisulpho acid H is first combined, in a solution
containing some free acetic acid, with one equivalent of the diazo-derivatives of
nitraniline (m. or p.), amidoazobenzol and then combined in an alkaline solution
with an other diazo-compound, such as diazo-benzol and its homologues, diazo-
naphtalene, diazonitrobenzol, diazoazo-benzol, tetrazodiphenyle. The resulting
coloring matters dye wool blackish green shades, the fastness of which is increased
by the use of a chrome mordant.
1
11001
CARPMAEL & Co.,
Agents for the Applicant.
COMPLETE SPECIFICATION.
Production of Amidonaphtholsulpho Acids and of Dye-stuffs
therefrom.
1, 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:-
The objects of this Specification are certain additions or improvements referring
to the inventions described in Patents No. 16,699, 19,3300 & 1742". The said
inventions relate to the manufacture of azo-dyes, deriving from amidonaphthol-
sulpho acids. In connection therewith there have since been found new processes
for preparing amidonaphtholsulpho acids & new coloring matters from those acids
& from the analogous compounds described in the above named Patents.
COMPLETE SPECIFICATION.
Production of Amidonaphtholsulpho Acids and of Dye-stuffs
therefrom.
1, 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 :—
The objects of this Specification are certain additions or improvements referring
to the inventions described in Patents No. 16,6998, 19,3300 & 1742". The said
inventions relate to the manufacture of azo-dyes, deriving from amidonaphthol-
sulpho acids. In connection therewith there have since been found new processes
for preparing amidonaphtholsulpho acids & new coloring matters from those acids
& from the analogous compounds described in the above named Patents.
I. AMIDONAPHTHOLSULPHO ACIDS.
a.) The naphtylaminetrisulphonic acid which is obtained by nitration & reduction
of the naphtalenetrisulpho acid described in Patent No. 15,716, is heated at
about 170-190 Centigrade with caustic alkalies in open or closed vessels. From
the acidulated solution of the smelt the amidonaphtholdisulpho acid separates in the
form of a colorless crystalline powder.
This acid shows all the properties of the acid H described in Patent No. 1742º1
& seems to be identical with the same.
It can therefore be substituted in all those processes which I have described or
shall describe, wherein acid H is used & is therefore included in the respective
claims.
b.) A new naphtalenetrisulpho acid is produced by further sulphonation of
naphtalene beta disulpho acid. A mononitro-derivative is obtained by nitration,
which, treated with reducing agents, yields a new naphtylaminetrisulpho acid.
The neutral sodium salt of the latter is easily soluble in water with a green
fluorescence. The acid salt is difficultly soluble. The diazo-acid is difficultly
soluble & is entirely precipitated by common salt. If, for instance, 20 kg. of the
said naphtylaminetrisulpho acid are heated for 6 hours up to 180 deg. C. together
with 25 kg. of caustic soda & 35 litres water in an autoclave, the formation of a
new amidonaphtholdisulpho acid takes place, which can be isolated by acidulating
the cold solution of the resulting smelt. The free acid is somewhat soluble in
water. Its diazo-derivative, precipitable by common salt, shows a characteristic
orange color, changing by alkalies into blue."
c.) The naphtalene beta monosulpho acid subjected to a strong action of nitric
acid is substituted by two nitro groups. The dinitronaphtalene beta monosulpho
acid is reduced in the known manner, for instance with iron & acetic acid. The
resulting diamidonaphtalene beta sulpho acid, which in the form of the free acid is

page_text: nearly insoluble in cold water, can easily be isolated. Heated under pressure with
diluted mineral acid to 120 deg. C. the diamido acid is decomposed. One of the
amido groups is split off & an hydroxyl group enters into the molecule. The new
amido-naphthol beta sulpho acid thus obtained is nearly insoluble in cold water.
d.) The beta naphtylamine gamma disulpho acid is not the only product of the
disulphonation of beta naphtylamine. There are always formed larger or smaller
quantities of isomeric acids, varying according to the conditions of the process. If
therefore, instead of the pure beta naphtylamine gamma disulpho acid the crude
material is used, which results from the said sulphonation, the amido naphthol
sulpho acid as well as the coloring matters deriving from the latter are altered in a
certain degree. Diamine black (the benzidine-derivative) for instance gets a more
violet shade. The general properties of the dyestuffs, however, remain unchanged.
nearly insoluble in cold water, can easily be isolated. Heated under pressure with
diluted mineral acid to 120 deg. C. the diamido acid is decomposed. One of the
amido groups is split off & an hydroxyl group enters into the molecule. The new
amido-naphthol beta sulpho acid thus obtained is nearly insoluble in cold water.
d.) The beta naphtylamine gamma disulpho acid is not the only product of the
disulphonation of beta naphtylamine. There are always formed larger or smaller
quantities of isomeric acids, varying according to the conditions of the process. If
therefore, instead of the pure beta naphtylamine gamma disulpho acid the crude
material is used, which results from the said sulphonation, the amido naphthol
sulpho acid as well as the coloring matters deriving from the latter are altered in a
certain degree. Diamine black (the benzidine-derivative) for instance gets a more
violet shade. The general properties of the dyestuffs, however, remain unchanged.
II. ISOMERIC AMIDONAPHTHOLSULPHO ACID USED IN THE PROCESSES
OF FORMER PATENTS.
e.) The acid described under b.) combines in the well known manner, described in
the Specifications of the former Patents, with diazo or tetrazo compounds, forming
coloring matters which in their shades resemble those deriving from the amido-
naphtholdisulpho acid H.
Tetrazodiphenyle & its analogues (such as the tetrazo-derivatives of tolidine,
methylbenzidine, diamidoethoxydiphenyle, diamidodiphenolether, diamidostilbene-
disulpho acid, etc.) produce pure blue colors, if one molecule of the same is
combined in alkaline solution with two molecules of the said amidonaphtholdisulpho
acid. With only one molecule of this acid the tetrazodiphenyle (or the like) forms
intermediate compounds which react with one molecule of another amine or phenol.
Of great technical value are the mixed combinations containing alpha naphthol-
alpha sulpho acid or gamma amidonaphtholsulpho acid.
f.) The coloring matters which are obtained from tetrazo-compounds & the
amidonaphthol beta monosulpho acid (described under c.) are of blueish black
shades, not as deep as those of the gamma acid compounds, but also not as clear as
the derivatives of the acid H. The process of their preparation resembles that
described in Patent No. 16,69989.
9.) The beta amidonaphtholdisulpho acid which, (according to Patent
No. 15,175) is obtained by heating the beta naphtylamine trisulpho acid
(corresponding to the known beta naphtholtrisulpho acid) with caustic alkalies, can
also be used for the purpose of this invention.
By the action of tetrazodiphenyle or its analogues upon two equivalents of the
said acid in alkaline solution, black coloring matters are formed, which, however,
on account of their great solubility are not sufficiently resistant against washing.
But as it is known by Patent No. 16,6999 that the bodies of this kind possess a free
amido group which can be diazotised again, it is possible to fix the dyestuff by
diazotising it on the fibre & combining with naphthol or similar compounds. The
intermediate compounds which are prepared from one equivalent tetrazodiphenyle
or its analogues & one equivalent of the beta amidonaphtholdisulpho acid can be
used for making mixed colors. The combinations with gamma amidonaphtholsulpho
acid show remarkable properties.
III. NEW DYESTUFFS DERIVING FROM THE AMIDONAPHTHOLDISULPHO
ACID H.
h.) The blue coloring matters of Patent No. 1742" which result from the action
of tetrazodiphenyle & its analogues upon the amidonaphtholdisulpho acid H can be
diazotised with one or two molecules of nitrite & the diazo compounds can be
further combined with phenols or amines.
Example. 92 kg. of the coloring matter deriving from one equivalent of
benzidine & two equivalents of acid H, are dissolved in water & 7 kg. nitrite are

page_text: added to the solution which hereafter is acidulated. The greenish blue diazo
compound is brought into the alkaline solution of 11 kg. resorcine. The thus
obtained coloring matter dyes unmordanted cotton a deep green. Or the same
quantity of the blue dyestuff is transformed by 14 kg. nitrite into the green tetrazo
compound & the latter combined with 29 kg. alpha naphtylamine. The resulting
dyestuff can be fixed on unmordanted cotton. It gives a blueish black shade.
Instead of alpha naphtylamine or resorcine, m-phenylenediamine, m-toluylene-
diamine, beta naphthol or phenol can be used.
The process described in the above example is also applicable for those substances
which contain only one equivalent of acid H & which are produced by the action
of one molecule tetrazodiphenyle or a homologue thereof upon one molecule of
acid H & one molecule of an other amine or phenol such as gamma amidonaphthol-
sulphonic acid, salicylic acid, phenol, alpha naphtylamine, m-phenylenediamine.
Example. 71 kg. of the dyestuff produced by combination of one molecule of
tetrazodiphenyle with one molecule of salicylic acid & one molecule of acid H, are
dissolved in 1000 litres water. By addition of 9 kg. nitrite & 50 kg. muriatic acid
the diazo compound is formed, which separates in the form of a dark brown insoluble
precipitate. If the latter is filtered off & introduced into the alkaline solution of
11 kg. resorcine a dyestuff will be formed which dyes unmordanted cotton dark
green shades.
i.) By the presence of two reactive groups (NH, & OH) most amidonaphthol-
sulpho acids are enabled to absorb two molecules of diazo compounds. If the
acid H is combined with one molecule of a diazo compound in a solution containing
some free mineral acid, products are obtained which show the property of reacting
with a second molecule of a diazo compound in alkaline solution forming bodies of
the general formula:
Example. 13-8 kg. para-nitraniline are diazotised in presence of a sufficient
quantity of muriatic acid & a neutral solution of 32 kg. amidonaphtholdisulpho
acid H is added to the solution of the diazo body. Attention is to be paid that
always a certain quantity of mineral acid remains in the free state. A reddish
solution results, from which the coloring matter partially separates. By addition
of an excess of carbonate of soda all is dissolved with a blue shade. Then the
diazo-derivative of 9.3 kg. aniline is introduced into the solution, which is to be
kept alkaline. The coloring matter will be formed immediately & is then
precipitated & filtered off. It dyes animal fibres a greenish blue-black of great
intensity & fastness. By the application of chrome mordants the fastness can be
enhanced.
Products of similar shades & properties are obtained if instead of para-nitraniline,
meta-nitraniline or amidoazobenzol are used for the first combination. Nearly all
known diazo bodies may be used instead of diazobenzol for the second combination,
for instance, the diazc-derivatives of the following amido compounds: toluidine,
xylidine, anilinesulpho acid, nitraniline & their homologues, the naphtylamines,
naphtylaminesulpho acids, amidoazobenzol, amidoazobenzolsulpho acid or their
homologues, amidoazonaphtalenesulpho acids.
Tetrazo bodies such as tetrazodiphenyle & its analogues may also be used for the
second combination. In this case greenish black dyestuffs result, distinguished by
their affinity for the cotton fibre.
Having now particularly described & ascertained the nature of my said inven-
tion & in what manner the same is to be performed, what I claim is :
1.) The process of producing a new amidonaphtholdisulpho acid by heating with

page_text: caustic alkalies, the naphtylaminetrisulpho acid, which is obtained by sulphonating
the naphtalene beta disulpho acid, nitrating & reducing the thus produced
naphtalene beta trisulpho acid, substantially as described.
2.) The process of producing a new amidonaphtholmonosulpho acid by heating
with mineral acids the diamidonaphtalenemonosulpho acid which is prepared by
double nitration & reduction of the naphtalene beta monosulpho acid, substantially
as described.
3.) The process of producing new coloring matters by combining one molecule of
tetrazodiphenyle or its analogues with two molecules of the amidonaphtholsulpho
acids mentioned in the 1st & 2nd Claim or with two molecules of the amido-
naphtholdisulpho acid produced, according to Patent No. 15,175, by heating
naphtylamine beta trisulpho acid with caustic alkalies, substantially as described.
4.) The process of producing new mixed azo-coloring matters by combining one
molecule of tetrazodiphenyle or its analogues with one molecule of the amido-
naphtholsulpho acids mentioned in the 3rd Claim & one molecule of a phenol or an
amine, substantially as described.
5.) The process of producing new coloring matters by diazotising the dis-azo-
dyes deriving from one molecule of tetrazodiphenyle or its analogues & two
molecules of amidonaphtholdisulpho acid H by means of one or two molecules of
nitrite & combining the thus obtained diazoic compounds with phenols or amines,
substantially as described.
6.) The process of producing new coloring matters by diazotising the dis-azo-
dyes deriving from one molecule of tetrazodiphenyle or its analogues, one molecule
of amidonaphtholdisulpho acid H & one molecule of an other amine or phenol &
combining the thus obtained diazoic compounds with phenols or amines,
substantially as described.
7.) The process of producing new dis-azo-dyes by reacting with one molecule of
the diazo-derivatives of nitraniline or amidoazobenzol upon one molecule of amido-
naphtholdisulpho acid H in a solution containing a free mineral acid & combining
the thus obtained product in alkaline solution with a second molecule of a diazo
body or with half a molecule of a tetrazo body, substantially as described.
8.) The new substances & coloring matters hereinbefore described.
TATON Thia Inth
Janne
BXQV
Faron the lath day of Lennar
CARPMAEL & Co.,
Agents for the Applicant.
CARPMAEL & Co.,
Agents for the Applicant.