The Manufacture and Production of Secondary Disazo-dyes from Nitro-amido-phenol-sulphoacids.
Year: 1898

page_text: Date of Application, 28th June, 1898
Complete Specification Left, 24th Mar., 1899-Accepted, 13th May, 1899
The Manufacture and Production of Secondary Disazo-dyes from
Nitro-amido-phenol-sulphoacids.
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 from abroad by the Badische Anilin & Soda Fabrik of Ludwigshafen-
on-Rhine, in the Empire of Germany) to be as follows:-
My foreign correspondents have discovered a new and large class of azo-dyes being
the secondary disazo-dyes of nitro-amido-phenol-sulphoacids. A large number of
isomeric varieties of these bodies are possible, but none of them have been used
hitherto in the manufacture of secondary disazo-dyes, and the dyes of this class appear
to be especially valuable.
The nitro-amido-phenol-sulphoacids can be obtained, by the nitration of amido-
phenol-sulphoacids; by the sulphonation of nitro-amido-phenols; by the partial reduc-
tion of dinitro-phenol-sulphoacids or by analogous or equivalent reactions, which for the
most part merely constitute variations in the order in which the requisite groups
are combined with the benzene nucleus.
As middle-component in the manufacture of the new secondary disazo-dyes,
alpha-naphthylamine is used, or instead of alpha-naphthylamine, all the other
amido-bodies which are known to be suitable for use as so-called middle-components
can be employed. That is to say all such amido-bodies can be used as middle-
components which on treatment with the diazo-compound readily yield an amido-
azo-compound which can be diazotized and combined with ordinary components in
the usual way.
As third or end components all the components known to be capable of general
use for combination with diazo-compounds in the manufacture of azo-dyes can be
employed. As examples may be mentioned the naphthols and the naphthol-sulpho-
acids which are used in this way and alpha-naphthylamine, which latter can therefore
be used both as middle and end component.
This new class of dyes possesses members of various shades of colour; those
which at present appear to be of greater importance are of bluish and greenish
dark shades being practically black colours, suited for dyeing woollen goods yielding
fast shades. In most cases the dyed fabrics improve in the fastness of their colour on
treatment with chromates.
Doted this 00th day of T..... 1000
JOHNSONS & WILLCOX,
47 Lincoln's Inn Fields, London, W.C., Agents.

page_text: Add about seven hundred and fifty-six parts of para-amido-phenol-ortho-sulphoacid
(whilst stirring) to about three thousand two hundred parts of concentrated sulphuric
acid, containing about ninety-five per cent. real H₂SO, at the ordinary temperature.
When this is dissolved cool the mixture to a temperature of about minus five
degrees Centigrade, then add, slowly, a cool mixture of about four hundred parts of
nitric acid (containing about sixty-two per cent. HNO₂) and of about four hundred
parts of sulphuric acid monohydrate, taking care that the temperature remains
always below zero degrees Centigrade. When the mixing is effected pour the
nitration-inixture onto ice, wash the separated nitro-acid well with cold water,
press and dry.
It
The nitro-amido-sulphoacid so obtained is nearly insoluble in alcohol and in cold
water; it dissolves a little more readily in boiling water the solution being red and it
crystallizes out from this in the form of brilliant, pale reddish-brown needles.
yields a nono and a di-sodium salt. The mono-sodium salt dissolves in water the
solution being reddish-yellow, whilst the di-sodium salt dissolves very readily in
water the solution being deep-red. From each solution, after the addition of mineral
acid, the free acid generally separates out again in the form of crystals.
As middle component in the manufacture of the new secondary disazo-dyes alpha-
naphthylamine, or the sulphoacids thereof known as Cleve's acids are especially used,
but any other amido body which is known to be suitable for use as a so-called middle-
component can be employed, that is to say, any amido body can be used as middle-
component, which on treatment with the diazo-compound, readily yields an aido-azo
compound which can be diazotised and combined with ordinary components in the
usual way.
As third, or end, components any component known to be capable of use for
combination with diazo-compounds in the inanufacture of azo-dyes can be employed.
As examples inay be mentioned the naphthols and the naphthol-sulphoacids which
are used in this way, and alpha-naphthylamine, which latter can therefore.be used
both as middle and end component.
This new class of dyes possesses members of various shades of colour, those which
at present appear to be of greater importance are obtained with the aforementioned
components and are dark shades of blue and green being, practically black colours
suited for dyeing woollen goods and yielding fast shades. In most cases goods
dyed with these improve in the fastness of their colour on treatment with
chromates.
give the following examples for the production of the new disazo dves
PRODUCTION OF A NEW DISAZO DYE FROM ORTHO-NITRO-ORTHO-AMIDO-PHENOL PARA-
SULPHOACID AND ALPHA-NAPHTHYLAMINE AS MIDDLE COMPONENT AND R-SALT AS
END COMPONENT.
Dissolve about twenty-three-and-a-half parts of nitro-amido-phenol-sulphoacid in
about five hundred parts of water and diazotise by treatment with fifteen parts of
hydrochloric acid (containing about thirty per cent. HCI) and about seven parts of
sodium nitrite at the ordinary temperature. Pour the diazo solution into a solution
of about fifteen parts of alpha-naphthylamine in six hundred parts of water and
fifteen parts of hydrochloric acid (containing about thirty per cent. HCI). Stir at
a temperature of about thirty five degrees Centigrade till a test portion on filter paper
gives no reaction of diazo compound. This usually requires from ten to twenty-four
hours, the time depending principally upon the temperature maintained. Filter the
intermediate colouring-matter obtained and wash with cold water.

page_text: Dissolve the intermediate colouring-matter, obtained as above described, in about
two thousand five hundred parts of boiling water to which about seventeen parts
of caustic soda lye (containing about thirty-five per cent. Na. OH) are added. Allow
the solution to cool, and add seven-and-a-half parts of sodium nitrite in the form
of a concentrated solution. Pour this mixture into a dilute solution of sulphuric acid
containing about two hundred parts of ice, thirty parts sulphuric acid (containing
about ninety-five per cent. H₂SO,) and ninety parts of water. Stir, whilst mixing, and
subsequently-a precipitate separates out, which is at first of a dark colour and
gradually becomes brown. Filter, stir with cold water, and pour into a solution of
about thirty-five parts of beta-naphthol-di-sulphoacid R, which is rendered alkaline
with carbonate of soda. The formation of colouring-matter is soon completed. Add
common salt to complete the precipitation of the colouring matter and filter and
press. Purify, if necessary, by re-dissolving and re-precipitating. If desired
the combination can be effected without first collecting the diazo compound by
filtration.
The production of colouring-matters with other end-components is effected in a
similar manner. When alpha-naphthylamine is used as end component, it is of
course desirable to effect the combination in weakly acid solution and the colouring-
matter formed is subsequently converted into its sodium salt.
PRODUCTION OF DISAZO DYE FROM ORTHO-NITRO-PARA-AMIDO-PHENOL-ORTHO-SULPHOACID
AND CLEVE'S NAPHTHYLAMINE SULPHOACID AS MIDDLE COMPONENT AND R-SALT
AS END COMPONENT.
Dissolve about two hundred and thirty-four parts of ortho-nitro-para-amido-phenol-
ortho-sulphoacid (whilst adding two hundred and thirty parts of caustic soda,
containing about thirty-five per cent. real NaOH) in about two thousand parts of
water and add a concentrated solution of about seventy parts of sodium nitrite.
Add the mixture, whilst stirring, to about four hundred and fifty parts of hydrochloric
acid, containing about 30 per cent. HCl, which previously has been diluted with
about one thousand parts of water. The diazotation is usually finished in a few
minutes. Then pour the clear brown-red solution of the diazo compound into a
solution of two hundred and fifty parts, of the mixture of the sodium-salts of
the 1-naphthylamine-2¹- and 31-sulph.oacid in ten times the quantity of water. Heat,
whilst stirring, at a temperature of about forty degrees Centigrade. Cool after about
ten hours, filter the dyestuff, precipitate, press and day. The precipitate is usually
in the form of bronze-lustre crystals, which are difficultly soluble in water.
In a similar manner the combination with alpha-naphthylamine can be effected.
The colouring-matter so obtained yields a green powder, which is insoluble in cold
water.
Dissolve about nine hundred and eighty parts of the intermediate product (obtained
as above described) in about thirty thousand parts of boiling water, containing about
four hundred and sixty parts of caustic soda lye, containing about 35 per cent.
real NaOH. Cool very carefully, down to about zero degrees Centigrade and add to
the solution a concentrated solution of one hundred and forty parts of sodium nitrite.
Pour the mixture, whilst stirring and continuing to cool as described, into one thousand
parts of hydrochloric acid, containing about thirty per cent. real H Cl, which has been
diluted with about two thousand parts of water.
A green solution is obtained which, on the addition of much mineral acid, becomes
yellowish-brown. On strongly diluting it with water, or on the addition of sodium
acetate, or soda, it becomes deep blueish-violet.
Pour the diazo compound so obtained into a concentrated soda alkaline solution of
seven hundred parts of the sodium salt of beta-naphthol-disulphoacid (R-salt).
The combination is quickly finished. The precipitated dyestuff is filtered and
treated in the ordinary manner.

page_text: The production of other combinations is effected in a similar manner.
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 :-
The manufacture of secondary disazo dyes from a nitro-amido-phenol-sulphoacid, a
middle component and an end component, all substantially as herein before described.
Dated this 24th day of March 1899.
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents.