AT287710B - Process for the preparation of substituted 3-amino-sydnonimines and their salts - Google Patents

Description

  

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  Process for the preparation of substituted 3-amino-sydnonimines and their salts
The invention relates to a process for the preparation of substituted 3-amino-sydnonimines of the general formula
 EMI1.1
 
 EMI1.2
 

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 formula
 EMI2.1
 where Ri.

   Rz and Ra have the meaning given above, OR6 is the residue of an alcohol R OH and X is a halogen atom, is reacted with a nitrosating agent and the nitroso compound of the general formula thus obtained
 EMI2.2
 
 EMI2.3
 

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    1 to Rs and R6 perchloric acid; also organic acids, such as formic acid, acetic acid, propionic acid, oxalic acid, succinic acid, tartaric acid, citric acid, maleic acid, ascorbic acid, salicylic acid, methanesulfonic acid or toluenesulfonic acid.



   The compounds of general formula II used as starting materials are obtained by processes known per se, for example by reacting a disubstituted hydrazine salt with hydrocyanic acid and an aldehyde and then etherifying the Mannich base obtained in this way by means of an alcohol under the action of a hydrogen halide.



   The following examples are intended to explain the invention in greater detail without, however, restricting it: Example 1: 3-Dimethylaminosydnonimine.



   30 ml of water and 15 ml of concentrated hydrochloric acid are added to 12 g (0.2 mol) of 1,1-dimethylhydrazine with cooling. The mixture is cooled to 50 ° C. in an ice bath and a solution of 13 g (0.2 mol) of potassium cyanide in 26 ml of water is added over the course of 30 minutes. In the course of a further hour, 15 ml (0.2 mol) of a 40 part formaldehyde solution are added at the same temperature. The mixture is stirred for 1 hour, brought to room temperature and stirred for a further hour, then the solution is acidified (PH 3 to 4) in order to destroy unreacted potassium cyanide.



  After alkalization with an excess of sodium hydroxide solution, the Mannich base is extracted with chloroform, the chloroform solution is dried over sodium sulphate and the solvent is removed at low temperatures. The remaining liquid is dissolved in 50 ml of methanol and acidified by introducing gaseous hydrogen chloride. After the addition of ether, the hydrochloride of the Mannich base of melting point 129 to 1320 ° C. is obtained in a yield of 7710 d. Th.



   13.6 g (0.1 mol) of the hydrochloride of the Mannich base are added to 30 ml of chloroform and 23 ml of absolute ethanol. At a temperature of -50 ° C., 3.6 g (0.1 mol) of gaseous hydrogen chloride are passed in with stirring. After standing overnight at 40C, the hydrochloride of the imino ether is separated out by adding ether.



   Yield: 21 g (= 966 lu of theory).



   10.9 g (0.05 mol) of the imino ether hydrochloride of the formula
 EMI3.1
 are suspended in 50 ml of dimethylformamide and slowly added 3 ml of a 6.5m-nitrosyl chloride solution in acetic anhydride with stirring at a temperature of 5 C. The mixture is stirred at 100 ° C. for 1 hour and then poured into 300 ml of methanolic hydrochloric acid. The resulting solution is concentrated in vacuo at 30 ° C. to give a resin which is chromatographed on silica.

   The desired end product is obtained after elution with 10 to 2 rP / o methanol in benzene; Recrystallized from methanol / ether, 3-dimethylaminosydnonimine hydrochloride of melting point 178 ° to 1800 ° C. (decomposition) is obtained in a yield of 4.5 g (= 55% of theory).



    Example 2: 3-Diallylamino-4-ethyl-sydnonimine.



   0 ml of 4N hydrochloric acid are added at 100 ° C. to a solution of 35 g (0.31 mol) of 1,1-diallylhydrazine in 100 ml of water. The mixture is cooled to 50 ° C. in an ice bath and a solution of 26 g (0.4 mol) of potassium cyanide in 50 ml of water is added over the course of 30 minutes. The temperature is kept at i C and 23.3 g (0.4 mol) of propionaldehyde are added in the course of a further 40 minutes. The mixture is stirred for 1 hour, brought to room temperature and stirred for an additional hour. The solution is then acidified (pH 3 to 4) in order to destroy unreacted potassium cyanide.

   After alkalization with an excess of sodium hydroxide solution, the Mannich base is extracted with chloroform, the chloroform solution is dried over sodium sulfate and the solvent is removed at room temperature.



  The remaining Mannich base is distilled in vacuo at 95 to 105 C / 1 to 2 mm Hg; Excerpts: 53 g (= 940/0 d. Th.).



     17.9 g (0.1 mol) of the Mannich base are dissolved in 30 ml of chloroform and 23 ml of ethanol. 7.3 g (0.3 mol) of gaseous hydrogen chloride are passed in at -50C with stirring and the mixture is left to stand at -100C overnight. Then the solvent is removed in vacuo and the

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 oily imino ether hydrochloride of the formula
 EMI4.1
 dissolved in 100 ml of dimethylformamide. 6.55 g (0.1 mol) are added to this solution while stirring at 50C
Nitrosyl chloride, dissolved in 14 ml of acetic anhydride, slowly added dropwise. The mixture is stirred at 100 ° C. for 1 hour and then poured into 300 ml of methanolic hydrochloric acid.

   The resulting solution is im
Concentrated in vacuo at 30 ° C. and the remaining resin is chromatographed on silica. After elution with 10 to 20% methanol in benzene, 3-diallylamino-4-ethylsydnonimine hydrochloride with a melting point of 94 to 960C (decomp.) Is obtained in a yield of 15.7 g (= 640/0 of theory) .).



    PATENT CLAIMS:
1. Process for the preparation of substituted 3-aminosydnonimines of the general formula
 EMI4.2
 

** WARNING ** End of DESC field may overlap beginning of CLMS **.

 

Claims (1)

EMI4.3 EMI4.4 <Desc / Clms Page number 5> where Rl'1) and Ra have the abovementioned meaning, or the radical of an alcohol R6OH and X are a halogen atom, are reacted with a nitrosating agent and the nitroso compound of the general formula thus obtained EMI5.1 EMI5.2 Formula I (R4 = hydrogen) converted, if desired, converted into an acid addition salt in a manner known per se and / or acylated at the nitrogen atom 6 with the introduction of the R CO group. 2. The method according to claim 1, characterized in that the nitrosating agent used is nitrosyl chloride. EMI5.3 a hydrohalic acid or an acid anhydride is used. Publications that the patent office has considered to differentiate the subject matter of the application from the state of the art: Bulletin officiel de la Propriété FR-PS 1 496 056 No. 39 of September 29, 1967