DE2210882A1 - 4,5-bis-trifluoromethylimino-2-subst-thiazolidines - prepn - using n,n'-bis-trifluoromethyl-1,1,2,2-tetrafluoroethylenedia - Google Patents

Abstract

thiazolidines with pesticidal properties are produced by reacting cpds of formula (I): (where Z is a gp. R-N= or R1R2C=, and R, R1, R2 and R3 are H, is not >8C alkyl, alken2 and R3 are H, is not >8C alkyl, alkenyl or alkynyl opt. subst. by halogen, CN or lower alkylthio or alkoxy, opt. lower alkyl-substd. cycloalkyl, carbalkoxy, (is not >14C aryl)-(is not >2C alkyl) opt. subst. in the aryl residue by halogen, CN, NO2, lower alkyl, haloalkyl, lower alkoxy or lower alkylthio, or 5- to 7-membered heterocyclyl, or Z can be linked with the N-atom of the thiazolidine ring to form an additional 5- to 7-membered ring (the heterocycles opt. being fused with an opt. partially hydrogenated benzene ring and opt. substd. by halogen, CN, NO2 or lower alkyl)) with the cpd. CF3-NH-CF2-CF2-NH-CF3 in the presence of an HF-acceptor (pref. an alkali fluoride) at -50 to +100 degrees C.

Description

Special process for the preparation of 4,5-bis-trifluoromethylimino derivatives of thiazolidines The subject of the main application (German patent application P 20 62 348.7) is a chemically peculiar process for the preparation of new 4,5-bis-trifluoromethylimino derivatives of thiazolidines by reacting reactive isomeric forms of thiocarboxamide or uhiourea derivatives of the formula in which Z for the group RN = and the group and R, R ', R "and R"' stand for hydrogen, alkyl, alkenyl and alkynyl with up to 8 carbon atoms, it being possible for these groups to be substituted by halogen, cyano, lower alkoxy and alkylmercapto groups, furthermore for optionally lower alkyl-substituted cycloalkyl, then for carb = alkoxy etehen, also for aralkyl with up to 2 carbon atoms in the alkyl part and for aryl with up to 14 carbon atoms in the ring system, the aryl radicals optionally replaced by halogen, cyano, nitro, lower alkyl and haloalkyl , lower alkoxy and alkyl mercapto can be substituted, furthermore for 5- to 7-membered heterocycles or for those radicals which can connect Z to the N atom of the thiazolidine ring to form a further 5- to 7-membered ring (where the Heterocycles can also be fused to a benzene ring, which can optionally also be partially hydrogenated; in addition, the heterocycles can be substituted by halogen, cyano, nitr o and lower alkyl), with perfluoro-2,5-diazahexa-2,4-diene of the formula in the presence of a hydrogen fluoride acceptor in the temperature range between -50 and + 1200C. The 4,5-bis-tri = fluoromethylimino derivatives of thiazolidines obtained are distinguished by a good fungicidal, insecticidal and acaricidal action.

In a further embodiment of this process, it has now been found that the 4,5-bis-trifluoromethylimino derivatives of thiazolidines are obtained in a particularly advantageous manner if the thiocarboxamide or thiourine derivatives of the formula (I) with N, N'-his- (trifluoromethyl) -tetrafluoroethylene-1,2-diamine of the formula in the presence of a hydrogen fluoride acceptor in the temperature range between -50 and + 100 ° C.

It is surprising that the compounds expected above of the formula (I) with N, N'-bis (trifluoromethyl) tetrafluoroethylene-1,2-diamine of the formula (III) the 4,5-bis-trifluoromethylimino derivatives in a single reaction with a satisfactory yield of thiazolidines.

It was not to be expected that the diamine of the formula (iii) in the presence of mild hydrogen fluoride acceptors, such as. B. sodium fluoride, already at room temperature or below with prior elimination of hydrogen fluoride enters into a ring closure reaction with compounds of type (I).

As can be seen from the literature (German Offenlegungsschrift 2 013 433), temperatures are required for such rapid hydrogen fluoride elimination required in the range of 50 to 700C. Even with corresponding implementations in this Temperature range above 500C, in which hydrofluoric acid is quickly split off, was not to be expected that the bisamine (III) after successive elimination of hydrogen fluoride reacted uniformly in the manner described, without being known in the literature with itself Way to cyclize intramolecularly (J. Amer. Chem. Soc. 89, 5007 (1967)).

Finding this reaction was a technical advance achieved, since the diamine of the formula (III) is more readily available than the perfluoro-2,5-diazahexa-2,4-diene of formula (II).

If you use N, N'-diphenyl-thiourea (which reacts in its thiol form) and N, N'-bis (trifluoromethyl) -tetra = fluoroethylene-1,2-diamine as starting materials and sodium = fluoride as acid binding agent, so the course of the reaction can be represented by the following equation: The thiocarboxamide or thiocarboxamide to be used as starting materials. Thiourea derivatives are generally defined in their isomeric form by the above formula (1). In this formula, Z preferably stands for the group RN = and the group the radicals R, R ', R "and R" are preferably hydrogen, alkyl and alkenyl each having up to 6 carbon atoms, the latter two groups preferably being substituted by fluorine, chlorine, bromine and / or alkylmercapto groups, furthermore preferably for cyciopentyl and cyclohexyl, for carbomethoxy and carboethoxy, furthermore preferably for benzyl, for aryl with up to 10 carbon atoms in the ring system, the aromatic rings preferably by fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, isopropyl, chloromethyl, trifluoromethyl , Methoxy and methylmercapto can be substituted, further preferably for 5- and 6-membered heterocycles and preferably for those radicals which can connect Z to the N atom of the thiazole ring to form a 5- to ó-ring, the heterocycles preferably with can be fused to a benzene ring, which can be partially hydrogenated.

The thiocarboxamide or thiocarboxamide to be used as starting materials. Thiourea derivatives (which react from the general, isomeric formula (I)) are for the most part known and can be represented in a manner well known in the art; you get it z. B., when reacting thiocarbonic acid halides with ammonia or primary amines; many Thiourine = substance derivatives are also in a known manner from primary amines and Mustard oils can be represented. The following mustard oils are mentioned: methyl mustard oil, ethyl mustard oil, Butyl mustard oil, phenyl = mustard oil, p-chlorophenyl mustard oil.

The N, S'-bis (trifluoro = methyl) tetrafluoroethylene-1,2-diamine to be used as the starting material the formula (III) is known (cf. German Offenlegungsschrift 2 013 435).

All diluents include all inert organic solvents in question. These preferably include water-containing fluids, such as gasoline; also benzene, Toluene; Nitriles, such as aceto = nitrile; chlorinated hydrocarbons, such as. B. methylene = chloride, chloroform and chlorobenzene, ketones such as acetone.

All customary acid binders can be used as acid binders. May be mentioned alkali carbonates, alkali bicarbonates, tertiary amines, such as triethylamine, Dimethylaniline. Hydrogen fluoride acceptors to be used with preference in practice In particular, the alkali fluorides have proven, with sodium fluoride in particular is to be called.

The reaction temperatures can be varied within a relatively wide range will. In general one works between -50 and + 1000C, preferably between -30 and + 800C.

To carry out the process according to the invention, 1 is used Moles of the compound according to formula (I) t moles of N, N1-bis- (trifluoromethyl) tetrafluoroethylene-1,2-diamine of formula (III), the alkali fluoride is used in excess (about 5 to 7 mol), but the specified proportions can be exceeded or fallen short of made by up to 20 percent by weight without significantly lowering the yield will. It is expedient to leave the N, N'-bis (trifluoromethyl) tetrafluoroethylene-1,2-diamine to a suspension consisting of starting material, organic solvent and Hydrogen fluoride acceptor, drop. The fluoride is then filtered off and concentrated and recrystallizes. Another way of working up is that one water is added to the filtrate and the resulting residue is recrystallized if necessary.

As mentioned, the 4,5-bis-trifluoromethylimino derivatives which can be prepared according to the invention have of thiazolidines has pesticidal properties and can be used as pesticides Find. One possible application as an acaricide can be found in the following example of use emerged.

Example A Tetranychus test Solvent: 3 parts by weight of dimethylformamide Emulsifier: 1 part by weight of alkylaryl polyglycol ether Active ingredient formulation Mix 1 part by weight of active ingredient with the specified amount Solvent containing the specified amount of emulsifier and dilutes the concentrate with quantity, on the desired concentration.

With the active ingredient preparation, Mehrer rivers @@ haseolus vulgaris), which have a height of about @ um, sprayed dripping wet. This bean plant is strong infested with all stages of development of the common game (Tetranychus urticae).

After the specified times, the effectiveness of the active ingredient preparation w @@ determined by counting the dead animals. The degree of destruction thus obtained becomes given in%.

100% means that all spider mites have been killed, C% means that no spider mites have been killed.

Active ingredients, active ingredient concentrations, escape times n The results are shown in the following table: Table (plant-damaging mites) Tetranychus test Active ingredient Degree of active ingredient concentration in% after in, '8 days CH c) p-CH = NCU-NH-CHJ 0.2 100 CH3 -C \ J- * I-CH U 0.020.2 0 3 1 0.02 0 (known) N-CF3 0.2 100 RLN-CF3 0.02 100 0.002 98 Production examples Example 1: To 23 g (0.1 mol of N, N'-diphenylthiourea and 25 g (0.595 mol) of sodium fluoride in 100 ml of acetone, 27 g (0.1 mol) of N, N'-bis (trifluoromethyl) tetrafluoroethylene-1, 2-diamine is added dropwise with cooling at 0 ° C. The mixture is stirred for one hour at room temperature, the sodium fluoride and sodium hydrogen fluoride are filtered off and the filtrate is poured into one liter of ice water. The residue obtained is filtered off and recrystallized from methanol / water Melts at 118-119 ° C; the yield is 85% of theory.

Example 2: Analogously to Example 1, 30 g of the above compound are obtained with N-phenyl-N'-methylthiourea with a melting point of 168 ° -169 ° C. Yield: 78% of theory.

Claims (3)

Patent claims: Process for the preparation of 4,5-bis-trifluoromethylimino derivatives of thiazolidines, characterized in that thiocarboxamide or thiourea derivatives are used in their reactive, isomeric form of the formula in which Z for the group RN = and the group and R, R ', R "and R"' stand for hydrogen, alkyl, alkenyl and alkynyl with up to 8 carbon atoms, it being possible for these groups to be substituted by halogen, cyano, lower alkoxy and alkylmercapto groups, furthermore for optionally lower = alkyl-substituted cycloalkyl, then for carbalkoxy, also for aralkyl with up to 2 carbon atoms in the alkyl part and for aryl with up to 14 carbon atoms in the ring system, the aryl radicals optionally being replaced by halogen, cyano, nitro, lower alkyl and halogen alkyl, lower alkoxy and alkyl mercapto can be substituted, furthermore for 5- to 7-membered heterocycles or for those radicals which can connect Z to the N atom of the thiazolidine ring to form a further 5- to 7-membered ring (where the heterocycles can also be fused to a benzene ring, which can optionally also be partially hydriart, in addition, the heterocycles can be substituted by halogen, cyano, nitro and d lower alkyl), with N, N'-bis (trifluoromethyl) tetrafluoroethylene-1,2-diamine of the formula in the presence of a hydrogen fluoride acceptor in the temperature range between -50 and + 100 ° C. 2) Method according to claim 1, characterized in that A3 is used as the hydrogen fluoride acceptor an alkali fluoride is used. 3) Process according to claims 2 and 3, characterized in that Sodium fluorine is used as the hydrogen fluoride acceptor.