Improvements in the Manufacture of Azo Colouring Matters and of Materials for the same.
Year: 1892

page_text: Date of Application, 26th Aug., 1892
Complete Specification Left, 15th June, 1893-Accepted, 5th Aug., 1893
PROVISIONAL
SPECIFICATION.
Improvements in the Manufacture of Azo Colouring Matters and of
Materials for the same.
READ HOLLIDAY AND SONS LIMITED of Upperhead Row, Huddersfield in the
County of York, Manufacturing Chemists and KARL BERNHARD ELBEL Ph. D.,
of the same place Chemist do hereby declare the nature of this invention to be as
follows:-
The invention relates to the manufacture of azo colouring matters and of
materials for the same. The new materials are a series of condensed bodies made
from two molecules of an, aromatic amine or two different aromatic amines by
combining them with one molecule of methylal or other dioxymethylenether or of
a fatty aldehyde.
In the case of employing methylal the amines are heated with this body in the
presence of hydrochloric acid, or of another condensing agent, to temperatures
between 100° and 150° centigrade in an autoclave or suitable closed vessel for
several hours. In some cases it is necessary to employ an excess of the aromatic
amine. For instance if two cases have to be combined of which one reacts more
readily with methylal than the other an excess of the slower acting body has to be
employed, which often acts at the same time as a solvent for the other case; for.
instance orthotoluidine and a naphthylamine. In other cases the molecular
quantities are employed in the presence of alcohol or another solvent.
The fatty aldehydes as a rule form with primary aromatic amines at lower
temperatures in the absence of condensing agents intermediate compounds not
stable, which are transformed into stable methan, ethan, and other compounds by
heating them with an excess of the same or another aromatic amine in the presence
of hydrochloric acid or other condensing agents. The same bodies are formed by
heating the bases or mixtures of bases with a fatty aldehyde, and hydrochloric acid.
In some cases alcohol or another solvent has to be employed.
The fatty aldehydes employed are formaldehyde (the fact of the use of which
for the manufacture of the bodies mentioned in the Specification of Letters Patent
No. 20678 of 1889 granted to one Oliver Imray having been therein published is
known to us and we make no claim to such use, although these bodies can be made
with methylal) acetaldehyde and acrolein.
The new bodies made by the above mentioned methods form sulpho acids when
treated in the usual manners employed for the manufacture of sulphonated
compounds.
The new diamido bodies containing free amido groups, or their sulpho acids can
be diazotised and combined with aromatic amines or phenols and their sulpho,
carbo, or sulphocarbo, acids.
Valuable colours are formed if the new condensed bodies, or their sulpho acids
Combinations containing free not alkylized amido groups form valuable colours
of different shades when diazotised again and combined either on textile fibre or in
solution or suspension with aromatic amines, phenols and their sulpho, carbo, or
sulphocarbo acids.
Combinations with nitrodiazo compounds, for instance, paranitrodiazobenzol, are
reduced diazotised and combined with amines, or phenols and the like.

page_text: 2. COMBINATIONS WITH TETRAZO BODIES.
By tetrazo bodies we mean to include
Tetrazodiphenyl and its homologues
Tetrazodioxydiphenyl and its ethers
Tetrazooxydiphenyl and its ethers and homologues
Tetrazobenzol and its homologues
Tetrazonaphthalene
Tetrazofluorene
Tetrazostilbene
Tetrazoazobenzol and its homologues
1.etrazoazoxybenzol and its homologues
Tetrazobenzolazouapthalene as well as the sulpho and carbo acids of the above
mentioned.
These tetrazo bodies can be combined either with one, or two molecules of the
new diamido bases or their sulpho acids.
The combinations of one molecule of the tetrazo body and one molecule of one
of the new bodies form two series of colours. They are either combined with one
molecule of an aromatic amine or a phenol, or the like, or they are diazotised again
and combined afterwards.
The combinations with two molecules of the new bodies, or one molecule and one
molecule of another amine form colours of various shades if they are diazotised
again either on the fibre or in solution, or suspension and combined with amines,
phenol, their sulpho, carbo and sulpho carbo acids.
In all the above mentioned cases we mean to include by the expression phenols
aromatic monoxy, as well as, dioxy and amidooxy bodies.
Dated this 26th day of August 1892.
Tetrazo oxybenzol and its homologues
Tetrazobenzolazouapthalene as well as the sulpho and carbo acids of the above
mentioned.
These tetrazo bodies can be combined either with one, or two molecules of the
new diamido bases or their sulpho acids.
The combinations of one molecule of the tetrazo body and one molecule of one
of the new bodies form two series of colours. They are either combined with one
molecule of an aromatic amine or a phenol, or the like, or they are diazotised again
and combined afterwards.
The combinations with two molecules of the new bodies, or one molecule and one
molecule of another amine form colours of various shades if they are diazotised
again either on the fibre or in solution, or suspension and combined with amines,
phenol, their sulpho, carbo and sulpho carbo acids.
In all the above mentioned cases we mean to include by the expression phenols
aromatic monoxy, as well as, dioxy and amidooxy bodies.
Dated this 26th day of August 1892.
WM. BROOKES & SON,
Agents.
COMPLETE SPECIFICATION.
Improvements in the Manufacture of Azo Colouring Matters and of
Materials for the same.
We READ HOLLIDAY & SONS LIMITED of Upperhead Row, Huddersfield, in
the County of York, Manufacturing Chemists, and KARL BERNHARD ELBEL Ph.D.
of the same place, Chemist, 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:-
The invention relates to the manufacture of azo colouring matters and of materials
for the same.
The new materials are a series of condensed bodies made from two
molecules of an aromatic-amine or two different aromatic-amines by combining them
with one molecule of methylal or another dioxymethylenether or of a fatty
aldehyde.
In the case of employing methylal the amines are heated with this body in the
presence of hydrochloric acid or of another condensing agent to temperatures
between 100° and 150° centigrade in an autoclave or suitable closed vessel for
several hours.
In some cases it is necessary to employ an excess of the aromatic-amine. For
instance if two bases have to be combined of which one reacts more readily with
methylal than the other an excess of the slower acting body has to be employed,
which often acts at the same time as a solvent for the other base; for instance
orthotoluidine and alpha naphtylamine. In other cases the molecular quantities
are employed in the presence of alcohol or another solvent.
The fatty aldehydes as a rule form with primary aromatic-amines at lower

page_text: emperatures in the absence of condensing agents intermediate compounds not stable
which are transformed into stable methan, ethan and other compounds by heating
them with an excess of the same, or another aromatic-amine in the presence of
hydrochloric-acid, or other condensing agents.
The same bodies are formed by heating the bases, or mixtures of bases with
a fatty aldehyde and hydrochloric acid. In some cases alcohol, or another solvent
has to be employed.
The fatty aldehydes employed are formaldehyde (the fact of the use of which
for the manufacture of the bodies mentioned in the Specification of Letters
Patent No. 20678 of 1889 granted to one Oliver Imray having been therein
published is known to us and we make no claim to such use, although these bodies
can be made with methylal) acetaldehyde and acrolein.
Suitable amines for the above described condensation process are for instance ;
aniline, monomethylaniline, dimethylaniline, diethylaniline, ortho toluidine,
xylidine, alpha napthylamine, benzidine its homologues and methoxy and ethoxy
compounds.
Example 1. 50 lbs. of alpha napthylamine are heated with 15 gallons of water
in an enamelled pan provided with agitator and condensor.
When the alpha napthylamine is melted the temperature being about 50° centi-
grade, 30 lbs. of formaldehyde solution 40% are added and the whole mass agitated
and cooled till the intermediate compound begins to get solid.
The water containing the small excess of formaldehyde is then drawn off and
300 lbs. of dimethylaniline are added instead. When the napthylamine compound
is dissolved in the dimethylaniline gallon of hydrochloric acid 20 Bé. is added
and the temperature is raised to about 100° for 2 to 3 hours. The melt is now
made alkaline with caustic soda and the dimethylaniline is driven off by steam.
When the contents of the pan are cooled the new compound has separated as a
solid cake which is purified by dissolving it in dilute sulphuric acid and precipitating
it from the solution by an alkali.
Example 2. 50 lbs. of alpha napthylamine are dissolved in 120 lbs. of methylated
spirits and 12 lbs. of methylal. gallon of hydrochloric acid 20 Bé is then added,
and the mixture is heated in an autoclave to 130° for 2 to 3 hours. The alcohol is
now distilled off. The resulting body does not readily dissolve in dilute acids and
has to be sulphonated to be of use for the manufacture of azo colours.
The new bodies made by the above mentioned methods form sulpho-acids when
treated in the usual manners employed for the manufacture of sulphonated
compounds.
Example. Sulphonation of the body made by condensing one molecule of ortho
toluidine, one molecule of alpha napthylamine and one molecule of formaldehyde
or methylal; 50 lbs. of the new body are dissolved in 100 lbs. of sulphuric acid
66° Bé. then 100 lbs. of fuming acid containing 25 % SO, are added. The melt is
heated to water bath temperature till a sample is soluble in warm dilute ammonia.
It is then run into cold water. The new sulpho compound, a diamido-ortho-tolyl-
alpha-napthylmethandisulpho acid separates from the acid liquor is filtered and
washed.
The new diamido bodies containing free amido groups, or their sulpho acids can
be diazotised and combined with aromatic-amines, or phenols and their sulpho,
carbo, or sulphocarbo acids.
-
Example. 120 lbs. of dimethyldiamidophenylorthotolylmethan m.p. 91° — 9 2º
the body formed by the action of formaldehyde orthotoluidine on dimethylaniline,
are dissolved in 240 gallons of water and 200 lbs. of hydrochloric acid 20° Bé. and
diazotized with 35 lbs. of nitrate.
The diazo solution is then run into a cold solution of 180 lbs. of R. salt in
240 gallons of water and 100 lbs. of ammonia. The colour formed in this manner
5 dyes a scarlet on wool from a neutral or acid bath.
Valuable colours are formed if the new condensed bodies, or their sulpho acids
act on diazo, or tetrazo bodies.

page_text: 1. COMBINATIONS WITH DIAZO BODIES.
Combinations containing free not alkylised amido groups form valuable colours of
different shades when diazotized again and combined either on textile fibre or in
solution, or suspension with aromatic-amines, phenols and their sulpho, carbo, or
sulpho carbo acids.
Example. 35 lbs. of alpha napthylaminedisulphonate of sodium 1. 3. 6 dissolved
in 100 gallons of water are diazotized with 20 lbs. of hydrochloric acid and
7 lbs. of nitrite. This diazo liquor is run into a cold solution of 28 lbs. of
dimethyldiamidophenyl-alpha-naphyl-methan in 25 lbs. of hydrochloric acid and
100 gallons of water. After 24 hours the combination is complete and the
formed amidoazo body is diazotized again. For this purpose 7 lbs. of nitrite in
aqueous solution are added and the mixture is stirred for several hours it is then
run into a solution of 40 lbs. of R. salt and 30 lbs. of soda ash in 100 gallons
of water. The colour produced dyes wool a bluish black from an acid bath.
If the amido azo body formed by the combination of 35 lbs. of alpha napthyl-
aminedisulphonate of sodium 1.3 6. and 14 lbs. of alpha napthylamine is diazotized
again and put into reaction with 28 lbs. of dimethyldiamidophenyl-alpha-naphtyl-
methan dissolved in 50 gallons of water and 25 lbs. of hydrochloric acid, a colour
is formed which dyes a black on wool from a neutral salt bath. Combinations
with nitrodiazo compounds, for instance paranitrodia zobenzol, are reduced diazotized
and combined with amines, or phenols and the like.
Example. 100 gallons of diazoparanitrobenzol solution made from 42 lbs. of
para nitraniline, 75 lbs. of hydrochloric acid and 21 lbs. of nitrite are run into a
solution of 150 lbs. of diamido-ortho-tolyl-alpha naphtylmethandisulphonate of
sodium and 40 lbs. of soda ash in 200 gallons of water. After stirring for several hours
the mixture is warmed up to about 80° and a warm saturated solution of 220 lbs. of
crystallised sodiumsulphite is added. The liquor is then boiled up and filtered.
The colour is precipitated dissolved again in 300 gallons of water and diazotized
with 40 lbs. of nitrite and 140 lbs. of hydrochloric acid. After stirring for about an
hour the diazo liquor is run into cold solution of 280 lbs. of the alpha napthol-
disulphonate of sodium of the Specification of Letters Patent granted to Read
Holliday & Sons, Thomas Holliday and Paul Robert Emmanuel Seidler, No. 5103
of 1891 in 600 gallons of water and 70 lbs. of ammonia.
This mixture is agitated for three days. The colour is precipitated with common
salt.
It dvos a blue on unmandanted

page_text: They are either combined with one molecule of an aromatic-amine, or a phenol,
or the like, or they are diazotized again and combined afterwards.
The combinations with two molecules of the new bodies, or one molecule and one
molecule of another amine form colours of various shades if they are diazotized
again either on the fibre, or in solution, or suspension and combined with amines,
phenols, their sulpho, carbo and sulphocarbo acids.
Example 1. 37 lbs. of diamidostilbenedisulpho acid suspended in 50 gallons of
water are diazotized with 14 lbs. of nitrite and 40 lbs. of hydrochloric acid. The
tetrazo body is then entered into a cooled solution of 14 lbs. alpha napthylamine
in 50 gallons of water and 12 lbs. of hydrochloric acid. This mixture is stirred for
an hour, when 26 lbs. of diamido-ortho-tolyl-alpha-napthylmethan in 50 gallons
of water and 25 lbs. of hydrochloric acid are added. The formation of the colour
is complete after 12 hours stirring. It is then filtered off the acid liquor dissolved
in a hot solution of 12 lbs. of soda ash in 50 gallons of water and precipitated with
salt. The new colour dyes unmordanted cotton a deep purple shade from an
alkaline salt bath. It can be diazotized on the fibre and gives a fast dark violet
shade when combined for instance with metaphenylenediamine.
Example 2. The tetrazo solution made from 21 lbs. of tolidine is run into a
solution of 28 lbs. of dimethyldiamido-phenyl-alpha-napthylmemethan in 50 gallons
of water and 25 lbs. of hydrochloric acid. The formation of the intermediate body
is complete after 3 hours stirring.
It is then partly in solution and is easily diazotized by adding an aqueous
solution of 7 lbs. of nitrite. The liquor the colour of which is changed by the
action of the nitrite from violet to brown, is now run into a solution of 90 lbs. of
amido-oxyalphanaphtalenedisulphonate of sodium and 50 lbs. of soda ash in
100 gallons of water. The colour produced in this manner dyes unmordanted
cotton a fast greenish blue. When diazotized on the fibre and combined for
instance with metatoluylenediamine it changes into a bluish black.
In all the above mentioned cases we mean to include by the expression phenols
aromatic monoxy, as well as, dioxy and amidooxy bodies.
Having now particularly described and ascertained the nature of our said inven-
tion and in what inanner the same is to be performed, we declare that what we
claim is
1. The herein described process of making materials for the manufacture of
colouring matters from two molecules of an aromatic amine, or one of each of two
different aromatic amines by combining them with one molecule of methylal,
formaldehyde (excepting the cases hereinbefore mentioned) acetaldehyde and
acrolein.
2. The new diamido bodies made as described in the preceding claim.
3. The manufacture of sulpho acids of the new diamido bodies.
4. The manufacture of azo colouring matters from the new diamido bodies, or
their sulpho acids.
A. By combining the diazo compounds of the new diamido bodies, or of their
sulpho acids with amines, phenols, their sulpho, carbo and carbosulpho acids.
B. By combining the diamido bodies, or their sulpho acids with diazo
compounds.
C. By combining the new diamido bodies, or their sulpho acids with tetrazo
compounds as herein described.
5. The new azo colouring matters made as set forth in the preceding claim.
Dated the 5th day of June 1902.
WM. BROOKES & SON,
55 & 56, Chancery Lane, London, Agents for the Applicants.