Production of Violet and Blue Colouring Mattera of the Triphenyl- methane Group.
Year: 1896

page_text: Date of Application, 30th Dec., 1896-Accepted, 30th Jan., 1897
[Communicated from abroad by THE CHEMICAL WORKS, formerly SANDOZ, of
Busel, in the Swiss Republic, Chemical Manufacturers.]
Production of Violet and Blue Colouring Mattera of the Triphenyl-
methane Group.
I, WILLIAM EDWIN HEYS of 70 Market Street Manchester in the County of
Lancaster, Patent Agent, 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 alkylated derivatives of beta-naphthylamine such as methyl- or ethyl-phenyl-
beta-naphthylamine; methyl- or ethyl-tolyl-beta-naphthylamine; methyl- or ethyl-
xylyl-beta-naphthylamine; as well as alpha-naphthyl-beta-naphthylamine or
alpha-beta-dinaphthylamine, do not appear to have been used hitherto for the
production of colouring matters, and especially of those belonging to the triphenyl-
methane group..
These derivatives may be easily obtained by the alkylation of phenyl-beta-
naphthylamine or of its homolognes by the ordinary known method, either by
treatment with alkyl-bromide or with a mixture of hydrochloric acid and alcohol.
Methyl-phenyl-beta-naphthylamine crystallises in large colourless prisms which
melt at 52° C. Ethyl-phenyl-beta-naphthylamine forins white flakes melting
at 55° C..
My foreign correspondents have found that these derivatives, when combined
with tetramethyl-diamidobeuzophenone, or with tetraethyl-diamidobenzophenone,
form colouring matters which dye wool in very pure violet or blue shades and
which, owing to the presence of a beta-naphthyl group, pussess the valuable
property that they can be converted into sulphonic acid compounds by treatment
with fuming sulphuric acid, which compounds are distinguished by the purity of
their shades and their fastness to alkalies.
For the production of the new colouring matters according to this invention, the
following process may be adopted.
19.0 kilos. of methyl-phenyl-beta-naphthylamine,
200 kilos. of tetramethyl-diamidobenzophenone, and
7.0 kilos. of toluol
are mixed in a closed vessel on a water bath, by a suitable agitator. When the
mixture has become homogeneous, it is allowed to cool to about 30° C., when
13-5 kilos. of phosphorus oxychloride are added, care being taken to agitate.during
the whole of this operation. After about 15 minutes the reaction.commences and
the temperature rises to about 120° C. The mixture is kept at this temperature
for about an hour, the water bath being heated to boiling when required. After
cooling, the melt is powdered and dissolved in about 1000 litres of hot water. The
colouring matter separates on the addition of common salt, as resinous matter
having a coppery lustre. After drying, it can at once be converted into its sulpho
compound or it can be purified by washing with toluene, or by re-solution in

page_text: By proceeding in a similar way, but substituting the methyl-phenyl-beta-
naphthylamine by ethyl-phenyl-beta-naphthylamine in equivalent molecular
proportion, similar colouring matters are produced which dye a slightly bluer
shade.
To produce the sulphonic acids of these colouring matters the following process
may be employed.
EXAMPLE HII.
200 kilos. of the crude colouring matters produced as. herein before described,
are finely powdered and dissolved in 60 kilos. of cencentrated sulphuric acid of
100 per cent. strength. To this solution there is gradually added, with continued
stirring, about 40 kilos. of fuming sulphuric acid containing 54 per cent. of
anhydrous sulphuric acid, the temperature being carefully maintained at between
20° and 30° C. As soon as a sample dissolves in a large quantity of hot diluted
caustic soda solution, the mixture is poured on ice and the colouring matter is
afterwards separated by filtration. The separated matter is then dissolved in
about 1000 litres of hot water containing the necessary quantity of caustic soda, the
-solution is filtered. if necessary, and the colouring matter is precipitated with
common salt and acetic acid. The product, having been dried and ground to
powder, forms a blue-violet colouring matter easily soluble in hot water, which
dyes wool a very pure violet of the same shade as "acid violet 7 B," but in
distinction from that colouring matter, the new product has the great advantage of
being fast to alkalies.
Herein before there have been described colouring matters obtained by combining
tetramethyl-diamidobenzophenone with tertiary bases of the methyl-phenyl-beta-
.naphthylamine type. My correspondents have further found that certain secondary
bases, as for example alpha-beta-diuaphthylamine, obtained by condensing beta-
naphthol with alpha-naphthylamine, are also suitable for the production of
colouring matters which are distinguished by the ease with which they can be
converted into sulpho-compounds dyeing very pure blue shades. Thus :-
U kшos. of phosphorus oxychloride
are, for instance, mixed in a closed vessel provided with an agitator, and gently
heated until liquefied. After about 15 minutes, the temperature rises to about 115° C.
The product, which solidifies to a crystalline mass having a metallic lustre is
crushed and washed several times with hot water, and the resulting purified
I colouring matter forms small brown flakes which are difficultly soluble in water
but are soluble in alcohol with a blue colour. To convert it into its sulpho-
compound the following process may be employed.
EXAMPLE Y.
200 kilos. of the colouring matter produced as described under Example IV,
are dissolved in 50 kilos. of concentrated 10.) per cent. sulphuric acid, and to the
resulting solution, 30 kilos. of fuming sulphuric acid containing 54 per cent. of

page_text: anhydrous sulphuric acid, are gradually added at a temperature between 10°
and 15° C. As soon as a sample is soluble in hot dilute ammonia solution, the
mixture is poured upon ice and diluted with an abundance of water. The
precipitated colouring matter may be separated by filtration, be dissolved in about.
1000 litres of water containing some ammonia; and be re-precipitated by common
salt. It dyes wool, from an acid bath, a beautiful blue.
Having now particularly described and ascertained the nature of my said inven-
tion and in what manner the same is to be performed, as communicated to me by
my foreign correspondents, 1 declare that what I claim is :-
1. The herein before described process for the manufacture or production of
colouring matters which consists in combining tetramethyl- or tetraethyl-diamido-
benzophenone with tertiary derivatives of beta-naphthylamine of the methyl-
phenyl-beta-naphthylamine type, substantially as set forth.
2. The hereinbefore described process for the production of colouring matters.
which consists in combining tetramethyl- or tetraethyl-diamidobenzophenone with
secondary dorivatives such as alpha-naphthyl-beta-naphthylamine, substantially as.
set forth.
3. The hereinbefore described process for the production of colouring matters.
which consists in combining tetramethyl- or tetraethyl-diamidobenzophenone with
tertiary derivatives of beta-naphthylamine of the methyl-phenyl-beta-naphthylamine
type and converting the product into its sulpho compound, substantially as set.
forth.
4. The hereinbefore described process for the production of colouring matters
which consists in combining tetramethyl- or tetraethyl-diamidobenzophenone with.
secondary derivatives auch as alpha-naphthyl-beta-naphthylamine, and converting
the product into its sulpho compound, substantially as set forth.
5. As new substances, the new colouring matters produced by process claimed in.
the first claim, substantially as.herein before described.
6. As new substances, the new colouring matters produced by the process
claimed in the second claim, substantially as hereinbefore described.
7. As new substances, the new colouring matters produced by the process claimed
in the third claim, substantially as hereinbefore described.
8. As new substances, the new colouring matters produced by the process.
claimed in the fourth claim, substantially as herein before described.
Dated this 29th day of December A.D. 1896.
WILLIAM E. HEYS.