CH647243A5 - PHOSPHORO DERIVATIVES OF AMINOTHIOCARBAMIC ACID FLUORIDES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE. - Google Patents

Description

The present invention relates to novel phosphorde-30 derivatives of aminothiocarbamic acid fluorides as intermediates in a new process for the preparation of phosphorus derivatives of aminothiomethylcarbamates.

The intermediates mentioned have never been produced before, and the processes for their production are also new.

The N - [(phosphinyl) amino] thio and N - [(phosphinothioyl) amino] thiomethylcarbamates, a process for their preparation and formulations which contain these substances and are suitable for use as pesticides, that is to say as 40 pesticides, are disclosed in US Pat U.S. Patent No. 4081536, issued March 28, 1978. Phosphoroaminosulfenyl derivatives of the benzofurancar bamate and processes for their preparation are described in U.S. Patent No. 4024277, published May 17, 1977 45. These phosphoric acid derivatives of the aminothiomethylcarbamate pesticides can be prepared in addition to other compounds using the compounds according to the invention.

Furthermore, a detailed report describing the synthesis of the dialkylaminothio derivatives of the N-methylcarbamates by C.E 'Hatch is given in the publication in J. Org. Chem., 43.3953 (1978). In the processes described there, dialkylaminothiocarbamoyl fluorides are used in the synthesis of carbamate derivatives. This report also describes the manufacture of N-methylcarbamoyl fluoride, using solvents in the manufacturing process described therein and using an excess of hydrogen fluoride in the manufacture.

The manufacture of another carbamic acid fluoride is illustrated in 60, Swiss Patent No. 422755, for which a priority date of February 20, 1961 was claimed, the patent holder of which is Farbenfabriken Bayer AG. This patent is published as a short version in Derwent Abstract No. H1400 (= 11603). In process 65 described there, hydrogen fluoride is used as reactant and as solvent, optionally together with another solvent in a reaction with the substituted phenyl isocyanate, so that nothing is taken from this Swiss patent

647 243

could become what could somehow be the subject of the present invention.

A description of processes for the preparation of N-chlorothio-N-methylcarbamoyl fluoride and for the preparation of N-chlorothio-N-methylcarbamoyl chloride, hereinafter referred to as the compound of the formula IV, are given in relation to the preparation of the fluoride mentioned in German Offenlegungsschriften Nos. 1931054 and 2023 079 and with regard to the preparation of the chloride mentioned in US Pat. No. 3699163.

Furthermore, phosphoramide reactants, which are referred to here as compounds of the formula V, are listed in the book “Methods of Organic Chemistry” by Houben-Weyl, Volume 12, Part 2, on pages 610 and 760 regarding the thiophosphoramides and on pages 276 and 413 regarding phosphoramides. The specified book was published by GeorgThieme Verlag, Stuttgart, FRG, 1963. In addition, the publication by L. Anschiitz in Ber. 61,1264 (1928) called a benzothiophosphol chloride, from which the corresponding amides to be produced according to the invention can be produced.

The compounds according to the invention have the following formula

0

-0

or

(II "')

represents, in these formulas the radicals Zj, Z2.Z3.Z4, Z5 and Z6 are the same or different and have the meaning of hydrogen atoms, methyl or ethyl groups,

k is 0 or 1,

p has the value 3 or 4 and

R9 is a hydrogen atom, a lower alkyl group, a lower alkoxy group or a halogen atom. The compounds of formula II are prepared according to the invention by using a compound of formula III

15

20th

Cl-S-N-P

I.

*1

(m)

Y »

25th

o ii

F-C-N.

H,

with N-methylcarbamoyl fluoride of the formula

5-N-P / ^

(II)

30th

V

: k „n -! - f

CH.j

R,

wherein

I.

. H

implements.

Another new process for the preparation of the compounds of the formula II comprises the reaction of N-chlorothio-N-methyl-carbamoyl-fhiorid of the formula IV

Ri

X Y

is a lower alkyl group, a phenyl group, a substituted phenyl group, a phenyl-substituted lower alkyl group or an optionally substituted cycloalkyl group,

represents an oxygen atom or a sulfur atom,

and Y 'are the same or different from one another and are lower alkyl groups, lower alkoxy groups, lower alkylthio groups, optionally substituted cycloalkyl groups, phenyl groups, substituted phenyl groups, phenoxy groups, substituted phenoxy groups, thiophenoxy groups or substituted thiophenoxy groups or together form a radical which has the following formulas

40

CB ^ N

u

JL

(iv)

S-Cl

45 with a phosphoramide of the formula V

50

X

II

HN-P-

1

(v)

Z1

I1

Y «

-O-C-Z,

> c

(II1)

"CZ-Z ^ k> 5 o '

55 As already mentioned above, the new compounds of the formula II are intermediates and are used to prepare compounds of the following formula

(II ")

60

65

O CH, X X

ii 3 ii /

r-o-c-n-s-n-pc

I \

R1 Y '

used, in which formula R has the following meanings:

(I)

7

647 243

a) a grouping of the formula r3 R2

form in which n is 2 or 3 and the alkylene portion of the ring is unsubstituted or substituted with one or two methyl groups;

; further A and B together with the carbon atom to which they are attached, a heterocyclic radical having 2 sulfur atoms of the formula in which the radicals

R2, R3 and R4 are the same or different from one another and the meaning of hydrogen atoms, lower alkyl groups with 1-5 carbon atoms, halogen atoms, lower alkoxy groups with 1-5 carbon atoms, lower alkylthio groups with 1-5 carbon atoms, dialkylamino groups in which the two alkyl groups are identical to or different from one another and each have 1-3 carbon atoms and groups of the formula N = CHN (CH3) 2;

b) Groupings of the formula

S CH «)

10th

15

20th

B-C = N-

1

A

in which

A and B are the same or different from one another and the meaning of lower alkyl groups with 1-5 carbon atoms, lower alkylthio groups with 1-5 carbon atoms, phenylthio groups in which the phenyl radical is unsubstituted or substituted with 1 to 3 substituents which are the same as or are different from one another and have the meaning 30 of halogen atoms and alkyl groups with 1 to 4 carbon atoms, as well as monocyano-substituted alkylthio groups with 1 to 5 carbon atoms in the alkyl part, cyano groups, alkoxy groups with 1 to 5 carbon atoms, phenyl groups or hydrogen atoms, provided that 35 then when one of A and B is hydrogen, the other has the following formula

I.

form in which m is 2 or 3 and the alkylene part of the ring is unsubstituted or substituted with one or two methyl groups and c) a grouping of the formula

R6-C-S-R5

40

Rr must have in which

R5 is an alkyl group with 1 to 3 carbon atoms or a phenyl radical,

denotes an alkyl group with 1 to 3 carbon atoms, an alkyl group with 1 to 3 carbon atoms or a grouping of the formula in which

T and T 'are identical to or different from one another and have the meaning of hydrogen atoms or alkyl groups with 1-6 carbon atoms,

Rx is a lower alkyl group, an optionally substituted phenyl radical, a phenylalkyl radical in which the alkyl radical is a lower alkyl radical or optionally substituted, preferably alkyl-substituted cycloalkyl groups, X is an oxygen atom or sulfur atom; the remaining substituents are already defined above.

The compounds of the formula I defined above are obtained using the compounds of the formula II according to the invention by a compound of the formula II

r6 r7

î

ych

F-C-N '

50

S-N-P

-sr «

is in which

R8 is an alkyl radical and has the meaning of the same alkyl radical as the radical R5, or R5 and Rs together with the atoms to which they are bound 55 a heterocyclic radical of the formula which has 2 sulfur atoms

1

R,

I / 1

(ii)

Y «

in which

Rj, X, Y and Y 'have the same meaning as in formula I, with a compound of the formula

RAW

/ \

r6

in which

60 R has the same meaning as in formula I.

Examples of lower alkoxy groups which can occur in the compounds of the formula I are the following radicals: methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentoxy and also the isomeric forms of these groups.

65 Likewise, examples of lower alkylthio groups which may be present in the compounds of the formula I are the residues: methylthio, ethylthio, propylthio, isopropylthio, butylthio, pentylthio and also their isomeric forms.

647 243

Examples of lower alkyl radicals which may be present in the compounds of the formula I are the methyl radical, the ethyl radical, the propyl radical, the butyl radical and the pentyl radical and isomeric forms of these radicals.

Examples of cycloalkyl groups which can occur in the compounds of the formula I are the radicals: cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl, where these radicals can optionally carry methyl, ethyl and propyl groups as substituents, but the total number of carbon atoms of these radicals should be at most 9.

Examples of phenylalkyl radicals which can occur in the compounds of the formula I in which the alkyl radical is a lower alkyl radical are the following radicals: benzyl, phenethyl, phenpropyl, phenbutyl, phenpentyl and isomeric forms of these radicals.

Examples of substituted phenyl radicals which can occur in the compounds of the formula I are phenyl radicals which have lower alkyl groups, lower alkoxy groups, halogen atoms, nitro groups and cyano groups as substituents. There may also be three or more such substituents in the phenyl group and examples of such groups are the 4-propyl-2-methylphenyl group, the 2-chloro-4-methylphenyl group, the 3,4-diethoxyphenyl group and the 3-cyano-4-ethoxyphenyl group called. From a practical point of view, however, the substituents in the substituted phenyl radicals should be selected so that the total number of carbon atoms in these substituted phenyl groups does not exceed 10, which means that a substituted phenyl radical can be, for example, a 4-isobutylphenyl radical.

Examples of substituted phenoxy groups which can occur in the compounds of the formula I are phenoxy groups which bear lower alkyl groups, lower alkoxy groups, halogen atoms, nitro groups and cyano groups as substituents. In this case too, two or more such substituents can occur on the phenoxy groups and the following substituted phenoxy radicals may be mentioned as examples: the 4-propyl-2-methylphenoxy radical, the 2-chloro-4-methylphenoxy radical, the 3,4-diethoxyphenoxy radical, the 3-cyano-4-ethoxyphenoxy and the like. In this case too, the number of carbon atoms in these substituted phenoxy radicals should be limited so that a total of 10 carbon atoms is not exceeded, and the 4-isobutylphenoxy radical may be mentioned as an example of this.

Examples of substituted thiophenoxy radicals which can occur in the compounds of the formula I are thiophenoxy radicals which bear lower alkyl groups, lower alkoxy groups, halogen atoms, nitro groups and cyano groups as substituents. In this case, too, two or more such substituents may be present in the substituted thiopheneoxy radical and examples of such multi-substituted thiopheneoxy radicals are the 4-propyl-2-methyl-thiophene-oxy radical, the 2-chloro-4-methyl-thiopheneoxy radical and the 3,4-diet -thoxy-thiophenoxy radical called. In this case too, the total number of carbon atoms in such substituted thiophenoxy radicals should be limited so that the grouping does not have more than 10 carbon atoms in total, which means that the 4-isobutylthiophenoxy radical may be mentioned as examples.

The above-mentioned production process, namely the reaction of the hydroxy compounds with the phosphorus derivatives of the aminothiocarbamic acid halide intermediates of the formula II, is expediently carried out in an inert solvent, preferably in a polar one which does not have free protons (i.e. an aprotic) Solvents, and examples of such solvents include acetic acid nitrile, diethyl ether, tetrahydrofuran and dimethyl formamide. Furthermore, the reaction can preferably be carried out in the presence of an organic base, for example a trialkylamine, for example the triethylamine, or pyridine or

Lutidine, be carried out and expediently at temperatures which are in the range of 0-100 ° C and preferably in the range of 10-50 ° C.

According to another embodiment, the 5 reaction in question can be carried out in a two-phase system which is composed of an inert organic solvent, such as, for example, toluene or methylene chloride and an aqueous phase, a hydroxy compound, for example an alkali metal hydroxide, and a phase 10 transfer reagent are dissolved. Suitable phase transfer reagents are tetraalkylammonium halides, crown ether and benzyltrimethylammonium chloride. The reaction is expediently carried out at a temperature in the range from 0-100 ° C. and in particular in the range from 20-50 ° C.

The reaction product can be isolated in a conventional manner, for example by filtration, by evaporation of the solvent, by recrystallization or by chromatography.

Preferred compounds according to the invention have the following formulas

0 ch:

2s f-c-n:

x 11 /

s-n-p t \

/ 1

S ~ Zz

(cz £ z6) k fjrv c — z3

30th

(ch =). ci v

40

and in these formulas 50 Ri and R9 and Zj up to and including Z6, X, Yj, Y'i, k, p have the same meaning as in Formula I and also the corresponding chlorine compounds.

The new intermediates according to the invention, namely the carbamic acid fluorides of the formula II, are produced by one of the 55 following two production processes. One of these manufacturing processes is illustrated using Reaction Scheme A below:

60

65

X Y

1/

Cl-S-N-P.

(III)

Reaction scheme A O

F-C-N-H • OH,

-4

647 243

r

■ .F-C-N-S-N-P

i i \

. CHo R, V '(II)' J

The second production process, according to which the new intermediates of formula II are obtained, is illustrated by the following reaction scheme B:

Reaction scheme B

X Y

11 /

H-N-p;

i \

R "

Y «

+ CH ^ -IJ-C-F-S-Cl

(V).

(IV)

O X Y

"Il

F-C-N-S-N-P

i 1 \

CH3 Rjl Y «

(II)

The starting materials described are known from the literature. An improved process for the production of one of the two starting materials, namely N-methylcarbamoyl fluoride, is also described below.

It is known that N-methylcarbamoyl fluoride can be produced by the following procedure:

HF + CHNCO ch3nhcof.

However, solvents such as pentane or ether were used in the production of this product, so that the product mixture obtained could be treated and stored in conventional glass vessels.

It has now surprisingly been found that the N-methylcarbamoyl fluoride can easily be prepared according to the reaction scheme given above, but in high yields and in high purity, by using conventional glass reaction vessels and also anhydrous hydrogen fluoride in an excess of 0-50 %, preferably in an excess of 5-20%, based on the methyl isocyanate used, and furthermore in the absence of other solvents, with this reaction expediently having a temperature in the range from -50 to + 50 ° C., preferably in the range from —20 to 4-20 ° C. In addition to the improvement in this method,

that the reaction in question can be carried out in the absence of a solvent, this production process can now also be carried out in flow-type reaction vessels, either in a gas phase or in a condensed phase. The reaction is limited to a relatively small volume, which also has advantages in terms of effective cooling and restriction of dangerous materials to small spaces.

Compounds of the N-chlorothiophosphoramide type, which correspond to the formula III and which could be used as starting materials in reaction scheme A, have been described in the literature and reference should be made in this connection to US Pat. Nos. 4024277 and 4081536. If these compounds are not known, they can easily be prepared using suitable starting materials by the method described in the above-mentioned 5 US patents. The suitable starting materials are described below as phosphoramide starting materials of the formula V.

The reaction of the compounds of formula III with the N-methylcarbamoyl fluoride is expediently carried out in an inert solvent, preferably a polar aprotic solvent, for example in acetic acid nitrile or dimethylformamide and preferably in the presence of an organic base, in particular a tertiary one Amines such as triethylamine as an acid acceptor. In this reaction the temperature can range from -50 ° C to + 40 ° C and preferably in the range from -30 ° C to + 10 ° C. The intermediates thus obtained, namely the thiocarbamic acid refluoride of the phosphorus amide type, which have the formula II and preferably the formulas II ', II "and II"', can be isolated by 20 customary processes and they are as intermediates, so as they are obtained, usable, that is to say in the crude state, in order to carry out the reaction with the hydroxy compounds.

In the other production process, which is carried out according to Scheme B, an N-chlorothiomethylcarbamoyl fluoride of the formula IV is reacted with a corresponding phosphoramide of the formula V to produce the desired chemical product of the formula II. This reaction is conveniently carried out in a suitable inert solvent 30, such as using dimethylformamide, acetic acid nitrile, ether, tetrahydrofuran, toluene or methylene chloride, conveniently in the presence of an organic base such as triethylamine, which is preferably at temperatures in the range from -20 ° C to 35 + 50 ° C and in particular in the range from -20 ° C to + 10 ° C. The intermediates produced in this way can be isolated by customary working methods and in the form in which they are obtained, that is to say without further purification, they are suitable for reaction with the hydroxy compounds.

Although it was stated above that the new intermediates can be isolated in each of the two reaction schemes, it is still not necessary to separate the intermediates from the reaction mixture which is formed in their preparation before carrying out the further reaction with the hydroxy compounds, to produce the desired products of Formula I above.

The improved process for the preparation of N-methylcarbamoyl fluoride is explained using the following examples 50 and also the preparation of the new phosphorus-containing derivatives of the aminothiocarbamic acid halide intermediates, which have formulas II, II ', II "or II'" and are described new processes for the preparation of the products of the formula I. In these examples, special 55 embodiments of the invention are explained in more detail. It is clear to a person skilled in the art that the processes described can be modified in many ways, both with regard to the processes for the preparation of the methyl carbamate starting materials and with regard to the reaction conditions and other working techniques.

Preparation A Production of N-methylcarbamoyl fluoride 65 This is an improved production process.

21.8 g (1.09 mol) of anhydrous hydrogen fluoride are passed through a polyethylene tube in 72.5 g (1.27 mol) of methyl isocy-

example 1

647 243 10

anat initiated in a ice-methanol bath on a tem- The compound mentioned in the title falls under the formula II.

temperature of -10 ° C, this reaction is carried out in a solution of 14.9 g (70.8 mmol) of 0.0-diethyl-isopropyl in a conventional glass device. Once the addition of phosphoramidothioate and 9.8 ml (70.8 mmol) of triethylamine in 50 is complete, the excess of methyl isocyanate at 25 ° C. ml of tetrahydrofuran is removed dropwise over a period of 10 min to a and a pressure of 40-60 mm, whereby the product remains in 5 solution of 10.2 g (70.8 mmol) of N-chlorothio (methyl) carbamoyl form of a clear colorless liquid. The fluoride in 50 ml of tetrahydrofuran, which was cooled in an ice bath, was 83.75 g, corresponding to 99.7% of the theoretical amount. After all the material has been added,

Yield. This material is distilled at a pressure of 10 and the mixture is stirred for 114 hours at 0 ° C., diluted with 200 ml mm at 48 ° C. Ether, washes with ice-cold water, dries ûbèr sodium sul-

10 fat and concentrated under reduced pressure.

The residue obtained in this way shows identical absorptions and an identical nuclear magnetic resonance production of methyl-N - [[[[(diethoxyphosphinothioyl) -l-iso spectrum (proton resonance) as the yellow oil, which propylamino] thio] methyamino] carbonyl] oxy] äthanimidothioat hand product II of Example 1 was obtained and namely - This compound to be prepared corresponds to the formula I. 15 Lichv C = 0 and N-CH3. The crude product II] is suitable for a solution of 2.00 ml (14.3 mmol) of triethylamine in 5 ml of reaction with the methyl-N-hydroxyethaneimidothioate, which in

Dimethylformamide is described for 5 min to a solution of Example 1.

4.07 g (14.7 mmol) of diethoxy-N-chlorothio (isopropyl) thiophos-

phoramidundl, 11 g (15.0 mmol) N-methylcarbamoyl fluoridine Example 3

Given 15 ml of dimethylformamide, this last-mentioned 20th

Solution is cooled in an ice bath. Once the entire preparation of methyl-N - [[[methyl [[isopropyl (2-thioxo-l, 3, -2-

Mixture is added, stirring is continued for 2 hours at 0 ° C and dioxaphosphorinan-2-yl) amino] thio] amino] carbonyl] oxy] ether-diluted with ice-cold saturated sodium bicarbonate nimidothioate

Solution and shake out with hexanes. The organic phase The compound mentioned in the title corresponds to formula I.

is dried over magnesium sulfate and evaporated under reduced pressure. A solution of 13.0 g (66.6 mmol) of 2-isopropylamino) -2 pressure, leaving a yellow oil. The thioxo-l, 3,2-dioxaphosphorinane and 7.3 g (72 mmol) triethyl

Material is subjected to column chromatography using amine in 50 ml of tetrahydrofuran, dropwise over 10 times on a size C Merclc-Lobar column, mixing a mixture of 8.1 g (78.7 mmol) of sulfur dichloride in as eluent 2.5% ethyl acetate 50 ml of tetrahydrofuran added with cooling, so using in hexane. This gives the intermediate product which cools strongly so that the temperature in the range from -5 ° C. to 0 ° C. formula IIj, namely O, Ö-diethyl-isopropyl [[(fluorocarbonyl) me- is maintained. After the mixture has been added, thylamino] thiophosphoramidothioate is stirred in the form of a yellow oil. 2 h and then diluted with 100 ml ether. The reaction mixture

The infrared spectrum shows the v for the group C = O at 1790 is filtered under a nitrogen atmosphere and the filtrate cm "1. The nuclear magnetic resonance spectrum, proton resonance is concentrated under reduced pressure. The remaining oil nance shows a doublet (J = 1 cps), which is dissolved in the group of formula 35 in 50 ml of dimethylformamide and is added as N-CH3. Total portion 5.8 g (75.3 mmol) of N-methyl carbamoyl fluoride

The purified product was subjected to thin-layer chromatography and then dropwise 7.3 g (72 mmol) of triethylphosphate on silica gel in two different amines in 10 ml of dimethylformamide over a period of 10 min., And it was found that cooling this product in a cooling bath to the temperature at -25 ° C for chromatography on silica gel. Hold 40. Once the addition of the mixture is complete, stir

0.56 g (1.8 mmol) of the purified 0.0-diethyl-isopropyl-man for 2 h in a bath at a temperature of 0 ° C. The [[(fluorocarbonyl) methylamino] thio] phosphoramidothioate and mixture is then diluted with ether, washed with ice-cold water 0.22 g (2.1 mmol) of methyl N-hydroxyethane imidothioate and 0.3, dried and concentrated, the crude N-ml (2.2 mmol) of triethylamine being dissolved in 1.5 ml of acetic acid nitrile Dissolve methyl [[(isopropyl) -2-thioxo-l, 3,2-dioxaphosphorinan-2-yl) and leave the solution at room temperature for 45 amino] thio] carbamic acid fluoride of the formula II 'in the form of a rendl7h . Then diluted with a mixture of a portion of red oil remains.

Ethyl acetate and part of Skellysolve B, washes with The nuclear magnetic resonance spectrum, recorded in

Water, dries over magnesium sulfate and concentrated under reduced pressure. CDC13 of this material shows a doublet (Jf-h = i cps) for N-CH3, the pressure. The remaining yellow oil is from a center at 3.45 ppm.

Mixture of ether and Skellysolve B recrystallized, where 50 The infrared spectrum shows the absorption of the group C = O, 0.43 g of a yellow solid is obtained, which has a melting at v = 1785 cm "1.

point of 64-67 ° C. The carbamic acid fluoride of the formula II is 50 ml methyl

A second recrystallization gives a material, dissolved in lenchloride, and a solution of 7.00 g (66.6 mmol) which has a melting point of 69-71 ° C., no methyl N-hydroxyethane imidothioate and 1.00 g ( 6.04

Lowering of the melting point occurs when one mixes this material 55 mmoles of tetraethylammonium chloride and 3.20 g (80 mmoles) with a corresponding sample, which is prepared in a single pour after the procedure - sodium hydroxide in 50 ml of water in U.S. Patent No. 4081563. Then the mixture is stirred for 20 h at described. Room temperature, then separate the two phases from each other,

The results regarding the nuclear magnetic resonance washes the organic phase with water, dries over Magne (proton resonance) and the IR spectrum are identical to the 60sium sulfate and concentrates under reduced pressure.

Material that consists of the methyl-N- [f (methylamino) carbonyl] - The remaining oil is rubbed with ether,

oxyäthanimidothioat was prepared (see the 5th compound wherein 3.90 g of methyl N - [[[methyl - [[isopropyl- (2-thioxo-l, 3,2-in Example 5 of U.S. Patent No. 4081536. dioxaphosphorinane 2-yl) amino] thio] amino] carbonyl] oxy] -

precipitate äthanimidothioat of formula I in the form of a white solid 65. This corresponds to a yield of 15% of theory.

Example 2 The nuclear magnetic resonance spectrum (proton resonance

Preparation of 0,0-diethyl-isopropyl [[(fluorocarbonyl) methyl nanz) and the infrared spectrum of this compound are identical amino] thio] phosphoramidothioate with a corresponding material, which is based on methyl

11

647 243

15

20th

N - [[(methylamino) carbonyl] oxy] ethane imidothioate was prepared by the methods described in US Patent No. 4081536. The product has a melting point of 153-154 ° C.

5

Example 4

Preparation of N-methyl [[(isopropyl) (2-thioxo-l, 3,2-dioxa-phosphorinan-2-yl) amino] thio] carbamic acid fluoride The compound mentioned in the title corresponds to formula II and is used made by N-chlorothio (methyl) carb-amino acid fluoride.

A solution of 13.8 g (70.8 mmol) of 2- (isopropylamino) -2-thioxo-l, 3,2-dioxaphosphorinane and 9.8 ml (70.8 mmol) of triethylamine in 50 ml of tetrahydrofuran is added dropwise during 10 min to a solution of 10.2 g (70.8 mmol) of N-chlorothio (methyl) carbamoyl fluoride in 50 ml of tetrahydrofuran, which is cooled in an ice bath. After all the mixture has been added, the mixture is stirred at 0 ° C. for 1 h, diluted with 200 ml of ether, washed with ice-cold water, dried over sodium sulfate and finally concentrated under reduced pressure. The residue thus obtained shows identical values for the v of the group of the formula C = O and N-CH3 in the infrared absorption spectrum and in the nuclear magnetic resonance spectrum (proton resonance), such as the product which results from the carbamic acid-25 fluoride intermediate of the formula II Example 3 was obtained. This crude N-methyl [[(isopropyl) (2-thioxo-l, 3,2-dioxa-phosphorinan-2-yl) amino] thio] carbamic acid fluoride of the formula II ', which was obtained using N-chlorothio ( methyl) carb-aminic acid fluoride was obtained is also suitable for reaction with 30 methyl-N-hydroxyethaneimidothioate by the method described in Example 3.

Example 5

Preparation of methyl-n - [[[[(5,5-dimethyl-l, 3,2-dioxaphos-35-phorinan-2-yl) (tert-butyl) amino] thio] methylamino] carbonyl] -oxy] ethaneimidothioate The compound mentioned in the title corresponds to formula II '. Following the procedure described in Example 3, however, using 2-N- [chlorothio-40 (tert-butyl) amino] -5,5-dimethyl-2-thioxo-l, 3,2-dioxaphos -phorinan, which consists of 2- (tert-butylamino) -2-thioxo-l, 3,2-dioxapho-phorinan, that of 2- (tert-butylamino) -2-thioxo-l, 3,2-dioxaphos-phorinan and sulfur dichloride has been obtained, the magnetic resonance spectrum is obtained, and the infrared spectrum of this compound is identical to that of the corresponding product made from methyl N - [[(methylamino) carbonyl] oxy] ethane doate by the method described in the U.S. patent No. 4081536. This product has a melting point of 167-168.5 ° C. 50

The elementary analysis of this compound of the empirical formula Q4H28N3O4PS3 gave the following values:

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

55

Example 6

Preparation of N-methyl [[(tert-butyl) (2-thioxo-l, 3,2-dioxa-phosphorinan-2-yl) amino] thio] carbamic acid fluoride The compound mentioned in the title corresponds to the formula II '60 and it is made using N-chlorothio (methyl) carbamic acid fluoride.

Following the working procedure given in Example 4, but using 2- (tert-butylamino) -2-thioxo-l, 3,2-dioxaphosphorinane as starting material 65, the intermediate of formula II mentioned in the title is obtained , which is used in the working process described in Example 5 for reaction with methyl N-hydroxyethaneimidothioate45

can be drawn using methyl-N - [[[[[(5,5-dimethyl-l, 3,2-dioxaphosphorinan-2-yl) (tert-butyl) amino] thio] methyl-amino] carbonyl] oxy ] ethane imidothioate, which corresponds to formula I.

Example 7

Preparation of 2- (isopropyl) phenyl - [[cyclopentyl- (3a, 4,5,6,7,7a-hexahydro-2-oxo-l, 3,2-benzodioxaphosphol-2-yl) amino] thio] methyl carbamate

The compound mentioned in the title corresponds to formula I.

A solution of 16.3 g (66.6 mmol) of N-cyclopentyl-3a, 4,5,6,7,7a-hexahydro-2-oxo-l, 3,2-benzodioxaphosphol-2-amine and 7.3 g (72 mmol) of triethylamine in 50 ml of tetrahydrofuran is added dropwise over 10 minutes to a solution of 8.1 g (78.7 mmol) of sulfur dichloride in 50 ml of tetrahydrofuran, cooling during this addition to bring the temperature to the range of -5 to keep to 0 ° C. After all the material has been added, the mixture is stirred for 2 h and then diluted with 100 ml of ether. The reaction mixture is filtered under a nitrogen atmosphere and the filtrate is concentrated in vacuo. The residue is dissolved in 50 ml of dimethylformamide and 5.8 g (75.3 mmol) of N-methylcarbamoyl fluoride are added all at once, after which 7.3 g (72 mmol) of triethylamine in 10 ml of dimethylformamide are added dropwise over the course of 10 minutes. cooling in a cooling bath at a temperature of -25 ° C during the addition. Once all the material has been added, the mixture is stirred in a cooling bath at 0 ° C. for 2 h. The mixture is then diluted with ether, washed with ice-cold water, dried and concentrated, the crude N-methyl [[(cyclo- Pentyl) (3a, 4,5,6,7,7a-hexahydro-2-oxo-l, 3,2-benzodioxaphos-phol) amino] thio] carbamic acid fluoride, which corresponds to the formula II ", remains. This carbamoyl fluoride of formula II "is dissolved in 50 ml of methylene chloride and a solution of 7.00 g (66.6 mmol) of methyl N-hydroxyethane imidothioate and 1.00 g (6.04 mmol) of tetraethylammonium chloride and 3.20 g of 80 mmol) of sodium hydroxide in 50 ml of water is added all at once. The mixture is then stirred at room temperature for 20 hours and the two phases are separated. The organic phase is washed with water, dried over magnesium sulfate and concentrated under reduced pressure. The remaining oil is triturated with ether to the product 2- (isopropyl) phenyl [[cyclopentyl- (3a, 4,5,6,7a-hexahydro-2-oxo-l, 3,2-benzodioxaphosphol-2 -yl) -aminoy] thio] methyl carbamate, which corresponds to the formula I, precipitate.

Example 8

Preparation of N-methyl [[(cyclopentyl) (3a, 4,5,6,7,7a-hexa-hydro-2-oxo-l, 3,2-benzodioxaphosphol) amino] thio] carbamic acid fluoride

The compound mentioned in the title corresponds to the formula II ".

A solution of 17.36 g (70.8 mmol) of N-cyclopentyl-3a, 4,5,6,7,7a-hexahydro-2-oxo-l, 3,2-benzodioxaphosphol-2-amine and 9.8 ml (70.8 mmol) of triethylamine in 50 ml of tetrahydrofuran is added dropwise over a period of 10 minutes to a solution of 10.2 g (70.8 mmol) of N-chlorothio (methyl) carbamoyl fluoride in 50 ml of tetrahydrofuran, during which Adding in an ice bath cools. As soon as the whole amount has been added, the mixture is stirred at 0 ° C. for a hour, then diluted with 200 ml of ether, washed with ice-cold water, dried over sodium sulfate and evaporated under reduced pressure.

The product thus obtained has identical absorptions in the infrared spectrum and in the nuclear magnetic resonance spectrum (proton resonance), namely values for a of the group C = 0 and N-CH3, such as those for the carbamoyl fluoride intermediate of the formula II "in Example 7 This crude N-methyl [[(cyclopentyl) (3a, 4,5,6,7,7a-hexahydro-

647 243

12

2-oxo-l, 3,2-benzodioxaphosphoI) amino] thio] carbamic acid fluoride of the formula I is suitable for being reacted with the methyl N-hydroxy-ethaneimidothioate in the same manner as described in Example 7 .

Example 9

Preparation of Methyl-N - [[[[[[(2-methylpropyl) (2-thioxo-l, 3,2-benzodioxaphosphol-2-yl) amino] thio] amino] car-bonyl] oxy] ethane imidothioate

The compound mentioned in the title corresponds to the formula I '".

A solution of 16.2 g (66.6 mmol) of N- (2-methylpropyl) -2-thioxo-1,3,2-benzodioxaphosphol-2-amine and 7.3 g (72 mmol) of triethylamine in 50 ml of tetrahydrofuran is added dropwise over 10 minutes to a solution of 8.1 g (78.7 mmol) of sulfur dichloride in 50 ml of tetrahydrofuran, while cooling the addition to keep the temperature in the range of -5 to 0 ° C. As soon as all the material has been added, the mixture is stirred for 2 hours and then diluted with 100 ml of ether. The reaction mixture is filtered under a nitrogen atmosphere and the filtrate is evaporated in vacuo. The residue obtained in this way is dissolved in 50 ml of dimethylformamide and 5.8 g (75.3 mmol) of N-methylcarbamoyl fluoride are added all at once and then 7.3 g (72 mmol) of triethylamine in 10 ml of dimethylformamide are added dropwise during Added 10 min with cooling in a bath at a temperature of -25 ° C. After all the material has been added, the mixture is stirred for 2 hours in a cooling bath at a temperature of 0 ° C. The mixture is then diluted with ether, washed with ice-cold water, dried and concentrated, the crude N-methyl [[ (2-methylpropyl) (2-thioxo-l, 3,2-benzodioxaphosphol-2-yl) amino] thio] carbamic acid fluoride, which corresponds to the formula II '", remains. This carbamic acid fluoride is then dissolved in 50 ml of methylene chloride and a solution of 7.00 g (66.6 mmol) of methyl N-hydroxyethane imidothioate as well as 1.00 g (6.04 mmol) of tetraethylammonium chloride and 3.20 g (80 mmol) of sodium hydroxide in 50 ml of water The mixture is stirred at room temperature for 20 hours, then the phases are separated from one another and the organic phase is washed with water, then dried over magnesium sulfate and evaporated under reduced pressure. The oil which remains as a residue is rubbed with ether, around that as Product obtained methyl-N - [[[methyl [[(2-methylpropyl) (2-thioxo-l, 3,2-benzodioxaphosphol-2-yl) amino] thio] amino] car bonyl] oxy] ethane imidothioate, which precipitate which has formal.

Example 10

Preparation of N-methyl [[(2methylpropyl) (2-thioxo-l, 3,2-

benzodioxaphosphol-2-yl) amino] thio] carbamic acid fluoride

The compound mentioned in the title corresponds to the formula II "'.

A solution of 17.2 g (70.8 mmol) of N- (2-methylpropyl) -2-thioxo-l, 3,2-benzodioxaphosphoI-2-amine and 9.8 ml (70.8 mmol) of triethylamine in 50 ml of tetrahydrofuran added dropwise over 10 min to a solution of 10.2 g (70.8 mmol) of N-chlorothio (methyl) carbamoyl fluoride in 50 ml of tetrahydrofuran, which is cooled in an ice bath. After all the material has been added, the mixture is stirred for 1 h at 0 ° C., diluted with 200 ml of ether, washed with ice-cold water, dried over sodium sulfate and evaporated under reduced pressure. The remaining residue shows identical absorptions in the infrared spectrum and in the nuclear magnetic resonance spectrum (proton resonance), namely values for v for the group of the formula C = O and N-CH3 such as the carbamic acid fluoride of the formula II "', which was obtained according to Example 9. The carbamoyl fluoride thus obtained is suitable for using the methyl N-hydroxyethane imidothioate in the same

To be implemented as described in Example 9.

The intermediate N-methyl [[(isopro-5 pyl) (2-thioxo-l, 3,2-dioxaphosphorinan-2-yl) amino] thio] carbamic acid is converted into the intermediate product according to the working procedures described in Example 3 or Example 4 -fluoride prepared, which corresponds to the formula II, and this product is further used according to the working procedures described in Example 3, but using 2,3-dihydro-2,2-dimethyl-7-benzofuranol now Dihy-10 dro-2,2-dimethyl-7-benzofuranyI [fisopropyl (2-thioxo-l, 3,2-dio-xaphosphorinan-2-yl) amino] thio] methyl carbamate.

The infrared spectra and the nuclear magnetic resonance spectra are in agreement with the expected product. In the elemental analysis, the following values were found for the product of the Sum-15 formula CIgH23N204PS2, which has a molecular weight of 426494:

calc .: C 50.69 H 5.44 N6.57 found: C 50.73 H 5.97 N 6.52

The mass spectrum shows a molecular ion of mass 426. 20 Examples 1, 3, 5, 7 and 9 describe a process for the preparation of compounds of the formula I which proceeds via the new intermediates of the formula II which are produced by the reaction were, which is explained in Scheme A.

25 In Examples 2, 4, 6, 8 and 10, the same new intermediates of the formula II are prepared by the reaction which is explained in reaction scheme B. These intermediates can then be used in the corresponding examples for the preparation of the corresponding compounds of the formula I 30.

Accordingly, the preparation of the compounds of the formula I can be achieved by a process in which the production of the new intermediates is carried out using reaction scheme A or using reaction scheme 35 mas B. Accordingly, the new process for the preparation of the compounds of formula I can be carried out via Reaction Scheme A or Reaction Scheme B, which is described here.

Using the corresponding starting materials 40 according to the working methods described in Example 1 and Example 2, the new intermediates of the formula II according to the invention listed below were prepared:

45 0.0-di-n-propyl-N-methyl [[(fluorocarbonyl]) methylamino] thio] phosphoramidothioate,

0.0-di-n-propyl-N-n-propyl [[(fluorocarbonyl) methylamino] thio] phosphoramidothioate,

0,0-dimethyl-N-ethyl [[(fhiorcarbonyl) methylamino] thio] -50 phosphoramidothioate,

0,0-diisopropyl-N-methyl [[(fluorocarbonyl) methylamino] thiojphosphoramidothioat,

0.0-diphenyl-N-methyl [[(fluorocarbonyl) methylamino] thiojphosphoramidothioate, 55 0.0-diethyl-N-ethyl [[(fluorocarbonyl) methylamino] thio] phosphoramidothioate,

0,0-diethyl-N-2-phenylethyl [[(fluorocarbonyl) methylamino] thio] phosphoramidothioate,

0,0-diethyl-N-propyl [[(fluorocarbonyl) methylamino] thio] -60 phosphoramidothioate,

ö, 0-diethyl-N-isopropyl [[(fluorocarbonyl) methylamino] thiojphosphoramidothioat,

0.0-dimethyl-N-methyl [[(fluorocarbonyl) methylamino] thiojphosphoramidothioat, 65 0.0-dimethyl-N-isopropyl [[(fhiorcarbonyl) methylamino] thiojphosphoramidothioat,

0,0-diethyl-N-methyl [[(fluorocarbonyl) methylamino] thio] phosphoramidothioate,

0,0-diethyl-N-isopropyl [[(fluorocarbonyl) methylamino] thio] phosphoramidothioate,

0,0-diethyl-N-n-propyl [[(fluorocarbonyl) methylamino] thio] phosphoramidothioate,

0.0-diethyl-N-methl [[(fluorocarbonyl) methylamino] thio] phosphoramidothioate,

0,0-diethyl-N-phenyl [[(fluorocarbonyl) methylamino] thio] phosphoramidothioate,

0, S-dimethyl-N-methyl [[(fluorocarbonyl) methylamino] thio] phosphoramidothioate,

0-methyl-N-methyl [[(fluorocarbonyl) methylamino] thio] -P-phe-nylphosphonamidothioat,

0-methyl-N-isopropyl [[(fluorocarbonyl) methylamino] thio] -P-phosphonamidothioate,

0-methyl-N-methyl [[(fluorocarbonyl) methylamino] thio] -P-methyl-phosphonamidothioate,

0-isopropyl-N-isopropyl [[(fluorocarbonyl) methylamino] thio] -P-phenylphosphonamidothioate,

0-phenyl-N-methyl [[(fluorocarbonyl) methylamino] thio] -P-methyl-phosphonamidothioate,

0-isopropyl-N-isopropyl [[(fluorocarbonyl) methylamino] thio] -P-methylphosphonamidothioate,

0-methyl-N-isopropyl [[(fhiorcarbonyl) methylamino] thio] -P-methylphosphonamidothioate,

0-phenyl-N-isopropyl [[(fluorocarbonyl) methylamino] thio] -P-methylphosphonamidothioate,

0-phenyl-N-phenyl [[(fluorocarbonyl) methylamino] thio] -P-ethyl-phosphonamidothioate,

0-4-chlorophenyl-N-isopropyl [[(fluorocarbonyl) methylamino] thio] -P-methylphosphonamidothioate, 0-isopropyl-N-phenyl [[(fluorocarbonyl) methylamino] thio] -P-methylphosphonamidothioate,

0 - [(l, l'-biphenyl] -4-yl) -N-isopropyl [[(fluorocarbonyl) methylamino] thio] -P-methylphosphonamidothioate, 0-phenyl-N-ethyl [[(fluorocarbonyl) methylamino] thio] -P-phenyl-phosphonamidothioate,

0-phenyl-N-benzyl [[(fluorocarbonyl) methylamino] thio] -P-ethyl-phosphonamidothioate,

0-phenyl-N-phenyl [[(fhiorcarbonyl) methylamino] thio] -P-ethyl-phosphonamidothioate,

0-ethyl-N-phenyl [[(fluorocarbonyl) methylamino] thio] -P-phe-nylphosphonamidothioat,

0-phenyl-N-butyl [[(fluorocarbonyl) methylamino] thio] -P-ethyl-phosphonamidothioate,

0-2-chlorophenyl-N-phenyl [[(fluorocarbonyl) methylamino] thio] -P-ethylphosphonamidothioate,

0-4-chlorophenyl-N-phenyl [[(fluorocarbonyl) methylamino] thio] -P-ethylphosphonamidothioate,

O-phenyl-N-cyclohexyl [[(fluorocarbonyl) methylamino] thio] -P-ethylphosphonamidothioate.

In addition, suitable starting materials are used in the process mentioned above to prepare the new compounds of the formula II mentioned below:

0-ethyl-0-phenyl [[(fluorocarbonyl) methylamino] thio] phos-phoramidothioate,

0-ethyl-S-phenyl [[(fluorocarbonyl) methylamino] thio] phosphorus amidothioate,

0,0-diethylphenyl [[(fluorocarbonyl) methylamino] thio] phos-phoramide,

OPhenyl-N - [[(fluorocarbonyl) methylamino] thio] -N-methyl-P-phenylphosphoramidothioat,

0-phenyl-N - [[(fluorocarbonyl) methylamino] thio] -Np-nitro-phenyl-P-methylphosphoramidothioate, 0-phenyl-N - [[(fluorocarbonyl) methylamino] thio] -No-methyl-phenyl-P- ethyl phosphoramidothioate,

0-phenyl-N - [[(fluorocarbonyl) methylamino] thio] -N-m-trifluoromethylphenyl-P-ethyl-phosphoramidothioate,

13 647 243

0-phenyl-N - [[(fluorocarbonyl) methylamino] thio] -N-o-chlorophenyl-P-ethyl phosphoramidothioate,

0-Cyclohexyloxy-N - [[(fluorocarbonyl) methylamino] thio] -N-cy-clohexyl-P-ethylphosphoramidothioate, 5 0-p-nitrophenyl-N - [[(fluorocarbonyl) methylamino] thio] -N-phenyl-P ethyl phosphoramidothioate, 0-ethyl-N - [[(fluorocarbonyl) methylamino] thio] -N-methyl-P-ethyl phosphoramidothioate,

S-phenyl-N - [[(fluorocarbonyl) methylamino] thio] -N-methyl-P-io ethyl phosphoramidothioate, N - [[(fluorocarbonyl) methylamino] thio] -N-methyl-Pp-chlorophenyl-P-methylphosphinamidothioate , N - [[(fluorocarbonyl) methylamino] thio] -N-methyl-P, P-diethylphosphinamidothioate, 15 0-phenyl-N - [[(fluorocarbonyl) methylamino] thio] -N-methyl-P-phenylphosphonamide,

0-phenyl-N - [[(fluorocarbonyl) methylamino] thio] -N-methyl-P-ethylphosphonamidothioat,

0-phenyl-N - [[(fluorocarbonyl) methylamino] thio] -N-methyl-P-20 ethylphosphonamide,

0-ethyl-N - [[(fluorocarbonyl) methylamino] thio] -N-phenyl-P-ethylphosphonamide,

S-phenyl-N - [[(fluorocarbonyl) methylamino] thio] -N-phenyl-P-methylphosphonamidothioate.

25th

Other suitable starting materials are used in the processes described in Examples 3 and 5 and 4 and 6 in order to produce the corresponding new intermediate products of the formula II according to the invention, which are listed below:

f [isopropyl (5,5-dimethyl-2-thioxo-l, 3,2-dioxaphosphorinan-2-yl) amino] thio] methylcarbamic acid fluoride, 35 [[isopropyl (5,5-diethyl-2-thioxo-l , 3,2-dioxaphosphorinan-2-yl) amino] thio] methylcarbamic acid fluoride, [[ethyl (5,5-dimethyl-2-thioxa-l, 3,2-dioxaphosphorinan-2-yl) amino] thio] methyl carbamic acid fluoride, [[isopropyl (2-thioxo-l, 3,2-phospholan-2-yl) amino] thio] methyl-40 carbamic acid fluoride,

[[Isopropyl (4,4,6-trimethyl-2-thioxo-l, 3,2-dioxaphosphorinan-2-yl) amino] thio] methylcarbamic acid fluoride, [[cyclohexyl (5,5-diethyl-2-thioxo- l, 3,2-dioxaphosphorinan-2-yl) amino] thio] methylcarbamic acid fluoride, 45 [[cyclohexyl (5,5-dimethyl-2-thioxo-l, 3,2-dioxaphosphorinan-2-yl) amino] thio ] methylcarbamic acid fluoride, [[methyl (2-thioxo-l, 3,2-dioxaphosphorinan-2-yl) amino] thio] methylcarbamic acid fluoride.

50 Further new compounds of the formula II which were prepared by the process described here are the following:

[[Isopropyl (2-thioxo-4H-l, 3,2-benzodioxaphosphorinan-2-yl) -55 amino] thio] methylamino] methylcarbamic acid fluoride,

[[Methyl (2-thioxo-l, 3,2-dioxaphospholan-2-yl) amino] thio] methyl-carbamic acid fluoride,

[[Ethyl (hexahydro-2-oxo-l, 3,2-benzodioxaphospholan-2-yl) amino] thio] methylcarbamic acid fluoride, 60 [[isopropyl (2-oxo-l, 3,2-benzodioxaphospholan-2- yl) amino] -thiolmethylcarbamic acid fluoride,

[[Benzyl (5,5-diethyl-2-thioxo-l, 3,2-dioxaphosphorinan-2-yl) amino] thio] methylcarbamic acid fluoride, [[Methyl (2-thioxo-l, 3,2-dioxaphosphorinan -2-yl) amino] thio] -65 methyl carbamic acid fluoride.

If suitable starting materials are also used in the processes described in Examples 7 and 9 and 8 and 10

647 243

14

and, as described there, further new intermediates can be produced which correspond to the formula II "and II" '. These preferred intermediates are also the subject of the present invention.

Further intermediates of the formula II 'or II "in which X is an oxygen atom and additional intermediates of the formula II and II"' in which X is also an oxygen atom,

are produced by using suitable starting materials in the processes described in Examples 1, 3, 5 and 7 or in Examples 2, 4, 6 and 8.

Intermediates of formula II '", in which X is a sulfur atom, can be prepared in the same way by using appropriate starting materials in the working processes described in Example 9 and in Example 10, respectively.

m

Claims (6)

647 243 PATENT CLAIMS 1. Compound, characterized in that it has the formula II (II) in which Rj is a lower alkyl group, a phenyl group, a substituted phenyl group, a phenyl-substituted lower alkyl group or an optionally substituted cycloalkyl group, X represents an oxygen atom or a sulfur atom, Y and Y 'are identical or different from one another and are lower alkyl groups, lower alkoxy groups, lower alkylthio groups, optionally substituted cycloalkyl groups, phenyl groups, substituted phenyl groups, phenoxy groups, substituted phenoxy groups, thiophenoxy groups or substituted thiophenoxy groups or together form a radical which the following formulas r -o-c-z. (II *) > 5 -o-c-z, i 3 z4 cz z6) k -0 -0 -0 • 0 t-CH2> p (ii ") or (II '• •) 25th represents, in these formulas the radicals Zj, Z ;, Zj, Z4, Z5 and Z6 are the same or different and have the meaning of hydrogen atoms, methyl or ethyl groups, k is 0 or 1, p has the value 3 or 4 and R9 is a hydrogen atom, a lower alkyl group, a lower alkoxy group or a halogen atom. 2. A compound according to claim 1, characterized in that X is a sulfur atom and that it is one of the following compounds: 0,0-diethyl-N-propyl [[(fluorocarbonyl) methylamino] thio] phosphoramidothioate, 0,0-diethyl-N-isopropyl [[(fluorocarbonyl) methylammo] thio] phosphoramidothioate, 0,0-dimethyl-N-methyl [[(fluorocarbonyl) methylamino] thiojphosphoramidothioat. 0,0-dimethyl-N-isopropyl [[(fluorocarbonyl) methylamino] thio] phosphoramidothioate, 0.0-dimethyl-N-n-butyl [[(fluorocarbonyl) methylamino] thiojphosphoramidothioate, 5 0.0-diethyl-N-methyl [[(fluorocarbonyl) methylamino] thio] phosphoramidothioate, 0.0-di-n-propyl-N-methyl [[(fluorocarbonyl) methylamino] thiojphosphoramidothioate, 0.0-di-n-propyl-N-n-propyl [[(fluorocarbonyl) methyl-10 amino] thio] phosphoramidothioate, 0,0-dimethyl-N-ethyl [[(fluorocarbonyl) methylamino] thio] phosphoramidothioate, 0.0-diisopropyl-N-methyl [[(fluorocarbonyl) methylamino] thio] phosphoramidothioate, 15 0.0-diethyl-N-ethyl [[(fluorocarbonyl) methylamino] thio] phosphoramidothioate, 0,0-diethyl-N-phenyl [[(fluorocarbonyl) methylamino] thio] phosphoramidothioate, 0,0-diethyl-N-2-phenylethyl [[(fluorocarbonyl) methyl-20 amino] thio] phosphoramidothioate, 0,0-diphenyl-N-methyl [[(öuorcarbonyl) methylamino] thiojphosphoramidothioat, 0, S-dimethyl-N-methyl [[(fluorocarbonyl) methylamino] thiojphosphoramidothioat, 0-methyl-N-isopropyl [[(fluorocarbonyl) methylamino] thio] -P-phenylphosphonamidothioate, 0-methyl-N-methyl [[(fluorocarbonyl) methylamino] thio] -P-phe-nylphosphonamidothioat, 0-methyl-N-methyl [[(fluorocarbonyl) methylamino] thio] -P: methylphosphonamidothioate, 0-isopropyl-N-isopropyl [[(fluorocarbonyl) methylamino] thio] -P-phenylphosphonamidothioate, 0-phenyl-N-methyl [[(fluorocarbonyl) methylamino] thio] -P-methyl-phosphonamidothioate, 0-isopropyl-N-isopropyl [[(fluorocarbonyl) methylamino] thio] -P-methylphosphonamidothioate, 0-methyl-N-isopropyl [[(fluorocarbonyl) methylamino] thio] -P-methylphosphonamidothioate, 0-phenyl-N-isopropyl [[(fluorocarbonyl) methylamino] thio] -P-methylphosphonamidothioate, 0-phenyl-N-phenyl [[(fluorocarbonyl) methylamino] thio] -P-ethyl-phosphonamidothioate, 0-4-chlorophenyl-N-isopropyl [[(fluorocarbonyl) methylamino] thio] -P-methylphosphonamidothioate, 0-isopropyl-N-phenyl [[(fluorocarbonyl) methylamino] thio] -P-methylphosphonamidothioate, 0 - ([l, l'-biphenyl [4-yl) -N-isopropyl [[(fluorocarbonyl) methylamino] thio] -P-ethylphosphonamidothioate, 0-phenyl-N-ethyl [[(fluorocarbonyl) methylamino] thio ] -P-phenyl-50 phosphonamidothioate, 0-phenyl-N-benzyl [[(fluorocarbonyl) methylamino] thio] -P-ethyl-phosphonamidothioate, 0-ethyl-N-phenyl [[(fluorocarbonyl) methylamino] thia] -P-phe-nylphosphonamidothioat, 55 0-phenyl-N-butyl [[(fluorocarbonyl) methylamino] thio] -P-ethyl-phosphonamidothioate, 0-2-chlorophenyl-N-phenyl [[(fluorocarbonyl) methylamino] thio] -P-ethylphosphonamidothioate, 0-4-chlorophenyl-N-phenyl [[(β-carbonyl) methylamino] thio] -P-ethylphosphonamidothioate, 0-phenyl-N-cyclohexyl [[(fluorocarbonyl) methylamino] thio] -P-ethylphosphonamidothioate, [[Isopropyl (5,5-dimethyl-2-thioxo-l, 3,2-dioxaphosphorinan-2-yl) amino] thio] methylcarbamic acid fluoride, 65 [[tertiary butyl (5,5-dimethyl-2-thioxo -l, 3,2-dioxaphosphorinan-2-yl) amino] thio] methylcarbamic acid fluoride, [[isopropyl (5,5-diethyl-2-thioxo-l, 3,2-dioxaphosphorinan-2-yl) amino] thio ] methylcarbamic acid fluoride, 30th 35 40 45 60 3rd 647 243 [[Ethyl (5,5-dimethyl-2-thioxo-l, 3,2-dioxaphosphorinan-2-yl) amino] thio] methylcarbamic acid fluoride, [[Isopropyl (2-thioxo-l, 3,2-phospholan-2-yl) amino] thio] methyl-carbamic acid fluoride, [[Isopropyl (2-thioxo-l, 3,2-dioxaphosphorinan-2-yI) amino] thiojmethylcarbamic acid fluoride, [[Isopropyl (4,4,6-trimethyl-2-thioxo-l, 3,2-dioxaphosphorinane 2-yl) amino] thio] methylcarbamic acid fluoride, [[Cyclohexyl (5,5-diethyl-2-thioxo-l, 3,2-dioxaphosphorinan-2- yl) amino] thio] methylcarbamic acid fluoride, [[Cyclohexyl (5,5-dimethyl-2-thioxo-l, 3,2-dioxaphosphorinan-2- yl) amino] thio] methylcarbamic acid fluoride, [[Methyl (2-thioxo-l, 3,2-dioxaphosphorinan-2-yl) amino] - thio] methylcarbamic acid fluoride or N-methyl-N- [N-2-methylpropyl) (2-thioxo-l, 3,2-benzodioxa- phosphol-2-yl) amino] thio] carbamoyl fluoride. 3. A compound according to claim 1, characterized in that X is an oxygen atom in it and that it is either 0,0-diethyl-N-methyl [[(fluorocarbonyl) methylamino] thio] phosphoramidate or N-methyl-N - [[N-cyclopentyl) (3a, 4,5,6,7,7a-hexahydro-2-oxo-l, 3,2-benzodioxaphosphole) amino] thio] carbamoyl fluoride. 4. Process for the preparation of compounds of formula II (II) represents, in these formulas the radicals 7L \, Z2, Z3, Z4, Z5 and Z6 are the same or different from one another and have the meaning of hydrogen atoms, methyl or ethyl groups, 5 k is 0 or 1, p has the value 3 or 4 and R9 is a hydrogen atom, a lower alkyl group, a lower alkoxy group or a halogen atom, characterized in that a compound of the formula III Cl-S-N-P v i X r y1 15 1 with N-methylcarbamoyl fluoride of the formula (III) 20th -L chqn 3I H implements. 25 5. Process for the preparation of compounds of the formula 30th (II) wherein Ri is a lower alkyl group, a phenyl group, a substituted phenyl group, a phenyl-substituted lower alkyl group or an optionally substituted cycloalkyl group, X represents an oxygen atom or a sulfur atom, Y and Y 'are identical or different from one another and are lower alkyl groups, lower alkoxy groups, lower alkylthio groups, optionally substituted cycloalkyl groups, phenyl groups, substituted phenyl groups, phenoxy groups, substituted phenoxy groups, thiophenoxy groups or substituted thiophenoxy groups or together form a radical which the following formulas wherein 35 X 40 y 45 Rj is a lower alkyl group, a phenyl group, a substituted phenyl group, a phenyl-substituted lower alkyl group or an optionally substituted cycloalkyl group, represents an oxygen atom or a sulfur atom, and Y 'are the same or different from one another and are lower alkyl groups, lower alkoxy groups, lower alkylthio groups, optionally substituted cycloalkyl groups, phenyl groups, substituted phenyl groups, phenoxy groups, substituted phenoxy groups, thiophenoxy groups or substituted thiophenoxy groups or together form a radical which has the following formulas **1 I. -O-C-Z, > C (II ') ("CZeZ / -) k / 5 6 ' -O-C-Z " I 3 z ,. -0 -0 -0 <CH2) p R (II ") or 50 55 60 65 (II * '') (II ') (II ") or (II »'') 647 243 4th represents, in these formulas the radicals Zj, Z2, Z3, Z4, Z5 and Z6 are the same or different from one another and have the meaning of hydrogen atoms, methyl or ethyl groups, k is 0 or 1, p has the value 3 or 4 and R9 is a hydrogen atom, a lower alkyl group, a lower alkoxy group or a halogen atom, characterized in that the N-chlorothio-N-methyl-carbamoyl fluoride of the formula IV O JL (IV) CH ^ N s-cl with a phosphoramide of formula V (V) implements. 6. Use of the compounds of the formula Et O ii f-c-n h, ; _N_p X (ii) R, according to claim 1, wherein the substituents are defined in claim 1, for the preparation of compounds of the formula O CH- X A ii i 3 11 / r-o-c-n — s — n-p \ (I) b) Groupings of the formula b-c = n- ' i 10th 15 30th in which A and B are identical or different from one another and have the meaning of lower alkyl groups with 1-5 C atoms, lower alkylthio groups with 1-5 C atoms, phenylthio groups in which the phenyl radical is unsubstituted or has 1-3 substituents, which are identical to or different from one another and have the meaning of halogen atoms or alkyl groups with 1 to 4 carbon atoms, monocyano-substituted alkylthio groups with 1 to 5 carbon atoms in the alkyl part, cyano groups, alkoxy groups with 1 to 5 carbon atoms, phenyl groups or hydrogen atoms, provided that if one of the radicals A and B is hydrogen, the other radical is a grouping of the formula 20th r6-c-s-r5 25th this must in which R5 has the meaning of an alkyl radical with 1 to 3 carbon atoms or a phenyl radical, Rfl is an alkyl radical with 1 to 3 carbon atoms, R7 is an alkyl group with 1 to 3 carbon atoms or a grouping of the formula -sr » 35 40 is in which Rg the meaning of an alkyl group and the same Alkyl group such as the radical R5 or Rs and Rs together with the atoms to which they are attached form a heterocyclic radical of the formula which has 2 sulfur atoms (CH2) n 45 r) in which R has the following meanings: a) a grouping of the formula r3 R2 Ri in which R2, R3 and R4 are the same or different from each other and the meaning of hydrogen atoms, lower alkyl groups with 1-5 C atoms, halogen atoms, lower alkoxy groups with 1-5 C atoms, lower alkylthio groups with 1-5 C atoms, dialkylamino groups in which the two alkyl groups are identical to or different from one another and each have 1 to 3 carbon atoms and groups of the formula -N = CHN (CH3) 2; 50 / \ Rß form, in which 55 n is 2 or 3 and the alkylene portion of the ring is unsubstituted or substituted with 1 or 2 methyl groups; furthermore A and B together with the carbon atom to which they are attached form a heterocyclic radical of the formula which has 2 sulfur atoms 60 65 (ch2), - cim f \ c II 647 243 form, in which m is 2 or 3 and the alkylene part of the ring structure is unsubstituted or substituted with 1 or 2 methyl groups and c) a grouping of the formula CH, F-C-N ' Tp \ (Ii) Ri in which the leftovers T and T 'are identical to or different from one another and have the meaning of hydrogen atoms or alkyl groups having 1-6 carbon atoms; a lower alkyl group, an optionally substituted phenyl radical, a phenylalkyl radical in which the alkyl radical is a lower alkyl radical or optionally substituted cycloalkyl groups, X is an oxygen atom or sulfur atom, and Y 'are the same or different from one another and are lower alkyl groups, lower alkoxy groups, lower alkylthio groups, optionally substituted cycloalkyl groups, phenyl groups, substituted phenyl groups, phenoxy groups, substituted phenoxy groups, thiophenoxy groups or substituted thiophenoxy groups or together form a radical which has the following formulas P r <> I. ■ o-c-z. > c (II *) : cz5z6) k -o-c-z, I 3 (II1 M -0 -0 or he (II1 '') represents, in these formulas the radicals Zi, Z2, Z3, Z4, Z5 and Z6 are the same or different and have the meaning of hydrogen atoms, methyl or ethyl groups, Is 0 or 1, has the value 3 or 4 and is a hydrogen atom, a lower alkyl group, a lower alkoxy group or a halogen atom, characterized in that a compound of formula II in which io R1; X, Y and Y 'have the same meaning as in formula I, with a compound of the formula RAW 15 in which R has the same meaning as in formula I. 7. Use according to claim 6, characterized in that one of the following compounds is prepared: Methyl-N - [[[[[((diethoxyphosphinothioyl) isopropylamino] -20 thio] methylamino] carbonyl] oxy] etherimidothioate, Methyl-N - [[[[((l, l-dimethylethyl) (5,5-dimethyl-2-thioxo-l, 3,2-dioxaphosphorinan-2-yl) amino] thio] methylamino] carbonyl] -oxy] äthanimidothioat, or Methyl-N - [[[methyl [[(isopropyl) (2-thioxo-l, 3, -2-dioxaphospho-25 rinan-2-yl) amino] thio] amino] carbonyl] oxy] ether imidothioate. 35