Manufacture of Phthalöines by the Action of Mixed Anhydrides.
Year: 1895

page_text: Date of Application, 22nd July, 1895
Complete Specification Left, 21st Apr., 1896-Accepted, 6th June, 1896
PROVISIONAL SPECIFICATION.
[Communicated from abroad by ALFRED FISCHESSER & Co., of Lutterbach,
Alsace, Germany, Chemical Manufacturers.]
Manufacture of Phthalöines by the Action of Mixed Anhydrides.
I, CHARLES DENTON ABEL, of No. 28 Southampton Buildings, Chancery
Lane, in the County of London, Consulting Engineer, and Chartered Patent Agent,
do hereby declare the nature of this invention to be as follows:-
This invention relates to the manufacture of phthaleines by the action of mixed
anhydrides instead of phthalic acid or succinic acid anhydrides or resorcine or
metaamidophenol respectively, and alkyl or phenyl derivates of the metaamido-
phenol or cresol.
My foreign correspondents have observed that the so called mixed acid
anhydrides can, like simple anhydrides (such as phthalic or succinic acid
anhydrides) also form phthalëines.
Mixed anhydrides have been referred to in works such as Gerhardt Annalen
87, 81; Chiazzo Annalen 84, 108; Annalen 85, 23; Annalen 8, 220; and Malherbe
Annalen 91, 102.
The manufacture is simply effected by the action of the chloride of the one acid
on the sodium (or equivalent) salt of the other acid in such proportions that the
chlorine corresponds in quantity with the sodium or its equivalent.
Thus phthalic chloride and barium succinate produce the hitherto unknown
phthalyl-succinyl anhydride, a reaction which may be represented by the equation:
COCI
CH
+ Ba
°C,H₁ = C¸H¸¸
C2H4 + BaCl,.
124 grammes of phthalyl-succinyl-anhydride (1 molecule) and 274 grammes of
di-methyl-meta-amidophenol are melted in an oil bath at 170° to 175° C. for 3 to
4 hours, that is to say until the formation of colouring matter no longer increases,
and the molten mass, which was at first liquid, becomes viscid.
The mass which is of a deep violet red colour with metallic lustre, is, when cold,
finely pulverised and boiled with hydrochloric acid of 8 to 10 per cent. strength.
The solution in cooling precipitates the hydrochlorate of the new colouring matter
in the form of crystals which are readily soluble in hot or cold water. The new
rhodamines produce on silk and wool very fine bluish red tints extremely fast
against acids, soda, fulling, washing, air and light. The tints have a tinge more
yellowish than phthalic acid rhodamine. The new colouring matter is also well-

page_text: suited for dyeing cotton. In its properties it holds an intermediate place between
the corresponding products of the German Patent No. 44002 (dimethyl-meta-
amido-phenol-phthaleine) and of the German Patent No. 51983 (dimethyl-meta-
amido-phenol-succinine) and in some respects it is to be preferred to these.
Instead of dimethyl-meta-amido-phenol may be employed diethylmetaamido-
phenol, meta-amido-cresol, and its alkyl derivates, oxydiphenylamine, methyl-
phenyl-meta-amido-phenol.
Instead of the mixed anhydride mentioned in the example given, there may be
employed other mixed anhydrides, namely anhydride of phthalic acid with phthalic
.acid, phthalic acid anhydride and the chlorides thereof, succinic acid anhydride
and succinic acid, succinic acid anhydride and the chlorides of phthalic acids, and
thus there are obtained colouring matters more or less soluble in water, and of a
fiery yellow, red, violet to blue, with characteristic fluorescence and with remark-
able dyeing properties.
Dated this 22nd day of July 1895.
ABEL & IMRAY,
Agents for the Applicant.
Manufacture of Phthalëines by the Action of Mixed Anhydrides.
I, CHARLES DENTON ABEL, of No. 28 Southampton Buildings, Chancery
Lane, in the County of London, Consulting Engineer, and Chartered Patent
Agent, do hereby declare the nature of this invention and in what manuer the
same is to be performed to be particularly described and ascertained in and by
the following statement :-
This invention relates to the manufacture of phthaleines by the action of mixed
anhydrides instead of phthalic acid or succinic acid anhydrides on resorcine or
metaamidophenol respectively, and alkyl or phenyl derivates of the metaamido-
phenol or cresol.
My foreign correspondents have observed that the so called mixed acid
anhydrides can, like simple anhydrides (such as phthalic or succinic acid
anhydrides) also form phthalëines.
Mixed anhydrides have been referred to in works such as Gerhardt Annalen
87, 81 Chiazzo Annalen 84, 108; Annalen 85, 23; Annalen 8, 220; and Malherbe
Annalen 91, 102.
The manufacture is simply effected by the action of the chloride of the one acid
on the sodium (or equivalent) salt of the other acid in such proportions that the
chlorine corresponds in quantity with the sodium or its equivalent.
Thus phthalic chloride and barium succinate produce the hitherto unknown
phthalyl-succinyl anhydride, a reaction which may be represented by the equation.
The new anhydride is readily soluble cold in the ordinary organic solvents, still
more readily when hot. Hot saturated solutions precipitate, in cooling from
156° C., splendid white needles. (Phthalic acid anhydride melts at 128° Č., and
succinic acid anhydride at 122° C.)
These mixed anhydrides condense very readily with 2 or 4 molecules of resorcin,
meta-amido-phenol and its alkyl derivates to one molecule of anhydride, without
condensing agents

page_text: EXAMPLE.
124 grammes of phthalyl-succinyl-anhydride (1 molecule) and 274 grammes of
di-methyl-meta-amidophenol are melted in an oil bath at 170° to 175° C., for 3 to
4 hours, that is to say until the formation of colouring matter no longer increases,.
and the molten mass, which was at first liquid, becomes viscid.
The new
The mass which is of a deep violet red colour with metallic lustre, is, when cold,.
finely pulverised and boiled with hydrochloric acid of 8 to 10 per cent. strength.
The solution in cooling precipitates the hydrochlorate of the new colouring matter
in the form of crystals which are readily soluble in hot or cold water.
rhodamines produce on silk and wool very fine bluish red tints extremely fast.
against acids, soda, fulling, washing, air and light. The tints have a tinge more
yellowish than phthalic acid rhodamine. The new colouring matter is also well.
suited for dyeing cotton.
In its properties it holds an intermediate place between the corresponding
products of the German Patent No. 44002 (dimethyl-meta-amido-phenol-phthaleine).
and of the German Patent No. 51983 (dimethyl-meta-amido-phenol-succinine) and.
in some respect it is to be preferred to these.
Instead of dimethyl-meta-amido-phenol may be employed diethylmetaamido-
phenol, meta-amido-cresol, and its alkyl derivates oxydiphenylamine, methyl-
phenyl-meta-amido-phenol.
Instead of the mixed anhydride mentioned in the example given, there may be
employed other mixed anhydrides, namely anhydride of phthalic acid mixed with
phthalic acid, phthalic acid anhydride mixed with the chlorides thereof, succinic
acid anhydride mixed with succinic acid, succinic acid anhydride mixed with the
chlorides of phthalic acids, and thus there are obtained colouring matters more or
less soluble in water, and of a fiery yellow, red, violet to blue, with characteristic
fluorescence and with remarkable dyeing properties.
Having now particularly described and ascertained the nature of this inven-
tion and in what manner the same is to be performed, I declare that what I
claim is :-
1. Manufacture of phthalein colouring matters by causing mixed acid anhydrides
to react upon resorcin or metaamidophenol or cresol and their alkyl or phenyl.
derivatives, substantially as described.
2. The phthalëin colouring matters produced as set forth in the first claim.
" 1000