Manufacture and Production of Intermediate Products and of Colouring Matters therefrom
Year: 1898

page_text: Date of Application, 10th Feb., 1898
Complete Specification Left, 10th Nov., 1898-Accepted, 21st Jan., 1899
I
PROVISIONAL SPECIFICATION.
Manufacture and Production of Intermediate Products and of
Colouring Matters therefrom.
We, ARTHUR GEORGE GREEN, F.I.C., F.C.S., of 13, Kings Drive, Heaton Moor,
near Stockport, and ALEXANDER MEYENBERG, Ph.D., of 13, Nelson Street, Plymouth
Grove, Manchester, both Chemists to The Clayton Aniline Company Limited, of
Clayton, Manchester, in the County of Lancaster, do hereby declare the nature of
this invention to be as follows:-
This invention relates to the preparation of reduction products of the dinitro-
diphenyl-ethylene-disulphonic acid (otherwise called dinitrostilbenedisulphonic
acid)

page_text: to 17 lbs. of zinc dust (80% Zn) suspended in a solution of 12 lbs. of ammonium
chloride in 20 gallons of water. The mixture is rapidly agitated until the reduction
is complete and the crystals of the dinitro compound have completely dissolved.
The solution is then filtered from zinc oxide and the filtrate containing the hydroxyl-
amine is employed direct for the preparation of colouring matters.
CONVERSION OF THE HYDROXYLAMINE INTO COLOURING MATTERS.
The hydroxylamine exhibits the typical reactions and transformations of aromatic
hydroxylamines in general and owing to the chromophoric properties of the stilbene
group the products thus obtained are for the most part colouring-matters. Thus,
in addition to the above described transformation by acids, the hydroxylamine is
also converted into colouring-matters in the following ways:
(a) By oxidation with air, or other agents.
(4) By the action of caustic alkalies.
(c) By condensation with amines, phenols, amido-phenols, diamines, or their
sulphonic, or carboxylic, derivatives in alkaline solution.
(d) By condensation with nitro-compounds such as nitrobenzene, nitrotoluene,
nitrobenzene sulphonic acid; nitrotoluene sulphonic acid; and the like in
presence of caustic alkalies.
(e) By combination with aldehydes in neutral, or slightly acid, solution.
The production of colouring-matters by these reactions is illustrated by the
following examples :—
EXAMPLE 2.
A solution of the hydroxylamine obtained by reduction of 10 lbs. of dinitro-
diphenylethylene disulphonate of sodium, is diluted with water to 50 gallons, and
a stream of air is passed through it for several hours, until the solution no longer
gives a red colour on the addition of an alkali. The colour is precipitated by salt
filtered off and dried. It dissolves in concentrated sulphuric acid forming an
orange-red solution, and dyes yellow on unmordanted cotton. Its formation is
probably represented by the equation:
EXAMPLE 5.
A solution of the hydroxylamine obtained by reduction of 10 lbs. of dinitro-
diphenylethylene disulphonate of sodium as above is mixed with 30 gallons of
aqueous caustic soda (30% NaOH). After standing for several hours, or on gently
warming the red colour of the solution disappears and an orange precipitate is
thrown down. The solution is neutralised with hydrochloric acid and the colouring-
matter is filtered off and dried. It forms an orange powder which dyes a bright
reddish orange on unmordanted cotton. In concentrated sulphuric acid it dissolves
with a pure blue colour. Its formation is probably represented by the equation :

page_text: EXAMPLE .
10 gallons of the hydroxylamine solution, obtained by reduction of 2 lbs.
of dinitrodiphenylethylene-disulphonate of sodium, are mixed with 1 lb. of
paraphenylene diamine and 1 gallon of caustic soda (30% NaOH). The mixture is
heated at 90° C. for 2 or 3 hours until the red colour has completely disappeared.
It is then neutralised and the precipitated colour is filtered off and dried. The
product dyes orange on unmordanted cotton and can be diazotised and developed
upon the fibre. Similar products are obtained if the paraphenylene diamine be
replaced by metaphenylene diamine, aniline, toluidine, salicylic acid, amidophenols,
amidonaphthols, dehydrothiotoluidine sulphonic acid, benzidine, toluidine,
diamidostilbene disulphonic acid, and the like. Many of the condensation products
thus obtained contain amido groups and are therefore diazotisable either in
substance, or upon the fibre, giving, on development with the usual azo-dyestuff
components, various shades of yellow orange, red, brown and grey.
EXAMPLE 5.
10 gallons of the hydroxylamine solution, obtained by reduction of 2 lbs. of
dinitrodiphenylethylene disulphonate of sodium, are mixed with 2 lbs. of paranitro-
toluenesulphonate of sodium and gallon of aqueous caustic soda (30 % NaOH), and
heated for 1 or 2 hours at about 60° Contigrade until the red colour has disappeared.
The colour separates as a yellow granular precipitate which is filtered off and dried.
It dissolves in concentrated sulphuric acid, forming a crimson red solution. It dyes
yellow on unmordanted cotton.
If half the above quantity of paranitrotoluene sulphonic acid be employed a product
is obtained which differs from the above in dyeing a redder shade of yellow and in
dissolving in concentrated sulphuric acid to a violet-red solution.
REDUCTION OF THE HYDROXYLAMINE TO
ACID.
DIAMIDODIPHENYLETHYLENE DISULPHONIC
In the Specification of the aforesaid application for Letters Patent 5351 of 1897
there is described the preparation of diamidodiphenylethylenedisulphonic acid
(otherwise called diamidostilbene-disulphonic acid) by reduction of dinitrodiphenyl-
ethylenedisulphonic acid in acid solution. Further study of the reaction has shewn
that a bye-reaction due to the action of the acid present upon the hydroxylamine,
which is formed as an intermediate stage of the process, has a detrimental effect
upon the yield of diamidodiphenylethylenedisulphonic acid. If however the
reduction of the dinitrodiphenylethylenedisulphonic acid or of the above described
hydroxylamine be performed in a neutral solution an almost theoretical yield of
diamidodiphenylethylene disulphonic acid is obtained. The reducing agents most
suitable for this purpose are zinc dust and ammonium chloride zinc dust and salt,
ferrous hydrate, and the like. The reduction is performed under heat and is
continued until the first formed hydroxylamine has entirely disappeared as
indicated by a sample of the product giving no colouration with caustic soda or
with hydrochloric acid. The process is illustrated by the following example :–
EXAMPLE 6.
7 lbs. of dinitrodiphenylethylene disulphonate of sodium are dissolved in 2 gallons
n
e beduntachtained
7 lbs. of dinitrodiphenylethylene disulphonate of sodium are dissolved in 2 gallons
of boiling water. To the hot solution is added a paste of ferrous hydrate obtained
by adding 3 gallons of strong aqueous ammonia to a solution of 61 lbs. of ferrous
sulphate in 5 gallons of water. The mixture is boiled until the reduction is
complete and no hydroxylamine can be detected. The product is then filtered from
the black oxide of iron which is repeatedly extracted with hot water. The filtrate

page_text: is made acid with hydrochloric acid and the precipitated diamidodiphenylethylene-
disulphonic acid is filtered off, washed with water, and dried.
Dated this 10th day of February 1898.
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents.

page_text: in 20 gallons of water. The mixture is rapidly agitated until the reduction is
complete and the crystals of the dinitro compound have completely dissolved. The
solution is then filtered from zinc oxide and the filtrate, containing the
hydroxylamine, is employed direct for the preparation of colouring matters.
CONVERSION OF THE HYDROXYLAMINE INTO COLOURING-MATTERS.
The hydroxylamine exhibits the typical reactions and transformations of aromatic
hydroxylamines in general and, owing to the chromophoric properties of the
stilbene group, the products thus obtained are, for the most part, colouring matters.
Thus, in addition to the above-described transformation by acids, the hydroxylamine
is also converted into colouring-matters in the following ways:-
(a) By oxidation with air, or other agents.
(b) By the action of caustic alkalies.
(c) By condensation with amines, phenols, amido-phenols, diamines, or their
sulphonic, or carboxylic, derivatives in alkaline solution.
(d) By condensation with certain nitro- compounds, for instance with para-
nitrotoluenesulphonic acid in presence of caustic alkalies.
The production of colouring-matters by these reactions is illustrated by the
following examples :-
-
EXAMPLE 2.
A solution of the hydroxylamine, obtained by reduction of 10 lbs. of
dinitrodiphenylethylene disulphonate of sodium, is diluted with water to 50 gallons,
and a stream of air is passed through it for several hours, until the solution no
longer gives a red colour on the addition of an alkali. The colouring matter is
precipitated by salt, filtered off and dried. It dissolves in concentrated sulphuric
acid forming an orange-red solution, and dyes yellow on unmordanted cotton. Its
formation is probably represented by the equation:-
EXAMPLE 3.
A solution of the hydroxylamine, obtained by reduction of 10 lbs. of dinitro-
diphenylethylene disulphonate of sodium as above, is mixed with 30 gallons of
aqueous caustic soda (30% NaOH). After standing for several hours, or on gently
warming, the red colour of the solution disappears and an orange precipitate is
thrown down. The solution is neutralised with hydrochloric acid and the
colouring-matter is filtered off and dried. It forms au orange powder which dyes
a bright reddish-orange on unmordanted cotton. In concentrated sulphuric acid it
5 dissolves with a pure blue colour. Its formation is probably represented by the
equation :-

page_text: in substance, or upon the fibre, giving on development with the usual azo-dyestuff
components, various shades of yellow, orange red, brown and grey.
EXAMPLE 5.
10 gallons of the hydroxylamine solution, obtained by reduction of 2 lbs. of
dinitrodiphenylethylene disulphonate of sodium are mixed with 2 lbs. of
paranitrotoluene sulphonate of sodium and gallon of aqueous caustic soda
(30 % NaOH), and heated for 1 or 2 hours at about 60° Centigrade until the red
colour has disappeared. The colour separates as a yellow granular precipitate
which is filtered off and dried. It dissolves in concentrated sulphuric acid forming
a crimson red solution. It dyes yellow on unmordanted cotton.
If half the above quantity of paranitrotoluene sulphonic acid be employed a
product is obtained which differs from the above in dyeing a redder shade
of yellow and in dissolving in concentrated sulphuric acid forming a violet red
solution.
REDUCTION OF THE HYDROXYLAMINE TO DIAMIDO DIPHENYLETHYLENE DISULPHONIO
ACID.
In the Specification of the aforesaid Letters Patent 5351 of 1897 there is
described the preparation of diamido diphenylethylene disulphonic acid (otherwise
called diamidostilbene disulphonic acid) by reduction of dinitrodiphenylethylene
disulphonic acid in acid solution.
Further study of the reaction has shewn that a bye-reaction, due to the action of
the acid present upon the hydroxylamine which is formed as an intermediate stage
of the process, has a detrimental effect upon the yield of diamidodiphenylethylene
disulphonic acid. If, however, the reduction of the dinitrodiphenylethylene
disulphonic acid, or of the above described hydroxylamine, be performed in a
neutral solution, an almost theoretical yield of diamidodiphenylethylene disulpbonic
acid is obtained. The reducing agents most suitable for this purpose are zinc dust
and ammonium chloride, zinc dust and salt, ferrous hydrate, and the like. The
reduction is performed under heat and is continued until the first formed
hydroxylamine has entirely disappeared as indicated by a sample of the product
giving no colouration with caustic soda, or with hydrochloric acid. The process
is illustrated by the following example.
EXAMPLE 6.
7 lbs. of dinitrodiphenylethylene-disulphonate of sodium are dissolved in 2 gallons
of boiling water. To the hot solution is added a paste of ferrous hydrate obtained
by adding 3 gallons of strong aqueous ainmonia to a solution of 61 lbs. of ferrous
sulphate in 5 gallons of water. The mixture is boiled until the reduction is
complete and no hydroxylamine can be detected. The product is then filtered from
the black oxide of iron which is repeatedly extracted with hot water. The filtrate
is made acid with hydrochloric acid and the precipitated diamidodiphenylethylene-
disulphonic acid is filtered off, washed with water and dried.
7 lbs. of dinitrodiphenylethylene-disulphonate of sodium are dissolved in 2 gallons
of boiling water. To the hot solution is added a paste of ferrous hydrate obtained
by adding 3 gallons of strong aqueous ammonia to a solution of 61 lbs. of ferrous
sulphate in 5 gallons of water. The mixture is boiled until the reduction is
complete and no hydroxylamine can be detected. The product is then filtered from
the black oxide of iron which is repeatedly extracted with hot water. The filtrate
is made acid with hydrochloric acid and the precipitated diamidodiphenylethylene-
disulphonic acid is filtered off, washed with water and dried.

page_text: Having now particularly described and ascertained the nature of our said
invention and in what manner the same is to be performed we declare that what
we claim is
1. The manufacture and production of a hydroxylamine derivative of stilbene-
disulphonic acid by submitting the dinitrodiphenylethylene disulphonic acid of
Letters Patent 5351 of 1897 to gentle reduction in cold aqueous neutral solution,
substantially as hereinbefore described.
2. The manufacture and production of diamido-diphenylethylenedisulphonic acid
(diamidostilbene-disulphonic acid) by submitting the dinitrodiphenylethylene-
disulphonic acid of Letters Patent 5351 of 1897 (or the hydroxylamine derivative
of Claim 1) to complete reduction in neutral, or slightly alkaline, solution with
ferrous hydrate, zinc dust, and the like substantially as herein before described.
3. The manufacture and production of yellow and orange colouring-matters of
the stilbene series from the hydroxylamine derivative obtained according to
Claim 1.
(a) By heating with acids.
(b) By oxidation with air or other agents.
(c) By the action of caustic alkalies.
(d) By condensation with amines, phenols, amidophenols, diamines or their
sulphonic, or carboxylic, derivatives in alkaline solution.
(e) By condensation with paranitrotoluenesulphonic acid in the presence of
caustic alkalies all substantially as hereinbefore described.
ay of November 1898.
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents.