Year: 1887

page_text: Date of Application, 3rd Feb., 1887
Complete Left, 2nd Nov., 1887
Complete Accepted, 6th Dec., 1887
CH, N (CH), CON (C. H),.
The substituted benzamides are readily converted into halogen-compounds by the
action of halogen-phosphorus compounds, phosgen or thiophosgen. Thus, for
example, the body obtained from dimethylamidobenzodiphenylamine has probably the
11
C, H, N (C H,), C Cl, N (C, H,),.
"
The compounds obtained in this way can be " condensed again with tertiary
aromatic amines. This reaction finds its expression probably in the following
equation:

page_text: The latter compounds undergo by the action of water and ammonia transformations
rendering them suitable for being applied to the preparation of alkylised diamido-
ketones and of colouring matters of the class of the auramines. In the example
mentioned above the condensation product which may be termed the tetramethyl-
diamidobenzophenone-diphenylamine-chloride is thus decomposed.
1. If heated with water it is converted into the tetramethyldiamidobenzophenone
forming again diphenylamine.
2. If heated with ammonia, while it also forms again diphenylamine, it is converted
into the yellow colouring matter, known as “auramine.”
The raw materials employed in this process are all the chlorides of acid radicals
that are obtained from tertiary aromatic amines by the action of chloro-carbonic
oxide. The base necessary to the formation of the substituted benzamide, (which
however is not represented in the composition of the final product) may be any of the
known secondary aromatic bases.
For the conversion of the substituted benzamides into the corresponding halogen
compounds, the chloro-bromo-iodo-oxyhalogen-compounds of phosphorus or phosgen
or thiophosgen may be employed; the conversion will take place in the presence or
absence of indifferent solvents. The chlorocompounds with transmitted light shew
yellow to red tints; they have a somewhat metallic lustre; they are but sparingly
soluble in water, more easily in alcohol (giving yellow to red colours), but these
solutions become soon decomposed especially under the influence of heat, forming
again the benzo body.
The condensation of the chlorides by the action of tertiary bases proceeds smoothly,
generally at the temperature of the water bath, in presence or absence of condensation
agents, such as chlorzine. The condensation is best proceeded with directly on the
melting of the chloride.
In external appearance the bodies thus obtained are like the chlorides mentioned
above; they have the lustre of steel or bronze, and are soluble giving a deeper tint
(yellow to bluish red) with difficulty in water, more easily in alcohol. They are
more stable than the former, their solutions not decomposing unless when they are
boiled.
The decomposition is hastened by the presence of free nonorganic acid. They have
the characteristics of basic coloring matters, as they can be fixed on silk and mor-
daunted cotton, shewing colors more or less solid. Many variations may be made in
the gradual formation of the bodies in question, by employing in the preparation of
the chloride of the acid radical and in its condensation either one or different tertiary
bases. Thus there can be produced by this process not only symmetrical ketones but
also mixed ketones and their corresponding auramines.
The following are processes for producing the substances above referred to
Into 20 parts of dimethylaniline are introduced, while cooling
4 parts of phosgen, and afterwards there are added
6 parts of diphenylamine.
The commencement of the reaction is shewn by gentle heating and it is completed
hy half an hour's heating on a water bath. The mass, which at first liquefies, becomes
afterwards thick and pasty; it is carefully mixed with 15 parts of hydrochloric acid,
diluted by 200 parts of water and then a weak soda lye is added to the liquid until
it shews slight acid reaction. It is then filtered, the motherlye is converted into
dimethylaniline and the filtrate, after repeated washing, is dried, being dimethyl-
amidobenzodiphenylamine in the form of white crystalline powder. It has slightly
basic qualities, is soluble in sparingly diluted hydrochloric acid from which solution
on being more diluted it is partly precipitated; it is readily dissolved in benzol, with
difficulty in alcohol; and crystallises from the solution in white needles fusible at
178° C.
For preparing the chloride and for its condensation with dimethylaniline, 10 parts
of dimethylamidobenzodiphenylamine with 5 parts of phosphoroxychlorid are care
fully heated on the water-bath until the mixture is uniformly melted and shews

page_text: metallic lustre, the formation of the chloride being then completed. To this are
added 10 parts of dimethylaniline.
There is at first some spontaneous heating, after which the mass is heated on the
water-bath for about two hours.
The metallic lustre which at first disappears, reappears to a certain extent as the
condensation proceeds.
The tetramethyldiamidobenzophenone-diphenylamine-chloride is soluble in water
and alcohol giving a blueish red tint from the aqueous solution it is precipitated by
common salt shewing metallic lustre. After standing for a longer time and also
when the solutions are heated the coloring disappears gradually; it dyes mordaunted
cotton reddish violet.
In order to convert the condensation product into tetramethyldiamidobenzophenone
the fused mass shewing metallic lustre as above described, is digested with about five
times its volume of water with addition of some non-organic acid at a temperature of
50° to 70° C. until there is complete dissolution of the mass. This is then diluted
with about 20 parts of water; the excess of dimethylaniline, if there is any, is care-
fully neutralized by hydrochloric acid and the whole is filtered ; the "Ketone"
remains on the filter in admixture with diphenylamine. From the latter it is separated
by washing with alcohol and extraction with hydrochloric acid. After recrystallisation
it has a melting point of 173-174° C.
For the production of auramine the melted mass above described is digested with
50 parts of aqueous solution of ammonia at about 20 per cent., care being taken that
by the heat proceeding from the reaction the liquid is not caused to boil, and that
there be an excess of ammonia as long as portions of the melted mass remain
unattached. When the whole mass is dissolved, it is kept under agitation for a few
hours at a temperature of 50-60° C. The coloring matter separates, in admixture
with diphenylamine in crystalline form. The liquid is after complete evaporation of
the ammonia, carefully neutralised with hydrochloric acid, in order to dissolve the
excess of dimethylamine, then filtered, and the residue is extracted by warm water.
The auramine is precipitated from the aqueous solutions by the addition of common
salt, and the diphenylamine can be recovered from the undissolved portion.
Dated this 3rd day of February 1887
ABEL & IMRAY,
Agents for the Applicant.

page_text: Improvements in the Production of Alkylised Diamidobenzophenon-
aminechlorides and Conversion of the same into Alkylised
Diamidobenzophenones and Yellow Colouring Matters of the
Class of the "Auramines."
1, OLIVER IMRAY of No. 28 Southampton Buildings, Chancery Lane in the County
of Middlesex, Fellow of the Institute of Patent Agents 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 present invention relates to the production of mono- and di-substituted amides
of the dialkylised, amidobenzoic acids, of the halogen compounds of these amides,
further of the condensation products of these halogen compounds with tertiary bases,
and finally the production of the tetra-alkylised diamidobenzophenones from the
condensation products derived from the mono and disubstituted amides and the
production of tetra-alkylised diamido-benzophenoneamines from the condensation
products derived from the disubstituted amides.
In carrying out the invention 1 proceed as follows: The halogen-derivatives of the
said amides are condensed with tertiary bases and the condensation products thus
obtained are treated with water containing an acid or an alkali if benzophenones are
used and with ammonia either in watery or in alcoholic solution if benzophenone
amines are used.
The tetraalkylized diamidobenzophenones may also be obtained fron the conden-
sation products of the halogen compounds of mono-substituted di-alkyl-amido-
benzoic amides with tertiary bases by treating the same with acids and acidulated
water.
The mono- and disubstituted dialkyl-amido-benzoic-amides employed in the process
are obtained by the action of primary and secondary bases upon the chlorides of the
dialkyl-amido-benzoic acids, and the chlorides themselves by treating tertiary amines
with oxychloride of carbon (phosgene).
The halogen compounds of the substituted amides are produced by treating the
same with chloride of phosphorus or oxychloride of phosphorus, or, equally well,
with oxychloride of carbon. The action of these agents on the (so-called) carbonyle-
group of the amides in the cold is but slow and not very intense, but at higher
temperatures it will proceed more quickly. In practice it will be found advantageous
to proceed with the halogenisation and the subsequent condensation in one operation
by adding, for example oxychloride of phosphorus to a mixture of the amide
with a tertiary base and heating with the necessary precaution upon a waterbath.

page_text: FIRST EXAMPLE.
Into 20 parts by weight of dimethylaniline are introduced, while cooling:
4 parts by weight of phosgene and afterwards are added 6 parts by weight of
diphenylamine; the mass is now heated for to hour to 90 degrees centigrade,
when it will first liquify and afterwards becomes viscous.
It is now mixed with about 15 parts by weight of hydrochloric acid and about.
200 parts by weight of water, neutralized with a weak sodium lye until a smell of
di-methylaniline is just observable. It is now filtered and the residue, after
repeated washing, dried; this residue is the dimethyl-amido-benzo-diphenylamine,
which in this way is obtained in the form of a white crystalline powder.
The dimethyl-amido-benzo-diphenylamine has slight basic properties, dissolves in
sparingly diluted hydrochloric acid and is partially precipitated from the solution on
further dilution; it is easily soluble in benzol but with difficulty in alcohol and
crystallizes from the solution in white needles, having the melting point 178 degrees
centigrade (uncorrected).
The halogenisation and condensation of the body described above, with for example
dimethylaniline, is carried on in the following way.
10 parts by weight of dimethyl-amido-benzo-diphenyl-amine are heated with 5 parts
by weight of oxychloride of phosphorus until the mixture forms a uniform melt,
after having cooled down to ordinary temperature 10 parts by weight of dimethyl-
aniline are added, during which there will occur some spontaneous heating: after
cooling down again the mass is heated to about the temperature of a waterbath for
about 2 hours. There will result a dark syrupy mass with feeble metallic lustre, that
on cooling becomes nearly solid.
The condensation can also be carried on by mixing first the amide with the
dimethylaniline, adding then oxychloride of phosphorus and heating the whole. In
this case the heating must be conducted with great precaution, or by spontaneous
setting in of the reaction, the temperature might rise too high. It will be understood
that I do not restrict myself to the exact proportions of the several components of the
mixture given, as also, that with other quantities of oxychloride of phosphorus and of
dimethylaniline, as mentioned above, satisfying results may be obtained. Neither is
the formation of the condensation product restricted to a fixed temperature, but it
has been found advantageous to work at a temperature between 90 to 105 degrees
centigrade.
The condensation product, or as it may be called, the tetra-methyl-diamido-benzo-
phenon-diphenyl-amine chloride is with difficulty soluble in water and in alcohol more
easily, giving a blue-red color; froin the former solution it is separated with metallic
lustre by the addition of common salt. On standing a longer time or on being heated
the coloring of the solutions disappears by cause of decomposition.
Mordaunted cotton is dyed a red-violet.
For the conversion of the condensation-product into tetra-methyl-diamido-benzo-
phenone I proceed in the following manner; the melt above described is digested
with about the quintuple volume of water slightly acidulated by hydrochloric acid at
about 70 degrees centigrade until complete dissolution of the same, or until the
intensive carmine red coloring at the beginning has turned into green-to brown
yellow. The decomposition proceeds under separation of diphenylamine. The mass
is then diluted with about 20 parts by weight of water, carefully neutralizing the
excess of dimethylaniline, if there is any, with hydrochloric acid and filtering the
Ketone remaining in admixture with diphenylamine; from the latter it is separated
by washing with alcohol or extraction by hydrochloric acid. After recrystallisation it
has the melting point 173-174 degrees centigrade (uncorrected).
The decomposition of the condensation product can also be effected with other acids
than hydrochloric acid, also without any acid, and moreover by the addition of solid
alkalis.

page_text: acids by the action of aniline, orthotoluidine, paratoluidine, meta-xylidine, para-
dimethyl phenylendiamine, neta-phenylendiamine, botanaphthylamine and methyl-
aniline, ethylaniline, diphenylamine, alphaphenylnaphthylamine, betaphenylnaphthyl-
amine upon the chlorides of the dimethyl amido-diethylamido-ethylmethyl-amido-
benzoic acid substantially as herein described.
2. The production of halogencompounds of the mono- and di-substituted dialkyl-
amido-benzamides referred to in the preceding claim, by the action of chloride-, and
bromide-, oxychloride and oxybromide of phosphorus and oxychloride of carbon
upon these mono- and di-substituted dialkylamidobenzamides substantially as herein
described.
3. The production of condensation products from the halogen compounds referred
to in the preceding claim and the tertiary bases: dimethylaniline, diethylaniline,
ethylmethylaniline, methyl-diphenylamine substantially as herein described.
4. The production of tetraalkyldiamido benzophenones by treating the condensation
products referred to in the preceding claim with diluted acids, or alkalis and the
production of tetra-alkyldiamido-benzo-phenone-amines by treating the condensation
products derived from the disubstituted dialkyl-amido-benzamides with ammonia
substantially as herein described.
ABEL & IMRAY,
Agents for the Applicant.