CH620426A5 - Process for the preparation of new asymmetric N-substituted biscarbamoyl sulphides and their use as insecticides and acaricides - Google Patents

Description

The present invention relates to a process for the preparation of new asymmetric bis-carbamoyl sulfides of the following general formula:

O R R 'O

!! I II!

R ^ OC-N-S-N-C-ORz in which:

R and R 'individually represent C 1 -C 4 alkyl radicals,

Rx is a radical of formula:

R \

C = N — ouA C = N—, oubien w

R! is an alkynyl group when R2 denotes anything other than an alkenyl or alkynyl group;

R2 is different from Rt and represents an alkenyl, alkynyl, phenyl, benzofurannyl, benzothienyl, naphthyl or tetrahydro-naphthyl group, each of which may or may not be substituted with one or more halo, nitro, nitrile, alkyl, alkylthio, alkylthioalkyl, methylenedioxy radicals, amino, alkylamino, dialkyl-amino, alkoxycarbonylamino, dialkylaminoalkylene-imino, alkylcarbonylamino, formylamino, dicyanethylidene, alkoxy, alkynyloxy, phenoxy, phenyl, 2-dithianyl, 2-dithioIanyl, 2-dioxalanyl, 2-oxathianyl, 2-oxathianyl identical or different dioxanyl, or

R2 is a group of formula:

\

C = N— or A Ç = N—;

R3 is a hydrogen atom or an alkyl, alkylthio or cyano group;

R4 is an alkyl, alkylthio, alkylthioalkyl, alkoxy, alkanoyl, aroyl or alkoxycarbonyl group, each of which may or may not have one or more aliphatic, cyano, nitro, alkylthio, alkylsulfinyl, alkylsulfonyl, alkoxy, aminocarbonyl, alkylaminocarbonyl or dialkylaminocarbonyl substituents , or else R4 is a phenyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl group or a group of formula R5CONH— or R5CON (alkyl) - in which R5 is a hydrogen atom or an alkyl or alkoxy group, and

A is a divalent aliphatic chain completing a pentagonal or hexagonal nucleus, which contains one or two divalent oxygen or sulfur atoms or divalent sulfinyl or sulfonyl groups and which can also contain a divalent amino, alkylamino or carbonyl group, in any combination, or A can also complete a hexagonal nucleus which contains in any association three divalent sulfur atoms or divalent sulfinyl or sulfonyl groups; provided that the total number of aliphatic carbon atoms of R3, R4 and A, individually, may not exceed eight.

Preferred compounds are those in which R and R 'are methyl groups. The compounds of formula I display a very high degree of pesticidal activity linked with a significantly reduced toxicity to mammals and plants, compared to other known pesticides having a comparable spectrum of activity against insects, nematodes and arachnids parasites.

The asymmetric bis-carbamoyl sulfides of formula I are prepared by the process defined in claim 1, one embodiment of which is illustrated by the following general reaction scheme:

O R R 'O O R R' O

II I I I II I I II

FC-N-S-N-CF + RtOH ►RjOC — N — S — N — C- F

acid acceptor

O R R 'O O R R' O

II I I II II I I II

Ri OC-N-S- N-CF + R2OH> RiOC-N-S-N-C-OR2

acid acceptor in which R, R ', Ri and R2 have the definitions given above.

An equivalent of an oxime or of a hydroxyl reaction substance (RiOH or R2OH) is reacted with the bis-carbamoyl halide in the presence of an equivalent of an acid acceptor, preferably in an inert solvent, to produce the intermediate carbamatesulfenylcarbamoyl halide which is then reacted with the second oxime or the second hydroxyl reactant (RiOH if an R2OH compound was used in the first step; R2OH if a RiOH compound was used in the first step step), in the presence of an acid acceptor, to form the desired asymmetric bis-carbamate. The production of intermediate carbamatesulfenylcarbamoyl halides has been described in detail in United States patent application No. 636629 filed December 1, 1975 by Themistocles Damasceno Joaquim D'Silva. The acid acceptor used can be an organic or inorganic base such as triethylamine or sodium or potassium hydroxide. It is also possible to use a phase transfer agent such as a corona ether. Any conventional inert solvent can be used such as benzene, toluene, dioxane, tetrahydro-furan, ethyl ether, methylene chloride, etc.

This reaction can also be carried out in two-phase systems such as an aqueous solution of an inorganic base, forming one of the phases, with as the second phase an aromatic solvent containing a quaternary ammonium salt as transfer agent. phase. The reaction temperature is not critical. The reaction is essentially complete when carried out at room temperature. High temperatures can be used if it is desired to reduce the reaction time.

The hydroxyl compound and the reaction oxime which are used in the synthesis described above are known compounds which can be obtained by conventional methods (see, for example, United States patents Nos. 3752841.3726908 and 3843669 and Belgian patents Nos 813206 and 815513).

The bis-carbamoyl fluorides which are used as raw materials are prepared by reaction of HF with an appropriately substituted alkyl isocyanate, to form an alkylamino-carbonyl fluoride which can then be reacted with sulfur dichloride to obtain the fluoride of bis-carbamoyl constituting the desired raw material.

A representative example of an asymmetric bis-carbamoyl sulfide of formula I is given by the sulfide of N- [0- (N-methyl-carbamoyl) oxime of 2-methylthio-2-methylpropionaldehyde] and N- [0- (N-methylcarbamoyl) 1-methylthioacetaldehyde oxime] of formula:

ch3 o ch3 ch3 o ch3

I II I I II /

CH3S - c — c = N-O-C N-S-N — C-O-N = C

I "\

ch3 h SCH3

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Other representative examples of the new compounds of formula I are given below:

sulfide of N- [0- (N-methylcarbamoyl) oxime of 1-methylthioacetaldehyde] and N- [2-0- (N-methylcarbamoyl) oximino-

1.4-dithiane],

sulfide of N- [0- (N-methylcarbamoyl) oxime of 1-methylthioacetaldehyde] and N- [2,3-dihydro-2,2-dimethyl-7- (N-methyl-carbamoyloxy) benzofuran],

sulfide of N- [0- {N-methylcarbamoyl) oxime of 1-methylthio-acetaldehyde] and of N- (N-methylcarbamate of 3-isopropyl-phenyl),

N- [0- (N-methylcarbamoyl) oxime sulfide of 1-methylthioacetal-

dehyde] and N- (1-naphthyl N-methylcarbamate),

sulfide of N- [0- (N-methylcarbamoyl) oxime of 2-methylthio-2-methylpropionaldehyde] and N- (N-methylcarbamate

1-naphthyle),

sulfide of N- [Ó- (N-methylcarbamoyl) oxime of 1-methylthioacetaldehyde] and N- (N-methylcarbamate of 2-isopropoxyphenyl), sulfide of N- [0- (N-methylcarbamoyl) oxime of 1-methylthioacetaldehyde] and N- (4-dimethylamino- N-methylcarbamate)

3.5-xylyle),

sulfide of N- [0- (N-methylcarbamoyl) oxime of 2-methylthio-2-methylpropionaldehyde] and N- (N-methylcarbamate

3-isopropyl-4-methoxycarbonylaminophenyl),

sulfide of N- [0- (N-methylcarbamoyl) oxime of 2-methylthio-2-methylpropionaldehyde] and N- [2,3-dihydro-2,2-dimethyl-7- (N-methylcarbamoyloxy) benzofuran],

sulfide of 1-methylthio-N 'N- [0- (N-methylcarbamoyl) oxime, N'-dimethylcarbamoylformaldehyde] and 1-methylthioacetaldehyde N- [0- (N-methylcarbamoyl) oxime],

N- [0- (N-methylcarbamoyl) oxime sulfide of 2-methylsulfonyl-

2-methylpropionaldehyde] and N- [2,3-dihydro-2,2-dimethyl-7- (N-methylcarbamoyloxy) benzofuran],

N- sulfide [2,0- (N-methylcarbamoyl) oximino-1,4-dithiane]

and N- (3-isopropylphenyl N-methylcarbamate),

sulfide of N- [0- (N-methylcarbamoyl) oxime of 1-methylthioacetaldehyde] and N- [N-methylcarbamate of 4- (N ', N'-dimethylformamidino) -3,5-xylyl],

N- [0- (N-methylcarbamoyl) oxime of 1-methylthioacetaldehyde] and N- [0- (N-methylcarbamoyl) oxime of N ', N'-dimethylaminomethylenecarbamoyl) -l-methylthio-formaldehyde]

sulfide of N- [0- (N-methylcarbamoyl) oxime of 2-methylthio-2-methylpropionaldehyde] and N- (N-methylcarbamate

4-dimethylamino-3,5-xylyl),

sulfide of N-[0- (N-methylcarbamoyl) oxime of 3,3-dimethyl-1-methylthiobutanonne-2] and N- [0- (N-methylcarbamoyl) -oxime of 1-methylthioacetaldehyde],

N-[0- (N-methylcarbamoyl) oxime of 3,3-dimethyl-1-methylsulfonylbutanone-2] and N- [2,3-dihydro-2,2-dimethyl-7- (N-methylcarbamoyloxy) sulfide benzofuran],

sulfide of N- [0- (N-methylcarbamoyl) oxime of 3-methylsulfonyl-butanone-2] and N- [2,3-dihydro-2,2-dimethyl-7- (N-methyl-carbamoyloxy) benzofuran] ,

sulfide of N-[0- (N-methylcarbamoyl) oxime of 3,3-dimethyl-1-methylthiobutanone-2] and N- [0- (N-methylcarbamoyl) -oxime of 1-methylthioacetaldehyde],

sulfide of N- [0- (N-methylcarbamoyl) oxime of 2-cyano-2-methyl-propionaldehyde] and N- (1-naphthyl N-methylcarbamate),

sulfide of N- [0- (N-methylcarbamoyl) oxime of 1-methylthio-N ', N'-dimethylcarbamoylformaldehyde] and N- [2,3-dihydro-2,2-dimethyl-7- (N-methylcarbamoyloxy) benzofuran],

sulfide of 1- methylthiopyru-valdehyde N- [Ò- (N-methylcarbamoyl) oxime] and 1-methylthioacetaldehyde N- [0- (N-methylcarbamoyl) oxime],

sulfide of N- [2-0- (N-methylcarbamoyl) oximino-1,3-dithiolane] and N- (1-naphthyl N-methylcarbamate),

N- [5-methyl-4-0- (N-methylcarbamoyl) oximino- sulfide

1,3-dithiolane] and 1- naphthyl N- {N-methylcarbamate, N- [0- (N-methylcarbamoyl) oxime of 1- (2-cyanethyl-thio) acetaldehyde) and N- (N 1-naphthyl methylcarbamate), N- [0- (N-methylcarbamoyl) oxime sulfide of 1- (2-cyanethyl-thio) acetaldehyde) and N- [2,3-dihydro-2,2-dimethyl -7- (N-methylcarbamoyloxy) benzofuran],

sulfide of N- [4,5,5-trimethyl-2-0- (N-methylcarbamoyl) oximino-thiazolidine-3-one] and of N- [0- (N-methylcarbamoyl) oxime io of 1-methylthioacetaldehyde],

sulfide of N- [4,5,5-trimethyl-2-0- (N-methylcarbamoyl) oximino-thiazolidine-3-one] and of N- [3,5,5-trimethyl-2-0- (N- methyl-carbamoyl) oximinothiazolidine-4-one],

sulfide of N- [4-methyl-2-0- (N-methylcarbamoyl) oximino-is tetrahydro-1,4-thiazine-3-one] and N- (1-naphthyl N-methylcarbamate),

sulfide of N- [4-methyl-2-0- (N-methylcarbamoyl) oximino-tetrahydro-1,4-thiazine-3-one] and N- [0- {N-methyl-carbamoyl) oxime of l- (2-cyanethylthio) acetaldehyde], N- [4-methyl-2-0- (N-methylcarbamoyl) oximino-tetrahydro-1,4-thiazine-3-one] and N- [0- (N) sulfide -methyl-carbamoyl) 1-methylthioacetaldehyde oxime],

N- [5,5-dimethyl-4-0- (N-methylcarbamoyl) oximino-1,3-dithiolane] and N- (1-naphthyl N-methylcarbamate) sulfide, N- [2- (0- (N-methylcarbamoyl) oximino-1,4-dithiane] and N- [4-dimethylamino-3,5-xylyl N-methylcarbamate], N- [2- (0- (N-methylcarbamoyl) sulfide ) oximino-1,4-dithiane] and N- [3-isopropyl-4-methoxycarbonylamino- (N-methyl-carbamoyloxy) benzene],

3o sulfide of N- [0- (N-methylcarbamoyl) oxime of 1- (2-cyanethyl-thio) acetaldehyde] and of N- [N-methylcarbamate of 2- (2-di-thiolanyl) phenyl],

sulfide of N- [0- (N-methylcarbamoyl) oxime of 1- (2-cyanethylthio) -acetaldehyde] and of N- [2- (2-dioxa-35 lanyl) phenyl] N-

sulfide of N- [0- (N-methylcarbamoyl) oxime of 1-isopropylthio-acetaldehyde] and N- [N-methylcarbamate of 2-propynyl-oxyphenyl],

40 2,3- dihydro-2,2-dimethyl-7-benzofuranyl N- [N-methylcarbamate sulfide] and N- [propynyl N-methylcarbamate], N- [0- (N-methylcarbamoyl) sulfide oxime of 1- (2-cyanethyl-thio) acetaldehyde] and N- [4-phenoxy-phenyl N-methylcarbamate],

45 sulfide of N- [0- (N-methylcarbamoyl) oxime of 1-methylthio-N ', N'-dimethylcarbamoylformaldehyde] and of N- [N-methyl-carbamate of 2- (2-dithiolanyl) phenyl],

sulfide of N- [0- (N-methylcarbamoyl) oxime of 1- (2-cyanethyl-thioacetaldehyde) and N- [2-iso-propoxyphenyl N-methylcarbamate],

sulfide of N- [2-0- (N-methylcarbamoyl) oximino-1,3,5-trithiane] and of N- [2-isopropoxyphenyl N-methylcarbamate],

sulfide of N- [2-0- (N-methylcarbamoyl) oximino-1,3,5-trithiane] 55 and N- [N-methylcarbamate of 2- (2-oxathiolanyl) phenyl],

N- sulfide [2-0- (N-methylcarbamoyl) oximino-1,4-dithiane]

and N- [2-propynyloxyphenyl N-methylcarbamate], N- [5-methyl-4-0- (N-methylcarbamoyl) oximino-60 oxathiolane] sulfide and N- [4-phenoxyphenyl N-methylcarbamate], sulfide of N- [4,5,5-trimethyl-2-0- [N-methylcarbamoyl) oximino-thiazolidine-3-one] and N- [N-methylcarbamate of 2-propynyloxyphenyl],

sulfide of N- [3,5,5-trimethyl-2-0- [N-methylcarbamoyl] oximino-65 thiazolidine-4-one] and N- [N-methylcarbamate of 2- (2-dithiolanyl) phenyl].

The process according to the present invention is illustrated by the following examples.

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Example 1:

Preparation of the N, N-sulfide of [0- (N-methylcarbamoyï) oxime of 2-methylthio-2-methylpropionaldehyde ~ \ and of [0- (N-methyl-carbamoytjoxime of 1-methylthioacetaldehyde)

A. Poured dropwise, with stirring, 228 g (4.0 mol) of methyl iso-cyanate, over 20 min, into a polypropylene reaction vessel containing 80 g (4.0 mol) of HF in 1800 ml of toluene, cooled to -40 ° C. The reaction mixture is allowed to warm to 0 ° C and is kept at this temperature for 1 h. Then, 206 g (2 mol) of freshly distilled sulfur dichloride are added, then slowly, 346 g (4.4 mol) of pyridine between - 20 and 0 ° C. After stirring for 2 h at -10 ° C and for 16 h at room temperature, the reaction mixture is diluted with 500 ml of water. The toluene phase is again washed with three times 500 ml of water, it is dried and distilled, which gives 244 g (66%) of bis- (N-methyl-N-fluorocarbonylamino) sulfide boiling at 55-57 ° C / 0.25 mm and melting at 40-41 ° C.

Analysis for C4H6F2N2O2S:

Calculated: C 26.09 H 3.28 N 15.21%

Found: C 26.19 H 3.20 N 14.79%.

B. 0.687 g of triethylamine is added dropwise to a solution of 0.714 g of 1-methylthioacetaldoxime and 1.36 g of bis- (N-methyl-N-fluorocarbonylamino) sulfide in 15 ml of dioxane. After allowing the solution to stand for 20 h, it is diluted with water and extracted with ethyl acetate. The organic extract is washed with water, dried over magnesium sulfate and concentrated in vacuo to give 1.0 g of 0- [N-methyl-N- (N'-methyl- N'-fluoroformylaminosulfenyl) carbamoyl] oxime of 1-methylthioacetaldehyde which melts at 102-104 ° C after crystallization from a mixture of isopropyl ether and ethyl acetate.

Analysis for C7H12FN3O3S2:

Calculated: C 31.22 H 4.49 N 15.60%

Found: C 31.67 H 4.69 N 15.34%.

C. 1.01 g of triethylamine is added, with stirring, to a solution of 2.69 g of 0- [N-methyl-N- (N'-fluoroformylaminosulfenyl) -carbamoyl] oxime of 1-methylthioacetaldehyde and of 1, 33 g of 2-methylthio-2-methylpropionaldoxime in 50 ml of dioxane. After 48 h, the reaction mixture is diluted with water and extracted with ethyl acetate. The organic extract is washed with water, dehydrated and concentrated. The product obtained, namely the N, N-sulfide of [0- (N-methylcarbamoyl) oxime of 2-methylthio-2-methylpropional-dehyde] and of [0- (N-methylcarbamoyl) oxime of 1-methylthio-acetaldehyde ], is crystallized from isopropyl ether. 1.87 g of solid substance, melting at 99-101 ° C., are obtained.

Analysis for C12H22N4.O4S3:

Calculated: C 37.68 H 4.80 N 14.65%

Found: C 37.68 H 5.72 N 14.51%.

Example 2:

Preparation of N, N-sulfide of 0- (N-methylcarbamoyl) oxime of 1-methylthioacetaldehyde] and of [2- (0-N-methylcarbamoyl) -oximino-1,4-dithiane ~ \

1.01 g of triethylamine is added dropwise with stirring to a solution of 2.69 g of 0- [N-methyl-N- (N'-methyl-N'-fluoro-formylaminosulfenyl) carbamoyl] oxime. 1-methylthioacetaldehyde and 2-oximino-1,4-dithiane in 50 ml of dioxane. After stirring at room temperature for 48 h, the solid is collected by filtration. It is then dissolved in methylene chloride, the solution is washed with water, dried and concentrated, giving 2.2 g of [0- (N-methylcarbamoyl) N, N-sulfide 1-methylthioacetaldehyde oxime]

and [2-0- (N-methylcarbamoyl) oximino-1,4-dithiane]. After crystallization from a mixture of ethyl acetate and chloroform, the compound melts at 164-165 ° C.

Analysis for C11H18N4O4S4:

Calculated: C 33.15 H 4.55 N 14.06%

Found: C 33.06 H 4.55 N 13.80%.

Example 3:

Preparation of N. 2- sulfide of [2- {0- (N-methylcarbamoyl) -oximino-1,4-dithiane- [2-0- (N-methylcarbamoyl) oximino-3,5,5-trimethylthiazolidine-4-one]

1.05 g of triethylamine are added dropwise with stirring over 20 minutes to a suspension of 3.4 g of 2- [0- (N-methyl-N- (N'-methyl-N'-fluoroformylaminosulfenyl) carbamoyl) oximino] -3,5,5-trimethylthiazolidine-4-one and 1.5 g of 2-oximino-1,4-dithiane in 70 ml of toluene cooled to 15 ° C. After stirring for 17 h at room temperature, the reaction mixture is concentrated under reduced pressure. The residue is taken up in methylene chloride and washed with water. The organic phase is dehydrated and concentrated, giving 3.5 g of N- [2- (N-methylcarbamoyl) oximino-1,4-dithiane] and N- [2-0- (N- methylcarbamoyl) oximino-3,5,5-triethylthiazolidine-4-one.

After recrystallization from a mixture of ethyl acetate and isopropyl ether, the product melts at 170-171 ° C.

Analysis for C14H21N5O5S4:

Calculated: C 35.96 H 4.53 N 14.98%

Found: C 35.90 H 4.94 N 14.75%.

Example 4:

Preparation of N, N-sulfide of [N-methyl-N-propargyloxy-oxycarbonylamino] - [3,5,5-trimethylthiazolidine-4-one-2-0- (N-methylcarbarfioyl joxime]

0.55 g of triethylamine dissolved in 5 ml of toluene is added dropwise to a solution of 1.7 g of 2- [0- (N-methyl-N- (N'-methyl-N'-fluoroformylaminosulfenyl) carbamoyl ) oximino] -3,5,5-trimethylthiazolidine-4-one and 0.28 g of propargyl alcohol in 20 ml of toluene cooled to 10-15 ° C. After stirring for 20 h at room temperature, dilute the reaction mixture with water and ethyl acetate. The organic extract is washed with water, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The product obtained, namely the N, N-sulfide of [N-methyl-N-propargyloxycarbonylamino] - [3,5,5-trimethylthiazolidine-4-one-2-0- (N-methylcarbamoyl) -oxime] (0 , 52 g) melts at 96-96.8 ° C after crystallization from a mixture of isopropyl ether and ethyl acetate.

Analysis for Ci3Hi8N405S2:

Calculated: C 41.70 H 4.84 N 14.96%

Found: C 41.86 H 5.06 N 14.22%.

Example 5:

Preparation of N, N-sulfide of \ 0- (N-methylcarbamoyl) oxime ~ \ of 1-methylthioacetaldehyde and of [2,2-dimethyl-2,3-dihydro-7- (N-methylcarbamoyloxy) benzofuran]

1.87 g of triethylamine is added dropwise to a solution of 5.0 g of 1-methylthioacetaldehyde, and 1-methylthioacetaldehyde oxime [N-methyl-N- (N'-methyl-N'-fluoroformylamino-sulfenyl) carbamoyl] 3.05 g of 2,2-dimethyl-2,3-dihydrobenzofuran-7-ol in 50 ml of dioxane. After allowing the reaction mixture to stand for 18 h, it is quenched with 200 ml of water and the product is extracted with ethyl acetate. The organic extract is washed with water, dried over magnesium sulfate and concentrated under reduced pressure to give an oil. The product obtained, namely the N, N-sulfide of [0- (N-methylcarbamoyl) oxime] of 1-methylthio-acetaldehyde and of [2,2-dimethyl-2,3-dihydro-7- (N-methyl -carbamoyloxy) benzofuran] (4.3 g), melts at 141-144 ° C after crystallization from a mixture of ethyl acetate and isopropyl ether.

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Analysis for C17H23N3O5S2:

Calculated: C 49.38 H 5.60 N 10.16%

Found: C 49.59 H 5.63 N 10.34%.

Example 6:

Preparation of N, N-sulfide of [0- (N-methylcarbamoyl) oxime] of 2-methylthio-2-methylpropionaldehyde and \ _l- (N-methyl-carbamoyloxy) naphthalene ~ \

2.23 g of triethylamine are added to a solution of 6.5 g of 1- [N-methyl-N- (N'-methyl-N'-fluoroformylaminosulfenyl) -carbamoyloxy] naphthalene and 2.94 g of 2- methylthio-2-methyl-propionaldoxime in 100 ml of toluene and the reaction mixture is stirred for 18 h. This mixture is diluted with an additional volume of 100 ml of toluene and washed with a 100% solution of sodium carbonate and water. The organic phase is dried and concentrated in vacuo; thus obtaining 7.7 g of N, N-sulfide of [0- (N-methylcarbamoyl) oxime of 2-methylthio-2-methylpropionaldehyde] and [1-methylcarbamoyloxynaphthalene] in the form of a viscous oil. An aliquot is purified by dry column chromatography.

Analysis for C19H23N3O4S2:

Calculated: C 54.13 H 5.50 N9.96%

Found: C 53.19 H 5.56 N 9.58%.

Example 7:

Preparation of N, N-sulfide of [0- (N-methylcarbamoyl) oxime] of 1-methylthioacetaldehyde and \ N-methylcarbamate of l-naphthyl ~ \

The N, N-sulfide of [0- (N-methylcarbamoyl) oxime] of 1-methylthioacetaldehyde and of [1-naphthyl methylcarbamate] is prepared by following the procedure used in Example 6, by reaction of 3.88 g of 0- [N-methyl-N- (N'-methyl-N'-fluoro-formylaminosulfenyljcarbamoyl) oxime of 1-methylthioacetaldehyde with 2.07 g of 1-naphthol and 1.45 g of triethylamine used as acceptor acid.

4.1 g of product are obtained, melting at 88-90 ° C.

Analysis for Ci7Hl9N304S2:

Calculated: C 51.89 H 4.87 N 10.68%

Found: C 52.35 H 4.86 N 10.31%.

Example 8:

Preparation of N, N-sulfide of [0- (N-methylcarbamoyl) oxime ~ \ 1-methylthioacetaldehyde] and of [4-isopropylphenyl- (N-methylcarbamoyloxy)]

This compound is obtained by following the procedure of Example 6, by reaction of 3.56 g of 0- [N-methyl-N- (N'-methyl-N'-fluoroformylaminosulfenyl) carbamoyl] oxime of 1-methylthioacetaldehyde with 2.04 g of 4-isopropylphenol and 1.51 g of triethylamine as acid acceptor.

3.7 g of product are obtained, melting at 108-110 ° C.

Analysis for C16H23N3O4S2:

Calculated: C 49.85 H 6.01 N 10.90%

Found: C 49.22 H 6.07 N 10.97%.

Example 9:

Preparation of N, N-sulfide of [0- (N-methylcarbamoyl) oxime] of 1-methylthioacetaldehyde and of [4-tertiobutylphenyl- (N-methylcarbamoyloxy)]

This compound is prepared by following the procedure of Example 6 by reacting 3.56 g of 0- [N-methyl-N- (N'-methyl-N'-fluoroformylaminosulfenyl) carbamoyl] oxime of 1-methylthioacetaldehyde with 2.25 g of 4-tert-butylphenol and 1.51 g of triethylamine as an acid acceptor. 3.8 g of product are obtained, melting at 141-143 ° C.

Analysis for C17H25N3O4S2:

Calculated: C 51.10 H 6.30 N 10.51%

Found: C 50.69 H 6.37 N 10.59%.

Example 10:

Preparation of N, N-sulfide of \ 0- (N-methylcarbamoyl) oxime of l-methylthioacetaldehyde ~ \ and [0- (N-methylcarbamoyl) oxime of 1 - (2-cyanethylthio) acetaldehyde \

This compound is prepared by following the procedure of Example 3 by reaction of 2.88 g of oxime l- (2-cyanethyl) thioacetate and 4.75 g of 0- [N-methyl-N- ( N'-methyl-N'-fluoro-formylaminosulfenyl) carbamoyl] oxime of 1-methylthio-acetaldehyde in 75 ml of toluene and 2.02 g of triethylamine as acid acceptor. 5.2 g of product, melting at 121-123 ° C., are obtained.

Analysis for C12H19N5O4S3:

Calculated: C 36.62 H 4.87 N 17.80%

Found: C 36.48 H 4.81 N 17.44%.

Example 11:

Preparation of N, N-sulfide of [0- (N-methylcarbamoyl) oxime of 1-methylthioacetaldehyde] and of [0- (N-methylcarbamoyl) oxime of 1 -methylthio-N ', N'-dimethylcarbamoylformaldehy]

This compound is prepared by following the procedure of Example 3 by reacting 5.39 g of 0- [N-methyl-N- (N'-methyl-N'-fluoroformylaminosulfenyl) carbamoyl] oxime of 1-methylthioacetaldehyde with 3.24 g of 1-methylthio-N, N-dimethylcarbamoyl-formaldexime in 100 ml of toluene and 2.02 g of triethylamine as acid acceptor. 4.0 g of recrystallized product are obtained, melting at 121-123 ° C.

Analysis for C12H21N5O5S3:

Calculated: C 35.02 H 5.14 N 17.02%

Found: C 35.00 H 5.18 N 16.58%.

Example 12:

Preparation of N, N-sulfide of [0- (N-methylcarbamoyl) oxime] of 1-methylthioacetaldehyde and \ _l- (N-methylcarbamoyloxy) -4-nitrobenzene ~ \

This compound is prepared by following the procedure of Example 5, by reaction of 5.0 g of 0- [N-methyl-N- (N'-methyl-N'-fluoroformylaminosulfenyl) carbamoyl] oxime of 1-methylthioacetaldehyde with 2.59 g of 4-nitrophenol in 75 ml of dioxane and 1.87 g of triethylamine. Obtained 3.9 g of product melting at 164-165 ° C.

Analysis for Ci3Hi6N406S2:

Calculated: C 40.20 H 4.15 N 14.42%

Found: C 40.35 H 4.05 N 14.23%.

Example 13:

Preparation of N, N-sulfide of \ 0- (N-methylcarbamoyl) 1-methylthioacetaldehyde oxime] and of [0- (N-methylcarbamoyl) -l-methylthio-1-ethoxycarbonylformaldehyde oxime ~ \ This compound is obtained by following the procedure of Example 3 by reacting 5.38 g of 0- [N-methyl-N- (N'-methyl-N'-fluoroformylaminosulfenyl) carbamoyl] oxime of 1-methylthioacetaldehyde with 3.26 g of 1 -methylthio-1-ethoxycarbonyl-formaldexime in 75 ml of toluene and 2.02 g of triethylamine as acid acceptor. 6.02 g of product are obtained, melting at 99-100 ° C.

Analysis for C12H20N4O6S3:

Calculated: C 34.94 H 4.89 N 13.58%

Found: C 34.76 H 5.00 N 13.41%.

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Example 14:

Preparation of N, N-sulfide of [0- (N-methylcarbamoyl) oxime of 1-methylthioacetaldehyde] and of _ (N-methylcarbamoyloxy) -5,6,7,8-tetrahydronaphthalene

This compound is prepared by following the procedure of Example 6 by reacting 2.0 g of 0- [N-methyl-N- (N'-methyl-N'-fluoroformylaminosulfenyl) carbamoyl] oxime of 1-methylthioacetaldehyde with 1.1 g of 5,6,7,8-tetrahydro-1-naphthol in 50 ml of toluene and 0.75 g of triethylamine as acid acceptor. 2.3 g of product are obtained, melting at 119-120 ° C.

Analysis for C17H23N3O4S2:

Calculated: C 51.36 H 5.83 N 10.57%

Found: C 51.16 H 5.86 N 10.44%.

Example 15:

Preparation of \ 0- (N-methylcarbamoyl) -oxime of 1-methylthioacetaldehyde] and [0- (N-methyl-carbamoyl) -4-methylthio-3-methylphenyl]

This compound is obtained by following the procedure of Example 6, by reaction of 3.56 g of 0- [N-methyl-N- (N'-methyl-N'-fluoroformylaminosulfenyl) carbamoyl] oxime of 1-methylthioacetaldehyde with 2.77 g of 4- (methylthio) -m-cresol in 100 ml of toluene and 1.81 g of triethylamine as acid acceptor. 3.2 g of product are obtained, melting at 98-99 ° C.

Analysis for Q5H21N3O4.S3:

Calculated: C 44.64 H 5.24 N 10.41%

Found: C 44.40 H 5.08 N 10.25%.

Example 16:

Preparation of N, N-sulfide of [0- (N-methylcarbamoyl) oxime of 1-methylthioacetaldehyde] and of [4-methoxycarbonylamino- (N-methylcarbamate) -3-isopropylphenyl ~ \

This compound is obtained by following the procedure of Example 6 by reaction of 4.0 g of 0- [N-methyl-N- (N'-methyl-N'-fluoroformylaminosulfenyl) carbamoyl] oxime of 1-methylthio- acetaldehyde with 3.75 g of 4-methoxycarbonylamino-3-isopropyl-phenol in 75 ml of toluene and 1.81 g of triethylamine as acid acceptor. 3.6 g of product are obtained, melting at 113-115 ° C.

Analysis for CiaH ^ N ^ O ^:

Calculated: C 47.14 H 5.72 N 12.22%

Found: C 46.86 H 6.05 N 12.11%.

Example 17:

Preparation of N, N-sulfide of [0- (N-methylcarbamoyl) oxime of 1-methylthioacetaldehyde] and of [3- [and 4) -isopropylphenyl- (N-methylcarbamoyloxy)]

This compound is obtained by following the procedure of Example 6 by reaction of 2.69 g of 0- [N-methyl-N- (N'-methyl-N'-fluoroformylaminosulfenyl) carbamoyl] oxime of 1-methyl- thioacetaldehyde with 1.36 g of a 60:40 mixture of the meta and para isomers of isopropylphenol in 50 ml of dioxane and 1.01 g of triethylamine as acid acceptor. The crude product weighs 2.18 g. An aliquot is purified by chromatography.

Analysis for C16H23N3O4S2:

Calculated: C 49.85 H 6.01 N 10.90%

Found: C 48.14 H 5.90 N 11.07%.

Example 18:

Preparation of N, N-sulfide of \ 3,4,5-trimethylphenyl- (N-methyl-carbamoyloxy)] and of [0- [N-methylcarbamoyl) oxime of 1-methylthioacetaldehyde]

This compound is obtained by following the procedure of Example 6 by reaction of 3.55 g of 0- [N-methyl-N- (N'-methyl-

N'-fluoroformyaminosulfenyl) carbamoyl] oxime of 1-methyl-thioacetaldehyde with 2.72 g of 3,4,5-trimethylphenol in 100 ml of toluene using 2.02 g of triethylamine as acid acceptor. 3.1 g of product melting at 97-99 ° C. are obtained.

Analysis for C16H23N3O4S2:

Calculated: C 49.85 H 6.01 N 10.90%

Found: C 49.57 H 5.97 N 10.89%.

Example 19:

Preparation of [2,4-dinitro-6-sec.-butylphenyl- (N-methylcarbamoyloxy)] N.N-sulfide and of methylthioacetaldehyde [0- (N-methylcarbamoyl) -oxime]

This compound is obtained by following the procedure of Example 6 by reacting 3.56 g of 0- [N-methyl-N- (N'-methyl-N'-fluoroformylaminosulfenyl) carbamoyl] oxime of 1-methylthioacetaldehyde with 4.3 g of 2,4-dinitro-6-sec.-butylphenol in 100 ml of toluene and 1.8 g of triethylamine as an acid acceptor. After crystallization from methanol, the compound melts at 129-130 ° C.

Analysis for C17H23N5O8S2:

Calculated: C 41.71 H 4.74 N 14.31%

Found: C 41.60 H 4.52 N 14.22%.

Example 20:

Preparation of N. 3- sulfide of N 3- (N ', N'-dimethylamino) phenyl - (. N-methylcarbamoyloxy)] and of [0- (N-methylcarbamoyl) -oxime of 1-methylthioacetaldehyde]

This compound is obtained by following the procedure of Example 6 by reacting 3.55 g of 0- [N-methyl-N- (N'-methyl-N'-fluoroformylaminosulfenyl) carbamoyl] oxime of 1-methyl- thioacetaldehyde with 1.78 g of 3-dimethylaminophenol in 150 ml of toluene and 1.52 g of triethylamine, as an acid acceptor. After purification, 1.3 g of product melting at 108-109 ° C. are obtained.

Analysis for C15H22N4O4S2:

Calculated: C 46.61 H 5.74 N 14.50%

Found: C 46.33 H 5.52 N 14.19%.

Example 21:

Preparation of N, N-sulfide of 4-formylamino-3-methylphenyl- (N-methylcarbamoyloxy)] and of \ 0- (N-methylcarbamoyl) -oxime of 1-methylthioacetaldehyde]

This compound is obtained by following the procedure of Example 6 by reaction of 4.04 g of 0- [N-methyl-N- (N'-methyl-

N'-fluoroformylaminosulfenyl) carbamoyl] oxime of 1-methylthioacetaldehyde with 2.67 g of 4-N, N-dimethylformamidino-metacresol in 200 ml of toluene and 1.56 g of triethylamine as acid acceptor. After conventional treatment and purification by column chromatography, 0.7 g of melting product is isolated at 143-145 ° C.

Analysis for C15H2oN405S2:

Calculated: C 44.98 H 5.03 N 13.99%

Found: C 44.87 H 4.98 N 13.79%.

Example 22:

Preparation of N, N-sulfide of [] -naphthyl- (N-methylcarbamoyl-oxyj] and of [2- (0- (N-methylcarbamoyl) oximino) -l, 4-dithiane] This compound is obtained according to the mode procedure of Example 6, by reaction of 5.0 g of 1- [N-methyl-N- (N'-methyl-N'-fluoroformylaminosulfenyl) carbamoyloxy] naphthalene with 2.42 g of 2-oximino-1, 4-dithiane in 100 ml of toluene and 1.64 g of triethylamine, as acid acceptor, 5.0 g of product melting at 148-150 ° C. are obtained.

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Example 24:

Preparation of N, N-sulfide of [2-0- (N-methylcarbamoyl) -oximino-1,4-dithiane ~ \ and of [2,3-dihydro-2,2-dimethyl-7- (N-methylcarbamoyloxy) benzofuran]

This compound is obtained by following the procedure of Example 6, by reaction of 3.13 g of 2- {0- [N-methyl-N- (N'-

Analysis for Ci8H19N304S3:

Calculated: C 49.41 H 4.38 N9.60%

Found: C 48.70 H 4.28 N 9.53%.

Example 23:

Preparation of N, N-sulfide of [0- (N-methylcarbamoyl) oxime of 1-methylthioacetaldehyde] and of [4- (2-cis-7) -octadienyl- (N-methylcarbamoyloxy) benzene]

This compound is obtained by following the procedure of Example 6 by reacting 3.5 g of 0- [N-methyl-N- (N'-methyl-N'-fluoroformylaminosulfenyl) carbamoyl] oxime of 1-methylthioacetaldehyde with 2.63 g of 4- (cis-2,7) -octadienylphenol in 150 ml of toluene and 1.31 g of triethylamine as acid acceptor. The oily residue is purified by column chromatography to give 1.9 g of an oil.

Analysis for C21H29N3O4S2:

Calculated: C 55.85 H 6.47 N9.30%

Found: C 55.22 H 6.39 N9.22%.

methyl-N'-fluoroformylaminosulfenyl) carbamoyl} oximino} -1,4-dithiane with 1.65 g of 2,3-dihydro-2,2-dimethylbenzo-furan-7-ol, in 150 ml of toluene and 1.01 g of triethylamine as acid acceptor. The crude product is purified by chromatography on a dry column and an amorphous solid substance is obtained.

Analysis for C18H23N3O5S3:

Calculated: C 47.24 H 5.07 N 9.18%

Found: C 46.04 H 5.03 N 8.81%.

Example 25:

Preparation of N, N-sulfide of [2-0- {N-methylcarbamoyl) -oximino-1,4-dithiane ~ \ and of [4-isopropyl- (N-methylcarbamoyl-oxy) benzene]

This compound is obtained by following the procedure of Example 6, by reaction of 3.13 g of 2-0- [N-methyl-N- (N'-methyl-N'-fluoroformylaminosulfenyl) carbamoyl] oximino-1 , 4-dithiane with 1.36 g of 4-isopropylphenol in 150 ml of toluene 20 and 1.01 g of triethylamine. After column chromatography, 1.1 g of product melting at 129-131 ° C. are obtained.

Analysis for C17H25N304S3:

Calculated: C 47.53 H 5.40 N9.70%

Found: C 47.40 H 5.27 N9.73%.

The compounds of Examples 26-41 were prepared by the methods of Examples 1 to 25. The physical properties of these compounds are indicated in Table 1:

5

Table 1:

Melting points and elemental analysis of the carbamoyloximes of formula:

OR R 'O

II I I 11 Ri — OC — N — S-N — CO — R,

Example R!

R2

R

R '

P.F.

(° C)

Brute formula

Calculated Found (%)

C H N

26

27

28

29

30

-CH2C = CH

-ch2c = ch h3c-c = n-I

sch3

h3c-c = n-I

SCH3

h3c-c = n-I

sch3

0

1

CH; £

■ C11-

CH (CH3); Cl

C (CH3) 3

Hl? H

12 "25

-CH3 -CH3 Oil C17H16N204S 59.29 4.68 8.14

59.45 4.57 8.00

-CH3 -CH3 Oil C15H18N204S 55.88 5.63 8.69

55.18 5.42 8.82

-CH3 -CH3 63-65 Ci6H23N304S2 49.74 6.08 10.84

49.85 6.01 10.90

-CH3 -CH3 139-140 C17H24C1N304S2 47.04 5.57 9.68

46.92 5.48 9.79

-CH3 -CH3 74-77 C25H4iN304S2 58.67 8.02 8.21

58.01 8.06 8.44

31

32

H3C-C = N-I

sch3

h3c-c = n-I

sch3

C9HL9

-CH3 -CH3 65-68 C22H35N304S2 56.26 7.51 8.95

56.40 7.69 8.93

-CH3 -CH3 126-127 Cj9H2IN304S2 54.39 5.05 10.02

53.76 4.73 10.06

Table 1 (continued) OR R 'O I! I II! R! -Oc-n-s-n-co-R2

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Example Rj

R

R '

m.p.

(° c)

Brute formula

Calculated Found (%)

C H N

33

34

35

36

37

38

39

40

41

h3c-c = n-I

sch3 h3c-c = n-

I

sch3

h3c-c = w-I

sch3

° ~ o

J ^ OCHjCrCH

0

o h3c-c = n- -n = c-c-c6h5

sch3

ch3

ch3

-ch3

96-98

c17h23n3o5s2

49.37 49.08

5.60 5.56

10.16 10.19

ch3

-ch3

129-130

c19h21n305s2

52.40 52.26

4.86 4.65

9.64 9.69

ch3

-ch3

98-100

c19h21n3o5s2

52.40 52.05

4.86 4.72

9.64 9.56

ch3

-ch3

81-83

ci6H21n304s4

42.92 42.75

4.73 4.61

9.39 9.34

ch3

-ch3

Oil c16h21n3o6s2

46.26 46.02

5.10 5.13

10.11 9.92

ch3

-ch3

96-97

c16h23n3o5s2

47.86 47.36

5.77 5.57

10.47 10.39

ch3

-ch3

110-111

ca6H19N3o5s2

48.35 48.49

4.28 4.84

10.57 10.33

ch3

-ch3

182-185

CioH16n404s5

28.83 28.47

3.87 3.83

13.45 13.01

ch3

-ch3

155-157

c16h2oN4o5s2

46.58 46.62

4.88 4.93

13.58 13.49

Some representatives of the new compounds have been tested to determine their pesticidal activity against mites and certain insects including an aphid, a caterpillar, a beetle and a fly.

Suspensions of the test compounds were prepared by dissolving 1 g of each compound in 50 ml of acetone containing, in solution, 0.1 g (10% by weight of the compound) of a surfactant alkylphenoxypolyethoxyethanol as emulsifying or dispersing agent. The resulting solution was mixed with 150 ml of water to obtain about 200 ml of a suspension containing the compound in a finely divided form. The mother suspension thus prepared contained 0.5% by weight of the compound. The test concentrations in parts per million by weight used in the tests described below were obtained by suitable dilutions of the mother suspension with water. The test methods were as follows:

Foliar spray test, bean aphid

Adults and nymphs of the bean aphid (Aphisfabae Scop.) Raised on potted cress plants, at 18.3-21 ° C and at a relative humidity of 50 to 70%, constitute the insects of test. For the purpose of the test, the number of aphids per pot was

been standardized to 100-150 by eliminating plants carrying an excessive number of aphids.

n / a The test compounds were formulated by diluting the mother suspension with water, so as to form a suspension containing 500 parts of test compound per million parts of final formulation.

Potted plants (1 pot per test compound) infested with 100-150 aphids are placed on a turntable and spray treated with 100-110 ml of the test compound formulation, using a spray gun DeVilbiss set to 2.8 bar air pressure. This application, which lasts 25 s, is sufficient to wet the plants until drops 60 come off. In a control test, infested plants were also treated by spraying 100 to 110 ml of an aqueous acetone emulsifier solution which did not contain the test compound. After spraying, the pots are laid down on a sheet of white, standardized tracing paper, on which lines have been previously drawn with a ruler to facilitate counting. The temperature and humidity in the test room during the 24 h stay period are 18.3-21 ° C and 50-70%, respectively. Aphids that fall on paper and are unable to stay

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on their legs after being straightened are considered dead. The movement of aphids remaining on the plants is closely observed, and those which are unable to move in the longitudinal axis of the body when stimulated with a tip are considered dead. The percentage of mortality is noted for the various concentration rates.

Bait test, after leaf spraying, armyworm

Legionary caterpillars (larvae of the butterfly Spodoptera eridania (Cram.)), Reared on bean plants of the Tendergreen variety at a temperature of 28.7 + 2.3 ° C and a relative humidity of 50 + 5% constitute the test insects.

The test compounds are formulated by diluting the mother suspension with water, so as to form a suspension containing 500 parts of test compound per million parts of final formulation. Tendergreen bean plants of uniform height and age, grown in pots, are placed on a turntable and spray treated with 100 to 110 ml of test compound formulation using a De spray gun Vilbiss set to a pressure air pressure of 0.7 bar. This application, which lasts 25 s, is sufficient to wet the plants until drops come off. In a control test, 100 to 110 ml of an aqueous acetone emulsifier solution which does not contain the test compound are also sprayed onto infested plants. After drying, the pairs of leaves are detached and each leaf is placed in a 9 cm diameter petri dish, the bottom of which is lined with a wet filter paper. 5 random tracks are introduced into each box and the boxes are closed. The closed boxes are marked and kept for 3 days at 28.7-31 ° C. Although the caterpillars can easily consume the entire leaf in the 24 hour period, no more food is added. Caterpillars that are unable to move in the body's longitudinal axis, even when stimulated with a point, are considered dead. The percentage of mortality is noted for various concentration rates.

Foliar spray test, Mexican ladybug

The test insects consist of fourth-instar larvae of the Mexican ladybug (Epilachna varivestis, Muls.) Reared on bean plants of the Tendergreen variety at a temperature of 28.7 + 2.3 ° C and relative humidity 50 + 5%.

The test compounds are formulated by diluting the mother suspension with water, so as to obtain a suspension containing 500 parts of the test compound per million parts of final formulation. Tendergreen bean plants of uniform height and age, grown in pots, are placed on a turntable and spray treated with 100 to 110 ml of the test compound formulation using a DeVilbiss spray gun set to a pressure air pressure of 0.7 bar. This application, which lasts 25 s, is sufficient to wet the plants until drops come off. In a control test, infested plants are also sprayed with 100 to 110 ml of an aqueous acetone emulsifier solution which does not contain the test compound. After drying, the pairs of leaves are detached and each leaf is placed in a 9 cm diameter petri dish, the bottom of which is lined with a wet filter paper. Then five randomly selected larvae are placed in each box and the boxes are closed. The closed boxes are marked and kept at a temperature of 28.7 ± 2.3 ° C for 3 days. Although the larvae can easily consume the leaf in 24 to 48 hours, no more food is added. Larvae that are unable to move in the body's longitudinal axis, even when stimulated, are considered dead.

Bait test, housefly

Adult house flies (Musca domestica L.) aged 4 to 6 days, reared in accordance with the standards of the Chemical Specialties Manufacturing Association ("Blue Book", McNair-

Dorland Co., N.Y., 1954; pp. 243-244,261) at 28.7 ± 2.3 "C and a relative humidity of 50 ± 5%, constitute the test insects. The flies are immobilized and individuals, male and female, are transferred to a formed cage a normal household colander, about 12.7 cm in diameter, which is placed upside down on a surface covered with wrapping paper. The test compounds are formulated by diluting the mother suspension with a 10% by weight solution of sugar, so as to obtain a suspension containing 500 parts of the test compound per million parts of final formulation, by weight. 10 ml of the test formulation are introduced into a soufflé dish containing a square absorbent cotton pad of 2.7 cm side. This cup serving as bait is introduced and centered on the absorbent paper, under the cleaning colander, before the introduction of the anesthetized flies. The flies held captive are at even feeding on the bait for 24 h at a temperature of 28.7 + 2.3 ° C and at a hu relative humidity of 50 + 5%. Flies that remain completely immobile when stimulated with a tip are considered dead.

Foliar spray test, mites

Adults and nymphs of the spider mite (Tetra-nychus urticae Koch) reared on bean plants of the Tendergreen variety at a temperature of 28.7 ± 2.3 ° C and a relative humidity of 50 + 5% constitute the test organisms. Infested leaves from a mother crop are placed on the primary leaves of two bean plants 15.2 to 20.3 cm high, grown in a 6.45 cm diameter earthen pot. 150 to 200 mites (that is, a sufficient number for the test) are passed from excised leaves to fresh plants over a 24-hour period. After the 24 h transfer period, the excised leaves are removed from the infested plants. The test compounds are formulated by diluting the mother suspension with water, so as to form a suspension containing 500 parts of the test compound per million parts of final formulation. The potted plants (one pot per compound) are placed on a turntable and treated by spraying with 100-110 ml of the test compound formulation using a DeVilbiss spray gun set at a manometric air pressure of 2, 8 bars. This application, which lasts 25 s, is sufficient to wet the plants until drops come off. In a control test, infested plants are also sprayed with 100 to 110 ml of an aqueous solution containing acetone and an emulsifier at the same concentrations as the formulation of the test compound, but not containing the test compound. . Plants treated by spraying are maintained at a temperature of 28.7 ± 2.3 ° C and a relative humidity of 50 ± 5% for 6 days, then a mortality count of motile forms is carried out. The microscopic examination of the motile forms is carried out on the leaves of the test plants. Anyone who is able to move when stimulated with a point is considered to be alive.

Nematicidal test

The test organisms used consist of infectious migratory larvae of the midge nematode (Meloidogyne incognita var. Acrita) reared in greenhouses on the roots of cucumber plants. Infected plants are removed from the culture and the roots are very finely chopped. A small amount of this inoculum is added to a jar of about 0.51 containing about 180 cm3 of soil. The jars are capped and incubated for one week at room temperature. During this period, the nematode eggs hatch and the larval forms migrate into the soil.

10 ml of the test formulation is added to each of the two jars for each dose tested. After the addition of the chemical agent, the jars are capped and their contents are properly agitated on a ball mill for 5 min. Test compounds are formulated by a standard method which consists of dissolving them in acetone, adding an emulsifier to the solution and

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dilute it with water. Primary selection tests are carried out at a dose of 3.33 mg of the test compound per jar.

The closed jars are kept at room temperature for 48 h, then their contents are transferred into 7.6 cm pots. Then sow cucumber seeds 5 (cultivated plant chosen as indicator) in the pots and install the pots in the greenhouse, where they are given normal care for about three weeks. The cucumber plants are then removed from the pots,

the soil is removed from the roots and the amount of midge is visually assessed. 10

The results of these tests are shown in Table 2. In these tests, the pesticidal activity of the compounds at the dose indicated against aphids, spider mites, armyworms (CL), Mexican bean ladybugs (CH) and housefly, has been assessed as follows:

A = excellent destruction B = partial destruction C = no destruction.

In the activity test against nematodes (Nem) the activity was evaluated as follows:

1 = strong cididogeny, as in the case of untreated plants 2 = moderate cididogeny

3 = slight cecidogeny 25

4 = very low cididogeny 5 = no blotchiness, perfect control.

The presence of the dashes means that the test has not been carried out.

Phytotoxicity test

Experiments have also been carried out to determine the phytotoxicity of certain compounds towards healthy plants. Solutions of the compounds were prepared as indicated above, so as to obtain a test compound concentration of 2500 parts per million. The test plants are treated by spraying with the method described above with regard to the foliar spray test against mites, so as to deliver approximately 100 ml of test solution to the leaves of each plant subjected to the 'test. The spray-treated plants and the control plants are set aside for about 1 h, so that their leaves can dry, then they are placed in the greenhouse. After 10 days, the plants are examined individually, to determine the degree of deterioration of their foliage. An estimation score equal to 1 means that there is no perceptible alteration; 5 means that the plant is dead, and notes 2, 3 and 4 indicate intermediate degrees of deterioration based on the number of damaged leaves and their degree of deterioration.

Mammalian toxicity

The oral toxicity of certain compounds to mammals has also been evaluated by conventional methods. The representative animal chosen in this experiment was the rat. The results obtained in this test are expressed by the number of milligrams of composition per kilogram of body weight of the animal necessary to reach a mortality rate of 50% (LD50).

The results of these tests are also summarized in Table 2:

Table 2: Biological activity

Ex. Compound

Chip- Aca- CL CH Mou- Ném ron rien che

Toxicity

Phytotoxicity

oral,

Hari

To-Co-Soy Corn

rat cot mate ton-

(mg /

deny

kg)

0ch3 ch3 o chs

III I II I

1 ch3-c = nocn-s-n — c-o-n = c-c-sch3 a I I I

sch3 h ch3

0 Clio Cil 0

he 1 d 1 3 he

2 C1I, -C = N0C-N-S-N C-O-Nv i /

SCH3 S

O CH-, CH. O

t, i -J I J II

CU3 NOC-N-S-N C-O-N ^

\ // ^

3 \ V

0

S S

A A A A 5 2.1 2 1 1 2 1

A A A A A 5 190.0 11 111

C A A A A 1 160 1 2 1 2 2

CIl3 Cll3

ÛC11- »CH-, O

bed j i j m

- ■ ^ 3 HOCtl-S-îl C-0-CH2-C = CH g

CH

CHj CH j

C A A A 1

112 2 2

620426

12

Table 2 (continued)

Ex. Compound

Chip- Aca- CLCH Mou- Ném Toxi-

Phytotoxicity

nothing nothing quoted

oral,

Hari

To-Co-Soy Corn

rat cot mate ton-

(mg /

deny

kg)

OCH, CH, O

ni -> i J n ch -, - c = nocn-s-n c-q h

1 o "" W "

J I

seil.

.0, C1I3

ch3

CH. OCH, CH, O

i 3 ti i J i J n

CllnS-C - C ^ nocn-S-N— C-0 J i i ch3h

0 Cil-, Clio 0

II I J I J II

ch3-c = noc-n-s-n c-0

seil.

o in ch., o t »I J I J II

8 ch., - c = noc-n-s-n c-0

• J I

sch.

b a 5 15.9 2

a 4 2.97 1

a 4,160.0 1

1111

1 1

a 4,160.0 1,111

ch (.ch3) 2

0 cht each o n i j i j n

9 c11 -.- c-noc-n-s-n c-0

D 1

SCHi c (ch3) 3

o ch3 ch3o III I II 10 ch3-c = noc-n-s-n— c-o-n = c-ch3

I I

sch3 ncch2ch2s

OCiU CH, 0

n I J l J n

"/

eyelash

11 CH -, - C = HOCN-S-N C-0-N = * C-CN

\ \

SCH, SCH, CH,

a 3,226.0

al 67.3 1 1 1

a - 14.1 1 1 1

OCH, CH., O

n i J i J n

12 CH, -ONOCN-S-N C-

J i

SCH,

och3 ch3 o o

III I II II

13 ch3-c = nocn-s-n — c-o-n = c-coc2h5 a

I I

sch3 sch3

a 1,453.0 1

1111

a 3,160.0 1,111

och- ch, o

<l | J I -J II

14 ch., - c = h0cn-s-n— c-0

J i

SCH-

a 4,285.0 1

1111

13

Table 2 (continued)

620,426

Ex. Compound

Chip- Aca- CLCH Mou- Ném

Toxi

Phytotoxicity

nothing nothing quoted

oral,

Hari

Corn To

Co-Soy

rat cot mate ton-

(mg /

deny

kg)

0 Clin u I -

cu-:

O

ti

15 c11, -c-n0c-n-s-n - c-0

• J I

scll-

ch.

sch.

at 4

40.0 1

0 c1u clio 0

He doesn't ^ He

16 ch3-c = noc-n-s-n — c-0

sch.

ch- (ch3) 2

17

och, ch-, 0

III J t J (I

ch, -c = n0cn-s-n— c-0

-1 i sch.

a 4 28.3 1

a 4,126.0 1

1111

1111

cii (cii3i2

18

o ch-, ch., 0

Ut J 1 O II

19

NO,

a 4 95.1 1

at 1

1111

20

21

0 ch. ch.o

It * 1 J I ^ 11

ch „-c = noc-n-s-n — c-0 J i sch3

och. ch.o

He ! J I Jll ch3-c = nocn-s-n — c-0

c1i „

\

ch.

sch,

at 4

at 4

1 1

1111

620,426

14

Table 2 (continued)

Ex. Compound

Chip- Aca- CLCH

Mou- Ném

Toxi

Phytotoxicity

nothing nothing quoted

oral,

Hari

To-Co-Soy Corn

rat cot mate ton-

(mg /

deny

kg)

22

Ö CH. CH, U

n I J t -> u

.NOC-N-S-N — C-0

a a 4,453.0 1 1 1 1

23

OC11, CH, 0

n i J i J n

CH, -C = NOCN-S-N C-0

SCH3

CH2 = CHCH2CK2CH2CH = C11CH2

a a -

24

OCH. CH, 0

n i J i J n

NOCN-S-N C-0

ch,

CH,

a a 5 20 1 1 1

25s

0 CH, CH, 0 n (J i J n

HOC-N-S-N C-0

chcch3) 2

a a -

1 1 1

26

0 CH-

9:39 a.m.

0-C N - S -N -C-0CH2C = CH

a a4

1111

0 CH, CH, 0

h i j i "mi

27 0-C N -S -N -C-0CH2CrCH

CH-,

a to 5

1 1 1

0CH „CH30

ft I J "He

28 CH3-C = N0CN - S -n -C-Q SCH,

a a

40 1 1 1

15

620,426

Table 2 (continued)

Ex. Compound

Chip- Aca- CLCH Mou- Ném

Toxi

Phytotoxicity

nothing nothing quoted

oral,

Hari

To-Co-Soy Corn

rat cot mate lon-

(mg /

deny

kg)

29

och, ch, 0

it i J i J ri ch, -ç = nocn - s - n - c

'31

sch och, ch, 0

h j j i j ii ch3-c = n0cn - s -n - c 30 öch,

x]

X-

ch-c-ch

4h

THIS

3 t "'3

a b a a a 5

11111

a b a a a 4

1112 1

d12h25

och, ch, 0

i j • j ii

• 'f

31 sch ch, -ç = nocn - s - n - c -3

a c a a a 5> 640 1 1 1 1 1

-9H19

och, ch, 0

II I J I J ||

. . 3

àCHi \ = / \ ^ /

32 ch3-ç = nocn -s-n a c a a a 4

2 112 1

och, ch, 0

It ♦ "J I JM

33 ch -c = nocn -s-n -c-0

1 OCH,

Q 3

I

ch2ch = ch2

a b a a a 5

1113 1

0 ch, ch, 0

11 1 1 M _

34 ch3 - ^ = noc-n-s-n -c-oh ^^ o- ^ j) a b a a a -> 640

11111

0Ç1I

35 CH3-c-nocn scll,

ti a c a a a -

11111

36

ch

IP3 f "3f

> -ç = nocn -s-n -c-

ach,

a c a a a 4 50.4 1 1 1 1 1

37

IF »

ch -c = nocn-s -n -ò — 1

3 D

sch,

a a a a a 4

2 112 2

620 426 16

Table 2 (continued)

Hx. Chip Compound- Aca- CL CH Mou- Ném Toxi- Phytotoxicity

nothing nothing quoted

oral, Hari- Corn To- Co-Soy rat cot mate ton-

(mg / deny kg)

M çh

38 ch3- <j> n0cn -s -n -c-0 [3 a a a a a - 63.5 11112

SCH-,

0 "

O-CH

CHi

39

° f3 fH3j ch, c = n0cn-s-n -C-0

a a a a a 3 160 1 1 1 2 2

sch-,

40 CH -C = N0I j SCH,

och, çh-, q

1L-Ï io-s. <3

b c a a a 5 11111

och3 ch3o o

I! I I II II

41 ch3-c = nocn-s-n — c-o-n = c-c-c6h5 a sch3 ch3

b a a a 1 - 11111

It should be noted that the insects and other parasites used in the above tests are only examples of a wide variety of parasites which can be destroyed using the new compounds of the invention.

The compounds of the invention can be applied as insecticides, acaricides and nematicides by methods well known to those skilled in the art. Pesticide compositions containing these compounds as active ingredient usually contain a support and / or a diluent, solid or liquid.

Suitable diluents or liquid carriers include water, petroleum distillates or other liquid carriers with or without surface active agents. Liquid concentrates can be prepared by dissolving one of these compounds using a non-phytotoxic solvent such as acetone, xylene or nitrobenzene and dispersing the active substances in water using suitable surface active emulsifiers and dispersants.

The choice of dispersing and emulsifying agents and the amount used is dictated by the nature of the composition and the ability of the agent to facilitate the dispersion of the active substance. In general, it is desirable to use the agent in as small a quantity as possible compatible with the desired dispersion of the active substance in the sprayable composition, so that rain does not re-emulsify this substance after its application to the plant and does not do not remove it by washing the plant. Non-ionogenic, anionogenic or cationic dispersants and emulsifiers, for example the condensation products of alkylene oxides with phenol and organic acids, alkylarylsulfonates, complex ether alcohols, quaternary ammonium compounds, etc., can be used to this end.

In the preparation of a wettable powder or a dusting powder or granular compositions, the active ingredient is dispersed in and on a suitably divided solid support such as clay, talc, bentonite, diatomaceous earth, fuller's earth, etc. In the formulation of wettable powders, the above-mentioned dispersing agents, as well as lignosulfonates can be included.

The required quantity of active substances of the invention can be applied per hectare treated, in a volume of 10 to 20001 or more of vehicle and / or liquid diluent or in a weight of approximately 5.5 to 550 kg of support and / or inert solid diluent. The concentration in the liquid concentrate usually ranges from about 10 to 95% by weight and, in solid formulations, from about 0.5 to about 90% by weight. Satisfactory compositions in the form of sprayable liquors, powders for dusting or granules for general applications contain about 0.27 to 16.5 kg of active substance per hectare.

The pesticides of the invention protect against attack by insects, mites and nematodes of plants or another material to which the pesticides are applied. With regard to plants, they have a large margin of safety, since when used in sufficient quantity to destroy or repel insects, they do not burn or damage the plant, and they resist atmospheric factors such as removal by washing under the action of rain, decomposition by ultraviolet light, oxidation or hydrolysis in the presence of moisture, or at least prevent this decomposition, this oxidation or this hydrolysis significantly reduces the desirable pesticidal characteristic of the active substances or gives them undesirable characteristics, for example phytotoxicity. The active substances are compatible with other constituents encountered in the spraying operation and they can be used in the soil, on the seeds or on the roots of plants, without these altering these seeds or these roots. It is possible to use, where appropriate, mixtures of the active compounds of the invention, as well as combinations of these compounds with other compounds endowed with biological activity.

45

50

55

r

Claims (11)

620,426 i 1. Process for the preparation of a new compound corresponding to the formula: OR R 'O R! -OC-N-S-N-C-OR2 in which: R and R 'individually represent C1 to C4 alkyl radicals, Rj is a radical of formula: R, \ / ' C = N— or A = N—, or else R, Rj is an alkynyl group when R2 denotes something other than an alkenyl or alkynyl group; R2 is different from Rj and represents an alkenyl, alkynyl, phenyl, benzofurannyl, benzothienyl, naphthyl or tetrahydro-naphthyl group, each of which may or may not be substituted with one or more halo, nitro, nitrile, alkyl, alkylthio, alkylthio-alkyl radicals, methylenedioxy, amino, alkylamino, dialkylamino, alkoxy-carbonylamino, dialkylaminoalkylene-imino, alkylcarbonylamino, formylamino, dicyanethylidene, alkoxy, alkynyloxy, phenoxy, phenyl, 2-dithianyl, 2-dithiolanyl, 2-dioxalanyyl, 2-oxathanyl Identical or different 2-dioxanyl, or else R2 is a group of formula: R, Ri \ / ' C = N— or Ä r \ :NOT- 3. Method according to claim 1, characterized in that Rx is a group \. C = N- (I) 4. Method according to claim 1, characterized in that Rt is a group C = N— 5. Method according to rèveJRfication 3, characterized in that R2 is a group V R3 is a hydrogen atom or an alkyl, alkylthio or cyano group; R4 is an alkyl, alkylthio, alkylthioalkyl, alkoxy, alkanoyl, aroyl or alkoxycarbonyl group, each of which may or may not carry one or more aliphatic, cyano, nitro, alkylthio, alkylsulfinyl, alkylsulfonyl, alkoxy, aminocarbonyl, alkylaminocarbonyl or dialkylaminocarbonyl , or else R4 is a phenyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl group or a group of formula R5CONH— or R5CON (alkyl) in which R5 is a hydrogen atom or an alkyl or alkoxy group, and A is a divalent aliphatic chain completing a pentagonal or hexagonal nucleus, which contains one or two divalent oxygen or sulfur atoms or divalent sulfinyl or sulfonyl groups and which can also contain a divalent amino, alkylamino or carbonyl group, in any combination, or A can also complete a hexagonal nucleus which contains in any association three divalent sulfur atoms or divalent sulfinyl or sulfonyl groups; provided that the total number of aliphatic carbon atoms of R3, R4 and A, individually, may not exceed eight, characterized in that a compound of formula OR R 'O is reacted Il I I II RiOC — N — S —N — CF with a compound of formula R2OH, or by reacting a compound of formula OR R 'O II I I II FC-N-S-N-COR2 with a compound of formula Rj OH in the presence of at least one equivalent of an acid acceptor, formulas in which R, R ', Rx and R2 have the meanings given above. 2. Method according to claim 1, characterized in that R 'is a methyl group. C = N— / 6. Method according to claim 3, characterized in that R2 is a group 7. Method according to claim 1, characterized in that 25 A is a group - SCH2CH2SCH2 -. 8. Method according to claim 1, characterized in that one prepares. 8. Process according to claim 1, characterized in that the N, N-sulfide of [0- (N-methylcarbamoyl) oxime of 1-methylthioacetaldehyde] and of [2- (N-methylcarbamoyl) oximino is prepared. -1,4-dithiane], [0- (N-methylcarbamoyl) oxime of 2-methyl-thio-2-methylpropionaldehyde] and [1- (N-methylcarbamoyloxy) -naphthalene] N, N-sulfide, 35 N, N-sulfur of [0- (N-methylcarbamoyl) oxime of 1-methylthioacetaldehyde] and of [N-methylcarbamate] of 1-naphthyl, [4-isopropylphenyl- (N-methylcarbamoyl-oxy)] and [0- (N-methylcarbamoyl) oxime 1-methylthioacetaldehyde] N, N-sulfide, 4d N, N-sulfide [4-tert-butylphenyl- (N-methylcarbamoyloxy)] and [0- (N-methylcarbamoyl) oxime of 1-methylthioacetaldehyde], the N, N-sulfide of [0- (N-methylcarbamoyl) oxime of 1-methylthioacetaldehyde] and [0- (N-methylcarbamoyl) oxime of 45 1 - (2-cyanethylthio) acetaldehyde], N, N-sulfide of [0- (N-methylcarbamoyl) oxime of 1-methylthioacetaldehyde] and [1- (N-methylcarbamoyloxy) -5,6,7,8-tetrahydronaphthalene], N, N-sulfide of [3-isopropylphenyl- (N-methylcarbamoyl-5 "oxy)] and of [0- (N-methylcarbamoyl) oxime of 1-methylthioacetaldehyde], [1-naphthyl- (N-methylcarbamoyloxy)] and [2- (0-N-methylcarbamoyl) oximino-1,4-dithiane) N, N-sulfide, N, N-sulfide of [2- (0- (N-methylcarbamoyl) oximino-1,4,555 dithiane] and of [2,3-dihydro-2,2-dimethyl-7- (N-methylcarbamoyl-oxy ) benzofuran], N, N-sulfide of [2-0- (N-methylcarbamoyl) oximino-1,4-dithiane] and of [4-isopropyl- (N-methylcarbamoyloxy) -benzene], • f.u the N, N-sulfide of [2- (2-dithiolanyl) phenyl- (N-methylcarba-moyloxy)] and of [0- (N-methylcarbamoyl) oxime of 1-methylthioacetaldehyde], the N, N-sulfide of [2-isopropoxyphenyl- (N-methylcarba-moyloxy)] and of [0- (N-methylcarbamoyl) oxime of 1-methylthio- <1? acetaldehyde], [2-propynyloxyphenyl- (N-methylcarbamoyl-oxy)] and [0- (N-methylcarbamoyl) oxime 1-methylthioacetaldehyde] N, N-sulfide, or 3 620,426 [4-nonylphenyl- (N-methylcarbamoyloxy) and [0- (N-methylcarbamoyl) oximede 1-methylthioacetaldehyde] N, N-sulfide. 9. Use of the new compounds of formula I defined in claim 1 as active ingredients of an insecticide, acaricide or nematicide composition. 10. Use according to claim 9 of a compound as defined in one of claims 2 to 8.