DD275672A1 - PROCESS FOR PREPARING N HIGH 1-ACYL-N HIGH 2-ARYL / ALKYL-N HIGH 3-AMIDOYLGUANIDINES - Google Patents

Abstract

The invention relates to a process for the preparation of N1-acyl-N2-aryl / alkyl-N3-amidoylguanidinen of the general formula I in which R is an aryl, optionally substituted on the phenyl nucleus or polysubstituted aryl group; Hetaryl, or benzothiazol-2-yl group; R 2 is an alkyl or aryl, optionally mono- or polysubstituted or substituted on the phenyl nucleus aryl group or benzothiazol-2-yl group. The aim of the invention is to produce N1-acyl-N2-aryl / alkyl-N3-amidoylguanidine in a simple, economically auspicious way. According to the invention are substituted under simple reaction conditions substituted N1-acyl-N2-aryl / alkyl-S-methyl-isothioureas with substituted Carbonsaeurehydraziden in alcohol, such as. As ethanol reacted. N1-Acyl-N2-aryl / alkyl-N3-amidoylguanidines are important as intermediates for crop protection agents and possible pharmaceuticals. Formula I

Description

Field of application of the invention

The invention relates to a process for the preparation of N'-acyl-N'-aryl / alkyl-N'-amidoylguanidinen of the general formula I in which R is an aryl, optionally substituted on the phenyl nucleus aryl group, hetaryl or 8enzothiazol -? - yl group mean. These compounds are important intermediates for the synthesis of pesticides and possible pharmaceuticals.

It is known that some substituted N-phenyfquanidines and N-acylguanidines, which are insecticidal, fungicidal and bactericidal, can be used as possible pesticides and pesticide intermediates, respectively, and possible intermediates for pharmaceuticals, e.g. the N-phenylguanidine with hypotensive effect, represent.

Characteristic of the known technical solutions

So far, only substituted guanidines, u.a. N-phenyl- and N-acylguanidines are known (compare BRD-patent 2616936 and US-patent 3914306), which are obtained according to known methods by e.g. Cyanamide be reacted with substituted anilines. Furthermore, N-acylguanidines are described (cf. DD-2006186), which are obtained by reacting substituted aryl or hetary amides with carbodiimides. On the basis of isothiocyanates with amines and anilines (compare Angew. Chem. 77.549 (1965) and Chem. Ber. 99.2885 (1966)) and of imide dichlorides with various substituted amines (cf.: Angew. Chem. 77,430 (cf. 1965] and Tetrahedron Letters [1966], 1753) as well as by aminolysis of N-dichloromethylenecarboxylic acid (compare J. Am. Chem. Soc., 34 (1912), 164, Chem. Ber. 100 (1967), 2669) are also guanidines No N'-acyl-N'-aryl / alkyl-N'-amidoyl-guanidines of the general formula I have been described

 This class of substances is accessible on the basis of new starting materials.

Object of the invention

The aim of the invention is to produce N'-acyl-N ² -aryl / alkyl-N ³ -amidoyl-guanidines by economically favorable processes.

Explanation of the essence of the invention

The object of the invention is to prepare N'-acyl-N'-aryl / alkyl-N'-amidoylguanidines by a simple, economically favorable process.

According to the invention, N'-acyl-N'-aryl / alkyl-N'-amidoylguanidines of the general formula (I)

, / N ² HR ² RCN ¹ = C (

J ^ ³ H-NH-CR ¹

in which

R is aryl, optionally substituted on the phenyl nucleus or polysubstituted aryl; Hetaryl ·; Pyrid-2,3,4-yl;

Benzothiazol-2-yl; R ^{1 is} aryl; optionally substituted on the phenyl nucleus or polysubstituted aryl ·; Benzothiazol-2-yl ·; stands,

R ^{2 is} aryl, optionally substituted on the phenyl nucleus once or several times predominantly by halogens substituted aryl group,

Alkyl ·,

prepared by reacting N'-acyl-N'-aryl / alkyl-S-methylisothiohamstoifen of the general formula II, in which R and R ^{2 have} the same meaning as in formula I, with substituted CarbonsSurehydraziden of the general formula III, in which R * has the same meaning as in formula I, in absolute alcohol, like ϊ. B. ethanol heated for about 4-6 hours under reflux, concentrated after cooling and treated with water. The method according to the invention is illustrated by equation 1. By the method according to the invention, for example, the compounds in the embodiments can be produced.

embodiments

example 1

N'-IPyrid ^ -oyD-N'-phenyl-N'-phenylamidoyl-guanidinoO.OI.MolN'-t-pyrid-Z-oyD-N'-phenyl-s-methyl-isothloharnstoif (for comparison, see. Prakt. Chem. 324 (1982), 629) are abs. In 30ml. Ethanol heated for about 6 hours with 0.015 mol of benzhydrazide at reflux. The solution is then immersed and mixed with a little water. The solid product formed is filtered off and recrystallized from ethanol. Mp: 198-20ΓΟ Yield: 45%

Analysis for C ₃₀ H ₁₇ N ₆ O ₂ (359.2) calc .: C 66.87 H4.73 N 19.49 • χ Found .: C 65.93 H 4.86 N 20.00> IR (KBr ): γNC / C01625, 1570; CONH1680, 1595-NH-3115, 3280Cr ₁ -T ¹

Example 2

N ¹ - (Benzothiazol-2-oyl) -N ² phenyl-N ³ -phenylamldoyl-guanidine as described above from 0.01 mol of N '- (benzothiazol-2-oyD-N'-phenyl-S-met' ^! isothiourea and 0.02 mole of Benhydrazid.

F .: 188-190 ° C Yield: 60% Analysis for Cj ₂ H ₁₇ N ₆ CS (415.2) calc .: C 63.63 H 4.09 N 16.86 S 7.71 Found: C 64 , 10 H 3.99 ν 16.78 S 7.70 IR (KBr): γ CO / NC1630, 1570; CONH1705,1595 NH 3145,3185,3230cm "'.

Example 3

N ¹ - (benzothiazol-2-oyl) -N ² -phenyl-N ³ - (benzothlazol-2-amidoyl) -guanidine as described above from 0.02 mol of N'-f-benzothiazole-o-di-amide at 0.03 mol benzothiazol-2-yl-hydrazide.

M.p .: 210-212 ⁰ C. Yield: 75% Analysis for C ₂₃ H ₁ ČNES ₂ O ₂ (472.2) calc .: C 58.49 H 3.39 N 17.79 S 13.55 Found .: C 58.03 H 3.36 N 18.28 S 12.97 IR (KBr): γ CO / NC 1655.1540; CONH1680,1590; NH 3180,3280,3380cm ~ '.

/ NH-R ²

R-C-N = C (+ rI-c-NH-NH.

I ^ qrn II '

O ^bCH 3 O

I i

-CH, SH

R-C-N = C II

NH-R ²

VIH-NH-C II

-R ¹

, \

Claims (1)

A process for the preparation of N ¹ acyl-N ² -aryl / alkyl-N ³ -amidoylguanidinen of the general formula I in which R is an aryl, optionally substituted on the phenyl nucleus aryl group, hetaryl or benzothiazol-2-ylgrup pe mean , characterized in that substituted ISP-acyl-N'-aryl / alkyl-S-methylisothioureas of the general formula II in which R and R ^{2 have} the same meaning as in formula I, with substituted Carbonsäurehydraziden of the general formula III, in the R ^{1 has} the same meaning as in formula I has been heated in ethanol at reflux and then treated with water. For this 1 page formulas