DE380578C - Process for the preparation of sulfur-containing compounds of aminonaphthalene and aminooxynaphthalene sulfo acids - Google Patents

Description

Process for the preparation of sulfur-containing derivatives of aminonaphthalene and Aminooxynaphthalene sulfonic acids. As is well known, sulfuric sulfur is extreme against water sensitive. Just the humidity of the air causes the yellow liquid cloudy in a few moments with excretion of sulfur. By exposure Hydrochloric acid, sulfur and sulphurous acid are formed quickly from water, the latter being the latter probably from hypothetical acid that was initially formed H2 S @ O., the chloride of which is sulfur chloride, emerges (cf. G in e 1 i n - K r a u t, Handbook of Inorganic Chemistry, Volume I / II [igo9], Page i 9o to 1C91.

Experiments have shown that the above implementation, ure of the sulfur chloride just as quickly occurs when one is at normal temperature or even at o ° pure sulfur chloride in a thin stream in strongly stirred aqueous solutions of Lets flow in alkali acetates or salts of other organic acids.

It was therefore unforeseeable and completely surprising that the above-described decomposition of sulfuric chloride does not take place when one uses sulfuric chloride to the aqueous solutions or suspensions of the salts of aminonaphthlialinsulfonic acids can act in the presence of alkali acetate.

Under such circumstances, completely new types of sulfur are created in the core Compounds that are both valuable starting materials for different dye syntheses Kind as well as capable of physiological application.

The reaction between sulfur chloride and aminonaphthalene sulfonates i visibly passes through several stages, which are both in their constitution as quinoid, colored and as uncolored benzoid @ e compounds as well as partly in their sulfur content differ from each other. The first reaction product is relatively unstable and gradually turns into a more stable intermediate product on prolonged digestion over, which in turn by alkalis and strong acids at elevated temperature, mostly with partial elimination of the absorbed sulfur into a third product which is the last and most stable stage of the process. This Final product is obtained in either a quinoid or leuco form.

The salts of aminooxynaphthalenesulfonic acids can also be dissolved in water Solution or suspension with sulfur chloride Presence of alkali acetates Convert into sulfur-containing compounds by saponification with acids or Alkalis are converted into lower-sulfur products.

In order to get to technically usable connections, it is not necessary to carry out the mentioned treatment with acids or alkalis in the heat, but one can also pass through the intermediate bodies that were initially created as such Fill in with mineral acids. Connections are thus obtained that contain all of the imported sulfur still chemically bound.

Particularly high-sulfur `` compounds can be produced if sulphurisation is carried out at a low temperature with the use of larger amounts of sulfuric chloride along with the equivalent amount of acetate. In this way one arrives at water-soluble ones Sulfur compounds up to a content of more than 5o percent sulfur, which the sulfur when heated, especially in neutral and alkaline solutions, in part in elemental, often colloidal form, partly as weak, volatile acid.

Example i.

2: 1.5 parts of i-ainonaphthalene-4-sulfonic acid sodium and 27.2 parts crystallized sodium acetate is dissolved in 300 parts of water. In the 14 to 15 parts of sulfur chloride are gradually added to the solution with rapid stirring let flow in a thin stream. The solution thus obtained is left for a few hours stand in mild heat, turning the color bright purple-brown. Then it will be entered so much soda until the liquid reacts permanently alkaline, and the Temperature increases until the gradually deposited sulfur does not increase. It is filtered, acidified with hydrochloric acid and common salt is added until it is complete Precipitation too. When dried, the acid forms a gray powder that is sparingly soluble in water, which still contains molecular sulfur added and is very easy in the air oxidized. If it is boiled in water with access to air, it gradually goes into Solution, the liquid turning deep bottle green, finally blue-green. the The oxidation that has occurred here is easily brought to an end by chromic acid, and one thus obtains a cornflower blue compound that is perfectly permanent and both reduced to the poorly soluble leuco body by alkaline and acidic reducing agents which in turn can be easily oxidized to the blue quinone.

The analyzes of pure leucoic acid and pure quinoid acid result for the former N = 454 percent, S == 22.9 percent, for the oxidation product N - 4.23 percent, S - 21.22 percent. These numbers correspond to; or approximately one Ratio of i atom N to 2 atoms S.

Similar products are obtained from 4er i-Ainins® -naphthalene-5-monosulfonic acid (Laurent). EXAMPLE 22.3 parts of a mixture of i-aminoriaphthalene-6- and 7-monosulfonic acid (Cleve) are suspended in zoo parts of water and converted into the sodium salt with soda. Then 30 parts of crystallized sodium acetate are stirred in. 15 parts of chlorofluoric acid are allowed to flow into the sodium salt suspension obtained, with stirring. This gives an olive-brown solution which is immediately made clearly acidic to Congo finite hydrochloric acid and boiled for some time, then soda is added until an alkaline reaction is achieved and the sulfur which has separated out is filtered off while hot. It is now made Congo sour again and felled with table salt. The dried acid is a bright green powder. which is easily soluble in water. With HvIrosulfit and alkali, an orange-colored solution is created, from which cotton is dyed in reseda green, soapy tones.

The green acid can be diazotized as well as with diazo bodies combine, but in both cases only a part reacts in this sense, so that a mixture of isomeric bodies is presumably present here.

Analysis of the pure acid gives N- .I, 43 percent, S _ 31.86 percent, for C, o H7 0, NS, calculated: N _-_: 1., 65 percent, S - 31.88 percent. Example 3. 2.2.3 parts of 2-minonaphthalene-6-sulfonic acid are dissolved in 500 parts of hot water with the addition of 5.3 parts of soda and converted into a suspension of the sodium salt by cooling. After addition of 27.2 parts of crystallized sodium acetate, 2.5 parts of sulfuric chloride are introduced. 100 parts of normal sodium hydroxide solution are now added and then 7.5 parts of sulfuric chloride are added: the mixture is stirred for a few hours at gentle heat, then made alkaline with soda, heated to the boil, the sulfur that has separated out is filtered off and the deep yellow-brown solution is precipitated with salt . The dried, light yellow compound is easily soluble in water and can be vetted with hydrosulphite, zinc dust or sodium sulphide. The compound is not uniform, but can be broken down by suitable treatment into a colorless, low-sulfur body and a strongly yellow-colored, sulfur-rich body.

The analysis of the sodium salt of the colorless compound gives: N = 4.97 percent, S - 17.4o percent, Na - 8.6 percent, for CZO H14 0s hT. S3 Na, calculated: N-5.07 percent, S - 17.39 percent, Na - 8.33 percent. For the sodium salt of the yellow quinoid acid was found: N-4.71 percent, S ._-_ 20.86 percent, calculated for Clo Ha O, NS-Na: N -4.56 percent, S - 20, 84 percent.

An analogous product is 2-aminonaphthalene-7-monosulfonic acid F. Example 4.

24 parts of 2-amino-8-oxynaphthalene-6-sulfonic acid are suspended in about 300 parts of water and converted into the sodium salt with the necessary amount of soda. After 28 parts of sodium acetate have been added, 8 parts of chlorofluoric acid are allowed to flow in at normal temperature with stirring, a solution of 4 parts of aza-soda in water is then added, followed by another 8 parts of chlorofluoric acid. The result is a bottle-green solution and only a negligible excretion of sulfur. After adding 8 parts of concentrated hydrochloric acid, the mixture is stirred at moderate heat for a few hours, the sulfur is filtered off, saturated with salt and the deep emerald green solution is precipitated cold by adding concentrated hydrochloric acid. The dried compound pressed out is a dark gray palver which dissolves easily in water, ir 2, # 'atrium acetate or cold soda solution with an emerald green color. The compound contains 2 atoms of sulfur for every 1 atom of nitrogen (found: 18.76 percent S, 4.32 percent N) and has the character of a double compound in that, by suitable treatment, it turns into a crystallized azure-blue quinone, which is found for 1 atom of nitrogen Contains 3 atoms of sulfur and can be broken down into 2-amino-8-oxynaphthalene-6-sulfonic acid. Both the blue quinone and the green double compound are converted back into the starting material by heating them with alkalis, splitting off the sulfur introduced. Example 5. 30 parts of the acidic sodium salt of i-amino-8-oxynaphthalene-4,6-disulfonic acid are dissolved in 300 to 400 parts of water and the amount of alkali necessary for conversion into the disodium salt. After 30 parts of sodium acetate have been added, 15 to 16 parts of chlorofluoride are allowed to flow into the clear solution with stirring at ordinary temperature. The mixture is stirred for some time at a moderately elevated temperature and then saponified by boiling the solution which has been rendered acetic or alkaline, the sulfur that has separated out is filtered off, acidified with hydrochloric acid and salted out. Acid saponification gives a gray-green product, and more alkaline saponification a yellow-green product. These two compounds do not show any significant differences, dissolve easily in water, in concentrated sulfuric acid with a deep blue-green color, do not give a diazo compound with nitrous acid, but combine with diazo bodies smoothly to form bluer dyes than the unsulfurized aminooxynaphthalene sulfonic acid. The products contain a little more than 2 atoms of sulfur for every 1 atom of nitrogen (found: 16.75 percent S, 3.20 percent N).

You can refrain from saponification; a deposition of the intermediate product but proves to be unsuitable because of its high solubility. It leaves Neither does its saponification product @diazotize in the usual way, but one can .the solution directly with diazo compounds in the usual way. D.iazobenzene produces z. B. a red-blue, easily soluble azo dye, while As is well known, only one red color is obtained with unsulphurized aminooxynaphfalinsulphonic acid. Example 6. The violet-brown acetic acid solution of the sulfurized solution obtained according to Example i i-aminonaphthalene-4-sulfonic acid is, instead of neutralizing with soda, of minor Impurities filtered off; then precipitated cold with 32 parts of concentrated hydrochloric acid. The pressed precipitate is dried. A brown-violet powder is obtained, which is clearly soluble in cold soda solution, but separates sulfur when cooked in .the leuco acid described in Example i passes. From .this and he there In the blue-green acid described above, the compound is distinguished by its sulfur content. After appropriate purification by flowing around it, it shows a nitrogen content of 4.75 percent, a sulfur content of 28.29 percent, these. Numbers - correspond a ratio of 1 atom of nitrogen to 2.5 atoms of sulfur.

The brown-purple compound dissolves in concentrated sulfuric acid with a deep red-violet color. Example 7. The olive-brown obtained according to Example 2 Solution of the sulfurized i-aminonaghthalene-6- (7-) monosulfonic acid is filtered, cooled in ice water and stirred with so much concentrated hydrochloric acid until the Intermediate product is completely deposited. It is pressed, dried and preserved pale earth-brown powder, that easily in water and also in cold water Soda is clearly soluble. It can be diazotized; by boiling with soda or caustic soda it works: with the separation of some loosely bound sulfur into a green product above. It is converted into the green product of Example 2 by boiling in acidic solution transferred, whereby some sulfur is also split off. The earth brown product dissolves in concentrated sulfuric acid with violet-red, the green acid with blue color.

The sulfur content of the brown intermediate body is a little higher than that of the green compound described in Example 2. However, the difference seems to be here to be derived only from a little adsorbed colloidal sulfur, which occurs during boiling coagulates. The intermediate body shows after appropriate cleaning by dissolving a nitrogen content of 4.48 percent, a sulfur content of 32.5 percent. These numbers correspond to a ratio of 1 atom of nitrogen to 3.2 atoms of sulfur.

The same applies to the example with regard to diazotizability and combinability 2 said. Example B.

That according to Example 3 from 2-aminonaphthalene-6-monosulfonic acid sodium The clear solution obtained is stirred for a few hours at 50 to 60 ° and filtered off from impurities. One cools down and falls with more concentrated Hydrochloric acid or salt out. The product is a green-gray to green powder, which dissolve in water and can be precipitated again unchanged by mineral acids.

The intermediates of the I, 5-, 1,8- and 2, j-aminonaphthalene monosulfosites can be isolated in an analogous manner. Example g. 170.5 parts of sodium 1-aminonaphthalene-4-sulfosate and 28o parts of sodium acetate are dissolved in 1500 parts of water. While stirring, 135 parts of chlorofluoric acid are gradually added in a thin stream at 0 ° to 5 °. The clear orange-brown solution is carefully neutralized with caustic soda or soda and the new compound is carrion-salted. The sodium salt is dried at a low temperature and can be converted into the more stable free acid by dissolving it in water and precipitating it with hydrochloric acid. The purified compound contains approximately 42 percent sulfur and 3.6 percent nitrogen. So there are 5 atoms of sulfur for every 1 atom of nitrogen. Example io.

In the orange-brown solution of the doubly sulphurised aminonaphthalene @ 4-sulphonic acid obtained according to Example g, 28o parts of sodium acetate are recently dissolved and 135 parts of chlorofluoride are allowed to flow in under the same working conditions. The solution has remained clear and has hardly changed its color. Sodium hydroxide solution is now carefully allowed to flow in until it is neutral and it is cooled well. Here, the sodium salt of the new compound is completely eliminated. It is dried at low temperature. so it dissolves again clearly in lukewarm water. It contains one I atom of nitrogen. 8.5 atoms of sulfur. When the free acid is dissolved and precipitated, some sulfur is easily split off, and the ratio of nitrogen to sulfur drops to 1: 8. The purified acid contains 54.4 percent sulfur and 3 percent nitrogen.

By repeated dissolving, sulfur is gradually split off, so that compounds can be obtained both by sulfurization and by degradation, in which the ratio of nitrogen to sulfur I: 5.5, I: 6, i: 6.5, I: 7, I : 7.5 consists. 'Just like i-aminonaphthalene-4-sulfonic acid, the others can Aminonaphthalinonosulfonic acids are sulfurized. For example differs the fourfold sulfurized I-aminonaphthalene-5-sulfonic acid of S the sulfurized one I aminonaphthalene-4-sulfonic acid only because of its greater solubility.

Claims (1)

PATENT-AxSPRTCIIR: I. Process for the preparation of sulfur-containing Descendants of the aminonaphthalene and aminooxvnaphthalene sulfonic acids, characterized in that that sulfur chloride is added to aqueous solutions or suspensions of the salts of aminonaphthalene or aminooxynaphthalene sulfonic acids in the presence of alkali acetates and the intermediate products formed, optionally with acids or alkalis treated at elevated temperature. Embodiment: the method of claim I therein consisting of the intermediates initially obtained as such by precipitation with: separates mineral acids in solid form. 3. embodiment of the method according to Claims i and 2, consist of 1 that one on I 1vlol. Aminonaphthalene sulfonic acid allows more than 1 mole of sulfur chloride to act at, low temperature.