DE2902647A1 - ANGULAR BRACKETS OPEN (PHOSPHINYL) - AMINO ANGLE BRACKETS FOR -THIO- AND ANGULAR BRACKETS FOR (PHOSPHINOTHIOYL) AMINO ANGLE BRACKETS FOR- THIO-METHYLCARBAMATE, PROCESS FOR THEIR PRODUCTION AND, USE OF CAUGHT OF CAUGHNES CURVES - Google Patents

Description

Henkel, Kern, Feiler & Hänzel patent attorneys

. 9λ Registered Representatives

before the
European Patent Office

Möhlstrasse 37
D-8000 Munich 80

Tel .: 089 / 982085-87 Telex: 0529802 hnkld Telegrams: ellipsoid

Dr.P / rin

THE UPJOfIN COMPAITX "
Kalamazoo, Mich., V.St.A.

H - [(Phosphinyl) -amino] -thio- and N - [(Phosphinothioyl) -amino} · thio-methylcarbamate, process for their preparation, use the same means suitable for controlling insect pests and for controlling insect pests

909832/0579

description

The invention relates to new organic compounds, processes for their preparation and their use as pesticides, in particular phosphinic acid derivatives of aminothiomethyl carbamates.

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 are acylaminothio derivatives of methyl carbamate pesticides, namely N - [(Phosphlnyl) -amino] -thio-methylcarbamate, known. As far as is known, phosphinic acid derivatives of aminothiomethylcarbamate pesticides have not yet been derived from cyclic pesticides Phosphoramidothioates produced.

The invention was based on the object of producing methyl carbamate pesticides, the effectiveness of which the effectiveness of the parent compounds against insect pests is at least equivalent, but usually superior. In particular, methyl carbamate pesticides are said to be decreased mammalian toxicity, decreased phytotoxicity and longer residual activity to be provided.

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

0 CH ₃ X J

Il I II /

C N S N P

9 09832/057 9

O CH ₃

I! I.

-0 C N S-

IL

-P X ^ z ₂

(CZ ₅ Z ₆ ) _k

'C ~ Z ₃

0 CH

I \\

o — C N — S — N P

(CH ₂ ),

0 CH ₃ X η

Il I ti /

R ο —C N S N P

where mean:

R is a remainder of the formula!

a)

909832/0579

- 22 -

in which Rp, R ₇ and R-, which can be the same or different, each represent a hydrogen or halogen atom, a short-chain alkyl group with 1 to 5 carbon atoms inclusive, a short-chain alcohol with 1 to 5 carbon atoms inclusive ( en), a short-chain alkylthio radical with 1 up to and including 5 carbon atom (s), a dialkylamino radical, the alkyl parts of which, identically or differently, can have 1 up to and including 3 carbon atoms ^), or represent a radical of the formula -N = CHN (CHj) ₂ ;
b)

B-C = N-

wherein A and B, which can be the same or different and each represent a short-chain alkyl radical with 1 up to and including 5 carbon atom (s), one short-chain Alkylthio radical with 1 up to and including 5 carbon atom (s), a monocyanosubstituted alkylthio radical with 1 to 5 carbon atoms inclusive), a phenylthio radical, the phenyl part of which is optionally by 1 to 3 (identical or different) substituents consisting of halogen atoms or short-chain alkyl radicals with 1 to 4 carbon atom (s) inclusive, a cyano radical, an alkoxy radical having 1 to 5 carbon atom (s) inclusive, a phenyl radical or a hydrogen represent atom, with the proviso that in the case that B stands for a hydrogen atom, A of the formula:

«7
909832/0579

corresponds to, where mean:

Rc is an alkyl radical with 1 to 3 carbon inclusive atom (s) or a phenyl radical;

Rg is an alkyl radical with 1 to 3 carbon inclusive atom (s); and

an alkyl radical with 1 up to and including 3 carbon atom (s) or an ^ est of the formula
-SRq, in which R _{Q is} an alkyl radical corresponding to the alkyl radical represented by R, -, or

c and Rq together with the atoms to which they are attached, a heterocyclic ring containing two sulfur atoms of the formula:

in which η = 2 or 3 and the alkylene part of the Ring is optionally substituted by one or two methyl radical (s);

or A and B together with the carbon atom
to which they hang, a heterocyclic ring containing two sulfur atoms of the formula:

(CH ₂ )

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

R ^ is a short-chain alkyl radical, an optionally substituted one Phenyl radical, a phenyl-substituted short-chain alkyl radical or a cycloalkyl radical j

X is an oxygen or sulfur atom; Y and Y ¹ , which can be identical or different, each represent a short-chain alkyl, alkoxy or alkylthio radical, a cycloalkyl radical, an optionally substituted phenyl radical, an optionally substituted phenoxy radical or an optionally substituted thiophenoxy radical;

Zj. to Zg, which can be the same or different, in each case a hydrogen atom or a methyl or ethyl radical;

R is a hydrogen or halogen atom or a short-chain alkyl or alkoxy radical;

k = 0 or 1 and

ρ = 3 or 4.

"Short-chain alkoxy radicals" are, for example, methoxy, Ethoxy, propoxy, isopropoxy, butoxy, pentoxy radicals or understand their isomers. Under "short-chain alkylthio" are, for example, methylthio, ethylthio, propylthio, Isopropylthio, butylthio or pentylthio radicals or their To understand isomers.

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"Short-chain alkyl radicals" include, for example, methyl, To understand ethyl, propyl, butyl or pentyl radicals or their isomers. "Cycloalkyl radicals" are, for example Cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl radicals, optionally represented by methyl, ethyl or propyl radicals a total of 9 carbon atoms can be substituted to understand.

"Phenyl-substituted alkyl radicals" are, for example To understand benzyl, phenethyl, phenpropyl, phenbutyl or phenpentyl radicals or their isomers.

“Substituted phenyl radicals” are, for example, phenyl radicals substituted by short-chain alkyl or alkoxy radicals, halogen atoms, nitro radicals or cyano radicals. Here, the phenyl radicals can also carry combinations of substituents and for example, from 4-propyl-2-methyl-, 2-chloro-4-methyl-, 3,4-Diäthoxy- or 3-cyano-4-äthoxyphenylresten exist. In practice, "substituted phenyl radicals" are limited to a total of 10 carbon atoms, so that the 4-isobutylphenyl radical, for example, forms the limit.

"Substituted phenoxy radicals" are short-chain alkyl or alkoxy radicals, halogen atoms, i-nitro radicals or cyano radicals to understand substituted phenoxy radicals. The phenoxy radicals in question can also carry combinations of substituents and consist, for example, of 4-propyl-2-methyl, 2-chloro-4-methyl, 3j4-diethoxy or 3-cyano-4-ethoxyphenoxy radicals. The substituted phenoxy radicals are limited to a total of 10 carbon atoms, so that the limit, for example forms the 4-isobutylphenoxy radical.

Under "substituted thiophenoxy radicals" are by short-chain Alkyl or alkoxy radicals, halogen atoms, nitro radicals or

909832/0579

To understand cyano radicals substituted thiophenoxy radicals. These can also carry combinations of substituents and. for example from 4-propyl-2-methyl, 2-chloro-4-methyl or 3,4-diethoxythiophenoxy radicals exist. The substituted thiophenoxy radicals are limited to a total of 10 carbon atoms, so that, for example, the limit of the 4-isobutylthiophenoxy radical forms.

The new N - [(phosphinyl) amino] thio and according to the invention N-L (phosphinothioyl) -aminoj-thio-methylcarbamate pesticides der According to the invention, formula I is obtained by reacting a suitable methyl carbamate precursor with an N- (halothio) phosphinamide. This implementation can be shown schematically as follows:

_R _0 OB N-H + Cl-SNR - ^ ROCNSNP

Ri Y

III Il

In the formula scheme, the radicals R, R ^, X, Y and Y ^{1 have} the meaning given.

The reaction takes place in the cold, preferably at a temperature of -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. The use of non-polar and somewhat polar solvents can catalyze the reaction Copper (I) chloride and aluminum chloride can also be used.

§09832 / 067

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The compounds of the formulas I, I ', I "and I" are obtained and purified in a conventional manner. Filtration, solvent evaporation, chromatographic processes and / or crystallization are used for this purpose. Some of the compounds are obtained in crystalline form, while others are purified in oily form. The phosphinic acid-N-chlorthioamide of formula II are obtained by reaction of the corresponding phosphinic acid amides with sulfur at a temperature of about -20 ° to +25 ⁰ C in the presence of a suitable acid acceptor and of an inert inorganic medium. The phosphinamides are either readily available or can be prepared by known processes, for example by Ilouben-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 formulas:

0 CH ₃

II I -C —N — 0— C — N— S— Ν— Ρ la

A Ri ^ Y *

0 CH ₃ X / CZ ₂

-C = N- 0— C— N— S —NP (CZ ₅ Z. _a ) k ^! ' ^a

A Ri \ / ^C r ^f3

0 CH ₃

- 20 -

I " ¹ a

B-C = N-O-C-N-S

wherein A and B, which can be the same or different, for short-chain alkyl radicals with 1 to 5 carbon atoms inclusive, short-chain alkylthio radicals with 1 to 5 carbon atoms inclusive, monocyanosubstituted alkylthio radicals with 1 to 5 carbon atoms inclusive, phenylthio radicals whose phenyl moiety can be substituted by 1 to 3 identical or different substituents consisting of halogen atoms and short-chain alkyl radicals with 1 to 4 carbon atoms inclusive, cyano radicals, alkoxy radicals with 1 to 5 carbon atom (s) inclusive or phenyl radicals stand and R ₁ , X, Y, Y ¹ , Z ₁ to Zg, R _& , k and ρ have the unspecified meaning.

Some of the compounds of the formula Ia in which Y and Y ^{1 are} a radical of the formula:

No. ₁

-0-CZ ₂

-0-CZ ₃

form, in which Z ₁ to Zg and k have the meaning given, show an unexpected crystallinity. So did

- 50 -

for example the compound W-t [(^ L (5,5-dimethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl) tert-butylamino jthio smethylamino) carbonyl] oxy £ ethanimidothioate proven to be extremely crystalline. The physical ones that can be traced back to the crystallinity Properties facilitate the isolation of the reaction product from the reaction mixture. You can also use the highly crystalline compounds provide pesticidal agents in the form of wettable powders. These remedies have highly beneficial ones Properties, e.g. reduced solidification, high flowability and high concentrations of active Cons ilen.

In the following preparation examples, the preparation of in the preparation of the novel compounds according to the invention of the formula I required reactants explained.

Production example 1

Reaction participants 0, O-diethyl-H- (chlorothio) -W- (n-propyl) -phosphoramidothioate:

A solution of 2.98 g (0.014 mol) of 0,0-diethyl-n-propylpnosphoramidothioat in 10 ml of hexane and 2 ml of triethylamine is slowly and with stirring in a solution of 1.0 ml (0.016 mol) of sulfur dichloride at ^{0 ° C} entered in 10 ml of hexane. During the strong reaction, a strong precipitation of triethylamine hydrochloride takes place. After adding a further 20 ml of hexane, the reaction mixture is stirred for 30 minutes at a temperature of 0 ° to 5 ° C. and then filtered. The resulting filtrate is concentrated to a pale yellow oil by evaporating the hexane under reduced pressure. The oil contains the desired 0, O-diethyl-W- (chlorothio) -n-propylphosphoramidothioate, which can be used for further reaction with W-methyl carbamates.

909832/05

Creation example 2

Reaction participants O, O-diethyl-N- (chlorothio) -N-isopropylphosphoramidothioate:

A solution of 9.95 g (0.0471 Hol) Ο, Ο-diethyl isopropyl phosphoramidothioate and 6.5 ml of triethylamine is slowly and with stirring into a cooled solution of 3.0 ml (0.047 mol) Sulfur dichloride and 150 ml of hexane entered. During the Addition and subsequent stirring for 30 minutes, the temperature is kept at 0 ° to 5 ° C. After filtering the Reaction mixture, those on the filter are precipitated Salts washed with hexane. The filtrate and the hexane wash are combined, followed by the hexane is evaporated under reduced pressure. This gives the desired reactant, 0,0-diethyl isopropyl phosphoramidothioate in the form of an orange oil.

The following examples are intended to explain the invention in more detail.

example 1

Preparation of the compound 4- (Dimethylamine) -3,5-xylyl ~ iL (^ iäthoxyphosphinothioyl) -n-propylamino jthio ^ methyl carbamate:

The crude 0,0-diethyl-N- (chlorothio) -n-propylphosphoramidothioate obtained according to Preparation Example 1 is cooled in an ice bath and treated with 2.79 g (0.013 mol) 4- (dimethylamine) -3,5-xylylmethylcarbamate in the form of a Solution in 20 ml of dimethylformamide, which contains 2 ml of triethylamine added, mixed. After the reaction mixture has been stirred for 4 hours at a temperature of 25 ^° C., it is diluted with hexane. Now the organic solution is washed with ¥ water, dried over anhydrous sodium sulfate and by evaporating the organic

909832/0679

The solvent was freed from these under reduced pressure. The evaporation residue obtained in this way is transferred to a Florisil column. The chromatogram obtained in this way is first developed with a solvent mixture of 10% by weight diethyl ether in petroleum ether and then with 30% diethyl ether in petroleum ether. Collecting the eluate that appeared last and removing the solvent by evaporation under reduced pressure gives the desired 4- (dimethylamino) -3,5-xylyl- Si (diethoxyphosphinothioyl) -n-propylaminoJthio]: methylcarbamate in the form of a yellow oil.

The elemental analysis of the compound C ^ qH ^ ü ^ O ^ PSp gives the following Values:

Calculated: C 49.22 H 7.39 N 9.06 Found: C 49.84 H 7.89 N 8.52.

Example 2

Preparation of the compound 2-isopropoxyphenyl - ^ [(diethoxyphosphinothioyl) anilino] thio} methyl carbamate:

Part A : Preparation of the reactant 0,0-diethyl-N- (chlorothio) -phenylphosphoramidothioate:

A solution of 6.69 g (0.0314 mole) of 0,0-Diäthylphenylphosphoramidothioat, 25 ml of ether and 4.4 ml (0.032 mol) of triethylamine is added dropwise with stirring over 30 min to a cooled to -10 ⁰ C solution of 2 , 0 ml (0.031 mol) of sulfur dichloride and 25 ml of diethyl ether were added. Thereafter, stirring is continued in the cold for 30 minutes. The precipitate formed in this way is filtered off, whereupon the filter cake is washed with diethyl ether. The original filtrate is combined with the ether washing liquid, whereupon the ether is reduced

3Q9832 / 0579

which pressure is evaporated. This gives the desired 0,0-Dxäthyl-N- (chlorothio) phenylphosphoramidothioate in the form of a yellow oil.

Part B; 2-Isopropoxyphenyl {[(diethoxyphosphinothioyl) anilino Jthio ^ methylcarbamate:

The O, O-diethyl-N- (chlorothio) phenylphosphoramidothioate obtained as a yellow oil according to Part A is dissolved in the minimum amount of diethyl ether (about 5 ml), whereupon the ethereal solution is converted into a solution of 6.34 g cooled ^{to O 0 C (} 0.030 mol) of 2-isopropoxyphenylmethylcarbamate and 20 ml of dimethylformamide is added. The reaction mixture obtained is allowed to ^{warm to a temperature of 25 °} C. with stirring and then stirred at this temperature for about 4 hours. The mixture is then diluted with 100 ml of water and extracted with diethyl ether. After the ethereal phase has been separated off, it is washed with water and dried over anhydrous sodium sulfate. The ether is then removed by evaporation under reduced pressure. The oily evaporation residue obtained in this way is chromatographed through a silica gel column. The development takes place with methylene chloride. After removal of the methylene chloride by evaporation under reduced pressure, 1.02 g of crude product is obtained in the form of an amber-colored oil. This is brought from petroleum ether having a boiling point range between 30 ° and 60 ⁰ C for crystallization to give 2-isopropoxyphenyl ^ [(diäthoxyphosphinothioyl) anilino] thiojmethylcarbamat i)
receives.

Bamat in the form of colorless crystals, mp 69 ° C ⁰ to 70.5

The elemental analysis of the compound C ₂₁ H _{2 QN 2} O ₅ PS ₂ gives the following values:

calculated: C. 52 , 04 E. 6th "03 K 5 , 78 found: C. 52 , 03 II 6th , 18 N 5 , 78. Example 3

Preparation of 2-isopropoxyphenyl-4 [(diethoxyphosphinothioyl) -n-propylamino] thio ^ methylcarbamate i

Corresponding to Example 2, Part B, but replacing the 0,0-diethyl-H- (chlorothio) phenylphosphoramidothioate by 0,0-diethyl-N- (chlorothio) -n-propylphosphoramidothioate one obtains the corresponding 2- ± sopropoxyphenyl- | [(diethoxyphosphinothioyl) · n-propylaminojthio ^ methylcarbamate in the form of an amber Oil.

The elemental analysis of the compound CL QH ^ NpO ₁ -PS ₂ gives the following values:

Calculated: C 47.98 H 6.94 H 6.22 Found: C 47.47 H 6.90 W 6.26.

Example 4

Preparation of the compound 3-isopropylphenyl - ^ [(diethoxyphosphinothioyl ) isopropylamino jthio ^ methylcarbamate:

Corresponding to Example 2, parts A and B, but with replacement of the 0,0-diethylphenylphosphoramidothioate and the 2-isopropoxyphenylmethylcarbamate with 0,0-diethylisopropylphosphoramidothioate or 3-isopropylphenylmethylcarbamate is obtained 3 ~ Isopropylphenyl-i [(diethoxyphosphinothioyl) isopropylamino J- ^ methyl carbamate in the form of an amber colored oil.

The elemental analysis of the compound C _{1 QHz 1} N ₂ O ^ PS ₂ gives the following values:

909832/0579

calculated: C 49.75 II 7.19 i-6.45 Found: C 49.43 K 7.09 N 6.39.

Example 5

Preparation of methyl-N-S [(■ £ [(dimethoxyphosphinothioyl) methylamino jthio] methylamino) carbonyl ioxy ^ ethanimidothioate:

Based on the known compound Hethyl-II- ^ L (^ ethylamino) carbonyl ioxy} ethane imidothioate and a suitable phosphoramidothioate according to example 2, part B, the following new N- [(phosphinyl) amino j thiocarbamates and N - [(phosphinothioyl) amino] thiocarbamates are obtained:

methyl-LJ ■ [ '(£ [(dimethoxyphosphinothioyl) methylamino jthio ^ methylamino) carbonyljoxy ^ äthanimidothioat, mp: 57 ° to 5O ⁰ C.

The elementary analysis of the compound CgPI ₁₈ H ₃ S ₃ O ^ P gives the following values:

Calculated: C 27.66 II 5.22 H 12.10 found: C 27.88 H 5.27 N 11.95.

Methyl-K - ^ [({[(dimethoxyphosphinothioyl) isopropylamino] thio} -methylamir.o) carbonyl] oxyjäthanimidothioat, mp: 88 ° to 89 ⁰ C.

The elemental analysis of the compound C ^ tL ^ N ^ O ^ PS, · gives the following Values:

Calculated: C 31.99 H 5.91 N 11.19 found: C 31.99 PI 5.86 N 10.93.

Methyl-IJ - ^ [(^ [(dimethoxyphosphinothioyl) -n-butylamino] thioj methylamino) carbonyl] oxyfäthanimidothioat, mp: 60 ° to 61 ⁰ C.

909832/0579

The electrical analysis of the compound C ₁₁ IIp. IJ ₇ O ^ .PS ^ gives the following values:

Calculated: C 33.92 H 6.21, U 10.79 found: C 33.84 H 6.26 H 10.44.

Hethyl-III [(IL (diethoxyphosphinothioyl) methylamino] thio [methylamino] carbonyl] oxy Ethanimidothioate.

The elemental analysis of the compound C ^ HppIi ^ O ^ PtU gives the following fourth:

calculated: C 31.99 H 5.91 11.19 Found: C 32.00 II 5.96 N 10.58.

Hethyl-J- [({[(diatlioxyphosphinotliioyl) isopropylaminojthiofmethylamino) carbonylIoxyτäthanimidothioat, Mp: 72 ° to 73 ° C.

The elementary analysis of the compound C ^ plip ^ IUü ^ PS- gives the following Values:

Calculated: C 35.71 II 6.50 H 10.41 found: C 35.77 Ii 6.74 H 10.09.

Methyl H-i | _ ( \ [ (diethoxyphosphinothioyl) -n-propylamino-thiofmethylamino) carbonyl ioxylethane imidothioate.

The elemental analysis of the compound Ο ^^ Ηρ ^ Κ ^ Ο, PS ^, gives the following Values:

Calculated: C 35.71 H 6.50 H 10.41 found: C 35.48 II 6.46 N 9.82.

909832/0579 BATH ORIGINAL

Ethyl-Ιί -'_ [ (\ [ (diethoxyphosphinothioyl) anilino jthio / methylamino) carbonyl ioxy ^ ethanimidothioate, m.p .: 68 ° to 69 ° C.

The elemental analysis of the compound C. p. IL ,, IJ ^ 0, PS ^ gives the following Values:

Calculated: C 41.17 H 5.53 Ii 9.60 found: C 40.80 II 5.43 N 9.37.

Methyl ii- ^ [( l [ (diethoxyphosphinyl) methylamino] thio ^ methylamino) carbonyl ioxy ^ ethanimidothioate.

The elementary analysis of the compound Cj ₀ II ₀₂ IkOc-PS ₂ results in the following values:

Calculated: G 33.42 II 6.17 H 11.69 found: C 33.26 H 6.17 N 11.20.

Methyl K- 1 [ ( i_ [(methoxy (methyl thio) phosphinyl) methylamino] thioj methylamino) carbonyl ioxy ^ ethanimidothioate, amber oil.

The elementary analysis of the compound CgILgI ^ uOr PS ^ gives the following Values:

Calculated: C 27.66 K 5.22 N 12.09 found: C 27.44 H 5.50 II 11.60.

Methyl-Kj | _ (i L (methoxy (phenyl) phosphinothioyl) isopropylamino J-thio | methylamino) carbonylJoxy / äthanimidothioat, mp: 103 ° to 105 ⁰ C.

The elemental analysis of the compound C ^, -IL ,. 1J, O _Z PSp gives the following values:

9 09832/0579

"bad original

.39-

Calculated: C 42.74 Ii 5.74 K 9.97 found: C 42.62 H 5.67 N 10.02.

Hethyl-H- ■> [( {[ (methoxy (phenyl) phosphinothioyl) methylamino J-thio]; methylamino) carbonyl ioxyethane imidothioate, m.p .: 109 ° bis

The elementary analysis of the compound C ,, ^ Hp ₀ H-, S- ^ O ^ P gives the following values:

Calculated: C 39.68 H 5.12 N 10.68 Found: C 39.73 H 5.32 ii 10.92.

Methyl-N- £ [(\ [(methoxy (methyl) phosphinothioyl) methylamino] thio ^ methylamino) carbonyljoxyjäthanimidothioat, mp: 87 ° to 88 ⁰ C.

Elemental analysis of the compound CqIIjqN-O ^ S ^ P gives the following ^v ferte:

Calculated: C 28.99 H 5.47 N 12.68 found: C 29.61 H 6.00 IJ 12.84.

Hethyl-ll- {[(\ _ [(isopropoxy (phenyl) phosphinothioyl) isopropylamino] thio ^ methylamino) carbonyljoxy ^ äthanimidothioat, mp: 100 ° to 102 ⁰ C.

The elementary analysis of the compound C ^ HpgK ^ O ^ S ^ p gives the following Values:

Calculated: C 45.42 H 6.28 H 9.34 Found: C 45.00 H 6.54 N 9.32.

909832/0579

Hethyl-H- ^ L (IL (methyl (phenoxy) phosphinothioyl) methylamino] thio | methylamino) carbonyl] oxyfethane imidothioate, pp: 65 ° to 67 ° C.

The elemental analysis of the compound C ^^ ELqN ^ O ^ PS gives the following Values:

Calculated: C 39.68 H 5.12 N 10.68 Found: C 39.74 H 5.30 N 10.79.

Methyl-N- \ [(\ j_ (isopropoxy (methyl) phosphinothioyl) isopropylamino Jthiol; methylamino) carbonyl] oxy} äthanimidothioat, mp: 90 ° to 92 ⁰ C.

The elementary analysis of the compound CL 0 ^ 26 ^ ^ 5 ^ 5 ^er Si "bt the following values:

Calculated: C 37.19 H 6.76 N 10.84 Found: C 37.39 H 7.06 N 10.72.

J methyl-N- [(^ [(methoxy (methyl) phosphinothioyl) isopropylamino J-thio ^ methylamino) carbonyl] oxyläthanimidothioat, mp: 91 ° to 93 ⁰ C.

The elemental analysis of the compound C ₁₀ H ₂₂ N ₅ O ^ PS ₅ gives the following values:

Calculated: C 33.41 H 6.17 N 11.69 found: C 33.42 H 6.43 N 11.90.

I-Iethyl-N- ^ C (IC (methyl (phenoxy) phosphinothioyl) isopropylamino] -thio ^ methylamino) carbonyl] oxy ^ ethanimidothioate, Mp: 70 ° to 72 ° C.

909832/0 5 79

The elemental analysis of the compound C ^ ₅ H ₂ ^ W-rO-, PS, gives the following values:

Calculated: C 42.74 H 5.74 N 9.97 found: C 42.99 H 5.98 N 9.93.

Methyl-ii-4 [(I [(ethyl (phenoxy) phosphinothioyl) anilino Jthio ^ -me methylamino) carbonyl] oxy] äthanimidothioat, mp: 74 ° to 76 ⁰ C.

Elemental analysis of the compound C ^ EU «N ^ O ^ PS-. results in the following ¥ ¥ utes:

Calculated: C 48.60 H 5.14 K 8.95 found: C 48.74 H 4.98 N 9.03.

Methyl-11-.ί L (£ L (4-chlorophenoxy (ethyl) phosphinothioyl) isopropyl aminojthio} methylamino) carbonyl ioxy ^ ethanimidothioate, m.p .: 65 ° up to 66 ° C.

The elemental analysis of the compound C ^ gP ^ cCli ^ O ^ S ^ P gives the following Values:

Calculated: C 40.89 H 5.36 Ii 8.94 Cl 7.54 found: C 41.08 115.48 N 9.14 Cl 7.62.

Methyl-N- 1 [({[(methyl (isopropoxy) phosphinothioyl) anilino] thio} methylamino) carbonyl] oxy | äthanimidothioat, mp: 76 ° to 78 ⁰ C.

The elemental analysis of the compound C,, -HpAN ^ O-zPS, gives the following Values:

Calculated: C 42.73 H 5.74 N 9.97 found: C 42.68 H 5.92 N 10.02.

909832/0579

- in -

Methyl Ni [( ί L (t L'1 »1 '-biphenyl] -4 ~ yloxyyäthylphosphinothioyl) -isopropylamino Jthio ^ ^ ethylamino) carbonyl ioxy ^ ethanimidothioate, as a pale yellow oil.

The elemental analysis of the compound C ₂₂ H ₃₀ IJ ₃ O ₃ PS ₃ gives the following values:

Calculated: C 51.64 H 5.91 N 8.21 Found: C 52.00 H 6.10 W 8.04.

Methyl II {L (i L (phenyl (phenoxy) phosphinothioyl) ethylamino] thio \ - methylamino) carbonyljoxy} äthanimidothioat as white crystals of a Pp of 122 ° to 123 ⁰ C.

The elemental analysis of the compound C ₁₇ H ₂ ^ N ₇ O ₃ PS ₃ gives the following values:

Calculated: C 48.60 H 5.15 N 8.95 found: C 48.56 H 5.23 N 9.04.

Methyl N- ^ [(H (ethyl (phenoxy) phosphinothioyl) benzylamino Jthio j- methylamino) carbonyl] oxy} ethanimidothioate as a pale yellow oil.

The elemental analysis of the compound Cp ₀ H ₂ ^ Ii ₅ O ₅ PS ₃ gives the following values:

Calculated: C 49.67 H 5.42 N 8.69 Found: C 49.64 H 7.19 N 8.41.

Methyl-NI [({[(ethyl (phenoxy) phosphinothioyl) -4-chloroanilino] -thiojmethylamino) carbonyl] oxy \ äthanimidothioat as white crystals, mp 69 ° to 71 ⁰ C.

909832/0579

The elementary analysis of the compound CJqH ₂₃ ClN ₃ O ₃ PS ₃ gives the following values:

Calculated: C 45.28 H 4.60 N 8.34 found: C 47.62 H 5.12 IJ 8.00.

Methyl Ni [ ({ [(ethoxy (phenyl) phosphinothioyl) benzylamino] thio ^ methylamino) carbonyl] oxy £ ethanimidothioate as a yellow viscous oil.

The elementary analysis of the compound C ₂ Qn ₂ ^ iJ ₃ O ₃ PS ₃ gives the following values:

Calculated: C 49.67 H 5.42 N 8.69 Found: C 46.43 H 5.07 N 7.80.

Methyl N-- £ [(^ [(ethyl (phenoxy) phosphinothioyl) -n-butylamino J-thio | methylamino) carbonyl Ioxy} ethanimidothioate as yellow oil.

The elemental analysis of the compound C ^ H ₂₈ N ₃ O ₃ PS ₃ gives the following values:

Calculated: C 45.42 H 6.28 N 9.35 Found: C 45.46 H 6.42 N 8.62.

Methyl N - ^ [({[(2-chlorophenoxy (ethyl) phosphinothioyl) anilino] thio ^ methylamino) carbonyl] oxy ^ ethanimidothioate as yellow oil.

The elemental analysis of the compound C ^ QH _{23 ClK 3} O ₃ PS ₃ gives the following values:

Calculated: C 45.28 H 4.60 N 8.34 Cl 7.03 Found: C 45.81 H 4.74 N 8.38 Cl 7.44.

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Methyl-W - * [(ϊ L (4-chlorophenoxy (ethyl) phosphinothioyl) anilino J-thio> methylamino) carbonyl] oxyfäthanimidothioat in the form of white crystals, mp 60 ° to 62 ⁰ C.

The elemental analysis of the compound C _{1 QHp 3} ClII ₃ O ₃ PS ₃ gives the following values:

Calculated: C 45.28 Ii 4.60 H 8.34 Cl 7.03 found: C 46.25 K 4.92 H 7.87 Cl 6.88.

Methyl-Ni [(H (ethyl (phenoxy) phosphinothioyl) cyclohexylamine J-thioi; me methylamino) carbonyl joxy \ äthanimidothioat in the form of white crystals, mp 129 ° to 130 ⁰ C.

The elemental analysis the Compound C. I9 ¹¹ 30th N ₃ O ₃ Pi D ₃ results in the following values: calculated: C 47, 98 Ii 6.36 N 8th , S3 found: C. 48, 14 II 6.57 N 8th , 94.

Methyl-Ii- \ L (£ L (ethyl (phenoxy) phosphinothioyl) -p-nitroanilino jthiofmethylamino) carbonyl] oxy ^ ethanimidothioate.

Methyl N - {[ (\ [(ethyl (phenoxy) phosphinothioyl) -o-methylanilino] -thio} methylamino) carbonyl] oxy f ethanimidothioate.

Hethyl-N- j [({[(ethyl (phenoxy) phosphinothioyl) -m-trifluoromethylanilino Jthio] methylamino) carbonyl] oxy j äthanimidothioat.

Methyl IJ- {[(\ [ (ethyl (phenoxy) phosphinothioyl) -o-chloroanilino J-thiojmethylamino) carbonyl / oxy} ethanimidothioate.

Hethyl-Nj L (i L (cyclohexyloxy (ethyl) phosphinothioyl) cyclohexylamino] thio? Methylamino) carbonyl ioxy ^ ethanimidothioate.

Methyl-N- {[({[ (ethyl (p-nitrophenoxy) phosphinothioyl) anilinojthio | methylamino) carbonyl] oxy ^ ethanimidothioate and

909832/0579

Methyl N - ^ [ ({ L (ethoxy (phenyl) phosphinothioyl) anilino Jthio} -methylamino) carbonyl ioxyfethanimidothioate.

Example 6

Starting from suitable O - [(^ ethylamino) carbonyl joximes from 2-alkyl-1,3-dithiolane-2-carboxaldehydes and suitable phosphoramidothioates the following compounds are obtained according to example 2, part B:

2-methyl-1,3-dithiolane-2-carboxaldehyde, 0 - (^ [(β-diethoxyphosphinothioyl) anilino Jthio} methylcarbamoyl) oxime.

2-IIIethyl-1,3-dithiolane-2-carboxaldehyde, 0- ({ [(diethoxyphosphino thioyl) methylamino] thio f methylcarbamoyl) oxime.

2-methyl-1,3-dithiane-2-carboxaldehyde, 0- (f [(phenoxy (phenyl) phosphinothioyl) ethylamino Ithio f methylcarbamoyl) oxime.

2-ethyl-1,3-dithiane-2-carboxaldenyne, 0- (\ [ (diethoxyphosphinothioyl) anilinoJthio | methylcarbamoyl) oxime.

2-ethyl-1,3-dithiane-2-carboxaldehyde, 0- ( { [(diethoxyphosphinothioyl) anilino] thio} methylcarbamoyl) oxime.

2-ethyl-1,3-diethyl-2-carboxaldehyde, 0- (^ [(ethoxy (phenoxy) phosphinothioyl ^ ethylamino jthio | methylcarbamoyl) oxime, 2-ethyl-1,3-dithiane-2-carboxaldehyde, 0 - ({[(ethoxy (thiophenoxy) -phosphinothioyl) methylamino jthio ^ methylcarbamoyl) oxime and 2-hetliyl-1,3-dithiane-2-carboxaldehyde, 0- ({['(diethoxyphosphinoyl) anilino jthio (methylcarbamoyl) oxime.

Example 7

Starting from the known compound 0 - [(^ ethylamino) carbonyl Joxim of 1,3-ithiolan-2-one and suitable phosphoramidothioates the following compounds are obtained according to example 2, part B:

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1,3-thiolan-2-one, O- ({[ (diethoxyphosphinothioyl) methylamino] thio \ methylcarbamoyl) oxime.

1,3-dithiolan-2-one, 0- (\ [ (diethoxyphosphinyl) methylamino jthio} -me tliylcarbamoyl) oxime.

1,3-dithiolan-2-one, 0 - ({f (diethoxyphosphinothioyl) anilino] thio / methylcarbamoyl) oxime.

1,3-Dithiolan-2-one, 0- (\ [(Pheno ^ (phenyl) phosphinothioyl) methylamino jtiiiofmethylcarbamoyl) oxiine and 1,3-Dithiolan-2-one, 0 - (^ L (Phenoxy (phenyl) phosphinothioylEthylamino] thio ^ methyloarbamoyl) oxime.

Example 8

Starting from the known compound 2,3-dihydro-2,2-dimethyl-7-benzofuranylmethylcarbamate and suitable phosphoramidothioates are obtained according to Example 2, Part B, the following Links:

2,3-Dihydro-2,2-dimethyl-7-benzofuranyl- | [(diethoxyphosphinothioyl) methylamino jthio fmethylcarbamate, 2,3-dihydro-2,2-dimethyl-7-benzofuranyl- ^ [(ethyl (phenoxy) phosphinothioyl) methylamino methylcarbamate, 2,3-dihydro-2,2-dimethyl-7-benzofuranyl - {[(diethoxyphosphinothioyl) ethylamino] thio \ methylcarbamate, 2,3-dihydro-2,2-dimethyl-7-benzofuranyl - {[( diethylphosphinotliioyl) methylamino jthio ^ methylcarbamate, 2,3-dihydro-2,2-dimethyl-7-benzofuranyl- ^ L (ethoxy (phenyl) phosphinothioyl) anilino jthio fmethylcarbamate, 2,3-dihydro-2,2-dimethyl-7- benzofuranyl-i L (ethoxy (ethyl) phosphinothioyl) methylamino jthiofmethylcarbamate, 2,3-dihydro-2,2-dimethyl-7-benzofuranyl- {[ (ethyl (thiophenoxy) phosphinothioyl) methylamino jthiof methylcarbamate, 2,3-dihydro-2 , 2-dimethyl-7-benzofuranyl- ^ L (p-chlorophenyl (methyl) phosphinothioyl) methylamino jthiof methylcarbamate,

909832/0579

- ue -

2,3-Dihydro-2,2 ~ dimethyl-7-benzofuranyl - C [(diethoxyphosphinyl) methylamino Thio ^ methyl carbamate,

2,3-Dihydro-2,2-dimethyl-7-benzofuranyl - ^ [(ethyl (phenoxy) phosphinyl) methylamino] thio \ methyl carbamate, 2,3-dihydro-2,2-dimethyl-7-benzofuranyl - ^ [(phenoxy (phenyl) phosphinyl) methylamino jthio} methyl carbamate, 2,3-dihydro-2,2-dimethyl-7-benzofuranyl- \ [ (ethoxy (ethyl) phos ~ phinyl) anilino jthiof methylcarbamate and 2,3- Dihydro-2,2-dimethyl-7-benzofuranyl - ^ [(methyl (thiophenoxy) phosphinyl) anilino thio ^ methyl carbamate.

Example 9

Methyl-N- {L ({L (5,5-dimethyl-2 »thioxo-1,3,2-dioxaphosphorinan-2-yl) isopropylamino Ethioimethylamino) carbonyl ioxyethane imidothioate:

A solution of 3.00 g of (13 _S 4 mmoles) of 5,5-dimethyl ~ 2 "-isopropylamino-2-thioxo-i, 3s, 2-dioxaphosphorinane and 1.9 ml (13.5 mmoles) of triethylamine in 20 ml Tetrahydrofuran is added dropwise over the course of 20 minutes to a stirred solution of 100 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 hour. The mixture is then mixed with 0.25 g of copper (I) chloride and then, dropwise, with a solution of 2.17 g (13.4 mmol) of methyl N - ^ [(^ ethylamino) carbonyl / oxyjethaneimidothioate and 1.90 ml (13.5 mmol) of triethylamine in 20 ml of tetrahydrofuran are added. 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 chromato-

909832/0579

graphed, a mixture of ethyl acetate and Skellysolve B in a ratio of 2: 3 ^{X is} used as the eluent. The chromatographed product is recrystallized from ethyl acetate, methyl N - ^ [({[(5,5-dimethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl) isopropylamino] thio] methylamino) carbonyl ioxy} ethanimidothioate is obtained, mp 114 ° to 115 ⁰ C in the form of a white solid. The nuclear magnetic resonance spectrum and IR spectrum correspond to the expected structure.

The elemental analysis of the compound C ^ HpgN ^ O, PS, gives the following Values:

calculated: C. 37, 58 H 6, 31 N 10, 11 found: C. 37, 63 Ii 6, 25th N 10, 11. Example 10

Methyl-N-jT ({ C (5,5-dimethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl) tert-butylamino] thio ^ methylamino) carbonyl Ioxy} ethanimidothioate:

A solution of 7.4 g (31 mmol) of 2-tert-butylamino-5,5-dimethyl-2-thioxo-1,3,2-dioxaphosphorinane and 4.4 ml (31 mmol) of triethylamine in 50 ml of tetrahydrofuran is added dropwise within 20 min in 20 ml of tetrahydrofuran was added with stirring into a cooled to a temperature of 0 ⁰ C solution of 2.0 ml (31 mmoles) of sulfur dichloride. When the addition is complete, the mixture is ^{stirred for 30 minutes at a temperature of 0} ° C., whereupon the mixture is treated with 0.3 g of copper (I) chloride and then dropwise over the course of 20 minutes with a solution of 5.1 g (31 mmol ) Methyl N - {[(methylamino) carbonyl] oxyjethane imidothioate and 4.4 ml (31 mmol) of triethylamine in 50 ml of tetrahydrofuran are added. When the addition is complete, the mixture is stirred for 2 hours while warming to room temperature

909832/0579

is left. Thereafter, the mixture is diluted with ethyl acetate and washed with water. The separated organic solution is dried over magnesium sulfate and concentrated under reduced pressure. The evaporation residue obtained in this way is treated with a 1: 2 mixture of ether and hexane to precipitate a crude product. After two recrystallizations from methanol to obtain an analytically pure material, mp 167 ° to 168.5 ⁰ C. The nuclear magnetic resonance spectrum and IR spectrum correspond to the expected structure.

The elemental analysis of the compound C ₁ ^ H ₂₃ N ₅ O ^ PS gives the following values:

Calculated: C 39.14 H 6.57 N 9.78 found: C 39.45 H 6.73 N 9.87.

Example 11

Methyl-N- % [ (£ [cyclohexyl (5,5-dimethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl) amino] thio] methylamino) carbonyl] oxyjethanimidothioate:

A solution of 12.4 g of 2-cyclohexylamino-5,5-dimethyl-2-thioxo-1,3,2-dioxaphosphorinane and 6.55 ml of triethylamine in 50 ml of tetrahydrofuran is transferred to a temperature within 15 minutes with stirring from -5 ° to ^{0 0} C cooled solution of 3.0 ml of sulfur dichloride in 50 ml of tetrahydrofuran entered. When the addition is complete, 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 pounds of methyl-H- { [ (methylamino) carbonyl] oxy] ethanimidothioate and 6.55 ml of triethylamine in 50 ml of tetrahydrofuran were added. When the addition is complete, the mixture is stirred, allowing it to warm to room temperature over a period of 75 minutes.

90 9 832/0579

290264?

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. When the semi-solid evaporation residue is recrystallized from ethyl acetate / hexane, 9.36 g of methyl-N - {[(| [cyclohexyl (5,5-dimethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl) amino]] are obtained thio? methylamino) carbonyl ioxy / ethanimidothioate in the form of a white pesticide with a melting point of 138 ° to 14O ⁰ C.

The elemental analysis of the compound C, AL · ^ MJd. PS-, gives the following values:

Calculated: C 42.18 H 6.64 N 9.22 Found: C 42.39 H 6.71 N 9.32.

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

Example 12

Methyl-N - {[(£ [isopropyl (5,5-diethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl) amino] thio} methylamino) carbonyl] oxyj ethanimidothioate:

A solution of 10.94 g of 5,5-diethyl-2-isopropylaInino-2-thioxo-1,3,2-phosphorinane and 6.05 ml of triethylamine in 50 ml of tetrahydrofuran is added dropwise over the course of 15 minutes to a temperature of -5 ° to 0 ⁰ C cooled solution of 2.72 ml of sulfur dichloride entered in 50 ml of tetrahydrofuran. After the addition has ended, the mixture is ^{stirred for 1 hour at a temperature of 0} ° C., whereupon 0.10 g of copper (I) chloride and then a solution of 7.06 g of ethyl-N - {[(( methylamino) carbonyl] oxyethane imidothioate and

09832/0579

2302647

6.05 ml of triethylamine in 50 ml of tetrahydrofuran are added. 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 over silica gel, a 1: 1 mixture of ethyl acetate and hexane being used for elution. Recrystallization from ethyl acetate / hexane gives methyl N - ^ [(| [isopropyl (5,5-diethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl) amino] thio \ methylamino) carbonyljoxy ^ äthanimidothioat in the form of a white solid, mp 123 ° to 124.5 ⁰ C.

The elemental analysis of the compound C., -HUqN ^ O λ PS ^ gives the following Values:

calculated: C. 40 , 61 H 6, 82 N 9 , 48 found: C. 40 , 83 H 6, 91 N 9 , 60

The nuclear magnetic resonance spectrum and IR spectrum correspond to those expected Structure.

Example 13

Appropriate based on suitable methyl carbamates and phosphoramidothioates Example 10 gives the following connections:

[isopropyl (2-thioxo-1,3,2-phospholan-2-yl) amino] -thioymethyl-amino) carbonyl-ioxyethane-imidothioate, Fp: 120 ° to

The elemental analysis of the compound C ₁ QE ₂₀ N ₃ O ^ PS. * Gives the following values:

§098 32/0573

Calculated: C 32.16 H 5.40 N 11.25 Found: C 32.17 H 5.31 N 11.49.

Methyl-! L ({[cyclohexyl (5,5-diethyl-2-thioxo-1,3,2-dioxaphosphorinane-2-yl) amino jtJtiio ^ ethylamino) carbonyl] oxy} äthanimidothioat, mp: 155 ° to 157 ⁰ C.

The elemental analysis of the compound C ₁₀ II ₇ , N ^ O, PS-, gives the following fourth:

Calculated: C 44.70 H 7.09 N B.69 found: C 44.96 H 7.11 N 8.81.

Methyl-f [({[isopropyl (2-thioxo-1,3,2-dioxaphosphorinane-2-yl) amino] thio | methylamino) carbonylJoxy ^ äthanimidothioat, mp: 153 ° to 154 ⁰ C.

The elemental analysis of the compound C ₁₁ H ₂₂ N ₇ O ^ PS gives the following values:

Calculated: C 43.10 H 5.72 N 10.84 Found: C 34.21 H 5.87 N 11.13.

Methyl - ^ [({[ethyl (5,5-dimethyl-2-thioxo-1,3,2-dioxaphosphorinane-2-yl) amino] thio \ methylamino) carbonyl] oxy) äthanimidothioat, mp: 111 ° to 112 ⁰ C.

The elemental analysis of the compound C ₁₂ H ₂ ^ N, 0 ^ PS, gives the following values:

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

909832/057 9

Methyl-Ιί- χ [({[isopropyl (4,4,6-trimethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl) amino jthio ^ methylamino) carbonyl joxyj- ethanimidothioate, Pp: 123 ° to 127 ° C

The elemental analysis of the compound C ^, Hp «N-, O ^ PS ^ gives the following fourth

Calculated: C 39.24 H 6.35 N 9.80 found: C 39.76 II 6.94 N 9.76.

Methyl IT- ^ [(-f [(2-thioxo-4li-1,3,2-benzodioxaphosphorin-2-yl) isopropylamino] thio ^ ethylamino) carbonyl] oxyfethanimidothioate, methyl N - ^ [ ({ [(2 -thioxo-1,3,2-dioxaphospholan-2-yl) methylamino] thio | methylamino) carbonyl / oxyethaneimidothioate, methyl IT- [l [ [[ethyl (hexahydro-2-oxo-1,3,2-benzodioxaphospholane-2 -yl) amino JtMo f-methylamino) carbonyl] oxy | ethanimido thioate, methyl N - {[({[isopropyl (2-oxo-1,3,2-benzodioxaphospholan-2-yl) amino] thio} methylamino) carbonyl] oxy} ethanimidothioate, methyl N - {[(f [benzyl (5,5-diethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl) amino, thio ^ methylamino) carbonyl] oxy ^ ethanimidothioate and

Methyl N- {[ (f [methyl (2-thioxo-1,3,2-dioxaphosphorinan-2-yl) amino] thio / methylamino) carbonyl ioxy ethane imidothioate, m.p. 94-96 ° C.

The compounds of the formulas I, I ¹ , I "and I ¹ " are effective pesticides for controlling invertebrate pests in agriculture, industry and in the home. The compounds in question were compared with the starting methyl carbamates.

Representative pest species, for example, from the order "Lepidoptera", in particular the southern army worm

909 8 32/0 579

(SAW) (Erodenia eridania Cramer), the tobacco budworm (TBW) (Heliothis virescens) and the cabbage sparmer (CL) (Trichoplusia ni), from the order "Acarina" in particular the double-spotted Leaf spider mite (TSSM) (Tetranychus urticae Koch), from the order "Diptera" in particular the house fly (HF) (Musca domestica) Linnaeus) or the yellow fever mosquito (YFM) (Aedes aegypti), from the order "Orthoptera, especially the cricket (HC) (Acheta domesticus Linnaeus) or the German cockroach (GC) (Blatella germanica Linnaeus) or from the order "Coleoptera" in particular the cotton boll beetle (BW) (Anthonomus grandis Boheman) is used.

The effectiveness against invertebrate pests could already be determined at concentrations of 0.5 ppm, depending on the pest species will. Some invertebrate pests are more sensitive to the compounds of the invention than others, still others can be very resistant. As a rule, the compounds of the formula I are used in concentrations of about 30 up to about 6000 ppm are used.

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 phytotoxic. The mammalian toxicity is partly given.

4- (Dimethylamine) -3,5-xylyl ^ L (diethoxyphosphinothioyl) -n-propylamino jthioj methyl carbamate:

Insect dose mortality

SAW 100 ppm 100

YFI-I 0.6 ppm 100

909832 / 0S7§

Methyl-N - [[({[(diethoxyphosphinothioyl) isopropylamino] thio} -me thylamino) carbonyl] oxyj "ethanimidothioate:

Insect crowd mortality

SAW 3.3 ppm 100

CL 3.3 ppm 100

BW 50 ppm 60

PIF 25 ppm 80

YFM 1.0 ppm 100

Methyl-N- {[({[(methoxy (phenyl) phosphinothioyl) isopropylamino] -thiojmethylamino) carbonyljoxy ^ ethanimidothioate:

Insect crowd mortality

SAVi 3.3 ppm 90

CL 3.3 ppm 50

HF 25 ppm 50

BW 25 ppm 80

Methyl-N- £ [({[cyclohexyl (5,5-dimethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl) amino] thio] methylamine) carbonyl] oxy} ethanimido

thioate: lot ppm mortality insect 11 ppm 70 SAW 11 ppm 87.5 CL 11 95 TBW

Mammalian toxicity - oral LD ₅₀ (rats)> 8000 mg / kg

Methyl-N - {[({[isopropyl (5,5-diethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl) amino] thio} methylamino) carbonyl] oxy | ethanimidothioate:

909832/0 5 7

Insect crowd mortality

SAW 11 ppm 60

CL 11 ppm 95

TB 11 ppm 100

Mammalian toxicity - oral LD ^ q (rats) > 2000 mg / kg

Methyl H-4 [({[isopropyl (2-thioxo-1,3,2-phospholan-2-yl) amino] thio} methylamino) carbonyl ioxyethane imidothioate, Fp: 120 ° to 122 ° C:

Insect crowd mortality

SAW 11 ppm 40

CL 11 ppm 48

TB 11 ppm 45

Methyl-N- ^ [({[cyclohexyl (5,5-diethyl-2-thioxo-1,3,2-dioxaphosphorinane-2-yl) amino] thio Jme methylamino) carbonyljoxyjäthanimidothioat, mp: 155 ° bis157 ° C:

Insect crowd mortality

SAW 11 ppm 70

CL 11 ppm 77.5 '

TB 11 ppm 95

Mammalian toxicity - oral LDc ₀ (rats) > 8000 mg / kg

Methyl-N- £ [({[isopropyl (2-thioxo-1, 3, 2-dioxaphosphorinan-2-yl) · amino] thio} methylamino) carbonyl joxyj'äthanimidothioat, mp: 153 ° to 154 ⁰ C:

909832/0579

Insect crowd mortality

SAW 11 ppm 56

CL 11 ppm

TB 11 ppm

Mammalian toxicity - oral LD ^ ₀ (rats)> 2000 mg / kg

Methyl-iM [({[ethyl (5,5-dimethyl-2-thioxo-1,3,2-dioxaphosphorinane-2-yl) amino] thio i * methylamino) carbonyl Joxyjäthanimidothioat, mp: 111 ° to 112 ⁰ C:

Insect crowd mortality

CL 11 ppm 56

Methyl N- · ^ L (f [isopropyl (4,4,6-trimethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl) amino / thio / methylamino) carbonyl ioxy / ethanimidothioate, m.p .: 123 ° up to 127 ⁰ C:

Insect crowd mortality

CL 11 ppm 92.5

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. These Acetonic solutions are made as such or in with a Tween 20 "moistening water" or with a 10% cane sugar containing "Moistening water" is applied in a diluted form. The "dampening water" as such contained 0.132% (v / v) IVeen 20 (Polyoxyethylene sorbitan monolaurate).

909832 / 0B79

The tests with the Southern Army Arm and the Cabbage Spanner were made carried out on leaves of the Uenderson limabush bean. This broad bean has two primary leaves per seedling. The leaves were immersed in an emulsion of the compound to be tested in the "dampening water", whereupon they dry were left. Then they were placed on a moistened filter disk in a plastic Petri dish of diameter 9 cm. Five larvae of each of the insects to be tested were placed on the leaves, whereupon the lid of the Petri dishes removed and the Petri dish set aside for further evaluations. For every treatment dose three parallel tests were carried out.

The cricket test was carried out by adding 5 ml portions the acetone solution were pipetted into Petri dishes with a diameter of 9 cm. Then the acetone was smoked off. 10 cricket pupae were then placed in each treated Petri dish, whereupon the lid was put back on. Three parallel tests were carried out for each treatment dose.

The tests with the house fly and with the cotton boll beetle were carried out by placing a cotton ball in the Size of a golf ball with 10 ml of a preparation of the test Compound made using a "dampening water" containing 10% cane sugar saturated. The saturated pad was then placed in a scoop attached to the inside wall surface of a waxed paper cup was attached. The paper cup had a capacity of 141.7 g. 10 adult house flies or 10 cotton boll beetles were placed in the waxed paper cups, which were then covered with a plastic lid for further observation were covered. Two parallel tests were carried out for each treatment dose.

909 8-3 2/0579

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

The tests, which were dtirchgeführt using the southern armyworm, the Keimchens, the boll weevil, the Ilausfliege and carbon tensioner were at 22 ° C, the tests were carried out using the yellow fever mosquito larvae, were run at a temperature of 27 ⁰ C calmly.

The tests aimed at killing the insects were evaluated after 24, 48 and 72 hours, respectively. Among the killed insects were dying insects or insects left on the ground are also counted. ·

In further tests, the phytotoxicity, the residual efficacy and the toxicity to mammals were tested by using, for example, methyl N - {[ ({ [(diethoxyphosphinothioyl) isopropylamino] thio ^ ethylamino) carbonyl Ioxy} ethanimidothioate with the starting compound methyl N - / [( methylamino) carbonyl] oxyethane imidothioate was compared. A scale was used where 0 indicates no damage and 10 stands for complete death of the plant. The new compounds according to the invention are generally less phytotoxic than the parent compound and significantly less phytotoxic to sensitive plants, for example the eggplant plant. Typically, the inventive methods have

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bonds have an average phytotoxicity index im Range from about 1.0 to 1.5 at a concentration of 300 to 600 ppm after an exposure time 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 effectiveness (on the leaves) against larvae of the southern army worm on lima bean seedlings. The compound according to the invention methyl N- \ [ ( { [(diethoxyphosphinothioyl) isopropylamino ]thio fmethylamino) carbonyl ]oxyfethanimidothioate still gives 100% mortality 7 weeks after the treatment has been carried out. The activity of the parent compound in the equivalent amount has already decreased to 20? Ό after 14 days.

In a comparison of the oral toxicity, which was carried out with male rats, the compound according to the invention methyl li ^ [({ L (diethoxyphosphinothioyl) isopropylamino Jthio ^ methylamino) carbonyl Ioxy} ethanimidothioate has been found to be less than a quarter as toxic as the methyl carbamate parent compound. The oral LD ^ Q values are 105 mg / kg body weight and 17 to 24 mg / kg body weight.

As already stated, the compounds of the formula Ia are particularly effective. For example, the compound methyl Nf [ (j [(ethyl (phenoxy) phosphinothioyl) anilino Jthio] methylamino) carbonyl Ioxy ^ ethanimidothioate has up to 3 times the insecticidal activity of the parent compound methyl N - ^ [(methylamino) carbonyl ioxy} ethanimidothioate ( Methomyl) against Lepidopterus species, for example the southern army worm (SAW) and the cabbage wrench.

The tests outlined show that the compounds according to the invention are able to solve the problems set and

909832 / OS79

make a significant contribution in the field of pesticides. They also show that the N - [(phosphinyl) -amino] -thio- and N - [(phosphinothioyl) amino] thio-methylcarbamate for the control of harmful insects in the form of the pure compound, as they were prepared according to the examples, in the form of technically pure compounds from large-scale production or in the form of mixtures of special compounds can be used. On the other hand, it may be useful for practical reasons to the skilled person on the Field of pesticides agents with a diluting carrier and, if necessary, other auxiliaries that facilitate the distribution of the promote active compounds to control pests and to increase effectiveness and economy, to hand.

There are a large number of diluents or carriers that those for use in the field of pest control and are suitable for the preparation of pesticidal agents using the compounds according to the invention. Typically dispersible carrier materials are used. Such carrier materials can contain further auxiliaries, for example wetting agents, emulsifiers, adhesion-improving agents Agents and other components that indirectly contribute to an improvement in effectiveness.

The new carbamates according to the invention of the formulas I, I ', I "and I" ¹ can be used against insects, roundworms (nematodes) and mites. They can be used in the form of pesticidal agents, for example dusts, wettable powders, emulsifiable concentrates, aqueous dispersions, solutions and flowable creams. The agents in question can be applied to any location, for example on soil, on plants, on leaves, on seeds or on other parts of plants.

0 9 8 3 2/0579

Granular agents can be applied to the floor or surfaces after they have been prepared. Furthermore, the Compounds according to the invention of the formulas I, I ·, I "and I" ' be the only active ingredient in a pesticidal agent, or the particular pesticidal agent may have more Active ingredients with insecticidal, miticidal or nematocidal activity contain.

Those compounds according to the invention of the formulas I, I ¹ , I ″ and I ″ ¹ which are solid can easily be processed into dusts by grinding a mixture of the compound (s) in question and a powdery carrier material with one another. This grinding is usually done using a ball mill, hammer mill, or air-blower atomization.

Conveniently, the particle size of the individual particles is less than 60 microns. Preferably 95% of the particles have a particle size less than 50 microns, about 75% of the particles exhibit a particle size of 5 to 20 microns. Dusts of the specified fineness, size reduction or distribution are usually free-flowing powders and can be used on animals, inanimate objects, fruit trees and crops and applied to the soil in such a way that suitable spreading or coverage is achieved. The dusts are suitable especially good for the control of insects and mites, and zv / ar by using the pesticidal agents concerned dusted with airplanes. Dusts are also suitable for application to the underside of foliage.

Typical examples of suitable powdery carrier materials are natural clays, e.g. China clay, Georgia clay, bard clay, Attapulgite, kaolin and bentonite clay. Minerals can be found in

/ 0 57a

their natural form, as they are obtained from the earth, are used. Examples are talc, pyrophillite, Quartz, diatomaceous earth, puller earth, chalk, sulfur, materials containing silica, such as silica and silicates, and the same. Furthermore, the minerals in question can be chemically modified. Examples of this are more washed Bentonite or colloidal silica. Finally, organic substances in flour-like form are also suitable, e.g. Wood, walnut shells, soybean meal, cottonseed meal, tobacco meal and free flowing hydrophobic starches.

Dusts are also obtained by dissolving the phosphinic acid derivatives of the aminothiomethylcarbamate pesticides of the formulas I, I ¹ , I "and I"'in a volatile solvent, for example methylene chloride, mixing the resulting solution with a powdery carrier and then evaporating the solvent.

The proportion of powdery carrier and active compound of the formula I, I ¹ , I "and I" ¹ can vary widely depending on the intended use, the control of roundworms (nematodes) or mites and the treatment conditions. As a rule, dusts can contain up to about 90% by weight of active ingredient.

Pesticidal compositions according to the invention in the form of dispersible powders are obtained by incorporating a surface-active agent into a powdery composition prepared in the manner described. When about 0.1 to about 12% surfactant is incorporated into a powdered agent, the resulting dispersible powder is particularly well suited for further mixing with water for spraying on inanimate objects and products, fruit trees, crops, the soil and live animals , e.g. livestock. The dis-

909832/0579

Pergeable powders can be mixed with water to make any concentration of active ingredient. The mixture can then be applied in such an amount that you get the desired application amount and the uniform Distribution achieved. With this versatility in mind, the dispersible powders according to FIG Invention preferably from about 5 to about 80% active ingredient contain.

Typical examples of surface-active agents which are suitable for the production of pesticidal agents according to the invention in the form of dispersible powders are alkyl sulfates and sulfonates, e.g. Glycerol mannitan laurate, polyalkyl ether condensates of fatty acids, lignosulfonates and the like. Preferred surface-active agents are mixtures of sulfonated oils and polyalcohol carboxylic acid esters (Emcol 11-77), mixtures of polyethoxyethanols (Tritone X-151, X-161, X-171), for example approximately equal parts of sodium kerylbenzenesulfonate and isooctylphenoxypolyethoxyethanol with about 12 ethoxy groups, and mixtures of calcium alkylaryl sulfonates and polyethoxylated vegetable oils (Agrimul N ₂ S). Of course, the sulfates and sulfonates mentioned are preferably used in the form of their soluble salts, for example their sodium salts. All of these surfactants are capable of lowering the surface tension of water in concentrations of about 3/4% or less. If necessary, dispersible powders are also obtained using mixtures of surface-active agents of the types mentioned.

909832/0 570

-Sk-

A suitable dispersible powder is obtained, for example, by mixing and grinding 327 kr; Georgia tone, 4.5 kg of isooctylphenoxypolyethoxyethanol ('i'riton X-100) as Lasting agent, 9 kg of a polymeric sodium salt of a substituted Benzoid long-chain sulfonic acid (Daxad 27) as a dispersant and 113 kg of the active ingredient, e.g. the compound of Example 2. The obtained dispersible Powder has the following percentage composition (data in parts by weight, unless otherwise noted):

Active ingredient 25 / ό Isooctylphenoxypolyäthoxyäthanol - Λ% polymeric sodium salt of a substituted benzoid long-chain sulfonic acid 2% Georgia clay 72%.

If you have such a dispersible powder in an amount of Dispersed 4.54 kg in 379 liters of water, a sprayable one is obtained Agent with about 0.3% (3000 ppm) of active ingredient, which is against insects or mites on plants, fruit trees or other whereabouts of the insects or pebbles are applied or sprayed on the ground to combat iiematodes can.

If necessary, dispersants, e.g. methyl cellulose, Polyvinyl alcohol, sodium lignin sulfonates and the like, dispersible Powders according to the invention are incorporated. Adhesive or sticky agents, e.g. vegetable oils, naturally occurring gums, casein, Zonarez B, a range of polymerized terpenes, Unicez 709, one based on maleic acid resin based, polypols, partially dimerized resin acids and Dpolymerx, a dimeric resin acid, and the like can also be used. Corrosion inhibitors, e.g.

909832/0 5 79

Epichlorohydrin, and anti-foaming agents, e.g. stearic acid, are added will. Methods for incorporating these agents into pesticides are known to those skilled in the art.

The novel compounds of the formulas I, I ¹ , I ″ and I ″ ¹ 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 insoluble in water, 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 go into solution in the water with any excess of compound of formula I, I ¹ , I ", or I" ¹ precipitating out of solution. In an oil-in-water emulsion, the solvent phase is dispersed in the aqueous phase, the dispersed phase containing the active ingredient. In this way an even distribution of an active ingredient which is insoluble in water is achieved in an aqueous spray. A solvent carrier in which the novel compounds of the formulas I, I ', I "or I" are highly soluble, should suitably be such as to obtain pesticidal compositions of relatively high concentration of the active ingredient. Sometimes a solvent carrier (s), with or without cosolvent, can be used to make concentrated solutions of the active ingredient. The main consideration here, however, is to use a water-immiscible solvent for the active ingredient in order to keep the compound in solution for a range of concentrations required for application to insects and mites.

909832/0579

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

The concentration of active ingredient in the emulsifiable concentrates is expediently about 5 to about 50, preferably about 10 to about 40% by weight. A concentrate with 20 % by weight 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 3.79 l of medium, a mixture of 700 parts being obtained of active ingredient per million parts of liquid vehicle. Similarly, 1.06 liters of a 20% concentrate can be mixed with 155 liters of water to give a pesticidal agent having about 1200 ppm of active ingredient. In the same way, more concentrated

909832/0579

Prepare te solutions on the active ingredient.

The pesticidal compositions according to the invention in concentrate form, which are ultimately in the form of aqueous dispersions or emulsions are to be used, humectants, i.e. agents that prevent the agent from becoming dry in contact with the Delay, contain, material to which it is applied. Suitable humectants are, for example, glycerine, Diethylene glycol, solubilized lignins such as calcium lignin sulfonate, and the like.

Pesticidal compositions according to the invention in granular form are suitable for application to the soil if a permanent effect is desired will. Granular agents or granulates can easily be scattered by hand, over large areas or localized, e.g. in rows. The individual granules can be any size from 0.246 to 1.651, preferably from 0.351 to 0.833 mm. The granular agents or granules obtained by dissolving the active compound in a solvent such as methylene chloride, xylene or acetone and applying it of 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. Possibly the impregnated, granulated absorbent carrier can be provided with a coating. This coating preserves the Integrity of the grain until it hits an object or site suitable for the release of the active ingredient, is applied.

The application rates on insects, mites, the ground or any other site depend on the type of control to be controlled Harmful organism, the presence or absence of beneficial organisms,

90983 2/0579

the temperature conditions during the treatment and the application process and the effectiveness of the application. As a rule, insecticidal and miticidal activity is achieved, when the compounds are in concentrations of about 5 to about 2000 ppm, preferably from about 30 to about 1000 ppm, be applied. For nematodes, 4.5 bic are 22.7 kg each 4050 m required.

The pesticidal agents according to the invention with the new thiocarbamates of the formulas I, I ¹ , I ″ and I ″ ¹ can be applied to insects, mites, nematodes, the ground or any other site by customary known methods. For example, a floor area, 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. Dusts can be applied using powder atomizers or 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 for household application process to relatively dilute agents in a dispersible insecticidal carrier. So For example, a dust aerosol may contain about 0.1 to 5.0% active ingredient and otherwise deodorized kerosene.

Of course, when using the invention Compounds as pesticidal agents the most diverse variations are required. This depends, for example, on the Insect pest infestation, the insect pest to be controlled,

90983 2/0579

- 68 -

the specific site to be treated, the plant species, the prevailing weather conditions, e.g. the temperature, the relative humidity, lie, dew and the like.

909832/0579

Claims (61)

Pat ent claims Λ). N-l '(Phosphinyl) -amino] -thio- and N - [(Phosphinothioyl) -amino] -thio-methylcarbama te of the general formula: 0 PH ₃ X / ^ R_O_S_ll_S-Nk (CZ ₅ Z ₀ ) k I \ c ~ z ₃ where mean: R is a residue of the formula: a) in which R ₂ , R ₃ and R ^, which can be the same or different, each represent a hydrogen or halogen atom, a short-chain alkyl group with 1 to 5 carbon atoms inclusive, a short-chain alkoxy group with 1 to 5 carbon atoms inclusive , a short-chain alkylthio radical containing 1 to 5 carbon atoms inclusive, a Ö098 3-2 / 0679 Dialkylamino radical, the alkyl parts of which can be identical or different and have 1 to 3 carbon atom (s) inclusive, or represent a radical of the formula -N = CHN (CH ₃ ) ₂ ; B-C = N- wherein A and B, which can be the same or different and each represent a short-chain alkyl radical with 1 up to and including 5 carbon atom (s), one short-chain Alkylthio radical with 1 to 5 carbon atoms inclusive, a monocyanosubstituted alkylthio radical with 1 to 5 carbon atoms inclusive), a phenylthio radical, the phenyl part of which is optionally by 1 to 3 (identical or different) substituents consisting of halogen atoms or short-chain alkyl radicals with 1 to 4 carbon atom (s) inclusive, a cyano radical, an alkoxy radical having 1 to 5 carbon atom (s) inclusive, a phenyl radical or a hydrogen represent atom, with the proviso that in the case that B stands for a hydrogen atom, A of the formula: R ₆ -CSR ₅ «7 corresponds to, where mean: Rc is an alkyl radical with 1 to 3 carbon atoms inclusive (en) or a phenyl radical; Rg is an alkyl radical with 1 to 3 carbon atoms inclusive; and
an alkyl radical with 1 up to and including 3 carbon 909832/0579 fuel atom (s) or a radical of the formula -SRg, in which R _{Q is} an alkyl radical corresponding to the alkyl radical represented by R 1, or Rc and Rq together with the atoms to which they are attached hang, a heterocyclic ring containing two sulfur atoms of the formula: in which η = 2 or 3 and the alkylene part of the Ring is optionally substituted by one or two methyl radical (s); or A and B together with the carbon atom to which they are attached contain one containing two sulfur atoms heterocyclic ring of the formula: where m = 2 or 3 and the alkylene part of the ring optionally is substituted by one or two methyl radical (s) represent, or §09832 / 0879 c) _{R is} a short-chain alkyl radical, a optionally substituted phenyl radical, a phenyl-substituted short-chain alkyl radical or a cycloalkyl radical; X represents an oxygen or sulfur atom and Z ₁ to Zg, which can be identical or different, each represent a hydrogen atom or a methyl or ethyl radical and
k = 0 or 1. 2. Compounds according to claim 1, characterized in that they correspond to the formula given in which X is a Sulfur atom. 3. Compounds according to claim 1, characterized in that they correspond to the formula given in which X is a Oxygen atom. 4. Compounds according to claim 2, characterized in that they correspond to the formula given in claim 1, wherein R for an alkanimido radical of the formula B-C = N-, in which A represents a hydrogen atom or a short-chain alkyl radical xmd B denotes a short-chain alkylthio radical. 909832/0579 5. Compounds according to claim 4, characterized in that they correspond to the formula given in claim 1, wherein Z ₁ - and Zg are short-chain alkyl radicals. 6. Compounds according to claim 4, characterized in that they correspond to the formula given in claim 1, wherein Z ^ to Zg stand for hydrogen atoms. 7. Compounds according to claim 4, characterized in that they correspond to the formula given in claim 1, wherein Zp, Zc and Zg stand for short-chain alkyl radicals. 8. Compounds according to claim 5, characterized in that they correspond to the formula given in claim 1, wherein R _{1 is} a short-chain alkyl radical. 9. Compounds according to claim 6, characterized in that they correspond to the formula given in claim 1, wherein R-I stands for a short-chain alkyl radical. 10. Compounds according to claim 7, characterized in that they correspond to the formula given in claim 1, wherein R _{1 is} a short-chain alkyl radical. 11. Compounds according to claim 5, characterized in that they correspond to the formula given in claim 1, wherein R _{1 is} a cycloalkyl radical. 12. Methyl-N-f [(· »[(5,5-dimethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl) isopropylamino] thio] methylamino) carbonyl] oxy | - ethanimidothioate. 909832/0 57 13. Methyl N- £ [( ίί (5,5-dimethyl-2-thioxo-1,3,2-dioxlphosphorinan-2-yl) tert -butylamino / thiolmethylamino) carbonyl Ioxy} ethanimidothioate. 14. Methyl-N- £ [(U'isopropyl (5,5-diethyl-2-thioxo-1,3,2-phosphorinan-2-yl) amino Jthio} amino) carbonyl joxy} ethanimidothioate. 15. Methyl N- {[ ({[ethyl (5,5-dimethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl) amino jthio} methylamino) carbonyl] oxy ^ ethanimidothioate. 16. Methyl-N- ^ [({[isopropyl (2-thioxo-1,3, 2-phospholane-2-yl] amino) thio ^ methylamino) carbonyl] oxy} äthanimidothioat. 17. Methyl-N- ^ [({[isopropyl (2-thioxo-1,3,2-dioxaphosphorinan-2-yl) amino) Ethio (methylamino) carbonyl] oxyethane imidothioate. 18. Methyl N- [(f [isopropyl (4,4,6-trimethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl) amino Ethio} methylamino) carbonyl (oxy) ethanimidothioate. 19. Methyl N - ^ [(([cyclohexyl (5,5-diethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl) amino) Jthio} methylamino) carbonylJoxy | - ethanimidothioate. 20. Methyl Nf [( { [cyclohexyl (5,5-dimethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl) amino jthio} methylamino) carbonyl Ioxy ^ - ethanimidothioate. 21. Methyl-N- {[(^ [methyl (2-thioxo-1,3,2-dioxaphosphorinan-2-yl ) amino jthio ^ methylamino) carbonyl joxy jäthanimidothioat. 909832/0579 22. Use of K - [(phosphinyl) eminojthio- and N - [(phosphinothioyl) -amino] -thio-methylcarbamates according to claim 1 for controlling harmful insects by bringing into contact (the insects susceptible to the compounds in question) with an effective amount (of the compounds concerned). 23. Use of compounds of the formula given in claim 1, in which X is a sulfur atom, according to claim 22nd 24. Use of compounds of the formula given in claim 1, in which X is an oxygen atom, according to claim 22nd 25. Use of compounds of the formula given in claim 1, in which X stands for a sulfur atom and Z ₁ and Z _{2 are} short-chain alkyl radicals, according to claim 22. 26. Use of compounds of the formula given in claim 1, in which X stands for a sulfur atom and Z ₁ to Zg represent hydrogen atoms, according to claim 22 « 27. Use of compounds of the formula given in claim 1, in which X stands for a sulfur atom and Z ₁ , Z, and Zg represent short-chain alkyl radicals, according to claim 22. 28. Use of compounds of the formula given in claim 1, in which X is a sulfur atom, Z ₁ and Z _{2 are} short-chain alkyl radicals and R _{1 is} a short-chain alkyl radical, according to claim 22. 29. Use of compounds of the formula given in claim 1, in which X is a sulfur atom, Z ₁ to Zg water §09832 / 0579 represent hydrogen atoms and R ^ a short-chain alkyl radical means according to claim 22. 30. Use of compounds of those specified in claim 1 Formula in which X is a sulfur atom, Z ^, Z, - and Zg represent short-chain alkyl radicals and R- a short-chain Means an alkyl radical according to claim 22. 31. Use of compounds of the formula given in claim 1, in which X is a sulfur atom, Z ,, and Zp are short-chain alkyl radicals and R _{1 is} a cycloalkyl radical, according to claim 22. 32. Use of Methyl-N ~ £ [( {[ (5,5-dimethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl) isopropylamino] thio} methylamino) carbonyl] oxy} ethanimidothioate, Methyl-N- £ L (£ C (5,5-dimethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl) tert -butylamino jthio ^ methylamino) carbonyl] oxy} ethanimidothioate, Methyl N- { [(^ [isopropyl (5,5-diethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl) amino] thio} methylamino) carbonyl] oxy} ethanimidothioate and / or Methyl N- | [(f [ethyl (5,5-dimethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl) amino] thiojmethylamino) carbonyl] oxy \ ethanimidothioate
according to claim 22. 33. Use of Methyl-N - / [({[isopropyl (2-thioxo-1,3,2-dioxaphospholan-2-yl) amino] thio} methylamine) carbonyl] oxy | ethanimidothioate and or 909832/0579 2302647 Methyl-N- {C ({[isopropyl (2-thioxo-1,3,2-dioxaphosphorinan-2-yl ) amino] thio} methylamino) carbonyl] oxy ^ ethanimidothioate, according to claim. 22nd 34. Use of Methyl N- { [( { [isopropyl (4,4,6-trimethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl) amino] thio ^ methylamino) carbonyl] oxyjethanimidothioate according to claim 22. 35. Use of Methyl N - ^ [({[cyclohexyl (5,5-dimethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl) amino Jthio} methylamino) carbonyl] oxy | ethane imidothioate and / or Metbyl-N - [[ ({ [cyclohexyl (5,5-diethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl) amino jthio} methylamino) carbonyl] oxy? - ethanimidothioate according to claim 22. 36. Means for controlling harmful insects from or with a biologically effective amount of at least one N - [(phosphinyl] amino] thio and / or N - [(phosphinothioyl) amino] thio methyl carbamate the formula given in claim 1 and optionally an auxiliary or carrier. 37. Means according to claim 36, characterized in that there is at least one compound of those specified in claim 1 Contains formula in which X is a sulfur atom. 38. Means according to claim 36, characterized in that there is at least one compound of those specified in claim 1 Contains formula in which X is an oxygen atom. 39. Means according to claim 38, characterized in that it at least one compound of those specified in claim 1 909832/0579 Contains formula in which X represents an oxygen atom and R represents an alkanimido radical of the formula B-C = N, in which A denotes a hydrogen atom or a short-chain alkyl radical and B denotes a short-chain alkylthio radical stands. 40. Means according to claim 39, characterized in that it link contains at least one of the formulas specified in claim 1, wherein X represents an oxygen atom, R represents an alkanimido radical of the formula B-C = N, in which A is t
A. Denotes hydrogen atom or a short-chain alkyl group and B denotes a short-chain alkylthio group, and Z _c and Zg correspond to short-chain alkyl groups. 41. Means according to claim 39, characterized in that there is at least one compound of the claim. 1. Specified Contains formulas in which X is an oxygen atom, R is an alkanimido radical of the formula B-C = N, in which Rather, A denotes a hydrogen atom or a short-chain alkyl radical and B denotes a short-chain alkylthio radical, and Zy, until Zg corresponds to atoms of water. 42. Means according to claim 39, characterized in that there is at least one compound of those specified in claim 1 Contains formulas in which X is an oxygen atom, R is an alkanimido radical of the formula B-C = N, in which Rather, A denotes a hydrogen atom or a short-chain alkyl radical and B denotes a short-chain alkylthio radical, and Z ₂ , Zc and Zg correspond to short-chain alkyl radicals. 909 8-3 2/0579 43. Means according to claim 40, characterized in that there is at least one compound of those specified in claim 1 Contains formula in which X represents an oxygen atom, R represents an alkanimido radical of the formula B-C = N, in which A denotes a hydrogen atom or a short-chain alkyl group and B denotes a short-chain alkylthio group, Zc and Zg correspond to short-chain alkyl groups and R ₁ denotes a short-chain alkyl group. 44. Means according to claim 41, characterized in that there is at least one compound of those specified in claim 1 Contains formula in which X represents an oxygen atom, R represents an alkanimido radical of the formula B-C = N, in t A which A represents a hydrogen atom or a short-chain alkyl radical and B represents a short-chain alkylthio radical, Z ₁ to Zg correspond to hydrogen atoms and R _{1 represents} a short-chain alkyl radical. 45. Means according to claim 42, characterized in that there is at least one compound of those specified in claim 1 Contains formula in which X represents an oxygen atom, R represents an alkanimido radical of the formula B-C = N, in which A represents a hydrogen atom or a short-chain alkyl radical and B represents a short-chain alkylthio radical, Z ₂ »Zc and Zg correspond to short-chain alkyl radicals and R _{1 represents} a short-chain alkyl radical. 46. Means according to claim 40, characterized in that it contains at least one compound of the formula given in claim 1, in which X stands for an oxygen atom, R 909832/0579 represents an alkanimido radical of the formula B-C = N, in t A which A denotes a hydrogen atom or a short-chain alkyl group and B denotes a short-chain alkylthio group, Zc and Zg correspond to short-chain alkyl groups and R ₁ denotes a cycloalkyl group. 47. Composition according to claim 36, characterized in that it is used as an active ingredient Methyl-Nf [( {[ (5,5-dimethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl) isopropylamino] thio ^ methylamino) carbonyl] oxy | ethanimidothioate, Methyl-N- {( '(£ [(5,5-dimethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl) tert-butylamino] thiojmethylamino) carbonyl] oxy } - ethanimidothioate, Methyl-N- S C (^ [isopropyl (5,5-diethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl) amino] thio} methylamino) carbonyl] oxy | ethanimido thioate and / or Methyl N - {[({[ethyl (5,5-dimethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl) amino] thio] methylamino) carbonyl ioxy ^ ethanimidothioate
contains. 48. Composition according to claim 36, characterized in that it is used as an active ingredient Methyl N- {[({ [isopropyl (2-thioxo-i, 3,2- .phospholan-2-yl) amino jthioj methylamino) carbonyl] oxy ^ ethanimidothioate and / or Contains methyl N- { [([ [isopropyl (2-thioxo-1,3,2-dioxaphosphorinan-2-yl) amino] thiojmethylamino) carbonyl] oxy ^ ethanimidothioate. 49. Composition according to claim 36, characterized in that it is used as the active ingredient 9.0 9832/0579 Methyl N- \ [(£ [isopropyl (4,4,6-trimethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl) amino] thio} methylamino) carbonyl] oxy | - ethanimidothioate
contains. 50. Composition according to claim 36, characterized in that it is used as an active ingredient Metbyl-N-JL ( I [cyclohexyl (5,5-dimethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl) amino] thio | methylamino) carbonyl] oxy | ethanimidothioate and / or Methyl Nf [( [ [cyclohexyl (5,5-diethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl) amino] thiojmethylamino) carbonyl ioxy ^ - ethanimidothioate
contains. 51. Agent according to one of claims 47 to 50, characterized in that that, as an auxiliary or carrier, it is an easily dispersible auxiliary or an easily dispersible one Includes carrier. 52. Gown according to claim 51, characterized in that it Contains water as an aid or carrier. 53. Agent according to claim 52, characterized in that there is also a surface-active agent and a finely divided Contains solid. 54. Agent according to claim 51, characterized in that the concentration of active ingredient is 0.5 to 75%. 55. H - [(phosphinyl) -amino] * hio- and N - [(phosphinothioyl) -amino] -thio-methylcarbamate of the formulas: 909832/0579 O CH ₃ X O- Il I II / C-Ν-S-N-P (CH ₂ ) P I "a R — 0 — C — Ν — S — N — P I "'a where mean: R is a remainder of the formulas :,
a) in which R ₂ , R3 and R ^, which can be the same or different, each for a hydrogen or halogen atom, a short-chain alkyl group with 1 to 90983 2/0579 including 5 carbon atom (s), a short-chain alkoxy radical with 1 to 5 carbon atoms inclusive, a short-chain alkylthio radical with 1 to 5 carbon atoms inclusive, a dialkylamino radical, the alkyl parts of which may be the same or different and 1 to 3 carbon atoms inclusive ( e) may have, or represent a radical of the formula -N = CHN (CH ^) ₂ ;
b) B-C = N- wherein A and B, which can be the same or different and each represent a short-chain alkyl radical with 1 up to and including 5 carbon atom (s), one short-chain Alkylthio radical with 1 to 5 carbon atoms inclusive, a monocyanosubstituted alkylthio radical with 1 to 5 carbon atoms inclusive), a phenylthio radical, the phenyl part of which is optionally by 1 to 3 (identical or different) substituents consisting of halogen atoms or short-chain alkyl radicals with 1 to 4 carbon atom (s) inclusive, a cyano radical, an alkoxy radical having 1 to 5 carbon atom (s) inclusive, a phenyl radical or a hydrogen represent atom, with the proviso that in the case that B stands for a hydrogen atom, A of the formula: R ₆ -CSR ₅ «7 corresponds to, where mean: 909832 / 0B79 an alkyl radical with 1 to 3 carbon atoms inclusive (en) or a phenyl radical; an alkyl radical with 1 to 3 carbon atoms inclusive (s); country an alkyl radical having 1 to 3 carbon atom (s) inclusive or a radical of the formula -SRg, in which Rq stands for an alkyl radical corresponding to the alkyl radical represented by R ₁ -, or IL and Rq together with the atoms to which they are attached, a heterocyclic ring containing two sulfur atoms of the formula: in which η = 2 or 3 and the alkylene part of the Ring is optionally substituted by one or two methyl radical (s); or A and B together with the carbon atom to which they are attached contain one containing two sulfur atoms heterocyclic ring of the formula: 9 0 9832/0579 where m = 2 or 3 and the alkylene part of the ring optionally is substituted by one or two methyl radical (s) represent, or c) a short-chain alkyl radical, an optionally substituted phenyl radical, a phenyl-substituted short-chain Alkyl radical or a cycloalkyl radical; X is an oxygen or sulfur atom; R _{0 is} a hydrogen or halogen atom or a short-chain alkyl or alkoxy radical; ρ = 3 or 4 and k = 0 or 1. 56. Use of N - [(phosphinyl) -amino] -thio- and N-C (phosphinothioyl) -amino] -thio-methylcarbama th according to claim 55 for controlling harmful insects by bringing them into contact (the insects susceptible to the compounds concerned) with an effective amount (of the compounds concerned) . 57. Means of controlling insect pests from or with a biologically effective amount of at least one N - [(phosphinyl) -ainino Jfchio- and / or W- [(phosphinothioyl) -amino] -thio-methylcarbamate of the formulas given in claim 55 and optionally an auxiliary or carrier. 909832/0579 58. Process for the preparation of N - ((Phosphinyl) -amino] -thio- and N- (_ (Phosphine thioyl) -amino] -thio-methylcarbamates according to Claim 1, characterized in that a compound of the formula: 0 CH, it ι ■> R-O-C-C-N-H wherein R has the meaning given in claim 1, with a compound of the formula: wherein R ₁ , k, X and Z ₁ to Zg have the meaning given in claim 1, is reacted. 59. The method according to claim 58, characterized in that one Methyl-N- {L '(U (5 »5-dimethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl) isopropylamino] thio £ me thylamino) carbonyl] -oxy} -ethanimidothioate, Methyl-N- ^ [({[(5,5-dimethyl-2-thioxo-1,3,2-dioxoqphosphorinan-2-yl) tert-butylamino] thio | methylamino) carbonyl] oxy | - ethanimidothioate, . Methyl N- { [(^ [isopropyl (5,5-diethyl-2-thioxo-1,3,2-phosphorinan-2-yl) amino] thio | methylamino) carbonyl] oxyf ethanimidothioate, 909832/057 9 Methyl-N - {[( { [ethyl (5,5-dimethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl) amino] thio ^ ethylamino) carbonyl] © xy ^ ethanimidothioate, Methyl-N- £ C (£ [isopropyl (2-thioxo-1,3,2-phospholan-2-yl) -amino-thiofmethylamino) carbonyl-oxy} ethanimidothioate, methyl-N- | [(^ [isopropyl (2-thioxo- 1,3,2-dioxaphosphorinan-2-yl) amino (thiojmethylamino) carbonyl] oxy | ethanimidothioate, methyl-N- I [(£ [isopropyl (4,4,6-trimethyl-2-thioxo-1,3,2- dioxaphosphorinan-2-yl) amino] thio | methylamino) carbon} * ·! ] oxyj ethanimidothioate, Methyl-N- { [ {{ [cyclohexyl (5,5-diethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl) amino] thio} methylamino) carbonyl] oxy ^ ethanimido thioate, Methyl-W - ^ [({[cyclohexyl (5,5-dimethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl) amino] thio ^ methylamino) carbonyl] oxy | - ethanimidothioate or Methyl N- \ [ (| [methyl (2-thioxo-1,3,2-dioxaphosphorinan-2-yl) -amino jthio | methylamino) carbonyl] oxy | ethanimidothioate. 60. The method according to claim 58, characterized in that one clones methyl-N- {[({ [cyclohexyl (5,5-dimethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl) amino] thio ^ methylamino) carbonyl] oxy} ethanimidothioate. 61. Process for the preparation of N - [(Phosphinyl) -amino] -thio- and N - [(phosphinothioyl) -amino] -thio-methylcarbamates according to Claim 55, characterized in that a compound the formula: 0 CH ^ R-O-C-N-H wherein R has the meaning given in claim 55, 909832/0579 with a connection of the formula: Cl-S-N -P (CH ₂ ), wherein R ₁ , X and ρ have the meaning given in claim 55, to a compound of the formula 1 "a or with a compound of the formula: Cl-S-N-P ι Ra wherein R ^, R _Q and k have the meaning given in claim 55 ι cL own, converts to a compound of formula 1 ^Ml a. 909832/0579