Year: 1888

page_text: Date of Application, 2nd July, 1888
Complete Specification Left, 28th Aug., 1888
Complete Specification Accepted, 5th Oct., 1888
[Communicated from abroad by MESSRS. WIRTH & Co., of Frankfort-on-the-Main, in
the Empire of Germany, Acting as Agents of the firm of K. Oehler, of
Offenbach, in the Empire of Germany.]
I, HENRY HARRIS LAKE, of the firm of Haseltine, Lake & Co., Patent Agents,
Southampton Buildings, in the County of Middlesex, do hereby declare the nature
of this invention to be as follows:-
This invention relates to a method of producing yellow basic dye stuffs called
benzoflavines as hereinafter set forth.
The said invention is carried into practice in the following manner, that is to say,
One molecule of benzaldehyde is allowed to act upon a mixture of one molecule of an
aromatic metadiamine and one molecule of its bydrochlorate or sulphate; by this
action I obtain tetramido-substitution-derivatives of triphenylmethane or its homo-
logues.
The
process goes on in such a way that first one molecule of the aldehyde and one
molecule of the base form a combination corresponding to the benzylidenaniline
(C, H, N=CH C, H.) which combines with a salt of the base forming a triphenyl-
methane derivate.
The formation of the latter also takes place, when benzaldehyde is acting upon the
neutral salts of the metadiamine under certain conditions.
These new tetramines treated by means capable of separating ammonia give
hydrodiamidophenylacridines which by oxydation form diamidophenylacridines which
I call benzoflavines.
The benzoflavines are pure yellow dye stuffs well suited for dyeing cotton mordanted
with tannic acid.
As an example of the method of proceeding I will describe the production of a
benzoflavine from metatoluylendiamine.

page_text: 1. PRODUCTION OF THE FIRST INTERMEDLATE COMPOUND.
MONOBENZYLIDEN-METATOLUYLENDIAMINE.
12 lbs. of metatoluylendiamine and water are mixed to a paste and 12 lbs. of
benzaldehyde added. The mass involves heat and separates the new compound as a
half liquid resin, which becomes hard after some time, it is then pulverised washed
and dried.
TETRAMIDODITOLYLPHENYLMETHANE.
"'
75 lb. of monobenzyliden-metatoluylendiamine and 85 lbs. of sulphate of inetatoluyl
endiamine are heated together to 60-70 in 500 lbs. of water until the whole is
dissolved. Then dilute with more water and precipitate the leukohase formed by
adding alkalies.
Instead of first separating the monobenzyliden-metatoluylendiamine and then
condensing with a salt of the metadiamine it is also possible to produce the tetramido-
hases in one operation for which the following 3 examples are given.
a) Mix 48 lbs. of sulphate of metatoluylendiamine with 20 lbs. of caustic lye
of 40 and 30, of water. To this pasto add 10, 6 lbs. of benzaldehyde dissolved
in 24 . of alcohol of 95° T. and heat the whole to 60° as long as necessary to
dissolve all ingredients. The solution is then diluted with water and the base formed
is precipitated with soda or caustic lye, washed, pressed an I dried.
G1 lbs. of metatoluylendiamine and 98 lbs. of its hydrochlorate are dissolved in
200 lbs. of alcohol and then 53 lbs. of benzaldehyde are poured in. The whole mass is
heated for some time on the water bath to 70 or 80 until the precipitation of the
muriatic salt of the tetramidobase, which is dissolved with difficulty in alcohol, is
finished the mass which has a pulpy consistency is allowed to cool and is then
filtered. The hydrochlorate of the new base formel is wa-bed with alcohol and
gathered on a filter; it is a pure substance if pure materials were used, it has the
formula (HN, 2 H (1.
c) A mixture of 140 lbs. of sulphate of metatoluylendiamine and 200 lbs. of alcohol
of 50 and 25 lbs. of benzaldehyde is heated for several hours to the boiling point in
an apparatus with a reflux refrigerator. During this operation the salt of the
metatoluylendiamine is slowly dissolved and the sulphate of tetramidoditolylphenyl-
methane is separated in form of a sandy crystalline power of the following com-
position ('„ H¸ N, 2 H, SO, and can be directly used.
24
3) PRODUCTION OF THE 3RD INTERMEDIATE COMPOUND
HYDRODIAMIDODIMETHYLPHENYLACRIDINE.
#) I take 100 lbs. of the hydrochlorate of the tetrainidoditolylphenylmethane, and
500 hs. of muriatic acid of 13° und heat them for several hours in an autoclave up
to 160°. After cooling one finds in the autoclave a fast cake of fine needles of the
hydrochlorate of hydrodiumidodimethylphenylacridine which can be used for the
production of the dye stuff without further purifiention.
b) 100 lbs. of sulphato of tetraumidoditolylphenyl methane are dissolved in 360 lbs.
of muriatic acid of 16, 5% and heated for several hours in an autoclave. After
cooling, the salt of the hydrolase is filtered off washed and used for the production of
the dye stuff as in example 4.
21
The composition of the hydrolase is expressed by the formula Ha Na
Lustead of muriatic acid sulphuric acid, phosphoric acid, chloride of zine and the
like may be used to obtain the same result.
4) PRODUCTION on the dye stuff callen BENZOFLAVINES.

page_text: when it is tried to crystallize the salts of the hydrobase. It would therefore be
sufficient to blow air into the solution of the hydrobase, but better results are obtained
by using other slowly acting oxidizing bodies such as for example sesqui chloride
of iron.
I proceed by mixing a diluted hydrochloric solution of 100 lbs. of the hydrobase
with a 30% solution of 350 lbs. of sesqui chloride of iron cooled with ice. The dye
stuff immediately precipitates as a yellow voluminous mass, which is filtered, pressed
and dried.
If the oxidation takes place in the presence of chloride of zinc the precipitate
forms a double compound of the dye stuff with chloride of zinc.
Instond of metatouly lendi umine one may also use metaphenylendiamine for
the production of benzoflavinus and the processes will be all the same as above
described.
If in the above proceedings N 1 and 2 for the production of monobenzyliden-
metatoluylen-diamine and of tetraamidoditolylphenyl-phenyl-methane instead of
benzaldehyde, its substitution products such as toluylaldehyde or nitro-benzaldehyde
are used, the corresponding substituted intermediate compounds, for instance nitro-
tetraamidoditolylphenyl-methane (as hereinafter mentioned as nitrotetramidobase) are
obtained and may be used to make substituted benzoflavines. The way of pro-
ceeding being the same as for the nonsubstituted benzaldehyde I need not repeat the
description of the method of working.
The nitrotetramidobases which are obtained with nitrobenzaldehyde and metadiamines
can also be produced by nitrification of tetramidobases in the following manner.
10 lbs. of sulphate of tetramidoditolylphenyl methane are dissolved in 50 lbs. of
sulphuric acid of 66°³ and mixed slowly at the temperature of 5-1500 with 4, 6 lbs.
of nitrifying acid mixture consisting of 2 parts of sulphuric acid of 66° and 1 part
of nitric acid of 44° B. This mass is diluted with water and the nitroleukobase is
precipitated by adding a solution of soda; it is purified by dissolving in diluted acids
filtering and precipitation by alkalies. The sulphate of the nitroleukobase, which is
dissolved with difficulty in diluted alcohol can also be used for the production of the
pure nitrolenkobase itself.
The nitrotetramidobases can also be used for the production of amidobenzoflavinos.
Al I dronika the uundustion of Pow amidobenzoflavina
1.) PRODUCTION OF THE 1ST INTERMEDIATE COMPOUND
PENTAAMIDODITOLYLPHENYLMEI HANE.
26, 5 lbs. of the hydrochlorate of the Para nitroleukobase are mixed with a warm
mixture of 45 lbs. of tin dichloride and 120 lbs. of muriatic acid of 22, 5° B; when
the reduction, which is taking place is finished, the solution obtained is diluted with
water and treated with sulphuretted hydrogen until all the tin is eliminated; an
addition of alkalios to the liquid filtered off, precipitates the base in a crystalline form,
which is colorless and easily soluble in boiling water; the aqueous solutions of the
salts of this base are colored red-brown by adding sesquichloride of iron whilst
5
2.) PRODUCTION OF THE 2D INTERMEDIATE COMPOUND
HYDROTRIAMIDODEMETHYLPHENYLAORIDINE.
10 lbs. of pentaamidoditolylphenylmethane are heated together with 60 lbs. of muriatic
acid of 160 in an autoclave for several hours up to 160° C; after cooling the hydro-
triamidodimethylphenylacridine formed is found to be almost entirely precipitated; it
is filtered off, washed with water and dried. Obtained in this manner it forms an
0 orange colored crystalline powder; from its watery solution the free base will be pre-
cipitated in the shape of yellow white flakes by the addition of alkalies.

page_text: 3.) PRODUCTION OF THE PARA-AMIDORENZOFLAVINE.
30 lbs. of the hydrobase are dissolved in 30 lbs. of murintic acid of 22, 5° B, diluted
with much water containing some chlorido of zinc; 150 lbs. of a 20% solution of
sosqui chloride of iron are allowed to run slowly into the above solution of the hydro-
base and the dye stuff precipitates at once. It is filtered off, washed with a diluted
solution of common salt, pressed and dried. It has the same properties as the other
Benzoflavines.
The benzoflavines dissolve with some difficulty in cold water and somewhat easier
in hot water; diluted acids precipitate them from their watery solutions. The solution
of benzoflavinos in concentrated sulphuric acid is yellow or has a pronounced yellow
greenish fluoresence. Very characteristic of the Benzoflavines is the intensive yellow
greenish fluoresence of the neoholic solutions which disappear by adding diluted acids.
The bases of the dyo stuffs are colorless, insoluble in water but soluble in alcohol and
other.
Dated this 2nd day of July 1888
HASELTINE, LAKE & Co.,
45, Southampton Buildings, London, W.('.,
Agents for the Applicant.

page_text: vr 100
INI MAMEDIATE COND
MONOBENZYLIDENMETATOLUYLENDIAMINE.
12 lbs. of metatoluylendiamine and water are mixed to a paste and 12 lbs. of
benzaldehyde added. The mass involves heat and separates the new compound as a
half liquid resin, which becomes hard after some time, it is then pulverized washed
and dried.

page_text: Instead of first separating the monobenzyliden-metatoluylendiamine and then
condensing with a salt of the metadiamine it is also possible to produce the
tetramidobases in one operation for which the following three examples are given.
T.
a) Mix 18 s. of sulphate of metatoluylendiamine with 20 lbs. of caustic lye of 40°
and 30 lbs. of water. To this paste add 10,6 lbs. of benzaldehyde dissolved in 24 lbs. 5
of alcohol of 95° and heat the whole to fit degrees as long as necessary to dissolve all
ingredients. The solution is then diluted with water and the base formed is precipi-
tated with soda or caustic lye washed, pressed, and driel.
6) 61 lbs. of melatoluylandiamine and 98 s. of its hydrochlorate are dissolved in
200 has, of alcohol and then 53 lbs. of benzaldehyde are poured in. The whole mass
is heated for some time on the water bath to 70 or 80 until the precipitation of the
muriatic salt of the tetramilobase which is dissolved with dithculty in alcohol, is
finished; the mass which has a pulpy consistency is allowed to cool and is then filtered.
The hydrochlorate of the new base forme is washed with alcohol and gathered on
a filter; it is a pure substance if pure materials were used, it has the formula 1
CN2H CI.
པ
e) A mixture of 100 lbs. of sulphate of metatoluylendiamine and 200 lbs. of
alcohol of 50, and 25 b, of benzaldehyde is heated for several hours to the
boiling point in an apparatus with a reflux refrigerator. During this operation the
salt of the metatolus lendiamine is slowly dissolved and the sulphate of totramidoditolyl- 2
phenylmethane is separated in form of a sandy crystalline powder of the following
composition C. H. N₁, 2 H, 80, and can be directly used.

page_text: its substitution products such as toluylaldehyde or nitro benzaldehyde are used, the
corresponding substituted intermediate compounds for instance nitro-tetraamidoditolyl-
phenylmethane (as heroinafter mentioned nitrotetramidobase) are obtained and may
be used to make substituted benzoflavines. The way of proceeding being the same as
for the non substituted bonzaldehyde I need not repeat the description of the method
of working.
The nitrotetramidobases which are obtained with nitrobenzaldehyde and meta-
diamines can also be produced by nitrification of tetrainidobases in the following
manner.
10 lbs. of sulphate of tetramidoditolylphenylmethane are dissolved in 50 lbs. of
sulphuric acid of 68° B. and mixed slowly at the temperature of 5-15° C. with 4,
6 lbs. of a nitrifying acid mixture consisting of 2 parts of sulphuric acid of 66° B.;
and 1 part of nitric acid of 44° B. This mass is diluted with water and the nitro-
leukobase is precipitated by adding a solution of soda; it is purified by dissolving
in diluted acids, filtering, and precipitation by alkalies. The sulphate of the nitro-
leukobase which is dissolved with difficulty in diluted alcohol can also be used for the
production of the pure nitroleukobase itself.
The nitrotetramidobases can also be used for the production of amidobenzoflavines.
As example. I describe the production of paraamidohenzoflavine
THE FIRST INTERMEDIATE COMPOUND
PENTAAMIDODITOLYLPHENYLMETHANE.
;
26, 5 lbs. of the hydrochlorate of the para-nitroleukobase are mixed slowly with a
warm mixture of 45 lbs. of tin dichloride and 120 lbs. of muriatic acid of 22, 5° B.
when the reduction which is taking place is finished the solution obtained is diluted
with water and treated with sulphuretted hydrogen until all the tin is eliminated; an
addition of alkalies to the liquid filtered off precipitates the base in a crystalline form
which is colorless and easily soluble in boiling water; the aqueous solutions of the
salts of this base are coloured red-brown by adding sesqui-chloride of iron whilst
heating.
0
2. PRODUCTION OF THE 2D INTERMEDIATE COMPOUND
HYDROTRIAMIDODIMETHYLPHENYLACRIDINE.
10 lbs. of pentaamidoditolylphenylmethane are heated together with 60 lbs. of
muriatic acid of 16° B. in an autoclave for several hours up to 160° C.; after cooling,
the hydrotriamidodimethylphenylacridine formed is found to be almost entirely
precipitated it is filtered off, washed, with water, and dried. Obtained in this manner
it forms an orange coloured crystalline powder; from its watery solution the free
base will be precipitated in the shape of yellow white flakes by the addition of
alkalies.
3. PRODUCTION OF THE PARA AMIDOBENZOFLAVINE.
30 lbs. of the hydrobase are dissolved in 30 lbs. of muriatic acid of 22, 5° B.
diluted with much water containing some chloride of zinc; 150 lbs. of a 20% solution
of sesqui chloride of iron are allowed to run slowly into the above solution of the
hydrobase and the dye stuff precipitates at once. It is filtered off washed with a
diluted solution of common salt, pressed and dried. It has the same properties as the
other benzoflavines.
The benzoflavines dissolve with some difficulty in cold water and somewhat easier in
hot water diluted acids precipitate them from their watery solutions. The solution
of benzoflavines in concentrated sulphuric acid is yellow and has a pronounced yellow
greenish fluorescence. Very characteristic of the benzoflavines is the intensive

page_text: yellow greenish fluorescence of the alcoholic solutions which disappears by adding
diluted acids. The bases of the dye-stuffs are colorless insoluble in water but soluble
in alcohol and ether.
Having now particularly described and ascertained the nature of the said inven-
tion and in what manner the same is to be performed as communicated to mo
by my foreign correspondent I declare that what I claim is
First. The method of producing monobenzyliden-or substituted monobenzyliden
combinations of metaphenylendiamine and motatoluylendiamine by the action of one
molecule of benzaldehyde or toluylaldehyde or nitrobenzaldehyde on one molecule of
the said bases substantially as set forth.
Second. The method of producing tetranmidoderivatives of triphenylmethan and
its substitution products by the action of the aldehydes mentioned in the first claim on
a mixture of one molecule of the bases named in the said claim with one molecule of
the salt of these bases substantially as set forth.
Third. The method of producing the tetra amido bases mentioned in the second
claim by the action of the aldehydes mentioned in the first claim on the neutral salts
of the amines as named in the first claim substantially as set forth.
Fourth. The method of producing nitrotetraamidoditolylphenylmethan by the
nitrification of tetramidoditolylphenylmethan substantially as set forth.
Fifth. The method of producing pentamido derivatives of the di and tritolylphenyl-
methan by the reduction of nitrotetraamidodi- and tri-tolyl phenylmethan substantially
as set forth.
Sixth. The method of producing hydrodiamidophony lacridine or its substitution
products from the amidoderivatives of the di and tritolyl-phenylmethan mentioned
in the second and fourth claims by heating with bodies capable of separating ammonia
substantially as set forth.
Seventh. The method of producing yellow dye-stuffs called benzoflavines by the
oxydation of the hydroacridines described in the sixth claim with slowly oxydizing
bodies.
قسم
Dated this 20th day of August 1888.
HASELTINE, LAKE & Co.,
45, Southampton Buildings, London, W.C.,
Agents for the Applicant.