GB2053921A - Phosphorus-containing N- methyl-N-substituted-carbamyl Fluorides, Their Preparation and Use in Preparing Pesticidal Compounds - Google Patents

Abstract

Novel compounds of formula II <IMAGE> wherein R1 is alkyl, optionally substituted phenyl, phenylalkyl or cycloalkyl; X is oxygen or sulfur; and Y and Y' are each alkyl, alkoxy, alkylthio, cycloalkyl or optionally substituted phenyl, phenoxy or phenylthio or Y and Y' together are alkylenedioxy, cycloalkylenedioxy or phenylenedioxy. These compounds are useful as intermediates in the preparation of known aminothiomethylcarbamate pesticides, by reaction with a compound of formula ROH, R being optionally substituted phenyl, optionally substituted imino or dihydrobenzofuranyl. The novel intermediates are prepared from Cl-S-NR1-P(X)YY' and a N- methylcarbamylhalide or from HNR1- P(X)YY' and a N-chlorothio-N- methylcarbamyl halide.

Description

SPECIFICATION N-methyl-N-substituted-carbamyl Fluorides. their Preparation and Use in Preparing Pesticidal Compounds Pesticidal N-[(phosphinyl)amino]thio- and N-[(phosphinothioyl)amino]thiomethylcarbamates, a process for their preparation, and formulations containing them, are described in US Patent Specification No. 4,081,536, its corresponding British Patent Application No. 1617/78, and in British Patent Publication No.2,01 5,527A. Phosphoroaminosulfenyl derivatives of benzofuran carbamates and their preparation are disclosed in US Patent Specification No. 4,024,277. The present invention relates to a new method for preparing these aminothiomethylcarbamates.

The synthesis of dialkylaminothio derivatives of N-methylcarbamates is described by Hatch, J.

Org. Chem. 43, 3953 (1978), which also disloses the use of dialkylaminothiocarbamoyl fluorides in the synthesis of carbamate derivatives.

The use of phosphoramide reactants is described in Methoden der Organischen Chemie (Houben Weyl) Vol.12. part 2, pages 610, 760 (thiophosphoramides) and pages 276,413 (phosphoramides), Georg Thieme Verlag (Pub.), Stuttgart, Germany, 1963. In addition, Anschiitz et al., Ber. 61,1264 (1928) discloses a benzothiophosphol chloride.

According to the present invention, a process for preparing a compound of formula I

wherein R is selected from (a) phenyl optionally substituted by one to 3 substituents which are independently selected from C1-5 alkyl, halogen, C15 alkoxy, C15 alkylthio, di(C~3 alkyl)amino in which the C13 alkyl groups are the same or different, and -N=CHN(CH3)2;; (b) ABC=N- wherein A and B are the same or different and are each hydrogen, C15 alkyl, C15 alkoxy, C15 alkylthio optionally substituted by a cyano group, cyano, phenyl or phenylthio optionally substituted by one to three substituents which are independently selected from halogen atoms and C14 alkyl radicals:

wherein R5 is C13 alkyl or phenyl;R6 is C13 alkyl and R7 is C1-3 alkyl or the same alkylthio group as R5S-;

wherein R6 is as defined above and n is 2 or 3, (CH2)n being optionally substituted by one or two methyl groups;

wherein m is 2 or 3, (CH2)m being optionally substituted by one or two methyl groups; and

wherein T and T' are the same or different and are each hydrogen or C16 alkyl; R1 is C15 alkyl, phenyl, substituted phenyl, C7-11 phenylalkyl or cycloalkyl; X is oxygen or sulfur; and either Y and Y' are indpendently selected from C15 alkyl, C15 alkoxy, C15 alkylthio, cycloalkyl, phenyl, substituted phenyl, phenoxy, substituted phenoxy, phenylthio or substituted phenylthio, or Y and Y' are taken together and are of formula I', I" or I"'

wherein Z, to Ze are the same or different and are each hydrogen, methyl or ethyl, k is O or 1, p is 3 or 4 and R9 is hydrogen, C15 alkyl, C15 alkoxy or halogen; comprises reacting a compound of formula II

wherein R1,X, Y and Y' are as defined above, with a compound of the formula ROH, wherein R is as defined above.

The compounds of formula II, defined above, are novel and are a further aspect of this invention.

Definitions and examples of C15 alkyl, C15 alkoxy, C15 alkylthio, cycloalkyl, C7~" phenylalkyl and substituted phenyl are to be found in British Patent Publication No. 2,015,526A. Substituted phenoxy and substituted phenylthio are to be construed analogously to substituted phenyl.

The reaction of the formula II intermediate with the compound of formula ROH may be conducted in an inert solvent, preferably an aprotic polar solvent such as acetonitrile, ethyl ether, tetrahydrofuran or dimethylformamide and in the presence of an organic base, e.g. a trialkylamine such as triethylamine, pyridine or lutidine, at a temperature from 0 t 100, preferably 10 to 50, OC.

Alternatively, the reaction may be conducted in a two-phaseystem consisting of an inert organic solvent such as toluene or methylene chioride and an aqueous phase in which the hydroxy compound, an alkali metal hydroxide and a phase transfer reagent are dissolved. Suitable phase transfer reagents include tetraalkylammonium halides, crown ethers and benzyltrimethylammonium chloride. The reaction is conducted at O to 100, preferably 20 to 500C. The product of the process may be isolated by conventional means such as filtration, solvent evaporations, crystallization or chromatography.

The compounds of formula II may be prepared by reacting a compound of formula Ill CI--SS-NRR,-P(X)W' Ill wherein R1,X, Y, and Y' are as defined above, with a N-methylcarbamyl halide.

N-methylcarbamyl chloride and N-methylcarbamyl fluoride are known. The latter is preferred, and a process for its preparation is disclosed by Hatch, supra, although a more satisfactory process is described and claimed in British Patent Application No. 8,017,582 filed on even date herewith.

N-chlorothiophosphoramides of formula Ill are disclosed and claimed in British Patent Application No. 7,925,933 (Serial No. ). They can be prepared by reaction of sulfur dichloride with a phosphoramide of formula V HNR,--P(X)W V wherein R1, X, Y and Y' are as defined above. The phosphoramides are readily available or can be prepared by known methods; see Methoden der Organischen Chemie (Houben-Weyl) 12, part 2, p 413 and 12, p. 1, Georg Thieme Verlag, Stuttgart, Germany (1963).

The preparation of the compounds of formula II by the above method is conducted in an inert solvent, preferably a polar aprotic solvent such as acetonitrile or dimethylformamide, and in the presence of a tertiary organic base such as triethylamine as an acid acceptor. The temperature of the reaction may be -50 to +40, and is preferably -30 to + 1 00C.

An alternative process for preparing compounds of formula II comprises reacting a compound of formula V as described abpve with a N-chlorothio-N-methylcarbamyl halide.

The preparation of N-chlorothio-N-methylcarbamyl fluoride, which is the preferred halide for use in the above reaction, is described in German Offenlengungsschriften Nos. 1,931,054 and 3,023,079.

The preparation of N-chlorothio-N-methylcarbamyl chloride is described in US Patent Specification No.

3,699,163.

This alternative process for preparing compounds of formula II may be conducted in a suitable inert solvent such as dimethylformamide, acetonitrile, ether, tetrahydrbfuran, toluene or methylene chloride in the presence of an organic base such as triethylamine, at a temperature of from -20 to 50, preferably -20 to 1 00C.

The novel intermediate may be isolated from the reaction mixture by conventional means, but it is not necessary to separate the intermediate before further reaction with the hydroxy compound in obtaining the desired product of formula I.

The following Preparations and Examples illustrate the invention.

Preparation of N-methylcarbamyl Fluoride Method of Preparation Anhydrous hydrogen fluoride (21.8 g, 1.09 mol) is passed through polyethylene tubing into methyl isocyanate (72.5 g, 1.27 mol) cooled in an ice-methanol bath at 100 using ordinary glass equipment. After the addition is complete the excess methyl isocyanate is removed at 250 and 40-60 mm to leave the product as a clear colorless liquid (83.75 g; 99.7%). The material distills at 480, 10 mm.

Example 1: Methyl N-[[[[[(diethoxyphosphinothioyl)-1isopropyla mino]thio] methylaminojcarbonyljoxyjethanimidothioate. Ir A solution of triethylamine (2.00 ml, 14.3 mmol) in dimethylformamide (5 ml) is added over 5 minutes to a solution of diethoxy N-chlorothio(isopropyl)thiophosphoramide (4.07 g, 14.7 mmol) and N-methylcarbamoyl fluoride (1.11 g, 15.0 mmol) in dimethylformamide (15 ml) cooled in an ice bath.

After the addition the mixture is stirred at 0 for two hours then diluted with ice cold saturated sodium bicarbonate and extracted with hexanes. The extract is dried aver magnesium sulfate and concentrated under reduced pressure to leave a yellow oil. The material is chromatographed through a Merck size C Lobar column eluting with 2.5% ethyl acetate in hexanes to give the intermediate 11r, O,O-diethyl isopropyl[[(fluorocarbonyl)methylamino]thiophosphoramidothioate, as a yellow oil. The ir spectrum shows a V C=O at 1 790 cm-1 and the pmr spectrum displays a doublet (J=1 cps) for the N-CH. A two-way tic of the purified product indicates the material to be unstable toward chromatography on silica gel.The purified O,O-diethyl isoprapyl[[(fluorocarbonyl)-methylamino]thio]phosphoramidothioate (0.56 g, 1.8 mmol), methyl N-hydroxyethanimidothioate (0.22 g, 2.1 mmol), and triethylamine (0.3 ml, 2.2 mmol) are dissolved in acetonitrile (1.5 ml) and the solution kept at room temperature for 17 hours, diluted with a one to one mixture ethyl acetate-Skellysolve B, washed with water, dried over magnesium sulfate and concentrated under reduced pressure. The residual yellow oil is crystallized from ether-Skellysolve B to give a yellow solid (0.43 g), m.p. 64--7 A A second recrystallization gives material of m.p. 69-71 0, undepressed on admixture with a corresponding sample prepared according to the procedures disclosed in U.S. Patent No. 4,081,536.The pmr and ir spectra are identical to material prepared from methyl N-[[(methylamino)carbonyUoxyiethanimidothioate. (See the fifth compound in Example 5, U.S. Patent No.4,081,536).

Preparation 1 O,O-diethyl isopropyl [[(fluflrncarbonyl)methyla minojthiojphosphoramidothioate Ili A solution of O,O-diethyl isoprnpylphosphoramidothioate (14.9 g, 70.8 mmol) and triethylamine (9.8 ml, 70.8 mmol) in tetrahydrofuran (50 ml) is added dropwise over 10 minutes to a solution of Nchlorothio(methyl)carbamoyl fluoride (10.2 g, 70.8 mmol) in tetrahydofuran (50 ml) cooled in an ice bath. After the addition the mixture is stirred for 1.5 hours atOD, diluted with ether (200 ml), washed with ice cold water, dried over sodium sulfate and concentrated under reduced pressure.The residue shows identical absorptions in the ir and pmr spectra for V C=0 and N-CH3 as obtained for the yellow oil that is intermediate llX of Example 1. The crude lla product is suitable for reaction with methyl Nhydroxyethanimidothioate as in Example 1.

Example 2 Methyl N- [[[methyI[[isopropyl(2-thioxo-1.3 ,2-dioxaphosphorinan-2- yl )amino]thio]aminocarbonyl]oxy]ethanimidothioate 1' A solution of 2--(isoprnpylamino)-2-thioxo- 1 3,2-dioxaphosphorinane (13;0 g, 66.6 mmol) and triethylamine (7.3 g, 72 mmol) in tetrahydrofuran (50 ml) is added dropwise over 10 minutes to a solution of sulfur dichloride (8.1 g, 78.7 mmol) in tetrahydrofuran (50 ml) with cooling to maintain a temperature of --5 to 00. After the addition the mixture is stirred for two hours then diluted with ether (100 ml). The reaction mixture is filtered under nitrogen and the filtrate concentrated under reduced pressure.The residual oil is dissolved in dimethyl formamide (50 ml} and N-methylcarbamoyl fluoride (5.8 g, 75.3 mmol) added at once followed by dropwise addition of triethylamine (7.3 g, 72 mmol) in dimethylformamide (10 ml) over 10 minutes with cooling in a bath at 250. After the addition the mixture is stirred for two hours in a bath at 00. The mixture is diluted with ether, washed with ice cold water, dried and concentrated to leave the crude N-methyl[[(isopropyl)2-thioxo-1 ,3,2- dioxaphosphorinan4-yl)amino]thio]carbamic fluoride II' as a red oil. The pmr spectrum (CDCl3) of this material exhibits a doublet (f-H=1 cps) for NCH3 centered at 3.45 ppm.The infra-red spectrum shows V C=O at 1785 cm-1. The carbamic fluoride II' is dissolved in methylene chloride (50 ml) and a solution of methyl N-hydroxyethanimidothioate (7.00 g, 66.6 mmol), tetraethylammonium chloride (1.00 g, 6.04 mmol) and sodium hydroxide (3.20 g, 80 mmol) in water (50 ml) is added at once. The mixture is stirred for 20 hours at room temperature, the phases separated, and the organic phase washed with water, dried over magnesium sulfate and concentrated under reduced pressure. The residual oil is triturated with ether to precipitate methyl N-[[[methyl-[[isopropyl(2-thioxo-1 ,3,2- dioxaphosphorinan-2-yl)amino]thio]amino]carbonyl]oxy]ethanimidothioate 1' (3.90 g, 1 5%) as a white solid.The pmr and ir spectra are identical to corresponding material prepared from methyl N [[(methylamino)carbonyl]oxy]ethanimodothioate according to the procedures disclosed in U.S. Patent No. 4,081,536. m.p. 153-1 540C.

Preparation 2 Preparation of N-methyl[[(isopropyl)(2-thioxo-1 ,3,2-dioxaphosphorinan-2- yl)amino]thio]carbamic Fluoride 11' using N-chlorothio(methyl)carbamic Fluoride A solution of 2-(isopropylamino)-2-thioxo-1,3,2-dioxaphosphorinane (13.8 g, 70.8 mmol) and triethylamine (9.8 ml), 70.8 mmol) in tetrahydrofuran (50 ml) is added dropwise over 10 minutes to a solution of N-chlorothio(methyl)carbamoyl fluoride (10.2 g, 70.8 mmol) in tetrahydrofuran (50 ml) cooled in an ice bath. After the addition the mixture is stirred for 1.5 hours at 00, diluted with ether (200 ml), washed with ice cold water, dried over sodium sulfate and concentrated under reduced pressure.The residue shows identical absorptions in the ir and pmr spectra for V C=0 and N-CH3 as obtained from the carbamic fluoride intermediate II' of Example 2. The crude N-methyl[[(isopropyl)(2 thioxo-1 ,3,2-dioxaphosphorinan-2-yl)amino1thiocarbamic fluoride 11' using Nchlorothio(methyl)carbamic fluoride is also suitable for reaction with methyl Nhydroxyethanimidothioate as in Example 2.

Example 3 Methyl N-[([([(5,5-dimethyl-1 ,3,2-dioxaphosphorinan-2-yl)(tert- butyl)aminolthio] methylamino]carbonyl]oxylethanimidothioate II' Following the procedure given in Example 2 but using 2-N-[chlorothio(tert-butyl)amino]-5,5 dimethyl-2-thioxo-1 3,2-dioxaphosphorinane which is prepared from 2-(tert-butylamino)-2-thioxo 1 3,2-dioxaphosphorinane and sulfur dichloride the title compound 11' is obtained. The pmr and ir spectra are identical to corresponding material prepared from methyl N [[(methylamino)carbonyl]oxy]ethanimidoate according to the procedure in United States Patent No.

4,081,536. m.p. 167--168.50C.

Analysis: Calculated for C,4H28N304PS3: C, 39.14; H, 6.57; N, 9.78.

Found: C, 39.45; H, 6.73; N, 9.87.

Preparation 3 N-methyl [((tert-butyl)(2-thioxo-1 3 ,2-dioxaphosphorinan-2-yl)amino]thio]carbamic fluoride, ill', using N-chlorothio)methylcarbamic Fluoride Following the procedure given in Preparation 2 but using 2-(tert-butylamino)-2-thioxo-1 ,3,2- dioxaphosphorinane, the intermediate, II', is obtained which may be substituted in the procedures of Example 3 for reaction with methyl N-hydroxyethanimidothioate to obtain methyl N-[[[[[(5,5-dimethyl- 1 ,3,2-dioxaphosphorinan-2-yl)(tert-bul)amino1thio]methylaminojcarbonyI]oxyjethanimidothioate I' Example 4 2-(isopropyl)phenyl[[cyclopentyl(3a,4,5,6,7,7a-hexahydro-2-oxo-1 .3,2-benzodioxaphosphol-2- yl)amino]thio1 methylcarbamate l A solution of N-cyclopentyl-3a,4,5,6,7 ,7a-hexahydro-2-oxo-1 ,3,2-benzodioxaphosphol-2-amine (16.3 g, 66.6 mmol) and triethylamine (7.3 g, 72 mmol) in tetrahydrofuran (50 ml) is added dropwise over 10 minutes to a solution ofsulfurdichloride (8.1 g, 78.7 mmol) in tetrahydofuran (50 ml) with cooling to maintain a temperature of --5 to 00. After the addition the mixture is stirred for two hours then diluted with ether (100 ml). The reaction mixture is filtered under nitrogen and the filtrate concentrated in vacuo. The residue is dissolved in dimethyl formamide (50 ml) and N-methyl carbamoyl fluoride (5.8 g, 75.3 mml) added at once followed by dropwise addition of triethylamine (7.3 g, 72 mmol) in dimethyl formamide (10 ml) over 10 minutes with cooling in a bath at --250. After the addition the mixture is stirred for two hours in a bath at 00.The mixture is diluted with ether, washed with ice cold water, dried and concentrated to leave crude N-methyl[[(cyclopentyl)(3a,4,5,6,7,7a- hexahydro-2-oxo-1 ,3,2-benzodioxaphosphol)aminojthiojcarbamic fluoride II". The carbamoyl fluoride II" is dissolved in methylene chloride (50 ml) and a solution of methyl N-hydroxyethanimidothioate (7.00 g, 66.6 mmol), tetraethylammonium chloride (1.00 g, 6.04 mmol) and sodium hydroxide (3.20 g, 80 mmol) in water (50 ml) is added at once. The mixture is stirred for 20 hours at room temperature, the phases separated, and the organic phase washed with water, dried over magnesium sulfate and concentrated under reduced pressure.The residual oil is triturated with ether to precipitate the product 2-(isopropyl)phenyl[[cyclopentyl(3a,4,5,6,7a-hexahydro-2-oxo-1 ,3,2-benzodioxaphosphol-2- yl)a mino]thio] methylcarbamate 1" Preparation 4 N-methyl[[(cyclopentyl)(3a,4,5,6,7,7a-hexahydro-2-oxo-1 .3,2- benzodioxaphosphol)amino]thio] carbamic Fluoride II" A solution of N-cyclopentyl-3a,4,5,6,7,7a-hexahydro-2-oxo- 1 ,3,2-benzodioxaphosphol-2-amine (17.36 g, 70.8 mmol) and triethylamine (9.8 ml, 70.8 mmol) in tetrahydorofuran (50 ml) is added dropwise over 10 minutes to a solution of N-chlorothio(methyl)carbamoyl fluoride (10.2 g, 70.8 mmol) in tetrahydrofuran (50 ml) cooled in an ice bath.After the addition the mixture is stirred for 1.5 hours at 0 , diluted with ether (200 ml), washed with ice cold water, dried over sodium sulfate and concentrated under reduced pressure. The identical absorptions in the ir and pmr spectra for V C=0 and N-CH3 as obtained for the carbamoyl fluoride intermediate II" of Example 4. This crude N methyl[[(cyclopentyl)(3a,4,5,6,7,7a-hexahydro-2-oxo 1 ,3,2-benzodioxaphosphol)amino]thio]carbamic fluoride I" is suitable for reaction with methyl N-hydroxyethanimidothioate as in Example 4 above.

Example 5 Methyl N-[[[methyl [[(2-methylpropyl )(2-thioxo-1 ,3,2-benzodioxaphosphol-2- yl)a mino]thio]a mino]carbonyl]oxy]ethanim idothioate I"' A solution of N-(2-methylpropyl)-2-thioxo-1 ,3,2-benzodioxaphosphol-2-amine (16.2 g, 66.6 mmol) and triethylamine (7.3 g, 72 mmol) in tetrahydrofuran (50 ml) is added dropwise over 10 minutes to a solution of sulfur dichloride (8.1 g, 78.7 mmol) in tetrahydofuran (50 ml) with cooling to maintain a temperature of --5 to 00. After the addition, the mixture is stirred for two hours then diluted with ether (100 ml). The reaction mixture is filtered under nitrogen and the filtrate concentration in vacuo.The residue is dissolved in dimethyl formamide (50 ml) and N-methyl carbamoyl flouride (5.8 g, 75.3 mmol) added at once followed by dropwise addition of triethylamine (7.3 g, 72 mmol) in dimethyl formamide (10 ml) over 10 minutes with cooling in a bath at -250. After the addition the mixture is stirred for two hours in a bath at 00. The mixture is diluted with ether, washed with ice cold water, dried and concentrated to leave a crude N-methyl[[(2-methylpropyl)(2-thioxo-1,3,2- benzodioxaphosphol-2-yl)amino]thio]carbamic fluoride II"'.The carbamic fluoride is dissolved in methylene chloride (50 ml) and a solution of methyl N-hydroxyethanimidothioate (7.00 g, 66.6 mmol), tetraethylammonium chloride (1.00 g, 6.04 mmol) and sodium hydroxide (3.20 g,80 mmol) in water (50 ml) is added at once. The mixture is stirred for 20 hours at room temperature, the phases separated, and the organic phase washed with water, dried over magnesium sulfate and concentrated under reduced pressure. The residual oil is triturated with ether to precipitate the product methyl N [[[methyl[[(2-methylpropyl)(2-thioxo-1 ,3,2-benzodioxaphosphol-2- yl)amino]thio]amino]carbonyl]oxy]ethanimidothioate 1"'.

Preparation 5 N-methyl[[(2-methylpropyl)(2-thioxo-l .3,2-benzodioxaphosphol-2-yl)a mino]thio]carbamic fluoride 11"' A solution of N-(2-methylpropyl)-2-thioxo-1 ,3,2-benzodioxaphosphol-2-amine (17.2 g, 70.8 mmol) and triethylamine i9.8 ml, 70.8 mmol) in tetrahydrofuran (50 ml) is added dropwise over 10 minutes to a solution of N-chlorothio(methyl)carbamoyl fluoride (10.2 g, 70.8 mmol) in tetrahydrofuran (50 ml) cooled in an ice bath. After the addition the mixture is stirred for 1.5 hours at 00, diluted with ether (200 ml), washed with ice cold water, dried over sodium sulfate and concentrated under reduced pressure.The residue shows identical absorptions in the ir and pmr spectra for V C=0 and N-CH3 as obtained for the carbamic fluoride II"' of Example 5. This crude carbamoyl fluoride product is suitable for reaction with methyl N-hydroxyethanimidothioate as in Example 5.

Following the procedures in Example 2 or Preparation 2 the intermediate N-methyl[[(isopropyl)(2 thioxo- 1 ,3,2-dioxaphosphorinan-2-yl)amino]thio]carbamic fluoride II' is prepared and further reacted according to the procedures in Example 2 but using 2,3-dihydro-2,2-dimethyl-7-benzofuranol to obtain 2,3-dihydro-2,2-dimethyl-7-benzofuranyl [[isopropyl(2-thioxo-1 ,3,2-dioxaphosphorinan-2- yl)amino]thio]methylcarbamate.

Infrared and pmr spectra consistent with expected product: Calculated for C18H23N204PS2426.494: C, 50.69, H, 5.44, N, 6.57.

Found: C, 50.73, H, 5.97, N, 6.52.

Mass spectrum shows molecular ion 426.

Samples 1 through 5 uses a process for preparing compounds having Formula I through a novel intermediate II prepared by the reaction as shown in Scheme A. Preparations 1 through 5 prepare the same novel intermediates II by the reaction as shown in Scheme B, which can then be used in Examples 1 through 5 for the preparation of Formula I compounds. Thus, preparation of Formula I compounds can be accomplished by a process including the preparation of novel intermediates using Scheme A or using Scheme B. Therefore it is understood that novel processes to make compounds I of this invention are made through Scheme A or Scheme B described herein.

Appropriate starting materials are substituted in Example 1 and Preparation 1 according to the processes as described herein to prepare corresponding novel intermediates llr of the invention as follows: ~O,O-di-n-propyl metlyl[[(fluorocarbonyl)methylamino]thio]phosphoramidothioate, O,O-di-n-propyl n-pròpyl [[(fluorncarbonyl) methylamino]thio]phosphoramidothioate, O,O-dimethyl ethyl[[(uorocarbonyl) methyl a mino]thio]phosphoramidothioate, O,O-diisopropyl methyl[[{fluorocarbonyl)methylamino]thio]phosphoramidothioate, O,O-diphenyl methyl[[(fl uoroca rbonyl)methylamino]thio]phosphoramidothioate, O,O-diethyl ethyl [[(fluorocarbonyl)methylamino}thiojphosphoram idothioate, O,O-diethyl 2-phenylethyl[[(fl uorocarbonyl) methyla mino]thio]phosphoramidothioate, O,O-diethyl propyl[[(fluorocarbonyl)methylamino]thio]phosphoramidothioate, O,O-diethyl isopropyl [[(fluorocarbonyl)methylaminojthio]phosp ho ram idothioate, O,O-dimethyl methyl[[(fluorocarbonyl)methylamino]thio]phosphoramidothioate, O,O-dimethyl isopropyl [[(flourocarbonyl)methylamino]thio]phosphoramidothioate, O,O-diethyl methyi[[(fluorocarbonyl)methylamino]thio]phosphoramidothioate, O,O-diethyl isopropyl [[(fl uorocarbonyl)methylamino]thio]phosphoramidothioate, O,O-diethyl n-propyl[[(fl uorocarbonyl)methylamino]thiophosphora midothioate, O,O-diethyl methyl[[(fluorncarbonyl)methylaminothio]phosphoramidoate, O,O-diethyl phenyl[[(fluorocarbonyl] methylamino]thio]phosphoramidothioate, O,S-dimethyl methyl [[(fluorocarbonyl) methylamino]thio] phosphora midothioate, O-methyl-N-isopropyl-N-[[(fl uorocarbonyl) methylamino]thio]-P-phenylphosphona midothioate, O-methyl-N-methyl-N-[[(fluorocarbonyl) methylamino]thio]-P-phenylphosphona midothioate, O-methyl-N-methyl-N-[[(fluorocarbonyl) methylamino]thio]-P- methylphosphona midothioate, O-isopropyl-N-isopropyl-N-[[(fluorocarbonyl)methylamino]thio]-P-phenylphosphonamidothioate, O-phenyl-N-methyl-N-[[(fluorocarbonyl)methylamino]thio]-P-methylphosphona midothioate, O-isopropyl-N-isopropyl-N-[[(fl uorocarbonyl)methylaminojthio]-P-methylphosphona midothioate, O-methyl-N-isopropyl-N-[[(fluorocarbonyl)m ethylamino]thio]-P-methylphosphonamidothioate, O-phenyl-N-isopropyl-N-[[(flourocarbonyl) methylamino]thio]-P-methylphosphonamidothioate, O-phenyl-N-phenyl-N-[[(fl uorocarbonyl)methyiamino]thio]-P-ethylphosphona midothioate, O-4-chlorophenyl-N-isopropyl-N-[[(fI uorocarbonyl)methyla mino]thio]-Pmethylphosphonamidothioate, O-isopropyl-N-phenyl-N-[[(fluorocarbonyi)methylamino]thio]-P-methylphosphonamidothioate, 0-([1,1 '-biphenyl]-4-yl)-N-isopropyl-N-[[(fl uorocarbonyl)methylamino]thio]-P- ethylphosphonamidothioate, O-phenyl-N-ethyl-N-[[(fluorocarbonyl)methylamino]thio]-P-phenylphosphonam idothioate, O-phenyl-N-benzyl-N-[[(fluorocarbonyl) methyl am ino]thio]-P-ethylphosphona midothioate, O-phenyl-N-phenyl-N-[[(fluorocarbonyl)methylamino]thio]-P-ethylphosphonamidothioate, O-ethyl-N-phenyl-N-[[(fluorocarbonyl)methylamino]thio]-P-phenylphosphonam idothioate, O-phenyl-N-butyl-N-[[(fluorncarbonyl)methylamino]thioj-P-ethylphosphonamidothioate, 0-2-chlorophenyl-N-phenyl-N-[[(fluorocarbonyl) methylamino]thio]-P- ethylphosphonamidothioate, O-4-chlorophenyl-N-phenyl-N-[[(fl uorocarbonyl)methylamino]thio]-Pethylphosphonamidothioate, O-phenyl-N-cyclohexyl-N-[[(fluorocarbonyl) methylamino]thio]-P-ethylphosphonamidothioate.

In addition, appropriate starting materials are used in the above processes to prepare novel compounds 11r, as follows: O-ethyl-O-phenyl [[(fluorocarbonyl)methylamino]thio]phosphoramidothioate, O-ethyl-S-phenyl[[(fluorocarbonyl)methylamino]thio]phosphoramidothioate, O,O-diethyl phenyl [[(fluorocarbonyl)methylamino]thio]phosphoramide, O-phenyl-N-[[(fluorocarbonyl)methylamino]thio]-N-methyl-P-phenylphosphoramidothioate, O-phenyl-N-[[(fluorocarbonyl)methylamino]thio]-N-p-nitrophenyl-P- methylphosphoramidothioate, O-phenyl-N-{[(fluorocarbonyl)methylaniino]thio]- N-o-methylphenyl-P- ethylphosphora midothioate, O phenyl-N-[[(fluorocarbonyl)methylaminojthio]-N-m-tnfluoromethylphenyl-P- ethylphosphoramidothioate, O-phenyl-N-[[(fluorocarbonyl)methylamino]thio]-N-o-chlorophenyl-P- ethylphosphoramidothioate, O-cycloheXyloxy-N-[[(fluorocarbonyl)methylamino]thio]-N-cycloheXyl-P- ethylphosphoramidothioate, O-p-nitrophenyl-N-[[(fluorocarbonyl)methylamino]thio]-N-phenyl-P-ethylphosphoramidothioate, O-ethyl-N-[[(fl uorocarbonyl)methyla m i no]thio]-N-methyl-P-ethylphosphoramidothioate, S-phenyl-N-[[(fluorocarbonyl)methylamino]thio]-N-methyl-P-ethylphosphoramidothioate, N-[[(fluorocarbonyl)methylamino]thioj-N-methyl-P-p-chlorophenyl-P-methylphosinamidothioate, N-[[(fluorocarbonyl)methylamino]thio]-N-methyl-P,P-diethylphosinamidothioate, O-phenyl-N-[[(fluorocarbonyl)methylamino]thio]-N-methyl-P-phenylphosphonamide, O-phenyl-N-[[(fluorocarbonyl)methylamino]thio]-N-methyl-P-ethylphosphonamidothioate, O-phenyl-N-[[(fl uorocarbonyl)methyla mino]th io]-N-methyl-P-ethylphosphonamide, O-ethyl-N-[[(fluorocarbonyl)methylamino]thio]-N-phenyl-P-ethylphosphonamide, S-phenyl-N-[[(fluorocarbonyl)methylamino]thio]-N-phenyl-P-methylphosphonamidothioate.

Further, appropriate starting materials are substituted in Examples 2 and 3 and Preparations 2 and 3 according to the processes as described herein to prepare corresponding novel intermediates II' of the invention as follows: [[isopropyl(5,5-dimethyl-2-thioxo-1 ,3,2-dioxaphosphorinan-2-yl)amino]thio]methylcarbamic fluoride, [[isopropyl(5,5-diethyl-2-thioxo- ,3,2-dioxaphosphorinan-2-yl)amino]thio]methylcarbamic fluoride, [[ethyl(5,5-dimethyl-2-thioxa-1 ,3,2-dioxaphosphorinan-2-yI)amino]thio]methylcarbamic fluoride, [[isopropyl(2-thioxo- 1 ,3,2-phospholan-2-yl)amino]thio]methylcarbamic fluoride, [[isopropyl(4,4,6-trimethyl-2-thioxo- 1 ,3,2-dioxaphosphorinan-2-yl)amino]thiojmethylcarbamic fluoride, [[cyclohexyl(5,5-diethyl-2-th ioxo- ,3,2-dioxaphosphorinan-2-yI)amino]thio]methylcarbamic fluoride, [[cyclohexyl(5,5-dimethyl-2-thioxo-l .3 ,2-dicxaphosphorinan-2-yl)amino]thio]methylcarbamic fluoride, [[methyl(2-thioxo- 1 ,3,2-dioxaphosphorinan-2-yl)amino]thio] methylcarbamic fluoride.

Other novel II' compounds are prepared by the processes herein as follows: [[isopropyl (2-thioxo-4H- 1 ,3,2-benzodioxaphosphorina n-2 yl)amino]thio]methylamino]methylcarbamic fluoride, [[methyl(2-thioxo- 1 ,3,2-dioxaphospholan-2-yI)amino]thio]methylcarbamic fluoride, [[ethyl(hexahydro-2-oXo-1,3,2-benzodioxaphospholan-2-yl)amino]thio]methylcarbamic fluoride, [[isopropyl(2-oxo- 1 ,3,2-benzodioxaphopholan-2-yl)aminoJthio]methyIcarbamic fluoride, [benzyl(5,5-diethyl-2-thioxo-l ,3,2-dioxaphosphorinan-2-yl)amino]thio]m fluoride, [[methyl(2-thioxo- 1 ,3,2-dioxaphosphorinan-2-yl)amino]thio]methylcarbamic fluoride.

Additionally, appropriate starting materials are substituted in Examples 4 and 5 and Preparations 4 and 5 according to the processes as described herein to prepare corresponding novel intermediates II" and 11"' within the scope of the invention.

Further, intermediates II', and II" wherein X is oxygen, as well as, additional intermediates 11, and II"' wherein X is also oxygen, are prepared by using appropriate starting materials in the processes according to each of the Examples and Preparations 1, 2, 3 and 4 respectively as described above.

Intermediates II"' wherein X is sulfur may likewise be prepared by using corresponding starting materials in Example 5 and Preparation 5.

Finally, in the formulation of Compounds I prepared by the processes in the present invention for pesticidal utility conventional techniques are used as fully disclosed in United States Patent No.

4,081,536 and in United States Patent No.4,024,277.

Claims (73)

Claims

1. A process for preparing a compound of formula I

wherein R is selected from (a) phenyl optionally substituted by one to 3 substituents which are independently selected from C15 alkyl, halogen, C15 alkoxy, C15 alkylthio, di(C,, alkyl)amino in which the C1 alkyl groups are the same or different, and -N=CHN(CH)2;; (b) ABC=N- wherein A and B are the same or different and are- each each hydrogen, C15 alkyl, C15 alkoxy, C15 alkylthio optionally substituted by a cyano group, cyano, phenyl or phenylthio optionally substituted by one to three substituents which are independently selected from halogen atoms and C14 alkyl radicals;

wherein Rs is C13 alkyl or phenyl;R6 is C13 alkyl and R7 is C13 alkyl or the same alkylthio group as

wherein R6 is as defined above and n is 2 or 3, (CH2)n being optionally substituted by one or two methyl groups;

wherein m is 2 or 3, (CH2)m being optionally substituted by one or two methyl groups; and

wherein T and T' are the same or different and are each hydrogen or C16 alkyl; R, is C1-5 alkyl, phenyl, substituted phenyl, C7-11 phenylalkyl or cycloalkyl; X is oxygen or sulfur; and - either Y and Y' are independently selected from C1-5 alkyl, C15 alkoxy, C15 alkylthio, cycloalkyl, phenyl, substituted phenyl, phenoxy, substituted phenoxy, phenylthio or substituted phenylthio, or Y and Y' are taken together and are of formula 1', I" or 111r

wherein Z@ to Z6 are the same or different and are each hydrogen, methyl or ethyl, k is O or 1, p is 3 or 4 and Rg is hydrogen, C,, alkyl, C15 alkoxy or halogen; which comprises reacting a compound of formula II

wherein R1,X, Y and Y' are as defined above, with a compound of the formula ROH, wherein R is as defined above.

2. A process according to claim 1 wherein the product, of formula I, is a compound as claimed in any of claims 1 to 44 of British Patent Application No.1617/78.

3. A process according to claim 1 wherein the product, of formula I, is methyl N [[[[methyl(phenoxy)phosphinothioyl]isopropylaminojthio]methylamino]carbonyl]oxyjethanimidothioate or methyl N-[[[[[[ethyl(phenoxy)phosphinothioyi] n-butyla mino]thio] methylamino] carbonyl] oxy]ethanimidothioate.

4. A process according to claim 1 wherein R is 2,3-dihydro-2,2-dimethylbenzofuran-7-yl.

5. A process according to claim 4 wherein the product of formula I, is selected from 2,3-dihydro-2,2-dimethyl-7-benzofuranyl[(N-diethoxyphosphinyl)(N-methyl)aminosulfenyl]- [methyl]carbamate; 2,3-dihydro-2,2-dimethyl-7-benzofuranyl [(N-di-n-propoxyphosphinyl)(N-methyl)amino- sulfenylj[methyljcarbamate; 2,3-dihydro-2,2-dimethyl-7-benzofuranyl [N-di-n-propoxyphosphinyl)(N-n-propyl)amino- sulfenyl][methyl]carbamate; 2,3-dihydro-2,2-dimethyl-7-benzofura nyl [(N-di-ethoxyphosphinyl)(N-n-propyl)amino- sulfenyl][methyl]carbamate; 2,3-dihydro-2,2-dimethyl-7-benzofuranyl [(N-di-methoxyphosphinyl)(N-ethyl)aminosulfenylj[methyl]carbamate; 2,3-dihydro-2,2-dimethyl-7-benzofuranyl [(N-diisopropoxyphosphinyl)(N-methyl)amino- sulfenyl] [methyl]carbamate;; 2,3-dihydro-2 ,2-dimethyl-7-benzofuranyl [[(N-diethoxyphosphinyl)(N-ethyl)amino sulfenyl]]methyl]carbamate; 2,3-dihydro-2 ,2-dimethyl-7-benzofuranyl [(N-diphenoxyphosphinyl)(N-methyl)a mino sulfenyl] [methyl]carbamate; and 2,3-dihydro-2,2-dimethyl-7-benzofuranyl [(N-diethoxyphosphinyl)(N-2-phenylethyl)aminosulfenyl][methyl]carbamate.

6. A process according to claim 1 wherein the product, of formula I, is a compound as claimed in any of claims 1 to 20 of British Patent Publication No. 2,01 5,527A, or methyl N-[[[[[cyclohexyl(5,5 dimethyl-2Ahioxo- 1 ,3,2-dioxaphosphorinan-2-yl)amino]thio]methylamino]carbonyl]oxy]- ethanimidothioate.

7. A process according to claim 1 wherein the product, of formula I, is 2,3-dihydro-2,2di methyl-7-benzofuranyl [[isopropyl(2-thioxo- 1,3,2-dioxaph osphorinan-2-yl) ami no]thio] methylcarbamate.

8. A process according to claim 1 wherein the product, of formula I, is 2-(1-methylethoxy)phenyl [[cyclopentyl(3a,4,5,6,7,7a-hexahydro-2-oxo- ,3,2-benzodioxaphosphol-2-yt)amino]thio]methyl- carbamate.

9. A process according to claim 1 wherein the product, of formula I, is methyl N-[[[methyl[[(2 methylpropyl)(2-thioxo-1 ,3,2-benzodioxaphosphol-2-yI)amino]thiojaminojcarbonyl]oxyjethanimido- thioate.

10. A process according to claim 1 substantially as described in any of the Examples.

1 1.A compound of formula II as defined in claim 1.

12. A compound as claimed in claim 11 wherein X is sulfur.

13. A compound as claimed in claim 11 wherein X is oxygen.

14. A compound as claimed in any of claims 11 to 13 wherein R, is C15 alkyl, cycloalkyl or C7~" phenyla Ikyl.

15. A compound as claimed in any of claims 11 to 14 wherein Y and Y' are independently selected from C,, alkyl, C15 alkoxy, C,, alkylthio, cycloalkyl, phenyl, substituted phenyl, phenoxy, substituted phenoxy, phenylthio and substituted phenylthio.

1 6. A compound as claimed in claim 1 5 wherein Y and Y' are each Cie alkoxy.

17. O,O-Diethyl propyl[[(fluorocarbonyl)methylamino]thio]phosphoramidothioate.

18. O,O-Diethyl isopropyl[[(fluorocarbonyl)methylamino]thio]phosphoramidothioate.

1 9. O,O-Di methyl methyl [[(fluorocarbonyl) methyla mino]th io] phosphoramidothiate.

20. O,O-Dimethyl isopropyl[[(fluorocarbonyl)methylamino]thio]phosphoramidothioate.

21. O,O-Dimethyl n-butyl[[(fluorocarbonyl)methylamino]thio] phosphoramidothioate.

22. O,O-Diethyl methyl [[(fluorocarbonyl)methylaminojthio]phosphoramidothioate.

23. O,O-Di-n-propyl methyl [[(fluorocarbonyl)-methylamino]thiojphosphoramidothioate.

24. O,O-Di-n-propyl n-propyl [[(fl uoroca rbonyl)methylamino]thio] phosphoramidothioate.

25. O,O-Dimethyl ethyl[[(fluorocarbonyl)methylamino]thio]phosphoramidothioate.

26. O,O-Diisopropyl methyl[[(fluorocarbonyl)methylamino]thio]phosphoramidothioate.

27. O,O-Diethyl ethyl [[(fluorocarbonyl) methyla mino]thio] phosphoramidothioate.

28. O,O-Diethyl methyl[[(fluorocarbonyl)methylaminojthio]phoshoramidate.

29. O,O-Diethyl phenyl[[(fluorocarbonyl)methylamino]thio]phosphoramidothioate.

30. O,O-Diethyl 2-phenylethyl[[(fluoroca rbonyl)methyla m ino]thio] phosphoramidothioate.

31. O,O-Diphenyl methyl[[(fluorocarbonyl) methylamino]thio]phosphoramidothioate.

32. O,S-Dimethyl methyl[[(fluorocarbonyl)methylamino]thio]phosphoramidothioate.

33. O-Methyl-N-isopropyl-N-[[(fluorocarbonyl)methylamino]thio]-P- phenylphosphonamidothioate.

34. O-Methyl-N-m ethyl-N-[[(fl uoroca rbonyl) methyla m ino]th io]-P-phenylphosphona m idothioate.

35. OMethyl-N-methyI-N[[(fIuorocarbonyI)methylamino]thio]-P-methylphosphonamidothioate.

36. 0-Isopropyl-N-isopropyl-N-[[(fluorocarbonyl)methylaminojthio]-P-phenylphosphonamino- thioate.

37. 0PhenyINmethylN[[(fiuorncarbonyl)methylamino]thioJ-P-methylphosphonamidothioate.

38. O-lsopropyl-N-isopropyl-N-[[(fluorocarbonyl) methyla mino]thio]-P- methylphosphonamidothioate.

39. O-Methyl-N-isopropyl-N-[[(fluorocarbonyl)methylamino]thio]-P- methylphosphonamidothioate.

40. O-Phenyl-N-isopropyl-N-[[(fluorocarbonyl) methylamino]thio]-P- methylphosphonamidothioate.

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

42. o4ChlornphenyLNisoprnpyIN-[[(fiuorncarbonyI)methylamino]thio]-P- methylphosphonamidothioate.

43. O-lsopropyl-N-phenyl-N-[[(fluorocarbonyl ) methylamino]thio]-Omethylphosphonamidothioate.

44. 0-(4-B iphenylyl)-N-isop ropyi-N-[[(fluoroca rbonyl)m ethyla mi no]thio]-P- ethylphosphonamidothioate.

45. OPhenyl-N-ethyl-N-[[(fiuorncarbonyI)methyIaminojthio]-P-phenyIphosphonamidothioate.

46. O-Phenyl-N-benzyl-N-[[(fluorocarbonyl) methyla mino]thio]-P-ethylphosphonamidothioate.

47. O-Ethyl-N-phenyl-N-[[(fluorncarbonyl)methylaminothioj-P-phenylphosphonamidothioate.

48. O-Phenyl-N-butyl-N-[[(fluorocarbonyl)methylamino]thio]-P-ethylphosphonamidothioate.

49. O-2-Chlorophenyl-N-phenyl-N-[[(fl uorncarbonyI)methylaminothio]-P- ethylphosphonamidothioate.

50. 0-4-Chlorophenyl-N-phenyl-N-[[(fluorocarbonyl)methylamino]thioi-P- ethylphosphonamidothioate.

51. O-Phenyl-N-cyclohexyl-N-[[(fluorocarbonyi)-methylamino]thio]-P- ethylphosphonamidothioate.

52. A compound as claimed in any of claims 11 to 14 wherein Y and Y' are of formula I' as defined in claim 1.

53. A compound as claimed in claim 52 wherein k is one and Xe and Z6 are each methyl or ethyl.

54. A compound as claimed in claim 53 wherein Z2 is methyl or ethyl.

55. A compound as claimed in claim 52 wherein Z1 to Z6 are each hydrogen.

56. [[lsopropyl(5,5-dimethyl-2-thioxo-l ,3,2-dioxaphosphorinan-2-yl)amino]thio]methylcarbamic fluoride.

57. [[tert-Butyl(5,5-dimethyl-2-thioxo- 1 ,3,2-dioxaphosphorinan-2-yI)amino]thio]methylcarbamic fluoride.

58. [[lsopropyl(5,5-diethyl-2-thioxo-1 ,3,2-dioxaphosphorinan-2-yl)amino]thio]methylcarbamic fluoride.

59. [[Ethyl(5,5-dimethyl-2-thioxo- 1 ,3,2-dioxaphosphorinan-2-yi)amino]thio]methylcarbamic fluoride.

60. [[lsopropyl(2-thioxo-1 ,3,2-phospholan-2-yl)amino]thio]methylcarbamic fluoride.

61. [[lsopropyl(2-thioxo-1 ,3,2-phosphorinan-2-yl)amino]thio]methylcarbamic fluoride.

62. [[lsopropyl(4,4,6-trimethyl-2-thioxo- 1 ,3,2-dioxaphosphorinan-2- yl)amino]thio]methylcarbamic fluoride.

63. [[CycloheXyl(5,5-diethyl-2-thioXo-1,3,2-dioxaphosphorinan-2-yl)amino]thio]methylcarbamic fluoride.

64. [[Cyclohexyl(5,5-dimethyl-2-thioxo-1 ,3,2-dioxaphosphorinan-2- yl)aminojthio]methylcarbamic fluoride.

65. [[Methyl(2-thioxo-1 ,3,2-dioxaphosphorinan-2-yI)amino]thio]methylcarbamic fluoride.

66. A compound as claimed in any of claims 11 to 14 wherein Y and Y' are of formula I" as defined in claim 1.

67. N-Methyl [[(cyclopentyl)(3a,4,5,6,7a-hexa hydro-2-oxo- 1,3,2 benzodioxaphosphol)amino]thio]carbamoyi fluoride.

68. A compound as claimed in any of claims 11 to 14 wherein Y and Y' are of the formula 1"' as defined in claim 1.

69. N-Methyl-[[(2-methylpropyl)(2-thioxo- 1,3,2-benzodioxaphosphol-2-yl)amino]thio]carba moyl fluoride.

70. A compound as claimed in claim 11 substantially as described in any of the Examples.

71. A process for preparing a compound as claimed in claim 11, which comprises reacting a compound of formula Ill CI--SS-NRR,-P(X)W' III wherein R1,X, Y and Y' are as defined in claim 1, with N-methylcarbamyl fluoride.

72. A process for preparing a compound as claimed in claim 11, which comprises reacting a compound of formula V HNR,P(X)W' V wherein R1,X, Y and Y' are as defined in claim 1, with N-chlorothio-N-methylcarbamoyl fluoride.

73. A process according to claim 1 wherein the compound of formula II as defined therein is prepared by a process according to claim 71 or claim 72.