DE1961864A1 - 1,2,5-thiadiazole 1,1-dioxides - Google Patents

Abstract

1,1-dioxides Title cpds. of the formula (where X is NH or O and R is an opt. substd. aliphatic or araliphatic residues) useful as plastics additives and as intermediates for plant-protection agents are prepd. by reacting a 3-R-6-NHR-1,4,3,5-oxathiadiazin-2(3H)-one with HCN in the presence of a catalyst (pref. NaCN or dimethylsulphoxide) and optionally hydrolysing the resulting product in which X is NH.

Description

Derivatives of l-thia-2.5-diazole-1,1-dioxide.

The invention relates to new derivatives of l-thia-2,5-diazole-l, l-dioxide, the 4-amino-2, 3-dihydro-1-thia-2-diazole-1-dioxide as derivatives in the tautomeric forms respectively.

4-imino-tetrahydro-l-thia-? , 5-diazole-1-dioxide may be present and a method for their production.

The structure of the new compounds is given by the tautomeric formulas in which X is NH or 0 and R is an optionally substituted aliphatic or araliphatic radical.

Only the first of the two is specified below Formulations made use of what, however, should only be understood as an abbreviation is because each of the new compounds in both tautomeric forms or as a mixture both of which can exist.

The new compounds are obtained by adding compounds of the general formula in which R stands for an optionally substituted aliphatic or araliphatic radical, is reacted with hydrogen cyanide in the presence of catalysts and the imino derivative formed is optionally saponified.

Depending on whether the imino group HN = C- of the primarily resulting product is saponified in a manner known per se, a compound is obtained as the end product with X = NH or X = 0.

The procedure is explained using the following example: It shows that, surprisingly, carbon dioxide is split off and the hydrogen cyanide is incorporated with the formation of a five-membered ring.

Among aliphatic radicals, alkyl radicals with 1 to 24 are preferred 1 to 12 carbon atoms, alkenyl radicals with 2 to 18, preferably 2 to 6 carbon atoms as well as cycloalkyl radicals with preferably 5 or 6 carbon atoms in the ring system to understand.

The araliphatic radicals contain 1 to 4 in the aliphatic part, preferably 1 or 2 carbon atoms and up to 14 carbon atoms in the aromatic part (preferably the phenyl radical).

As substituents of the abovementioned aliphatic radicals and im aromatic part of the araliphatic radical are halogens (preferably fluorine, Chlorine, bromine), lower alkoxyl and carbalkoxyl groups, preferably with 1 to 4 carbon atoms, called.

The starting compounds used for the process can be obtained according to our own proposal by N-carbonyl-sulfamidsäurehaWgenide with isocyanates in a molar ratio of 1: 2 in the presence of halides of the elements the 1st to 4th subgroup or the IV. or V.

Main group of the periodic table or of substances that are at least partially converted into such halides in the reaction mixture, optionally in the presence of a solvent at temperatures between -70 ° and +700, and the resulting adducts of the general formula in which R has the meaning given above and Hal stands for halogen, according to a further proposal of our own, reacted with carboxamides or dimethyl sulfoxide or water or mixtures thereof.

Exemplary representatives of starting compounds include the following R radicals: methyl, ethyl, l-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl-propyl- ( 1), 2-methyl-propyl- (2), 2-fluoro-ethyl- (1), 2-chloro-ethyl- (1), 2-bromo-ethyl- (1), 6-chloro-hexyl- (l), 3-methoxy-propyl- (1), 3-butoxy-propyl- (l), carbethoxymethyl, l-dodecyl, l-hexadecyl, l-tetracosyl, allyl, octadecen- (9) -yl- (l), cyclopentyl, Cyclohexyl, benzyl, 4-chloro-benzyl, 2-phenyl-ethyl- (1), 3-phenyl-propyl- (1), 4-phenyl-butyl- (l)., Naphthyl- (1 ') -methyl, 4'-bromo-naphthyl- (1') -methyl, 2-naphthyl- (2 ') -ethyl- (1).

As catalysts for the process of the invention can be alkaline reactive substances or dimethyl sulfoxide are used; Alkaline substances in this sense are oxides, hydroxides, carbonates, cyanides, carboxylic acid salts and other alkaline salts of the alkali or alkaline earth metals and ammonia or organic bases such as amines, quaternary bases or amidines or their alkaline reactive compounds.

Examples include: potassium hydroxide, sodium cyanide, calcium acetate, Calcium oxide, triethylamine, pyridine, picolines, quinoline, N, N-dimethylbenzylamine, Benzyltrimethylammonium hydroxide and 1,5-diaza-bicyclo-Z, 3,27-nonene (5).

The amounts of catalyst can be varied widely. So can it catalytically active dimethyl sulfoxide as a solvent in the implementation of the Process serve, while when using sodium cyanide less than O, OlWew.%, based on the total mixture, sufficient to ensure that the implementation proceeds quickly to effect. In general, the catalyst or mixtures thereof are used in amounts of 0.01 to 1, preferably 0.05 to 0.2% by weight.

The process is carried out by using the heterocyclic starting compounds optionally mixed with hydrogen cyanide in the presence of a solvent and adds one of the catalysts mentioned.

The reaction is generally exothermic. It will be in the field from -50 ° to +1500, preferably between 0 ° and 700C.

If, through adequate cooling, hydrogen cyanide escapes is prevented, the use of positive pressure can be dispensed with.

The reactants can be used in stoichiometric amounts find, but the hydrogen cyanide can also be used in excess.

Practically all of them are non-acidic to carry out the process Solvents usable, such as hydrocarbons optionally substituted by halogen, Ether, - ketones, esters, hydrogen cyanide, nitriles, sulfoxides, sulfones, sulfonic acid esters and carbonamides.

Acetonitrile is particularly preferred.

The reaction products are generally good crystallizing compounds, which can easily be isolated by conventional methods. The primarily preserved Imino compounds (X = NH) work with dilute aqueous mineral acids on heating smoothly into the keto compounds (I = O) Uber.

They can be used as plastic auxiliary products as well as for the manufacture of pesticides Find use.

In the following examples, the temperature data relate to OC Example 1: 48.3 g (0.25 mol) of the compound were partially dissolved in 250 ml of acetonitrile with the addition of 15 ml of hydrogen cyanide. 0.5 g of sodium cyanide were added at 0 °. The strongly exothermic reaction, which set in immediately with the elimination of CO 2, was moderated by decomposition to such an extent that the temperature did not exceed 450. As soon as the reaction had ended, the mixture was evaporated to dryness at 12 torr and crystallized from 500 ml of ethyl acetate. 27.8 g (63%) of the compound were obtained the saponification product by heating with 2N hydrochloric acid with a yield of over 90% transforms.

The same result is achieved if you throw the implementation instead of using it Sodium cyanide catalyzed by the following substances: Potassium carbonate Sodium hydroxide Calcium acetate, triethylamine, pyridine, quinoline, benzyltrimethylammonium hydroxide and 1,5-diazabicyclo- [4,3,0] -nonen- (5).

Example 2.

The following compounds of the formula were made analogously to Example 1 manufactured: X = NH X = 0 R m.p. yield Fp. Yield C2H5 1560 70, '1740 83,' n-C3H7 75 ° 46% 101 ° 99% n-C4Hg 700 59% 930 86% Example 3: 4 g of the compound were heated to 450 with 10 ml of dimethyl sulfoxide and 1 ml of hydrogen cyanide until the elimination of carbon digxide was complete.

Then everything was distilled off at 50.degree. 3 g of the dried crystals gave 2.2 g of the compound recrystallized from 50 ml of acetonitrile 1.7 g of this substance, after boiling for ten minutes with 20 ml of 2N hydrochloric acid and 20 ml of n-butanol, gave 1.6 g of the compound on cooling Melting point after crystallization from acetonitrile 1050.

The starting compounds used for the process were obtained as follows: a) A mixture of 425 g (3 mol) of N-carbonyl sulfamic acid chloride and 342 g (6 mol) of methyl isocyanate was admixed with 3 ml of SnCl4 and cooled at 20 - 300 held. After 12 hours, the mass, which had solidified in the meantime, was finely ground with ice-cold ethyl acetate, filtered off with suction and dried. There were 632 (82,) of the adduct received from F. 106-1080.

127.8 (0.5 mol) of this compound were added in finely powdered form to 100 ml of formamide with stirring, the rate of addition being such that the mixture was heated to 700. Finally, the mixture was kept at 60-700 for a further 5 minutes by supplying heat. After adding 500 ml of ice water, the mixture was stirred at 0 ° for about 15 minutes, filtered off with suction and recrystallized from 300 ml of methanol. 64.8 g (67%) of the compound were obtained from melting point 1530.

b) A mixture of 28.3 g (0.2 mol) of N-carbonyl sulfamic acid chloride, 107.0 g (0.4 mol) of hexadecyl isocyanate and 0.3 ml of SnC14 was left to stand at 20-30. Crystallization occurred spontaneously after 5 days. The resulting adduct of the formula melted after crystallization from petroleum ether at 51-520.

14.8 g of this compound were dissolved in 30 ml of acetone, and a mixture of 2.5 ml of formamide and 2.5 ml of water was added. The spontaneously crystallizing product of the formula weighed 12.8 g (95%) after washing with acetone and drying. The melting point rose from 830 to 910 as a result of recrystallization from acetone. The other starting compounds used for the process (characteristic band in the IR spectrum at 1650 cm1) can also be obtained in an analogous manner.

Claims (6)

Patent claims: 1. Derivatives of l-thia-2,5-diazole-l, l-dioxide of the formula in which X stands for NH or 0 and R stands for an optionally substituted aliphatic or araliphatic radical. 2. Compounds according to claim 1, wherein R is an alkyl radical with 1 to 24 carbon atoms. 3. Process for the preparation of derivatives of l-thia-2,5-diazole-l, 1-dioxide, characterized in that compounds of the general formula in which R stands for an optionally substituted aliphatic or araliphatic radical, is reacted with hydrogen cyanide in the presence of catalysts and the imino derivative formed is optionally saponified. 4. The method according to claim 3, characterized in that as Catalysts oxides, hydroxides, carbonates, cyanides, carboxylic acid or other alkaline reacting salts of the alkali or alkaline earth metals or Ammonia, amines, quaternary bases, amidines or their alkaline reacting compounds used. 5. The method according to claim 3, characterized in that as Catalysts used sodium cyanide or dimethyl sulfoxide. 6. The method according to claim 3, characterized in that the Implementation in the presence of a non-acidic solvent. 7-. The method according to claim 6, characterized in that as Solvent acetonitrile used.