CH623034A5 - Process for the preparation of new carbamatesulphenylcarbamoyl fluorides - Google Patents

Abstract

The compounds of formula I, in which R and R' are alkyl groups and R'' is H, a hydrocarbon group or an alcohol, phenol or oxime residue, are prepared by condensing a corresponding N-alkylcarbamoyl fluoride with a compound of formula ClSN(R')-CO-R''. The compounds of formula I are useful as insecticides, acaricides and nematocides. They are also intermediates for the manufacture of other pesticides. <IMAGE>

Description

The subject of the present invention is a process for the preparation of new carbamatesulfenylcarbamoyl fluorides of the following general formula:

OR R 'O

II I I II

FC-N-S-N-C-R "(I)

wherein R and R 'are the same or different and are alkyl groups having from 1 to 4 carbon atoms; R "is:

a) a hydrogen atom or b) an alkyl, cycloalkyl, phenyl, phenylalkyl, naphthyl, alkenyloxy, alkynyloxy, phenoxy, 5,6,7,8-tetrahydro-naphthoxy, naphthoxy, benzofuranoxy, benzothienoxy or methylenedioxyphenoxy group be unsubstituted or substituted by 1 or more chloro, bromo, fluoro, cyano, nitro, alkyl, alkynyloxy, phenoxy, phenyl, 2-dithiolanyl, 2-dioxalanyl, alkoxy, haloalkyl, dialkoylamino, cyanoalkyl, dicyanoethylidene or alkyloylthio any association, or c) a group of formula:

/ R1

-ON = Cs ^ or —ON = C ^ ^ A;

R2

wherein R 1 is a hydrogen atom, an alkyl or alkylthio or cyano group; R2 is an alkyl, alkylthio, alkoxy, alkanoyl, alkoxycarbonyl, aminocarbonyl, alkyllaminocarbonyl or dialkoylaminocarbonyl group, all of which may be unsubstituted or substituted aliphatically in any association with one or more of the cyano, nitro, alkylthoyl, alkyl alkoxy, aminocarbonyl, alkyllaminocarbonyl, or dialkoylaminocarbonyl or R2 is a phenyl, aminocarbonyl, alkyllaminocarbonyl, dialkoylaminocarbonyl or R3CONH— or R3CON (alkyl) - where R3 is a hydrogen atom, an alkyl group or an alkoxy group; and A is a bivalent aliphatic chain completing a nucleus having 5 or 6 members which comprises 1 or 2 oxygen radicals, bivalent sulfur or sulfinyl or sulphonyl groups and which can also comprise a bivalent amino group, alkylamino or carbonyl, in n any association, provided that the total number of aliphatic carbon atoms in Ri, R2 and A separately does not exceed eight.

Preferred compounds according to the invention are those where R and R 'are both methyl groups.

Many of these compounds are themselves useful as insecticides, acaricides and nematocides. All these compounds are useful as intermediate compounds for the preparation of pesticidal compositions by reaction with oximes to form bis-carbamates linked by a sulfenyl group. For example, 1-methylthioacetaldehyde 0- [N-methyl-N- (N'-methyl-N'-fluoroformylaminosulfenyl) carbamoyl] -oxime can be reacted with 2-methylthio-2-methylpropionaldoxime in the presence of an acceptor acid to give N- [2-methylthio-2-methylpropionaldehyde-0- (N-methylcarbamoyl) oxime] -N- [1-methylthioacetaldehyde-0- (N'-methylcarbamoyl) oxime] sulfide, which has properties remarkable insecticides and acaricides. The preparation and the utility of these bis-carbamates prepared by the reaction of compounds according to the invention with oximes and other compounds containing an active hydrogen are described in more detail in the patent application USA N ° 636630 entitled " unsymmetrical bis-carbamate ”.

The reaction which is used for the preparation of the present compounds is represented by the following reaction scheme: OR R 'O OR R' O

11 1 li 1J, JT o JL „

FC — NH + C1S —N — C — R "►FC-N-S-CR"

acid acceptor

The reaction is carried out in the presence of an acid acceptor which can be an organic or inorganic base such as triethylamine, tetraethylenediamine, pyridine or hydroxide.

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sodium or potassium, preferably in proportion to at least one equivalent.

The reaction is also normally carried out in the presence of an inert solvent such as an ether, a chlorinated hydrocarbon or an aromatic solvent or any of the many inert organic solvents commonly used for these reactions. Examples of the inert solvents that can be used are methylene chloride, chloroform, dioxane, tetrahydrofuran, benzene, toluene, acetone, dimethoxyethane, dimethylformamide, acetonitrile, etc.

The reaction temperatures are not critical for the conduct of the reaction and can be between approximately - 50 ° C and approximately 100 ° C. Preferably, these reactions are carried out at a temperature between 0 and 40 ° C.

The N-alkylcarbamoyl fluorides used as starting materials can be conveniently prepared by the reaction of HF and an alkyl isocyanate.

The chlorosulfenyl compounds used as starting materials are known compounds which can be prepared in known manner. See for example USA patents Nos 3752841, 3726908, 3843669, 3843689 and Belgian patents Nos 813206 and 815513. The following examples illustrate the invention.

Example 1:

Preparation of N-methyl-N- (N'-methyl-N'-formyl-aminosulfenylcarbamoyl fluoride

To a solution of 9.0 g of HF in 100 ml of toluene cooled to -50 ° C was added 25.6 g of methyl isocyanate. After stirring for 45 min and allowing the mixture to warm to -10 ° C, 56.4 g of N-methyl-N-formyl-aminosulfenyl chloride dissolved in 300 ml of toluene was added. 45.4 g of triethylamine was added dropwise over half an hour while the temperature was maintained between 0 and 8 ° C by external cooling. After stirring for 1 h at room temperature, the reaction mixture was diluted with 200 ml of ice water. The organic layer was separated, washed with water, dried and then concentrated. Distillation of the residue gave 22.4 g of product which boiled at 60-62 ° C / 0.2 mm.

Analysis for C4H7FN2O2S:

Calculated: C 28.91 H 4.24 N 16.86 Found: C 29.01 H 4.43 N 16.26.

Example 2:

Preparation of N-methyl-N- (N'-methyl-N'-acetylaminosulfenyl) carbamoyl fluoride

To a solution of 13.32 g of HF in 100 ml of toluene cooled to -50 ° C, 38.05 g of methyl isocyanate was added. The reaction mixture was allowed to warm to approximately 8 ° C and stirred at this temperature for A h. Then 93.0 g of N-methylacetylaminosulfenyl chloride dissolved in 250 ml of toluene were dissolved and then 67.4 g of triethylamine was added dropwise. The temperature was maintained at 0-5 ° C during the addition. After stirring at room temperature for 1 hr, the reaction mixture was diluted with 200 ml of water. The toluene extract was further washed with water, dried with magnesium sulfate and evaporated in vacuo. Distillation of the residue gave 40.0 g of product which boiled at 70-74 ° C / 0.5 mm.

Analysis for C5H9FN2O2S:

Calculated: C 33.32 H 5.03 N 15.55 Found: C 32.71 H 5.02 N 15.13.

Other compounds which can be prepared in an analogous manner are the following:

N-Methyl-N- (N'-propyl-N'-formylaminosulfenyl) carbamoyl-fluoride,

N-Methyl-N- (N'-butyl-N'-acetylaminosulfenyl) carbamoyl-fluoride,

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2.3-Dihydro-2-methyl-7- [N-methyl-N- (N'-methyl-N'-fluoro-formylaminosulfenyl) carbamoyloxy] benzofuran,

1- [N-Methyl-N- (N'-methyl-N'-fluoroformylaminosulfenyl) -carbamoyloxy] -5,6,7,8-tetrahydronaphthalene,

2-Methyl-2-methylsulfonylpropionaldehyde 0- [N-methyl-N- (N'-fluoroformylaminosulfenyl) carbamoyl] oxime,

1 -Isopropylthioacetaldehyde 0- [N-methyl-N- (N'-methyl-N'-

fluoroformylaminosulfenyl) carbamoyl] oxime, 2-Methyl-2-methoxypropionaldehyde 0- [N-methyl-N- (N'-methyl-

N'-fluoroformylaminosulfenyl) carbamoyl] oxime, 1 - (2-Cyanoethylthio) acetaldehyde 0- [N-methyl-N- (N'-methyl-

N'-fluoroformylaminosulfenyl) carbamoyl] oxime, 2-Methyl-2-cyanopropionaldehyde 0- [N-methyl-N- (N'-methyl-

N'-fluoroformylaminosulfenyl) carbamoyl] oxime, 1 -N-Methylthio-1-dimethylcarbamoylformaldehyde 0- [N-methyl-N- (N'-methyl-N'-fluoroformylaminosulfenyl) carbamoyl],

2 - {{0- [N-methyl-N- (N'-methyl-N'-fluoroformylamino-sulfenyl) carbamoyl] oximino}} - 4-methyltetrahydro-1,4-thiazin-3-one,

1 -Methylthio-3,3-dimethylbutanone-2 0- [N-methyl-N- (N'-methyl-N'-fluoroformylaminosulfenyl) carbamoyl] oxime, 2 - {{0- [N-methyl-N- (N '-methyl-N'-fluoroformylaminosulfenyl) -

carbamoyl] oximino}} - 1,3-dithiolane, 4 - {{0- [N-methyl-N- (N'-methyl-N'-fluoroformylamino-

sulfenyl) carbamoyl] oximino}} - 5,5-dimethyl-1,3-dithiolane, 4 - {{0- [N-methyl-N- (N'-methyl-N'-fluoroformylaminosulfenyl) -

carbamoyl] oximino}} -5-methyl-1,3-oxathiolane, 2 - {{0- [N-methyl-N- (N'-methyl-N'-fluoroformylamino-

sulfenyl) carbamoyl] oximino}} -3,3-dimethyl-1,4-dithiane, 2 - {{0- [N-methyl-N- (N'-methyl-N'-fluoroformylaminosulfenyl) -

carbamoyl] oximino}} - 3-isopropylthiazolidin-4-one, 2 - {{0- [N-methyl-N- (N'-methyl-N'-fluoroformylamino-

sulfenyl) carbamoyl] oximino}} -4,5,5-trimethylthiazolidin-3- one, 4-Dimethylamino-3,5-xylyl-N-methyl-N- (N'-methyl-N'-fluoro-

formylaminosulfenyl) carbamate, 4-Methoxycarbonylamino-3,5-xylyl-N-methyl-N- (N'-methyl-N'-fluoroformylaminosulfenyl) carbamate,

2-Isopropoxyphenyl-N-methyl-N- (N'-methyl-N'-fluoroformyl-aminosulfenyl) carbamate,

3-sec-Butylphenyi-N-methyl-N- (N'-methyl-N'-fluoroformyl-aminosulfenyl) carbamate,

3.4-Xylyl-N-methyl-N- (N'-methyl-N'-fluoroformylamino-sulfenyl) carbamate,

3,4-Methylenedioxyphenyl-N-methyl-N- (N'-methyl-N'-fluoro-formylaminosulfenyl) carbamate,

4-Methylthio-3,5-xylyl-N-methyl-N- {N'-methyl-N'-fluoroformyl-aminosulfenyl) carbamate,

2-Dioxalanylphenyl-N-methyl-N- (N'-methyl-N'-fluoroformyl-aminosulfenyl) carbamate,

1-Methylthioacetaldehyde 0- [N-butyl-N- (N'-methyl-N'-fluoro-formylaminosulfenyl) carbamoyl] oxime,

2-Methyl-2-methylthiopropionaldehyde 0- [N-methyl-N- (N'-isopropyl-N'-fluoroformylaminosulfenyl) carbamoyl] -oxime,

2-Methyl-2-methoxypropionaldehyde 0- [N-methyl-N- (N'-butyl-N'-fluoroformylaminosulfenyl) carbamoyl] oxime,

2.4-Dinitro-6-sec-butylphenyl-N-methyl-N- (N'-methyl-N'-fluoroformylaminosulfenyl) carbamate,

2,6-di-tert-butyl-4- {2,2-dicyanoethylidene) phenyl-N-methyl-N- (N'-methyl-N'-fluoroformylaminosulfenyl) carbamate,

3-Isopropylphenyl-N-methyl-N- (N'-methyl-N'-fluoroformyl-aminosulfenyl) carbamate,

4-Isopropylphenyl-N-methyl-N- (N'-methyl-N'-fluoroformyl-aminosulfenyl) carbamate,

3.5-di-tert-butyl-4- [N-methyl-N- (N'-methyl-N'-methyl-N'-fluoroformylaminosulfenyl) carbamoyloxy] benzylidene malononitrile,

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1 -Cyano-2,2-dimethylpropionaldehyde 0- [N-methyl-N-

(N'-methyl-N'-fluoroformylaminosulfenyl) carbamoyl] oxime, l-MethyIsu! Fonyl-3,3-dimethylbutanone-2 0- [N-methyl-N- (N'-methyl-N'-Fluoroformylaminosulfenyl) carbamoyl] -oxime,

3-Methylsulfonylbutanone-2 0- [N-methyl-N- (N'-methyl-N'-

fluoroformylaminosulfenyl) carbamoyl] oxime, N-Methyl-N- (N'-methyl-N'-dodecanoylaminosulfenyl) -carbamoylfluoride.

All of the compounds of the present invention can be prepared simply and in excellent yield by the process described above simply by choosing the appropriate reactants to obtain the desired compound.

A selection of the new compounds was evaluated to determine their pesticidal activity against mites, nematodes 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 the compound in 50 ml of acetone in which 0.1 g (10% of the weight of the compound) of an alkylphenoxypolyethoxyethanol was dissolved as an emulsifying surfactant or of dispersion. The solution obtained was mixed in 150 ml of water to obtain approximately 200 ml of a suspension containing the compound in finely divided form. The mother suspension thus prepared contained 0.5% by weight of compound. The test concentrations in ppm by weight used for the tests described below were obtained by appropriate dilutions of the mother suspension with water. The test procedures were as follows:

Spray test of Aphis fabae Scop. on the foliage

The test insects were adults and nymphs of Aphis fabae Scop. grown on dwarf nasturtium plants in pots at 18-21 ° C and a relative humidity of 50-70%. For the purposes of the test, the number of aphids per pot was standardized to 100-150 by pruning the plants containing too many aphids.

The test compounds were made up by diluting the mother suspension with water to obtain a suspension containing 500 parts of test compound per million parts of final composition.

Potted plants (one pot per test compound) infested with 100-150 aphids were placed on a turntable and sprayed with 100-110 ml of test compound composition using a "DeVilbiss" sprayer set to 2.8 kg / cm2 (40 psig) relative air pressure. This application, which lasted 25 s, was sufficient to wet the plants until they ran out. As a control, a water-acetone-emulsifier solution containing no test compound was also sprayed onto the infested plants. After spraying, the pots were placed on their side on a sheet of standard white mimeograph paper where lines had been drawn beforehand to facilitate counting. The temperature and humidity in the test chamber during the 24 h hold period were: 18-21 ° C and 50-70% respectively The aphids that fell on the sheet of paper and were unable to stand after that they were straightened were considered dead. The remaining aphids on the plants were observed carefully for movement and those that were unable to shift the length of the body when stimulated by pushing them were considered dead. The percent mortality was noted for various concentration rates.

Spray test of Prodenia eridania, (Cram.) On leaves

The test insects were Prodenia eridania (Cram.) Larvae reared on "Tendergreen" bean plants at a temperature of 27 ± 3 ° C and a relative humidity of 50 + 5%.

The test compounds were made up by diluting the mother suspension with water to obtain a suspension containing 500 parts of test compound per million parts of final composition. "Tendergreen" bean plants were placed in standard height and age pots on a turntable and sprayed with 100-110 ml of test compound composition using a set "DeVilbiss" sprayer at a relative air pressure of 0.7 kg / cm2. This application, which lasted 25 s, was sufficient to wet the plants until they ran out. As a control, 100-110 ml of a water-acetone-emulsifier solution containing no test compound was also sprayed onto the infested plants. When they were dry, the pairs of leaves were separated and each was placed in a 9 cm Petri dish lined internally with moistened filter paper. 5 larvae, statistically chosen, were introduced into each box and the boxes were closed. The closed cans were labeled and kept at 27-29 ° C for 3 days. Although the larvae can easily consume the entire leaf within 24 hours, no other foods have been added. Larvae that were unable to move the length of the body, even when stimulated by pushing them, were considered dead. The percent mortality was noted for various concentration rates.

Spray test rf'Epilachna varivestis, Muls. on leaves

The test insects were four fourth molt larvae of Epilachna varivestis, Muls. grown on Tendergreen bean plants at a temperature of 27 + 3 ° C and a relative humidity of 50 + 5%.

The test compounds were made up by diluting the mother suspension with water to obtain a suspension containing 500 parts of test compound per million parts of final composition. Plants of "Tendergreen" beans in standard height and age pots were placed on a turntable and sprayed with 100-110 ml of test compound composition using a "DeVilbiss" sprayer set to a relative air pressure of 0.7 kg / cm2. This application, which lasted 25 s, was sufficient to wet the plants until runoff. As a control, 100-110 ml of a water-acetone-emulsifier solution containing no test compound was also sprayed onto infested plants. When they were dry, the pairs of leaves were separated and then each was placed in a 9 cm Petri dish lined internally with a moistened filter paper. 5 larvae, statistically chosen, were introduced into each box and the boxes were closed. The closed cans were labeled and kept at 27 + 3 ° C for 3 days. Although the larvae can easily consume the leaf within 24-48 h, no other food has been added. Larvae that were unable to move the length of the body even after stimulation were considered dead.

Bait test for flies

The test insects of Musca domestica, L. adults 4 to 6 days old reared according to the indications of "The Chemical Specialties Manufacturing Association" ("Blue Book, McNair-Dorland Co., NY", 1964; pp 243-244, 261) under controlled conditions of 27 + 3 ° C and a relative humidity of 50 + 5%. The flies were immobilized by anesthetizing them with carbon dioxide and 25 immobilized individuals, males and females, were transferred to a cage which consisted of a standard colander for food of about 127 mm in diameter which was inverted on a surface covered with wrapping paper. The test compounds were made up by diluting the mother suspension with a 10% by weight sugar solution to obtain a suspension containing 500 parts of test compound per million parts by weight of final composition. 10 ml of the test composition was added to a blowing cup containing a 25 x 25 mm square pad of absorbent cotton. This baited cup was introduced and centered on the blotting paper under the front food colander to introduce anesthetized flies. The caged flies were left to eat the bait for 24 h at a temperature of 27 ± 3 ° C and a relative humidity of 50 + 5%. Flies that did not show

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sign, movement when pushed were considered dead.

Mite spray test on leaves

The test organisms were adults and nymphs of Tetranychus urticae Koch with two spots raised on "Tendergreen" bean plants at 27 + 3 ° C and at a relative humidity of 00 + 0%. Infested leaves from a standard crop were placed on the first leaves of two 152-203 mm tall bean plants growing in a 64 mm soil pot. 150-200 mites were transferred, a sufficient number for testing from the cut leaves to fresh plants within 24 h. After the 24 hr transfer period, cut leaves were removed from the infested plants. The test compounds were made up by diluting the mother suspension with water to obtain a suspension containing 500 parts of test compound per million parts of final composition. Potted plants (one pot per compound) were placed on a turntable and sprayed with 100-110 ml of composition of the test compound using a "DeVilbiss" sprayer set to a relative air pressure of 2.8 kg / cm2. This application lasted 25 s and was sufficient to wet the plants until runoff. As a control, 100-110 ml of aqueous solution was also sprayed containing the same concentrations of acetone and emulsifier, but containing no test compound; the sprayed plants were kept at 27 + 3 ° C and at a relative humidity of 00 +% for 6 days and then the mobile forms were counted for mortality. The microscopic examination for the mobile forms was done on the leaves of the test plants. Every organism capable of moving when pushed was considered to be alive.

Nematocidal test

The test organism used was the infectious migratory larvae of Meloidogyne incognits va acrita, reared in the greenhouse on the roots of cucumber plants. The infected plants were removed from the culture and the roots were very finely chopped. A small amount of this inoculum was added to a pointed jar containing approximately 180 ml of soil. A lid was put on the jars and incubated for one week at room temperature. During this period, the nematode eggs were hatched and the larval forms migrated into the ground.

10 ml of the test composition was added to each of the two jars for each dose tested. After the addition of the chemical compound, a lid was placed on the jars and the contents were thoroughly mixed in a ball mill for 5 min.

The test compounds were made up by a standard method of acetone solution added with an emulsifier and diluted with water. The primary control trials were conducted at 3.33 mg of the test compound per jar.

The jars with their lids were left at room temperature for 48 h and then the contents were transported in 76 mm jars. Then, the cucumber seeds were sown in the pots as an indicator crop and placed in the greenhouse where they were cared for in the usual manner for approximately three weeks.

The cucumber plants were then removed from the pots, the soil was removed from the roots and the amount of scab formation was assessed visually.

The results of these tests are shown in Table I below. In these tests, the pesticidal activity of the compounds was evaluated as follows:

A = excellent control.

B = partial control.

C = no control.

Dashes indicate that the test was not conducted.

(Finally patent table)

The compounds having a pesticidal activity envisaged by the present invention can be applied as insecticides, acaricides and nematocides according to the methods known to those of the art. Pesticide compositions containing the compounds as active toxic agents usually include a vehicle and / or a diluent, either liquid or solid.

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

The choice of dispersing agents and emulsifiers and the amount used are dictated by the nature of the composition and the power of the agent to facilitate the dispersion of the toxic agent. Generally, it is advantageous to use as little of the agent as possible, taking into account the desired dispersion of the toxic agent in the liquid to be sprayed so that rain does not re-emulsify the toxic agent after it application to the plant and do not wash it off the plant. Nonionic, anionic or cationic dispersing agents and emulsifiers can be used, for example the condensation products, oxide, alkylene with phenol and organic acids, alkylaryl sulfonates, complex ether alcohols, quaternary ammonium compounds, etc.

For the preparation of a wettable powder or granular composition, the active ingredient is dispersed in a solid vehicle suitably divided for example, clay, talc, bentonite, diatomaceous earth, fuller's earth , etc. For the composition of wettable powders, the above-mentioned dispersing agents can be included as well as lignosulfonates.

The quantity of toxic agents necessary envisaged here can be applied per 4046 m2 treated in 3.785 to 7571 or more of liquid vehicle and / or diluent agent or in approximately 2.268 to 226.8 kg of inert solid vehicle and / or diluent . The concentration in the liquid concentrate usually ranges from 10 to 95% by weight and in the solid compositions from about 0.5 to 99% by weight. Spray liquids, powders or granules suitable for general use contain approximately 0.1344 to 6.804 kg of active toxic agent per 4046 m2.

The pesticides considered here prevent attack by insects of mites and nematodes on plants or other materials to which the pesticides are applied and they have a relatively high residual toxicity. As far as plants are concerned, they have a high safety margin since when used in sufficient quantity to kill or hunt insects they do not burn and do not damage the plant and they are resistant to bad weather including leaching caused by rain, decomposition by ultraviolet light, oxidation or hydrolysis in the presence of moisture or finally a decomposition, oxidation or hydrolysis which would materially reduce the beneficial pesticidal property of toxic agents or which would communicate disadvantageous properties for example phytotoxicity to toxic agents. Toxic agents are so chemically inert that they are now compatible with virtually any other component of the spray program and can be used in soil, seeds or plant roots without damaging seeds or plant roots. plants.

As noted above, the present compounds are also useful as intermediates for the preparation of more complex pesticidal compounds.

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Table I

Ex. Compose Aphid Mite Prodenia Epilachna Fly Nematode eridania varivestis domestic (Cram.) Muls.

::? '-. -. .

2 N-Methyl-N- fluoride (N'-methyl-N'- C C C C B B

âeétylaminosulfényl) carbamoyl

4 1-Methylthioacetaldehyde 0- [N-methyl-N- A A A A A A (N'-methyl-N'-fluoroformylaminosulfenyl) -

carbamoyl] oxime

5 2-Methyl-2-methylthiopropionaldehyde A A A A A -0- [N-methyl-N- (N'-inethyl-N'-iluoro-

formylaminosulfenyl) carbamoyl] oxime

6 2,3-Dihydro-2,2-dimethyl-7- [N-methyl-N- A B A A A A (N'-methyl-N'-fluorocarbonylamino-

sulfenyl) carbamoyloxy] benzofuran

7 2- {0- [N-Methyl-N- (N'-methyl-N'- B B A A A -fluoroformylaminosulfenyl) carbamoyl] -

oximino} -3,5,5-trimethylthiazolidin-4-one

8 l- [N-Methyl-N- (N'-methyl-N'-fluoroformyl- A C A A C aminosulfenyl) carbamoyloxy] naphthalene

9 2- {0- [N-Methyl-N- (N'-methyl-N'- A A A A A fluoroformylaminosulfenyl) carbamoyl] -

oximino} -l, 4-dithiane

11 3-Isopropylphenyl-N-methyl-N- (N'- A C A A A -fluoroformylaminosulfenyl) carbamate

12 3,4,5-Trimethylphenyl-N-methyl-N- (N'- A C A A A C methyl-N-fluoroformylaminosulfenyl) -

carbamate

16 2-Isopropoxyphenyl-N-methyl-N- A C C A A A (N'-methyl-N'-fluoroformylaminosulfenyl) -

carbamate

17 l- [N-methyl-N- (N'-methyl-N'-fluoro- A C A A A A formylaminosulfenyl) carbamoyloxy] -

5,6,7,7-tetrahydronaphthalene

18 2-Propynyloxyphenyl-N-methyl-N'- A A A A A A (N'-methyl-N'-fluoroformylaminosulfenyl) -

carbamate

R

Claims (5)

623034 1. Process for the preparation of a new compound of formula: OR R 'O II I I 11 FC-N-S-N-CR "(I) characterized in that a compound of formula is reacted: GOLD II I FC-NH with a compound of formula: R 'O I II C1S-N-C-R " in the presence of an acid acceptor; R and R 'are the same or different and are alkyl groups having from 1 to 4 carbon atoms, R "is a) a hydrogen atom or b) an alkyl, cycloalkyl, phenyl, phenylalkyl, naphthyl, alkenyloxy group , alkynyloxy, phenoxy, naphthoxy, 5,6,7,8-tetrahydronaphthoxy, benzofuranoxy, benzothienoxy or methylenedioxyphenoxy all of which may be unsubstituted or substituted by one or more chloro-, bromo, fluoro-, cyano, nitro, alkyl, alkynyloxy radicals , phenoxy, phenyl, 2-dithiolanyl, 2-dioxalanyl, alkoxy, haloalkyl, dialkoyl-amino, cyanoalkyl, dicyanoethylidene or alkylthio in any combination or c) a group of formula: / Rl ✓ "—N -ON = C ^ or —ON = <^ ^ A; R2 in which R! is a hydrogen atom, an alkyl, alkylthio or cyano group, R2 is an alkyl, alkylthio, alkoxy, alkanoyl or alkoxycarbonyl, aminocarbonyl, alkylamino-carbonyl or dialkoylaminocarbonyl group which all may be unsubstituted or substituted aliphatically at any association with one or more cyano, nitro, alkylthio, alkylsulfinyl, alkylsulfonyl, alkoxy, aminocarbonyl, alkoylaminocarbonyl or dialcoylaminocarbonyl group or R2 is a phenyl, aminocarbonyl, alkyloyinocarbonyl, dialcoylaminocarbonyl group or R3CON— R3CON- hydrogen, an alkyl or alkoxy group and A is a bivalent aliphatic chain which completes a nucleus having 5 or 6 members which comprises one or two divalent oxygen or sulfur atoms sulfinyl or sulphonyl groups and which can also comprise a bivalent amino group , alkylamino or carbonyl in any combination provided that the total number of aliphatic carbon atoms in Ri, R2 and A individually does not exceed 8. 2. Use of the compounds of formula I defined in claim 1 as insecticides, acaricides and nematids. 2 3. Use according to claim 2 of 1-methylthioacetal-dehyde 0- [N-methyl-N- (N'-methyl-N'-fluoroformylamino-sulfenyl) carbamoyl] oxime. 4. Use according to claim 2 of 2-methyl-2-methyl-thiopropionaldehyde 0- [N-methyl-N- (N'-methyl-N'-fluoro-formylaminosulfenyl) carbamoyl] oxime. 5. Use according to claim 2 of 2- {0- [N-methyl-N- (N'-methyl-N'-fluoroformylaminosulfenyl) carbamoyl] -oximino} -3,5,5-trimethylthiazolidin-4-one.