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Publication numberUS3868449 A
Publication typeGrant
Publication dateFeb 25, 1975
Filing dateJan 14, 1974
Priority dateDec 21, 1972
Publication numberUS 3868449 A, US 3868449A, US-A-3868449, US3868449 A, US3868449A
InventorsMagee Philip S
Original AssigneeMagee Philip S
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Insecticidal o,s-dihydrocarbyl-n-acylphosphoroamidothioates and s,s-dihydrocarbyl-n-acylphosphoroamidodithioates
US 3868449 A
Abstract  available in
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United States Patent 91 Magee Feb. 25, 1975 INSECTICIDAL O,S-DIHYDROCARBYL-N-ACYLPHOS- PHOROAMIDOTHIOATES AND S,S-DIHYDROCARBYL-N-ACYLPHOS- PHOROAMIDODITHIOATES [76] Inventor: Philip S. Magee, lgnatia, Calif.

[22] Filed: Jan. 14, 1974 [21] Appl. No.: 432,929

Related U.S. Application Data [60] Division ofSer. No. 317,315, Dec.21, 1972, Pat. No. 3,801,680, which is a continuation-in-part of Ser. No. 13,846, Feb. 24, 1970, Pat. No. 3,716,600, which is a continuation-in-part of Ser. No. 810,383, March 25, 1969, abandoned.

[52] U.S. Cl 424/217, 424/216, 424/220 [51] Int. Cl A01n 9/36 [58] Field of Search 424/216, 217, 220

Primary Examiner-Stanley J. Friedman Assistant Examiner-D. W. Robinson Attorney, Agent, or FirmJ. A. Buchanan,- Jr.

20 Claims, No Drawings INSECTICIDAL O,S-DIHYDROCARBYL-N-ACYLPHOS- PHOROAMIDOTHIOATES AND S,S-DII-IYDROCARBYL-N-ACYLPI-IOS- PHOROAMIDODITHIOATES CROSS-REFERENCE TO RELATED APPLICATIONS This application is a division of application Ser. No. 317,315, filed Dec. 21, 1972, now U.S. Pat. No. 3,801,680, issued Apr. 2, 1974, which. in turn is a continuatiomin-part of application Ser. No. 13,846, filed Feb. 24, 1970, now U.S. Pat. No. 3,716,600, which in turn is a continuation-in-part of application Ser. No. 810,383, filed Mar. 25, 1969, now abandoned.

DESCRIPTION OF THE PRIOR ART U.S Pat. No. 3,309,266 teaches that O-alkyl-S-alkyl phosphoroamidothioates are insecticidal. U.S. Pat. No. 3,649,723 teaches that O-alkyl-S-unsaturated hydrocarbylphosphoroamidothioates are insecticidal. U.S. Pat. No. 3,201,446 teaches that 0,0-diethyl-N- trichloroacetylphosphoroamidethioate [N-- (diethoxyphosphinothioyl)-2,2,2-trichloroacetamide] is useful as an insecticide. Russian Pat. No. 253,483, issued on Sept. 30, 1969 to G. V. Protopopova et al., discloses the use of O,S-dialkyl-N- alkylthiocarbonylphosphoroamidothioates, e.g.,

CHSS

as insecticides. L. Almasi et al, Chem. Ber. 100 2626 (1967) and Chem. Ber. 99 3293 (1966), disclose O- ethyl-S-methyl-N-benzoylphosphoroamidothioate, O- ethyl-S-methyl-N-p-chlorobenzoylphosphoroamidothioate and O-ethyl-S-methyl-N-p-methylbenzoylphosphoroamidothioate.

DESCRIPTION OF THE INVENTION The phosphoroamidothioates and phosphoroamidodithioates of this invention are represented by the formula (I):

R-Y 0 i 1(0H2)u--XR -N Ra wherein R and R individually are alkyl, alkenyl or alkynyl of up to 6 carbon atoms, Y and X individually are oxygen or sulfur, n is whole number of from 1 to 6, preferably 1 or 2, R is alkyl of 1 to 6 carbon atoms, aryl of up to carbon atoms substituted with up to 2 (0 to 2) fluorine, chlorine or bromine atoms, and R is hydrogen or alkyl of l to 6 carbon atoms.

Representative alkyl groups which R, R, R and R may represent include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, sec-pentyl and hexyl. Representative alkenyl of 3 to 6 carbon atoms which R and R may represent include allyl, 2-butenyl, 2- hexanyl, etc. Representative alkynyl of 3 to 6 carbon atoms which R and R may represent include 2- propynyl, 2-butynyl, 2-hexynyl, etc. Preferred R, R,

cially methyl. The preferred R groups is hydrogen.

Representative hydroca'rbyl aryl R groups include phenyl, naphthyl, aralkyl of 7 to 10 carbon atoms, e.g., benzyl, Z-phenylethyl, 3-tolylpropyl, 4-phenylbutyl, and alkaryl of 7 to 10 carbon atoms, e.g., 2- methylphenyl, 3-methylphenyl, 4-methylphenyl, 2,4- dimethylphenyl, 3,5-diethylphenyl and 4-t-butylphenyl. Representative halo substituted aryl R group include halophenyl of 1 to 2 fluorine, chlorine or bromine atoms such as 2-fluorophenyl, 3-chlorophenyl, 4- bromophenyl, 2,4-dichlorophenyl, 3,5-dibromophenyl, etc.; and haloaralkyl and haloalkaryl of 7 to 10 carbon atoms and 1 to 2 fluorine, chlorine or bromine atoms such as 2-fiuorobenzyl, 4-chlorobenzyl, 2,4- dibromobenzyl, 2-(4-chlorophenyl)ethyl, 3-(2- fluoraphenyl)propyl, 2-chloro-4-methylphenyl, 3-fluoro-4-methylphenyl, etc.

thioates of formula (I) are: O-allyl-S-methyl-N- methoxyacetylphosphoroamidothioate, O-propargyl-S:

methyl-N-ethoxyacetylphosphoroamidothioate, O- methyl-S-ethyl-N-ethyl-N-propoxyacetylphosphoroamidothioate, O-propyl-S-allyl-N- methoxyacetylphosphoroamidothioate, O-methyl-S- allyl-N-butoxyacetylphosphoroamidothioate, O- methyl-S-methyl-N-pentoXyacetylphosphoroamidothioate, O-methyl-S-methyl-N-hexoxyacetylphosphoroamidothioate, O-isopropyl-S- isopropyl-N-3-methoxypropionylphosphoroamidothioate, O-methyl-S methyl-N- 3-ethoxypropionylphosphoroamidothioate, O-allyl-S-allyl-N- isopropyl-N-3-propoxypropionylphosphoroamidothioate, O-methyl-S-methyl-N-3-isopropoxypropionylphosphoroamidothioate, O-methyl-S-methyl-N-methyl-N-4- methoxybutyrylphosphoroamidothioate, O-methyl-S- methyl-N-4-propoxybutyrylphosphoroamidothioate,

O-butyl-S-methyl-N-4-ethoxybutyrylphosphoroamidothioate, O-2-butenyl-S-butyl-N-5- methoxypentanoylphosphoroamidothioate, O-methyl- S-methyl-N-S-methoxybutanoylphosphoroamidothioate, O-methyl-Smethyl-N-S-pentoxypentanoylphosphoroamidothioate, O-methyl-S-methyl-N-6- methoxyhexanoylphosphoroamidothioate, O-methyl-S- methyl-N-6-isopropoxyhexanoylphosphoroamidothioate, O-methyl-S-pentyl-N-7-methoxyheptanoylphosphoroamidothioate, and O-methyl-S-methyl-N-7- hexoxyheptanoylphosphoroamidothioate.

Representative N-alkylthioalkanoylphosphoroamidothioate of formula (I) are: O-methyl-S- allyl-N-methylthioacetylphosphoroamidothioate, O- allyl-S-methyl-N-methyl N-ethylthioacetylphosphoroamidothioate, O-methyl-S-methyl-N- propylthioacetylphosphoroamidothioate, O-propargyl- S-methyl-N-butylthioacetylphosphoroamidothioate, O-rnethyl-S-methyl-N-pentylthioacetylphosphoroamidothioate, O-methyl-S-methyl-N- hexylthioacetylphosphoroamidothioate, O-methyl-S- methyl-N-3-methylthiopropionylphosphoroamidothi- O-allyl-S-allyl-N-3-ethylthiopropionylphosphoroamidothioate, O-ethyl-S-ethyl-N-3- isopropylthiopropionylphosphoroamidothioate, O- methyl-S-methyl-N-3-propylthiopropionylphosphoroamidothioate, O-4-hexen yl-S-methyl-N-3- butylthiopropionylphosphoroamidothioate, O-methyl- S-methyl-N-4-sec-butylthiobutyrylphosphoroamidothi- 3,5-dibromo-4-ethylphenyl,.

oate, O-propyl-S-isopropyl-N-isopropyl-N-4- methylthiobutyrylphosphoroamidothioate, O-methyl- S-methylN-4-ethylthiobutyrylphosphoroamidothioate, O-allyl-S-methyl-N-S-methylthiopentanoylphosphoroamidothioate, O-allyl-S-methyl-N- ethylthiopentanoylphosphoroamidothioate, O-propyl- S-2-pentenyl-N-6-methyllthiohexanoylphosphoroamidothioate, and O-hexyl-Spentyl-N-7- methylthioheptanoylphosphoroamidothioate.

Representative N-aryloxyalkaonylphosphoroamidothioates of formula (I) are: O-methyl-S-methyl-N-pbromophenoxyacetylphosphoroamidothioate, O- methyl-S-allyl-N-(3-methylphenoxy)acetylphosphoro amidothioate, O-allyl-S-propargyl-N- 3-benzyl-oxypropionylphosphoroamidothioate and O- methyl-S-methyl-N-4-(4-chlorophenoxy)butyrylphosphoroamidothioate.

Representative N-arylthioalkanoylphosphoroamidothioates of formula (I) are: O-methyl-S-methyl-N-4- chlorophenylthioacetylphosphoroamidothioate, O- propargyl-S-methyl-N-isopropyl-N- benzylthioacetylphosphoroamidothioate, O-ethyl-S- methyl-N-3-(2,4-dichlorophenylthio)propionylphosphoroamidothioate, O-allyl-S-allyl-N-3-(4- methylphenylthio)propionylphosphoroamidothioate and O-isopropyl-S-methyl-N-3-(pchlorobenzylthio)propionylphosphoroamidothioate.

Representative N-alkoxyalkanoylphosphoroamidodithioates of formula (I) are: S-methyl-S-allyl-N-methyl- N-methoxyacetylphosphoroamidodithioate, S- propargyl-S-methyl-N-ethoxyacetylphosphoroamidodithioate, S-methyl-S-ethyl-N-propoxyacetylphosphoroamidodithioate, S-propyl-S-methyl-N- methoxyacetylphosphoroamidodithioate, S-allyl-S- allyl-N-butoxyacetylphosphoroamidodithioate, S- methyl-Smethyl-N-pentoxyacetylphosphoroamidodithioate, S-methyl-S-methyl-N-hexoxyacetylphosphoroamidodithioate, S-isopropyLS-isopropyl-N- isopropyl-N-3-methoxypropionylphosphoroamidodithioate, S-methyl-S-methyl-N-3-ethoxypropionylphosphoroamidodithioate, S-methyl-S-methyl-N-3- propoxypropionylphosphoroamidodithioate, S-methyl- S-methyl-N-3-isopropoxypropionylphosphoroamidodithioate, S-2-butenyl-S-methyl-N-4- methoxybutyrylphosphoroamidodithioate, S-methyl-S- methyl-N-4-propoxybutyrylphosphoroamidodithioate, S-butyl-S-methyl-N- 4-ethoxybutyrylphosphoroamidodithioate, S-butyl-S-butyl-N- 5methoxypentanoylphosphoroamidodithioate, S- methyl-S-methyl-N-S-methoxypentanoylphosphoroamidodithioate, S-allyl-S-allyl-N-S- pentoxypentanoylphosphoroamidodithioate, S-methyl- S-methyl-N-6-methoxyhexanoylphosphoroamidodithioate, S-methyl-S-methyl-N-6-isopropoxyhexanoylphosphoroamidodithioate, S-methyl-S-pentyl-N-7- methoxyheptanoylphosphoroamidodithioate. and S- methyl-S-methyl-N-7-hexoxheptanoylphospshoroamidodithioate.

Representative N-alkylthioalkanoylphosphoroamidodithioate of formula (I) are: S-methyl-S- methyl-N-methylthioacetylphosphoroamidodithioate, S-methyl-S-methyLN-ethylthioacetylphosphoroamidodithioate, S-methyl-S-methyl-N- methyl-N-butylthioacetylphosphoroamidodithioate, S-allyl-S-allyl-N-pentylthioacetylphosphoroamidodithioate, S-methyl-S methyl-N-hexylthioacetylphosphoroamidodithioate, S-methyl-S-methyl-N-3- methylthiopropionylphosphoroamidodithioate, S- methyl-S-methyl-N-3-ethylthiopropionylphosphoroamidodithioate S-ethyl-S-ethyl-N-3- isopropylthiopropionylphosphoroamidodithioate, S- methyl-S-methyl-N-3-propylthiopropionylphosphoroamidodithioate, S-methyl-S-methyl-N-3- butylthiopropionylphosphoroamidodithioate, S- methyl-S-methyl-N-4-sec-butylthiobutyrylphosphoroamidodithioate, I S-methyl-S-methyl-N-4- methylthiobutyrylphosphoroamidodithioate, S-methyl- S-methyl-N-4-ethylthiobutyrylphosphoroamidodithioate, S-methyl-S-allyLN-isopropyl-N-5- methylthiopentanoylphosphoroamidodithioate, S- propyl-S-propargyl-N-S-ethylthiopentanoylphosphoroamidodithioate, S-propyl-S-butyl-N-6- methylthiohexanoylphosphoroamidodithioate and S- hexyl-S-pentyl-N-7-methylthioheptanoylphosphoramidodithioate.

Representative N-aryloxyalkanoylphos phoroamidodithioates of formula (I) are: S-allyl-S- methyl-N-methyl-N-p-bromophenoxyacetylphosphoroamidodithioate, S-methyl-S-methyl-N-( 3- methylphenoxy)acetylphosphoroamidodithioate, S- ethyl-S-ethyl-3-benzyl0xypropionylphosphoroamidodithioate and S-propargyl-S-methyl-N-4-(4- chlorophenoxy)butyrylphosphoroamidodithioate.

Representative N-arylthioalkanoylphosphoroamidodithioates of formula (I) are: S-methyl-S- methyl-N-4-chlorophenylthioacetylphosphoroamidodithioate, S-allyl-S-allyl-N-benzylthioacetylphosphoroamidodithioate, S-ethyl-S-methyl-N-3-(2,4- dichlorophenylthio)propionylphosphoroamidodithioate, S-methyl-S-methyl-N-3-(4- methylphenylthio)propionylphosphoroamidodithioate and S-isopropyl-S-propargyl-N-propyl-N-3-(pchlorobenzylthio)propionylphosphoroamidodithioate.

The preferred compounds of formula (I) are O,S- dialkyl-N-alkoxyalkanoylthiophosphorothioate (Y and X are oxygen). The most preferred compounds are 0,- S-dialkyl-N-alkoxyalkanoylphosphoroamidothioates wherein R, R and R are alkyl of l to 3 carbon atoms, n is l or 2, or R is hydrogen.

The compounds of formula (I) may be prepared by acylating an appropriate O-hydrocarbyl-S- hydrocarbylphosphoroamidothioate or S-hydrocarbyl- S-hydrocarbylphosphoroamidodithioate. o-alkyl-S- alkylphosphoroamidothioates and their preparation are disclosed in U.S. Pat. No. 3,309,266. O-alkyl-S- unsaturated hydrocarbylphosphoroamidothioates and their preparation are disclosed in U.S. Pat. No. 3,649,723. 7

Conventional acylating agents, such as acyl halides, ketenes and acid anhydrides and conventional acylating conditions may be used in this reaction. Alkoxyalkanoyl and alkylthioalkanoyl chlorides are preferred acylatingagents.

This acylation reaction (illustrated with an acyl chloride as the acylating agent) may be represented by the propylthioacetylphosphoroamidodithioate, S-allyl-S- following equation:

RY 0 R-Y\(T) PNH R -X(CH2)n Cl PNC(CH2)nX-R HCl R 6 3 R s 1 be carried out at about to 60C. in the presence of solvents such a methylene chloride, chloroform, tetrahydrofurnn and benzene. Pressure is not critical in this reaction. For convenience, atmospheric or autogenous pressure will be used. Under normal conditions, stoichiometric proportions or a slight deficiency of acylating agent will be used. The acylation will usually take 2 to 24 hours to reach completion. The reaction product may be purified by conventional extraction and recrystallization techniques.

N-acylated phosphoroamidothioates of this invention may also be prepared by acylating an appropriate 0,0- dialkyl phosphoroamidothionate and then isomerizing the resulting N-acylphosphoroamidothionate with an alkylating agents to produce the O-alkyl-S-alkyl-N- acylphosphoroamidothioate. This reaction scheme is represented (using an acyl chloride as the acylating wherein R represents an alkylating agent corresponding to R. This acylation may be carried out by the same techniques described above for the acylation reaction depicted in equation (1). The acylation reaction (2) is also described in applicants U.S. application Ser. No. 148,139, filed May 28, 1971. The reaction between the N-acylphosphoroamidothionate and the alkylating agent may be done according to the procedures described in US. Pat. No. 3,309,266 for reacting 0,0- dialkylphosphoroamidothionate with an alkylating agent.

Suitable alkylating agents represented by R include alkyl, alkenyl, and alkynyl halides, particularly iodides, e.g., methyl iodide, ethyl iodide, allyl iodide, propargyl iodide, butyl iodide, etc. and dialkyl/dialkenyl sulfates, e.g., dimethyl sulfate, diethyl sulfate, diallyl sulfate and dihexyl sulfate.

Alternatively, the 0,0-dihydrocarbyl-N-acylphosphoroamidothioate (VI) can be converted to the O,S- dihydrocarbylphosphoroamidothioate (VII) by treating the 0,0-compound (VI) with a sodium alkyl mercaptide (VIII) to form the S-sodium salt and alkylating the S-sodium salt to form the O,S-compound (VII). This reaction scheme is represented by the following equatrons:

(VI) (VIII) wherein R is alkyl.

The metalation reaction depicted in equation (4) is conducted by contacting substantially equimolar amounts of the reactants (VI) and (VIII) in the liquid phase in an inert solvent at a temperature of 10-100C. The reaction is complete within 10 hours, more usually in 5 hours or less. The sodium salt product (IX) may be used for further reaction without separation.

The alkylation of the sodium salt (IX) is effected by mixing substantially equimolar amounts of sodium salt (IX) and the alkylating agent R in an inert solvent at a temperature of in the range of 080C, preferably 25-60C. The product (VII is isolated by conventional methods, e.g., extraction, chromatography, etc.

The phosphoroamidothioate compounds may also be prepared by amidating an appropriate 0,0- dihydrocarbylphosphorothiochloridate to obtain an O,- O-dihydrocarbyl-N-acylphosphoroamidothioate and isomerizing said N-acylphosphoroamidothioate with an alkylating agent as described above. This reaction scheme is illustrated by the following set of equations:

T T CI-P-Cl RSH RS-P-CI 1101 The above reactions are preferably carried out in the presence of a weak base, such as the organic amines, for example pyridine, dimethyl aniline, triethyl amine, etc. The base is preferably present in an amount at least equal to the moles of mercaptan. An inert organic solvent, such as diethyl ether, tetrahydrofuran, dioxane, dichloromethane, etc. may be present. The reaction temperatures are generally in the range of to 13C., preferably 0 to C. The reaction time necessary to complete the addition of the mercaptan to the phosphorous oxychloride will range from about 1 to hours. The S-hydrocarbyl-S-hydrocarbylphosphorochloridodithioate product can be purified by distillation, crystallization or chromatography, if desired.

The second step of the preparation, i.e. amidation, is carried out by adding gaseous ammonia or an amine to a solution of the S-hydrocarbyl-S- hydrocarbylphosphorochloridodithioate according to the following equation:

RS RS wherein R, R and R have the same significance as previously defined.

The reaction is preferably carried out in an inert organic solvent, such as benzene, toluene, xylene and the like, at temperatures in the range of 10 to 75C., preferably 40 to 60c. Completion of the reaction is indicated by cessation of ammonium chloride precipitation. Following the reaction, the crude product can be isolated by filtration and then separated from ammonium chloride by selective extraction with a solvent, such as acetone, methanol or similar organic materials.

The 0,0-dihydrocarbylphosphoroamidothioate compounds used to prepare the compounds of the invention are prepared by the following reactions:

The above reactions 11-13 are conducted by essentially the same procedures described for reactions 8-10.

EXAMPLES The following examples described methods which may be used to prepared the phosphoroamidothioates and phosphoroamidodithioates of this invention. Representative compounds prepared by these methods are tabulated in Table I.

EXAMPLE I Preparation of O,S-dimethyl-N-methoxyacetylphosphoroamidothioate.

A mixture of 45 g (0.5 mole) methoxyacetic acid and g (0.675 mole) thionyl chloride was heated at 50C. for 30 minutes. The reaction mixture was evaporated under reduced pressure to give the crude methoxyacetyl chloride.

A 15.5 g sample of the crude methoxyacetyl chloride was added to 20 g (0.142 mole) O,S-dimethylphosphoroamidothioate in 80 ml methylene dichloride. The reaction mixture was refluxed for 3 hours and then poured into 50 ml of water. The mixture was neutralized with aqueous sodium bicarbonate solution and extracted with methylene dichloride. The methylene dichloride extracts were dried over magnesium sulfate, filtered and evaporated under reduced pressure to give the crude product. The crude was chromatographed on silica (methylene dichloride/acetone eluant) to give the product as an oil. The elemental analysis of this product is tabulated in Table I.

EXAMPLE II Preparation of O,S-dimethyl-N-ethylthioacetylphosphoroamidothioate.

A mixture of 14.1 g (0.1 mole) O,S-dimethylphosphoroamidothioate, 13.8 g (0.1 mole) ethylthioacetyl chloride and 40 ml methylene dichloride was refluxed for 2 hours. The reaction mixture was worked-up and purified by chromatography on silica by a procedure similar to that of Example I. The elemental analysis of this product is tabulated in Table 1.

EXAMPLE Ill EXAMPLE IV Preparation of O,S-dimethyl-N- phenylthioacetylphosphoroamidothioate.

A mixture of 9 g 0,0-dimethyl-N- phenylthioacetylphosphoroamidothioate, 1.8 g dimethyl sulfate and 9 ml chloroform was refluxed for about 3 hours. The crude reaction mixture was chromatographed in silica (methylene dichloride/hexane eluants) to give the product. Elemental analysis on the product is tabulated in Table I.

EXAMPLE V Preparation of O,S-dimethyl-N-bromoacetylphoroamidothioate. 1

This compound was prepared by the reaction of O,S- dimethylphosphoroamidothioate and bromacetyl chloride in methylene chloride by a procedure similar to that of Example IV. The product was purified by chromatography or silica (methylene dichloride/acetone eluants). Elemental analysis on the product is tabulated in Table I.

EXAMPLE VI Preparation of S,S-dimethyl-N-acetylphosphoroamidodithioate.

A solution of 73.2 g (0.48 mole) of phosphorous oxychloride in 300 ml of dry diethyl ether was charged to a 1 liter flask at a temperature of C. A solution of 76.2 g (0.96 mole) of pyridine and 49 g (1.0 mole) of methyl mercaptan in 400 ml. of diethyl ether was added slowly to the flask containing phosphorous oxychloride over a 2-hour period of time, maintaining the temperature from 0C. to 5C. The mixture was then stirred for an additional 6 hours at temperatures of 0 to C. After 18 hours of standing at 0C. the crude reaction product was separated from the solid residue, stripped of solvent and purified to give 31.7 g of a liquid S,S- dimethylphosphorochloridodithioate.

The above S,S-dimethylphosphorochloridodithioate was then charged with 500 ml of toluene to a 1 liter flask and ammonia gas added slowly at a temperature of 50 to C. When the temperature started to drop, ammonia addition was stopped. The reaction was held at 50C. for /2 hour and then cooled to room temperature and filtered. The filtrate was stripped of solvent under vacuum, then purified to give 6.6 g of S,S- dimethylphosphoroamidodithioate. The compound had a melting point of 103-105C., and the following N, S, P analysis:

S,S-dimethylphosphoroamidodithioate was dissolved in 250 ml of dichloromethane and charged to a 500 ml flask. 39.3 g 90.5 mole) of acetylchloride was added. The solution was refluxed for 2 hours and stored at room temperature for 18 hours. The dichloromethane and excess acetylchloride were removed by evaporation and the product dissolved in 250 ml of dichloromethane to which was added 250 ml water containing sufficient calcium hydroxide to give a pH of 7 after thorough mixing. The organic phase was separated from the aqueous phase and the S,S-dimethyl-N- acetylphosphoroamidodithioate recovered from the organic phase as an oil (3.7 g). Analysis was as follows:

LII

(PSC1 at 0-10C. The resulting reaction mixture was cooled in a DRY-lCE/acetone both while 80 g (1 mole) a 50% sodium hydroxide solution was added. After the addition was completed, the reaction mixture was stirred at about 25C forl 1 hours, diluted with 200 ml water and 50 ml chloroform. The organic phase was separate, dried over magnesium-sulfate, filtered and evaporated under reduced pressure. The residue was distilled to 31.3 g of 0,0-diallylphosphorochloridothioate, b.p. 7274C (0.15 mm Hg).

The above 0,0-diallylphosphorochloridothioate (30 g) and 500 ml benzene were then charged to a flask and ammonia (10 g) in 100 m1 benzene was slowly added. A heavy precipitate was formed in an exothermic reaction. The reaction was evaporated to give a cloudy white liquid. The liquid was diluted with 50 ml methylene chloride and refluxed with 10 g of ammonium hydroxide for V2 hour. The organic-layer was washed with water, dried over magnesium sulfate, filtered and evaporated to give 20 g of 0,0-diallylphosphoroamidothioate.

A 10 g (0.0518 mole) sample of the above 0,0- diallylphosphoroamidothioate, 6 g (0.059 mole) acetic anhydride, 40 ml methylene chloride and 1 ml phosphoric acid was refluxed for 3 hours. The reaction mixture was diluted with 50 ml water and 100 ml aqueous saturated ammonium chloride solution. The aqueous solution was extracted with methylene chloride. The methylene chloride extracts were washed with aqueous ammonium chloride solution, dried over magnesium sulfate and evaporated to give 10.4 g of 0,0-dial1yl-N- acetylphosphoroamidothioate.

A mixture of 10 g (0.0425 mole) of the above 0,0- diallyl-N-acetylphosphoroamidothioate, 4.3 g (0.0425 mole) sodium n-butyl mercaptide and 40 ml methanol was refluxed for 4 hours and then evaporated under reduced pressure to give the crude S-sodium-O-allyl-N- 'acetylphosphoroamidothioate salt. The salt, 6 g dimethyl sulfate and 40 ml acetonitrile were then refluxed for 25 hours. A heavy precipitate formed. The reaction mixture was filtered and the filtrate was evapcalculated Found orated under reduced pressure to give 9 g of a yellow liquid residue. The residue was chromatographed on 2 silica (hexane/methylene chloride/acetone eluants) to '72 P 15.52 14.08 give the S-methyl-O-allyl-N-acetylphosphoroamidothioate product as an oil. Elemental analysis for C H NO PS showed: EXAMPLE V11 Preparation of O-allyl-S-methyl-N-acetylphos- Calculmed Found phoroamidothioate.

A 68 g (1.1 mole) sample of allyl alcohol was added g :g-g lg-g dropwise to 84 g (0.5 mole) phosphorous thiochloride TABLE I No. Compound Melting Point Elemental Analysis %P 708 Cale. Found Cale. Found 1 0.S-dimethyl-N-methoxyacetylphosphoroamidothioate 01] 14.53 13.70 6.59 6.25 2 O.S-dimethyl-N-3-methoxypropiony1- phosphoroamidothioate 011 13.61 13.23 6.15 5.85 3 0.5-dimethyl-N-3-hutoxypropionylphosphoroamidothioate 011 11.5 10.5 1 1.9 11.1 4 O.S-dimethyl-N-3-isopropoxypropionylphosphoroamidothioate oil 12.1 1 1.93 12.55 12.13 5 O,S-dimethyl-N-eth lthioacetylphosphoroamidot ioate 011 12.72 11.72 6 O,S-dimethyl-N-3-methylthiopropionylphosphoroamidothioate 133-135 12.7 11.0

TABLE I Continued No. Compound Melting Point Elemental Analysis %P 705 Calc'. Found Calc. Found 7 O,S dimethyl-N-4-methy1thiobutyry1- phosphoroamidothioate 76-78 12.02 12.27 8 O.S-dimethyl-N-phenoxyacetylphosphoroamidothioate oil 11.25 10.82 1 1.62 1 1.68 9 O,S-dimethyl-N-Z,4-dichlorophenoxyacetylphosphoroamidothioate 95100 7.8 9.0 l O,S-dimethyl-N-phenylth ioacetylphosphoroamidothioate oil 10.6 10.15 22.8 20.62 1 l S,S-dimethyl-N-acetylphos horoamidodithioate oil 15.52 14.08 32.1 31.04 12 O-allyl-S-methyl-N'acety1p osphoroamidothioate oil 14.8 14.62 15.4 15.8

UTILITY The compounds of this invention were tested as follows to illustrate their insecticidal activity. Test results An acetone solution of the candidate toxicant containing a small amount of nonionic emulsifier was diluted with water to 30 ppm. cucumber leaves infested with the cotton aphids were dipped in the toxicant soluare reported Table 20 tion. Mortality readings were then taken after 24 hours.

TABLE 11 Compound No. 1 7a Mortality Cabbage Looper Cockroach Housefly Mite Aphid 1 100 100 100 100' 90 2 2O 90 96 70 O 3 30 0 0 96 (30 ppm) 0 4 94 100 (100 ppm) 39 (30 ppm) 0 5 90 100 100 90 22 6 O 100 60 94 7 O 100 60 39 8 100 (625 ppm) 100 100 100 9 100 100 90 39 (30 ppm) 0 I0 100 (625 ppm) 94 30 99 85 l l 0 60 100 97 98 12 90 100 100 85 ppm) 90 TEST PROCEDURES Cabbage lopper (Trichoplusia ni):

An acetone solution of the candidate toxicant containing a small amount of nonionic emulsifier was diluted with water to 500 ppm. Cabbage leaf sections were dipped in the toxicant solution and dried. The sections were then infested with cabbage looper larve. 4

Mortality readings were taken after 24 hours. American Cockroach (Periplaneta americana L.):

A 500 ppm acetone solution of the candidate toxicant was placed in a microsprayer (atomizer). A random mixture of anesthetized male and female roaches was placed in a container and 55 mg. of the abovedescribed acetone solution was sprayed on them. A lid was placed on the container. A mortality reading was made after 24 hours.

Housefiles (Musca domestica L.):

A 500 ppm acetone solution of the candidate toxicant was placed in a microsprayer (atomizer). A random mixture of anesthetized male and female flies was placed in a container and 55 mg. of the above described acetone solution was sprayed on them. A lid was placed on the container. A mortality reading was made after 24 hours.

Two-spotted Mites (Tetramuchus urticae):

An acetone solution of the candidate toxicant containing a small amount of nonionic emulsifier was diluted with water to 100 ppm. Pinto bean leaves which were infested with mites were dipped in the toxicant solution. Mortality readings were taken after 24 hours.

Aphids (Aphis gossypii Glover):

In addition to the specific formulations and application techniques described above, one or more of the compounds of this invention may be applied in other liquid or solid formulations to the insects, their environment or hosts susceptible to insect attack. For example, they may be sprayed or otherwise applied directly to plants or soil so as to effect control of insects 5 coming into contact therewith.

Formulations of the compounds of this invention will comprise a toxic amount of one or more phosphoroamidothioate and/or phosphoroamidodithioate and a biologically inert carrier. Usually they will also contain a wetting agent. Solid carriers such as silica, clay, talc, sawdust and the like may be used in such formulations. Liquid diluents which may be used with these compounds include water and aromatic solvents. In addition these formulations may contain other compatible pesticides, plant growth regulators, fillers, stabilizers, attractants and the like.

The term insecticide and insect as used herein refer to their broad and commonlyunderstood usage rather than to those creatures which in the strict biological sense are classified as insects. Thus, the term insect" is used not only to include small invertebrate animals belonging to the class lnsecta but also to other related classes of arthropods whose members are segmented invertebrates having more or fewer than six legs, such as spiders, mites, ticks, centipedes, worms and the like.

As will be evident to those skilled in the art, various modifications of this invention can be made or followed, in the light of the foregoing disclosure and discussion, without departing from the spirit or scope of the disclosure or from the scope of the following claims.

I claim:

1. An insecticidal composition comprising an insecticidally effective amount of a compound of the formula wherein R and R individually are alkyl, alkenyl or alkynyl of up to 6 carbon atoms, Y and X individually are oxygen or sulfur, n is a whole number of from 1 to 6, R is alkyl of l to 6 carbon atoms, aryl of up to carbon atoms substituted with up to 2 fluorine, chlorine or bromine atoms, and R is hydrogen or alkyl of l to 6 carbon atoms, in a biologically inert carrier.

2. The composition of claim 1 wherein R and R indi-,

vidually are alkyl of up to 6 carbon atoms.

3. The composition of claim 2 wherein R is alkyl of l to 6 carbon atoms and Y and X are oxygen.

4. The composition of claim 2 wherein R, R and R are alkyl of l to 3 carbon atoms and n is l or 2, and R is hydrogen.

5. The composition of claim 1 wherein the compound is O,S-dimethyl-N-methoxyacetylphosphoroamidothioate.

6. The composition of claim 2 wherein R is alkyl of l to 6 carbon atoms, Y is oxygen and X is sulfur.

7. The composition of claim 6 wherein R, R and R are alkyl of l to 3 carbon atoms, R is hydrogen and n is l, 2 or 3.

8. The composition of claim 7 wherein R and R are methyl, R is ethyl, and n is l.

9. The composition of claim 2 wherein R is phenyl substituted with up to 2 fluorine, chlorine or bromine atoms and n is l.

10. The composition of claim 9 wherein R and R are methyl, R is phenyl, Y is oxygen and X is oxygen.

11. A method of killing insects which comprises contacting said insects with an insecticidally effective amount of a compound of the formula R-Y o c- (CH2) -X-R2 n P-N wherein R and R individually are alkyl, alkenyl or alkynyl of up to 6 carbon atoms, Y and X individually are oxygen or sulfur, n is a whole number of from l to 6, R is alkyl of l to 6 carbon atoms, aryl of up to 10 carbon atoms substituted with up to 2 fluorine, chlorine or bromine atoms, and R is hydrogen or alkyl of l to 6 carbon atoms.

12. The method of claim 11 wherein R and R individually are alkyl of up to 6 carbon atoms.

13. The method of claim 12 wherein R is alkyl of 1 to 6 carbon atoms and Y and X are oxygen.

14. The method of claim 12 wherein R, R and R are alkyl of l to 3 carbon atoms and n is l or 2, and R is hydrogen.

15. The method of claim 11 wherein the compound is O,S-dimethyl-N-methoxyacetylphosphoroamidothioate.

16. The method of claim 12 wherein R is alkyl of l to 6 carbon atoms, Y is oxygen and X is sulfur.

17. The method of claim 16 wherein R, R and R are alkyl of l to 3 carbon atoms, R is hydrogen and n is l, 2 or 3.

18. The method of claim 17 wherein R and R are methyl, R is ethyl, and n is l.

19. The method of claim 12 wherein R is phenyl substituted with up to 2 fluorine, chlorine or bromine atoms and n is 1.

20. The method of claim 19 wherein R and R are methyl, R is phenyl, Y is oxygen and X is oxygen.

Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US4299783 *Apr 28, 1980Nov 10, 1981Chevron Research Company1-Alkylsulfonyl-3-substituted phosphinylthio- or phosphinothioylthio-propenes
US4900733 *Oct 13, 1987Feb 13, 1990E. I. Dupont De Nemours & Co.N-acyl phosphonamidothioates and dithioates
US6576661Oct 27, 2000Jun 10, 2003Bayer AktiengesellschaftActive ingredient combination having insecticidal and acaricidal characteristics
US6818670Apr 11, 2003Nov 16, 2004Bayer AktiengesellschaftActive ingredient combination having insecticidal and acaricidal characteristics
US6900190Mar 15, 2001May 31, 2005Bayer AktiengesellschaftActive substance combinations having insecticidal and acaricidal properties
US7060692Aug 21, 2001Jun 13, 2006Bayer Cropscience AgActive ingredient combinations comprising insecticidal and acaricidal properties
Classifications
U.S. Classification514/120, 987/193
International ClassificationC07F9/00, C07F9/24
Cooperative ClassificationC07F9/2479, C07F9/2487
European ClassificationC07F9/24C9, C07F9/24C9Q