CH638815A5 - N - ((PHOSPHINYL) -AMINO) -THIO- AND N - ((PHOSPHINOTHIOYL) -AMINO) -THIO-METHYLCARBAMATES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE IN PESTICIDES. - Google Patents

Description

The invention relates to an N- [phosphinyl) amino] thio-methylcarbamate, processes for their preparation and their use in pesticides.

55 substituted thio derivatives of methyl carbamate pesticides are known from U.S. Patents 3,781,331 and 3,794,733. From BE-PS 860 844 acylaminothio derivatives of methyl carbamate pesticides, namely N - [(phosphinyl) amino] thio-methyl-carbamate, are known. As far as is known, phosphine-60 acid derivatives of aminothiomethylcarbamate pesticides have not yet been prepared from cyclic phosphoramidothioates.

The invention was based on the object of providing methyl carbamate pesticides, the effectiveness of which is at least equivalent to that of the mother compounds against harmful insects, but is generally superior. In particular, methyl carbamate pesticides with reduced toxicity to mammals, reduced phytotoxicity and longer residual effects are to be provided.

638 815

6

The invention thus relates to N - [(phosphinyl) amino] thio and N - [(phosphinothioyl) amino] thio methylcarbamate pesticides of the formula

0

II

■ c-

CH3

I.

N— S-

y 1

/ T,

(ÇZsZa) k

I \ f "

'4

w in which mean:

R is a radical of the formula: a)

«3

25th

in which R2, R3 and R4, which may be the same or different, each for a hydrogen or halogen atom, an alkyl group with 1 to 5 carbon atoms, an alkoxy radical with 1 to 5 carbon atoms, an alkylthio radical with 1 to 5 carbon atoms, one Dialkylamino radical, the alkyl parts of which are identical or different and have 1 to 3 carbon atoms, or represent a radical of the formula -N = CHN (CH3) 2;

form where n = 2 or 3 and the alkylene portion of the ring is optionally substituted by one or two methyl groups;

30 or A and B together with the carbon atom to which they are attached form a heterocyclic ring containing two sulfur atoms of the formula:

35

b)

B

- C 1

A

N -

40

in which A and B, which may be the same or different, and each an alkyl radical having 1 to 5 carbon atoms, an alkylthio radical having 1 to 5 carbon atoms, a monocyano-substituted alkylthio radical having 1 to 5 carbon atoms, a phenylthio radical, the phenyl part of which may be by 1 to 3 the same or different substituents from the group halogen or alkyl radicals having 1 to 4 carbon atoms is substituted, represent the cyano radical, an alkoxy radical with 1 to 5 carbon atoms, a phenyl radical or a hydrogen atom, with the proviso that in the event that B represents a hydrogen atom , A of the formula:

R / r - C - S - Rc

45

where m = 2 or 3 and the alkylene part of the ring is optionally substituted by one or two methyl radicals, or c)

"7

corresponds, in which mean:

Rs is an alkyl radical having 1 to 3 carbon atoms or the phenyl radical;

Rö is an alkyl radical with 1 to 3 carbon atoms; and R7 is an alkyl radical having 1 to 3 carbon atoms or a radical of the formula -SRs, in which Rs represents an alkyl radical corresponding to the alkyl radical represented by Rs, or

Rs and Rs together with the atoms to which they are attached form a heterocyclic ring of the formula containing two sulfur atoms:

50

55 in which

Ri is a lower alkyl radical, an optionally substituted phenyl radical, a phenyl-substituted lower alkyl radical or a cycloalkyl radical;

X is an oxygen or sulfur atom,

60 Zi to Zö, which are the same or different and denote hydrogen or the methyl or ethyl radical and k is 0 or 1.

p = 3 or 4.

Alkoxy radicals with 1-5 C atoms are methoxy, ethoxy, pro-65 poxy, isopropoxy, butoxy, pentoxy radicals or their isomers. Alkylthio radicals with 1-5 C atoms are methylthio, ethylthio, propylthio, isopropylthio, butylthio or pentylthio radicals or their isomers.

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Alkyl residues with 1-5 C atoms are methyl, ethyl, propyl, butyl or pentyl residues or their isomers. Cycloalkyl radicals are understood to mean, for example, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl radicals, which may optionally be substituted by a total of 9 carbon atoms by methyl, ethyl or propyl radicals.

Phenyl-substituted lower alkyl radicals are benzyl, phen-ethyl, phenpropyl, phenbutyl or phenpentyl radicals or their isomers.

Substituted phenyl radicals are, for example, lower alkoxyl or alkoxy radicals, halogen atoms, nitro radicals or unsubstituted phenyl radicals. The phenyloxy combinations can carry substituents and can be, for example, 4-propyl-2-methyl, 2-chloro-4-methyl, 3,4-diethoxy or 3-cyano-4-ethoxyphenyl residues. In practice, substituted phenyl radicals are limited to a total of 10 carbon atoms, so that the limit is formed, for example, by the 4-isobutylphenyl radical.

The process for the preparation of the new compounds of the formula I is characterized in that a compound of the formula o ch, N I J r-o-c-n-h

(III)

with a compound of the formula

(II)

implements, wherein R, Ri, k, X and Zi-Ze have the meaning given above.

The reaction is usually carried out in the cold, preferably at a temperature of from −20 ° to +25 ° C. in the presence of a suitable acid acceptor and an inert organic medium. Examples of suitable acid acceptors are trialkylamines, e.g. Triethylamine, pyridine and lutidine. Examples of organic reaction media are dimethylformamide, diethyl ether, hexane, tetrahydrofuran and acetonitrile. If non-polar and somewhat polar solvents are used, copper (I) chloride and aluminum chloride can also be used to catalyze the reaction.

The compounds of formula I can be obtained and purified in a conventional manner. For this purpose, filtration, solvent evaporation, chromatographic methods and / or crystallization are preferably used. Some of the compounds can be obtained in crystalline form, others are purified in oily form. The phosphinic acid N-chlorothioamides of the formula II are generally obtained by reacting the corresponding phosphoric acid amides with sulfur dichloride at a temperature of about −20 ° to +25 ° C. in the presence of a suitable acid acceptor and an inert inorganic medium. The phosphinic acid amides are either readily available or can be obtained by known methods, e.g. according to Houben-Weyl "Methods of Organic Chemistry", Volume 12, Part 2, page 413 and Volume 12, Part 1, Pages 529 and 595, Georg Thieme Verlag, Stuttgart, Federal Republic of Germany, 1963.

Compounds preferred according to the invention are those of the formula:

35

0 CH3 X

III H

B-C ^ N-0-C-N-S-N-P

l l

H

/

(CZ5Za) | <

V

(Ia)

wherein A and B, which may be the same or different, represent 2

low alkyl radicals with 1 to 5 carbon atoms, low i *

Alkylthio radicals with 1 to 5 carbon atoms, monocyanosub- I

substituted alkylthio residues with 1 to 5 carbon atoms, Phe- 60 "* 0" C ~ Zz nylthio residues, the phenyl part of which by 1 to 3 identical or different

different substituents from the groups halogen and alkyl- (c Z 5 Z 3) 1,

residues with 1 to 4 carbon atoms, may be substituted, yf

Cyano residues, alkoxy residues with 1 to 5 carbon atoms or "0" C "Z

Phenyl radicals are and Ri, X, Zi to Ze and k the above 65> 3

bene meaning. 1

Some of the compounds of formula Ia, in which Y and Y '^ 4 are a radical of the formula:

638 815

form, in which Zi to Ze and k have the meaning given, show an unexpected crystallinity. For example, the compound N - {[(j [(5,5-dimethyl-2-thioxo-l, 3,2-dioxaphosphorinan-2-yl) tert-butylamino] thio} methyl-mino) carbonyl] oxy } ethanimi-

dothioate proven to be extremely crystalline. The physical properties due to the crystallinity facilitate the isolation of the reaction product from the reaction mixture. Furthermore, the highly crystalline compounds can be used to provide pesticidal agents in the form of wettable powders. These agents have highly advantageous properties, e.g. reduced solidification, high fluidity and high concentrations of active ingredients.

example 1

Methyl-N - {[(l [(5,5-dimethyl-2-thioxo-l, 3,2-dioxaphosphori-nan-2-yl) isopropylamino] thio} methylamino) carbonyl] oxylätha-nimidothioate:

A solution of 3.00 g (13.4 mmol) of 5,5-dimethyl-2-iso-propylamino-2-thioxo-l, 3,2-dioxaphosphorinane and 1.9 ml (13.5 mmol) of triethylamine in 20 ml of tetrahydrofuran is added dropwise within 20 min to a stirred solution of 1.00 ml (15.7 mmol) of sulfur dichloride in 20 ml of tetrahydrofuran at room temperature. When the addition is complete, the reaction mixture is stirred at room temperature for 1 h. Now the mixture with 0.25 g of copper (I) chloride and then dropwise with a solution of 2.17 g (13.4 mmol) of methyl N - {[(methylamino) carbonyl] -oxy] ethaneimido-thioate and 1.90 ml (13.5 mmol) of triethylamine in 20 ml of tetrahydrofuran. After stirring for 2 hours at room temperature, the mixture is diluted with water and extracted with ethyl acetate. The separated organic phase is washed with water, dried over magnesium sulfate and then concentrated under reduced pressure. The oily evaporation residue obtained in this way is chromatographed on silica gel, a mixture of ethyl acetate and Skellysolve B in a ratio of 2: 3 being used as the eluent. The chromatographed product is recrystallized from ethyl acetate, whereby methyl-N - {[({[(5,5-dimethyl-2-thioxo-l, 3,2-dioxaphosphorinan-2-yl) isopropylamino] thiolmethylamino) carbonyl] oxyläthanimi -dothioate in the form of a white solid with an mp of 114 ° to 115 ° C. The nuclear magnetic resonance spectrum and IR spectrum correspond to the expected structure.

The elementary analysis of the compound C13H26N3O4PS3 gives the following values:

calc .: C37.58 H6.31 N 10.11 found: C 37.63 H 6.25 NI 0.11

Example 2

Methyl-N-f [(f [(5,5-dimethyl-2-thioxo-1,3,2-dioxaphosphori-nan-2-yl) tert-butylamino] thio) methylamino) carbonyl] oxylätha-nimidothioate:

A solution of 7.4 g (31 mmol) of 2-tert-butylamino-5,5-dimethyl-2-thioxo-l, 3,2-dioxaphosphorinane and 4.4 ml (31 mmol) of triethylamine in 50 ml of tetrahydrofuran added dropwise within 20 min with stirring to a solution of 2.0 ml (31 mmol) of sulfur dichloride in 20 ml of tetrahydrofuran cooled to a temperature of 0 ° C. When the addition is complete, the mixture is stirred at a temperature of 0 ° C. for 30 minutes, whereupon the mixture is mixed with 0.3 g of copper (I) chloride and then dropwise within 20 minutes with a solution of 5.1 g (31 mmol ) Methyl-Nl [(methyl-lamino) carbonyl] oxy} ethane imidothioate and 4.4 ml (31 mmol) of triethylamine in 50 ml of tetrahydrofuran is added. When the addition is complete, the mixture is stirred for 2 hours while being allowed to warm to room temperature. The mixture is then diluted with ethyl acetate and washed with water. The separated organic solution is over

Magnesium sulfate dried and concentrated under reduced pressure. The evaporation residue obtained is treated with a 1: 2 mixture of ether and hexane to precipitate a crude product. After recrystallization from methanol twice, an analytically pure material with an mp of 167 ° to 168.5 ° C. is obtained. The nuclear magnetic resonance spectrum and IR spectrum correspond to the expected structure.

The elementary analysis of the compound C14H28N3O4PS3 gives the following values:

calc .: C39.14 H 6.57 N9.78 found: C 39.45 H 6.73 N9.87.

Example 3

Methyl-N - {[({[cyclohexyl (5,5-dimethyl-2-thioxo-l, 3,2-dioxa-phosphorinan-2-yl) amino] thio} methylamino) carbo-nyl] oxy) ethaneimidothioate:

A solution of 12.4 g2-cyclohexylamino-5,5-dimethyl-2-thioxo-l, 3,2-dioxaphosphorinane and 6.55 ml of triethylamine in 50 ml of tetrahydrofuran is stirred within 15 minutes in a temperature of - 5 ° to 0 ° C cooled solution of 3.0 ml of sulfur dichloride in 50 ml of tetrahydrofuran. After the addition has ended, the mixture is stirred for 45 minutes at a temperature of 0 ° C. and then with 0.20 g of copper (I) chloride and finally within 15 minutes with a solution of 7.67 g of methyl N - {[ (methylamino) carbo-nyl] oxy} ethane imidothioate and 6.55 ml of triethylamine in 50 ml of tetrahydrofuran. When the addition is complete, the mixture is stirred, allowing it to warm to room temperature within 75 minutes. Then the mixture is diluted with water and extracted with ethyl acetate. The extracts obtained are washed with water, dried over magnesium sulfate and concentrated under reduced pressure. Recrystallization of the semi-solid evaporation residue from ethyl acetate / hexane gives 9.36 g of methyl N - {[() [cyclohexyl (5,5-dimethyl-2-thioxo-l, 3,2-dioxaphos-phorinan-2-yl) amino] thio} methylamino) carbonyl] oxy} ethane midothioate in the form of a white solid, mp 138 ° to 140 ° C.

The elementary analysis of the compound C16H30N3O4PS3 gives the following values:

calc .: C42.18 H6.64 N9.22 found: C 42.39 H 6.71 N9.32.

The nuclear magnetic resonance spectrum and the IR spectrum correspond to the expected structure.

Example 4

Methyl-N - {[({[isopropyl (5,5-diethyl-2-thioxo-l, 3,2-dioxaphos-phorinan-2-yl) amino] thiolmethylamino) carbonyl] oxy} ethanol midothioate:

A solution of 10.94 g of 5,5-diethyl-2-isopropylamino-2-thioxo-l, 3,2-phosphorinane and 6.05 ml of triethylamine in 50 ml of tetrahydrofuran is added dropwise within 15 minutes to a temperature of -5 ° to 0 ° C cooled solution of 2.72 ml of sulfur dichloride in 50 ml of tetrahydrofuran. After the addition had ended, the mixture was stirred at a temperature of 0 ° C. for 1 h, then 0.10 g of copper (I) chloride and then a solution of 7.06 g of methyl N - {[(methylamino ) carbo-nyl] oxy) ethane imidothioate and 6.05 ml of triethylamine in 50 ml of tetrahydrofuran. The mixture is then stirred and allowed to warm to room temperature within 1 h. Now it is diluted with water and extracted with ethyl acetate. The extracts obtained are washed with water, dried over magnesium sulfate and concentrated under reduced pressure. The oily evaporation residue obtained in this way is chromatographed on silica gel, a 1: 1 mixture of ethyl acetate and hexane being used for the elution. When recrystallizing from ethyl acetate / hexane

8th

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

9

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there is obtained methyl N - {[({[isopropyl (5,5-diethyl-2-thioxo-l, 3,2-dioxaphosphorinan-2-yl) amino] thio) methylamino) carbo-nyljoxyläthanimidothioat in the form of a white solid mp 123 ° to 124.5 ° C.

The elementary analysis of the compound C15H30N3O4PS3 gives the following values:

calc .: C 40.61 H 6.82 N9.48 found: C 40.83 H 6.91 N9.60.

The nuclear magnetic resonance spectrum and IR spectrum correspond to the expected structure.

Example 5

Starting from suitable methyl carbamates and phosphoramidothioates according to Example 2, the following compounds are obtained:

Methyl N - {[({[isopropyl (2-thioxo-l, 3,2-phospholan-2-yl) amino] thiolmethylamino) carbonyl] oxy} ether imidothioate, mp: 120 ° to 122 ° C.

The elementary analysis of the compound C10H20N3O4PS3 gives the following values:

calc .: C 32.17 H 5.40 NI 1.25 found: C 32.17 H 5.31 NI 1.49.

Methyl - {[(([cyclohexyl (5,5-diethyl-2-thio-l, 3,2-dioxaphos-phorinan-2-yl) amino] thio} methylamino) carbonyl] oxy} ethane midothioate, mp: 155 ° to 157 ° C.

The elementary analysis of the compound C18H34N3O4PS3 gives the following values:

calc .: C 44.70 H 7.09 N8.69 found: C 44.96 H7, ll N8.81.

MethylH [({[isopropyl (2-thioxo-1,3,2-dioxaphosphorinan-2-yl) amino] thio} methylamino) carbonyl] oxy} ether imidothioate, mp: 153 ° to 154 ° C.

The elementary analysis of the compound C11H22N3O4PS3 gives the following values:

calc .: C 43.10 H 5.72 N 10.84 found: C 34.21 H 5.87 N 11.13.

Methyl - {[(f [ethyl (5,5-dimethyl-2-thioxo-l, 3,2-dioxaphosphorinan-2-yi) amino] thiolmethylamino) carbonyl] oxy} ethaneim idothioate, mp: 111 ° to 112 ° C.

The elementary analysis of the compound C12H24N3O4PS3 gives the following values:

calcd. C 35.90 H 6.03 N 10.47 found: C 36.13 H 6.22 N 10.26.

Methy 1-Nf [(([isopropyl (4,4,6-trimethyl-2-thioxo-1,3,2-di-oxaphosphorinan-2-yl) amino] thiolmethylamino) carbo-nyl] oxy} ethaneimidothioate, mp: 123 ° to 127 ° C.

The elementary analysis of the compound C14H27N3O4PS3 gives the following values:

calc .: C 39.24 H 6.35 N9.80 found: C 39.76 H 6.94 N9.76

Methyl-N-l [(((((2-thioxo-4H-l, 3,2-benzodioxaphosphorin-2-yl) -isopropylamino] thio} methylamino) carbonyl] oxy} etheriothothothate,

Methyl-N-f [({[(2-thioxo-l, 3,2-dioxaphospholan-2-yl) methylamino] thio} methylamino) carbonyl] oxy (ethane imidothioate,

Methyl-N - ([({[ethyl (hexahydro-2-oxo-l, 3,2-benzodioxaphos-pholan-2-yl) amino] thio} methylamino) carbonyl] oxy) ethanimi-dothioate,

Methyl N - ([(([isopropyl (2-oxo-l, 3,2-benzodioxaphospholan-2-yl) amino] thio} methylamino) carbonyl] oxylethane imidothioate,

Methyl-N - {[({[benzyl (5,5-diethyl-2-thioxo-l, 3,2-dioxaphos-phorinan-2-yl) amino] thio} methylamino) carbonyl] oxy} ethanol midothioate and

Methyl N-f [(([methyl (2-thioxo-l, 3,2-dioxaphosphorinan-2-yl) amino] thiolmethylamino) carbonyl] oxylethane imidothioate, mp 94 ° to 96 ° C.

The new compounds of the formulas represent effective pesticides for controlling invertebrates in agriculture, industry and at home. The compounds in question were compared with the starting methyl carbamates.

Representative pest species were, for example, 5 from the order «Lepidoptera», in particular the southern army worm (SAW) (Prodenia eridania Cramer), the tobacco bud worm (TBW) (Heliothis virescens) and the cabbage vise (CL) (Trichoplusia ni), from the order « Acarina »especially the double-spotted leaf spider mite (TSSM) (Tetrany-10 chus urticae Koch), from the order« Diptera »especially the house fly (HF) (Musca domestica Linnaeus) or the yellow fever mosquito (YFM) (Aedes aegypti), from the order« Orthoptera in particular the Heimchen (HC) (Acheta dome-sticus Linnaeus) or the German cockroach (GC) (Biais tella germanica Linnaeus) or from the order «Coleoptera» in particular the cotton capsule beetle (BW) (Anthonomus grandis Boheman).

The effectiveness against invertebrate pests could already be determined at concentrations of 0.5 20 ppm, depending on the type of pest. Some invertebrate pests are more sensitive than others to the compounds according to the invention, while others can be very resistant. As a rule, the compounds of the formula I are used in concentrations of about 30 to about 6000 ppm. As a rule, the compounds according to the invention show a mortality activity corresponding to the starting methyl carbamate, but at the same time they are less toxic and phyto-toxic. Mammalian toxicity is partially reported.

Methyl-N - {[(l [cyclohexyl (5,5-dimethyl-2-thioxo-l, 3,2-dioxa-30 phosphorinan-2-yl) amino] thio} methylamino) carbo-nyl] oxy) ethaneimidothioate:

35

insect

amount

mortality

SAW

11 ppm

70

CL

11 ppm

87.5

TBW

11 ppm

95

40

Mammalian toxicity - oral LDso (rats)> 8000 mg / kg

Methyl-N-l [(([isopropyl (5,5-diethyl-2-thioxo-l, 3,2-dioxaphos-phorinan-2-yl) amino] thiolmethylamino) carbonyl] oxy} ethanol-45 midothioate:

insect

amount

mortality

50

SAW

CL

TB

11 ppm 11 ppm 11 ppm

60 95 100

55 Mammalian toxicity

- oral LDso (rats)> 2000 mg / kg

Methyl-N-l [({[isopropyl (2-thioxo-l, 3,2-phospholan-2-yl) amino] thio} methylamino) carbonyl] oxylethane imidothioate, mp. 120 ° to 122 ° C:

60

insect

amount

mortality

65 SAW CL TB

11 ppm 11 ppm 11 ppm

40 48 45

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10th

Methyl N - {[(f [cyclohexyl (5,5-diethyl-2-thioxo-l, 3,2-dioxa-phosphorinan-2-yl) amino] thio} methylamino) carbonyloxylätha-nimidothioate, mp. 155 ° bis 157 ° C;

insect

amount

mortality

SAW

11 ppm

70

CL

11 ppm

77.5

TB

11 ppm

95

Mammalian toxicity - oral LDso (rats)> 8000 mg / kg

Methyl N - {[(l [isopropyl (2-thioxo-l, 3,2-dioxaphosphorinan- 15 2-yl) amino] thio} methylamino) carbonyl] oxy} ethaneimidothioate, mp. 153 ° to 154 ° C:

insect

amount

mortality

SAW

11 ppm

56

CL

11 ppm

TB

11 ppm

20th

Mammalian toxicity - oral LDso (rats)> 2000 mg / kg

Methyl-N - {[({[ethyl (5,5-dimethyl-2-thioxo-1,3,2-dioxaphos-phorinan-2-yl) amino] thiolmethylamino) carbonyl] oxy} ethane midothioate, mp. 111 ° to 112 ° C: 30

insect

amount

mortality

CL

11 ppm

56

35

Methyl-N - {[({[isopropyl (4,4,6-trimethyl-2-thioxo-l, 3,2-dioxa-phosphorinan-2-yl) amino] thio} methylamino) carbo-nyl] oxy} ether imidothioate , Mp 123 to 127 ° C:

insect

amount

mortality

CL

11 ppm

92.5

40

45

The details of the mortality test are as follows: Preparation of the Chemicals Tested: Analytically pure samples of the various compounds are dissolved in acetone 50. These acetone solutions are applied as such or in a form diluted with a Tween 20 "dampening water" or with a "dampening water" containing 10% cane sugar. The "dampening water" as such contained 0.132% (v / v) Tween 20 (polyoxyethylene sorbitan monolaurate). 55

The Southern Army Worm and Cabbage Teaser tests were performed on Henderson lima bean bean leaves. This bush bean has two primary leaves per seedling. The leaves were immersed in an emulsion of the compound to be tested in the "dampening water" and then allowed to dry. Then they were placed on a moistened filter disc in a plastic petri dish with a diameter of 9 cm. Five larvae of the insects to be tested were placed on the leaves, whereupon the lid of the Petri dishes was removed and the Petri dish was set aside for 6 s for further evaluations. Three parallel experiments were carried out for each treatment dose. The cricket test was performed by

5 ml portions of the acetone solution were pipetted into Petri dishes with a diameter of 9 cm. Then the acetone was smoked. 10 crested dolls were now placed in each treated petri dish, after which the lid was replaced. Three parallel experiments were carried out for each treatment dose.

The tests on the house fly and the cotton capsule beetle were carried out by saturating a cotton ball the size of a golf ball with 10 ml of a preparation of the compound to be tested, which was prepared using a “dampening water” containing 10% cane sugar. The saturated swab was then placed in a portioning cup which was attached to the inner wall surface of a waxed paper cup. The paper cup had a capacity of 141.7 g. 10 adult house flies or 10 cotton capsule beetles were placed in the waxed paper cups, whereupon they were covered with a plastic lid for further observation. Two parallel experiments were carried out for each treatment dose.

The larvae of the yellow fever mosquitoes were tested by adding 100 ml of distilled water with suitable amounts of a solution of the compound to be tested in the "dampening water" or the acetone solution. The water was in a waxed paper cup with a capacity of 141.7 g. Now 10 yellow fever mosquito larvae were placed in the paper cups and 24 hours later dried yeast was added. Two comparative experiments were carried out for each treatment dose.

The tests carried out using the Southern Army worm, the cricket, the cotton capsule beetle, the house fly and the cabbage stretcher were carried out at 22 ° C, the tests carried out using the yellow fever mosquito larvae were carried out at a temperature of 27 ° C calmly.

The tests aimed at killing the insects were evaluated after 24.48 and 72 hours, respectively. Dying insects and insects left on the ground were also counted among the insects killed.

In further experiments, the phytotoxicity, the residual efficacy and the toxicity to mammals were tested by comparing with methyl-N - {[(methylamino) carbonyl] oxy} äthanimi-dothioate. A scale was used, on which 0 indicates no damage and 10 stands for complete plant death. The new compounds according to the invention are generally less phytotoxic than the mother compound and significantly less phytotoxic to sensitive plants, e.g. the eggplant plant. The compounds according to the invention typically have an average phytotoxicity index in the range from approximately 1.0 to 1.5 at a concentration of 300 to 600 ppm after an exposure period of 8 days. The parent connection has corresponding index values from 4.25 to 5.0.

The compounds according to the invention were also tested for their residual activity (on the leaves) against larvae of the southern armyworm on lima bean seedlings. A compound according to the invention generally gives 100% mortality 7 weeks after the treatment has been carried out. The activity of the mother compound in an equivalent amount has already decreased to 20% after 14 days.

When compared to oral toxicity, which was carried out with male rats, a compound according to the invention was found to be less than a quarter as toxic as the methyl carbamate mother compound. The oral LD 50 values are 105 mg / kg body weight or 17 to 24 mg / kg body weight.

As already stated, the inventive

11 638 815

bonds particularly effective. For example, one can be used. Examples include talc,

such compound the up to 3 times the insecticidal activity of pyrophillite, quartz, diatomaceous earth, Fuller's earth, chalk, mother compound against Lepidopterus species, for example the sulfur, silicic acid-containing materials such as silicic acid

Southern Army Worm (SAW) and the Cabbage Tree. and silicates and the like. Furthermore, the concerned

The tests described show that the minerals according to the invention are chemically modified. examples for this are

Compounds are able to solve the tasks and washed bentonite or colloidal silica. Finally, a noteworthy contribution in the field of pesticides is also made from organic substances in flour-like forms. They also show that the N - [(Phos form, for example wood, walnut shells, soybean meal, cotton

phinyl) amino] thio and N - [(phosphinothioyl) amino] thio seed flour, tobacco flour and free-flowing hydrophobic starches,

Methyl carbamates to control insect pests in the form of 10 dusts can also be obtained by using the phosphine

the pure compound as prepared according to the examples of the acidic derivatives of aminothiomethylcarbamate pesticides, in the form of technically pure compounds of the formula I in a volatile solvent, e.g. Methylene

large-scale production or in the form of mixtures of chloride, dissolves the solution obtained with a powdered Tr.

special connections can be used. ger mixes and then evaporates the solvent.

On the other hand, for practical reasons, the proportion of powdered carrier and active compound

sig, the expert in the field of pesticides agents of the formula I can, depending on the intended use, with a diluting vehicle and possibly other control of roundworms (nematodes) or mites

Aids that the distribution of active compounds to and treatment conditions are very different. In

Combating pests and increasing the effectiveness of the rule can provide dusts up to about 90% by weight of active life and economy. 20 component included.

There are a large number of diluents or pesticides according to the invention in the form of dispersing agents.

Carrier materials for use in the field of powder are preferably obtained by incorporating one

Pest control and for the preparation of pesticide surfactants in the manner described

Means produced using the compound according to the invention. If a dusty fertilizer are suitable. Typically, about 25 to about 12% surfactant dispersible agents are incorporated.

Carrier materials used. Such carrier materials will remain, the dispersible obtained may contain other auxiliaries, e.g. Wetting agents, emulsifying powder especially good for further mixing with water gates, agents that improve adhesion and other components for spraying on inanimate objects and products,

which indirectly contribute to an improvement in effectiveness. Fruit trees, crops, soil and live animals e.g.

The new carbamates according to the invention of the formula I 30 livestock. The dispersible powders can be used with water for the production of any concentrations of active ingredient against insects, roundworms (nematodes) and mils. They can be mixed in in the form of pesticides. The mixture can then be used in such a manner, e.g. of dusts, wettable powders, emulsifiable amounts, that the desired application

Concentrates, aqueous dispersions, solutions and flow quantity and the even distribution achieved. Can be used under common creams. The agents in question can take account of this versatility.

can be applied to any location, e.g. on soils, on ren powder according to the invention preferably about 5 to about

Plants, on leaves, on seeds or on other parts of plants. Contain 80% active ingredient.

Granular agents can be applied to the floor after they have been prepared. Typical examples of pesticidal agents or on surfaces. Furthermore, the compounds of the formula I which are suitable according to the invention in the form of dispersible powders and the only 40 surface-active agents are alkyl sulfates and sulfonates, e.g.

be an active ingredient in a pesticidal agent, or that alkylarylsulfonates, sulfosuccinic acid esters, polyoxyethylene

respective pesticidal agents can also contain other active ingredients with sulfates, polyoxyethylene sorbitan monolaurate, alkylaryl poly

insecticidal, miticidal or nematocidal activity contain ether sulfates, alkylaryl polyether alcohols, alkylnaphthalenesulfonates. nate, quaternary alkylammonium salts, sulfated fatty acids

Those compounds of formula 45 according to the invention and their esters, sulfated fatty acid amides, glycerolmanni

I, which are solid, can easily be processed into dusts, tanlaurate, polyalkyl ether condensates of fatty acids, ligninsul-by a mixture of the compound (s) in question and a fonate and the like. Preferred surface-active agents powdered carrier material are mixed with one another are mixtures of sulfonated oils and of polyalcohol carbon

the. This grinding is usually carried out using usable acid esters (Emcol H-77), mixtures of polyethoxyethano

a ball mill, a hammer mill or by air oils (Tritone X-151, X-161, X-171), for example approximately the same fan atomization. Parts of sodium kerylbenzenesulfonate and isooctylphenoxypo-

The particle size of the individual ethoxyethanol with about 12 ethoxy groups, as well as mixtures

particles less than 60 microns. Preferably 95% of the genes have calcium alkyl aryl sulfonates and polyethoxylated ones

Particles less than 50 microns in size, such as vegetable oils (Agrimul N2S). Of course they can

75% of the particles show a particle size of 5 to 20 55 preferably called sulfates and sulfonates in the form of their

Micron. Dusts of the fineness mentioned, size reduction or soluble salts, for example their sodium salts, are used

Distribution are usually free-flowing powders. You can be brought. All of these surface-active agents on animals, on inanimate objects and on fruit trees are in order to lower the surface tension of water

Harvest plants and so applied to the soil are capable of concentrations of about 1% or less. Disper-

that an appropriate distribution or coverage is achieved. 60 geable powders can also be obtained with

The dusts are particularly suitable for combating surfaces using mixtures of surfactants, insects and mites, by using the species in question.

the pesticide means dusted with airplanes. Suitable dusts A suitable dispersible powder is obtained for example

also for application to the underside of foliage. by mixing and grinding 327 kg of Georgia

Typical examples of suitable powdered carrier material - 65 ton, 4.5 kg isooctylphenoxypolyäthoxyäthanol (Triton X-100)

materials are natural clays, e.g. Chinaton, Georgia clay, bar as wetting agent, 9 kg of a polymeric sodium salt of a substi-

den clay, attapulgite, kaolin and bentonite clay. Minerals could be benzoid long-chain sulfonic acid (Daxad 27) as a dis-

NEN in their natural form, such as pergents and 113 kg of the active ingredient. That get

638 815

12

The dispersible powder has the following percentage composition (details in parts by weight, unless stated otherwise):

Active ingredient 25%

Isooctylphenoxypolyäthoxyäthanol 1%

polymeric sodium salt of a substituted 2% benzoid long chain sulfonic acid Georgia clay 72%

When such a dispersible powder is dispersed in an amount of 4.54 kg in 3791 water, usually a sprayable agent with about 0.3% (3000 ppm) of active ingredient is obtained which is effective against insects or mites on plants, fruit trees or others Locations of the insects or mites can be applied or sprayed onto the ground to control nematodes.

Optionally, dispersants, e.g. Methyl cellulose, polyvinyl alcohol, sodium lignin sulfonates and similar dispersible powders according to the invention are incorporated. Furthermore, adhesive or sticky agents, e.g. Vegetable oils, naturally occurring gums, casein, Zona-rez B, a series of polymerized terpenes, Unicez 709, a resin based on maleic acid, polypoles, partially dimerized resin acids and Dolymerx, a dimeric resin acid and the like can also be used. Corrosion inhibitors, e.g. Epichlorohydrin and anti-foaming agents, e.g. Stearic acid can be added. Methods for incorporating these agents into pesticides are known to those skilled in the art.

The novel compounds of the formula I according to the invention can also be applied to insects, mites, objects or a site in the form of aqueous sprays without a solid carrier. However, since the compounds as such are relatively water-insoluble, they are preferably dissolved in a suitable inert organic solvent carrier. The solvent carrier should expediently be immiscible with water, so that an emulsion of the solvent carrier in water can be produced. For example, if a water-miscible solvent carrier, such as ethanol, is used, the solvent carrier will dissolve in the water, with any excess compound of formula I precipitating out of the solution. In an oil-in-water emulsion, the solvent phase can be dispersed in the aqueous phase, the dispersed phase containing the active ingredient. In this way, an even distribution of a water-insoluble active ingredient is achieved in an aqueous spray. A solvent carrier in which the new compounds of the formula I are highly soluble should expediently be such that pesticidal agents of a relatively high concentration of the active ingredient are obtained. Sometimes one or more solvent carriers with or without cosolvent can be used to make concentrated solutions of the active ingredient. However, the main consideration here is to use a water-immiscible solvent for the active ingredient so that it will keep in solution for a concentration range required for application to insects and mites.

The emulsifiable concentrates according to the invention can thus be obtained by dissolving the active ingredient and a wetting agent in a water-immiscible solvent carrier, e.g. a solvent carrier which is soluble in water at a temperature of the order of 20 ° to 30 ° C in an amount of less than 2.5% by volume, such as cyclohexanone, methyl propyl ketone, summer oils, ethylene dichloride, aromatic hydrocarbon, such as Benzene, toluene or xylene, or a high-boiling petroleum hydrocarbon such as kerosene, diesel oil and the like. Optionally, a cosolvent such as methyl ethyl ketone, acetone, isopropanol and the like can be used together with the solvent carrier to improve the solution of the active ingredient. Aqueous emulsions are then obtained by mixing the respective solution with water up to the desired concentration of active ingredient. The surface-active agents used in the aqueous emulsions according to the invention correspond to the surface-active agents already mentioned. If necessary, mixtures of surface-active agents can of course also be used.

The concentration of active ingredient in the emulsifiable concentrates is expediently from about 5 to about 50, preferably from about 10 to about 40,% by weight. A concentrate with 20 wt .-% of the compound dissolved in a water-immiscible solvent of the type described can be mixed with an aqueous medium in an amount of 13 ml of concentrate to 3.791 medium, whereby a mixture with 700 parts of active ingredient per million parts of liquid carrier. Similarly, 1.061 of a 20% concentrate can be mixed with 1551 water to give a pesticidal agent with about 1200 ppm of active ingredient. In the same way, more concentrated solutions of active ingredients can be prepared.

The pesticidal compositions according to the invention in concentrate form, which are ultimately to be used in the form of aqueous dispersions or emulsions, can contain humectants, i.e. Agents that delay the drying of the agent in contact with the material to which it is applied. Suitable humectants are, for example, glycerin, diethylene glycol, solubilized lignins, e.g. Calcium lignin sulfonate and the like.

Pesticides according to the invention in granular form are suitable for application to the soil if a long-term effect is desired. Granular agents or granules can easily be scattered by hand, over large areas or localized, e.g. in rows. The individual granules can have any size from 0.246 to 1.651, preferably from 0.351 to 0.833 mm. The granular agents or granules are obtained by dissolving the active compound in a solvent, such as methylene chloride, xylene or acetone, and applying the solution to a certain amount of a granulated absorbent carrier. Examples of granulated absorbed carriers are ground corn cobs, ground walnut shells, ground peanut shells and the like. If necessary, the impregnated, granulated absorbent carrier can be provided with a coating. This coating preserves the integrity of the grain until it is applied to an object or site that is suitable for releasing the active ingredient.

The application amounts to insects, mites, the soil or another site depend on the type of harmful organism to be controlled, the presence or absence of useful organisms, the temperature conditions during the treatment and the application method and the effectiveness of the application. As a rule, insecticidal and miticidal activity is achieved if the compounds are applied in concentrations of from about 5 to about 2000 ppm, preferably from about 30 to about 1000 ppm. For nematodes, 4.5 to 22.7 kg per 4050 m2 are required.

The pesticidal compositions according to the invention with the new thiocarbamates of the formula I can be applied to insects, mites, nematodes, the soil or another site by customary known processes. For example, a floor surface, a building or plants can be treated by applying a wettable powder from a hand-operated backpack sprayer. If you want to treat livestock, you can work with immersion baths.

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

Dusts can be applied by powder atomizers or by manually operated atomizing devices. Creams and ointments can be applied to the skin or objects for long-term protection against insects or mites.

The active compounds according to the invention can also be processed for application in the home to relatively dilute agents in a dispersible insecticidal carrier. For example, a dust aerosol can contain about 0.1 to 5.0% active ingredient and otherwise deodorized kerosene.

13 638 815

Of course, a wide variety of variations may be required when using the compounds according to the invention as pesticides. This depends, for example, on insect infestation, the insect to be controlled in each case, the site to be treated specifically, the type of plant, the prevailing weather conditions, e.g. temperature, relative humidity, rain, dew and the like.

Claims (8)

638 815 2nd PATENT CLAIMS 1. N - [(phosphinyl) amino] thio and N - [(phosphinothioyl) amino] thio methyl carbamates of the formula .0 CHa li I -c — N S- x 11 / ^ ■ N P (CZ5Zs) k G) \ si 1A in which mean: R is a radical of the formula: a) R « a radical of the formula -SRs in which Rs represents an alkyl radical corresponding to the alkyl radical represented by Rs, 20 or Rs and Rs together with the atoms to which they are attached form a heterocyclic ring of the formula containing two sulfur atoms: 25th 30th in which R2, R3 and R4, which may be the same or different, each for a hydrogen or halogen atom, a lower alkyl group with 1 to 5 carbon atoms, a lower alkoxy group with 1 to 5 carbon atoms, a lower alkylthio group with 1 to 5 carbon atoms, a dialkylamino radical, the alkyl parts of which are identical or different and have 1 to 3 carbon atoms, or a radical of the formula -N = CHN (CH3) 2; Form 35, in which n is 2 or 3 and the alkylene part of the ring is optionally substituted by one or two methyl radicals; or A and B together with the carbon atom to which they are attached form a heterocyclic ring of the formula containing two sulfur atoms: 40 b) b - C I a = n - V in which A and B, which may be the same or different, each having a lower alkyl radical having 1 to 5 carbon atoms, a lower alkylthio radical having 1 to 5 carbon atoms, a monocyano-substituted alkylthio radical having 1 to 5 carbon atoms, a phenylthio radical, the phenyl part of which may be represented by 1 up to 3 identical or different substituents from the group halogen or alkyl radicals with 1 to 4 carbon atoms is substituted, the cyano radical, an alkoxy radical with 1 to 5 carbon atoms, the phenyl radical or hydrogen, with the proviso that in the case, if B for represents a hydrogen atom, A form a radical of the formula in which m is 2 or 3 and the alkylene part of the ring is optionally substituted by one or two methyl radicals, or c) 55 - C 1 - S - R, 60 CH; CH: is what mean: Rs is an alkyl radical having 1 to 3 carbon atoms or the phenyl radical; Ro is an alkyl group with 1 to 3 carbon atoms; and R7 is an alkyl radical having 1 to 3 carbon atoms or wherein Ri is a lower alkyl radical, an optionally substituted phenyl radical, a phenyl-substituted lower alkyl radical or a cycloalkyl radical; X is an oxygen or sulfur atom; and Zi-Z «are identical or different and are hydrogen, methyl or ethyl and k is 0 or 1. 638 815 2. As a compound according to claim 1: methyl-N - [[[[[(5,5-dimethyl-2-thioxo-l, 3,2-dioxaphosphori-nan-2-yl) isopropylamino] thio] methyl-amino] carbonyl] oxy] etha-nimidothioate, Methyl-N - [[[[[(5,5-dimethyl-2-thioxo-l, 3,2-dioxaphosphori-nan-2-yl) tert-butylamino] thio] methylamino] carbonyl] oxy] etha-nimidothioate, Methyl-N - [[[[[isopropyl (5,5-diethyl-2-thioxo-1,3,2-phospho-rinan-2-yl) amino] thio] amino] carbonyl] oxy] ethane imidothioate, methyl-N - [[[[[(ethyl (5,5-dimethyl-2-thioxo-l, 3,2-dioxaphos-phorinan-2-yl) amino] thio] methylamino] carbonyI] oxy] ethanimido-dothioate, Methyl N - [[[[[isopropyl (2-thioxo-1,3,2-phospholan-2-yl) amino] thio] methylamino] carbonyl] oxy] ethanimidothioate, Methyl N - [[[[isopropyl (2-thioxo-l, 3,2-dioxaphosphorinan-2-yl) amino] thio] methylamino] carbonyl] oxy] ethane imidothioate, methyl N - [[[[isopropyl ( 4,4,6-trimethyl-2-thioxo-l, 3,2-dioxa- phosphorinan-2-yl) amino] thio] methylamino] -carbonyl] oxy] ethanimidothioate, Methyl-N - [{[[[cyclohexyl (5,5-diethyl-2-thioxo-l, 3,2-dioxa-phosphorinan-2-yl) amino] thio] methylamino] carbo-5 nyl] oxy] ethane imidothioate , Methyl-N - [[[[[cyclohexyl (5,5-dimethyl-2-thioxo-l, 3,2-dioxa-phosphorinan-2-yl) amino] thio] methylamino] -carbo-nyI] oxy] ethanimidothioate and Methyl N - [[[[[methyl (2-thioxo-1,3,2-dioxaphosphorinan-2-io yl) amino] thio] methylamino] carbonyl] oxy] ethanimidothioate. 3. Methyl-N-fffiïcyclohexyl (5,5-dimethyl-2-thioxo-1,3,2-di-oxaphosphorinan-2-yl) amino] thio] methylamino] carbo-nyl] oxy] ethaneimidothioate as a compound according to claim 2 . 4. Pesticidal agent, characterized in that it contains at least one new compound of the 15 active ingredient formula 0 CHa Il I C— N S- in which mean: R is a radical of the formula: a) radical having 1 to 5 carbon atoms, represent the phenyl radical or hydrogen, with the proviso that, if B is a hydrogen atom, A is a radical of the formula 35 40 I. - c I. - s - rr in which R2, R3 and R4, which may be the same or different, each for a hydrogen or halogen atom, a lower alkyl group with 1 to 5 carbon atoms, a lower alkoxy group with 1 to 5 carbon atoms, a lower alkylthio group with 1 up to 5 carbon atoms, a dialkylamino radical, the alkyl parts of which are identical or different and have 1 to 3 carbon atoms, or a radical of the formula -N = CHN (CH3) 2; b) b - c = n -I a is, in which mean: Rs is an alkyl radical having 1 to 3 carbon atoms or the phenyl radical; Rö is an alkyl radical with 1 to 3 carbon atoms; and 45 R? an alkyl radical having 1 to 3 carbon atoms or a radical of the formula -SRs in which Rs represents an alkyl radical corresponding to the alkyl radical represented by Rs, or Rs and Rs together with the atoms to which they are attached 50 form a heterocyclic ring containing two sulfur atoms of the formula: 60 wherein A and B, which may be the same or different, each having a lower alkyl radical having 1 to 5 carbon atoms, a lower alkylthio radical having 1 to 5 carbon atoms, a monocyano-substituted alkylthio radical having 1 to 5 carbon atoms, a phenylthio radical, the phenyl part of which may be represented by 1 up to 3 identical or different substituents from the group halogen or alkyl radicals with 1 to 4 carbon atoms is substituted, the cyano radical, an alkoxy form where n is 2 or 3 and the alkylene portion of the ring is optionally substituted by one or two methyl groups; or A and B together with the carbon atom to which they are attached form a heterocyclic ring containing two sulfur atoms of the formula: 638 815 form v, in which m is 2 or 3 and the alkylene part of the ring is optionally substituted by one or two methyl radicals, or c) wherein Ri is a lower alkyl group, an optionally substituted phenyl group, a phenyl-substituted lower alkyl group or a cycloalkyl group; X is an oxygen or sulfur atom; and Zi-Zs are the same or different and are hydrogen, Is methyl or ethyl and k is 0 or 1, contains. 5. Pesticidal composition according to claim 4, characterized in that it is at least one of the compounds as active ingredient Methyl-N - [[[[((5,5-dimethyl-2-thioxo-l, 3,2-dioxaphosphori-nan-2-yl) isopropylamino] thio] methylamino] carbonyl] oxy] etha-nimidothioate, 0 ch3 II I -c— N S- Methyl-N - [[[[[(5,5-dimethyl-2-thioxo-1,3,2-dioxaphosphori-nan-2-yl) tert-butylamino] thio] methylamino] carbonyl] oxy] etha-nimidothioate, Methyl-N-ffffisopropylC 5,5-diethyl-2-thioxo-1,3,2-phospho-s rinan-2-yl) amino] thio] amino] carbonyl] oxy] ethanimidothioate, methyl-N - [[[[ [ethyl (5,5-dimethyl-2-thioxo-l, 3,2-dioxaphos-phorinan-2-yl) amino] thio] methylamino] carbonyl] -oxy] ethani midothioate, Methyl N - [[[[isopropyl (2-thioxo-l, 3,2-phospholan-2-io yl) amino] thio] methylamino] carbonyl] oxy] ethane imidothioate, methyl N - [[[[isopropyl (2-thioxo-l, 3,2-dioxaphosphorinan-2-yl) amino] thio] methylaminolcarbonyl] oxy] ethanimidothioate, Methyl-N - [[[[[isopropyl (4,4,6-trimethyl-2-thioxo-l, 3,2-dioxa-phosphorinan-2-yl) amino] thio] methylamino] carbo-15 nyl] oxy ] ethanimidothioate, Methyl-N - [[[[[cyclohexyl (5,5-diethyl-2-thioxo-l, 3,2-dioxa-phosphorinan-2-yl) amino] thio] methylamino] carbo-nyl] oxy] ethanimidothioate, Methyl-N - [[[[[cyclohexyl (5,5-dimethyl-2-thioxo-l, 3,2-dioxa-20 phosphorinan-2-yl) amino] thio] methylamino] carbo-nyl] oxy] ethanimidothioate or Methyl-N - [[[[[methyl (2-thioxo-l, 3,2-dioxaphosphorinan-2-yl) amino] thio] methylamino] carbonyl] oxy] ethanimidothioate. 25 6. Pesticidal composition according to claim 5, characterized in that it is methyl-N - [[[[[cyclohe-xyl (5,5-dimethyl-2-thioxo-l, 3,2-dioxaphosphorinan-2-yl ) contains amino] thio] methylammo] carbonyl] oxy] ethanimidothioate. 30 7. Process for the preparation of new compounds of the formula • N- I. Ri / V " ) | < u in which mean: R is a radical of the formula a) b) b - C = I A n - in which R2, R3 and R4, which may be the same or different, each for a hydrogen or halogen atom, a lower alkyl group having 1 to 5 carbon atoms, a lower alkoxy radical having 1 to 5 carbon atoms, a lower alkylthio radical having 1 to 5 carbon atoms, a dialkylamino radical, the alkyl parts of which are identical or different and have 1 to 3 carbon atoms, or a radical of the formula -N = CHN (CH3) 2; wherein A and B, which may be the same or different, and each have a lower alkyl radical having 1 to 5 carbon atoms, a lower alkylthio radical having 1 to 5 carbon atoms, a monocyano-substituted alkylthio radical having 1 to 5 carbon atoms, a phenylthio radical, the phenyl part of which may optionally be present is substituted by 1 to 3 identical or different substituents from the group halogen or alkyl radicals with 1 to 4 carbon atoms, the cyano radical, an alkoxy-o radical with 1 to 5 carbon atoms, the phenyl radical or hydrogen, with the proviso that in the case if B is a hydrogen atom, A is a radical of the formula .- 65 - 1 C 1 r. - s - r. is what mean; 5 638 815 Rs is an alkyl radical having 1 to 3 carbon atoms or the phenyl radical; Re is an alkyl group with 1 to 3 carbon atoms; and Rv is an alkyl radical having 1 to 3 carbon atoms or a radical of the formula -SRs, in which Rs represents an alkyl radical corresponding to the alkyl radical represented by Rs, or Rs and Rs together with the atoms to which they are attached form a heterocyclic ring of the formula containing two sulfur atoms: form where n is 2 or 3 and the alkylene portion of the ring is optionally substituted by one or two methyl groups; or A and B together with the carbon atom to which they are attached form a heterocyclic ring of the formula containing two sulfur atoms: V form where m is 2 or 3 and the alkylene part of the ring is optionally substituted by one or two methyl radicals, or implements, wherein R, Ri, k, X and Zi-Z «have the meaning given above. 8. The method according to claim 7, characterized in that one produces one of the following compounds: Methvl-N-ff [[[Y 5.5-dimethvl-2-thioxo-1.3.2-dioxaphosphori-nan-2-yl) isopropylamino] thio] methylamino] carbonyl] oxy] etha-nimidothioate, Methyl-N - [[[[[(5,5-dimethyl-2-thioxo-1,3,2-dioxophosphori-20 nan-2-yl) tert-butylamino] thio] methylamino] carbonyl] oxy] etha-nimidothioate , Methyl-N - [[[[[isopropyl (5,5-diethyl-2-thioxo-l, 3,2-phosphoraninan-2-yl) amino] thio] methylamino] carbonyl] oxy] ethanimido thioate, 25 methyl-N - [[[[[(ethyl (5,5-dimethyl-2-thioxo-l, 3,2-dioxaphos-phorinan-2-yl) amino] thio] methylamino] carbonyl] oxy] ethanimidothioate, Methyl N - [[[[isopropyl (2-thioxo-l, 3,2-phospholan-2-yl) amino] thio] methylamino] carbonyl] oxy] ethanimidothioate, 30 Methyl N - [[[[isopropyl (2-thioxo-l, 3,2-dioxaphosphorinan-2-yl) amino] thio] methylamino] carbonyl] oxy] ethanimidothioate, Methyl-N - [[[[[isopropyl (4,4,6-trimethyl-2-thioxo-l, 3,2-dioxa-phosphorinan-2-yl) amino] thio] methylamino] -carbonyl] oxy] ethanimidothioate, 35 methyl N - [[[[[cyclohexyl (5,5-diethyl-2-thioxo-l, 3,2-dioxa-phosphorinan-2-yl) amino] thio] methylamino] -carbo-nyl] oxy ] ethanimidothioate, Methyl N - [[[[[cyclohexyl (5,5-dimethyl-2-thioxo-l, 3,2-dioxa-phosphorinan-2-yl) amino] thio] methylamino] carbo-40 nyl] oxy] ethane imidothioate and Methyl N - [[[[[methyl (2-thioxo-l, 3,2-dioxaphosphorinan-2-yl) amino] thio] methylamino] carbonyl] oxy] ethanimidothioate. 9. The method according to claim 8, characterized in that one methyl-N - [[[[[cyclohexyl (5,5-dimethyl-2-thioxo-l, 3,2- 45 dioxaphosphorinan-2-yl) amino] thio] methylamino] -carbonyl] oxy] ethanimidothioate. wherein Ri is a lower alkyl radical, an optionally substituted phenyl radical, a phenyl-substituted lower alkyl radical or a cycloalkyl radical; X is an oxygen or sulfur atom; and Zi-Zs are identical or different and are hydrogen, methyl or ethyl and k is 0 or 1, characterized in that a compound of the formula o ch-li I J r-o-c-n-h with a compound of the formula