Manufacture of Azo Colouring Matters, and of New Bases for Use therein.
Year: 1895

page_text: Date of Application, 30th July, 1895
Complete Specification Left, 29th Apr., 1896-Accepted, 20th June, 1896
Manufacture of Azo Colouring Matters, and of New Bases for Use
therein.
I, OLIVER IMRAY of No. 28 Southampton Buildings, Chancery Lane in the
County of London, Chartered Patent Agent do hereby declare the nature of this
invention to be as follows:-
My foreign correspondents have found that by combining amido-ammonium bases
of the generic formula (aromatic radical) II'
NH2
N(alk), X
with amines or phenols,
valuable basic azo colouring matters are produced. The said colouring matters
can be dyed on cotton mordanted with tannin and do not show the sensitiveness to
acids which is possessed by the ordinary basic azo-colouring matters.
It has been found that aromatic amido-ammonium bases of the above generic
formula and their salts, can be produced in various ways, as by reduction of
nitro-ammonium bases or azo-ammonium bases, or even, by the alkylation of
diamines, in which an amido group is protected before alkylation, as in the acidyl,
alkyled, or azo derivatives, and subsequent regeneration of the amido group.
The amido-ammonium bases employed in the following examples, viz., m-amido-
phenyl-trimethyl-ammonium, m-amido-phenyl-dimethyl-ethyl-ammonium, m-amido-
p-methyl-phenyl-trimethyl-ammonium, have been produced from the corresponding
nitro-derivatives by reduction, these nitro-derivatives having been produced by
alkylising aromatic nitro-bases, for instance m-nitraniline, m-nitro-dimethyl-aniline,
m-nitro-p-toluidine, or also by nitrating the phenyl or tolyl trialkyl-ammonium
bases. For example
m-amido-phenyl-trimethyl-ammonium is produced by grouping alkyl halogen
together with m-aze-dimethylaniline, and subsequently separating by reduction.
p-amido-phenyl-trimethyl-ammonium is produced by the action of alkyl halogen
acetyl-p-dimethyl-phenylendiamine or benzyliden-p-dimethyl-phenylen-
diamine, and subsequent separation of the acetyl- or benzyliden-amido-ammonium
upon
base.
In the following examples these methods and the new compounds will be
described.
1) 20 kilos. of m-nitrophenyl-trimethyl-ammonium-chloride are mixed with
50 litres of water and 50 kilos. of hydrochloric acid, and 20 kilos. of zinc chips
are gradually introduced into the mixture. Reaction takes place very readily with
great generation of heat. After sufficient concentration, the double zinc salt of
m-amido-phenyl-trimethyl-ammonium chloride separates from the solution.
2) 1 kilo. of m-nitro ammonium chloride is dissolved in 10 litres of water, and
into the hot solution there is introduced gradually the suitable amount of zinc
dust. The reduction takes place with energetic ebullition produced by the heat of
the reaction.
3) 1 kilo. of m-nitro ammonium chloride is heated with 7 kilos. of 40 per cent.
"

page_text: bisulphite solution to about 80° C. The conversion is effected in a short time with
violent ebullition of the solution, and a crystalline flour separates, consisting of
NCHA
the sulphaminate salt of the ammonium base C, H₂
NH
SO3.
On being boiled with acids, it yields the corresponding salts of the ammonium
base.
m-amido-phenyl-trimethyl-ammonium-zinc chloride forms large, colourless prisms
which are very readily soluble in hot water, and are also readily soluble in cold
water.
m-amido-phenyl-trimethyl-ammonium chloride is produced by mixing the solution
of the double chloride of zinc with the calculated amount of sodium carbonate,
removing the zinc carbonate, then evaporating, and extracting the residue with
alcohol.
Then the compound crystallizes in colourless rhombical cakes or tablets which
are very readily soluble in hot alcohol and also especially in water.
m-amido phenyl trimethyl ammonium chloride hydro chloride crystallises in
water in colourless prisms, and is very readily soluble in water.
m-nitro phenyl dimethyl ethyl ammonium chloride forms highly lustrous prisms
of large size. It is soluble with difficulty in cold water, but is moderately soluble
in hot water.
m-amido-phenyl dimethyl ethyl ammonium zinc chloride is, as regards
appearance and properties, entirely similar to the zinc salt of the afore described
trimethyl base.
m-nitro-p-methyl-phenyl-trimethyl ammonium bromide forms lustrous thick
yellowish prisms, and is moderately soluble in cold and hot water, also in hot
alcohol.
m-amido-p-methyl phenyl trimethyl ammonium zinc chloride crystallises in
colourless long prisms, and is readily soluble to a certain degree in cold water.
m-amido-p-methyl-phenyl trimethyl ammonium chloride produced from the
double zinc salt by reaction with sodium carbonate, forms colourless prisms readily
soluble.
p-nitrobenzyl tri-methyl ammonium chloride forms needles that are extremely
soluble in water.
p-amidobenzyl tri-methyl ammonium chloride is obtained in the form of syrup;
the salt is very readily soluble.
p-nitro benzyl tri-ethyl ammonium chloride crystallises in coarse needles which
are very readily soluble in water.
p-amido-benzyl tri-ethyl ammonium chloride has not been obtained in the form
of crystals, because it is very readily soluble.
4. p-acetyl amido di-methyl aniline, having fusing point 130° C. is heated on a
water-bath with an amount of iodine-methyl corresponding to one molecule. The
p-acetyl amido phenyl-tri-methyl ammonium iodide thereby produced is moderately
soluble in water. It decomposes at 225° C. The corresponding chloride is also
readily soluble in water. It crystallises from alcohol in the form of small scales
which become decomposed on being heated to 215° C. In order to produce from
it p-amido phenyl trimethyl ammonium, it may be boiled with 6-10% hydro-
chloric acid. The double zinc salt of the amido ammonium base may be precipitated
from the solution by means of zinc chloride. The solution also may be employed
directly for the production of azo colours.
5. On treating p-acetylamido diethyl-aniline having fusing point 104° C. in the
same manner, there is obtained p-acetyl amido phenyl-di-ethyl methyl, ammonium
iodide, which decomposes at 195° C. The analogous chloride decomposes at about
170° C. On boiling it with dilute acid it produces the solution (capable of
being diazotised) of the p-amido-phenyl-di-ethyl methyl ammonium base.

page_text: 6. Benzyliden-p-amido dimethyl aniline (one molecule) dissolved with a small
excess of iodine methyl (1 molecule) in methyl alcohol is boiled in a return-flow
cooler. After a short time the henzyliden-p-amido phenyl tri-methyl ammonium-
iodide separates; it is almost insoluble in alcohol. On heating with steam in the
presence of hydrochloric acid the benzyliden compound is split up, and at the same
time the benz-aldehyde is driven off. Then the aqueous solution can be acted upon
with bleaching chloride in order to produce the p-amido-phenyl-tri-methyl
ammonium chloride. This compound is extremely soluble in water; it crystallises
in minute prisms. Zinc chloride is employed to separate from the solution the
double zinc salt which crystallises in large prisms and which is readily soluble in
water.
7. Tetra-methyl-m-m-di-amido-azo benzol (produced by alkaline reduction from
m-nitro di-methyl-aniline) is dissolved in about five times the amount of methyl
alcohol, and boiled with a quantity (corresponding to 2-3 molecules) of iodine methyl.
After heating this for several hours, the ammonium iodide that has become
precipitated in pulverulent forin, is separated; it forms small orange coloured
scales, having fusing point 225° C.
The chloride corresponding to this iodide forms flat needles which melt and
decompose at about 200° C. By reducing, for example, with zinc and hydrochloric
acid, there is produced from the ammonium chloride, the in-amido phenyl trimethyl
ammonium base which is identical with the base that is produced by reduction
from m-nitrophenyl trimethyl ammonium chloride.
The amido ammonium bases can be diazotised in the usual manner, and combined
with amines or phenols. The following examples will serve to explain the process
for the production of azo colours from the said bases.
1) 1 kilo. of double chloride salt of zinc or the equivalent amount of another
salt of m-amido-pbenyl trimethyl ammonium, is dissolved in 10 litres of water and
diazotised by the addition of 0.7 kilos. of concentrated hydrochloric acid and
0-195 kilos. of nitrite. The diazo solution is allowed to flow into a weak acetate
suspension of B-naphthol. The yellow red solution, on receiving an addition of
common salt or zinc chloride, precipitates the colouring matter. When the latter
is dried, it has the form of a yellow-red powder.
2) If the diazo solution, prepared as above described, be mixed with an aqueous
solution of 0.31 kilos. of resorcin, there is produced in a short time a paste of
small red-yellow crystals of a mono-azo-colouring matter.
3) If the diazo solution obtained in the same manner, be mixed with half the
quantity of resorcin, and sodium acetate be added, there is produced a diazo
colouring matter which can be salted out of the solution. When dried, it is in
the form of a yellow brown powder.
4) The diazo solution of i kilo. of double zinc salt is mixed with an aqueous
solution of 0.31 kilos. of m-phenylen-diamine with or without an addition of acetate.
On addition of common salt or of an acetate the colouring matter precipitates; it
an be crystallised out from hot water.
If, instead of the salts of m-amidophenyl trimethyl ammonium, there be
employed in the examples given above, the salts of m-amidophenyl dimethyl ethyl
ammonium, of m-amido-p-methyl phenyl trimethyl ammonium, or of p-amido
phenyl trimethyl ammonium, or if instead of naphthol, resorcin or phenylen
diamine as a component, toluylendiamine and 2.3 dioxynaphthaline be employed,
colouring matters similar to those above described are obtained. The new
colouring matters are yellow, red yellow, or brown red powders which are soluble
in water and which dye cotton mordanted with tannin, yellow, red yellow or brown
yellow.

page_text: m-amido yellow-red pow-yellow-brown yellow crystal-
phenyl-tri-
der, soluble in
methyl am-
monium
m- amido
phenyl-di-
methyl-
water with a
red yellow
colour; in
concentrated
H₂SO₁, with
carmine red
powder, soluble
in water with
brown - yellow
colour; in
concentrated
H2SO4, yellow-
brown
line powder,
soluble in water
with pure yel-
low colour; in
concentrated
H₂SO, with
yellow colour
brown
reildish
powder, soluble
in water with
brownish yel-
low colour; in
concentrated
H2SO4, yellow-
brown
yellow brown
powder. soluble
in water with
brown colour;
in concentrated
H₂SO₁, yellow
brown
red brown pow-
der, soluble in
water with
brown colour;
in concentrated
HI,SO, violet
m-amido-p- powder of the
methyl-
phenyl-tri-
methyl am-
monium
colour of red
lead, soluble in
water with red-
yellow colour;
in concentrated
H₂SO, violet
brown crystal-
line powder,
soluble in water
with
brown
yellow-colour;
in concentrated
H₂SO₁ yellow-
dark yellow brown powder,
powder soluble
in water with
pure yellow
colour; in
concentrated
H₂SO₁ light
11
soluble in water
with brownish
yellow colour
in concentrated
H₂SO4, yellow
brown
soluble in water
with brown
colour
in
brown crystal- brown powder,
line powder
soluble in water
with brown
yellow colour;
in concentrated
H₂SO yellow
concentrated
H₂SO blue-
violet

page_text: p-amido-yellow red pow-yellow-brown yellow crystal-
phenyl-
tri-me-
thyl-am-
monium
der soluble in
water with red
yellow colour
in concentrated
H₂SO, with
carmine-red
colour
powder, soluble
in water with
brown yellow
colour in con-
centrated
H₂SO, yellow
brown
line powder,
soluble in water
with pure yel-
low colour; in
concentrated
H₂SO, with
light yellow
reddish brown
powder soluble
in water with
brownish yel-
low colour; in
concentrated
H₂SO, yellow-
brown
yellow brown
powder soluble
in water with
brown colour;
in concentrated
H₂SO, yellow
brown
red-brown pow
der soluble in
water with
brown colour
in concentrated
H.SO, yellow
brown

page_text: their derivatives, valuable basic azo colouring matters are produced. The said
colouring matters can be dyed on cotton mordanted with tannin and do not show
the sensitiveness to acids which is possessed by the ordinary basic azo-colouring
Inatters.
It has been found that aromatic amido-ammonium bases of the above general
formula and their salts, can be produced in various ways, as by reduction of nitro-
ammonium bases or azo-ammonium bases, or even by the alkylation of diamines, in
which one amido group is protected before alkylation, as in the alkoyl, alkylide or
azo-derivatives and subsequent regeneration of the amido group.
In the following are given as examples a description of the new methods and of
some of the compounds obtained therefrom. The nitro ammonium bases described
below are obtained by alkylation of the nitro bases or by nitration of the corre-
sponding ammonium bases.
1.) 2 kilos. of m-nitrophenyl-trimethyl-ammonium chloride are mixed with 5 litres
of water and 5 kilos. of hydrochloric acid, and 2 kilos. of zinc chips are gradually
introduced into the mixture. Reaction takes place very readily with great
generation of heat. After sufficient concentration, the double zinc salt of m-amido-
phenyl-trimethyl-ammonium-chloride separates from the solution.
2.) 1 kilo. of m-nitro-phenyl-trimethyl ammonium chloride is heated with 7 kilos.
of 40 per cent. sodium bisulphite solution to about 80° C. The conversion is
effected in a short time with violent ebullition of the solution and a crystalline
flour separates out, consisting apparently of the sulphaminate salt of the ammonium
Dase.
m-amido-phenyl-trimethyl-ammonium-zinc-chloride forms large, colourless prisms
which are very readily soluble in hot water and are also readily soluble in cold
water.
m-amido-phenyl-trimethyl-ammonium-chloride is produced by mixing the solution
of the double chloride of zinc with the calculated amount of sodium carbonate,
removing the zinc carbonate, then evaporating and extracting the residue with
alcohol. The compound crystallises in colourless tablets which are very readily
soluble in hot alcohol and also especially in water.

page_text: m-nitrophenyl-dimethyl ethyl ammonium chloride forms highly lustrous prisms
of large size. It is soluble with difficulty in cold water, but is moderately soluble
in hot water.
m-amido-phenyl-dimethyl ethylammonium zinc chloride is, as regards appearance
and properties, quite similar to the zinc salt of the afore described trimethyl base.
m-nitro-p-methyl-phenyl-trimethyl-ammonium bromide forms lustrous thick
yellowish prisms and is moderately soluble in cold and hot water. also in hot alcohol.
m-amido-p-methyl-phenyl-trimethyl-ammonium zinc chloride crystallises in
colourless long prisms, and is readily soluble to a certain degree in cold water.
ta-amido-;-methyl-phenyl-trimethyl-ammonium-chloride produced from the double
zinc salt by reaction with sodium carbonate, forms colourless prisms readily soluble
in water.
3) p-acetyl amido-di-methyl aniline, having fusing point at 130° C. is heated on
a water bath with one molecular proportion of methyl iodide. The p-acetyl amido
phenyl trimethyl ammonium iodide thereby produced is moderately soluble in
water. It decomposes at 325° C. The corresponding chloride is also readily
soluble in water. It crystallises from alcohol in the form of small scales which
become decomposed on being heated to 215° C. In order to produce from it
p-amido-phenyl-trimethyl-ammonium, it may be boiled with 6 to 10% hydrochloric
acid. The double zinc salt of the amido animonium base may be precipitated from
the solution by means of zinc chloride. The solution also may be employed
directly for the production of azo colours.
4.) On treating p-acetylamido-di-ethyl aniline having fusing point at 104° C. in
the same manner there is obtained p-acetyl amido-phenyl di-ethyl methyl ammonium
iodide, which decomposes at 195° C. The analogous chloride decomposes at
about 170° C. On boiling it with dilute acid it produces the solution of the p-amido-
phenyl di-ethyl methyl ammonium base.
5.) Benzyliden p-amido di-methyl aniline (one molecule) is boiled with one
molecule of methyl iodide in methyl alcohol solution. After a short time the
benzyliden p-amido-phenyl trimethyl ammonium iodide separates, it is almost
insoluble in alcohol. On heating with steam in the presence of hydrochloric acid
the benzyliden compound is split up. The aqueous solution can then be acted upon
with chloride of lead in order to produce the p-amido phenyl trimethyl ammonium
chloride. This compound is extremely soluble in water; it crystallises in fine
prisms. Zinc chloride is employed to separate froin the solution the double zine
salt which crystallises in large prisms and which is readily soluble in water.
6.) Tetra-methyl-m-m-di-amido azobenzol (produced by alkaline reduction from
m-nitro-di-methyl aniline) is dissolved in about five times the amount of methyl
alcohol and boiled with a quantity (corresponding to 2-3 molecules) of methyl
iodide. After heating this for several hours, the ammonium iodide that has become
precipitated as powder, is separated; it forms small orange coloured scales, having
fusing point at 225° C.
The chloride corresponding to this iodide forms flat needles which melt and
decompose at about 200° C. By reducing, for example, with zinc and hydrochloric
acid, there is produced from the ammonium chloride, the m-amido-phenyl-trimethyl-
ammonium base which is identical with the base that is produced by reduction
from m-nitrophenyl-trimethyl ammonium chloride.
7.) Nitro-ß naphthyltrimethyl ammonium sulphate, produced by the nitration
of B-naphthyltrimethyl ammonium in a solution of concentrated sulphuric acid,
when reduced with zinc and hydrochloric acid, gives amido-ẞ-naphthyltrimethyl
ammonium chloride, which separates out in the form of its zinc double salt in thin
needles (soluble with difficulty).
The amido ammonium bases can be diazotised in the usual manner and combined
with ainines or phenols. The following examples will serve to explain the process
for the production of azo colours from the said bases.
1.) 1 kilo. of the zinc chloride double salt or the equivalent amount of another

page_text: salt of m-amido-phenyl-trimethyl ammonium is dissolved in 10 litres of water and
diazotised by the addition of 0.7 kilos. of concentrated hydrochloric acid and
0.195 kilos. of nitrite. The diazo solution is allowed to flow into a suspension of
B-naphthol acidulated with acetic acid. The yellow red solution, on receiving an
addition of common salt or zinc chloride, precipitates the colouring matter.
the latter is dried, it has the form of a yellow red powder.
When
2.) If the diazo solution, prepared as above described, be mixed with an aqueous
solution of 0.31 kilos. of resorcinol there is produced in a short time a paste of
small red-yellow crystals of a mono-azo colouring matter.
3.) If the diazo-solution, obtained in the same manner, be mixed with half the
quantity of resorcinol and sodium acetate be added, there is produced a disazo-
colouring matter which can be salted out of the solution. When dried, it forms a
yellow brown powder.
4.) The diazo solution of 1 kilo. of the same double zinc salt is mixed with an
aqueous solution of 0.31 kilos. of m-phenylen-diamine; on addition of common salt
the colouring matter is precipitated, it can be crystallised by means of hot water.
If instead of the salts of m-amidophenyl-trimethyl ammonium, there be employed
in the examples given above the salts of m-amido-phenyl-dimethyl-ethyl ammonium,
of m-amido-p-methyl-phenyl-trimethyl ammonium, of p-amido phenyl trimethyl
ammonium or of amido-ß-naphthyltrimethyl ammonium or if instead of naphthol,
resorcinol or phenylen diamine as a component, toluylen diamine, 2-3 dioxynaphtha-
line, p-xylidine, m-di-methyl amidophenol, m-di-ethyl-amido-phenol, 2-7 dioxy-
naphthaline mono ethyl ether, 2.7 naphthylendiamine o-oxy-chinoline or 2.8 amido-
naphthol be employed, colouring matters similar to those above described are
obtained.
By a modification of the procedure the same or similar colouring matters as the
above mentioned are obtained, if for this purpose the order of reactions be changed;
whilst according to the described method the amido-ammonium bases are first
obtained and from these the ammonium azo colouring matters, according to the
modified method, amido azo colouring matters are first obtained which are ultimately
changed into ammonium azo colouring matters; this method is illustrated by the
following examples.
1.) p-dimethylamido-benzol azo ẞ-naphthol, a bluish black powder, crystallisable
from toluol, insoluble in water, and which can be prepared by combining diazotised
dimethyl-p-phenylen-diamine with B-naphthol, is heated with methyl iodide at a
temperature of 90° to 100° C.; the previously dark blue mass is thus changed into
an orange yellow product, soluble in water, which is the iodide of the ammonium
azo colouring matter. The corresponding chloride is readily soluble in water.
2.) By combining the diazotised di-methyl-p-phenylen-diamine with resorcinol,
p-dimethyl amido benzol azo-resorcinol is produced, a black powder insoluble in
water; when dissolved in benzol and boiled with the corresponding quantity of
methyl iodide, it gives the iodide of the ammonium azo colouring-matters, which,
when crystallised from hot water, produces orange yellow crystals. The corre-
sponding chloride is readily soluble in water.
3.) p-di-ethylamido-benzol-azo 2-3 di-oxynaphthaline, a black blue brilliant
powder, insoluble in water, alkalies and acids and crystallisable from alcohol or
benzol, is produced from diazotised di-ethyl-p-phenylen-diamine with 2-3 dioxy-
naphthaline; on heating the compound with methyl iodide under pressure at a
temperature of about 100° C., the iodide of the ammonium azo colouring matter is
formed, which crystallises from water, forming brilliant violet brown crystals.
The chloride produced therefrom, gives a brown powder (soluble in hot water with
a brown colour, but insoluble in alcohol, the colouring matter dyes cotton mordanted
with tannin a fast yellow brown.
The new colouring matters are yellow, red yellow, brown red or brown powders,
which are soluble in water and which dye cotton mordanted with tannin, yellow,
red yellow or brown.

page_text: m-amido-yellow red pow-
phenyl
Trimethyl
ammonium
der soluble in
water with a
yellow brown yellow crystal- reddish brown
powder soluble
in water with
brown yellow
red yellow
colour; in
colour; in
m- amido -
concentrated concentrated
H₂SO, with
H₂SO,yellow-
carmine red
colour
brown
phenyl di-
methyl
ethyl am-
line powder,
soluble in water
with pure yel-
low colour; in
concentrated
H₂SO, with
yellow colour
powder, soluble
in water with
brownish yel-
low colour in
concentrated
H,SO, yellow-
brown
yellow brown
powder, soluble
in water with
brown colour;
in concentrated
H₂SO, yellow-
brown
red brown pow-
der soluble in
water with
brown colour;
in concentra-
Led H.SO.
violet
m-amido-powder of the
p-methyl- colour of red
phenyl-tri- lead, soluble in
methyl am- water with red
monium
yellow colour;
in concentrated
H₂SO violet
red
brown crystal- dark yellow brown powder brown crystal- brown powder,
line powder,
soluble in water
with brown
yellow colour;
in concentrated
H₂SO, yellow-
brown
powder soluble
in water with
pure yellow
colour: in
concentrated
H₂SO light
yellow
soluble in water
with brownish
yellow colour
in concentrated
H,SO, yellow
brown
line powder
soluble in water
with brown
yellow colour;
in concentrated
H₂SO, yellow
brown
soluble in
water with
brown colour
in concentra-
ted H,SO,
blue-violet
4'

page_text: yellow red pow-yellow brown yellow crystal- reddish brown yellow brown red-brown pow-
der, soluble in
water with red
yellow colour
in concentrated
H,SO, with
carmine-red
colour
powder, soluble
in water with
brown yellow
colour
in
concentrated
H₂SO, yellow
brown
line powder,
soluble in water
with pure yel-
low colour; in
concentrated
H₂SO with
light yellow
powder soluble
in water with
brownish yel-
low colour; in
concentrated
H₂SO, yellow
brown
powder soluble
in water with
brown colour
in concentrated
H₂SO, yellow
brown
der soluble in
water with
brown colour;
in concentrated
H,SO, yellow
brown

page_text: Having now particularly described and ascertained the nature of the said inven-
tion and in what manner the same is to be performed, I declare that what I
claim is :-
1. Process for the manufacture of aromatic amido ammonium bases such as are
herein referred to, in the form of their salts,
a) by reducing the corresponding nitro ammonium bases.
b) by alkylising and then decomposing the said mono-alkoyl, mono-alkyliden
or mono azo derivatives of a diamine.
2. Process for the manufacture of basic azo colouring matters such as are herein
referred to,
a) by diazotising aromatic amido ammonium bases and combining them with
phenols, amines, or their derivatives.
b) by transforming amido azo colouring matters such as are herein referred to,
into ammonium azo colouring matters; by the action of alkylhalsgenide.
3. The amido ammonium bases obtained as set forth in the first claim, in the
form of their salts.
4. The azo colouring matters obtained as set forth in the second claim.
Dated this 29th day of April 1896.
ABEL & IMRAY,
Agents for the Applicant.