aprovements in the Manufacture and Production of Rosaniline Derivatives.
Year: 1890

page_text: Date of Application, 16th Sept., 1890
Complete Specification Left, 12th June, 1891-Accepted, 18th July, 1891
PROVISIONAL SPECIFICATION.
aprovements in the Manufacture and Production of Rosaniline
Derivatives.
I, BENJAMIN WILLCOX of 47 Lincolns Inn Fields, in the County of Middlesex,
atent Agent, do hereby declare the nature of this invention (which has
en communicated to me from abroad by Farbenfabriken vormals Friedrich
ayer and Company of Elberfeld in the Empire of Germany) to be as
lows:-
This invention relates to the production or manufacture of rosaniline derivatives
means of processes in which diamido benzhydrol and its alkylised derivatives in
e amido group are caused to react upon aromatic hydrocarbons and their
droxyl- and nitro- substitution products as well as the sulpho and carbo acids
ereof my foreign correspondents having discovered that these bodies can be
adily combined in the presence of dehydrating agents with the aforesaid hydrols
form leuco bodies which by oxidation can be made to yield valuable dye-stuffs
colouring matters as hereinafter explained.
Practically useful results are obtained with the following materials namely :-
Diamido benzhydrol
Dialkyl monamido benzhydrols
Tetra alkyl diamido benzhydrols
1. Meta and para nitro monalkyl amido benzhydrols
Meta and para nitro dialkyl amido benzhydrols
2.
Likewise with the amido benzhydrols corresponding
with the last named nitro bodies
and
(a) benzene, toluol, xylols, mesityls, psuedo cumol,
anthracene, phenanthrene, retene, fluorene.
(b) phenol, cresol resorcin, pyrogallol, amido phenols,
On the one hand
alpha naphthol, beta naphthol, all the known dioxy On the other hand
naphthalenes and amido naphthols as well as the nitro
substitution products the sulpho and carbo acids of
all these substances enumerated under a and b.
Concentrated sulphuric acid is preferably employed when a condensing agent is
quired. Many compounds combine together in the presence of concentrated
lphuric acid even at atmospheric temperature, others require a temperature o
pout 60 degrees Centigrade and some few have to be heated to 100 and 130
egrees Centigrade.
The end of the reaction is known in all cases by the disappearance of the
When neither of the tw
ellow colour which the melt displays at first.
omponents contains a nitro group the colour of the melt changes from yellow to
clear brownish colour, in the presence of a nitro group a brown yellow
ppears.
The products resulting from the hydrocarbons phenols and their nitr
erivatives are precipitated with soda or acetate of soda after being poured
to water.
The bases being filtered washed and pressed can either be directly oxidised
the known manner in an acetic acid solution to form basic colouring matter
they can be sulphurised isolated with salt of lime and then oxidised in the
ual manner.
The bodies resulting from the carbon acids of the compound
ereinbefore enumerated can be precipitated out of the sulphuric acid solution

page_text: which rapidly takes up oxygen from the air and thereby acquires a beautiful
yellow green colour.
The base obtained can be converted into a beautiful green dye by oxidation or it
may be first reduced and then oxidised or it may be reduced, sulphurised and
oxidised into a blue green acid colouring matter. All these last mentioned
operations can be performed in the known manner.
EXAMPLE IV. COLOURING MATTER FROM TETRA METHYL DIAMIDO
BENZHYDROL AND SALICYLIC ACID.
27 parts of tetra methyl diamido benzhydrol and 14 parts of salicylic acid are
intimately mixed and introduced into 110 parts of concentrated sulphuric acid with
stirring and cooling.
When all the materials are dissolved the temperature is slightly raised until the
yellow colour of the melt has changed to a brownish tint.
800 parts of water are then poured in whereupon the melt forms a clear solution.
By adding 79 parts of a 30 per cent. paste of lead peroxide the liquid acquires a
deep blue green colour. After standing for a considerable time the lead sulphate
is separated by filtration and the colouring matter is precipitated in the form of
deep black blue flakes with soda or sodium acetate. This product is practically
insoluble in water or in ammonia and diluted alkalies.
In diluted mineral acids, and in glacial acetic acid, it dissolves with a blue green
colour.
When partly in suspension and partly in soliition in diluted acetic acid'it dyes
chromed wool a réd violet-that is past to fulling.
The reaction proceeds in an analogous manner when the salicylic acid is replaced
by other phenols (naphthöls) or their carbo or sulpho acids.
EXAMPLE V. COLOURING MATTER FROM PARA NITRO DIMETHYL AMIDO
BENZHYDROL + SALICYLIC ACID.
27 parts of para hitro dimethyl amido benzhydrol are intimately mixed with
15 parts of salicylic acid and introduced into 12 parts of cold concentrated sulphuric
acid. The mass dissolves in the form of a yellow liquid with rise of temperature.
After being poured out upon ice and diluted with 80 parts of water the materials are
filtered and the resulting nitro body is precipitated from the filtrate with carbonic
acid or a fixed alkali or ammonia. From the product thus obtained a nitro
colouring matter can be produced by oxidation or it may be reduced in the usual
manner the resulting material being oxidised with lead peroxide in an acetic acid
solution. Both colouring matters dye chromed wool in colours that are fast to
fulling.
EXAMPLE VI. COLOURING MATTER FROM
DIAMIDO
NAPHTHOL SULPHO-ACID 1.8.
BENZHYDROL AND
22 parts of diamido benzhydrol and 23 parts of naphthol sulpho acid 1-8 are
intimately mixed and introduced into 110 parts of concentrated sulphuric acid
with stirring and cooling. When all the materials are dissolved the temperature
is slightly raised until the yellow colour has changed to a brownish tint. The
melt is then poured into 800 parts of water and forms a clear solution. On the
addition of 79 parts of a 30 per cent. lead peroxide paste the liquid turns a deep
green colour.
After standing for a considerable time the sulphate of lead is separated by
filtration and the colouring matter is precipitated in deep black-blue Hakes with
soda or sodium acetate. It dyes chromed wool a blue green.
Dated this 16th day of September 1890.

page_text: heating. The colouring matter or dye is to be precipitated from the filtered acid
solution by neutralizing with sodium-carbonate.
The colouring matters thus obtained dye wool, mordanted with chromium salts, a
violet to blue-black colour.
The new leuco-sulpho acids resulting from the several above mentioned sulpho
acids are purified in the usual manner by changing them into calcium salts and are
thereupon oxidised and changed into the sodium salts; mono sulpho acids may be
directly oxidised in sulphuric acid solution and the dyestuff is separated from the
filtered solution on addition of sodium carbonate or acetate.
The following are given as examples of the manufacture of tri- and di-phenyl-
naphthyl-methane-colouring matters according to this invention. The parts are by
weight.
EXAMPLE I. COLOURING MATTER FROM TETRA-METHYL-DIAMIDO-
BENZHYDROL + BENZENE.
27 parts of tetra-methyl-diamido-benzhydrol are dissolved in 150 parts of
sulphuric acid (66 Baumé) and thoroughly shaken after cooling, with 7-8 parts of
benzene. The solution is at first of a yellow colour but soon after becomes a clear
brownish colour and pellucid, the temperature rising at the same time about
20 degrees Centigrade. After pouring into water the base produced can be
precipitated by the carbonates or hydroxides of alkalies or by ammonia and
oxidised into a dye in the known manner.
When equivalent quantities of the other hydro-carbons are employed the reaction
takes place in the same manner.
EXAMPLE II. COLOURING MATTER FROM TETRA-ETHYL-DIAMIDO-
BENZHYDROL + BENZOIC ACID.
זיז
32-6 parts of tetra-ethyl-diamido-benzhydrol are heated with 15 parts of benzoic
acid and 200 parts of concentrated sulphuric acid to 100 degrees Centigrade for
two hours; the melt is then poured on to ice, diluted with 1,000 parts of water and
the cooled solution is oxidised by means of 79 parts of a paste of lead-dioxide
containing 30 per cent. of the latter. After separating the lead sulphate by
filtration either an excess of sodium carbonate or sodium acetate is added to the
solution thus obtained or the latter is accurately neutralized with soda.
The resulting precipitate after washing forms a green paste which produces,
on wool mordanted with chromium salts, green shades which are fast against
milling.
EXAMPLE III. COLOURING MATTER FROM DIMETHYL-DIETHYL-DIAMIDO-
BENZHYDROL PARA-NITRO-PHENOL.

page_text: separates which rapidly absorbs oxygen from the air and thereby acquires a
yellowish green colour.
The base thus obtained may be changed into a beautiful green dye by oxidation,
or it may be first reduced and then oxidised, or it may be reduced, sulphonated and
then dxidised into a blueish groantacid bolousing matter.
operations can be performed in the known manner.
operations can be performed in the known manner.
EXAMPLE IV. COLOURING MATTER FROM TETRA-METHYL-DIAMIDO-
BENZHYDROL AND SALICYLIC ACID.
27 parts of tetra-methyl-diamido-benzhydrol and 14 parts of salicylic acid are
thoroughly mixed and introduced into 110 parts of concentrated sulphuric acid
whilst stirring and cooling.
When both the ingredients are dissolved the temperature is slightly raised until
the yellow colour of the melt has changed to a brownish colour. On pouring into
800 parts of water a clear solution of the melt results.
On adding 79 parts of a paste of lead dioxide, containing 30 per cent. of the
latter, the liquid acquires a deep blue-green colour. After standing for a time the
lead sulphate is separated by filtration and the colouring matter is then precipitated
(in the form of deep blackish-blue flakes) by sodium acetate or sodinin'carbonate.
This product is almost insoluble in water, in ammonia and in diluted alkalies. It
dissolves in diluted mineral acids and in glacial acetic acid with a blueish-green
colour.
When partly suspended and partly dissolved in diluted acetic acid it dyes
wool mordanted with chromium salts a red-violet colour that is fast against
milling.
The reaction proceeds in an analogous manner when instead of salicylic acid
other phenols (naphthols) or their carboxy or sulpho acids, are employed.
EXAMPLE V. COLOURING MATTER FROM PARA-NITRO-DIMETHYL-AMIDO-
BENZHYDROL + SALICYLIC ACID.
27 parts of para-nitro-dimethyl-amido-benzhydrol are mixed with 14 parts of
salicylic acid and added to 12 parts of cold concentrated sulphuric acid. A yellow
liquid results the temperature rising. This liquid is poured upon ice, and after
making up by addition of water to 80 parts is filtered and the nitro compound is
precipitated from the solution by means of alkaline carbonate or hydroxide or
ammonia. This nitro-product, after having been reduced in the usual manner,
yields on oxidation with manganese dioxide in an acetic acid solution, a colouring
matter that dyes wool mordanted with chromium salts violet-red shades fast against
milling.
EXAMPLE VI. COLOURING MATTER FROM DIAMIDO-BENZHYDROL AND
NAPHTHOL-SULPHO ACID 1.8.
A mixture of 22 parts of diamido-benzhydrol and 23 parts of 1.8 naphthol-sulpho
acid is introduced into 110 parts of concentrated sulphuric acid whilst stirring and
cooling. After the ingredients are dissolved the temperature is slightly raised
until the yellow colour has changed to a brownish tint. By pouring the melt
into 800 parts of water a clear solution is obtained the colour of which is
changed to a deep green on the addition of 79 parts of a 30 per cented lead dioxide
paste.
After standing for several hours the sulphate of lead is separated by filtration,
and the colouring matter can be precipitated in deep black-blue flakes by means of
sodium acetate or sodium carbonate. It dyes wool, mordanted with chromium salts,
a blueish-green.

page_text: 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.
First The process for the manufacture of a series of so called leuco rosaniline
compounds by acting with molecular proportions of tetra-methyl-diamido-benzhydrol
upon molecular proportions of phenol, ortho- and para-phenol, sulpho acid, phenol-
d-sulpho acid (obtained by sulphonation of phenol), ortho-meta, and para-
cresol,-
First ne process for the manufacture of a series of so called leuco rosaniline
mpounds by acting with molecular proportions of tetra-methyl-diamido-benzhydrol
on molecular proportions of phenol, ortho- and para-phenol, sulpho acid, phenol-
-sulpho acid (obtained by sulphonation of phenol), ortho-meta, and para-
esol,-
resorcin,
pyrogallol
alpha- and beta-naphthol.
benzoic acid.
salicylic acid.
sulphosalicylic acid (obtained by sulphonation of salicylic acid).
para-hydroxy-benzoic acid.
ortho-hydroxy-para-toluylic
acid.
para-cresol-ortho-carboxy acid.
beta-resorcylic acid.
alpha-hydroxynaphthoic acid and its sulpho derivative,
beta-naphthol carboxy acid and its sulpho product.
beta-hydroxy naphthoic acid (melting at 216 degrees Centigrade).
sulpho beta-hydroxy naphthoic acid (obtained by sulphonation of the latter
acid) gallic acid.
naphthalene alpha- and beta-monosulpho acid,
alpha-naphthol-alpha-monosulpho acid (Neville Winther)
alpha-naphthol-alpha-mono-sulpho acid (Clive),
alpha-naphthol-alpha-mono-sulpho acid (1.8).
beta-naphthol-alpha-mono-sulpho acid of the German Patent No. 18,027.
beta-naphthol-delta-mono-sulpho acid.
beta-naphthol-beta-mono-sulpho acid (Schäffer) or beta-naphthol-disulpho acid
G and R.
the presence of dehydrating agents, especially of concentrated sulphuric acid.
Second-The process for the manufacture of tri-phenyl-methane or diphenyl-
phthyl-methane derivatives by combining molecular proportions of dimethyl- -
ethyl-diamido-benzhydrol with molecular proportions of
salicylic acid.
ortho-hydroxy-para-toluylic acid or alpha-hydroxy-naphthoic acid.
means of dehydrating agents, particularly of concentrated sulphuric acid.
Third-The production of rosaniline like dye stuffs by oxidising the leuco
mpounds obtained according to the first and second claims in sulphuric acid
lution by lead dioxide.
Fourth As new articles of manufacture the leuco products and colouring matters
ch as result according to the processes herein before described.
Dated the 12th day of June 1891.
J. H. JOHNSON & Co.,
Agents.