Manufacture of New Coloring Matters from Naphthyl-glycines.
Year: 1891

page_text: COMPLETE SPECIFICATION.
Manufacture of New Coloring Matters from Naphthyl-glycines.
I, EMIL VON PORTHEIM, Proprietor of the firm Kinzelberger & Co. Chemical
Works, at No. 8 Herrengasse. Prague, Bohemia, 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 :-
'
I have observed that the a and the ẞ naphthyglycine prepared according to the
statements of O. Jolles, Ber. XXII 2372, will combine readily with the tetrazo-
compounds of diparadiamines of the diphenyl series to form coloring matters that
are of technical value, as they have the property of dyeing cotton directly in an
alkaline bath.
If one molecule of a p-diamine is converted by known methods into its tetrazo
compounds and is caused to flow into an alkaline, acetic or alcoholic solution of
two molecules of one of the two glycines, there will be readily formed after a short
time, the corresponding tetrazo coloring matter. But if only one molecule of the
glycine be taken, and this is acted upon by one molecule of the tetrazo body. there
are formed quantitatively insoluble intermediate products, which still possess a free
diazo group and are consequently capable of reacting with a farther molecule of a
phenole, amine, naphthole, or their sulpho acids, carbon-acids and other substitution
products, yielding mixed coloring matters, which can however also be produced
with the same effect by causing a molecule of glycine to react upon an intermediate
product from a molecule of a tetrazo body and a molecule of an amine or phenole,
or their sulpho-acids. For the final results it is however immaterial whether the
combination with the glycines be effected first or afterwards.
While, in the production of the coloring matters no difference can be observed
between the two glycines as both combine smoothly and rapidly, the resulting
respective coloring matters show however essentially different properties. Thus for
example a naphthylglycine combined with tetrazodiphenyl gives a blue red easily
soluble coloring matter, while ẞ naphthylglycine combines with tetrazo diphenyl to
form a coloring matter insoluble in water; generally speaking, naphthylglycine
requires one or more sulpho groups in addition to render it soluble in water.
The coloring matters from a glycine shew the property of a naphthylamine of
being affected by acids, while those from ẞ naphthyl-glycine are tolerably acid
proof, which properties can be judged, in the case of the a coloring matters, in
the aqueous or the alcoholic solution, and in the case of the coloring inatters of the
B series, in the alcoholic solution, as the coloring matters of the a and ẞ series
along with the unsulphonised p-diamines are easily dissolved in spirit.
The following may serve as examples of the production of the coloring matters.
1. 18.4 kilos. of benzidine or an equivalent quantity of a salt is converted by
means of 50 kilos. hydrochloric acid of 33 p.c. and 13.8 kilos. sodium nitrite into
tetrazo diphenylchloride; and a solution of 40.2 kilos. a naphthyl glycine, which is
maintained alkaline by means of carbonate of soda, is poured in slowly under
continual stirring. After a lapse of some time the forination of the coloring
matter is completed.
The filtered and dried coloring matter forms a dark powder which is easily
soluble in water with a blue-red color, and which dyes cotton in an alkaline bath
with a blue-red color, that is readily taken up.
2. The tetrazo body formed of 18.4 kilos. of benzidine is entered into 20.1 kilos.
of a naphthylglycine, maintained alkaline; after some stirring the whole of the
tetrazo body will be used up, and the insoluble intermediate product will have
been separated as a dark precipitate; if now 245 kilos. of ẞ naphthylamine
ẞ mono sulphonate of soda be added, and the mixture be stirred for some time,

page_text: there will be forined a tetrazo coloring matter which differs from the former
coloring matter from 2 molecules of glycine by its yellower tint and its greater
resistance to the action of acids.
3. 24.6 kilos. benzidine sulphone are converted in the known manner into the
tetrazo body by means of 13-8 kilos. of sodium nitrite and this is then added slowly
to 40.2 kilos. of naphthyl glycine which is maintained alkaline by means of
carbonate soda.
The coloring matter is formed at once, and, after working up, it forms a dark
powder which in an alkaline bath dyes cotton a bine color of the tint of azo blue.
4. 23.6 kilos. of benzidine monosulpho-acid is converted in acid solution into its
tetrazo body by means of 13.8 kilos. of nitrite and is poured into an alkaline
solution of 402 kilos. of naphthylglycine. The coloring matter is at once formed.
It is easily soluble in water, and dyes cotton with a blue-red tint, it is not very
easily affected by acids and is well taken up.
The coloring matters enumerated in the following table have hitherto proved of
Denzidine strpnon distiphonic acid
Benzidine sulphon disulphonic-acid
DRUC.
soluble
soluble
a glycme
ẞ glycine bluc
The coloring matters prepared as above described are noticeable on several
grounds.
Thus for example the coloring matter from one molecule of benzidine and two
molecules of a glycine is probably the first technically valuable tetrazo coloring
matter which is maintained in aqueous solution by the group CH,COONa in the
amido group.
The blue coloring matter from benzidine sulphone and a glycine is the only
cotton blue besides sulpho azurine which is not a naphthole derivative.
Particular advantages arise for the said new coloring matters from the fact that
derivatives of a and B naphthylamine are here dealt with, as, in addition to their
greater purity and good taking quality, they are much more alkali-resisting than
the tetrazo coloring matters that are naphthole derivatives, and are equal to them
in tint.
Thus the coloring matter from benzidine and a glycine can be compared as
regards tint with Congo corinth G, while that from benzidine sulphone and
a glycine may be compared with azo blue, while both Congo corinth & and azo
blue a far more dull in color and sensitive to alkalis than the said glycine colors.
Having now particularly described and ascertained the nature of this inven-
tion and in what manner the same is to be performed, 1 declare that what I
claim is:
1. A manufacture of new coloring matters produced by the combination of the
tetrazo bodies of dipara diamines with a and 3 naphthylglycine.

page_text: 2. A manufacture of mixed coloring matters produced from one molecule of the
tetrazo bodies of the following diamines: benzidine, tolidine, their monosulpho
acids, and disulpho acids, sulphones, benzidine sulphoudisulpho acids, and one
molecule of the said glycines, the intermediate product thus obtained being made
to act upon a further molecule of an amine, phenole, naphthole, their sulpho acids,
carbon acids, and other reacting substitution products.
Dated this 15th day of December 1891.
ABEL & IMRAY,
Agents for the Applicant.