DE2042660A1 - 5-amino-triazolone derivs - useful as plant - protection agents - Google Patents

Abstract

Title cpds. of formula (I) (where R1 and R2 are aliphatic aromatic or heterocyclic residues, or NR'R2 is a ring system opt. also contg. further hetero atoms, and R3 and R4 are H or aliphatic, aromatic or heterocyclic residues, or one of R3 adn R4 can also be a group COR5, SO2R5, CONHR5 or CSNHR5 in which R5 is H or an aliphatic, aromatic or heterocyclic residue) which are of use as plant-protection agents, are prepd. by reacting R'R2N-C(Hal)=N-CO-OR (where R is an aliphatic, aromatic or heterocyclic residue and Hal is halogen) with R3-NH-NH-R4 at -30 to +100 degrees C (pref. 0-80 degrees C), pref. in an inert diluent.

Description

New 5-amino-triazolone derivatives The invention relates to new 5-amino-1,2,4-triazolone- (3) and a process for their preparation. It has been found that new aminotriazolones are obtained if compounds of the general formula are used in which R, R1 and R2 denote an aliphatic, aromatic or heterocyclic radical and R1 and R2, also both together, together with the N atom, can be part of a ring system which can also contain further heteroatoms, Hal stands for halogen with hydrazine -Derivatives of the general formula R3NH-NHR4 (11) in which R3 and / or R4 represents hydrogen, aliphatic, aromatic or heterocyclic radicals or one of the two radicals represents the groups R / -CO-, R5-So2-, R5NH-Co- or R is NHCS, where 2 'R5 is hydrogen, an aliphatic, aromatic or heterocyclic radical, and is reacted at temperatures from about -30 ° C. to 100 ° C. It is preferably carried out at 0 ° to 80 ° C. and, if appropriate, in the presence of a diluent.

The new compounds obtained according to the invention have the general formula in which R1, R2, R3 and R4 have the meaning given above.

Aliphatic radicals R, R1 to R5 are preferably straight-chain or branched, saturated or unsaturated hydrogen radicals with up to 25 carbon atoms, which can contain up to 2 double or one triple bond, and cycloaliphatic Radicals with 5, 6, 7, 8, 10 or 12 carbon atoms in the ring system; the aliphatic Residues can optionally also be substituted by, for example, aryl (bis to C20 in the ring system, preferably phenyl and naphthyl radical), aroxy (up to 0io im Ring system, preferably chlorine, bromine, alkoxy (C1-C6), nitro, halogen (fluorine, chlorine, , Aryl mercapto (phenyl). Phenyl), alkyl mercapto (C1-C6). Aru;, erca [tp- (phenyl), Cyano, rhodanic, carbon esters - (Cl-C12, aryl to C20 in the ring system), Carbonaiid dialkyl-amino (C1-C8) or acylamino (c1-o6, phenyl) radicals.

The aromatic radicals R, R11, R2, R3, R4 and R5 are aromatic hydrocarbon radicals with up to 20 carbon atoms (preferably with up to 14 carbon atoms), in particular with up to 10 carbon atoms (phenyl, naphthyl radical) in the ring system. The aromatic radicals R1 can also contain bridge members, such as alkylene, cycloalkylene, -O-, -S-, -SO-, -SO2- The aromatic radicals R, R1, R2, R3, R4 and R5 can carry as substituents, for example: alkyl, alkylamino, dialkylamino, alkoxy radicals with up to 12 carbon atoms (Alkyl, each preferably with up to 6 carbon atoms, aryl and aroxy groups (but preferably phenyl, phenoxy), the same halogen (preferably fluorine, chlorine, bromine), -CHO, carbon ester (aliphatic radicals C1-12, preferably C1- 6, phenyl, benzyl), carbonamide, alkylsulfonyl with alkyl C1-12, preferably C1.6, arylaulfonyl, preferably phenylsulfonyl, sulfonic ester (aliphatic radicals Cl ~ 12, preferably C16, phenyl, benzyl), sulfonamide, acyl, (Aliphatic radical C2-12, preferably C2-6, benzoyl), cyano, rhodanide, alkyl mercapto (C1-12, preferably C1-6), Arglwercapto (preferably phenyl) or acylmercapto (aliphatic radical C2 -12, preferably C2-6, benzoyl -) groups and max. 2 102 groups.

Preferred heterocyclic radicals R, R1, R2, R3, R4 and R5 are used 5-, 6- or 7-membered ring systems with one or more heteroatoms such as 0, N or S in the ring system into consideration. R1 and R2 or R3 and R4 together stand for a ring system, which can also contain further heteroatoms, is in particular to 5-, 6- or 7-ring systems such as Piperidine, pipecoline, morpholine, Pyrrolidines, decahydroquinolines, tetrahydroisoquinolines, dodecahydrocarbazole, benzotriazole, Imidazole or hexamethyleneimine thought.

"Halogen" preferably means fluorine, chlorine, bromine.

The components of the used for the process according to the invention Formula I are based on our own proposals from cyanamides and carbonic acid ester halides to obtain.

For example, the cyanamides from the reaction of the cyanamides mentioned in the following list with the carbonic acid derivatives mentioned in the list of carbonic acids and terhalides ”can be added Compounds I obtained are used in the reaction.

List of cyanamides: The amines from the following are used: dimethylamine, diethylamine, di-n (iso) propylamine, di-n- (iso-, tert.) Butylamine, diallylamine, dibenzylamine, methylstearylamine, methylbenzylamine, dicyclohexylamine, N -Methyl-aniline, N-ethyl-aniline, diphenylamine, N-methyl-naphthylamine, piperidine, morpholine, pyrrolidine, tetra- or decahydroquinoline or -isoquinoline, perhydrocarbazole, hexamethyleneimine N, N'-dimethyl-, -ethyl-, -isopropyl -ethylenediamine, -propylenediamine, -hexamethylenediamine, -phenylenediamine, 4,4'-bis- (methylaminisophenyl) -methane, -ethane, -propane, -ether, -thioether, -sulfone, 4,4'-bis- (methylamino) -benzophenone, accordingly according to DBP 1 248 030 available cyanamides.

List of carbonic acid ester halides: As carbonic acid ester halides come for the preparation of (I) into consideration: The fluorides, chlorides, bromides or Iodides, for example, the following carbonic acid esters: carbonic acid methyl ester, ethyl ester, - chloroethyl ester, -dichloroethyl ester, -trichloroethyl ester, -bromoethyl ester, -tribromo ethyl ester, -fluoroethyl ester, -trifluoroethyl ester, -methoxyethyl ester, -phenoxyethyl ester, -o, m, p-methyl-phenoxyethyl ester, -o, m, p-chlorophenoxyethyl ester, -phenylethyl ester, -nitroethyl ester, -cyanethyl ester, -methylmercaptoethyl ester, -acetylpropylester, -propylester, -butylester, -isobutylester, -stearylester, -palmitylester, -oleylester, -einnamylester, -phenylester, -methylphenylester, -chlorophenylester, -di (tri, tetra, penta) -chlorophenylester, -dimethylaminophenylester, -nitrophenylester, -di (tri) -nitrophenylester, -methoxyphenylester -phenoxyphenylester, -acetylphenyl ester, -cyanophenyl ester, -methyl mercaptophenyl ester, -co (a) -naphthyl ester, -pyridyl ester, -chinoyl ester, -benzixidazolyl ester, -benztriazolyl ester, -benzthiazolyl ester.

However, only simple esters such as methyl, ethyl, trichloroethyl, Phenyl-EBter is used because the ester group is split off in the course of the reaction and xomit does not appear in the end product.

Hydrazine derivatives that can be used in the reaction, for example are: hydrazine, methyl, ethyl, n- and isopropyl, n- and iso- and tert-butyl, Octyl, dodecyl, palmityl, stearyl, oleyl, allyl, phenyl, methylphenyl, halophenyl, Di-, tri-, polyhalophenyl-, nitrophenyl-, methoxyphenyl-, methylmereaptophenyl-, Cyanophenyl, naphthyl, pyridyl, quinoyl hydrazine, each of which is N, N'-disubstituted Hydrazines with the substituents just listed, formylhydrazine, acethydrazide, Benzhydrazide, isonicotinic acid hydrazide, methanesulfhydrazide, benzenesulfhydrazide, Semicarbazide, thiosemicarbazide, phenylsemicarbazide, methylsemicarbazide, phenylthiosemicarbazide, methylthiosemicarbazide.

The method according to the invention is illustrated by way of example using the following reaction equations: The reaction can be carried out in such a way that the hydrazine (II) is initially charged in an inert diluent (namely 1 mole per mole of compound I, and 1 mole for the HCl to be captured), and then the compound of the formula I is added. But you can just as well choose the reverse procedure. The reaction is usually very exothermic and is carried out in the cold.

In the case of less reactive components, the mixture can be mixed with one another up to 100 ° C be heated. It is preferably used in the temperature range from about -30 to + 1000C 0 ° to 800 worked. If the hydraein hydrochloride precipitates on its own, it will through Removed suction, the hydrochloride falls, if appropriate after concentration of the solvent together with the end product (III) made, the salt is made by washing with water removed from the mixture.

The preferred diluents are ethers, such as diethyl ether, Dioxane, alcohols such as ethanol, nitriles such as acetonitrile, esters such as ethyl acetate and optionally halogenated or nitrated hydrocarbons such as benzene, toluene, light gasoline, petroleum ether, nitrobenzene, chlorobenzene, methylene chloride, chloroform or carbon tetrachloride is used. Waeser can also be present.

The compounds according to the invention are new and show effectiveness as a pesticide.

Example 1: 15.3 g (0.06 mol) are placed in 50 ml of ether and 50 ml of methylene chloride. At 0, 13 g (0.12 mol) of phenylhydrazine are added dropwise. After stirring at room temperature, distilling off the solvent, stirring the residue with water, filtering off with suction and drying, 12 g (= 86% of the DL) of the crude are obtained which, after recrystallization from alcohol, melts at 176-1770C.

Analysis: C12H16N4O (232) CHNO Calc .: 62.1% 6.9% 24.2% 6.9% Def .: 62.5% 6.9% 24.3% 6.9 ffi was used in Example 1, the from m.p. 230 - 231 ° C analysis: C6H12N40 (156) CHNO calc .: 46.2% 7.7% 35.9 ffi 10.25% def .: 46.4% 7.9% 36.2% 10.3% Methyl hydrazine and after the precipitated methylhydrazine hydrochloride has been filtered off with suction and the filtrate has been concentrated of m.p. 83-84 ° C.

Analysis CgH14N40 (194) CHNO Calc .: 55.7% 7.2% 28.9% 8.3% Found: 55.6% 7.6% 28.8% 8.7% Example 4: Analogously to Example 1, phenylhydrazine and Analysis: C13H14N40 (molar weight, 242) CHNO Calc .: 64.5% 5.8, 23.2% 6.6% Found: 63.5% 6.5% 23.5% 6.8% Example 5 : Analogously to Example 3 is obtained from methylhydrazine and of m.p. 88-89 ° C.

Analysis: C7H14N4O (molar weight 170) CHNO calc .: 49.4% 8.25% 33.0% 9.4% found: 49.6% 8.1 X 33.5% 9.59 'Example 6: 5.2 g (0.02 Mole) are dissolved in 30 ml of methylene chloride and 7 g (0.04 mol) of benzenesulfhydrazide, dissolved in 30 ml of Droxan, are added. After stirring for one day at room temperature, the precipitated hydrochloride of benzene sulfhydrazide (4 g) is filtered off with suction, the mother liquor is concentrated and stirred with ether. This gives 4.8 g (= 89%) des from fp: dec. from 146 ° C analysis: C10H12N4O3S (molar weight 268) CH NOS calc .: 44.8% 4.48% 20.9% 17.9% 11.9% found: 45.2% 4.8% 21, 3% 18.1% 11.4% Example 7: Analogously to Example 2, hydrazine hydrate and the of m.p. 249-250 ° C.

Analysis: C9H10N4O (molar weight 190) CHNO calc .: 56.9% 5.3% 29.4% 8.4% found: 56.9% 5.4% 29.0% 9.2% Example 8: Analogously to Example 2, hydrazine hydrate and the mp 218-219 ° C analysis: C10H12N40 (molar weight 204) CHNO calc .: 58.9% 5.89% 27.45% 7.85% found: 58.7% 5.6% 27.9 % 8.2% Example 9: Analogously to Example 2, hydrazine hydrate and the from fp: dec. from 34000.

Analysis: C6H10N402 (molar weight 170) CHNO Calc .: 42.3% 5.9% 32.94 18.8% Found: 41.3% 6.1% 33.6% 19.7% Example 10: Analogous Example 2 is obtained from and in dioxane that of melting point: 210 - 220 ° C (conversion) Analysis: C13H1, N503 (molar weight 289) CHNO Calc .: 54.0% 5.2% 24.2% 16.6% Found: 53.7% 5, 2% 24.1% 17.3% Example 11: Analogously to Example 2, thiosemicarbazide is obtained, suspended in dioxane and the from melting point: 3300C (dec.) Analysis: C7H11N502S (Malgew. 229) CHNO calc .: 36.7% 4.8, 30.6% 14.0% found: 37.0% 5.4% 29, 6% 14.4% The preparation of the starting compounds used for the process is illustrated by the following example: 39 g (0.4 mol) of diethyl cyanamide and 110 g (0.7 mol) of phenyl chloroformate are heated together at 100 ° for 8 hours. At 80 °, the unreacted starting materials are then distilled off in vacuo (water jet).

The yellow-brown, oily residue (78 g) is distilled in an oil pump vacuum. First of all, there are strong signs of decomposition, which then almost completely stop after the distillation. The distillation gives 64.9 g (= 64% of theory) des as a colorless oil with a bp = 153-1600C / 0.1-0.3 Torr.

Also the other output compounds used for the process can be obtained in an analogous manner.

Claims (4)

P a t e n t a n s p r ü c h e 1. Compounds of the general formula in which R1 and R2 denote an aliphatic, aromatic or heterocyclic radical and it and R auen, together with the N atom, can both be part of a ring system which can also contain further heteroatoms, R3 and / or R4 denote hydrogen, aliphatic or aromatic or heterocyclic radicals or one of the two radicals is the grouping R5C0, R5S02, R5NHCO- or R5NHCS, where R5 is hydrogen, an aliphatic, aromatic or heterocyclic radical. 2. Process for the preparation of new triazolone derivatives, characterized in that compounds of the general formula are used in which R, R1 and R2 denote an aliphatic, aromatic or heterocyclic radical and R1 and R2, together with the N atom, can also both be part of a ring system which can also contain further heteroatoms, with hydrazine derivatives of the general formula R3HN -NHR4 in which R3 and / or R4 is hydrogen, aliphatic, aromatic or heterocyclic radicals or one of the two radicals is the grouping R5-CO-, R-SO2-, RIVHCO- or R5NHCS-, where R5 is hydrogen, an aliphatic , aromatic or heterocyclic radical, at temperatures of about -30 to 1000C. 3. The method according to claim 2, characterized in that one is in the presence of a diluent works. 4. Process according to Claims 2 and 3, characterized in that one works at 0 - 80 ° C.