IMPROVEMENTS IN THE MANUFACTURE OF DYES OR COLOURING STUFFS
Year: 1884

page_text: PROVISIONAL
DIECITICATION
I, EMIL CAPITAINE of 89 Chancery Lane, in the County of Middlesex, Engineer
do hereby declare the nature of the said invention for "IMPROVEMENTS IN THE
MANUFACTURE OF DYES OR COLOURING STUFFS" a communication from Adolf
Ewer and Paul Pick of Klosterstrasse, Berlin, in the German Empire to be as
follows:-
These improvements relate to the production of dyes or colouring stuffs which
vary in colour from yellow to brown yellow, by the action of cyanic acid and its
derivatives, on primary, secondary, and tertiary aromatic amines, or on tetra-
alkylised (tetra-alkylirt) diamido-benzophenone.
Cyanic acid or better still, its derivatives of the urea series, like urea itself, yield
dyes varying in colour from yellow to brown yellow by being heated with the salt
of a primary, secondary, or tertiary aromatic amine or with a tetra-alkylised
diamido-benzophenone,, with or without the application of means of condensation.
1. As derivatives of cyanic acid, are to be considered the ethers of the same, and
the products of condensation of cyanic acid and its ethers, as for example ;-
cyanuric acid, cyanuric ethyl ether, etcetera, urea, the ether of the same, the
phenylised (phenylirt), toluidinised, xylitised (xylylirt) cumolised (cumylirt) and
naphtalised derivatives of urea, carbamic acid and its ethers, urethanes, and its
ethers as also the sulpho-cyanic acid derivatives.
2. Tertiary amines which are of consideration for the production of dyes, are
di-methylaniline, ethylmethylaniline, di-ethylaniline, methyl-amylaniline, ethyl-
amylaniline, and di-amylaniline.
Secondary amines are methylaniline, ethyl aniline, amylaniline, methylortho-
toluidine, ethylorthotoluidine, and amyl-orthotoluidine.
Primary amines of importance are aniline and orthotoluidine.
3. As derivatives of diamidobenzophenone may be considered tetra-inethyle, di-
methyle-diethyle, tetra-ethyle, di-methyldiamyle, di-ethyldiamyle, and the tetra-
anyldiamidobenzo-phenone.
4. Instead of an aromatic amine, or tetra-alkylised diamidobenzophenone, a
mixture of both may be employed in the proportion of two of the former to one of
the latter.

page_text: 5. As a means of condensation use may be made of chloride of zinc, chloride of
magnesium, chloride of calcium, chloride of aluminium, pyrosulphate of potassium,
in this latter case as also for the following media of condensation, viz, pyro-
phosphoric salts, phosphoric chloride, phosphoric oxychloride, chloride of silicium,
fluoride of silicium, chloride of boron and fluoride of boron, the free bases are
employed instead of the salts.
With reference to the colouring properties of the several dyes or colouring stuffs,
it is to be remarked that:-
-
The dyes derived from tertiary amines or from tetra-alkylised benzophenones
may be applied direct.
The dyes derived from primary or secondary amines do not dye so well, yet by
introducing alkylic groups (alkylgruppen) excellent dyes are obtained.
Pure yellow is dyed by the dyes derived from a cyanic acid derivative of
the fat series and from a tertiary aromatic amine or a tetra-alkylised diamido-
benzophenone.
Gold yellow is dyed by the dyes from an orthotoluidinised metaxylised
(metaxylylirt) or cumolised carbamic acid or urea derivative, and a tertiary
aromatic amine or tetra-alkylised diamidobenzophenone. The word metaxylised
or metaxylolised signifies what contains the metaxylol residuum C, H,. The word
cumolised signifies what contains the Cumol residuum Cumol being C, H₁ and
Cumol residuum C, H₁.
Orange red is dyed from a phenylised (phenylirt) or paratoluidinised carbamic
acid or urea derivative and a tertiary aromatic amine or tetra-alkylised diamido-
benz phenone.
Brown yellow is dyed by the dyes from an a. or ẞ. naphtalised carbamic acid or
urea derivative, and a tertiary aromatic amine or a tetra-alkylised diamidobenzo-
phenone.
The following examples illustrate the technical application of the process.
1st example. 20 kilogrammes of di-methylaniline are saturated with dry muriatic
acid gas. To this composition is added 20 kilogrammes of chloride of zinc and
5 kilogrammes of urea. This is then heated gradually up to between 220 and
230 degrees Celsius and maintained at this temperature for about six hours. The
liquid composition is of a deep yellow colour and upon cooling becomes a pellucid
brown yellow substance, which is pulverised and the free chloride of zinc extracted
with cold water. Then the residue is treated with boiling water and filtered, the
filtered product being precipitated with kitchen salt. The precipitated dye or
colouring stuff is purified by subjection to repeated solution and precipitation or
by repeated crystallisation by means of hot water. The resulting product is a
yellow crystal powder. The watery solution of the dye is of a pure yellow colour
like a picric acid solution and dyes wool, silk and tanned cotton a greenish yellow..
2nd example. 25 kilogrammes of bi-muriatic tetra-methyldiamidobenzophenone
are heated with 20 kilogrammes of chloride of zinc, and 4.5 kilogrammes of urea
during about ten hours at a temperature of between 190 and 200 degrees Celsius.
The composition is subjected to the same treatment as that given in the 1st example
and a yellow similar to that described in the first example is obtained.
3rd example. 10 kilogrammes of tetra-methyldiamidobenzophenone, 11, kilo-
grammes of muriatic di-methyl aniline, 8 kilogrammes of di-phenylic urea, and
20 kilogrammes of chloride of zinę are heated during 10 hours at a temperature of
about 200 degrees Celsius. The resulting dye is purified in a known manner, and
gives a brilliant red orange colour.

page_text: COMPLETE SPECIFICATION.
I, EMIL CAPITAINE of 89 Chancery Lane, in the county of Middlesex, Civil
Engineer, do hereby declare the nature of this invention for "IMPROVEMENTS IN
THE MANUFACTURE OF DYES OR COLOURING STUFFS," and in what manner the
same is to be performed, as communicated to me from abroad by Ewer and
Pick, of Berlin, Prussia, to be particularly described and ascertained in and by the
following statement:-
:-
-
This invention relates to the production of dyes or colouring matters varying
from yellow to brown-yellow, and it consists in treating aromatic amines or their
salts, or certain other derivatives thereof with cyanic acid or its derivatives, and
with condensing-mediums.
When a primary, secondary or tertiary amine, or a salt of one of the said amines,
or a tetra-alkylated diamido-benzo-phenone, is melted together with cyanic acid in
the presence of a condensing-medium, as for instance anhydrous chloride of zinc, a
more or less beautiful, valuable yellow or brown-yellow colouring matter of great
dyeing power is formed in the molten mass.
A like effect is produced by the following derivatives of cyanic id: The ethers
of the said acid, the products of condensation of the same and their ethers, such as
cyanuric acid, cyanuric ethyl-ether and others, moreover, the derivatives of the
urea series including urea itself and its ether, the substitution-products of urea
of the aromatic series, viz. the phenylated, toluylated, xylylated, cumylated and
naphtylated derivatives of urea and their ethers, carbamic acid and its ethers,
urethanes, biuret, allophanic acid and its ethers, and isocyanic acid. Likewise the
sulpho-derivatives of cyanic, isocyanic and cyanuric acids, and consequently also
the sulpho-compounds of urea and of the said derivatives of the same may be
employed.
Of the aromatic amines the following are of importance for the process:
The primary amines: Aniline and ortho-toluidine.
The secondary amines: Methyl-aniline, ethyl-aniline, amyl-aniline, methyl-
orthotoluidine, ethyl-orthotoluidine and amyl-orthotoluidine.
The tertiary amines: Dimethyl-aniline, ethyl-methyl-aniline, diethyl-aniline,
methyl-amyl-aniline, ethyl-amyl-aniline and dyamyl-aniline.
In addition to these, such derivatives of tertiary aromatic amines may be used,
which consist of two molecules of one of the said amines united by one molecule of
carbonyl (CO) replacing a portion of the hydrogen of the former, and which are
called tetraalkylated diamido-benzo-phenones. The most efficient substances of
this class are: Tetramethyl,-dimethyl-diethyl,- tetraethyl,- dimethyl-diamyl-, diethyl-
diamyl-, and tetraamyl-diamido-benzo-phenone.
The condensing-mediums to be made use of, are: Firstly, in case the amines or
their derivatives are used in basic state, pyrosulphate of potassiuin, meta-and
pyrophosphates, protochloride, perchloride and oxychloride of phosphorus, and the
chlorides and fluorides of silicium, and boron; secondly, when salts of the amines
or their derivatives are' employed, the chlorides of zinc, of magnesium, of calcium
and of aluminium.

page_text: In respect to the sulpho-derivatives of cyanic-acid and urea, it is to be observed
that these act substantially in like manner, as the oxygenated compounds; but
with such of the said sulpho-derivatives as belong to the fatty series, the process
proceeds less favourably than with those belonging to the aromatic series. But,
when to the said sulpho-derivatives of the fatty-series metallic oxides are added, as
for instance oxide of lead or of zinc, the process again comes off in the same manner
as with the oxygenated derivatives.
As regards the particular colour of the dyes to be obtained according to the
invention, I shall mention the following, resulting from tertiary aromatic amines
and from tetraalkylated diamido-benzo-phenones:
Pure yellow, by treatment of one of the said substances with cyanic acid or a
derivative thereof belonging to the fatty series.
Golden yellow, by treatment with orthotoluilated; metaxylated or cumylated
derivatives of carbamic acid or urea.
Orange-red, by means of phenylated or paratoluilated carbamic acid or urea..
: Brown-yellow, by the employment of a-naphtylated or 6-naphtylated carbamic
acid or urea.
"
The mode of carrying out the process I shall explain by some examples:
1,20 kilograms of dimethyl-aniline are saturated with dry hydrochloric gas. To
the mass heated to. 130° Centigrade at first 20 kgr: of dry and finely powdered
chloride of zinc, and subsequently 5 kgr of urea, also dry and well powdered, are
added by constant stirring. The temperature is thereupon slowly increased to 180°
or 200° C. and maintained at this point for about six hours. Upon becoming cold
the molten mass solidifies and then forms a pelluoid brown-yellow substance.
From this substance, after having been pulverized, the free chloride of zinc is
first extracted by cold water. The residue is thereupon treated with boiling water,
the liquid portion filtered off, and the dye or colouring matter precipitated out
therefrom by common salt. The resulting product is purified by repeated dissolution
in hot water and precipitation or crystallization. A crystalline powder is thus
obtained, the aqueous solution of which is of pure yellow colour alike to that of a
solution of picric acid, and dyes wool, silk, and cotton yellow with a greenish hue.
A similar pigment may be produced in analogous manner from ethyl-aniline.
2., 25 kilograms of bihydrochlorate of tetramethyl-diamido-benzo-phenone
together with 20 kgr. of chloride of zine and 4.5 kgr. of urea are heated and kept
for about 10 hours at a temperature of 190 to 200° Centigr. From the mass
treated in like manner as stated in the first example, a pigment of similar colour is
obtained.
3., 10 kgr of tetramethyl-diamido-benzo-phenone, 11.5 kgr of hydrochlorate of
dimethyl-aniline, 8 kgr :,of diphenyl-urea and 20 kgr. of chloride of zinc are heated
during 10 hours at a temperature of about 200° Centigr. The pigment extracted
in the usual manner imparts to the materials dyed therewith, an ardent orange
colour inclining to red.
4., 10 kgr. of the hydrochlorate of ethyl-aniline, 4.2 kgr of carbanil-amide and
10 kgr of chloride of zinc are heated during 6 hours to 180° or 200° Centigrade.
The pigment separated out and purified as stated, dyes reddish orange.
The pigments resulting from primary or secondary amines are in themselves
inferior to those obtained from tertiary amines, or from tetra-alkylated diamido-
benzo-phenones; but the derivatives of the same produced by the introduction of
substances of the methyl, ethyl, phenyl and other analogous groups are of like value
for dyeing purposes.
The aforesaid proportions in which the different substances are to be mixed, may
be considerably varied; but preferably the proportion of the amine or its derivative,
or the salt thereof to the cyanic acid or its substitute entering into the process,
should be such that the pigment will constitute a neutral salt.
When strong inorganic acids are caused to act on pigments produced as described,
these pigments will be decomposed into ammonia or a primary aromatic amine
and an alkylated or non-alkylated diamido-benzo-phenone. Thus, when a tertiary.

page_text: aromatic amine enters into the process, the diamido-benzo-phenone split off under
the said condition, will be tetra-alkylated. The pigments of this class I do not
claim as an article of manufacture, inasmuch as they have heretofore already been
produced according to a method differing from mine. In case equal molecular parts
of a tertiary and a secondary amine are employed, the diamido-benzo-phenone
separated out by the acid will be trial kylated; if a secondary aromatic amine alone
is used, it will be dial kylated; if the pigments are obtained from equal chemical
parts of a secondary and a primary amines, the diamido-benzo-phenone splitting
off will be mono alkylated, and, finally, if a primary aromatic amine alone is made
us of, a non-alkylated diamido-benzo-phenone will result from the treatment by the
acid. The pigments characterized by any of the latter four reactions I do claim as
a new article of manufacture.
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
1. The process of producing yellow to brown-yellow dyes or colouring matters
by melting, together aromatic amines or their derivatives, with cyanic acid or its
derivatives, and with condensing-mediums, all substantially as and for the purpose
herein before specified.
2. As an article of manufacture yellow to brown-yellow dyes or colouring matters
produced by melting together certain aromatic amines or their derivatives, as
specified, with cyanic acid or its derivatives and with condensing mediums, and
which are decomposed by strong mineral acids into ammonia or a primary aromatic
amine and a diamido-benzo-phenone containing three or a less number of molecules
of alkyl, substantially as and for the purpose herein before set forth.
Dated this trant" sighth day of March 1005