Manufacture of New Colouring Matters Dyeing Cotton without Mordants.
Year: 1896

page_text: Date of Application, 7th Mar., 1896-Accepted, 18th Apr., 1896
[Communicated from abroad by THE SOCIETY OF CHEMICAL INDUSTRY IN
BASLE, Basle, Switzerland, Chemical Manufacturers.]
Manufacture of New Colouring Matters Dyeing Cotton without
Mordants.
I, OLIVER IMRAY, of 28 Southampton Buildings, in the County of London,
Chartered Patent Agent, do hereby declare the nature of this invention and in
what manner the same is to be performed to be particularly described and
ascertained in and by the following statement :-
Although by their nature constituting dyes capable of dyeing wool, the monoazo-
aldehyde colouring matters, produced by the reaction of diazo-benz-aldehyde upon
the compounds that are usually combined with diazo bodies for the production of
azo colouring matters, have not been susceptible hitherto of industrial application,
on account of these colouring matters not offering any advantage as compared with
the ordinary mono azo colouring matters which are much cheaper.
It has already been endeavoured to transform the mono-azo-aldehyde-colouring
matters derived from para-diazo-benz-aldehyde and from certain compounds that
are generally combined with the diazo bodies for the production of azo dyes, into
colouring matters of greater value by condensing them with the aromatic
hydrazine.
The mono-azo-aldehyde colouring matters thus condensed with phenyl-hydrazine,
appear in effect to have undergone an advantageous modification, as they dye
wool blue, while before their condensation with phenyl-hydrazine, they dyed
wool red.
My correspondents have made the surprising discovery that the azo-aldehyde
colouring matters derived from the aromatic para-diazo-aldehydes and the compounds'
which are generally combined with diazo bodies for the production of azo-colouring
matters can be transformed into new disazo coloring matters by their condensation
NH,
with diamide
NH,
which has not yet been employed in the colouring matter
industry. The products subjected to this transformation entirely lose their
primitive character as wool dyes, but, on the other hand, the new products of
condensation obtained can be employed advantageously for the dyeing of
unmordanted cotton, in a salt, neutral or alkaline bath. According to the mono-
azo-aldehyde e louring matters employed, there will be obtained a whole series of
important disazo colouring matters, characterized by the purity of their tints and
their dyeing unmordanted cotton yellow, orange, brown, red, violet blue, violet-
black, and blue-black.
In correlation with the modification to which the dyeing properties of the
mono-azo-aldehyde colouring matters are subjected by their condensation with:
diamide, the other properties of these colouring matters are also subject to changes;
thus their solubility becomes less, their sensitiveness to acids is increased and
their tint is changed from orange to red and from red to violet and even
to blue.
These characteristic modifications are only produced-as will be presently fully
explained,-with mono-azo colouring matters derived from paradiazobenzaldehyde

page_text: and its substitution products and not with those derived from meta-liazo-benz-
aldehyde.
For the preparation of these new disazo colouring matters, my correspondents
generally take the identical or different molecules of the intermediate products
dissolved or suspended in water alkaline, neutral, or preferably slightly acidulated
for instance, with acetic acid, and on these they cause to act a dilute solution of a
diamide molecule at water bath temperature, until there is no farther change of
tint of the colouring matter. The solution is then alkalised and the colouring
matter is precipitated by addition of salt.
The new colouring matter answers generally to the following constitution formula
R-N N-A-HC-N-N=CH-A-N=N-R (1), in which
R signifies an aromatic amine, a phenol, an amido phenol or one of their sulpho-
carboxyl or sulphocarboxyl derivatives; and A signifies the phenyl, tolyl,
sulpho-phenyl or sulpho-tolyl radical of para-diazo-benzaldehyde, para-diazo-
toluyl-aldehyde or their sulpho derivatives.
The reaction producing this colouring matter takes place according to the
following formula
in which R and A have the same meaning as above.
As intermediate products, capable of being coupled by diamide must be considered
all the aldehydazo colouring matters, derivatives of para-diazo-benzaldehyde and
its substitution products such as para-diazo-toluyl-aldehyde and the mono-sulpho-
conjugates of para-diazo-benzaldehyde and the compounds capable of being
combined with diazo bodies for the formation of azo colouring matters, and, among
those compounds, may be more especially mentioned the aromatic amines the phenols,
the amido phenols and their sulpho, carboxyl, and sulpho-carboxyl derivatives,
such as
The naphthylamine mono-sulphonic acids 2.6, 2.7 and 2.5,
The mono-methyl or mono-ethyl-3 naphthylamine sulphonic acids 2.6 and 2.7,
obtained, for instance, by suitable sulphonations of mono-alkyl B-naphthylamine.
The B-naphthylamine disulphonic acid 2.3.6:-
The a-naphthylamine mono-sulphonic acids, 1.4, 1.5, 1.6 and 1.7 :-
The a-naphthylamine disulphonic acids 1.4.7 and 1.4.8-
The B-naphthol-mono-sulphonic acids, 2.5, 2.6, 2.7, and 2.8:-
The B-naphthol-disulphonic acids 2.6.8, 2.3.6 and 2.3.7 :-
The a-naphthol-mono-sulphonic acids 1.3, 1.4, 1.5, 1.7 and 1.8:-
The a-naphthol-disulphonic acids 1.4.7, 1.4.8, 1.3.6, 1.3.7 and 1.3.8;-
The a-oxynaphthoic acid and its monosulphonic acid 1.2.4 and disulphonic
acid 1.2.4.7-
The B-oxynaphthoic acid 2.3 and its sulpho-derivatives :-
The dioxynaphthoic acids 1.7.2, 2.8.3 and 2.6.3 :-
The dioxynaphthoic-n.ono-sulphonic acids 2.8.3.6 and 1.7.2.4:-
The amido-naphthol-mono-sulphonic acids 1.8.2, 1.8.7, 1.8.3, 1.8.6, 1.8.4, 1.8.5,
1.6.3, 1.3.6, 1.6.4, 1.7.3, 1.5.2, 1.5.6, 2.5.7, 2.5.8, 2.7.3, 2.8.5, and 2.8.6 :-
The amido-naphthol-disulphonic acids 1.8.3.6, 1.8.4.6, 1.8.4.7, 1.8.2.4, 1.6.3.7.
1.6.3.5, 1..3 7, and 2.8.3.6:
The amido-oxynaphthoic-mono-sulphonic acid 2.8.3.6 :-

page_text: The amidonaphthols 1.7, 1.8, 1.5, 2.8, 2.7.
The naphthylene-diamines 1.5, and 2.7 as well as the naphthylene-diamine-mono:
sulphonic acids, 1.3.6 2.3.6 and 1.3.7 and the mono sulphonic acids of dioxy-
naphthaline 1.3 and of amide-naphthol 1.3.
Instead of coupling two molecules of aldehyde azo colouring matters with a
molecule of diamide there may be first added a molecule of diamide to two
molecules of the compounds which are generally combined with diazo bodies for
the preparation of azo colouring matters and then added to this mixture the two
molecules of paradiazo aldehydes so as to cause these last to act in one
operation on the diamide and the two molecules of the compounds above mentioned;
but this mode of operating can only be employed for the combinations effected in
acid solution, such for instance, as a solution acidulated with acetic acid.
As to the tints of the substantive colouring matters obtained by coupling
aldehydediazo colouring matters by means of diamide, it is to be observed that the
amines, the phenols and amido phenols of the benzene series furnish colours varying
from yellow and orange to brown, whilst the derivatives of the naphthylamines
and the naphthols give colours varying from red to violet, and, finally, that the
derivatives of the amidonaphthols and dioxy naphthalines and the mono azo
colouring matters derived from the latter give colours varying from dark violet
and blue to black.
By substituting for the aldehyde mono azo colouring matters in the process just
described, secondary disazo colouring matters, which are produced by the combina-
tion of one molecule para-diazo-benzaldehyde or para diazo toluyl aldehyde, para-
diazo benzaldehyde-sulpho acid, or para diazo toluyl aldehyde sulpho acid, with
one molecule of a naphthylamine, paraxylidine, para cresidine, 1.6 or 1.7 naphthyl-
amine mono sulpho acid (Cleve) naphthylamine-ether sulpho acid. 1.2.6 or 1.2.7,
naphthylamine ether 1.2, amido naphthol mono sulpho neid 2.8.6, 2.5.7, amido
naphthol disulpho acids 2.8.3.6, 2.8.4.6, 1.8.3.6, 1.5.3.7, 1.8.2.4, amido-nigrotinic acid
(all amido naphthol derivatives being combined in alkaline solution), then farther
diazotising the intermediate products thus obtained with one molecule of nitrous
acid and subsequent combination with one molecule of an aromatic amine, phenol
or their substitution products and in particular those of these compounds which
have been herein before mentioned, there will also be produced new poly azo
colouring matters which dye directly unmordanted cotton, mainly in dark tints
varying from brown to violet, blue, black, and greenish black.
If, instead of combining identical molecules of aldehyde azo colouring matters
with a molecule of diamide, combination is made of a molecule of diamide
successively with the different molecules of aldehyde azo colouring matters; there
are obtained, after preliminary formation of an intermediate product comprising a
radical of the type CH = N-NH₁₂; mixed disazo colouring matters having tints
intermediate to those of the corresponding symmetric disazo colouring matters,

page_text: whilst, if a molecule of diamide is made to act on a mixture of aldehyde azo
colours, there are obtained either mixed disazo colouring matters or a mixture of
symmetric disazo and mixed disazo colouring matters.
If the two molecules of aldehyde azo colouring matters which have to be coupled
by diamide, or only one of them are or is obtained by combining para-diazo-benz-
aldehyde or para-diazo-toluyl-aldehyde or their sulpho conjugate derivatives with a
compound capable of uniting two diazo groups, such as meta-dioxy-benzols
(resorcine &c.) meta-amido-phenols, meta diamines (meta phenylene, and meta
toluylene diamine) certain sulphonic acids of dioxy naphthaline 1.8 and of amido
naphthol 1.8 (dioxy naphthaline disulphonic acid 1.8.3.6 and amido naphthol
disulphonic acids 1.8.3 6, 1.8.4.6 and 1.5.3.7), dioxy naphthoic-mono-sulphonic acid
(of the Patent No. 14161 of 1892), diamnido naphthaline disulphonic acid 1.8.3.6,
amido naphthol mono sulphonic acid 2.8.6 &c. there can be obtained new polyazo
colouring matters answering the one or the other of the two formulæ.
the disazo colouring matters of formula (5) being combined with two mole-
cules of any diazo body, and those of formula (6) with one molecule of any
diazo body.
Polyazo colouring matters still more complex can be obtained answering to the

page_text: diamido-diphenol-ethers, diamido stillbene, disulphonated diamido-stillbene diamido--
diphenylamine &c. in one or other of the three following ways, namely,
(1) By means of the aldehyde polyazo colouring matters of the formula R-N
=N-D-N-N-P-N-N-A-CHO (9). obtained by coupling a
molecule of the aromatic para-diazo-aldehydes mentioned with a molecule of the
intermediate products resulting from the union of one molecule of the tetrazo
derivative of one of the aromatic para-diamines mentioned and of a molecule of
an aromatic amine, a phenol, an amido phenol, or their sulpho, carboxyl or sulpho
carboxyl derivatives, by a molecule of one of the compounds above mentioned as
capable of uniting themselves to two diazo groups belonging to two different
bodies, the said aldehyde polyazo colouring matters being condensed with diamide
in the proportion of one molecule of diamide to two identical or different molecules
of the said aldehyde polyazo colouring matters, or of one molecule of diamide to
one molecule of the said aldehyde polyazo colouring matters and one molecule of.
one of the aldehyde monoazo colouring matters formerly mentioned.
(2) By means of simple or mixed aldehyde disazo colouring matters having
the formula (5) or (6) by combining one molecule of the disazo colouring matter
of formula (5) with two molecules of the intermediate product resulting from the
union of one molecule of the tetrazo derivative of one of the aromatic para-
diamines above mentioned with a molecule of an aromatic amine, a phenol, an
amido phenol or their sulpho, carboxyl or sulphocarboxyl derivatives, or by com-
bining one molecule of the disazo colouring matter of formula (6) with a molecule.
of a like intermediate product.
(3) By means of the aldehyde disazo colouring matters having the formulæ (5).
and (6), by combining first a molecule of the matter of (5) with two molecules of
the tetrazo derivative of one of the aromatic para-diamines mentioned, and then.
the intermediate product thus obtained with two molecules of aromatic amines,.
phenols, amidophenols, or their sulpho, carboxyl or sulphocarboxyl derivatives, or by
combining a molecule of the matter of formula (6) with a molecule of the tetrazo
derivative of one of the aromatic para-diamines mentioned, and then the intermediate-
product thus obtained with a molecule of aromatic amines, phenols, amido phenols,.
or their sulpho, carboxyl, or sulphocarboxyl derivatives.
The substantive colouring matters above described may also be obtained by
condensing two molecules of aromatic para-diazo-aldehydes above mentioned.
(para-diazo-benzaldehyde, paradiazotoluylaldehyde and their sulpho acids) or of
corresponding isodiazo compounds with a molecule of diamide, so as to obtain.
coupled diazo compounds having the general formula,
and constituting a new class of tetrazo bodies which can be transformed in the
same way as the other known tetrazo compounds into diazo or polyazo colouring
matters.
Further, by combining a molecule of tetrazo bodies according to formula (10).
with a molecule of aromatic amines, phenols, amido-phenols or their sulpho,
carboxyl or sulphocarboxyl derivatives, intermediate products are obtained which.
include a free diazo group, and of which a molecule can be combined with a molecule-
of one of the compounds usually combined with diazo bodies for the manufacture of
azo colouring matters, in order to furnish a mixed diazo colouring matter, or
of which two molecules can be combined with a molecule of one of the compounds
above mentioned as capable of uniting with two azo groups belonging to different
bodies in order to furnish a polyazo colouring matter.
If, on the other hand, two molecules of tetrazo bodies according to formula (10).
are coupled by a molecule of a body capable of uniting with two different azo
groups in the manner set forth in the English Patent No. 14,483 dated 30th July
1895, new products are obtained containing still two free diazo groups, and capable
of combining with two molecules of aromatic amines, phenols, amidophenols or their

page_text: of 13 parts of the intermediate product derived from paradiazo-benzaldehyde and
orthocresotinic acid (orthooxytolinic) and of 2 parts of the intermediate product
derived from diazobenzaldehyde and naphthylamine sulphonic acid 2.6, this
mixture being suspended in 75 parts of water acidulated with acetic acid, and the
operation being farther carried on as in Example 1.
EXAMPLE 5.
A red violet colouring matter is produced when for the aldehyde azo body above
mentioned there are substituted 4 parts of the intermediate product resulting from
the coupling of para-diazo-benzaldehyde with amido-naphthol sulphonic acid G in
acid solution.
If diamide be made to act on the product resulting from the combination of
equivalent quantities of diazo-benzaldehyde and amido-naphthol mono-sulphonic
acid 2.8.6 or nigrotinic acid in alkaline solution a diazo colouring matter is obtained
which dyes dark violet.
EXAMPLE 6.
By condensation of 0.8 parts of sulphate of diamide (as in Example 4) with
5 parts of the intermediate product derived from para-diazo-benzaldehyde and
amido-naphthol disulphonic acid 1.8.3.6 combined in alkaline solution, there is.
obtained, without change in the mode of operating, a new colouring matter which
appears in form of a powder with metallic lustre, is readily soluble in hot water
and dyes non-mordanted cotton directly a blue violet tint, which, again diazotising
the dye on the fibre and combining it farther with an aromatic meta-diamine, can:
be changed to green-black. By diazotising this dye on the fibre and combining it
farther with naphthol, the shade can be changed to black.
EXAMPLE 7.
8 parts of hydrochlorate of paramido-benzaldehyde are dissolved in water with
addition of 10 parts of hydrochloric acid; the solution is cooled with ice aud
diazotised by means of 3-5 parts of sodium nitrite. After filtration, the solution of
the diazo derivative thus obtained is run into an aqueous solution of 16 parts of
amido-naphthol disulphonic acid 1.8.3.6 which is cooled with ice and contains
excess of sodium acetate. The mass is left for about 12 hours, neutralised with
soda which changes the red violet colour of the solution to blue violet, and finally
there is added to the mass a solution of diazo-benzol obtained in the known manner
by diazotising 47 parts of aniline. After leaving the mass for 12 hours the
colouring matter formed is almost entirely precipitated, the material is then heated
to boiling, the colouring matter still in solution is precipitated by salt, pressed and
dried. The colouring matter thus formed constitutes a powder with bronze lustre,
its solution in water gives a blue colour, and dyes wool in an acid bath deep blue-
black shades fast to fulling.
If, in the preceding operation, for the amido-naphthol disulphonic acid 1.8.3.6
be substituted isomeric amido-naphthol-disulphonic acid 1.8.4.6 or 1.5.3.7, and if
also for the diaze-benzol be substituted nitro-diazo-benzol or other diazo bodies or
intermediate products obtained from a molecule of a tetrazo body derived from one
of the paradiamines mentioned and from a molecule of an aromatic amine, a phenol,

page_text: an amidophenol or a sulpho carboxyl or sulphocarboxyl derivative of these bodies
there is obtained a series of aldehyde polyazo derivatives capable of being
condensed with diamide.
In order to couple, by means of diamide, the disazo colouring matter described
above, 6 parts of the colouring matter derived from para-diazo-benz-aldehyde,
from amido-naphthol sulphonic acid 1.8.3.6, and from diazo-benzol are dissolved in
about 200 parts of water; to this solution is added the acetic acid necessary to
give it a pronounced acid character, and finally there is added a solution of
diamide obtained by dissolving 0-8 parts of sulphate of diamide in 8 parts of
a ten per cent. solution of carbonate of soda. On heating, the reaction mass,
a change of colour from blue to blue-black can be seen; or that one of the amido
groups first acts alone; after a time there is seen to separate as a precipitate
dianhydro compound more hard to dissolve. After heating about three quarters
of an hour, the material is alkalised by adding carbonate of soda, it is left to
digest for about half an hour, the colouring matter is precipitated by addition of
salt, filtered and dried.
The colouring matter is in form of a powder with metallic lustre, readily soluble
in water with steel blue colour, it dyes non mordanted cotton indigo-blue.
The condensation of diamide above described according to which an amido
group of the diamide acts alone may be observed in a great number of condensa-
tions by the change of colour produced, and it furnishes excellent means of
obtaining mixed products of condensation, so that, by the choice of differently
coloured aldehyde azo colouring matters, a great variety of tints may be
.obtained.
EXAMPLE 8.
Of the aldehyde disazo colouring matter which dyes wool green-black and is
obtained by combining equivalent quantities of para-diazo-benzaldehyde, amido-
naphthol disulphonic acid 1.8.3.6 and para-nitro-diazo benzol in a manner similar
to that set forth at the beginning of the preceding example, 6.5 parts are digested
with 1-6 parts of sulphate of diamide (dissolved as usual with addition of about
16 parts of carbonate of soda) at first cautiously in dilute acetic solution, until the
change of colour takes place. To the product of condensation are then added
27 parts of the aldehyde mono-azo colouring matter derived from para-dinzo-benz-
aldehyde and salicylic acid, and the material is heated for about half an hour.
The rest of the operation is carried on as usual.
The colouring matter obtained constitutes a black powder very readily soluble
in hot water, dyeing non-mordanted cotton green.
EXAMPLE 9.
The aldehyde azo colouring matter obtained with equivalent quantities of
para-diazo-benz-aldehyde and amido-naphthol disulphonic acid 1.8.3.6 in acid solu-
tion, is condensed with diamide in the proportion of two molecules of the colouring
matter to one molecule of diamide, and one molecule of the coupled disazo
colouring matter thus obtained is combined with one or two molecules of a diazo
-compound, such for instance as diazo-benzol, nitro-diazo-benzol or the intermediate
products resulting from the combination of tetrazo-diphenyl, tetrazo-ethoxy-
diphenyl, tetrazo-ditolyl, tetrazo-diphenylamine or tetrazodiphenol-alkyl-ether
with salicylic acid, ortho-cresotinic acid, a naphthol-a sulphonic acid, the dioxy
naphthoic-mono sulphonic acids, the amido-naphthol sulphonic acid G, the amido-
naphthol disulphonic acid 1.8.3.6 &c. Thus there are obtained blue, black and
green colouring matters which dye cotton without mordant.

page_text: dioxy-naphthaline disulphonic acid be combined with an equivalent quantity of an
aromatic para-diazo aldehyde, and two molecules of the azo aldehyde colouring
matter thus obtained be coupled by means of diamide the product of condensation
obtained will furnish :-
matters.
a. If one molecule, be combined with two molecules of a tetrazo compound
derived from an aromatic para-diamine-new coupled tetrazo derivatives
which by their combination with two identical or different molecules of
phenol, naphthol phenylene-diamine, naphthylamine, naphthol sulphonic
acid, or amidonaphthol sulphonic acid, will give new poly-azo colouring
b. If one molecule be combined with one molecule of the tetrazo derivative of
a paradiamine and one molecule of a simple diazo body, or simply with one
molecule of the tetrazo derivative of a para-diamine-new complex tetrazo
compounds, which by their combination with a molecule of an amine, phenol,
amido phenol or their sulpho, carboxyl or sulpho carboxyl derivatives, give
very varied poly azo colouring matters.
EXAMPLE 11.
47 parts of hydrochlorate of paramido-benzaldehyde are dissolved hot in one
part of water, in adding 35 parts by volume of concentrated hydrochloric acid
of 24.4 per cent., and this solution, after cooling to 15° to 20° C., is diazotised with
about 25 parts of sodium nitrite at 95 per cent. On the other hand a solution
of 3 parts of sulphate of diamide in 30 parts of a solution of carbonate of soda of
10 per cent. is prepared, and finally the solution of diamide is combined with the
solution of hydrochlorate of paradiazo-benzaldehyde at a low temperature such
as 5° C.
The solution of the newly formed tetrazo body, which when heated (and even
when cold if left to itself for a long time) decomposes with disengagement of
nitrogen, combines in the usual manner, preferably in acetic or alkaline solution,
with the aromatic amines, phenols, amido phenols, and their sulpho, carboxyl or
sulphocarboxyl derivatives, which react most readily, to form diazo colouring
matters dyeing non-mordanted cotton.
In the same manner there may be condensed with one molecule of diamide, two
molecules of para-diazobenzaldehyde-orthosulphonic acid, or one molecule of para-
diazo-benzaldehyde-orthosulphonic acid, and one molecule of para-diazo-benz-
aldehyde or one molecule of para-diazbenzaldehyde &c.
For preparing substantive colouring matters for cotton, for example, by means
of the tetrazo compound obtained as above (tetrazo derivative of the dibenzylidene
diamide derivative) there is advantageously employed directly the product of the
reaction still in solution in the liquid in which it has been produced, and the process
is carried on as follows:-
3 parts of the sodium salt of naphthylamine-mono sulphonic acid 2.7 are dissolved
in water, in adding 6 parts of acetate of soda, and there is added of the product
of condensation of hydrochlorate of paradiazo-benzaldehyde with diamide obtained
in the above described manner and still in solution in the liquid in which it was
generated, that is to say, 1-65 parts of this product of condensation derived from
1-57 parts of hydrochlorate of paramido benzaldehyde.
The combination takes place at once, but requires nevertheless a certain time for
completion. The colouring matter is then mostly already in the precipitated form
and the portion of the colouring matter remaining in solution, is precipitated by.an
addition of salt; the colouring matter is separated by filtration and is dried. It
constitutes a powder with metallic lustre, dyeing non mordanted cotton a
bright red.
If, in this example for the naphthylamine sulphonic acid be substituted 48 cub.
centims. of a solution containing 8.2 per cent.in volume, of naphthol-disulphonic
acid 1.3.8. and carbonate of soda in desired quantity, there will be obtained, by
n

page_text: proceeding in an analogous manner, the colouring matter in the form of powder
with strong metallic lustre, and dyeing non mordanted cotton a very pure red-violet.
EXAMPLE 12.
By the combination of the two diazo groups of the tetrazo body resulting from
the condensation of two molecules of aromatic para-diazo-aldehyde with one molecule
of diamide, with two different compounds, there are obtained mixed disazo colouring
matters. For example, gd of the solution of the tetrazo body obtained according
to Example 11 is made to act upon the aqueous solution of a mixture of 0-95 part
of metamido-phenol sulphonic acid and of 1.25 part of naphthyl-amine-mono
sulphonic acid 2.6, in the presence of 6 parts of carbonate of soda; or the said
tetrazo body is first combined with 0.95 part of metamido-phenol sulphonic acid in
the presence of 6 parts of carbonate of soda, and there is then added to the resulting
intermediate product which still contains a free diazo group, a solution of 1.25 parts
of B-naphthylamine sulphonic acid 2.6.
The colouring matter, separated in the ordinary manner, forms a red powder
which dyes non-mordanted cotton a red-brown.
In an analogous manner there are obtained, in substituting for the amido phenol
sulphonic acid, and the naphthylamine-mono sulphonic acid 2.6 other compounds
capable of readily combining with a diazo group, and which have been indicated at
the commencement hereof, simple or mixed colouring matters, dyeing cotton
without mordants, which are identical or analogous to those that can be obtained
according to the Examples 1'to 6 above given:
EXAMPLE 13.
The preparation of the same substantive colouring matters for cotton also
succeeds if, instead of starting from the aromatic para-diazo-aldehydes, one starts
with the aromatic iso-diazo-aldehydes.
For example, to the diazo solution obtained according to the beginning of
Example 11, there is added an excess of soda lye and the mass is left to itself
until the non formation of a colouring matter by the addition of a sample taken
from this mass to ß-naphthol in alkaline solution proves the transformation into
nitrosamine. If there be then added as has been indicated in Example 11, 3 parts
of sulphate of diamide there will be precipitated after dilute acetic acid has been
added to the mass, an iso tetrazo anhydro compound which cannot be immediately
combined with amines, phenols, amido phenols, or their sulpbo, carboxyl or sulpho
carboxyl derivatives, and which will not pass to the condition of normal tetrazo
compound until after it has been left to itself for a long time, preferably in
the presence of an excess of acid, the said normal tetrazo compound being
capable of combining, like the tetrazo bodies of the two preceding examples,
with amines phenols, amido phenols and their sulpho,- carboxyl or sulpho-
carboxyl derivatives, which react most readily, giving colouring matters identical
with those obtained with the coupled aromatic diazo aldehydes.
EXAMPLE 14.
If the tetrazo derivatives of dibenzylidene diamide derivative obtained in alkaline
liquor according to Example 11 be combined with an equivalent quantity of the
intermediate products obtained by the combination of diazo-benzol, nitro-diazo-
benzol &c. with amido-naphthol di-sulphonic acid 1.8.3.6 in acid bath, there are
obtained new intermediate products which by their combination with phenols,
resorcine, phenylene-diamine, amido-naphthol sulphonic acids &c., furnish polyazo
colouring matters of a green, green-black, blue &c. colour.

page_text: combining in alkaline solution two molecules of the intermediate products obtained
according to Example 12, with one molecule of oue of the above mentioned com-
pounds capable of readily coupling two diazo groups, such for example as meta-
amido-phenols, or in combining 2 molecules of the tetrazo derivative of
di-benzylidene-diamide derivative with one molecule of a similar compound capable
of uniting with two diazo groups, such for example as amido-naphthol disulphonic
acid 1.8.3.6, so as to obtain coupled tetrazo compounds, according to the English
Patent No. 14483 of 1895 in the preparation of which the tetrazo derivative of
dibenzylidene diamide derivative can he replaced by any one of the known tetrazo
bodies, and in combining the simple or mixed coupled tetrazo bodies thus obtained
with two molecules, either identical or different, of aromatic amines phenols, amido
phenols or their sulnho carboxyl or sulpho carboxyl derivatives.
As has been first herein stated, this process can be simplified in this sense,
that the combination of the aromatic paradiazo-aldehydes with the aromatic
amines, phenols, amidophenols and their sulpho, carboxyl, and sulphocarboxyl
derivatives and the condensation with diamide, can be united in one single
operation, without deciding at present whether in this case there is first
formation of the aldehyde mono-azo colouring matters and condensation of the
latter with the diamide, or whether there is first formed the anhydro-tetrazo
compound, which then combines with the aromatic amines, phenols, amido phenols
and their sulpho, carboxyl, or sulpho-carboxyl derivatives, or whether the two
kinds of reactions are produced simultaneously, side by side.
This simplified mode of operating has been found particularly advantageous in
the case where the combination of the para-diazo-aldehydes with the aromatic
amines, phenols, amidophenols and their sulpho, carboxyl and sulpho-carboxyl
derivatives succeeds in slightly acid solution; for instance in acetic solution, but it
is not applicable in the cases where the combination takes place in alkaline
solution.
Thus the colouring matter indicated in Example 2, derived from naphthylamine
mono-sulphonic acid 2.7, can be obtained by dissolving on the one hand 3-5 parts of
the soda salt of naphthylamine-monosulphonic acid 2.7 1 part of sulphate of
diamide and about 6 parts of acetate of soda (the mineral corresponds to the
anhydrous salt) by diazotising on the other hand, in the usual manner, a solution
of 12 parts of paramido-benzaldehyde in 150 parts of water, to which are added,
for example 5 to 6 parts of hydrochloric acid of 24 per cent., and adding the
solution of the diazo derivative thus obtained to the above mentioned solution
of B-naphthylamine sulphonic acid and of diamide. The precipitation of the
colouring matter then takes place at the end of a few moments. After having
digested the mass with carbonate of soda the colouring matter, still in solution, is
precipitated by an addition of salt, and it is then filtered, pressed and dried.
It is to be understood that I do not limit myself to the proportions given nor to
the other conditions of the various operations hereinbefore described, as these may
vary according to the bodies which enter into reaction, and according to the
practical conditions which obtain in the industries of the manufacture of azo
colouring matters, and which are known by all persons versed in these
manufactures.
Furthermore in the above described manufacture of substantive colouring
matters for cotton, for the diamide can be substituted diamide hydrate, a diamide
salt, or those diamide compounds which on being added to the reaction compounds
give free diamide, diamide hydrate or a diamide salt.
The above described colouring matters not only dye non-mordanted cotton,
paper, linen, and jute in a salt, neutral or alkaline bath, but also wool and silk in a
neutral bath.

page_text: e colouring matters which contain amido-naphthol sulphonic acids (combined
kaline solution) or a-naphthylamine or naphthylamine sulphonic acid 1.6 or 1.7,
e again diazotised on the fibre and in subsequently developing the colouring
er on the fibre by means of naphthol, resorcine, aromatic meta diamines,
s of naphthylamines, they produce violet, blue, black and green tints very fast
shing.
aving now particularly described and ascertained the nature of my said inven-
and in what manner the same is to be performed I declare that what I
is:-
The manufacture of colouring matters, called "diamide colouring matters
g cotton without a mordant:
(a) By the condensation of one molecule of diamide
NH,
"
with two mole-
cules, either identical or different, of the aldehyde mono-azo colouring
matters resulting from the combination of the aromatic para-diazo-aldehydes,
such as para-diazo-benzaldehyde, para-diazotoluylaldehyde, and their
sulpho derivatives, with aromatic amines, phenols, amido-phenols and their
sulpho, carboxyl, and sulpho-carboxyl derivatives, and in particular those
of such bodies which have been indicated at the beginning of the
Specification.
(6) By the condensation of one molecule of diamide with two molecules,
either identical or different, of the aldehyde-disazo colouring matters which
result from the combination of one molecule of the aromatic para-diazo-
aldehydes indicated in (a) and one molecule of any diazo body, with one
molecule of a compound capable of uniting with two diazo groups belonging
to different molecules, such as for instance, the meta-dioxy-benzols
(resorcine &c.) the metamido-phenols, the aromatic meta-diamines (meta
phenylene-diamine and metatoluylene-diamine), certain sulphonic acids of
dioxy-naphthalene 1.8, and of amido-naphthol 1.8 (dioxy-naphthalene
disulphonic acid 1.8.3.6 and amido-naphthol disulphonic acids 1.8.3.6, 1.8.4.6
and 1.5.3.7) dioxynaphthoic-mono sulpho acid of English Patent No. 14161
of 1892, diamido-naphthalene disulphonic acid 1.8.3.6, amido-naphthol mono-
sulpho acid 2.8.6.
c) By the condensation of one molecule of diamide with one molecule of one
of the aldehyde disazo colouring matters, indicated in (b) and one molecule
of one of the aldehyde mono-azo colouring matters indicated in (a).
(d) By the combination of two molecules of any diazo bodies with one
molecule of aldehyde dis-azo colouring matters, which result from the
condensation of one molecule of diamide with two molecules of aldehyde
mono-azo colouring matters obtained by the combination of oue molecule of
one of the aromatic para-diazo-aldehydes mentioned in (a) with one of the
bodies capable of combining with two diazo groups belonging to different
molecules mentioned in (b).
(e) By the combination of one molecule of any diazo body with one molecule
of the aldehyde disazo colouring matters that result from the condensation
of one molecule of diamide with one molecule of one of the aldehyde
mono-azo colouring matters mentioned in (a) and one molecule of one of the
aldehyde mono-azo colouring matters mentioned in (d).
(f) By the condensation of one molecule of diamide with two molecules either
identical or different, of the aldehyde poly-azo colouring matters obtained in
coupling, by means of one molecule of one of the bodies susceptible of
combining with two diazo groups belonging to different molecules, mentioned
in (b) one molecule of the aromatic para-diazo-aldehydes mentioned in (a)
and one molecule of the intermediate products which result from the union

page_text: of one molecule of the tetrazo derivatives of the aromatic para-diamines such
as benzidine, ethoxy-benzidine, tolidine, the diamido-diphenol alkylethers,.
diamido-stillbene, disulpho-diamido-stillbene diamido-diphenylamine &c.,.
and one molecule of the aromatic amines, phenols, amido phenols, and their
sulpho, carboxyl, and sulpho-carboxyl derivatives, and in particular those
of these compounds which have been indicated at the beginning of the-
Specification.
7) By the condensation of one molecule of diamide with one molecule of one-
of the aldehyde poly-azo colouring matters indicated in (f) and one
molecule of the aldehyde mono-azo colouring matters mentioned in (a).
) By the combination of one molecule of the aldehyde disazo colouring
matters mentioned in (d) with two molecules of the intermediate products
indicated in (f) which result from the union of one molecule of the tetrazo
derivative of an aromatic para-diamine and one molecule of an aromatic
amine, phenol, amido-phenol or of a sulpho, carboxyl or sulpho-carboxyl
derivative of these bodies, and in particular of those of such compounds or
bodies which have been mentioned at the beginning of this Specification.
) By the combination of one molecule of the aldehyde disazo colouring
matters mentioned in (e) with one molecule of the intermediate products.
indicated in (f) and which result from the union of one molecule of the
tetrazo derivative of an aromatic para-diamine and one molecule of au
aromatic amine, phenol, amido phenol or of a sulpho, carboxyl or sulpho-
carboxyl derivative of these bodies, and in particular those of these
compounds which have been indicated at the beginning of the Specification.
) By the combination of one molecule of aldehyde disazo colouring matters.
mentioned in (d), with two molecules of the tetrazo-derivative of one of the
aromatic para-diamines mentioned in (f) and by the subsequent combination.
of the intermediate product thus obtained with two molecules of aromatic
amines, phenols, amido-phenols and their sulpho,- carboxyl and sulpho-.
carboxyl derivates, and in particular those of these compounds which have
been indicated at the beginning of the Specification.
) By the combination of one molecule of aldehyde disazo colouring matters
mentioned in (e) with one molecule of the tetrazo derivative of one of the
aromatic para-diamines mentioned in (f) and by the subsequent combination
of the intermediate product thus obtained with one molecule of aromatic
amines, phenols, amido-phenols, and the sulpbo, carboxyl and sulpho-
carboxyl derivatives of these bodies, and in particular those of these
compounds which have been indicated at the beginning of the Specification..
) By the condensation of one molecule of diamide with two molecules, either
identical or different, of the para-diazo-aldehydes indicated in (a) and by
the subsequent combination of one molecule of the tetrazo compound thus
obtained with two molecules, either identical or different, of amines, phenols,.
amido-phenols, and the sulpho, carboxyl and sulpho-carboxyl derivatives
of these bodies, and in particular those of such compounds which have
been indicated at the beginning of the Specification which react most.
readily.
n) By the condensation of one molecule of diamide with two molecules of
aromatic iso-para-diazo-aldehydes, and the conversion of the iso-tetrazo
compounds thus obtained in the manner described into corresponding normal
tetrazo compounds, and the subsequent combination of one molecule of these
tetrazo compounds with two molecules, either identical or different, of
aromatic amines, phenols, amido-phenols, and their sulpho, carboxyl, and
sulpho-carboxyl derivatives, and in particular those of such bodies that have
been mentioned at the beginning of the Specification.
) By the combining of one molecule of diamide, two molecules of the para-
diazo-aldehyde mentioned in (a) and two molecules of aromatic amines,
phenols, amido phenols, and their sulpho, carboxyl and sulpho-carboxyl

page_text: derivatives and in particular those of such compounds mentioned at the
beginuing of the Specification.
By the combination of two molecules of the tetrazo compounds which
result from the condensation of one molecule of diamide with two molecules
of the aromatic para-diazo-aldehydes mentioned in (a) with one molecule of
one of the bodies capable of coupling two diazo groups belonging to
different molecules mentioned in (b) and the subsequent combination of the
coupled tetrazo bodies thus obtained with two molecules, either identical
or different, of amines phenols, amido-phenols, and their sulpho, carboxyl
and sulpho-carboxyl derivatives, and in particular those of such bodies
mentioned at the beginning of the Specification.
p) By the combination of a molecule of the simple ar mixed tetrazo colouring
matters which result from the union of a molecule of the tetrazo bodies
obtained by condensation of a molecule of diamide with two molecules of the
aromatic para-diazo-aldehydes mentioned in (a) and of two identical or
different molecules of bodies capable of coupling two diazo groups belonging
to different molecules mentioned in (b) either with one or two molecules of
any diazo bodies, or with one or two molecules of the tetrazo derivatives of
the aromatic para-diamines mentioned in (f) or of the tetrazo bodies
obtained by the condensation of one molecule of diamide with two molecules
of the para-diazo-aldehydes mentioned in (a), and the combination of a
molecule of the intermediate product, obtained in these latter cases, with
one or two molecules of aromatic amines, phenols, amido-phenols and their
sulpho, carboxyl and sulpho-carboxyl derivatives, especially of those
of these compounds which have been mentioned at the beginning of this
Specification.
g) By the combination of a molecule of the mixed tetrazo colouring matters
which result from the union of a molecule of the tetrazo bodies obtained
by the condensation of a molecule of diamide with two molecules of the
para-diazo-benzaldehydes mentioned in (a) of a molecule of one of the bodies
capable of coupling two diazo groups belonging to different molecules
mentioned in (6), and of a molecule of aromatic amines, phenols, amido-
phenols and their sulpho, carboxyl, and sulphocarboxyl derivatives,
especially those of these compounds which have been mentioned at the
beginning of this Specification, either with a molecule of any diazo body or
with a molecule of the tetrazo derivatives of the aromatic para-diamines
mentioned in (f) or the tetrazo bodies obtained by the condensation of
one molecule of diamide with two molecules of the para-diazo-aldehydes
mentioned in (a) and the combination of a molecule of the intermediate
products obtained in these latter cases with a molecule of an aromatic
amine, phenol, amido-phenol, or their sulpho, carboxyl, or sulpho-carboxyl
derivatives especially those of these bodies mentioned at the beginning of
this Specification.
r) By the combination of a molecule of one of the bodies capable of coupling
two diazo groups belonging to different molecules mentioned in (b) with a
molecule of the intermediate products which result from the union of a
molecule of the aromatic amines, phenols, amido-phenols or their sulpho,
carboxyl or sulpho-carboxyl derivatives especially those of these compounds
mentioned at the beginning of this Specification, and of a molecule of the
tetrazo bodies obtained by the condensation of a molecule of diamide with
two molecules of the aromatic para-diazo-aldehydes mentioned in (a) and
with a second molecule of these same intermediate products, or with a
molecule of the intermediate products which result from the union of the
tetrazo derivatives of the aromatic para-diamines mentioned in (f) with a
molecule of the aromatic amines, phenols, amido-phenols, or their sulpho,
carboxyl or sulpho-carboxyl derivatives, and especially those of these com-

page_text: pounds which have been mentioned at the beginning of this Specification, or
also with a molecule of any diazo body.
) By the combination of one molecule of diamide with two equal or different
molecules of the secondary disazo colouring matters which are obtained by
the combination of one molecule of aromatic para-diazo-aldehydes mentioned
in (a) with one molecule of a-naphthylamine, paraxylidine, para-cresidine,
naphthylamine mono-sulpho acid 1.6 or 1.7, naphthylamine ether sulpho
acid 1.2.6 or 1.2.7, naphthylamine ether 1.2, amido-naphthol mono sulpho
acids 2.8.6 and 2.5.7, amido naphthol disulpho acids 2.8.3.6, 2.8.4.6, 1.8.3.6,
1.5.3.7 and 1.8.2.4, and amido nigrotinic acid (all the. amido-naphthol
derivatives being combined in alkaline solution), then farther diazotizing
the intermediate products thus obtained and their subsequent combination
with one molecule of aromatic amines, phenols, amido-phenols and their
sulpho carboxyl and sulpho-carboxyl derivatives, and in particular those
of such components that have been mentioned in the beginning of the
Specification.
As new products.
2) The colouring matters called "diamide colouring matters" dyeing non
mordanted cotton, which can be obtained according to Claim I.
3) The intermediate products suitable for the manufacture of the said
colouring matters which dye non mordanted cotton and which are
constituted.
.
(1) By the aldehyde disazo colouring matters mentioned in Claim I
in (b), (d) and (e) :-
(2) By the aldehyde polyazo colouring matters mentioned in Claim I
in (f)-
(3) By the products resulting from the combination of a molecule of the
aldehyde disazo colouring matters mentioned in Claim I in (d) with two
molecules of the tetrazo derivative of one of the aromatic para-diamines
mentioned in Claim I in (f).
(4) By the products resulting from the combination of one molecule of the
aldehyde disazo colouring matters mentioned in Claim I in (e) with a
molecule of the tetrazo derivative of one of the aromatic para-diamines
mentioned in Claim I in (f).
(5) By the tetrazo bodies resulting from the combination of a molecule of
diamide with two molecules of the para-diazo-aldehydes mentioned in
Claim I, in (a).
(6) By the iso-tetrazo bodies resulting from the condensation of a molecule
of diamide with two molecules of an aromatic iso-para-diazo-aldehyde.
(7) By the products resulting from the combination of two molecules of the
tetrazo bodies mentioned in Claim II in (5) with one molecule of one of
the bodies capable of coupling two diazo groups belonging to different
molecules mentioned in Claim I in (b): and
(8) By the products resulting from the combination of one molecule of the
tetrazo bodies mentioned in Claim II in (5) with one molecule of aromatic
amines, phenols, amido-phenols, or their sulpho, carboxyl. or sulpho-
carboxyl derivatives.
Dated this 7th day of March 1896.
ABEL & IMKAY,
Agents for the Applicant.