DE115410C

DE115410C -

Info

Publication number: DE115410C
Application number: DENDAT115410D
Authority: DE

Description

KAISERLICHESIMPERIAL

PATENTAMT.PATENT OFFICE.

Die in Patent 106961 beschriebene p-Dinitrostilben-o-disulfosä'ure verhält sich bei der Einwirkung oxydirender Agentien verschieden, je nach dem Oxydationsmittel, welches hierbei zur Verwendung gelangt. Läfst man z. B. Chromsäure auf die Dinitrostilbendisulfosäure einwirken, so wird letztere zu Carbonsäuren oxydirt und weiterhin völlig zerstört. Dagegen ist es möglich, durch vorsichtige Einwirkung von in neutraler oder schwach alkalischer Lösung wirkenden Oxydationsmitteln, wie Permanganaten oder unterchlorigsauren Salzen, ausgehend von der Dinitrostilbendisulfosäure, zu einem Körper zu gelangen, der alle Eigenschaften eines aromatischen Aldehyds besitzt und wahrscheinlich p-Nitro-o-sulfobenzaldehyd ist.The p-dinitrostilbene-o-disulfonic acid described in patent 106961 It behaves differently in the action of oxidizing agents, according to the oxidizing agent which is used comes to use. If you let z. B. chromic acid to dinitrostilbene disulfonic acid act, the latter is oxidized to carboxylic acids and furthermore completely destroyed. Against it it is possible by careful exposure to in neutral or weakly alkaline Solution-acting oxidizing agents, such as permanganates or hypochlorous acid salts, starting from the dinitrostilbene disulfonic acid, to arrive at a body that has all the properties of an aromatic aldehyde and probably p-nitro-o-sulfobenzaldehyde is.

COHCOH

NO₂.NO ₂ .

Dieser Aldehyd ist durch die folgenden Eigenschaften charakterisirt:This aldehyde is characterized by the following properties:

1. Essigsaures Phenylhydrazin fällt aus der wässerigen, mit Natriumacetat versetzten Lösung der Nitroaldehydsulfosäure ein braunrothes flockiges Hydrazon.1. Phenylhydrazine acetic acid precipitates from the aqueous solution to which sodium acetate has been added nitroaldehyde sulfonic acid is a reddish brown, flaky hydrazone.

2. Salzsaures Semicarbazid fällt aus einer solchen Lösung ein in gelben Nädeichen krystallisirendes Semicarbazid.2. Hydrochloric acid semicarbazide precipitates from such a solution something that crystallizes in yellow oaks Semicarbazide.

3. Hydrazinsulfat fällt aus einer solchen Lösung ein in gelben Nadeln krystallisirendes Benzalazin.3. Hydrazine sulphate precipitates from such a solution, which crystallizes in yellow needles Benzalazine.

4. Durch Condensation der Aldehydsulfosäure mit tertiären und secundären aromatischen Aminen entstehen Leukobasen, welche durch Oxydation blaugrüne, alkaliechte Triphenylmethanfarbstoffe liefern.4. By condensation of the aldehyde sulfonic acid with tertiary and secondary aromatic Amines are formed from leuco bases, which oxidize blue-green, alkali-proof triphenylmethane dyes deliver.

5. Die wässerige Lösung der Aldehydsulfosäure reducirt F eh ling'sehe Lösung in der Wärme.5. The aqueous solution of the aldehyde sulfonic acid reduces F eh ling's solution in the Warmth.

Es hat sich ferner ergeben, dafs auch die in den Patenten 38735 und 79241 als Azoxybezw. Dinitrosostilbendisulfosäure beschriebenen Körper, die als Mikadogelb oder Directgelb in den Handel kommen, bei Einwirkung von Chromsäure zerstört werden, hingegen bei vorsichtiger Oxydation mit Permanganaten zu Körpern oxydirt werden, die alle Eigenschaften aromatischer Aldehyde zeigen. Folgende Beispiele mögen das Verfahren näher erläutern.It has also been found that the in patents 38735 and 79241 as Azoxybezw. Dinitrosostilbene disulfonic acid described as Mikado Yellow or Direct Yellow come on the market, be destroyed by the action of chromic acid, but more cautious Oxidation with permanganates can be oxidized to form bodies which show all the properties of aromatic aldehydes. The following examples may explain the procedure in more detail.

Example I.

Zu einer Lösung von 12 kg dinitrostilbendisulfosaurem Natron in 250 1 Wasser, welche durch äufsere Kühlung auf ca. 5 bis 10⁰C. abgekühlt sind, läfst man allmählich unter stetem Rühren eine Lösung von 5 kg Permanganat in 100 1 Wasser einfliefsen. Die vom abgeschiedenen Braunstein durch Filtration getrennte Lösung wird am besten unter Kohlensäureeinleitung zum Trocknen eingedampft und das Natriumsalz des Nitrosulfobenzaldehyds soTo a solution of 12 kg dinitrostilbendisulfosaurem soda in 250 1 of water, which are cooled by outward cooling to about 5 to 10 ⁰ C., one läfst gradually under constant stirring, a solution of 5 Kg einfliefsen permanganate in 100 1 of water. The solution separated from the precipitated manganese dioxide by filtration is best evaporated to dryness while passing in carbonic acid, and so is the sodium salt of nitrosulfobenzaldehyde

Claims

obtained as a pale yellow colored crystalline powder which is extremely easily soluble in water.

In addition, for most technical purposes it is not necessary to separate the aldehyde, the solution that has been freed from the manganese dioxide can be used directly for this purpose.

The same aldehyde is also formed directly - albeit less advantageously - by the oxidation of p-nitrotoluenesulfonic acid by means of excess hypochlorite or hypochlorite. Hypobromite solution, in which case that of dinitrostilbene disulfonic acid precedes its formation. One solves z. B. 12 kg of p-nitrotoluene-o-sulfonic acid sodium in about ten times the amount of water, runs with constant stirring at normal temperature 70 1 of a hypochlorous acid sodium solution, which contains 150 g active NaOCl per liter, increases the temperature to 80 ° and lasts for a few hours; the p-nitro-o-sulfobenzaldehyde can be deposited by salting out.

Example II.

44.2 kg of the product designated as dinitrosostilbene disulfonic acid in patent specification 79241 respectively. of the yellow dye (Mikado yellow) described in Patent 38735 are dissolved in about 500 1 of water and dissolved at a temperature of about 40 ⁰ C. slowly with 20 kg of permanganate oxidizes in 400 1 of water.

The precipitated manganese dioxide is filtered off and the filtrate, which is only faintly colored evaporated to dryness or salted out in weakly acidic solution.

So you get an orange-yellow or. brownish yellow, easily soluble crystalline powder, which shows the above-mentioned reactions like the aldehyde described in Example I. In contrast to the starting material, it has no coloring properties at all more.

The aldehyde sulfonic acids obtained in this way are intended to be used for the preparation of triphenylmethane dyestuffs Find use.

Pa τ f. Nt claims:

ι. Process for the preparation of substituted benzaldehyde - ο - sulfonic acids, consisting of that in the nucleus substituted stilbenodisulfonic acids with in neutral or oxidizing agents with a weak alkaline solution, preferably potassium permanganate, be oxidized.

2. As special embodiments of the reaction marked under 1. a) the Oxidation of dinitrostilbene disulfonic acid to p-nitro-o-sulfobenzaldehyde, b) oxidation in the patents 38735 and 79241 as Azoxy- bezw. Dinitroosstilbene disulfonic acid designated body to aldehydes.