The Manufacture and Production of New Azo-dyes, and of a Component for use in their Manufacture.
Year: 1893

page_text: Date of Application, 6th Feb., 1893
Complete Specification Left, 6th Nov., 1893-Accepted, 16th Dec., 1893
PROVISIONAL SPECIFICATION.
The Manufacture and Production of New Azo-dyes, and of a
Component for use in their Manufacture.
I JAMES YATE JOHNSON of 47 Lincolns 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
Ludwigshafen on Rhine in the Empire of Germany) to be as follows:-
This invention relates principally to the manufacture of new azo-dyes of various
types which are obtained by the use of a new amido-naphthol-monosulpho acid in
suitable ways as hereinafter set forth.
:
The said amido-naphthol-mono-sulpho acid is obtained by melting the corre-
sponding beta-naphthylamine disulpho acid with a caustic alkali. The said naph-
thylamine-disulpho-acid is obtained in admixture with another disulpho acid by
further sulphonating the 2.4' naphthylamine sulpho acid and its preparation and
isolation are described by Armstrong and Wynne in the Proceedings of the
Chemical Society 1890 page 128. These authors ascribe the constitution 2.4¹.2¹
to this acid.
Now my foreign correspondents have found that on treating this disulpho acid in
the caustic alkaline melt at a temperature of about from one hundred and sixty to
one hundred and eighty degrees centigrade the new amido-naphthol-mono-sulpho-
acid is obtained. This appears to possess the constitution represented by the
formule
This new amido naphthol-sulpho acid hereinafter called "the new component”
yields a large number of most valuable dyes.
I. Dis-azodyes capable of dyeing unmordanted vegetable fibre can be obtained
by the combination of one molecular proportion of a tetrazo-compound with two
As instances of
molecular proportions of the new component in alkaline solution.
tetrazo compounds I mention those from diamido-carbazole, diamido diphenylene
ketoxime, benzidine tolidine, dianisidine and paraphenylene-diamine (by the aid of
its acetyl compound). The dyes obtained from these tetrazo compounds on union
with the new component in alkaline solution are mostly of a blue or violet shade.
II. Mixed disazo-dyes can be obtained by replacing one molecular proportion
of the new component by one molecular proportion of another component (amido-
or phenolic body or sulpho- or carboxylic derivatives thereof) in the combination
with tetrazo compounds as mentioned under I.
III. The dyes so obtained according to I and II can themselves be diazotised
and combined with amido and phenolic bodies. This can be effected either on the
fibre or in the free state.
IV. In combining the new component with tetrazo and diazo compounds as set
forth under I and II, two series of dyes differing from one another in shade and
properties are obtained according to whether the union is effected in the presence
of an alkali or of an acid. Thus the dyes so obtained on combination in acid

page_text: solution are for the most part of a redder or yellower (less blue or violet) shade
than that of the corresponding dyes formed in the presence of an alkali.
Dated the 6th day of February 1893.
J. H. JOHNSON & Co.,
47, Lincoln's Inn Fields, W.C., Agents.
COMPLETE SPECIFICATION.
The Manufacture and Production of New Azo-dyes, and of a
Component for use in their Manufacture.
I, JAMES YATE JOHNSON of 47 Lincolns 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 and Soda Fabrik
of Ludwigshafen-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 :-
This invention relates principally to the manufacture of new azo dyes of various
types which are obtained by the use of a new amido-naphthol-mono-sulpho acid
in suitable ways as hereinafter set forth.
The said amido-naphthol-mono-sulpho acid is obtained by melting the corre-
sponding beta-naphthyl-amine-disulpho acid with a caustic alkali. The said
naphthylamine-disulpho acid is obtained-in admixture with other disulpho acid-
by further sulphonating the 2.4' naphthylamine sulpho acid, and its preparation
and isolation are described by Armstrong and Wynne in the Proceedings of the
Chemical Society 1890 page 128. These authors ascribe the constitution 2.4.21.
to this acid.
My foreign correspondents have found that on treating this disulpho acid in the
caustic alkaline melt at a temperature of about from one hundred and sixty to
one hundred and ninety degrees centigrade the new amido-naphthol-mono-sulpho
acid is obtained (see Example 1). This appears to possess the constitution
represented by the formula
This new amido-naphthol-sulpho acid, hereinafter called "the new component,"
yields a large number of most valuable dyes.
I. Dis-azo-dyes capable of dyeing unmordanted vegetable fibre can be obtained
by the combination of one molecular proportion of a tetrazo-compound with two
molecular proportions of the new component in alkaline solution. As instances of
tetrazo compounds I mention those from diamido-carbazole, diamido-diphenylene
ketone, diamido-diphenylene-ketoxine, benzidine, tolidine, dianisidine and para-
phenylene-diamine (by the aid of its acetyl compound). The dyes obtained from
these tetrazo compounds on union with the new component in alkaline solution are
mostly of a blue or violet shade (see Example 2).
II. Mixed dis-azo-dyes can be obtained by replacing one molecular proportion
of the new component by one molecular proportion of another component (amido
or phenolic-body or sulpho- or carboxylic-derivatives thereof) in the combination
with tetrazo compounds as mentioned under I (see Examples 3 and 4).
The following are the components which my foreign correspondents chiefly
recommend for use in the manufacture of the mixed disazo-dyes:-beta-naphthol-
disulpho acid R, 1.4 alphanaphthol-alpha-sulpho acid, alpha-naphthylamine,

page_text: chrysoidine sulpho acid (obtained by combination of diazo-sulphanilic acid with
meta-phenylene-diamine), meta-phenylene- and toluylene-diamine, naphthionic acid
and salicylic acid. The two last named components must be combined with the
tetrazo-body employed before the new amido-naphthol sulpho acid.
III. The dyes so obtained, according to I and II can themselves be diazotized
and combined with amido- or phenolic-bodies on the fibre in the well-known way
(see Green Journal of Society of Chemical Industry 1888, 179).
As components for use on the fibre in this way my foreign correspondents chiefly
recommend, alpha- and beta-naphthol, resorcinal, meta-phenylene- and toluylene
diamine, ethyl-beta-naphthylamine, alpha, amido-beta-naphthol-ether, para-amido-
diphenyl-amine and 1.4 alpha-naphthol-alpha-sulpho acid.
IV. In combining the new component with tetrazo- and disazo-compounds as set
forth under I and II two series of dyes differing from one another in shade and
properties are obtained according to whether the union be effected in the presence
of an alkali or of an acid. Thus the dyes so obtained on combination in acid
solution are for the most part of a redder or yellower (less blue or violet) shade
than that of the corresponding dyes formed in the presence of an alkali (see
Example 5).
The following examples afford instances of the manner in which this invention can
be carried into practical effect but many changes can be introduced in the various
cases without departing from the invention.
EXAMPLE 1.
PREPARATION OF THE NEW AMIDO-NAPHTHOL-SULPHO ACID.
Mix together about fifty parts of the sodium salt of the hereinbefore mentioned
beta-naphthylamine disulpho acid, about one hundred and fifty parts of caustic soda
and about thirty parts of water and heat the mixture to a temperature of about
one hundred and seventy to one hundred and ninety degrees centigrade for about
one hour. To determine the completion of the reaction take test-portions of the
melt at short intervals, dissolve in water and add hydrochloric acid. When no
further increase in the quantity of amido-naphthol-sulpho acid which precipitates
on cooling is observed the operation may be interrupted and the whole worked up.
For this purpose break up the melt when cold and add it to a mixture of three
hundred parts of ice and seven hundred parts of hydrochloric acid (containing about
thirty per cent. real acid HCI). The liquid becomes hot, and on cooling the amido-
5 naphthol-sulpho acid separates out as a crystalline powder. Filter, wash with cold
water, press, and dry.
The new amido-naphthol-monosulpho acid is a greyish, or white, crystalline
powder, not very soluble in cold water, more soluble on heating, almost insoluble
in alcohol, and readily soluble in alkali. From the alkaline solutions it is gradually
O precipitated on the addition of an acid.
PREPARATION OF A NEW DISAZO-DYE FROM BENZIDINE AND THE NEW
AMIDO-NAPHTHOL-MONO-SULPHO ACID.
Prepare a solution of tetrazo-diphenyl by treating about eighteen and a half parts
of benzidine in the well-known way and pour the tetrazo-solution into an ice cold
dilute soda solution and then immediately add a solution of about forty eight parts
of the new amido-naphthol-mono-sulpho acid. Stir for about four hours filter,
press, and dry.
In the same manner the dyes can be obtained from all the other diamido-bases
mentioned under I with the exception of para-phenylene-diamine. The dyes from
this base are obtained as aforesaid by the use of the acetyl-compound thereof:
(See also the following example.)

page_text: PREPARATION OF MIXED DISAZO DYES FROM PARA-PHENYLENE-DIAMINE AND
THE NEW AMIDO-NAPHTHOL-MONO-SULPHO ACID.
Prepare the diazo-compound from about fifteen parts of acetyl-para-phenylene
proceeding in the manner described in the Specification of German Letters Patent
No. 42814 (Friedländer, Fortschritte der Thurfarbenfabrikation II 446) and com-
bine it in alkaline solution with about twenty five parts of the sodium salt of alpha-
naphthol-alpha sulpho acid (Nevill and Winther's acid). Saponify the product and
diazotize the resulting amido-azo compound with about seven parts of sodium
nitrite and the requisite quantity of hydrochloric acid and run the diazo compound
into a solution of about twenty four parts of amido-naphthol-sulpho acid and
one hundred parts of calcined soda in about one thousand parts of water.
PREPARATION OF MIXED AZO-DYES FROM BENZIDINE, THE NEW AMIDO-
NAPHTHOL-MONO-SULPHO ACID AND OTHER COMPONENTS.
Prepare the tetrazo-diphenyl solution in the usual way from about thirteen parts
of benzidine chlorhydrate, seven hundred and fifty parts of water, seventeen parts
of hydrochloric acid (containing about thirty per cent. real acid HCl) and
seven parts of sodium nitrite in ten per cent. solution. Pour the tetrazo-solution
into a mixture of about seven parts of salicylic acid about forty parts of calcined
soda and about two hundred and fifty parts of water.
When the production of the intermediate products is complete add a solution of
about twelve parts of the new amido-naphthol-sulpho acid, about thirty parts of
calcined soda, and about two hundred and fifty parts of water. After some time
boil the mixture and precipitate the dye with common salt.
Prepare a solution of tetrazo-ditolyl in the well known way from about fourteen
and two tenths parts of tolidine chlorhydrate, seven parts of sodium nitrite and
seventeen parts of hydrochloric acid (thirty per cent. HCI) run this solution into a
mixture of about twenty four parts of amido-naphthol-mono-sulpho acid dissolved
in about six hundred parts of water, with the aid of about sixty five parts of soda
solution, containing about thirty five per cent. Na2CO3) and acidify with about
one hundred and fifty parts of acetic acid (containing about thirty per cent. real
acid C,HO). In the same solution are also dissolved about thirty three parts of
acetate of soda. After a short time the combination is effected. Isolate and
collect the dye in the usual way.
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:
(1.) The manufacture of the new amido-naphthol-sulpho acid hereinbefore
described and referred to as the new component, by treating the so called
2.4.2 naphthylamine-disulpho acid in the caustic alkaline melt.
(2.) As a new product the new amido-naphthol sulpho acid hereinbefore
described and termed the new component such as can be obtained substantially in
the manner herein before described and claimed in the foregoing claiming clause,
and the use of the said new component in the manufacture of azo dyes.
(3.) The manufacture of symmetrical disazo dyes by the combination of the

page_text: tetrazo compounds hereinbefore mentioned with the aforesaid new component
in alkaline or acid solution and substantially in the proportions herein before
described.
(4.) The manufacture of mixed disazo-dyes from the tetrazo compounds herein-
before mentioned the aforesaid new component and the other components herein-
before set forth, all substantially as hereinbefore described.
(5.) The conversion of the dyes referred to in the foregoing third and fourth
claiming clauses into other new dyes by diazotizing on the fibre and then combining
with the components hereinbefore recommended for this purpose.
(6.) As new products the new azo-dyes derived from the aforesaid new component,
and such as can be obtained substantially as hereinbefore described and claimed
under the claiming clauses 3, 4 and 5.
1902
J. H. JOHNSON & Co.,
Agents.