DE188506C - - Google Patents

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'- M 188506 CLASS 12 q. GROUP

CHEMISCHE FABRIK von HEYDEN, AKT.-GES. in RADEBEUL b. DRESDEN.

of o- and p-guaiacol sulfonic acid.

Patented in the German Empire on July 25, 1905.

According to patent specification 109789, class 12, crystallized guaiacol sulfonic acid, namely orthoguayakol sulfonic acid, is obtained when guaiacol is treated with concentrated sulfuric acid while heating to 70 to 80 ° C. and the sulfurization mixture is precipitated with chloralkali. This information has proven to be incorrect. The crystallized product in question is not an acid at all, but a salt. Also, the assumption in that patent specification that only guaiacolorthosulfonic acid is formed in the sulfurization of guaiacol by heating with concentrated sulfuric acid to 70 to 80 ° is how. was found incorrect. Thorough investigations have shown that guaiacol is no exception to the rule, but behaves exactly like any other phenol with free ortho- and para-position when treated with sulfuric acid, namely a mixture when treated with concentrated sulfuric acid at a moderate temperature of ortho- and parasulphonic acid gives disulphonic acid when treated with concentrated sulfuric acid or oleum at elevated temperature. The product resulting from the process of the above patent specification is by no means a pure orthoguajakol sulfonic acid salt, but a mixture of the potassium salts of the two guaiacol sulfonic acids, which is very rich in paracompound.
It was also found that for the preparation of the mixture of guaiacol monosulfonic acids, heating to 70 to -80 ° has no special purpose, and that guaiacol monosulfonic acids, like other phenol monosulfonic acids, can be obtained smoothly by treatment with sulfuric acid at any temperature below 100 °, e.g. B. at 30 to 60 ⁰ C.

Tie mann and Koppe (Ber. D. Chem. Ges., Vol. XIV [1881], pp. 2019/20) report on the formation of two guaiacol sulfonic acids when treating guaiacol with the equivalent amount of sulfuric acid.

A smooth separation of ortho and paraguayacol sulfonic acids (although doubtful is whether the acid formed next to the parasic acid is actually the ortho acid in the following the latter designation is retained for the isomers of the parasic acid. Indeed should not be taken on this question.) by crystallization of the Alkali salts do not succeed because the solubility difference is not sufficient; in the best case succeeds in a part of the poorly soluble guaiacolparasulfosauren salt in the pure state to be deposited. On the other hand, it is easy to separate the two guaiacol sulfonic acids smoothly if you divide them into the basic ones Salts of the alkaline earths, earths or heavy metals transferred. The orthoguajakol sulfonic acid forms easily soluble, the parasic acid poorly soluble or insoluble basic salts

of alkaline earths, alkaline earths and heavy metals. So you can ortho and Separate parasacids by converting them into the salts just mentioned, the insoluble respectively sparingly soluble separated parasalt is usually separated from the orthosalt which remains in solution and the salts thus obtained in a known manner in the free acids BEZW. in their alkali salts ίο implements.

Example i.

The syrupy mixture with a high sulfuric acid content obtained when guaiacol is sulphurised - preferably at 30 to 60 ° C. - which easily solidifies to a crystal cake when standing, is converted in a known manner into the neutral lime salt and then Y _{2 is added to the dark-colored solution of this salt} Molecule Ca O, calculated on the amount of guaiacol, added in the form of a fine milk of lime while stirring. Instead of milk of lime, you can also use the equivalent amount of a mixture of Ca Cl ₂ + NH ₃ in aqueous solution or just ammonia liquid. The dark solution becomes discolored in the process, and considerable masses of colorless, prismatic crystals soon precipitate, which are insoluble in water and represent the basic calcium salt of guaiacol parasulfonic acid. With sulfuric acid it can be converted into free paraguajakol sulfonic acid, with alkali carbonate or bicarbonate it can be converted into paraguajakol sulfonic acid alkali. The salt of orthosulfonic acid remains in solution and can be processed in a known manner on free ortho acid or its alkali metal salts.

Example 2.

The mixture obtained by sulfurizing the guaiacol is converted into the neutral lead salt in a known manner and the boiling solution of the latter is then mixed with Y ₂ molecule Pb O, calculated on the guaiacol used, in the form of lead acetic acid. At the boiling point, only the paravalent compound separates out, while the orthodontic compound remains in solution and only precipitates when it cools down. The lead salts can be converted into free acid or alkali metal salts in a known manner.

The solution of lead acetate, made alkaline with ammonia, gives on the addition of parabezw. orthoguajakolsulfosaurem potassium a white precipitate, which dissolves in the heat of cooking with the orthosalt, with the Para connection remains unchanged.

Guaiacolortho- and -parasulfonic acids and their salts have the following characteristics Reactions:

1. Guaiacolorthosulfonic acid forms a monopotassium salt, which from water during voluntary evaporation in spherical aggregates, on addition of alcohol in fine needles with 2 molecules of crystal water separates out.

Guaiacol parasulfonic acid is a monopotassium salt, which is obtained from water in octahedral Crystals, which can combine to form columnar structures, crystallize out anhydrous.

2. Potassium guaiacolorthosulfonate easily dissolves in water; a solution saturated at 19 ^° C. contains 40 percent of the anhydrous salt.

Guaiacol parasulfonate of potassium is difficult to dissolve in water. A solution saturated at 19 ^° C. contains only 12 percent of the anhydrous salt.

3. Potassium guaiacolorthosulfonate remains completely clear and clear in aqueous solution mixed with ammonia after the addition of Ca CL ₂ , Ba Cl _{2, etc.}

Potassium guaiacol para sulfosate gives a heavy precipitate with the same treatment of basic calcium or barium salts, both of which are colorless and insoluble in water Crystallize prisms.

4. Potassium guaiacolorthosulfonate in an approximately 10% aqueous solution with added a few drops of concentrated nitric acid gradually gives a dark red color. Exercise without deposition of an insoluble nitro product.

Guajakolparasulfosaures potassium gives a precipitate of yellow Dinitroguajakol a melting point of 122 ⁰ at the same treatment C.

5. There are guaiacolorthosulfonic acid, coupled with diazobenzene in an alkaline solution, a brick red dye ,. which in the reduction is a sparingly soluble p-aminoguajakolo-sulfonic acid supplies whose dilute aqueous solution with ferric chloride solution shows a 'golden yellow color.

In the same process, guaiacol parasulfonic acid produces an orange dye, its Reduction to a readily soluble o-aminoguajakol-p-sulfonic acid leads, the dilute aqueous solution of which turns a strong wine-red color with ferric chloride solution.

Reaction 3 and Reaction 4 are best suited for the rapid detection of guaiacol parasulfonic acid Salt or to demonstrate the absence of parasalt and the purity of a guaiacolorthosulfonic acid salt. By means of these reactions it is very easy to demonstrate in the test glass that z. B. the im Allegedly traded orthoguajakol sulfonic acid potassium, called thiocol, very Contains large amounts of the parachute compound.

Compared to the method known from patent specification 109789, class 12 thus the commercial progress of the present process in smooth extraction pure, free from the isomeric p-acid guaiacol-o-sulfonic acid or. their salts, a fact that z. B. for the therapeutic use of guaiacol-o-sulfonic acid from This is important because the p-sulfonic acid is known to have unpleasant side effects (See, for example, Hager's handbook of the Pharm. Praxis. New edition. 4. unchanged. [1905], Vol. L, p. 1257).

Claims (1)

Patent claim:
Process for the decomposition of mixtures of guaiacol-o- and -p-sulfonic acids, characterized in that the free acids or their salt solutions are converted in the usual way into the basic salts of alkaline earths, earths or heavy metals and the insoluble p-salt from the soluble one The o-salt is separated by the customary methods, after which the salts thus obtained can optionally be converted in a known manner into the free acids or their alkali metal salts.