IMPROVE- MENTS IN THE PROCESS OF MANUFACTURING CHLOROIODIC BASES
Year: 1884

page_text: We EUGEN OSTERMAYER, Doctor of philosophy of Bicberach, Wurttemberg,
German Empire, and' MAX DITTMAR, Doctor of philosophy of Konigsberg, Prussia,
German Empire do hereby declare the nature of the said invention for "IMPROVE-
MENTS IN THE PROCESS OF MANUFACTURING CHLOROIODIC BASES to be as follows:
If Pyridin, Chinolin, Naphtochinolin Anthrachinolin and their homologues in
hydrochloric solutions are treated with a liquid containing Todochloric hydrochlorate,
compounds are obtained which separate in crystals. From concentrated solutions.
of Chinoline the compound separates as a crystalline powder of yellow orange
colour. If this powder is washed with cold water until it appears of the color of
sulphur a substance is obtained which is of the following composition: C, H,
NI Cl and when boiled in a neutral aqueous solution it yields Iodine. Iodochloric
hydrochlorate can be produced either by introducing chlorine into water wherein
Iodine is suspended, or by treating an Iodine compound in hydrochloric acid
solution with an oxydising agent yielding with hydrochloric acid free chlorine in
the presence of Iodine and the salts thereof. In carrying this invention into
practice we advantageously proceed as follows.--5 Kilogram of Iodine are suspended
in four times the quantity of water then chlorine is introduced until the former is
dissolved. The solution of Iodochloric hydrochlorate is brought together with a
hydrochloric acid solution of 5.5 kilo' of Chinolin. The orange-yellow precipitate
thus formed is at once filtered and washed with water until it assumes a bright
sulphur-yellow colour; it is then pressed and further purified. Or 5 Kilogram of
Iodide of potassium are dissolved in 5 K'os of water and 25 k'os of hydrochloric
acid are added. To this solution 4-8 k'os of Nitrite of Sodium are gradually added
until a clear yellow solution is obtained.
When this solution is brought together with a hydrochloric acid solution of
3.85.K'os of Chinolin, a precipitate is formed and further treated in the above
described manner, analogous compounds are obtained when instead of Pyridia and
Chinolin their homologues are used; with the Chinolin both with those which are
alkylised in the benzolradicle alone (for instance Toluchinolin) or in the Pyridin-
radicle alone (for instance Chinaldin) and also with those alkylised in both radicles
simultaneously (for instance Toluchinaldin).,

page_text: Analogous combinations are moreover obtained when chlormethylates of the
above named bases, and also when the Chlormethylates of their Hydrogen and
Oxygen derivatives are employed.
1) 5 K'os of Iodide of Potassa are dissolved in 5 K'os of water and 25 K'os of
bydrochloric acid are added to the solution 4.8 Kilo's of Nitrite of Soda àre
gradually added to this solution and to the clear solution 5.5 K'os of Chinolin-
chlormethylate are added which has previously been dissolved in water. The
yellow precipitate thus formed is further treated as above set forth.
2) To the above mentioned Iodine solution obtained as stated from 5 K'os of
Iodide of potassium an aqueous solution of Tetrahydrochinolinchlormethylate is
added; the precipitate thereby obtained is further treated in an analogous manner
to that already described.
3) To an Iodine solution obtained by the process already described from 5 k'os
of Iodide of Potassa a solution of 6 k'os Oxychinolinchlormethylate is added; the
precipitate is treated analogously to what has been described.
By the reaction of like molecules of the chloriodised bases upon aromatic amines
red, blue and violet colouring matters are obtained.
For instance: 15 k'os Chloriodchinolin are treated to 110° with 13 k'os of
Dimethylanilin until the mass commences to solidify, the fused mass is then dissolved
in alcohol diluted with two volumes of water. From the solution so obtained the
blue-violet colouring matter directly separates in a crystalline state.
The blue-violet colouring matter is not readily soluble in water and directly
colours silk and wool when the alkaline solution of the same is brought into
hot dye-bath.
$
If aromatic Chorides are added at the fusion, say Benzylchloride, blue colouring.
matters result which have a slightly greenish tinge. For instance 15 k'os Chinolin-
.chloriodine are heated to 110° in an oilbath and together with 13 k'os of Dimethyl-
anilin and 6.2 k'os of Benzylchloride until the mass begins to solidify.
The fused material is boiled out with very dilute alcohol and filtered and the
colouring material then cristallizes out. It is not readily soluble in water but
readily in alcohol and directly colours wool and silk to a greenish blue.
Dated 04
P T700

page_text: We, EUGEN OSTERMAYER, Doctor of Philosophy, Bieberach, Würtemberg, and
MAX DITTMAR, Doctor of Philosophy, Königsberg Prussia, both in Germany do
hereby declare the nature of our invention for "IMPROVEMENTS IN THE PROCESS
OF MANUFACTURING CHLOROIODIC BASES "
and in what manner the same is to be
performed, to be particularly described and ascertained in and by the following
statement:
If Pyridine, Chinoline, Naphthochinoline Anthrachinoline and their homologues
in hydrochloric solutions are treated with a liquid containing Iodochloric hydro-
chlorate, compounds are obtained which separate in crystals. From concentrated
solutions of Chinoline the compound separates as a crystalline powder of yellow
orange colour. If this powder is washed with cold water until it appears of the
colour of sulphur, a substance is obtained which is of the following composition:
C, H, N I CI.
and when boiled in a neutral aqueous solution it yields Iodine. Iodochloric hydro-
chlorate can be produced either by introducing Chlorine into water wherein Iodine
is suspended or by treating an Iodine compound in hydrochloric acid solution with
an oxydising agent, or with substances yielding with hydrochloric acid free
Chlorine in the presence of Iodine and the salts thereof.
In carrying this invention, into practice we advantageously proceed as follows:
5 Kilogrammes of Iodine are suspended in four times the quantity of water,
then Chlorine is introduced until the former is dissolved. The solution of Iodo-
chloric hydrochlorate is brought together with a hydrochloric acid solution of
5.2 Ko' of Chinoline. The orange-yellow precipitate thus formed is at once
filtered and washed with water until it assumes a bright sulphur-yellow colour,
it is then pressed and further purified.
Or 5 K of Iodide of potassium are dissolved in 5 K of water and 25 Kº of
Hydrochloric acid are added. To this solution 48 K° of Nitrite of Sodium are
gradually added until a clear yellow solution is obtained. When this solution is
brought together with a hydrochloric acid solution of 3.85 K of Chinoline, a
precipitate is formed and further treated in the above described manner. Analogous
compounds are obtained when instead of Pyridine and Chinoline their homologues
are used; as regards the Chinoline homologues, not only with those which are
alkylised in the benzole radicle alone (for instance Toluchinoline) or in the
Pyridine radicle alone (for instance Chinaldine) but also with those alkylised in
both radicles simultaneously (for instance Toluchinaldine). Analogous combina-
tions or compounds are moreover obtained when Chloro-Methylates of the above-
named bases are used and also when the Chloromethylates of their Hydrogen and
Oxygen derivatives are employed. For instance as follows:
1) 5 K of Potassium Iodide are dissolved in 5 K° of water and 25 K° of
Hydrochloric acid are added; to the solution 4.8 K° of Nitrite of Sodium are
gradually added; to the clear solution 5.5 K" of Chinolinechlormethylato are

page_text: added which have been previously dissolved in water. The yellow precipitate
thus formed is further treated as above set forth.
2) To the above mentioned Iodine solution, obtained as stated from 5 Ko' of
Potassium Iodide, an aqueous solution of 56 Kilo's of Tetrahydrochinoline-
cblormethylate is added; the precipitate thereby obtained is further treated in a
manner analogous to that already described.
3) To an Iodine solution obtained by the process already described from 5 Ko' of
Potassium Iodide a solution of 6 Ko Oxychinolinechlormethylate is added; the
precipitate is treated analogously to what has been described.
By the reaction of like molecules of the chloroiodised bases upon aromatic
Amines, red, blue and violet colouring matters are obtained.
For instance: 15 K° of Chloriodchinoline are heated to 110° with 13 K of
Dimethylaniline until the mass commences to solidify; the fused mass is then
dissolved in Alcohol diluted with two volumes of water. From the solution
so obtained, the blue-violet colouring matter directly separates in a crystalline
state..
The blue violet colouring matter is not readily soluble in water and directly
colours silk and wool when the alkaline solution of the same is brought into the
hot dye-bath.
If, when fusing, aromatic Chlorides are added, say Benzylchloride, blue colouring
matters result which have a slightly greenish tinge. For instance, 15 K° of
Chinolinechloroiodine are heated to 110° in an oilbath together with 13 Ko' of
Dimethylaniline and 62 K of Benzylchloride until the mass begins to solidify.
The fused material is boiled out with very dilute alcohol and filtered and the
colouring material then crystallizes out. It is not readily soluble in water but
readily in alcohol and directly colours wool and silk to a greenish blue...
Having now particularly described and ascertained the nature of the said
invention and in what manner the same is to be performed, we declare that what
we claim is
1. A method of producing chloroiodised bases of Pyridine, Chinoline, Naptho-
chinoline Anthrachinoline and of their homologues and of chloroiodised chloro-
methylates of Chinoline, Pyridine, Tetrahydrochinoline and Oxychinoline by tlie
reaction of Iodochloric Hydrochlorate upon said compounds.
2. A method of manufacturing violet, red and blue colouring materials by the
reaction of Iodochlorised bases of the chinoline group such as Chinoline Iodo-
chloride, Iodochloride of Chinoline Chloro-Methylate, and the like upon aromatic
Amines such as Dimethylaniline, Diphenylamine, Paratoluidine, and the like, with
or without the addition of Benzylchloride or of other aromatic Chlorides.
Dated this 0th day of March 1885