Improvements in the Production of Green and "Blueish Green Coloring Matters.
Year: 1888

page_text: Date of Application, 15th Oct., 1888
Complete Specification Left, 9th July. 1889-Accepted, 5th Oct., 1889
PROVISIONAL SPECIFICATION
[Communicated from abroad by THE FARBWERKE VORMALS MEISTER, LUCIUS, AND
BRUNING, of Hoechst-am-Maine, in the Empire of Germany, a Company carrying
on business as Chemical Manufacturers.]
Improvements in the Production of Green and "Blueish Green
Coloring Matters.
I, 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 to be as follows:
In the Specification to the application to Patent No. 12796 dated September 4th
1888 was described a series of coloring matters that are to be considered as derivatives
of the meta-oxy-diamido-triphenylmethan
CH, OH (m)
4
C HÁC H, NH, (p)
`C, H, NH, (p)
and it was put prominently forward that the sulphonic acids of the meta-oxy-tetralkyl-
diamidotriphenylcarbinols
have valnable qualities.
C. HOH
C (OH) C, H, N (alk)a
C. H₁ N (alk),
Such sulphonic acids have been obtained by carrying out the following operations:
1. Condensing metanitrobenzaldehyde with 2 molecules of a. tertiary aromatic
amine (Ber. d. deutsch ch. Ges. 12. 802).
2. Reducing the metanitroleucobase to the meta-amidoleucobase.
3. Treatment of the meta-amidoleucobase with nitrous acid.
4. Sulphonating the meta-oxyleucobase thus formed and oxidizing the leucosulphonic
acid.
It has since been discovered by my correspondents that very fast acid coloring
matters are also obtained by direct sulphonation of the meta-amidoleucobases prepared
by the operation 2, and subsequent oxidation of the leucosulphonic acids.. The
identical acid coloring matters are also obtained by oxidation of the meta-amido-
leucobases and subsequent sulphonation of the formed basic coloring matters.

page_text: Afterwards the solution is heated for several hours to 60° C. until a sample dissolves
easily in water and also gives with diluted ammonia a clear solution of violet tint.
The mass of the reaction is now poured into water and converted into the calcium or
sodium salt in manner well known.
PROCESS FOR THE OXIDATION OF THE LEUCOSULPHONIC ACIDS.
From the calcium salts of the lencosulphonic acids hereinbefore mentioned are
prepared the corresponding coloring matters by oxidation with superoxides, such as
manganese superoxide, lead superoxide, barium superoxide, in presence of the
calculated quantity of mineral acids. The oxidation is carried out mutatis mutandis
according to the process described in the Specification No. 12,79688 ad 4.
The new coloring mattors are copper-red powders of metallic lustre and dissolve in
water quite easily with a blue tint. The aqueous solution behaves with mineral acids
and with alkalies in quite the same manner as the coloring matters derived from
meta-oxytetralkyldiamidotriphenylmethans. By the addition of an excess of mineral
acids the solution is colored green; the blue coloring does not disappear on the
addition of cold sola lye, neither on being boiled with diluted ammonia or soda
solution. The blue solution turns violet only when boiled with soda lye.
7
•
The new coloring matters dye wool and silk in acid bath a uniform blue green shade
and these shades excel in great fastness.
"PROCESS FOR THE CONVERSION OF THE
META-AMIDOTETRALKYLDIAMIDO-
TRIPHENYLCARBINOLS INTO ACID COLORING MATTERS:
The metaamidotetralkyldiamidotriphenylcarbinols are green coloring matters, which
according to E. and O. Fischer (Ber. d. deutsch chem. Ges. 12. S03) are obtained by
the oxidation of the corresponding meta-amidotetralkyldiamidotriphenylmethans.
These coloring matters is. the sulphates or chlorhydrates of
metaamidotetramethyldiamidotriphenylcarbinol,
metaamidotetraethyldiamidotriphenylcarbinol,
metaamidodimethyldiethyldiamidotriphenylcarbinol symmetric
(C, H, NCH, C₂ H₂),
C, H, NH,
CH
metaanidodimethyldiethyldiamidotriphenylcarbinol
not symmetric
CH-CH₁ N (CH3)2
CH, N (C, H₁),
,C H, NH.
metaamidotetramethyldiamidodiorthotolylphenylcarbinol,
metaamidotetraethyldiamidodiorthotolylphenylcarbinol,
metaamidodimethyldibenzyldiamidotriphenylcarbinol,
metaamidodiethyldibenzyldiamidotriphenylcarbinol,
metaamidodimethyldiphenyldiamidotriphenylcarbinol,
metaamidodiethyldiphenyldiamidotriphenylcarbinol
may be converted into acid coloring matters identical with those coloring matters
described under II. by treatment with sulphuric acid.

page_text: opic as foIIOWS
20 parts by weight of metaamidotetraethyldiamidotriphenylcarbinol are dissolved in
100 parts by weight of monohydrate and this solution heated to 70-80 degrees C.
until a sample gives with diluted ammonia a clear solution of pure blue color. The
mass of the reaction is then converted into the calcium or sodium salt in manner
well known.
Dated thin 15th .. COL11000
COMPLETE SPECIFICATION.
Improvements in the Production of Green and Blueish Green
Coloring Matters.
I, 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:-
In the Specification to patent No. 12796 dated September 4th 1888 was described a
series of coloring matters that are to be considered as derivatives of the meta-oxy-
diamido-triphenylmethan:
•
C₂ H₁ OH (m)
8
CHÚC H, NH, (p)
C. H₁ NH₂ (p)
2
and it was put prominently forward that the sulphonic acids of the meta-oxy-
tetralkyldiamidotriphenylcarbinols
have valuable qualities.
CH, OH
C (OH) C, H, N (alk),
C₁ H. N (alk),
Such sulphonic acids we have obtained by carrying out the following operations :-
1) Condensing metanitrobenzaldehyde with 2 molecules of a tertiary aromatic
amine (Ber. d. deutsch. ch. Ges. 12. 802).
2) reducing the meta nitroleucobase to the metaamidoleucobase.
3) treatment of the metaamidoleucobase with nitrous acid.
4) sulphonating the meta-oxyleucobase thus formed and oxidising the leucosulphonic
acid.
It has since been discovered by my correspondents that very fast acid coloring
matters are also obtained by direct sulphonation of the meta-amido-leucobases prepared
by the operation (2) or their methylated or ethylated derivatives and subsequent
oxidation of the leucosulphonic acids. The identical acid coloring matters are also
obtained by oxidation of the meta-amido-leucobases or their methylated or ethylated
derivatives and subsequent sulphonation of the formed basic coloring matters.

page_text: 30 parts by weight of metaamidotetraethyldiamidotriphenylmethan are dissolved
in 150 parts by weight of fuming sulphuric acid of 20 per cent. SO3. When the
solution is slightly heated or left standing for a considerable time, there is first. formed
a sulphonic acid, the ammoniacal salt of which is soluble with difficulty and therefore
gives a clear solution with hot diluted ammonia only. It is more advantageous
therefore, principally in view of the qualities of the resulting coloring matters to make
use of a sulphonic acid, the ammoniacal salt of which is casily soluble. To this effect
the liquid of the sulphonation is heated to from 90 to 100 degrees centigrade, until a
sample gives a clear solution with cold ammonia of 3 per cent. The mass of the
reaction is then converted into the calcium or sodium salt in manper well known.
The calcium salt is a powder easily soluble in water and in alcohol.
In the same manner I proceed for the preparation of the sulphonic acids respectively
of the calcium salts of these acids, from
metaamidotetramethyldiamidotriphenylmethan,
metaamidodimethyldiaethyldiamidotriphenylmethan symmetric

page_text: Somewhat different is the manner of preparing the sulphonic acid
leucobases that in the amide-group still contain aromatic (and therefore
sulphonated) rests such as benzyl, phenyl. The compounds appertaining t
are the following, viz. :—
metaamidodibenzyldimethyldiamidotriphenylmethan
C. HẠNH,
CHÁC, H, N (CH,) (C, H,)
G
6
4
`C H₁ N (CH₂) (C, H,)
metaamidodibenzyldiethyldiamidotriphenylmethan,
metaamidodiphenyldimethyldiamidotriphenylmethan,
metaamidodiphenyldiethyldiamidotriphenylmethan,
metaamidotrimethylbenzyldiamidotriphenylmethan,
metaamidotriethylbenzyldiamidotriphenylmethan,
metaamidodimethylethylbenzyldiamidotriphenylmethan,
metaamidodiethylmethylbenzyldiamidotriphenylmethan,
metaamidoethylmethyldibenzyldiamidotriphenylinethan symmetric,
metaamidomethylethylmethylbenzyldiamidotriphenylmethan,
metaamidomethylethylbenzyldiamidotriphenylmethan,
metaamidodimethyldibenzyldiamidotriphenylmethan non symmetric,
metaamidodiethyldibenzyldiamidotriphenylmethan non symmetric,
metaamidomethylethyldibenzyldiamidotriphenylmethan non symmetric,
monomethyl-m-amidodimethyldibenzyldiamidotriphenylmethan,
monoethyl-m-amidodimethyldibenzyldiamidotriphenylmethan,
dimethyl-m-amidodimethyldibenzyldiamidotriphenylmethan,
diethyl-m-amidodimethyldibenzyldiamidotriphenylmethan,
monomethyl-m-amidodiethyldi benzyldiamidotriphenylmethan,
monoethyl-m-amidodiethyldibenzyldiamidotriphenylmethan,
dimethyl-m-amidodiethyldibenzyldiamidotriphenylmethan,
diethyl-m-amidodiethyldibenzyldiamidotriphenylmethan.
The manner in which the sulphonation of these leucobases is carried out i
by the following example:
30 parts by weight of metaamidodiethyldibenzyldiamidotriphenylin
dissolved in 150 parts by weight of fuming sulphuric acid of 20 per cent
ordinary temperature is formed a sulphonic acid soluble with difficulty
Afterwards the solution is heated for several hours to 60 degrees centrigr
sample dissolves easily in water and also gives with diluted ammonia a clea
of violet tint. The mass of the reaction is then poured into water and con
the calcium or sodium salt in manner well known.

page_text: The oxidation is carried out mutatis mutandis according to the process described in
the before mentioned patent No. 1279688 ad (4).
The new coloring matters are copper-red powders of metallic lustre and dissolve in
water quite easily, with blue tint. The aqueous solution behaves with respect to mineral
acids and to alkalies in quite the same manner as the coloring matters deriving from
metaoxytetralkyldiamidotriphenylmethans. By the addition of an excess of mineral
acids the solution is colored green; the blue coloring does not disappear on the
addition in the cold of soda lye, neither or being boiled with diluted ammonia or soda
solution. The blue solution turns violet only when boiled with soda ye. The new
coloring matters dye wool and silk in acid bath a uniform blue green shade and these
shades excel in great fastness.
C. H, NH.
((OH)CH N (CH₂),
CH₁ N (C, H₂),
metaamidotetramethyldiamidodiorthotolylphenylcarbinol,
metaamidotetraethyldiamidodiorthotolylphenylcarbinol,
metaamidodimethyldibenzyldiamidotriphenylcarbinol,
metaamidodiethyldibenzyliamidotriphenylcarbinol,
metaamidodimethyldiphenyldiamidotriphenylcarbinol,
metaamidodiethyldiphenyldiamidotriphenylcarbinol,
metaamidotrimethylbenzyldiamidotriphenylcarbinol,
metaamidotriethylbenzyldiamidotriphenylcarbinol,
metaamidodimethylethylbenzyldiamidotriphenylcarbinol,
metaamidodiethylmethylbenzyldiamidotriphenylcarbinol,
metaamidoethylmethyldibenzyldiamidotriphenylcarbinol symm
metaamidomethylethylmethylbenzyldiamidotriphenylcarbinol,
metaamidomethylethylethylbenzyldiamidotriphenylcarbinol,
metaamidodimethyldibenzyldiamidotriphenylcarbinol non sym
metaamidodiethyldibenzyldiamidotriphenylcarbinol non symme
metaamidomethylethyldibenzyldiamidotriphenylcarbinol non sy
monomethyl-m-amidotetramethylliamidotriphenylcarbinol,
monoethyl-m-amidotetramethyldiamidotriphenylcarbinol,
dimethyl-m-amidotetramethyldiamidotriphenylcarbinol,

page_text: diethyl-m-amidotetramethyldiamidotriphenylcarbinol,
monomethyl-m-amidotetraethyldiamidotriphenylcarbinol,
monoethyl-m-amidotetraethyldiamidotriphenylcarbinol,
dimethyl-m-amidotetraethyldiamidoi riphenylcarbinol,
symmetric,
non symmetric,
diethyl-m-amidotetraethyldiamidotriphenylcarbinol,
monomethyl-m-amidodimethyldiethylliamidotriphenylcarbinol
monomethyl-m-amidoiimethyldiethyldiamidotriphenylcarbinol
monoethyl-m-amidodimethyldiethyldiamidotriphenylcarbinol symmetric,
monoethyl-m-amidodimethyldiethyldiamidotriphenylcarbinol non symmetric,
symmetric,
dimethyl-m-amidodimethyldiethyldiamidotriphenylcarbinol non symmetric,
diethyl-m-amnidodimethyldiethyldiamidotriphenylcarbinol symmetric,
diethyl-m-amidodimethyldiethyldiamidotriphenylcarbinol non symmetric,
monomethyl-m-amidodimethyldibenzyldiamidotriphenylcarbinol,
dimethyl-m-amidodimethyldiethy Idiamidotriphenylcarbinol
monoethyl-m-amidodimethyldibenzyldiamidotriphenylcarbinol,
dimethyl-m-amidodimethyldibenzyldiamidotriphenylcarbinol,
diethyl-m-amidodimethyldibenzyldiamidotriphenylcarbinol,
monomethyl-m-amidodiethyldibenzyldiamidotriphenylcarbinol,
monoethyl-m-amidodiethyldibenzyldiamidotriphenylcarbinol,
dimethyl-m-amidodiethyldibenzyldiamidotriphenylcarbinol,
diethyl-m-amidodiethyldibenzyldiamidotriphenylcarbinol,
may be converted into acid coloring matters identical with those coloring matters
described sub. II. by treatment with sulphuric acid.
I proceed for example as follows:-
20 parts by weight of metaamidotetraethyldiamidotriphenylcarbinol are dissolved in
100 parts by weight of monohydrate and this solution heated to 70-80 degrees
centigrade until a sample gives with diluted ammonia a clear solution of pure blue
color. The mass of the reaction is then converted into the calcium or sodium salt in
manner well known.
Having now particularly described and ascertained the nature of my said inven-
tion and in what manner the same is to be performed I declare that what I
claim is :-
1. The production of the sulphonic acids of metaamidotetralkyldiamidotriphenyl-
methans, that is to say, the sulphonic acids of:-
metaamidotetramethyldiamidotriphenylmethan,
metaamidotetraethyldiamidotriphenylmethan,
metaamidodimethyldiethyldiamidotriphenylmethan symmetric,
metaamidodimethyldiethyldianidotriphenylmethan non symmetric,
metaamidotetramethyldiamidodiorthotolylphenylmethan,
metaamidotetraethyldiamidodiorthotolylphenylmethan,
metaamidodimethyldibenzyldiamidotriphenylmethan,
metaamidodiethyldibenzyldiamidotriphenylmethan,
metaamidodimethyldiphenyldiamidotriphenylmethan,
metaamidodiethyldiphenyldiamidotriphenylmethan,
.metaamidotrimethylbenzyldiamidotriphenylmethan,
metaamidotriethylbenzyldiamidotriphenylmethan,
metaamidodimethylethylbenzyldiamidotriphenylmethan,
metaamidodiethylmethylbenzyldiamidotriphenylmethan,
metaamidomethylethylmethylbenzyldiamidotriphenylmethan,
metaamidomethylethylethylbenzyldiamidotriphenylmethan,
metaamidoethylmethyldibenzyldiamidotriphenylmethan symmetric,
metaanidodimethyldibenzyldiamidotriphenylmethan non symmetric,
metaamidodiethyldibenzyldiamidotriphenylmethan non symmetric,
metaamidomethylethyldibenzyldiamidotriphenylmethan non symmetric
monomethyl-m-amidotetramethyldiamidotriphenylmethan,

page_text: dimethyl-m-amidotetramethyldiamidotriphenylmethan,
diethyl-m-amidotetramethyldiamidotriphenylmethan,
monomethyl-m-amidotetraethyldiamidotriphenylmethan,
monoethyl-m-amidotetraethyldiamidotriphenylmethan,
dimethyl-m-amidotetraethyldiamidotriphenylmethan,
symmetric,
non symmetric
diethyl-m-amidotetraethyldiamidotriphenylmethan,
monomethyl-m-amidodimethyldiethyldiamidotriphenylmethan
manomethyl-m-amidodimethyldiethyldiamidotriphenylmethan
monoethyl-m-amidodimethyldiethyldiamidotriphenylmethan symmetric,
monoethyl-m-amidodimethyldiethyldiamidotriphenylmethan non symmetric,
dimethyl-m-amidodimethyldiethyldiamidotriphenylmethan symmetric,
dimethyl-m-amidodimethyldiethyliamidotriphenylmethan non symmetric,
diethyl-m-amidodimethyldiethyllian.idotriphenylmethan symmetric,
diethyl-m-amidodimethyldiethyldiamidotriphenylmethan non symmetric,
monomethyl-m-amidodimethyldibenzyldiamidotriphenylmethan,
monoethyl-m-amidodimethyldibenzylliamidotriphenylmethan,
dimethyl-m-amidodimethyldibenzyldiamidotriphenylmethan,
diethyl-m-amidodimethyldibenzyldiamidotriphenylmethan,
monomethyl-m-amidodiethyldibenzyldiamidotriphenylmethan,
monoethyl-m-amidodiethylbenzylliamidotriphenylmethan,
dimethyl-m-amidodiethyldibenzyldiamidotriphenylmethan,
diethyl-m-amidodiethyldibenzyldiamidotriphenylmethan,
by the action of sulphuric acid or fuming sulphuric acid upon these leucobase
2. The production of solid acid coloring matters by oxidising the sulpho
mentioned in the preceding claim with superoxides (lead superoxide, ma
superoxide, bariumsuperoxide) or similar agents.
3. The production of the same acid coloring matters referred to above
following carbinols :
metaamidotetramethyldianidotriphenylcarbinol,
metaamidotetraethyldiamidotriphenylcarbinol,
metaamidodimethyldiethyldiamidotriphenylcarbinol symmetric,
metaamidodimethyldiethyldiamidotriphenylcarbino! non symmetric,
metaamidotetramethyldiamidodiorthotolylphenylcarbinol,
metaamidotetraethyldiamidodiorthotolylphenylcarbinol,
metaamidodimethyldibenzyldiamidotriphenylcarbinol,
metaamidodiethyldibenzyldiamidotriphenylcarbinol,
metaamidodimethyldiphenyldiamidotriphenylcarbinol,
metaamidodiethyldiphenyldiamidotriphenylcarbinol,
metaamidotrimethylbenzyldiamidotriphenylcarbinol,
metaamidotriethylbenzyldiamidotriphenylcarbinol,
metaanidodimethylethylbenzyldiamidotriphenylcarbinol,
metaamidodiethylmethylbenzyldiamidotriphenylcarbinol,
metaamidomethylethylmethylbenzyldianidotriphenylcarbinol,
metaamidoethylmethyldibenzyldiamidotriphenylcarbinol symmetric,
metaamidomethylethylethylbenzyldiamidotriphenylcarbinol,
metaamidodimethyldibenzyldiamidotriphenylcarbinol non symmetric,
metaamidodiethyldibenzyldiamidotriphenylcarbinol non symmetric,
monomethyl-m-amidotetramethyldiamidotriphenylcarbinol,
inetaamidomethylethyldibenzyldiamidotriphenylcarbinol non symmetric,
monoethyl-m-amidotetramethyldiamidotriphenylcarbinol,
dimethyl-m-amidotetramethyldiamidotriphenylcarbinol,
diethyl-m-amidotetramethyldiamidotriphenylcarbinol,
monomethyl-m-amidotetraethy Idiamidotriphenylcarbinol,
monoethyl-m-amidotetraethyldiamidotriphenylcarbinol,
dimethyl-m-amidotetraethyldiamidotriphenylcarbinol,

page_text: symmetric,
non symmetric,
symmetric,
non symmetric,
diethyl-m-amidotetraethyldiamidotriphenylcarbinol,
monomethyl-m-amidodimethyldiethyldiamidotriphenylcarbinol
monomethyl-m-amidodimethyldiethyldiamidotriphenylcarbinol
monoethyl-m-amidodimethyldiethyldiamidotriphenylcarbinol
monoethyl-m-amidodimethyldiethyldiamidotriphenylcarbinol
dimethyl-m-amidodimethyldiethyldiamidotriphenylcarbinol symmetric;
dimethyl-m-amidodimethyldiethyldiamidotriphenylcarbinol non symmetric,
diethyl-m-amidodimethyldiethyldiamidotriphenylcarbinol symmetric,
diethyl-m-amidodimethyldiethyldiamidotriphenylcarbinol non symmetric,
monomethyl-m-amidodimethyldibenzyldiamidotriphenylcarbinol,
monoethyl-m-amidodimethyldibenzyldiamidotriphenylcarbinol,
dimethyl-m-amidodimethyldibenzyldiamidotriphenylcarbinol,
diethyl-m-amidodimethyldibenzyldiamidotriphenylcarbinol,
monomethyl-m-amidodiethyldibenzyldiamidotriphenylcarbinol,
monoethyl-m-amidodiethyldibenzyldiamidotriphenylcarbinol,
dimethyl-m-amidodiethyldibenzyldiamidotriphenylcarbinol,
diethyl-m-amidodiethyldibenzyldiamidotriphenylcarbinol,
by treating these carbinols with sulphuric acid or fuming sulphuric acid.
ABEL & IMRAY,
Agents for the Applicant.