Improvements in the Manufacture of Organic Combinations of Anhydride of Benzoic Orthosulphamide.
Year: 1899

page_text: Date of Application, 13th Dec., 1899-Accepted, 24th Mar., 1900
Improvements in the Manufacture of Organic Combinations of
Anhydride of Benzoic Orthosulphamide.
I, CLAUDE KENNEDY MILLS, of 23, Southampton Buildings, in the County of
London, Patent Agent, do hereby declare the nature of this invention (a communi-
cation to me from Auguste Lumière and Louis Lumière, both of 21, Rue Saint-Victor,
Lyon-Monplaisir, France, Manufacturers of Photographic Materials) and in what'
manuer the same is to be performed to be particularly described and ascertained.
in and by the following statement :-
In a German Patent dated December 9, 1885, Messrs. Fahlberg and List have
described a process of manufacture for obtaining saccharine salts of the alkaloids,.
quinine, cinchonine, strychnine and morphine.
This process has not been adopted probably because it is with difficulty that pure
salts are produced; that these salts are generally very soluble in water and do not
crystallize from their solutions which can more often be reduced to a pasty state with-
out crystallizing.
The communicators have discovered a method of isolating these substances in a-
pure and solid state by means of the following processes.
1. By treating the saccharinate of barium in a concentrated solution by the corre
sponding sulphates of alkaloids. For this purpose the concentrated solutions are
treated in water or in other solvents by a concentrated solution of saccharinate of
barium until the sulphate of barium no longer precipitates. After filtration the
solution is evaporated under 100°.
2. In those cases in which the combination formed is only slightly soluble in water
the communicators have been able to obtain it by treating the sulphate, the hydro-
chlorate, or any other soluble salt of the alkaloid by the salt of sodium, of ammonium
or any other soluble salt of saccharine.
The salt of ammonium generally answers better on account of its great solubility.
3. By dissolving the alkaloid and the saccharine in other liquids than water which
are suitable for the purpose such as ether, alcohol, chloroform, benzene, ligroin, etc.
and chosen in such a way that the salt formed is not soluble in the solvent or the
mixture of the solvents chosen.
By mixing these solutions, the combination of the bodies which they contain is
effected sometimes without heat, sometimes by slightly raising the temperature and
the salt formed is precipitated.
If with the alkaloids the direct action of saccharine does not, during the greater
part of the time give satisfactory results, the communicators have discovered that
other organic bodies having a basic action may form directly definite salts having
interesting properties, such are:-antipyrine, pyramidone, orthoforme, the formula,
of which is

page_text: According to the proportions and the bodies employed, monacid or diacid salts may
be made.
Here are a few examples:-
A. By double decomposition with the salt of barium of saccharine.
52 parts of saccharinate of barium and 31 parts of sulphate of monomethylaniline
are dissolved separately and respectively in 300 and 100 parts of boiling water; the
two solutions are mixed and afterwards little by little one or the other of the con-
stituents is added until a trial of the filtered liquor does not precipitate either by the
chloride of barium or by the sulphate of sodium; it is then filtered and evaporated
below 60° to a syrupy consistence, then it is cooled at -15° (15 degrees below zero);
the saccharinate of methylaniline crystallizes; it is dried in vacuo and finally high
dried.
Second Example: 10 parts of sulphate of codeine and 6-6 parts of saccharinate of
barium are separately dissolved in 50 parts of water and the two boiling solutions are
mixed; the exact saturation is completed as above described, the mixture is filtered
and evaporated to dryness with caution. The residue constitutes the saccharinate of
codeine.
B. By double decomposition with very soluble salts of saccharine: 50 parts of
sulphate of hydrazine and 76 parts of the salt of ammonium of saccharine are dis-
solved in 1000 parts of boiling water; by cooling the combination crystallizes.
C. By the employment of appropriate solvents: 180 parts of saccharine and 90
parts of pyridine are dissolved in 400 parts of warm alcohol at 95°; the combination
is immediately effected and crystallizes on cooling.
D. By the direct action of saccharine upon organic bases, other than the alkaloids
properly called, in aqueous solutions or in other solvents: 183 parts of saccharine and
188 parts of antipyrin are dissolved in the smallest possible quantity of boiling water;
by cooling the saccharinate of antipyrin crystallizes with almost quantitative yield.
By these processes the communicators have already prepared and studied the
following bodies which have neither hitherto been described nor obtained:
The saccharinate of antipyrin has the form of prismatic crystals, badly defined,
fusible at 145°-150° not very perfectly; 100 parts of water at 18° dissolves
0.56 parts; at 37° 0.74 and at 100° about 25 parts; very soluble in alcohol especially
when hot; slightly soluble when warm in benzene, chloroform and ether.
The saccharinate of pyramidon which crystallizes in acetic ether in large prismatic
crystals, very soluble in water, alcohol and chloroform, fusible at 125°.
The saccharinate of orthoforme which melts at 215° soluble to 3 per cent. in boiling
water, 100 parts water at 22° dissolves 0.35 parts; very soluble in warm alcohol,
slightly soluble in ether, insoluble in chloroform even when warm.
The saccharinate of amido-antipyrin, fine white needles melting at 140° then
solidifying to again remelt at 210°; very soluble in boiling water, in warm alcohol.
Insoluble in ether.
The saccharinate of pyridine; prismatic crystals very soluble in water which dis-
solves of it about its own weight; very soluble in alcohol, slightly so in chloroform.
Melting point 132°.
The saccharinate of phenetidine, fine crystals fusible at from 90° to 100° very
soluble in boiling water 9 per cent. at 20°, very soluble in warm alcohol, less so in
chloroform.
The saccharinate of anisidine; small crystals fusible at 151°, very little soluble in
water.
The saccharinate of piperazine, prisms fusible at 237°, water dissolves 8 per cent.
of it at 20°, very little soluble in alcohol even when boiling.
The saccharinate of hydrazine melts at 212°, soluble to 4 per cent. in water at 100°,
very soluble in alcohol.
The saccharinate of quinoline melts at 132°, soluble to 5 per cent. in cold
water.
The saccharinate of strychnine; small prismatic crystals melting at 240° by
decomposing; very slightly soluble in water, alcohol, and ether.

page_text: The saccharinate of caffeine, long needles fusible at 185° to 190°, very soluble in
alcohol, slightly so in water etc., etc.
All these products can be employed in industry as antiseptics and antiferments.
The temperatures herein mentioned are all of the Centigrade scale.
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 :-
The process of manufacture of combinations in which the anhydride of benzoic
orthosulphamide plays the part of an acid; this acid being combined with the
different organic bodies having a basic function, which processes are based on
the following reactions ;
1st. Action of saccharinate of barium on organic sulphates.
2nd Double decomposition of the alkaline saccharinates and specially of the
saccharinate of ammonium with the salts of organic bases.
3rd. Action of saccharine on the bases, without addition of water, in presence of
appropriate solvents.
4th. For organic bases other than the alkaloids, direct action of saccharine upon the
base in presence of water or any other solvent.
HARRIS & MILLS,
23, Southampton Buildings, London, W.C., Agents.