DE1145623B - Process for the preparation of hydrohalides and sulfates of 1-alkyl- or 1-aralkyl-substituted 2-imino-imidazolidines and 2-imino-hexahydropyrimidines - Google Patents

Description

Process for the preparation of hydrohalides and sulfates of 1-alkyl- or 1-aralkyl-substituted 2-imino-imidazolidines and 2-imino-hexahydropyrimidines The invention relates to a process for the preparation of hydrohalides and sulfates of 1-alkyl- or 1-aralkyl- substituted 2-imino-imidazolidines and 2-imino-hexahydropyrimidines of the general formula 1: where A denotes an aliphatic radical connected to the nitrogen atoms by a "B or a, carbon atoms or a cycloaliphytic radical connected by a, jB carbon atoms and R denotes a lipophilic group of 10 to 16 carbon atoms or an araliphatic group containing such a radical, characterized in that the hydrohalide or sulfate of a guanidine compound of the general formula II: where the symbols R and A have the above meaning, optionally heated to 120 to 150 ° C. in the presence of amyl alcohol.

In the general formulas I and II, R preferably denotes one Dodecyl or tetradecyl radical or an araliphatic group containing such a group Remainder, e.g. B. a (4'-dodecyl) benzyl radical.

The following radicals are examples of A in formulas I and II in question: alkylene radicals such as 1,2-ethylene, 1,2-propylene, 1,2- or 2,3-butylene, 1,3-propylene, 2-methyl-1, 3-propylene radicals and cycloalkylene radicals, such as 1,2-cyclopentylene or 1,2-cyclohexylene radicals, and their homologous derivatives.

By heating the salt of the guanidine compound of the general Formula II at 120 to 150 ° C takes place with elimination of ammonia, the ring closure to corresponding salt of the 2-imino-1, 3-di-N-heterocycle.

As a polar organic solvent with a boiling point above 110 ° C, in which the reaction is optionally carried out, can be, for. B. amyl alcohol use.

By adding equivalent amounts of strong alkalis, e.g. B. sodium or Potassium alcoholate, the salt of the 2-imino-1, 3-di-N-heterocycle is obtained free Base of the formula I. However, it is advantageous to use the heterocyclic nitrogen compounds of formula I in the form of their salts, e.g. B. in the form of their hydrochloride to store and to use.

The guanidine compounds used as starting materials of the general Formula II is obtained z. B. according to the method of German patent specification 1 107 215 by reacting a diamino compound of the formula R-NH-A-NH2 wherein R and A are above Is important with an S-alkyl or S-aralkylisothiourea. The guanidine compounds need in the synthesis of the heterocyclic nitrogen compounds of the formula II not to be isolated.

The heterocyclic nitrogen compounds which can be prepared according to the invention are colorless to slightly colored, crystalline to waxy, lightfast Substances that are soluble in water in the form of their salts with acids. The connections are valuable biocidal agents, which are characterized by a wide range of effects and good bactericidal properties Distinguish effect. They are also algicidal.

It is from the published documents of the German patent application F 14175 IVb / 12p known, 2-imino-imidazolidines, which in the 1-position is an alkyl or. Wear cycloalkyl radical by reacting corresponding N-monosubstituted ethylenediamines with a cyanogen halide in the presence of a solvent. The designated However, the process shows a new way to prepare 2-imino-imidazolidines, which avoids the use of cyanogen chloride, which is difficult to handle. Furthermore it was Surprisingly, that by heating from the guanidine compounds easily and in good Yield the heterocycles are formed.

Further details can be found in the following examples. In these examples, the parts are understood to be parts by weight. Parts by weight relate to parts of volume like kilograms to liters.

Example 1 1-decyl-2-imino-imidazolidine hydrochloride 55.5 parts of FB-decylaminoethylguanidine hydrochloride are heated to 130 to 135 ° C. for 1 hour in a preheated flask. Then the product is dissolved in 200 parts by volume of hot ethyl acetate. The hot solution is filtered and cooled to -10 ° C. Crude l-decyl-2-imino-imidazolidine hydrochloride crystallizes out and is filtered off. A colorless crystal powder with a melting point of 93 to 95 ° C. is obtained in a yield of 47 parts (90% of theory). Another recrystallization from ethyl acetate gives a purer product with a melting point of 101 to 103 ° C.

Example 2 l-Dodecyl-2-imino-imidazolidine-hydroiodide 79.6 parts of # -dodecylaminoethylguanidine hydroiodide are heated to 120 to 130 ° C. for 1 hour. After recrystallization from 100 parts by volume of ethyl acetate, l-dodecyl-2-imino-imidazolidine-hydroiodide is obtained as a white crystalline mass with a melting point of 89 to 90 ° C.

The yield is 61 parts, corresponding to 80% of theory.

Example 3 l-Dodecyl-2-imino-imidazolidine sulfate , B-Dodecylaminoäthylguanidinsulfat, prepared by heating 45.6 parts of N-dodecyl-1,2-diamino ethane and 27.8 parts of S-methyl isothiourea sulfate in 50 parts by volume of methyl alcohol and evaporation of the methyl alcohol, is with 50 parts by volume of n-amyl alcohol added, heated to 140 to 150 ° C for 4 hours while distilling off the solvent. The residue is then evaporated to dryness in vacuo, dissolved in methyl alcohol, decolorized with animal charcoal and the solvent removed again in vacuo, the N-dodecyl-2-imino-imidazolidine sulfate being obtained. This represents a waxy mass. It is obtained in a yield of 57 parts, corresponding to 94.5% of theory.

Analysis: Found ..... SO4 ion 15.2%, N 14.06%; calculated..... SO4 ion 15.9%, N 13.9%.

Example 4 1-Dodecyl-2-imino-4,5-tetramethylene-imidazolidine hydroiodide 13.2 parts of S-methylisothiourea hydroiodide are introduced into the solution of 17.1 parts of N-dodecyl-1,2-diamino-cyclohexane in 50 parts by volume of methyl alcohol at room temperature. After one hour, the methyl alcohol is distilled off from the 2-dodecylaminocyclohexylguanidine hydroiodide formed and the residue is stirred at 140 to 150 ° C. for 2 hours. It is now dissolved in 70 parts by volume of hot ethyl acetate and filtered for purification. After cooling to -10 ° C., 19.5 parts of 1-dodecyl-2-imino-4,5-tetramethylene-imidazolidine-hydroiodide crystallize out in a theoretical yield of 72%. These are triturated, washed with a little petroleum ether and dried. M.p. 92 to 93 ° C.

Example 5 1-Tetradecyl-2-ixnino-imidazolidine hydrochloride 67 parts of ß-tetradecylaminoethylguanidine hydrochloride are introduced into 10 parts by volume of hot n-amyl alcohol and heated to 130 to 140 ° C. for 1 hour.

The reaction product obtained with elimination of ammonia is now dissolved in 200 parts by volume of hot ethyl acetate. Crystallize on cooling to -10 ° C 58 parts of l-tetradecyl-2-imino-imidazolidine hydrochloride with a melting point of 150 to 152 ° C in a yield of 91.5%. When recrystallizing again Ethyl acetate gives a purer product with a melting point of 158 to 159 ° C.

Example 6 1-Dodecyl-2-imino-hexahydropyrimidine hydrochloride 64 parts of γ-dodecylaminopropylguanidine hydrochloride are heated to 140 to 150 ° C. for 3 hours. The reaction product is then dissolved in 200 parts by volume of hot ethyl acetate, filtered for purification and the solution cooled to -15 ° C., whereupon 1-dodecyl-2-imino-hexahydropyrimidine hydrochloride is obtained in colorless crystals. The yield is 71% of theory. After recrystallizing twice from ethyl acetate, the substance melts at 58 to 59 ° C.

Example 7 1-Dodecylbenzyl-2-imino-imidazolidine hydroiodide 30.52 parts of S-methylisothiourea hydroiodide are introduced into the solution of 44.52 parts of N- (4'-dodecylbenzyl) -1,2-diaminoethane in 100 parts by volume of methyl alcohol. The mixture is stirred for 3 hours at room temperature and then for 5 hours at boiling temperature. The solvent is distilled off from the resulting methyl alcoholic solution of p-dodecylbenzylaminoethylguanidine hydroiodide and the residue is heated to 130 to 140 ° C. for 2 hours. It is dissolved in 75 parts by volume of benzene. The solution is filtered and 300 parts by volume of petroleum ether are added, 1- (4t-dodecylbenzyl) -2-imino-imidazolidine-hydroiodide being obtained as a waxy mass. The yield is 57 parts, corresponding to 86.5% of theory.

Example 8 1-Dodecvl-2-imino-imidazolidine hydrochloride 61 parts of dodecylaminoethylguanidine hydrochloride are heated to 125 to 130 ° C. for 1 hour, ammonia escaping; the reaction product is dissolved in 700 parts by volume of hot ethyl acetate and filtered for purification. After cooling to -10 ° C., the l-dodecyl-2-imino-imidazolidine hydrochloride crystallizes out. It is filtered off, washed with a little ethyl acetate and dried. A product with a melting point of 110 to 113 ° C. is obtained in a yield of 52 parts, corresponding to 90 ° C. of theory.

After repeated recrystallization from ethyl acetate, the purer one melts Product at 119 to 120 ° C.

Claims (1)

PATENT CLAIM: Process for the preparation of hydrohalides and sulfates of 1-alkyl- or 1-aralkyl-substituted 2-imino-imidazolidines and 2-imino-hexahydropyrimidines of the general formula I: in which A denotes an aliphatic radical connected to the nitrogen atoms through os, β or o;, γ carbon atoms or a cycloaliphatic radical connected through os, β carbon atoms and R denotes a lipophilic group of 10 to 16 carbon atoms or an araliphatic group containing such a radical , characterized in that the hydrohalide or sulfate of a guanidine compound of the general formula II where the symbols R and A have the above meaning, optionally heated to 120 to 150 ° C. in the presence of amyl alcohol. Considered publications: German Auslegeschrift F 14175 IVb / 12p (announced on November 29, 1956).