The Manufacture and Production of New Sulpho Aoids of Certain Naphthalene Derivatives and of New Colouring Matters obtain- able therefrom.
Year: 1893

page_text: Date of Application, 2nd Feb., 1893
Complete Specification Left. 31st Oct. 1893-Accepted. 9th Dec.. 1893
PROVISIONAL SPECIFICATION.
The Manufacture and Production of New Sulpho Aoids of Certain
Naphthalene Derivatives and of New Colouring Matters obtain-
able therefrom.
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 and Soda Fabrik of
Ludwigshafen-on-Rhine, in the Empire of Germany,) to be as follows :-
This invention relates principally to the manufacture of a new alpha-naphthyl-
amine-disulpho acid, of a new amido naphthol sulpho acid, and of azo colouring-
matters derived therefrom.
The said alpha-naphthylamine disulpho acid may be considered as derived from
the so-called 14'-naphthylamine monosulpho acid. Attempts to prepare a disulpho
acid from this initial material have hitherto failed. My foreign correspondents
have discovered that by sulphonating the said 14'-monosulpho acid in the form of
its acetyl compound, the desired disulpho acid can be readily obtained, boing
produced in the form of its acetyl compound, which, however, readily parts with
its acetyl group. Examples of methods of producing the acetyl 14-naphthylamine
monosulpho acid and of its conversion into the disulpho acid are hereinafter given.
The new disulpho acid yields a diazo compound which forms azo-compounds
with phenolic and amido-bodies, and azo dyes can be obtained by the combination
of diazo- and tetrazo-compounds, but the principal use of the new disulpho acid it
is believed will be for the manufacture of the new amido-naphthol-mono-sulpho
acid.
This new amido-naphthol-mono-sulpho acid which appears to have the constitu-
tion represented by the formula
my foreign correspondents have discovered can be obtained by suitably melting
the new naphthylamine disulpho acid or salts thereof with a caustic alkali. This is
hereinafter described in Example 4.
My foreign correspondents have discovered that the new amido-naphthol-mono-
sulpho acid is capable of very extousive use in the manufacture of azo-dyes, as it
combines with diazo- and tetrazo-compounds, and can itself be diazotized and the
resulting diazo-compound be combined with phenolic and amido-compounds.
Moreover certain of the azo-dyes derived from the new amido-naphthol mono-
sulpho-acid cau themselves be diazotized (especially on the fibre) and combined
with a further component thereby giving dark to black shades. An example of
the production of a substantive dye is hereinafter given but a vast number of other
compounds can be obtained as set forth.
The following examples will servo to further illustrate the nature of the
invention but they are to be regarded as typical, the invention not being confined
thereto as it can be carried out in other ways. The parts are by weight.

page_text: EXAMPLE 3. MANUFACTURE OF THE NEW DISULPHO-ACID FROM ACETO-
ALPHA-NAPHTHALIDE.
Add about one part of aceto-alpha-naphthalide to about five parts of fuming
sulphuric acid containing about thirty-fivo per cent. free anhydride SO,. While
mixing maintain the temperature at about from zero to five degrees centigrade and
subsequently allow the mixture to stand at a temperature of about twenty-five to
thirty degrees contigrade for about twenty to twenty-four hours. Pour the
product onto about ten parts of ice, boil, and saturate the hot solution with common
salt, allow it to cool, collect the crystalline precipitato, pross, and dry.
EXAMPLE 4. Manufacture of the NEW AMIDO-NAPHTHOL MONOSULPHO
AOID.
Mix together about one hundred and fifty parts of caustic soda and about fifty
parts of water and heat the mixture to a temperature of about one hundred and
seventy degrees, then add about fifty parts of the acid sodium salt of naphthylamine
disulpho acid obtained as hereinbefore described or in any other way. Maintain
the temperature at about one hundred and sixty to one hundred and eighty degrees
centigrade for about one hour or until the end of the operation is seen from tests
made from time to time. To make those tests take a small portion of the melt,
dissolve it in a little water, acidify with hydrochloric acid, and allow it to cool.
When successive tests shew no further increase in the amount of precipitate forming
ou cooling the operation may be regarded as finished. When this point is ronchod
allow the melt to cool, break it up, and add to it a mixture of about four hundred
and fifty parts ice and about six hundred parts hydrochloric acid (containing about
thirty per cent. real acid HCl), allow the mixture to stand in the cold and then filter
off the amido-naphthol-sulpho-acid which separates out as a grey-white crystalline
precipitate.
The amido-naphthol-mono-sulpho acid so obtained is almost insoluble in cold
water; on treatment with nitrous noid it gives a diazo-compound which can be
obtained in the form of small orange-yellow needles. This diazo compound can be
used for the manufacture of azo-dyes by combination with amido-and phenolic bodies
and the amido-naphthol-mono-sulpho noid itself combines with dinzo- and tetrazo-
compounds to yield new azo dyes many of which possess very valuable properties.
EXAMPLE 5. PRODUCTION OF A BLUE SUBSTANTIVE Dyestuff.
Any diazo- or tetrazo-compound in ordinary use for the manufacturo of azo-dyes
can be used for combination with the new amido-naphthol-sulpho acid so that dyes
of various shades and properties can bo obtained. In particular I mention as
instances of tetraso-compounds which give good results, those from diamido-carbazol,
diamido-diphenylene, ketoxim, benzidine, tolidine, and dianisidine. In this example
I describe the production of a blue substantive dye from one molecular proportion
of diamido-carbazol and two molecular proportions of the new amido-naphthol-
mono-sulpho-acid. Prepare a solution of tetrazo-carbazol by treating about fourteen
and a half parts of diamido-carbazol-sulphate (in the form say of a 30% paste)
with about one hundred parts of ice, about fifty-soven parts of hydrochloric acid
(containing about 30 per cent. real acid HCl.) and a solution of about seven parts
of sodium nitrite. Prepare also a solution of about twenty four parts of the new
amido-naphthol-mono-sulpho-acid, about thirty nine parts of caustic soda lye
(containing about thirty five per cent. sodium hydrate NaOH), about thirty five
parts of calcined soda in about three thousand parts of water and into this solution
run the tetrazo-solution. Stir for several hours, boil and salt out the dye, filter
...

page_text: beautiful and intensely blue shades which are fast against washing and light and
withstand the action of acids wall. It can be diazotized on the fibre and combined
with phenolic- and amido-compounds giving dark to black shades some of which
possess very great fastness against washing, light, and acids.
In the last example instead of combining two molecular proportions of the new
amido-naphthol-mono-sulpho-acid with one molecular proportion of the tetrazo-
compound, one molecular proportion of another component may be used with one
molecular proportion of the new amido-naphthol-mono-sulpho-acid so that mixed
dis-azo-dyes results. In the same way mixed dis-azo-dyes can be prepared by
employing the other tetrazo compounds hereinbefore referred to.
Dated this 2nd day of February 1893.
J. H. JOHNSON & Co.,
47, Lincoln's Inn Fields, London, W.C.
COMPLETE SPECIFICATION.
The Manufacture and Production of New Sulpho Acids of Certain
Naphthalene Derivatives and of New Colouring Matters obtain-
able therefrom.
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 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 a new alpha-naphthyl-
amine-disulpho acid of a new amido-naphthol sulpho acid, and of azo-colouring-
matters derived therefrom.
.
The said alpha-naphthylamine disulpho acid may be considered as derived from
the so-called 14' naphthylamine monosulpho acid. Attempts to prepare a disulpho
acid from this initial material have hitherto failed. My foreign correspondents
have discovered that by sulphonating the said 1-4' monosulpho acid in the form of
its acetyl compound the desired disulpho-acid can be rendily obtained, being pro-
duced in the form of its acetyl compound, which however readily parts with its
acetyl group. Examples of methods of producing the acetyl 14 naphthylamine
monosulpho acid and of ita conversion into the disulpho acid are hereinafter given.
The new disulpbo-acid yields a diazo compound which forms nzo-compounds
with phonolic and amido bodies and azo-dyes can be obtained by the combination
of diazo and tetrazo compounds, but the principal uso of the new disulpho acid, it
is believed, will be for the manufacture of the new amido-naphthol-mono-sulpho
acid.
This new amido naphthol-mono-sulpho acid which appears to have the constitution
represented by the formula
my foreign correspondents have discovered can be obtained by suitably melting
the new naphthylamine disulpho acid or salts thereof with a caustic alkali. This
is hereinafter described in Example 4.
My foreign correspondents have discovered that the now amido-naphthol-mono-
sulpho acid is capable of very extensive use in the manufacture of azo-dyes, as it

page_text: combines with diazo- and tetrazo-compounds, and can itself be diazotized and the
resulting diazo-compound be combined with phenolic and amido-compounds.
Moreover certain of the azo-dyes derived from the new amido-naphthol-mono-
sulpho acid can themselves be diazotized (especially on the fibre) and combined
with a further component thereby giving brown-black, violet and black shades.
An example of the production of a substantive dye is hereinafter given but a vast
number of other compounds can be obtained as set forth.
The following examples will serve to further illustrate the nature of the inven-
tion but they are to be regarded as typical the invention not being confined thereto
as it can be carried out in many other ways.
The norte are he weight.
EXAMPLE 1. PREPARATION OF THE ACETYL-COMPOUND OF THE 1.4' NAPH-
THYL-AMINE-MONO-SULPHO ACID.
Mix together about five parts of 1-4 naphthyl-amine-mono-sulpho acid, about
thirty parts of glacial acetic acid, about three parts of anhydrous sodium acetate,
and about five parts of acetic anhydride and boil the mixture in a vessel provided
with an inverted condenser for about eight hours, or until a tost portion of the melt
practically no longer yields a diazo compound on treatment with nitrous acid.
When this point is reached heat in the oil bath to as completely as possible distil
off the acetic acid and any unchanged acetic anhydride. Dry the residue thoroughly.
The acetyl compound in the crude state so obtained contains sodium acotate
but it will as a rule be in a sufficiently puro condition for further use for ordinary
purposes.
If it be desired to obtain the acetyl compound in a purer state, mix the product
free from acetic acid and anhydride as above described in just sufficient water to
dissolve it and precipitate it with Glauber salt collect and dry. In this way the
acetyl compound is obtained as a white crystalline powder.
The acid obtained by proceeding as described in the foregoing example is con-
tained in the product which is described in the Specification of the lapsed German
Patent No. 42874. If desired it can be prepared by sulphonating aceto naphthalido
in a manner similar to that described in the said Specification, thus; mix together
about one part of aceto-alpha naphthalide and one part of anhydrous sodium
sulphate and add the mixture gradually to about five parts of fuming sulphurio
acid (containing about 23 per cent. free anhydride SO,). Cool this mixture well so
that its temperature remains at from zero to five degrees centigrade and allow it to
stand for about twelve hours in the cold and afterwards pour the mass onto about
five parts of ice. The acetyl compound of the mono-sulpho acid separates out as a
fine white crystalline powder.
In this way it is obtained admixed with other isomeric bodies but can nevertheless
be used for the preparation of the new naphthylamine disulpho acid.
EXAMPLE 2. PREPARATION OF THE NEW NAPHTHYLAMINE DISULPHO ACID.
Take the acetyl-compound resulting from the treatment of about five parts of
naphthylamine monosulpho acid as described in Example 1 either in the crude
state or after purifying as described and mix it with about forty parts of funning
sulphuric acid containing about thirty per cent. free anhydride 90. Stir, while
mixing, and cool so as to maintain the temperature between zero and fivo degrees
centigrado and allow the mixture to stand at a temperature of about twenty to
thirty degrees centigrade for about twelve or fifteen hours, or the end of the
reaction can be determined by taking a test portion from time to time diluting it
with water and boiling, and if, on cooling, no mono-sulpho acid which is but slightly
soluble in cold water separates out the reaction may be regarded as complete.
Pour onto about eighty parts of ice, beat the mixture so that it boils vigorously for
about half an hour to split off the acetyl group and allow it to cool. Collect the

page_text: crystalline precipitate which forms and if necessary recrystallize from common salt
solution.
The new disulpho acid is thus obtained in the form of an acid sodium salt, which
is readily soluble in cold water. On treatment with nitrous acid, the corresponding
djazo-compound is obtained and it can be obtained from concentrated solutions, by
adding common salt if necessary, in the form of pale yellow-needles. This diazo-
compound yields azo dyes on combination with amido- and phenolic-bodies, and as
aforesaid the disulpho acid is itself capable of combination with diazo-compounds
and the like.
The same disulpho acid can be obtained by sulphonating aceto alpha-naphthalide
beyond the degree hereinbefore described for the preparation of monosulpho acid,
but the product so obtained is admixed with isomeric bodies, it can however be used
in the production of the new amido-naphthol sulpho acid.

page_text: of the tetrazo-compounde hereinbefore mentioned with one molecular proportion of
the new amido-naphthol-mono-sulpho-acid and one molecular proportion of a third
component such as are herein before mentioned..
8. The production of brown-black, violet and black shades on the fibre by first
dyeing with one of the new dyes such as are claimed in the foregoing sixth and
seventh claiming clauses then diazotizing on the fibre and finally combining with
one of the further components hereinbeforo mentioned.
9. As new products the naphthylamine disulpho acid, the amido-naphthol-mono-
sulpho acid, and the azo-dyes obtainable therefrom all such as can be obtained
substantially as herein before described.
1009
J. H. JOHNSON & Co.,
Agents.