DE2210882B2 - Special process for the preparation of 43-bis-trifluoromethylimino derivatives of thiazolidines - Google Patents

Description

N— '

R '

I = NCF ₃

in which

Z for the group R-N = and the group

10

15th + 100 ⁰ C not with perfluoro-2 £ -diazahexa-2,4-diene, but with N, N'-bis (trifluoromethyl) -tetrafluoroethylene-1,2-diamine of the formula

CF ₂ -NH-CF ₃ CF ₂ -NH-CF ₃

performs

Z Process according to Claim t, characterized in that the hydrogen fluoride acceptor Sodium fluoride used

R '

C =

R '

20th

25th

stands and

R, R ', R "and R'" for hydrogen atoms, alkyl, Alkenyl · and alkynyl groups with up to 8 carbon atoms stand, these groups through Halogen atoms, cyano, lower alkoxy and alkyl mercapto groups can be substituted, also stand for optionally lower alkyl-substituted • ^, ycloalkyl groups, then stand for carbalkoxy groups, furthermore for aralkyl groups with up to 2 carbon atoms in the alkyl wedge and for aryl groups with up to 14 carbon atoms in the ring system stand, the aryl radicals optionally through Halogen atoms, cyano, nitro, lower alkyl and haloalkyl, lower alkoxy * and alkyl mercapto ribs can also be substituted for 5- to 7-membered heterocycles or those radicals which Z with the N »atom of the thiazolidine ring, forming a further 5- to 7-membered ring can connect, wherein the heterocycles can also be fused to a benzene ring, which can optionally also be partially hydrogenated, and the heterocycles can also be substituted by halogen atoms, cyano, nitro and lower alkyl groups,

according to patent 2062348.7-44, thereby marked draws that the implementation of the Thiocarbo./säureamid- or thiourea derivative in the reactive, isomeric form of the general formula

50

S-H

Z = C

Ν — Η

R "'

55

60

wherein Z and R '"have the meanings given above, in the presence of a hydrogen fluoride acceptor in the temperature range between -50 and

65 The subject of the main patent 2062 348.7 is under among other things a chemically unique process for the preparation of new 4,5-bis-triflucrmethyIimino-derivatives of thiazolidines by reaction of reactive isomeric forms of Thiocarbo.nsäureamid- 'or thiourea derivatives of the general formula

S-H

Z = C

Ν —Η

R '"

in which

Z for the group R-N = and the group

R '

C =

R '

stands and

R, R ', R "and R'" represent hydrogen atoms, alkyl, alkenyl and alkynyl groups with up to 8 carbon atoms stand, these groups being replaced by halogen atoms, Cyr ·: -, lower alkoxy and alkylmercapio groups may be substituted, furthermore represent optionally lower alkyl-substituted cycloalkyl groups, then represent carbalkoxy groups, furthermore represent aralkyl groups with up to 2 carbon atoms in the alkyl part and stand for aryl groups with up to 14 carbon atoms in the ring system, the aryl radicals optionally being replaced by halogen atoms, cyano, nitro, lower alkyl and haloalkyl ·, lower alkoxy and alkylnnercapto groups can be substituted, furthermore for 5 · to 7-membered heterocycles or those radicals which Z with the N atom of the thiazolidine ring below Can connect formation of another 5- to 7-ring, the heterocycles also with one Benzene ring can be fused, which can optionally also be partially hydrogenated, in addition, can the heterocycles can be substituted by halogen atoms, cyano, nitro and lower alkyl groups

with PerfIuor-2,5-diazahexa-2,4-diene of the formula

F. \

N-CF ₃

CCF N-CF ₃

OD

10

in the presence of a hydrogen fluoride-acceptor in the temperature range between -50 and +120 ⁰ C. The obtained 4,5-bis-trifluormethyIimino derivatives of thiazolidines are characterized by a good fungicidal, insecticidal and acaricidal activity.

In a further embodiment of this process, it has now been found that the 4,5-bis-trifluoromethylimino derivatives of thiarolidines are particularly advantageous Way then one obtains the thiocarboxamide or thiourea derivatives of the general formula (I) with N, N'-bis (trinuomethyl) -tetrafIuoräthylen-l ^ - diamine derFormula

15th

20th

CF ₂ -NH-CF ₃ CF ₂ -NH-CF ₃

in the presence of a hydrogen fluoride-acceptor in the temperature range jo sntrischen -50 to +100 ⁰ C reacting

SH

/ CF ₂ -NH-CF ₃

-N = C + I + 4NaF

\ CF ₂ -NH-CF ₃

NH

It can be described as surprising that the above-mentioned compounds of the general formula (J) with N, N'-bis (trifluoromethyl) tetrafluoroethylene-U2-diamine of the formula (III) in uniform reaction with give the 4 ^ -bis-trifluoromethylimino derivatives of thiazolidines in a satisfactory yield.

This is because it was not to be expected that the diamine of the formula (III) would enter into a ring closure reaction with compounds of type (I) in the presence of mild hydrogen fluoride acceptors, such as, for example, sodium fluoride, even at room temperature or below with prior elimination of hydrogen fluoride can be found in the literature (DE-OS 20 13 433), temperatures in the range from 50 to 70 ^° C. are required for such rapid elimination of hydrogen fluoride. Even with corresponding reactions in this temperature range above 50 ^° C., in which hydrogen fluoride is eliminated rapidly take place, it was not to be expected that the bisamine (III) would react uniformly in the manner described after successive elimination of hydrogen fluoride, without intramolecularly cyclizing with itself in a manner known from the literature (J. Amen formerly Soc. 89, 5007 [1967]) . By discovering this reaction, a technical advance was achieved, since the diamine of the formula (III) is more easily obtainable than the perfluoro ^^ - diazahexa - ^ - diene of the formula (ff).

If Ν, Ν'-diphenyl-thiourea (the one in its thiol form reacts) and N, N'-bis (trifluoromethyl) tetrafluoroethylene-1,2-diamine as starting materials and sodium fluoride as. Acid binder, so can the The reaction sequence can be represented by the following equation:

4NaHF ₂

I = N-CF ₃

The thiocarboxamide or thiourea derivatives to be used as starting materials are in their isomeric form is generally defined by the above formula (1). In this formula, Z stands for Group R-N = · and the group

R '

C =

R '

the radicals R, R ', R "and R'" preferably represent hydrogen atoms, alkyl and alkenyl groups each with up to 6 carbon atoms, the latter two groups preferably being substituted by fluorine, chlorine, bromine atoms and / or alkyl mercapto groups can, also preferably for cyclopentyl and cyclohexyl groups, for carbomethoxy and carboethoxy groups, also preferably for benzyl groups, for aryl groups with up to 10 carbon atoms in the ring system, the aromatic rings preferably se by fluorine, chlorine, bromine atoms, cyano, nitro, Methyl, ethyl, isoprcpyl, chloromethyl, trifluoron-; - ethyl, methoxy and methylmercapto groups can be substituted, furthermore preferably for 5- and ögüedrige heterocycles and preferably for such

Rests that Z with the N atom of the thiazole ring below Can connect formation of a 5- to 6-ring, whereby

the heterocycles preferably with a benzene ring can be fused, which can be partially hydrogenated.

The thiocarbons to be used as starting materials

acid amide or thiourea derivatives (derived from the general, isomeric general formula (I) react), are for the most part known and can in general are represented in a known manner; you get it z. B, if thiocarbonic acid halides are mixed with ammo reacts niak or primary amines; many thiourea derivatives are also made in a known manner primary amines and mustard oils. The following mustard oils are mentioned: methyl mustard oil, ethyl mustard oil, Butyl mustard oil, phenyl mustard oil, p-chlorophenyl mustard oil.

The N, N'-bis (trifluoromethyl) tetrafluoroethylene-1,2-diamine of the formula to be used as starting material (III) is known (cf. DE-OS 20 13 435). All inert organic

see solvents in question, this preferably includes Hydrocarbons such as gasoline; also benzene, toluene; Nitriles such as acetonitrile; chlorinated hydrocarbons, such as B, methylene chloride, chloroform and chlorobenzene, ketones, such as. B. acetone.

All customary hydrogen fluoride acceptors can be used Acid binders can be used. Alkali carbonates, alkali bicarbonates, tertiary amines such as triethylamine, dimethylaailine. Hydrogen fluoride acceptors to be used with preference in practice In particular, the alkali fluorides have proven, with sodium fluoride being mentioned in particular '

The reaction temperatures can be varied over a wide range. Is carried out between -50 and +100 ⁰ C, preferably between -30 and +80 ⁰ C.

To carry out the process according to the invention, 1 mol of the compound of the formula is used

10

15th

(I) I moles of N, N'-bis (trifluoromethyl) tetrafluoroethylene-1,2-diamine of formula (III), the alkali fluoride is in excess is used (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. The N, N'-bis (trifluoromethyl) -tetrafiuoräthylen-1,2-diamine is expediently allowed to form one Suspension, consisting of starting material, organic solvent and hydrogen fluoride acceptor, drops. The fluoride is then filtered off, concentrated and recrystallized. Another way of working up consists in adding water to the filtrate and optionally recrystallizing the resulting residue.

As mentioned, have those that can be represented according to the invention 4,5-bis-trifluoromethylimino derivatives of thiazolidines pesticidal properties and can be used as pesticides.

Preparation examples Example N-CF ₃

N-CF ₃

To 23 g (0.1 mol of Ν, Ν'-diphenylthiourea and 25 g (0495 mol) of sodium fluoride in 100 ml of acetone, 27 g (0.1 mol) of N, N'-bis (trifluoromethyl) tetrafluoroethylene-1, 2-diamine at 0 ⁰ C under cooling zugetropfL mixture is left for one hour at room temperature, stirred, filtered from sodium fluoride and sodium hydrogen fluoride, and ei the filtrate is stirred in a liter of ice water: the thus arising residue is abfillriert and recrystallized from methanol / Wassev the product is recrystallized. Melts at 118-119 ° C. The yield is 85% of theory.

Example

N-CF ₃

CH ₃ -

Analogously to Example 1, with N-phenyl-N'-methylt '"iourea 30 g of the above compound of mp .: 168-169 ° G Yield: 78% of theory.

Claims (1)

Patent claims: 1. Process for the preparation of 4,5-bis-trifluoromethylimino derivatives of thiazolidines of the general s my formula S-I = NCF. Z = C