The Manufacture and Production of New Sulpho Acids of Dioxy- naphthalene or Amido Naphthol and of Azo Colouring Matters therefrom.
Year: 1890

page_text: Date of Application, 26th Aug., 1890
Complete Specification Left, 26th May, 1891-Accepted, 27th June, 1891
PROVISIONAL SPECIFICATION.
The Manufacture and Production of New Sulpho Acids of Dioxy-
naphthalene or Amido Naphthol and of Azo Colouring Matters
therefrom.
I, BENJAMIN WILLCOX of 47 Lincolns Inn Fields in the County of Middlesex
Patent Agent do hereby declare the nature of this invention (which has been
communicated to me from abroad by Farben fabriken vormals Friedrich Bayer & Co.
of Elberfeld in the Empire of Germany) to be as follows:-
I. PROCESS FOR THE MANUFACTURE OF A NEW DIOXY-NAPHTHALENE-
DISULPHO-ACID.
By melting the alpha-naphthol-trisulpho-acid described in the Specification
annexed to the application for a German Patent dated May 17th 1890, No. K 7567 or
the sulphone (sulton) thereof with alkalies under certain conditions, one sulpho
group becomes replaced by hydroxyl and a new dioxy-naphthalene-disulpho-acid is
obtained which in the combination with diazo- and tetrazo combinations 'yields
colouring matters of remarkable beauty.
The new process of manufacture may be conducted as follows for example the
parts being by weight.
100 parts of the sodium salt of alpha-naphthol-trisulpho-acid are heated with
100 parts of hydrate of soda and 30 parts of water to about 200 degrees Centigrade
until a test portion or sample in an acetic acid solution with diazo-benzene ceases
to show any increase in the formation of colouring matter.
The alpha naphthol-trisulpho acid yields no colouring matter in an acetic acid
solution.
After dissolving the melt in 500 parts of hydrochloric acid at 18 per cent. the
new dioxy-naphthalene-disulpho acid crystallises on cooling in flat compact
colourless needles.
It differs essentially in its general properties from the known isomeric acids.
This new dioxy-naphthalene-disulpho-acid is especially well adapted for the
manufacture of azo colouring matters which are distinguished by their extreme
clearness and their eosine like brightness.
II. PROCESS FOR THE MANUFACTURE OF A NEW
SULPHO-ACID.
AMIDO-NAPHTHOL-MONO-
My foreign correspondents have discovered that alpha-naphthylamine-zeta-
disulpho-acid can be melted with alkalies in such a manner that the amido group
is 'not affected and only one sulpho group is replaced by hydroxyl.
The fusion proceeds with great readiness when one part of the alpha-naphthyl-
amine-zeta-disulpho-acid with 2.5 parts of soda containing 75 per cent. of NaOH
to which 10 per cent. of water is added is melted at a temperature which is not
allowed to rise above 210 degrees Centigrade. On dissolving the melt in mineral'
acid the new amido-naphthol-mono-sulpho-acid can be separated in fine white
needles.
It dissolves' with considerable difficulty in cold' water but dissolves more readily
in hot water and crystallises out of the latter in short compact white needles: Its'
alkaline salts are readily soluble in water. A neutral solution of the acid is
coloured a blackish-violet by the action of chloride of iron and is turned red by
chloride of lime in solution: This colouring disappears entirely on the addition of
a solution containing chloride of lime in excess.

page_text: The new acid presents the great advantage, compared to the beta-amido-
naphthol-mono-sulpho acid obtainable from beta-amido-naphthalene-disulpho-acid G,
of yielding with tetrazo compounds and with tetrazo-diphenyl in particular not
violet-black, but valuable blue-black colouring matters.
III. PROCESS FOR THE MANUFACTURE OF A NEW AMIDO-NAPHTHOL-
DISULPHO-ACID.
..
On melting with caustic alkalies at a temperature of from about 180 to 190
degrees Centigrade the naphthylamine-trisulpho-acid which is obtained by nitriting
and reducing the naphthalene-trisulpho-acid described in the Specification of the
German Patent No. 38281, my foreign correspondents have discovered that there
results a new amido-naphthol-disulpho-acid. The process of its manufacture is for
example conducted as follows:-
1 part of naphthylamine-trisulpho-acid is melted with 2 parts of caustic soda and
some water in an open pot heated to from 180 to 190 degrees Centigrade until the
melt is in the condition of a thin liquid and a test portion diluted with water shows
a blue-red fluorescence. From the melt mixed with the calculated quantity of
hydrochloric acid the new amido-naphthol-disulpho-acid separates almost quanti-
tatively in small clear needles.
The acid is moderately soluble in cold water and readily soluble in hot water.
With the aid of heat it reduces ammoniacal silver solutions. With chloride of iron
solutions it shows a brown-red colour and the saine effect is produced with chloride
of lime. On the addition of more solution of chloride of lime the colour almost
entirely disappears. Nitrous acid changes it into a diazo compound which when
boiled is converted into the dioxy-naphthalene-disulpho-acid herein before
described under head I. In an alkaline solution the acid presents a blueish-red
fluorescence.
IV. PROCESS FOR THE MANUFACTURE OF AZO COLOURING MATTERS FROM
THE NEW ACIDS HEREINBEFORE DESCRIBED UNDER I II AND III.
These new acids in combination with the diazo compounds of aniline of amido-
phenol-ether or its homologues as well as the sulpho-acids and nitro derivatives of
these substances yield very beautiful fuchsine red to violet colouring matter, with
the diazo derivatives of amido-azo-benzene and its homologues of alpha- and beta-
naphthylamine of amido-naphthol-ether and the sulpho acids of these substances, it
yields beautiful violet to blue colouring matters which are distinguished from other
azo dyes by the clearness of their shades.
By combining the new sulpho-acids herein before described with tetrazo-diphenyl-
tetrazo-ditolyl, tetrazo-phenyl-tolyl, tetrazo-diphenol-ether, tetrazo-ethoxy-diphenyl,
tetrazo ethoxy-phenyl-tolyl, tetrazo-stilbene, tetrazo-fluorene, tetrazo-naphthalene
and their sulpho and carbon acids or by combining the same with the diazo com-
pound of para-amido-acetanilide, splitting off the acetyl group' rediazotizing and
allowing the product to react upon amines, phenols, naphthols, dioxynaphthalenes,
amido-naphthols, or their sulpho or carbon-acids, substantive violet to blue
colouring matters are obtained which are well adapted for dyeing unmordanted
cotton in an alkaline bath. Similar dyeing properties are displayed by the azo
colouring matters which can be obtained with the aid of the diazo compounds of
dehydro-thio-toluidine and dehydro-thio-xylidine or their sulpho-acids.
In place of combining one molecular proportion of the above mentioned tetrazo
compounds with 2 molecular proportions of the new dioxy-naphthalene-disulpho-
acid or the amido-naphthol sulpho-acids these ingredients may be combined together
in equal molecular proportions so as to form an intermediate product which is then
combined with an amine, phenol, naphthol, dioxy-naphthalene or the sulpho- or
carbon-acids thereof in equal molecular proportions.
Inversely the same products may also be obtained by combining equal molecular

page_text: .2: COLOURING MATTER FROM DIAMIDO-DIPHENOL-ETHER AND AMIDO-
NAPHTHOL-MONO-SULPHO ACID.
A solution of tetrazo-diphenol-ether corresponding to 7 parts by weight of
nitrite is poured' with stirring into an icy cold solution of 30 parts of the sodium
salt of amido naphthol mono sulpho acid and 15 parts of acetate of sodium. The
formation of the colouring matter is accelerated by strongly agitating or stirring.

page_text: After standing for about 24 hours this operation is completed; the materials are
rendered alkaline and heated and the colouring matter being salted out is filtered,
pressed and dried.
Dated this 26th day of August 1890.
J. H. JOHNSON & Co.,
47, Lincoln's Inn Fields, London, W.C., Agents.
COMPLETE SPECIFICATION.
The Manufacture and Production of New Sulpho Acids of Dioxy-
naphthalene or Amido Naphthol and of Azo Colouring Matters
thereform.
I BENJAMIN WILLCOX of 47 Lincolns Inn Fields in the County of Middlesex
Patent Agent do hereby declare the nature of this invention which invention has
been communicated to me from abroad by Farbenfabriken vormals Friedrich
Bayer & Co. of Elberfeld in the Empire of (ermany and in what manner the same
is to be performed to be particularly described and ascertained in and by the
following statement :-
I. PROCESS FOR THE MANUFACTURE OF A NEW
DISULPHO ACID.
DIHYDROXY-NAPHTHALENE
By melting the alpha-naphtholtrisulpho acid described in the Specification of the
application for a German Patent dated May 17, 1890 No. K. 7567 or the cor-
responding naphthosultone-disulpho acid of the German Patent dated February 1st
1890, No. 56058 with alkalies under modified conditions one sulpho group becomes
displaced by hydroxyl and a new dihydroxynaphthalene-disulpho acid is obtained
which by combination with diazo and tetrazo compounds yields colouring matters
of remarkable beauty similar to those obtained according to the Specifications
of Letters Patent No. 13665 dated 29th August 1889 and No. 18517 dated
19th November 1889.
The process of manufacture may be performed as follows: the parts being
by weight. 100 parts of the sodium salt of alphanapthol-trisulpho acid, are heated
with 100 parts of sodium hydrate and 30 parts of water to about 200 degrees
Centigrade until a test portion in an acetic acid solution ceases
to shew any
increase in the formation of colouring matter after the addition of diazo-benzene,
this reaction being decisive as the alpha-naphthol trisulpho acid yields colouring
matter only with great difficulty in an acetic acid solution.
The new dihydroxy naphthalene-disulpho acid, on cooling crystallizes from the
solution of the melt in excess of diluted hydrochloric acid in compact flat colourless
needles.
It differs essentially in its general properties from the known isomeric acids.
This new dihydroxynaphthalenedisulpho acid (which experiments have proved
to be a disulpho acid of the 1.8 dihydroxynaphthalene) is especially adapted for
the manufacture of azo colouring matters which like the dye-stuffs of the
18 dihydroxynaphthalenemonosulpho acid of the aforesaid Specifications of
Patents No. 136658, and 185778, are distinguished by their extreme clearness and
their eosine like colour.
II PROCESS FOR THE MEANTZA CVETIDE AR
NEW AMIDON ABOUTHIOL

page_text: the alpha-naphthylamine-zeta-disulpho acid with 2.5 parts of soda containing
75 per cent. of sodium hydrate, to which 10 per cent. of water are added, is melted
at a temperature not rising above 200 degrees Centigrade. On dissolving the melt
in mineral acids the new amido-naphthol monosulpho acid separates in fine white
needles.
It dissolves with difficulty in cold water, but more readily in hot water and
crystallises from the latter in short compact white needles. Its alkaline salts are
easily soluble in water. A neutral solution of the acid is coloured a blackish-violet
by chloride of iron and is turned red by chloride of lime this colour being destroyed
however by an excess of the said chloride.
In comparison with the beta-amidonaphtholmono sulpho acid obtained from
beta-amidonaphthalene disulpho acid G the new acid is of high value as when
combined with tetrazo compounds, especially tetrazodiphenyl, it affords valuable
blueish-black (and not violet black) colouring matters.
III. PROCESS FOR THE MANUFACTURE OF A NEW AMIDONAPHTHOL-
DISULPHO ACID.
By melting with caustic alkalies at a temperature of from about 180 to
190 degrees Centigrade the naphthylaminetrisulpho acid obtained by nitrating
the naphthalenetrisulpho acid (described in the Specification of the German
Patent No. 38281) and reducing the same, according to the researches of my
foreign correspondents, a new amidonaphtholdisulpho acid results the manufacture
of which is performed in the following manner.
One part by. weight of naphthylaminetrisulpho-acid, two parts of caustic soda,
aud a little water are melted at a temperature from 180 to 190 degrees Centigrade
until the melt has become clear and mobile and a test portion on addition of water
shows a bluish red fluorescence. After treating the melt with the calculated
quantity of hydrochloric acid the new amidonaphtholdisulpho acid separates in
delicate needles and in almost theoretical quantity. The acid is moderately soluble
in cold water but readily in hot water and reduces ammoniacal silver solutions
on heating. Chloride of iron and of lime produce in the solutions of the acid
a brown red colour which however is destroyed by the chloride of lime in excess.
Nitrous acid changes it into a diazo-compound which by boiling with water is
converted into the dihydroxynaphthalene disulpho acid herein before described in
the first part of this Specification. In an alkaline solution the acid possesses a
blueish-red fluorescence.
The fusion process for producing the dihydroxynaphthalene disulpho acid or
the amidonaphtholsulpho acids as herein before described may be carried out in
open or closed vessels with or without the aid of pressure.
IV. PROCESS FOR THE MANUFACTURE OF AZO-COLOURING MATTERS FROM THE
NEW ACIDS HEREINBEFORE DESCRIBED UNDER HEADS I, II AND III.
These new acids when combined with the diazo-compounds of aniline, of
amidophenol ethers or their homologues as well as the sulpho acids and nitro
derivatives of the latter substances, yield exceedingly beautiful magenta-red to
violet colouring matters; by combining the aforesaid three auids with the diazo
compounds of amidoazobenzene and its homologues of alpha and beta-naphthylamine,
of amidonapthol ethers and the sulpho acids of these substances, violet to blue
colouring matters result which are especially distinguished by the clearness of
their shades.
By combining the sulpho acids herein before described with the tetrazo com-
pounds of benzidine orthotolidine, paradiamido phenylorthotolyl, para diamido
orthodiphenol ether, paradiamido alkyloxydiphenyl,. paradiamido alkyloxy-
phenyltolyl, paradiamidostilbene, diamidofluorene. diamidonaphthalene (-a)
or by combining any one of the three acids with the diazo compound of para

page_text: amido acetanilide, separating the acetyl group, rediazotising and allowing the
products thus obtained to act on amines, phenols, naphthols, dihydroxynaphthalenes
amidonaphthols or their. sulpho or carboxy acids substantive violet to blue colouring
matters result which are adapted for dyeing unmordanted cotton in an alkalinė
- bath. Similar dyeing properties are characteristic of the azo colouring inatters
derived from the diazo compounds of dehydrothiotoluidine and dehydrothioxylidine
or their sulpho acids.
Instead of combining one molecular proportion of the above mentioned tetrazo
compounds with two molecular proportions of the new dihydroxynaphthalenedi-
sulpho acid or the amidonaphthol sulpho acids, these ingredients may be combined
in equi-molecular proportions, intermediate products being formed, which are then
combined most practically in an acetic acid solution with equi-molecular proportions
of an amine, phenol, naphthol, dihydroxynaphthalene or the sulpho or carboxy
acids thereof.
The same products may also be obtained by combining equi-molecular pro-
portions of the intermediate product formed from one of the tetrazo compounds
herein before enumerated and an amine, a phenol, their sulpho or carboxy acids in
equi-molecular proportions with the new dihydroxynaphthalenedisulpho acid or
with the amidonaphtholsulpho acids.
By combining the aforesaid tetrazo compounds with one or two molecular pro-
portions of alpha naphthylamine or alpha amidonaphthol ether and after diazotising
these products combining the resulting tetrazo compounds with one molecular
proportion of an amine or phenol, naphthol, dihydroxynaphthalene, amidonaphthol
or their sulpho or carboxylic acids and one molecular proportion of the new sulpho
acids herein before described azo colouring matters are obtained which directly dye
cotton blue to blueish-black shades. Black to blueish black colouring matters for
wool however are obtained from the amidoazo products derived from the diazo
derivatives of aniline or its homologues, the amidophenols or naphthol ethers, alpha
and beta naphthylamine or their mono or disulpho acids and alpha naphthylamine
or alpha-amidonaphthol ether by diazotising and causing the products to act on the
new dioxynaphthalenedisulpho acid or the amido naphthol sulpho acid.
Colouring matters dyeing black on mordanted wool are obtained from the azo
colouring matters obtained from diazohydroxy-benzoic-acids, diazo-cresol-carboxy-
acids, diazo-hydroxy-benzoic-sulpho-acids, diazo-benzoic acids or diazo-phthalic-
acid and alpha-naphthylamine by diazotising them and coupling the products with.
the new dihydroxy naphthalenedisulpho acid or the amidonaphtholsulpo acids.
In producing all these colouring matters the diazo or tetrazo compound is to be
added to a solution of the dihydroxynaphthalene disulpho acid or of the amido-
naphthol sulpho acids which is maintained alkaline throughout the operation by.
means of soda, but the preparation of the colouring matter can also be effected in
presence of acetic acid.
If, when employing the tetrazo derivatives, it be desired to produce the inter-
mediate products, the dihydroxy-naphthalene-disulpho acid or either of the amido
naphtholsulpho acids is mixed with the tetrazo compound in equi-molecular
proportions in a solution made weakly acid by acetic acid and the mixture is allowed..
to stand at a low temperature until no more of the tetrazo compound can be detected
than is present in the solution; the intermediate product which is in the form of a.
precipitate suspended in the liquid is then combined with equi-molecular proportions
of one of the said amines, phenols, amidonaphthols or their sulpho acids in the well
known manner.
The following are given as examples of the manufacture of. these azo colouring.
matters the parts being by weight.

page_text: of 20 degrees Baumé and the necessary quantity of water; after cooling to 0 degrees
Centigrade the solution is diazotised in the usual manner with 7 parts of sodium
nitrite.
The diazo solution thus obtained is then allowed to flow into a solution
of 37-5 parts of the sodium salt of dihydroxynaphthalene disulpho acid and 30 parts
of acetate of sodium.
After standing for about o hours the production of the colouring matter is
completed. The product dyes wool and silk in acid baths beautiful red shades.
After standing for about onours the production of the colouring matter is
completed. The product dyes wool and silk in acid baths beautiful red shades.
2. COLOURING MATTER FROM PARADIAMIDO ORTHODIPHENOL ETHER AND
AMIDONAPHTHOLMONO SULPHO ACID.
A solution of tetrazodiphenol ether corresponding to 7 parts by weight of sodium
nitrite is poured into an icy cold solution of 30 parts of the sodium salt of amido-
naphtholmonosulpho acid and 25 parts of sodium carbonate, the solution being kept
stirred. The reaction is almost instantly completed. The colouring matter is
salted out filtered off, pressed and dried.
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 :-
I. The process for the manufacture of a new dihydroxynaphthalenedisulpho acid
consisting in inelting the sodium salt of alphanaphthol trisulpho acid (described in
the Specification of the application for German Patent dated May 17th 1890
No. K 7567) or the corresponding naphthosultonedisulpho acid (German Patent
dated February 1st 1890 No. 56058) with alkalies at about 200 degrees Centi-
grade.
II. The production of a new amidonaphtholmono sulpho acid by melting alpha
naphthylamine zeta-disulphoacid with alkalies at a temperature below 210° degrees
Centigrade.
III. The process for the manufacture of a new amidonaphtholdisulpho acid by
melting the naphthylamintrisulpho acid which is obtained by nitration and reduction
from the naphtalenetrisulpho acid described in the Specification of the German
Patent No. 38281 with alkalies at a temperature from about 180 to 190 degrees
Centigrade.
IV. The production of magenta-red to violet azo colouring matters by combining
equi-molecular proportions of the new dihydroxynaphthalene disulpho acid or the
new amidonaphtholsulpho acids with the diazo compounds of aniline, of amidophenol
ethers or their analogues or of the sulpho acids or the nitro derivatives of these
substances.
'
V: The production of violet to blue azo dye stuffs by the combination of any one
of the three new acids described in this Specification with the diazo compounds
of amido azo benzene and its homologues of alpha and beta-naphthylamine, of
amidonaphthol ethers or the sulpho derivatives of these substances.
VI. The process for the manufacture of substantive violet to blue colouring
matters by combining any one of the three new sulpho acids described in this
Specification with paratetrazodiphenyl, paratetrazoorthoditolyl, paratetrazophenyl-
orthotolyl, paratetrazoorthodiphenolether, tetrazoalkyloxydiphenyl, tetrazo-
alkyloxyphenyltolyl, tetrazostilbene, tetrazofluorene or tetrazonaphthalene (a, a)
or by combining any one of the new three acids described in this Specification with
the diazo compound of para amidoacetanilide then separating the acetyl group and
rediazotising and then combining the amidoazo-compounds thus obtained with
amines, phenols, naphthols, dihydoxynaphthalenes, amido-naphthols, their sulpho or
carboxylic acids.
VII. The production of new azo dyestuffs by combining any one of the aforesaid
three sulpho acids with equi-molecular proportions of dehydrothiotoluidine and
dehydrothioxylidine or their sulpho acids.

page_text: VIII. The process for the manufacture of new mixed substantive azo colouring
matters by combining the tetrazo compounds of the foregoing sixth claim with one
molecular proportion of the new dihydroxynaphthalene disulpho acid or the amido-
naphthol sulpho acids described in this Specification and with one molecular
proportion of an amine, phenol, naphthol or dihydroxynaphthalene or their sulpho
or carboxylic acids.
IX. The production of substantive dye-stuffs by combining one molecular pro-
portion of the above mentioned tetrazo compounds first with one molecular proportion
of an amine, phenol, naphthol, their sulpho or carboxylic acids and then with one
molecular proportion of any one of the herein before mentioned three new acids
described in Claims I to III of this Specification.
X. The process for the manufacture of blue to blueish black substantive azo
colouring matters consisting in combining the aforesaid tetrazo compounds with one
or two molecular proportions of alphanaphthylamine alpha amidonaphtholether,
diazotising the intermediate substances thus obtained and further combining there-
with first one molecular proportion of an amine, phenol, naphthol, dihydroxy-
naphthalene or amidonaphthol or their sulpho or carboxylic acids and then with
one molecular proportion of any one of the three new acids herein before mentioned.
"XI. The manufacture of black azo dye-stuffs by combining one molecular pro-
portion of the diazo derivatives of aniline or its homologues the amidophenols or
naphtholethers or of alpha or beta naphthylamine or their mono or disulpho acids,
with one molecular proportion of alpha naphthylamine or alpha-amido-naphtholethers,
diazotising the amidoazo compounds thus obtained and combining therewith one
molecular proportion of any one of the three new acids herein before inentioned.
XII. The production of black to blueish black colouring matters by combining
the diazo-derivatives of benzoic acids, hydroxybenzoic acids cresol carboxylic acids
hydroxybenzoic acids or phthalic acids with one molecular proportion of alpha
naphthylamine rediazotising the amidoazo compounds obtained and combining the
resulting diazo derivatives with one molecular proportion of the new dihydroxy-
napthalene disulpho acid or the new amidonaphthol sulpho acids hereinbefore
described.
XIII. As new articles of manufacture the new dihydroxynaphthalenedisulpho
acids and the two amidonaphtholsulpho acids such as are produced by proceeding
as described under the first, second and third claims of this Specification and the
colouring matters produced by means of these three acids as hereinbefore described
and claimed.