Improvements in and relating to the Manufacture and Production of Azo-dyes, and of Materials therefor.
Year: 1891

page_text: Date of Application, 21st Nov., 1801
Complete Specification Left, 19th Aug., 1892-Accepted, 24th Sept., 1892
PROVISIONAL SPECIFICATION.
Improvements in and relating to the Manufacture and Production
of Azo-dyes, and of Materials therefor.
I, JAMES YATE JOHNSON, of 47 Lincoln's Inn Fields, in the County of
Middlesex, Gentleman, do hereby declare the nature of this invention (which has
been communicated to me from abroad by the Badische Anilin & Soda-Fabrik,
of Ludwigshafen on Rhine, in the Empire of Germany,) to be as follows :-
In the Specification of Letters Patent No. 9676 of the year 1890 granted to
me, there is described the production of a 1-11 amido-naphthol mono-sulpho-acid
which, on combination with tetrazo-compounds, gives dyes which are however of a
dull colour. On converting this 1-11 amido naphthol sulpho-acid into its benzoyl,
or acetyl, derivatives and combining these new compounds with the tetrazo-
compounds of benzidine, tolidine and the like bright dyes are obtained which can
only be dyed on cotton from a caustic alkaline bath and it is only by the use of
tetrazo-compounds containing a sulpho, or carboxyl, group that substantive dyes.
which can be applied in the ordinary way from a soda or soap bath, are
obtained.
The present invention is based upon the production of a new isomeric 1·1'
amido-naphthol sulpho-acid and its use in the manufacture of new azo dyes. This
new acid combines with diazo- and tetrazo-bodies giving for the most part dull
colours, but can be converted into its acetyl, benzoyl, or similar, derivatives
and these yield with the tetrazo-compounds of benzidine and its analogues, bright
dyes which can be used in the ordinary way from the common alkaline, or soap,
bath. It is therefore in this case unnecessary to use the tetrazo-compounds of the
carboxy- or sulpho-derivatives of benzidine.
The following examples will serve to further illustrate and explain the nature of
the invention but they are merely to be regarded as typical and the invention is
not restricted to them.
EXAMPLE 1. PREPARATION OF A NEW ISOMERIC
SULPHO-ACID.
ין,!
AMIDO-NAPHTHOL-
The naphthylamine disulpho acid obtained by sulphonating the 11' naphthyl-
amine sulpho-acid, which forms a slightly soluble sodium salt (the so called
naphthylainine mono-sulpho-acid S, see the Specifications of English Patent
No. 15,775 of 1885 and German Patent No. 40571; and Friedländer, Vol. 1,
page 393 and following pages) serves as a material from which to start in pro-
ducing the desired new isomeric 11' amido naphthol sulpho acid, which is herein-
after, for the sake of distinction, called 1·1¹ hydroxy-naphthylamine-mono-sulpho
acid.
The parts are by weight.
Mix together one part of the sodium salt of the said naphthylamine disulpho
acid with three parts of caustic alkali, with the aid of a little water. Then heat
the mixture to from about two hundred to two hundred and thirty degrees
centigrade and maintain the heat until no increase in the quantity of 11' hydroxy-
naphthylamine-mono-sulpho acid formed, can be noticed, on dissolving test portions
of the melt in an excess of warm dilute hydrochloric acid and allowing the solution
to cool, when the desired acid separates out.
This point being reached, allow to cool, dissolve and acidify the melt with
dilute hydrochloric acid, containing about three per cent. of real acid. Boil till

page_text: the sulphurous vapours are driven off, then filter hot. From the filtered liquor
the 11 hydroxynaphthylamine-mono-sulpho acid separates out usually in the form
of light grey crystals.
The new 11 hydroxy-naphthylamine-mono sulpho acid is but slightly soluble
in either water or alcohol. Its alkaline salts are readily soluble in water and the
aqueous solutions when alkaline show a blueish-green fluorescence.
As aforesaid this new compound combines with diazo- and tetrazo compounds
and yields new azo dyes.
EXAMPLE 2. PRODUCTION OF THE BENZOYL DERIVATIVE OF 1.1'
HYDROXY-NAPHTHYLAMINE SULPHO-ACID.
Although in this example directions are given for the introduction of a benzoyl-
group only, into the molecule of the 111 hydroxy-naphthylamine compound still
other acid radicles may be introduced with good effect, by using the chlorides or
anhydrides of the corresponding acids, instead of the benzoyl-chloride hereinafter
described.
Dissolve about ten parts of 1.11 hydroxy-naphthylamine sulpho acid (obtained
as herein before described or in any other way) in the form of fine powder in a
solution of seven parts of calcined soda and ninety parts of water. Cool the
solution to about five degrees (+) centigrade, and then add carefully about five
and one fifth parts of benzoyl-chloride, shaking thoroughly and keeping the
temperature below ten degrees centigrade. Continue stirring for about an hour
after the addition is finished. The sodium salt, of the benzoylated acid separates
out and is filtered from the mother liquor, washed with salt solution, pressed and
dried.
The 11 hydroxynaphthylamine mono-sulpho acid containing an introduced acid
radicle combines with diazo and tetrazo compounds to yield azo dyes which are
for the most part brighter and more valuable than the corresponding compounds
obtained from the said mono-sulpho acid itself. In the following example the
preparation of a blue substantive dye by combination with the tetrazo compound
derived from benzidine is described, but a large number of other diazo or tetrazo
compounds can be used and dyes of various shades obtained.
EXAMPLE 3. PREPARATION OF A BLUE SUBSTANTIVE DYE.
Dissolve about twenty parts of the sodium salt of the benzoylated 1.11 hydroxy-
naphthylamine sulpho-acid, obtained as above described or in any other way, in a
solution of about fifteen parts of calcined soda in about six hundred and fifty parts
of water. To the cold solution add about one hundred parts of ice and then run
in a solution of tetrazo-diphenyl-chloride obtained in the usual way from about
four and three fifths parts of benzidine, sixteen and a half parts of hydrochloric
acid (containing about 30 per cent. HCI), two hundred and fifty parts of water,
fifty parts of ice and three and a half parts of sodium nitrite. Stir for about
twenty four hours at the ordinary temperature, boil and precipitate the dye from
the blue solution obtained by means of common salt; filter, press and dry.
The new substantive dye thus obtained is a dark brown powder with a slight
metallic sheen.
Dated this 21st day of November 1891.

page_text: COMPLETE SPECIFICATION.
Improvements in and relating to the Manufacture and Production
of Azo-dyes, and of Materials therefor.
I, JAMES YATE JOHNSON of 47 Lincoln's Inn Fields in the County of Middlesex,
Gentleman do hereby declare the nature of this invention (which has been com-
municated to me from abroad by the Badische Anilin & Soda Fabrik of Ludwig-
shafen on Rhine in the Empire of Germany) and in what manner the same
is to be performed to be particularly described and ascertained in and by the
following statement :-
In the Specification of Letters Patent No. 9676 of the year 1890 granted to me
there is described the production of a 11 amido-naphthol-imono-sulpho acid which,
on combination with tetrazo compounds gives dyes which are however of a dull
colour. On converting this 11 amido-naphthol-mono-sulpho acid into its benzol,
or acetyl derivatives and combining these new compounds with the tetrazo com-
pounds of benzidine tolidine and the like, bright dyes are obtained which can only
be dyed on cotton from a caustic alkaline bath and it is only by the use of tetrazo
compounds containing a sulpho, or carboxyl group that substantive dyes which can
be applied in the ordinary way from a soda, or soap bath are obtained.
The present invention is based upon the production of a new isomeric 11' amido
naphthol-sulpho acid and its use in the manufacture of new azo-dyes.
This new acid combines with diazo and tetrazo bodies giving for the most part
dull colours, but can be converted into its acetyl, benzoyl, or similar derivatives,
and these yield with the tetrazo compounds of benzidine and its analogues, bright
dyes which can be used in the ordinary way from the common alkaline or soap
bath. It is therefore in this case unnecessary to use the tetrazo compounds of the
carboxy or sulpho derivatives of benzidine.
The following examples will serve to further illustrate and explain the nature of
the invention and the manner in which it can be carried into practical effect, but I
do not confine myself to them as variation can be made without essentially.
changing the nature of the products. The parts are by weight :-
EXAMPLE 1. PREPARATION OF A NEW ISOMERIC 11 AMIDO NAPHTHOL-
SULPHO ACID.
The naphthylamine disulpho acid obtained by sulphonating the 1-1' naphthyl-
amine-sulpho acid, which forms a slightly soluble sodium salt (the so called
naphthylamine-mono sulpho-acid-S, see the Specification of Letters Patent
No. 15775 of 1885 and the Specification of the German Patent No. 40571 and
Friedländer, Vol. 1, page 393 and following pages) serves as a material from
which to start in producing the desired new isomeric 11' amido-naphthol-sulpho
acid which is hereinafter for the sake of distinction called 11 hydroxy-
naphthylamine-mono-sulpho acid.
Mix together one part of the sodium salt of the said naphthylamine-disulpho
Then heat the
acid with three parts of caustic alkali with the aid of a little water.
mixture to from about two hundred to two hundred and thirty degrees centigrade
and maintain the heat until no increase in the quantity of 11 hydroxy-naphthyl-
amine-mono-sulpho acid formed can be noticed, on dissolving test portions of the
melt in an excess of warm dilute hydrochloric acid and allowing the solution to
cool, when the desired acid separates out. This point being reached, allow the
melt to cool and dissolve and acidify it with dilute hydrochloric acid con-
taining about three per cent. of real acid. Boil till the sulphurous vapours are
driven off and then filter hot. From the filtered liquor the 11' hydroxy-naphthyl-
amine-mono sulpho acid separates out, usually in the form of light grey crystals.
The new 11 hydroxy naphthylamine mono-sulpho-acid is but slightly soluble in

page_text: aqueous solutions when alkaline shew a bluish green fluorescence.
As aforesaid this new compound combines with diazo and tetrazo compounds and
yields new azo-dyes.
EXAMPLE 2. PRODUCTION OF THE BENZOYL DERIVATIVE OF 1'11
JIYDROXY-NAPHTHYLAMINE-SULPHIO ACID.
Although in this example directions are only given for the introduction of a
benzoyl group into the molecule of the 111 hydroxy naphthylamine compound,
other acid radicles may be introduced with good effect, by using the chlorides or
anhydrides of the corresponding acids, instead of the benzoyl-chloride hereinafter
described.
Dissolve about ten parts of' 11' hydroxy naphthylamine sulpho acid (obtained as
herein before described or in any other way) in the form of fine powder, in a
solution of seven parts of calcined soda and ninety parts of water.
Cool the
solution to about five degrees (+) centigrade, and then add carefully thereto about
five and one fifth parts of benzoyl chloride, shaking or agitating thoroughly and
keeping the temperature below ten degrees centigrade. Continue the agitation for
about an hour after the addition is finished. The sodium salt of the benzoylated
acid separates out and is filtered from the mother liquor, washed with salt solution
pressed and dried.
The 11 hydroxy-naphthylamine mono-sulpho-acid containing an introduced acid
radicle combines with di-azo and tetrazo compounds to yield azo dyes which for the
most part dye brighter and more valuable shades than do the corresponding
compounds obtained from the said mono sulpho acid itself.
In the following example the preparation of a blue substantive dye by combination
with the tetrazo compound derived from benzidine is described, but a large number
of other diazo or tetrazo compounds can be used and dyes of various shades be
obtained.
EXAMPLE 3. PREPARATION OF A BLUE SUBSTANTIVE DYE.
Dissolve about twenty parts of the sodium salt of the benzoylated 1·1' hydroxy-
naphthylamine sulpho acid (obtained as hereinbefore described or in any other
way) in a solution of about fifteen parts of calcined soda in about six hundred and
fifty parts of water. Add to the cold solution about one hundred parts of ice and
then run in a solution of tetrazo-diphenyl-chloride which may he obtained in- the
isual way from about four and three-fifths parts of benzidine, sixteen and a half parts
of hydrochloric acid (containing about 30 per cent. HCl), two hundred and fifty
parts of water, fifty parts of ice, and three and a half parts of sodium nitrite. Stir
for about twenty four hours at the ordinary temperature, boil and precipitate the
dye from the blue solution obtained by means of common salt; filter, press,
and dry.
The new substantive dye thus obtained is a dark brown powder with a slight
metallic sheen.
Having now particularly described and ascertained the nature of the said
invention and in what manner the same is to be performed I declare that what
I claim is :-
1. The manufacture of substantive dyestuffs by the combination of processes
herein before described; namely, by melting the naphthylamine disulpho acid
hereinbefore mentioned with a caustic alkali to obtain a new 1-1 amido-naphthol-
mono-sulpho acid, then preparing from this a substitution compound with an
organic acid radicle and finally combining this substituted amido-naphthol-mono-
sulpho-acid with tetrazo-compounds (in particular with tetrazo-diphenyl and
tetrazo-ditolyl) all substantially as hereinbefore described.

page_text: 2. The manufacture of the new 11' amido naphthol-mono-sulpho-acid sub-
stantially as hereinbefore described.
3. The manufacture of substituted derivatives of 1·1' amido-naphthol-mono-
sulpho acids substantially as herein before described.
4. The application of 1·11 amido-naphthol mono-sulpho-acid or of its substituted
derivatives as hereinbefore explained in the manufacture of substantive dyestuffs
by combining them with tetrazo-compounds for the production of substantive dyes
all substantially as herein before described.
5. The new products such as are obtained as the result of the processes herein-
before claimed.
Dated this 19th day of August 1892.
J. H. JOHNSON & Co.,
Agents.