The Manufacture and Production of New Mordant Dyeing Colouring Matters, and Intermediate Products relating thereto.
Year: 1894

page_text: Date of Application, 12th Feb., 1894
Complete Specification Left, 1st Nov., 1894-Accepted, 15th Dec., 1894
PROVISIONAL DI DITINJE
The Manufacture and Production of New Mordant Dyeing Colouring
Matters, and Intermediate Products relating thereto.
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) to be as follows:-
-
This invention relates to the manufacture and production of new colouring
matters, which give bluish or greenish shades on goods inordanted with chrome,
alumina tin and the like, and of intermediate products relating thereto.
The new colouring-matters are obtained by the condensation of certain amido-
naphthol-sulpho acids with alkylated amido-benzhydrols. By this condensation
leuco-compounds are obtained. If these leuco compounds be carefully oxidized the
corresponding colouring matters, which apparently still contain the nitrogen of the
amido-naphthol-sulpho acid, are obtained. These are hereinafter called the inter-
mediate colouring matters and can be converted into the desired valuable mordant
dyeing products in either of two ways:-First, a more energetic oxidation may be
employed. This results in the formation of superoxidized products of quinonoid
character, and these upon weak reduction, are converted into the hydroquinone
products which are the desired valuable mordant-dyeing colouring matters. Or,
second, the aforesaid intermediate colouring matters can be converted into the
desired products by treatment with suitable reagents for effecting hydrolysis,
especially with hot soda solution.
As instances of the amido-naphthol-sulpho-acids which can be employed in this
new manufacture I mention the 1.2.3 and 1.2. 2¹ amido-naphthol-mono-sulpho
acids but other amido-naphthol-mono and di-sulpho acids can be employed.
The principal alkylated amido-benzhydrols which can be employed in this new
manufacture are the tetra-methyl and tetra-ethyl-diamido-benzhydrol.
The following example will serve to further illustrate the nature of the invention
but it merely describes its application in a typical case and in all cases the process
can be varied in many respects. The parts are by weight.

page_text: real acid H₂SO), stir well and whilst stirring add about thirty two parts of lead
peroxide paste (containing about eighty per cent. PbO,).
The liquid assumes an intensely blue colour which is caused mainly by the
presence of the intermediate colouring matter corresponding to the leuco compound.
If desired this can be precipitated by the addition of common salt and can then, by
boiling with soda solution or similar reagent as aforesaid, be converted into the
mordant-dyeing colour. But preferably add a further quantity (say about
sixty-four parts) of the lead peroxide paste to the aforesaid intensely blue solution
and continue stirring for about twelve hours, during which time the blue colour of
the solution should almost disappear and the superoxidized product of the reaction
should separate out in the form of a green crystalline precipitate. Filter, wash
with cold water dissolve in about one thousand eight hundred parts of water aud
about four hundred and fifty parts of concentrated sulphuric acid (containing about
cent. H₂SO) filter from lead sulphate and any excess of lead peroxide and
add to the filtrate about forty three parts of a solution of sodium bisulphite
(containing about twenty per cent. of total SO2). Allow to stand for about two or
three hours, when the yellowish-brown colour of the solution should turn to a
claret-red. Neutralize the main portion of the free mineral acid present by adding
an alkali until no further increase in the quantity of precipitate formed takes
place. The new mordant dyeing colouring-matter separates out as a blue
precipitate. Filter, dissolve carefully in cold dilute alkali-soda or ammonia, and
precipitate the salt so formed with common salt, filter, press and dry.
95
per
The dye so obtained fixes itself on alumina giving blue shades and on chrome
giving greenish-blue; these shades possess a very high degree of fastness against
the action of light, soap and fulling.
The manufacture can be modified if desired in that the leuco-compound is not
isolated prior to oxidation but the reaction product is directly oxidized in the
manner described after dilution with water.
By proceeding on the principles illustrated in the above example but using
certain other amido-naphthol-sulpho acids or other alkylated amido-benzhydrols,
as hereinbefore indicated analogous colouring-matters are obtained.
Dated the 12th day of February 1894.
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents.
COMPLETE SPECIFICATION.
The Manufacture and Production of New Mordant Dyeing Colouring
Matters, and Intermediate Products relating thereto.
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 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 to the manufacture and production of new colouring
matters which give bluish, or greenish, shades on goods mordanted with chrome
alumina, tin and the like, and to the manufacture and production of intermediate
products relating to the said new colouring matters.
In the process for the production of the new colouring matters according to this
invention certain amido-naphthol-sulpho-acids are condeused with alkylated amido-
benzhydrols. By this condensation leuco-compounds are obtained. If these
leuco-compounds be carefully oxidized the corresponding colouring matters which
apparently still contain the nitrogen of the amido-naphthol sulpho acid are obtained.
These are hereinafter called the intermediate colouring-matters and can be

page_text: converted into the desired valuable mordant dyeing products in either of two
ways: First; a more energetic oxidation may be employed. This results in the
formation of superoxidized products of quinonoid character and these upon weak
reduction are converted into the hydroquinonoid products which are the desired
valuable mordant dyeing colouring matters. Or, second: the aforesaid intermediate
colouring matters can be converted into the desired products by treatment with
suitable reagents for effecting hydrolysis, especially with hot soda solution.
The following amido naphthol sulpho-acids can be employed in this new
manufacture, viz. the 1. 2. 31, 1. 2. 2 and 1. 2. 11 amidonaphthol-mono-sulpho acids
and the alkylated amido-benzhydrols which can be used therein are the tetra-
methyl- and tetra-ethyl-diamido benzhydrol.
The following example will serve to further illustrate the nature of the invention
and the best manner with which I am acquainted for carrying it into practical
effect. In this example the application of the invention in a typical case is
described but in all cases the process can be varied in many respects. The parts
are by weight
Mix about twenty-seven parts of tetra-methyl-diamido-beuzhydrol and about
twenty four parts of amido-naphthol-mono-sulpho acid (NH,: OH: SO,H=1:2:3¹)
with about two hundred and ninety parts of acetic acid (containing about fifty per cent.
real acid CHO). Heat the mixture to boiling and maintain the heat until the
blue colour of the hydrol has disappeared or nearly so. This usually requires
about half an hour. Next allow it to cool when the main quantity of the leuco-
compound crystallizes out. Filter and wash with alcohol.
CONVERSION OF THE LEUCO COMPOUND INTO THE MORDANT DYEING
COLOURING MATTERS.
Dissolve about fifty parts of the leuco compound (such as can be obtained as
hereinbefore described) in about five thousand parts of water and forty two parts
of concentrated sulphuric acid (containing about ninety five per cent. real
acid H,SO stir well, and whilst stirring, add about thirty two parts of lead
peroxide paste (containing about eighty per cent. PbO₂).
The liquid assumes an intensely blue colour which is caused mainly by the
presence of the intermediate colouring matter corresponding to the leuco compound.
If desired this can be precipitated by the addition of common salt and can then, by
boiling with soda solution, (containing say about 5 per cent. Na₂CO₂) or similar
reagent, as aforesaid be converted into the mordant dyeing colour. This boiling is
continued until dye-tests effected in the ordinary way on chromed wool from a bath
containing acetic acid shew no further improvement. But it is preferred to add a
further quantity (say about sixty four parts) of the lead peroxide paste to the
aforesaid intensely blue solution and continue stirring for about twelve hours,
during which time the blue colour of the solution should almost disappear and the
superoxidized product of the reaction should separate out in the form of a green
crystalline precipitate. Filter, wash with cold water, dissolve in about one
thousand eight hundred parts of water, and about four hundred and fifty parts of
concentrated sulphuric acid (containing about 95, er cent. H,SO) filter from lead
sulphate and any excess of lead peroxide and add to the filtrate about forty-three
parts of a solution of sodium bisulphite (containing about twenty per cent. of
total SO,). Allow to stand for about two or three hours when the colour of the
solution should turn from a yellowish-brown to a claret-red. Neutralize the main
portion of the free mineral acid present by adding an alkali until no further
increase in the quantity of precipitate formed takes place. The new mordant
dyeing colouring-matter separates out as a blue precipitate. Filter, dissolve

page_text: :
!
r
carefully in cold dilute alkali (soda or ammonia) and precipitate the salt so formed
with common salt, filter, press and dry.
The dye so obtained fixes itself on alumina giving blue shades and on chrome
giving greenish-blue shades; these shades possess a very high degree of fastness
against the action of light soap and fulling.
The manufacture can be modified if desired in that the leuco-compound is not
isolated prior to oxidation but the reaction product is directly oxidized in the
manner described after dilution with water.
By proceeding on the principles illustrated in the above example but using the
other amido-naphthol-sulpho-acids hereinbefore mentioned or tetra-ethyl-di-amido
benzhydrol as herein before indicated analogous colouring matters are obtained.
Having now particularly described and ascertained the nature of this inven-
tion and in what manner the same is to be performed I declare that what I
claim is :-
:-
1. The manufacture of new mordant dyeing colouring-matters by first condensing
an amido-naphthol-sulpho acid herein before mentioned with tetra-alkyl-diamido
benzhydrol to obtain a leuco-compound and then superoxidizing these bodies to
quinonoid compounds and subsequently treating these with a weak reducing agent
substantially as herein before described.
2. The manufacture of new mordant dyeing colouring matters by first condensing
an amido-naphthol-sulpho-acid hereinbefore mentioned with tetra-alkyl-diamido-
benzhydrol, then oxidizing the resulting leuco-compound to the intermediate
colouring-matters and subsequently treating these with a suitable agent for effecting
-hydrolysis substantially as herein before described.
3. The manufacture of the new leuco-compounds by the condensation of an
amido-naphthol-sulpho-acid herein before mentioned with tetra-alkyl-diamido-
benzhydrol substantially as described.
4. The manufacture of the new intermediate colouring-matters by the oxidation
of the leuco-compounds substantially as herein before described.
5. The manufacture of the new products of quinonoid character by the
superoxidation of the leuco-compounds substantially as hereinbefore described.
6. The conversion of the new products of quinonoid character into the new
mordant-dyeing colouring-matters by weak reduction substantially as hereinbefore
described..
7. The manufacture of the new mordant-dyeing colouring matters and of the
new intermediate products herein before mentioned in the manner described in the
example.
8. As new products the new mordant-dyeing colouring matters, the new inter-
mediate colouring matters and the other intermediate compounds all such as can be
obtained substantially in the manner hereinbefore described.
Dated this 1st day of November 1894
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents.