The Manufacture and Production of a New Amido Sulpho Acid and of New Azo-dyes therefrom.
Year: 1893

page_text: Date of Application, 31st July, 1893
Complete Specification Left, 17th Apr., 1894-Accepted, 19th May, 1894
PROVISIONAL SPECIFICATION.
The Manufacture and Production of a New Amido Sulpho Acid and
of New Azo-dyes 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 & Soda Fabrik,
of Ludwigshafen-on-Rhine, in the Empire of Germany) to be as follows:-
This invention relates to the manufacture of a new disulphoacid of meta-
phenylene-diamine and to the production of azo dyes by combination of the said
disulphoacid with diazo-compounds.
By direct sulphonation of metaphenylene diamine only a monosulpho acid has up
to the present been obtained (ser Post and Hardtung, Annalen der Chemie 205, 104).
This acid on combination with diazo compounds for the most part yields dyes
giving colour shades similar to the corresponding metaphenylene diamine compounds
and the colours are very sensitive to acid.
My foreign correspondents have found however that by the use of the new
disulphoacid hereinafter described dyes can be obtained differing essentially from
those obtained from the monosulphoacid not merely in shade but also in possessing
greater resistance against the action of acid.
As instances of the new dyes I mention those obtainable by the aid of the
diazo-compounds derived from aniline, toluidine and xylidine. These resemble fast
yellow (amido-azo-benzul-sulphoacid) in their dyeing properties and in the shades
they yield upon wool but they are faster against the action of acids. Another of
the new dyes which possesses the important property of dyeing cotton without the
aid of a mordant, is the combination with the diazo compound derived from primuline
which yields orange-yellow shades possessing a considerable resistance to the
action of acids. It thus differs essentially from the corresponding dye derived from
the monosulphoacid which is very sensitive to acids.
A large number of other azo-dyes of all the various types can be prepared from.
the new disulphoacid besides those herein mentioned as instances.
The new disulpho acid is obtained by treating metaphenylene diamine or salts
thereof with fuming sulphuric acid, sufficient acid being taken that at least two
molecular proportions of free or available sulphuric anhydride (SO) are present
for one molecular proportion of meta-phenylene diamine. If this condition be
satisfied the strength of acid and temperature of treatment may be varied within
certain limits, though the ease with which the reaction can be effected increases as
the excess of fuming acid present or the strength thereof is increased. Thus when
using an acid containing about ten per cent. free anhydride a temperature of about
one hundred and twenty degrees centigrade may be necessary to effect the reaction
whilst with an acid containing about seventy per cent. SO, a temperature of about
seventy degrees may be sufficient.
The following test will serve as a guide when preparing the new disulpho-acid.
Take a test-portion of the sulphonation melt and combine it in alkaline solution
with diazo-primuline. The dye obtained will fix itself on cotton giving orange-
yellow shades if the production of the desired disulphoacid be complete. The
presence of unchanged meta-phenylene diamine or of the mono-sulpho acid thereof
causes the colour to be of a browner shade.
The carrying out of the invention in practice is capable of great variation but
the following instances of methods of applying it in a few typical cases will scive
to further illustrate the nature of the invention. The parts are by weight.

page_text: EXAMPLE 1. PRODUCTION OF THE NEW META-PHENYLENEDIAMINE-
DISULPHOACID.
Mix one part of meta-phenylene-diamine-hydrochlorate with about five parts of
fuming sulphuric acid containing about forty per cent. free anhydride, keep cool
whilst mixing and subsequently heat the mixture, at first for a few hours at about
one hundred degrees centigrade, and subsequently raise the heat to about one
hundred and twenty degrees and maintain it for about six to ten hours or until
the test above described indicates the end of the reaction. Pour the mixture into
ice water, neutralize with milk of lime, filter from the sulphate of lime, and convert
into sodium salt in the usual way. The solution of sodium salt so obtained may
be used directly in the manufacture of dyes. The free acid may also be isolated.
For this purpose concentrate the solution of the calcium or sodium salt by
evaporation and add an excess of strong hydrochloric acid to the concentrated
solution, filter and dry the precipitate of disulpho acid which separates out.
When
pure this is a white crystalline powder readily soluble in hot water but less soluble
in cold water.
EXAMPLE 2. PRODUCTION OF A NEW Azo DYE FROM ANILINE AND
META-PHENYLENE-DIAMINE-DISULPHO ACID.
Prepare a solution of diazobenzene chloride in the well-known way taking about
nine and three tenths parts aniline, about twenty seven parts hydrochloric acid
(containing about thirty per cent, real acid HCI) and about seven parts of sodium
nitrite. No more water than is necessary should be taken so that the solution
obtained may be as concentrated as possible. Run this whilst stirring well, into
an ice cold solution of about twenty-eight parts of meta-phenylene-diamine-disulpho
acid and about thirty parts of crystallized sodium acetate in about one hundred
parts of water. After mixing thoroughly allow the mixture to stand for some
time, say several days, then boil, saturate the solution with common salt and add a
little bydrochloric acid. The dye which separates out is pressed and dried. It
constitutes an orange-yellow powder soluble in water and dyes wool yellow from
the acid bath.
Instead of effecting the combination in acetic acid solution as herein described a
weakly alkaline solution can be used.
Homologous dyes can be obtained by using the equivalent weights of ortho- or
para-toluidine (ten and seven tenths parts) or of meta-xylidine (twelve and
one tenth parts) instead of the nine and three tenths parts of aniline specified in
the above example.
EXAMPLE 3. PRODUCTION OF A SUBSTANTIVE DYE FOR COTTON FROM
PRIMULINE AND META-PHENYLENE-DIAMINE-DISULPHO ACID.
Diazotize about one hundred and twelve parts of primuline in aqueous solution
by adding about sixteen parts of sodium nitrite and about one hundred and forty
parts of hydrochloric acid (30 per cent. HCI) in the well known way. Run the
mixture into an ice cold solution of about fifty-five parts of meta-phenylene-
diamine-disulpho acid and about one hundred and twelve parts of calcined soda in
about seven hundred parts of water. Stir well for about twenty four hours,
precipitate the dye with common salt press and dry. The dye so obtained
constitutes a red-brown powder which dyes cotton orange-yellow without the aid
of a mordant.
Dated this 31st day of July 1893

page_text: The Manufacture and Production of a New Amido Sulpho Acid and
of New Azo-dyes therefrom.
I, JAMES YATE JOHNSON of 47 Lincoln's Inn Fields in the County of London
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) 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 to the manufacture of a new disulpho acid of meta-
phenylene-diamine and to its application in the production of azo dyes by
combination of the said disulpho acid with diazo compounds.
.
By direct sulphonation of metaphenylene-diamine only a monosulpho acid has
up to the present been obtained. (See Post and Hardtung, Annalen der Chemie
205, 104.)
This acid on combination with diazo compounds for the most part yields dyes
giving colour shades similar to the corresponding metaphenylene-diamine compounds
and the colours are very sensitive to acid.
My foreign correspondents have found however that by the use of the new
disulpho acid hereinafter described dyes can be obtained differing essentially from
those obtained from the monosulpho acid not merely in shade but also in possessing
greater resistance against the action of acid.
The new dyes obtainable by the aid of the diazo-compounds derived from
aniline, toluidine and xylidine resemble "fast yellow" (amido-azo-benzol-sulpho
acid) in their dyeing properties, and in the shades they yield upon wool, but they
are faster against the action of acids. Another of the new dyes, which possesses
the important property of dyeing cotton without the aid of a mordant is obtained
by the aid of the diazo compound derived from primuline which yields orange
yellow shades possessing a considerable resistance to the action of acids.
differs essentially from the corresponding dye derived from the monosulpho acid
which is very sensitive to acids.
It thus
The new disulpho-acid is obtained by treating metaphenylene-diamine or salts
thereof with fuming sulphuric acid sufficient acid being taken that at least two
molecular proportions of free or available sulphuric anhydride (SO3) are present for
one molecular proportion of metaphenylene-diamine. If this condition be satisfied
the strength of acid and temperature of treatment may be varied within certain
limits, though the ease with which the reaction can be effected increases as the
excess of fuming acid present, or the strength thereof, is increased. Thus when
using an acid containing about ten per cent. free anhydride a temperature of about
one hundred and twenty degrees centigrade may be necessary to effect the reaction
whilst with an acid containing about seventy per cent. SO3 a temperature of about
seventy degrees may be sufficient.
The following test will serve as a guide when preparing the new disulpho-acid.
Take a test portion of the sulphonation melt and combine it in alkaline solution
with diazo-primuline.
The dye obtained will fix itself on cotton giving orange yellow shades if the
production of the desired disulpho-acid be complete.
The presence of unchanged meta-phenylene diamine or of the mono sulpho acid
thereof causes the colour to be of a browner shade.
The following examples will serve to further illustrate the nature of the
invention and the method of carrying it into practical effect. The details may be
varied in many respects without departing from the invention.
The parts are by weight.

page_text: before described; and the use of the said disulpho acid in the production of
azo-dyes.
(2.) The manufacture of new azo-dyes by the combination of the diazo-compounds
herein before mentioned with the meta phenylene-diamine disulpho-acid.
(3.) The manufacture of new azo dyes substantially in the manners herein before
described in Example 2 and in Example 3.
(4.) As new articles of manufacture the new meta-phenylene-diamine-disulpho-
acid and the new azo dyes derived therefrom all such as can be obtained in the
manner hereinbefore described.
Dated this 16th day of April 1894.
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, Agents.