NOVEL PHOSPHOROUS ESTERS OF CYANOHYDRINS, PESTICIDAL COMPOSITIONS INCLUDING SAME, AND METHODS OF CONTROLLING PESTS USING SAME

Abstract: Novel phosphorous esters of cyanohydrins which ex­ hibit outstanding pesticidal activity. A method of controlling pests by subjecting the pests to a pesticidally active amount of a compound of this invention is also covered. The esters have the general formula: wherein X is O or S; R and R₁ are the same or different and are independently hydrogen, lower alkyl (C₁-C₁₅), whereby C₃-C₁₅ can be branched or unbranched, and wherein the alkyl chain can be substituted or unsubstituted with alkylthio, alkoxy, or one or more halo; cycloalkyl (C₃-C₈), alkenyl, phenyl, benzyl, pyri­ dinyl, pyrimidinyl, furanyl, pyranyl, naphthalene, thiophene, all of which may be optionally substituted with one or more halogen, nitro, cyano, allyloxy, trihalomethyl, alkyl, alkylthio, alkoxy, or aryloxy, aryloxy alkyl, which can be further substituted with alkoxy, halogen, alkyl, or trihalomethyl groups; taken together R and R₁ may form a 5 or 6 membered carbocyclic ring. R₂ and R₃ can be the same or different and are independently: a) alkyl (C₁-C₁₀), b) alkylthio (C₁-C₈), c) haloalkyl (C₁-C₈), d) alkoxy (C₁-C₈) with the proviso that R₂ and R₃ may not be alkoxy at the same time, e) alkyl or dialkyl amino (C₁-C₈), f) phenyl or benzyl which can be optionally substituted with one or more nitro, cyano, halogen, triha­ lomethyl, alkyl, alkoxy alkylthio or aryloxy, g) thioaromatic radicals, and h) oxyaromatic radicals.

Description: NOVEL PHOSPHORUS ESTERS OF CYANOHYDRINS, PESTICIDAL COMPOSITIONS INCLUDING SAME, AND METODS OF CONTROLLING PESTS USING SAME Thic invention relates to novel phospl)osous esters of cyanobydrins and methods of preparing same. This invention is also directed to a pesticidal composition comprising an acceptable carrier and a pesticidally effective amount of a compound of this invention, as well as to a method of controlling pests which comprises subjecting the pests to a pesticidally effective amount of a compound of this invention. Certain phosphate esters of cyanobydrins are disclosed in U.S . Patent 2.963.533. which issued on December 20, 1960 and which is assigned to Shell Oil Company. The phosphates disclose2 in this patent are based on the diethyl chloso- phosphate moiety: EMI1.1 As an example, the patentee reacts acetone cyanohydrin with A to yeld Diethyl 1-cyano-1-methyl ethyl phosphate as shown below EMI1.2 According to the present invention one of the O-ethyl groups is replaced by an S-n-propyl group which unexpectedly increases the broad spectrum pesticidal activity over the compounds disclosed 'in U.S. Patent 2.965,533. The novel compounds can be represented by the following generic formula: EMI2.1 wherein X is O or S; R and R1 are the same or different and are independently hydrogen, lower alkyl (C1-C15). whereby C3- C15 can be branched or umbrached, and wherein the alkyl chain can be substituted or unsubstituted with alkylthio, alkoxy, or one or more halo; cycloalkyl (C3-Cg), alkenyl, phenyl, benzyl, pyridinyl. pyrimidinyl, furanyl, pyranyl, naphthalene. thiophene, all of which may be optionally substituted with one or more halogen.nitro.cyano.allyloxy trihalomethyl, alkyl. alkylthio, alkoxy. or aryloxy, aryloxy alkyl, which can be further substituted with alkoxy, halogen, alkyl1 or trihalomethvl groups; taken together R and R1 may form a 5 or 6 membered carbocyclic ring. R2 and R3 can be the same or different and are independently: a) alkyl (C1-C10). b) nlkylthio (C1-Ca), c) haloalkyl (C1-C8). d) alkoxy (C1-C8) with the proviso that R2 and R3 may not be alkoxy at the same time, e) alkyl or alkyl amino tCl-Cg), f) phenyl or benzyl which can be optionally substituted with one or more nitro, cyano, halogen, trihalomethyl, alkyl. alkoxy, alkylthio or aryloxy, g) thioaromatic radicals, and h) oxyaromatic radicals. Compositions falling within the above generic formula exhibit biological activity as pesticides to a greater or lesser extent. Some exhibit very powerful activity in extremely small dosages while others require larger dosages to be effective. in general, the compounds which are prefurred for pesticidal activity are those of the above generic formula wherein: X is O; R and R1 are the same or different and are independently hydrogen, lower alkyl (C1-C6). phenyl substituted with aryloxy, further substituted with halogen; R2. and R3 can be the same or different and are independently alkylthio and alkoxy (C1-C8) with the proviso that R2 and R3 may not be alkoxy at the same time. Compounds which are most preferred are represented by nomenclature and structure as follows: Structure EMI5.1 Nomenclature O-(&alpha;-Cyanobenzyl)-O-ethyl S-n-propylthiophosphate O-(2-Cyano-2-propyl)-O-ethyl S-n-propylthiophosphate O-(2-M+ethyl-1-cyanopropyl) O-ethyl-S-propylthiophosphate Nomenclature Structure EMI6.1 O-(&alpha; ;-Cyano-3-[2',4'-dicloropohenxybennyl)-O-ethyl-5-n-propylthiophosphate O-(1-Cyanoethyl)-O-ethyl S-propylthiophosphate In general, the phosphorous esters of this invention can be conveniently prepared utilizing appropriate aldehydes and ketones as starting materials-. These are converted to their corresponding cyanohydrins (1'-4) and then reacted with a phosphorylating group as shown below. EMI7.1 <tb> a <SEP> o <SEP> a <tb> <SEP> Cf <SEP> or <SEP> X <SEP> / X <SEP> ab <SEP> SC <SEP> /bWR3 < 2 <SEP> a <tb> <SEP> 1)504 <SEP> a <tb> <SEP> 2)CHoji <SEP> --ZL, <SEP> \,; <SEP> \ <SEP> 't2 <tb> <SEP> 0' <SEP> Cl' <tb> <SEP> Me <SEP> aQ <SEP> s <SEP> S1n <tb> <SEP> be <SEP> o <tb> <SEP> 4)eex <SEP> gg%81) <tb> wherein the values of X, R, R1, R2 and R3 are as indicated previously. According to the above scheme, the aldehyde or ketone (C) can be converted; to cyanohydrin (D) using one of the four methods listed or variations thereof. The choice of which method is used is dependent upon the substituents R and R1. Conversion of EMI7.2 <tb> C#D <tb> -using methods 1.2, and 3 are detalied in examples I, II and III. +Conversion of EMI7.3 <tb> D; <SEP> E <tb> occurs by reacting one equivalent of cyanohydrin with an appropriate chloro phosphorous compound in the presence of at least one equivalent of an acid ncceptor, preferably in an inert solvent. The acid acceptor utilized in this reaction scheme EMI8.1 <tb> (D#E) <tb> can be either an organic or inorganic base. Illustrative of organic bases that are useful acid acceptors are tertiary amines, such as triethyl. amine, 4-1,N-dinethylamino pyridine, pyridine, trimethyl amine, callidine or 1,4-diazobicyclo [2.2.2] octane; bases such as sodium carbonate and potassium carbonate are illustrative of inorganic bases that are useful acid acceptors. In general, any organic solvent that is inert to the reactants or reaction conditions may be employed in the reaction scheme shown above. Illustrat ve of organic solvents which are generally suitable for use in conducting these reactions are saturated, unsaturated and aromatic hydrocarbons, e.g. hexane, cyclohexane, octane, cyclohexene, dodecane, naptha, decalin, kerosene, cyclopentane, benzene, toluene, xylene, napthlene or the like; others such as dioxane, tetrahydrofuran, diethyl ether, l,2-dimethyoxybenzen, the dialkyl ethers of ethylene glycol, or propylene-glycol or chlorinated aliphatic hydrocarbons, as for example, chloroform, dicIloromethane 1,1-dichloroethane, carbon tetrachloride, and the like, are also acceptable. The reaction sequence EMI8.2 <tb> D#E <tb> may also be conducted in a solvent which functions as an acid acceptor. Illustrative of such multifunctional solvents are N,N-dimethy1anline, pyridine0 collodine or any like aromatic or heterocyclic tertiary amine compound The reaction sequence (C# D# E) can be conducted over a broad temperature and pressure range to yield the desired products, preferably, these reactions are conducted at a temperature of -400C to about 60-C and at atmospheric or autogeneous pressure. The phosphorous halides utilized as reactants in the scheme EMI9.1 <tb> D <SEP> E <tb> generally are known materials which can be obtained from commercial sources or prepared in accordance with conventional methods known to those skilled in the art. The following pesticidally active compounds are illustrative of compounds within the purview of the above generic formula and which can be conveniently prepared by the process of this invention simply by selecting appropriate reactants for use in the procedures described below. O-(1-cyanoethyl)-O-ethyl-S-n-propylthiophosphate. O-(2,2,2-trichloro-1-cyanoethyl)-O-ethyl-S-n propylthiophosphate. D-(2-methyl-1-cyanopropyl)-O-ethyl-S-n-propyl thiophosphate. 0-(2,2-dimethyl-l-cyanopropyl)-O-ethyl-S-n-propy7D thiophosphate. O-(2-cyano-2-propyl)-O-ethyl-S-n-propylthiophosphate. O-(1,1,1-trichloro-2-cyano-2-propyl)O-ethyl-S-n propylthiophosphate. O-(1,1,1-trichloro-2-cyano-2-propyl)-O-ethyl N-isopropyl phosphoroamidate O-(1,1,1-trichloro-2-cyano-2-propyl)-O-ethyl phenyl thionophosphonate. O-(l,l,1-trifluoro-2-cyano-2-propyl)-0-ethyl-S-n- propylthiophosphate. O-(1,1,1,3,3,3-hexanchloro-2-cyano-2-propyl)-O-ethyl S-n-propylthiophosphate. O-(1,1,3-trichloro-1,3,3-trifluoro 2-cyano-2-propyl)-0-ethyl-S-n-propylthiophosphate. O- (2-cyano-2-butyl)-0-ethyl-5-n-propylthiophosphate. O-(1-cyano-1-cyclopropyl ethyl)-O-ethyl-S-n-propylthio phosphate. O-(5-chloro-2-cyano-2-pentyl)-O-ethyl-S-n-propylthio phosphate. O-(l-cyanohexyl)-O-ethyl-S-n-propylthiophosphate. O-(1-cyanooctyl)-O-ethyl-S-n-propylthiophosphate. O-(3-methoxy-1-cyanobutyl)-O-ethyl-S-n-propylthio phosphate. O-(l-cyanocyclohexyl)-O-ethyl-S-n-propylthiophosphste. O-(l-cyanocyclohexyl)-O-ethyl-S-n-propylphosphorodi- thioate. O-(&alpha;-cyanobezyl)-O-ethyl-S-n-propylthiophosphate. O-(&alpha;-cyanobezyl)-O-ethyl-S-n-butylthiophosphate. O- ( -cyanobenzyl)-O-ethyl-S-n-propylphosphorodithioate O-(&alpha;-cyano-2-chlorobenzyl)-O-ethyl-S-n-propylthio- phosphate. O-(&alpha;-cyano-2-allyloxybenzyl)-O-ethyl-S-n-propyl- thiophosphate. O-(&alpha;-cyano-2-methylbenzyl)-O-ethyl-S-n-propylthio phosphate. O-(&alpha;-cyano-2-nitrobenzyl)-O-ethyl-S-n-propylthio phosphate. O-(&alpha;-cyano-3-fluorobenzyl)-O-ethyl-S-n-propylthio- phosphate. O-(&alpha;-cyano-3-trifluoromethylbenzyl)-O-ethyl-S-n- propylthiophosphate. O-(&alpha;-cyano-4-chlorobenzyl)-O-ethyl-S-n-propylthio- phosphate. O-(&alpha;-cyano-2,4-dichlorobenzyl)-O-ethyl-S-n-propyl thiophosphate. O-(&alpha;-cyano-2,6-dichlorobenzyl)-O-ethyl-S-n-propyl- thiophosphate. O-(d -cyano-3-nitro-2,6-dichlorobenzyl)-0-ethyl-S-n- propyithiophosphate. O-(&alpha;-cyano-2,3,4,5,6-pentafluoromethylbenzyl)-O-ethyl-S-n- propylthiophosphate. O-(2,4-dichloro-&alpha;-cyano-&alpha;-methylbenzyl)-O-ethyl-S n-propylthiophosphate. O-(2-bromo-1-cyano-3-phenyl-2-propenyl)-O-ethyl-S propylthiophosphate. O-(&alpha;-cyano-2-pyridylmethil)-O-ethyl-S-n-propylthio- phosphate. O-(&alpha;-cyano-6-methyl-2-pyridylmethil)-O-ethyl-S-n- propylthiophosphate. O-(&alpha;-cyano-1-(2-pyridylmethil)-O-ethyl-S-n-propyl thiophosphate. O-(&alpha;-cyano-3-phenoxybenzyl)-O-ethyl-S-n-propyl- thiophosphate. O-(&alpha;-cyano-3-phenoxybenzyl)-O-ethyl-S-icopropylthio phosphate. O-(&alpha;-cyano-3-phenoxybenzyl)-O-ethyl-S-n-propylphos- phordithioate. O-(&alpha;-cyano-3-phenoxybenzyl)-O-ethyl-ethyl-thiono- phosphonate. O-(&alpha;-cyano-3-(4'-chlorophenoxybenzyl)-O-ethyl-S-n propyithiophosphate. O-[&alpha;-cyano-6-(2,4-dichlorophenoxy)-2-pyridine methyl] O-ethyl-S-n-propylthiophosphate. 0-(8-cyuno-8-pentadecyl)-0-cthyl-S-n-propylthiophosphate. O- (5-cyano-5-tridecyl)-0-ethyl-S- n-propylthiophosphate . O-t3-cyano-3-Åaodecyl)-0-ethyl-S-n-propylthiophosphate. O-(5-ethoxy-3-cyano-3-pentyl)-0-ethyl-S-n-propyl - thiophosphate. O- (R- cyao- 3-me thylcyclohexyl) -O-ethyl-S-n-prDpyl- thiophosphate O-(&alpha;-cyano-2,4,6-trimethoxybenzyl)-O-ethyl-S-n- propylthiophosphate. O-(&alpha;-cyano-3-(4'-tertbutylphenoxybenzyl)-O-ethyl S-n-propylthiophosphata. O-(&alpha;-cyano-4-phenoxybenzyl)-O-ethyl-S-n-propyl thi ophosphate. O-(&alpha;-cyano-4-phenoxybenzyl)-O-ethyl-S-n-propylthio- phosphate. The following examples will illustrate the present invention. Example 1 Preparation of 0- ( -cyanobenzy)-O-ethyl- S-n-propylthiophosphate A 500 ml four-neck round bottom flask was equipped with a magnetic stirring bar. water con denser, addition funnel and drying tube. The glassware was dried and to this was charged 21.2 grams (0.2 mole) benzaldehyde and 19.5 grams (0.3 mole) potassium cyanide dissolved in 70 ml of water. The reaction flask was coolcd to 10-150C using a waterlice bath. To this was added 70 ml of 40% sulfuric acid over a 60 minute period. After the addition was complete, the reaction was allowed to warm to roo- temperature and stir for an additional two hours. At the end of this time the reaction mixture was extracted with carbon tetrachloride (3x75 ml), washed the combined carbon tetrachloride layers with water (2x50 ml), dried the carbon tetrachloride layer with anhydrous magnesium sulfate, filtered and concentrated to yield benzaldehyde ctanohydrin. To a 100 ml two-neck round bottom flask equipped with thermometer, water condenser and drying tube. magnetic stirring bar and heating mantel, was charged 5.0g (0.0376 mole) benzaldehyde cyanohydrin. 3.4g (0.043 mole) pyridine and 40 ml acetonitrile. The contents were then stirred for two hours at room temperature at which time 7.6g (0.0376 mole) of 0ethyl-S-n-propyl phosphorochloridate was added. The mixture was then stirred overnight at room temperature. The following day e TLC taken of the crude reaction mixture showed that the reaction had not gone to completion. 3.4g of (0.043 mole) of pyridine was added to the flask and the reaction mixture heated to 400C for four hours at which time the acetonitrile was removed under vacuum and the residue taken up. in 400 ml of ethyl ether and washed with water (2x100 ml). The ether layer is then dried with anhydrous magnesium sulfate, filtered and concentrated under vacuum. The resulting residue is then purified by means of a lou pressure liquid chromatography column to yield 2.4 gram of the desired product as an oil. (nD23 1.5118) Calcd for C13H18NO3P5: C,52.16; It,6.06 Found: C.52.26; H.6.05 Example 2 Preparation of O-(&alpha;-cyano-2,3,4 5.6-pentafluoru- benzyl)-O-ethyl-S-n-propylthiophosphate. A 100 ml round bottom flask fitted with thermometer, water condenser with. drying tube and magnetic stirring bar has charged into it 2.8 (.033 mole) acetone cyanohydrin, 3 drops triethylamine and 50 ml carbon tetrachloride. The reaction mixture is cooled to 0 C using a water/ice bath. 5.9 (.03 mole) of pentafluoro benzaldeyide is added to the reaction mixture at a rate which alloys the temperature to be maintained between 5-150C. After all the aldehyde is added the reaction is brought up to room temperature and stirred over-..ight. The reaction is cooled to 15 C (water/ice bath) and 2.4g (.03 mole) pyridine is added followed by the addition of 6.0g (.03 mole) O-ethyl-S-npropyl phosphoro chloridate while maintaining a temperature of less than 20-C. After the chloride is added the reaction is brought to room temperature and stirred overnight. Additional carbon tetrachloride is added to the reaction mixture and then the mixture is washed several times with water; dried over anhydrous magnesium sulfate, filtered and concentrated. The residue is then purified by means of a low pressure liquid chromatography column to yield 1.0 gram of 21 the desired product is @@@ @@@ @@@@@@@. Called for C13H13F5NO3PS: C,40.11; H,3.37 Found: C,40.63; H,3.15 Example 3 Preparation of O-(&alpha;-cyano-4-isopropylbenzyl)- O-ethyl-S-n-propylthiophosphate. A 100 ml round bottom flask fitted with thermometer, water condenser with drying tube and magnetic stirring ber has charged into it 6.0g (.0405 mole) 4-izopropylbenzaldehide, 4.8g (.0486 mole) trimethylsilyl cyanide, 50 ml methylene chloride and a catalytic amount of triphenyl phosphine and zinc chloride.. The material was stirred overnight at room temperature and then transferred to a 250 ml flask at which time 60 ml of ,3L1 hydrochloric acid was added and the mixture stirred for three hours at room temperature. The, material was taken up in ethyl ether, dried over anhydrous magnesium sulfate, filtered and concentrated in vacuum. To 7.2g (.041 mole) of the above concentrate dissolved. in 50 ml of ethyl ether was added 8.3g (.041 mole). 0-ethyl-S-n.-propyl phosphorochioridate at 100C. To this mixture was added 3.6g (.045 mole) pyridine while maintaining temperature below 20-C. After the addition of pyridine was complete the reaction was allowed to warm to room temperature and stir over the weekend. Uork-up consisted of filtering off solid (amine salt), washing the ether layer with water, drying the ether layer with anhydrous magnesium sulfate, filtering and concentrating in vacuum. The resulting residue is purified by means of a low pressure liquid chromatography column to yield 1.7 grams of the desired product as an oil n23 1.5055). Calcd for Ci6H24N03PS: C,59.81; H,7.49 Found: C,59.56; H,7.44 Examples 4-45 ilustrate other compounds of the present invention which were prepared by methods detailed in this invention. TABLE I Refractive Molecular Calculated (%) Found (%) Example Nomenclature Index ( C) Formula C H C H 4 O-(1-Cyanoethy)-O-ethyl-S- 1.4640 (23) C8H16NO3PS 40.50 6.75 39.16 6.93 propylthiophosphate 5 O-(2,2,2-Trichloro-1-cymoethyl)- 1,4940 C5H13ClNO3PS 28.21 3.85 26.82 3.65 O-ethyl-S-propylthiophospate Refractive Molecular Calculated (%) Found (%) Example Nomenclature Index ( C) Formula C H C H 6 O-(2-Methyl-1-cyanopropyl)- O- 1.4630 (23) C10H20NO3PS 46.77 7.60 47.21 7.83 ethyl-S-propylthiophosphate 7 O-(2,2-Dimethyl-1-cymoethyl)- 1.4500 C11H22NO3PSS 47.29 7.94 47.32 8.23 O-ethyl-S-propylthiophospate Refractive Molecular Calculated (%) Found (%) Example Nomenclature Index ( C) Formula C H C H 8 O-(2-cyan-2-propyl)-O-ethyl- 1.4580 (23) C9H18NO3PS 43.02 7.22 44.20 7.41 S-propylthiophosphate 9 O-(1,1,1-Trichlro-2-cyano-propyl)- - C9H15ClNO3PS 30.48 4.26 30.08 4.07 O-ethyl-S-propylthiophospate 10 O-(1,1,1-Trichloro-2-cyano-2-propyl)- 1.4755 (23) C9H16Cl3N2O3P 32.02 4.78 33.07 5.05 O-ethyl-n-isopropylphosphoromidato Refractive Molecular Calculated (%) Found (%) Example Nomenclature Index ( C) Formula C H C H 11 O-(1-Cyanocyclohexy)-O-ethyl- 1,4362 (23) C9H15F3NO3PS 34: :41 4.95 35.32 5.51 S-propylphosphorodithioste Refractive Molecular Calculated (%) Found (%) Example Nomenclature Index ( C) Formula C H C H 12 O-(1,1,3-Trichoro-1,3,3-trifluoro- - C9H12Cl3F3NO3PS 26.45 2.95 27.05 3.18 2-cyano-2-proyl)-O-ethyl-S-propylthio phosphate 13 O-(2-Cyano-2-butyl)-O-ethyl - C10H20MO3PS 45.27 7.60 Nesidue s-propylthiophosphate (50% Pure) Refractive Molecular Calculated (%) Found (%) Example Nomenclature Index ( C) Formula C H C H 14 O-(5-Chloro-2-cyano-2-pentyl)- - C11H21ClNO3PS 42.10 6.75 Residue O-ethyl-S-propylthiophosphate (80% Pure) 15 O-(1-Cyanohexyl)-O-ethyl-S-propyl- 1.4610 C12H24NO3PS 49.13 8.25 47.60 8.10 thiophosphate 16 O-(1-Cyanoctyl)-O-ethyl-S- 1,4645 (21) C15H30NO3PS 53.71 9.02 54.23 9.12 propylthiophosphate Refractive Molecular Calculated (%) Found (%) Example Nomenclature Index ( C) Formula C H C H 17 O-(3-liethoxy-1-cyanobutyl)- 1.4615 (21) C11H27NO4PS 44.75 7.46 45.19 7.37 O-ethyl-S-propylthiophosphate Refractive Molecular Calculated (%) Found (%) Example Nomenclature Index ( C) Formlua C H C H 18 O-(&alpha;-Cyanobenzyl)-O-ethyl- 1.5105 (25) C14H2ONO3PS 53.66 6.43 52.44 6.61 S-buylthiophospate 19 O-(&alpha;-Cyanobenzyl)-O-ethyl- 1.5415 (22) C13H18NO2PS2 49.50 5.75 48.48 5.94 S-propylphosphorodithioate Example Nomeclature Refractive Molecular Calculated (%) Found (%) Indox ( C) Formula C H C H 20 O-(&alpha;-Cyano-2-nitrobenzyl)- 1.5348 (24) C13H17N2O5PS 45.34 4.98 46.57 4.90 O-ethyl-S-propylthiophosphate 21 O-(&alpha;-Cyano-3-fluorobenzyl)-O- 1.5090 (23) C13H17FNO3PS 49.20 5.40 50.39 5.24 ethyl-S-propylthiophosphate 22 O-(&alpha; ;-Cyano-3-trifluoromethyl- 1.4785 (24) C14H17F3NO3PS 45.77 4.67 45.64 4.57 benzyl)-O-ethyl-S-propylthiophosphate Refractive Molecular Calculated (%) Found (%) Example Nomenclature Index ( C) Formlua C H C H 23 O-(&alpha;Cyano-4-Chlorobenzyl) ------- C13H17ClNO3PS 46.78 5.14 47.05 5.07 O-ethyl-S-propylthiophosphate 24 O-(&alpha;Cyano-2,4-dichlorobenzyl)- 1.5412 (22) C13H16Cl2NO3PS 42.40 4.38 43.65 3.94 O-ethyl-S-propylthiophosphate Example Nomenclature Refractive Molecular Calculated (%) Found (%) Index ( C) Formula C H C H 25 O-(&alpha;-Cyano-2,6-dichlorobenzoyl)- 1.5370 (21) C13H16Cl2NO3PS 42.40 4.38 42.94 4.72 O-ethyl-S-propylthiophosphate 26 O-(&alpha; ;-Cyano-3-nitro-2,6-dichloro- 1.5550 (21) C13H15Cl2N2O5PS 37.78 3.66 38.10 3.24 benzyl)-O-ethyl-S-propylthiophosphate Example Nomenclature Refractive Molecular Calculated (%) Found (%) Index ( C) Formula C H C H 27 O-(2,4-Dichloro-&alpha;-cyano-&alpha;- 1.5156 (23) C16H18Cl2NO3PS 43.99 4.75 41.65 4.62 methylbenzyl)-O-ethyl-S-propylthio phosphate 28 O-(&alpha;-Cyano-2-pyridylmethyl)- - C12H17N2O3PS 47.99 5.71 46.27 5.74 O-ethyl-S-propylthiophosphate Example Nomenclature Refractive Molecular Calculated (%) Found (%) Index ( C) Formula C H C H 29 O-(&alpha;-Cyano-6-methyl-2- 1.4990 (25) C13H19N2O3PS 49.67 6.09 48.10 6.47 pyridylmethyl)-O-ethyl-S-propyl thiophosphate 30 O-(&alpha; ;-Cyano-3-phenoxybenzyl)-O- - C19H22NO4PS 58.30 5.67 59.02 5.69 ethyl-S-propylthiophosphate Example Nomenclature Refractive Molecular Calculated (%) Found (%) Index ( C) Formula C H C H 31 O-(&alpha;-Cyano-3-phenoxybenzyl)- 1.5465 (22) C19H22NO4PS 58.30 5.67 57.75 5.68 O-ethyl-S-isopropylthiophosphate 32 O-(&alpha;-Cyano-3-phenoxybenzyl)- 1.5595 (24) C19H22NO3PS2 56.00 5.44 Residue O-ethyl-S-propylphosphorodithioate Example Nomenclature Refractive Molecular Calculated (%) Found (%) Index ( C) Formula C H C H 33 O-(&alpha;-Cyano-3-phenoxybenzyl)- 1.5550 (22) C16H20NO3PS 59.82 5.58 Residue O-ethyl-ethylthionophosphonate 34 O-(&alpha;-Cyano-3-(4'-chloro- - C19H21ClNO4PS 53.58 4.97 Residue phenoxybenzyl)-O-ethyl-S-propyl thiophosphate 35 O-[&alpha; ;-Cyano-6-(2',4'-dichloro- 1.5478 (23) C18H19Cl2N2O4PS 46.86 4.13 46.85 4.20 phenoxy)-2-pyridinemethyl] O-ethyl-S-propylthiophosphate Example Nomenclature Refractive Molecular Calculated (%) Found (%) Index ( C) Formula C H C H 36 O-(1,1,1-Trifluoro-2-cyano-2- 1.4362 (25) C9H15F3NO3PS 35.41 4.92 35.32 5.51 propyl)-O-ethyl-S-propylthiophosphate 37 O-(&alpha;-Cyano-2-bromobenzyl)-O-ethyl- 1.5390 (25) C13H17BrNO3PS 41.28 4.53 41.17 4.49 S-propylthiophosphate 38 O-(&alpha;-Cyano-3-cyanobenzyl)-O-ethyl- 1.5135 (23) C14H17N2O3PS 51.24 5.28 51.70 5.68 S-propylthiophosphate Example Nomenclature Refractive Molecular Calculated (%) Found (%) Index ( C) Formula C H C H 39 O-(&alpha;-Cyano-3-(benzyloxy)benzyl]- 1.5572 (23) C20H24NO4PS 59.24 5.97 59.92 6.04 O-ethyl-S-propylthiophosphate 40 O-(&alpha; ;-Cyano-4-phenylbenzyl)-O- 1.5790 (23) C19H22NO3PS 60.78 5.91 60.75 5.95 ethyl-S-propylthiophosphate 41 O-(&alpha;-Cyano-4-fluorobenzyl)-O- 1.4870 (23) C13H17FNO3PS 49.21 5.36 49.59 5.82 ethyl-S-propylthiophosphate Example Nomenclature Refractive Molecular Calculated (%) Found (%) Index ( C) Formula C H C H 42 O-(&alpha;-Cyano-3-nitrobenzyl)-O-ethyl- 1.5366 (23) C13H17N2O5PS 45.34 4.98 46.72 4.76 S-propylthiophosphate 43 O-(&alpha;-Cyano-3-(4-fluorophenoxy- 1.5392 (23) C19H21FNO4PS 55.73 5.13 56.33 5.27 benzyl)-O-ethyl-S-propylthiophosphate 44 O-(&alpha;-Cyano-3-(4-methylphenoxybenzyl)- 1.5348 (23) C20H24NO4PS 59.26 5.93 59.54 6.11 O-ethyl-S-propylthiophosphate 45 O-(&alpha; ;-Cyano-2,3-dichloro-4-methyl- 1.5430 (21) C14H18Cl2NO3PS 43.98 4.71 44.42 4.69 benzyl)-O-ethyl-S-propylthiophosphate Selected species, of the new compounds were evaluated to determine their particidal activity against mites, nematodes. and certain insects, including an aphid. n caterpillar. e beetle and a fly. Suspensions of the test compounds uere prepared by dissolving one gram of compound in 50 milliliters of acetone in which had been dissolved 0.1 gram (10 percent of the weight of compound) of an alkylphenoxy polyethoxyethanol surfactant, as an emulsifying or dispersing agent. The resulting solution was mixed into 150 milliliters of water to give roughly 200 milliliters of a suspension containing the compound in finely divided form. The thus-prepared stock suspension contained 0.5 percent by weight of compound. The concentrations in parts per million by weight employed in the tests described below ere obtained by appropriate dilutions of the stock suspension with water. The test procedures were ns follwos: Adults and nymphal stages of the bean aphid (Aphis çabee Scop.) reared on potted duarf nasturtium plants at 65-70 F. and 50 + 5 percent relative humidity, constituted the test insects. ror testing purposes. the n-ber of aphids per pot was standardized to 100-15D by trimming plants containing excess aphids. The test compounds were formulated by diluting the stock suspension vith water to give a suspension containing 500 parts of test compound per million parts of final formulation. The potted plants (one pot per compound tested) infested with 100-150 aphide, were placed on a revolving turntable and sprayed with 100-110 milliliters of test compound formulation by use of a DeVilbies spray gun set at 40 psig. air pressure. This application, which lasted 25 seconds, was sufficient to vet the plants to run-off. As a control, lOD-llO milliliters of a water-acetone-emusifier solution containing no test compound were also sprayed on infested plants. After spraying. the pots were placed on their sides on a sheet of white standard mimeograph paper which had been previously ruled to facilitate counting. Temperature and humidity in the test room during the 24 hour holding period were 65-70 F. and 5045 percent, respectively. Aphids which fell onto the paper and were unable to remain standing after being uprighted were considered dead. Aphids remaining on the plants were observed closely for movement and those which were unable to wove the length of the body upon stimulation by prodding were considered dead. Third instar larvae of the southern armyworm (Spodopters eridania. (Cram.)). reared on Tendergreen bean plants at a temperature of 80 + 5 F. and a relative hu-.id- ity of 50 + 5 percent, constituted the test insects. The test compounds were formulated by diluting the stock suspension with water to give a suspension con taming 500 parts of test compound per million parts of final formulation. Potted lendergrcen bean plants of standard height and nge were placed on a revolving turntable ond sprayed with 100-110 milliliters of test compound forwulation by u;e of a DeVilbios spray gun set ct 40 psie air pressure. This application. which lasted 25 seconds, was sufficient to wet plants to run-off. As a control, 100-110 milliliters of a water acetone-emulsifier solution containing no test, compound were also sprayed on plants. When dry, the paired leaves uere separated and each one was placed in a 9 centimeter Petro dish lined with moistened filter paper. Five randomly selected 1a larvae were introduced into each dish and the dishes were closed. The closed dishes vere labeled and held at 80-85 F. for three days. Although the larvae could easily consume the whole leaf, within twenty-four hours. no more food was added. Larvae which were unable to move the length of the body. even upon stimulation by prodding, were considered dead. Third ins tar larvae of the Mexican bean beetle (Epilachna verivestis, Muls.), reared on Tendergreen bean plants at & temperature of 80 # 5'T. and 50 # 5 percent relative humidity, were the test insects. The test compounds were formulated by diluting the stock suspension with water to give a suspension containing 500 parts of test compound per million parts of final formulation. Potted Tendergreen bean plants of standard height and age were placed on a revolving turntable and sprayed with 100-110 milliliters of test cm- pound formulation by use of a DeVilbiss spray gun set at 40 psig air pressure. This application, which lasted 25 seconds, was sufficient to wet plants to run-off. As a control, 100-110 milliliters of a wather-acetone-emulsifier solution containing no test compound were also sprayed on plants. When dry, the paired leavens were separated mud each was placed in a 9 centimeter Petri dish lined With moi:;tcned filter paper Five randomly selected larvae were introduced into etch dich, and the dishes were closed. The closed dishes were labeled and held et a tempersture of 80 + 5 F. for three days. Although the larvae could easily consume the leaf vithin 24 to 48 hours, no pore food was added. Larvae which vere unable to move the length of the body. even upon stimulation, were considered dead. Four to cix day old adult house flies (Musca domestica. L.), reared to the specifications of the Chemical Specialties Manufacturing Association (Blue Book, McNair-Dorland Co., N. Y. 1954; pages 243-244, 261) under controlled conditions of 80 + 5 F and 50 + 5 percent relative 'humidity, were the test insects. The flies were immobilized by anesthetizing with carbon dioxide and twenty five immobilized individuals, males and females, were transferred to a cage consisting of a standard food strainer about five inches in diameter which was inverted over a wrapping-paper-covered surface. The test compounds were formulated by diluting the stock suspension with a 10 percent (by weight) sugar solution to give a suspension containing 500 parts of test compound per million parts of final forinulation, by weight. Ten millilitr of the tcst formulation were added to a souffle cup containing a one-inch square of an absorbent cotton pad. This bait cup was introduced and centered on the blotting paper under the food sttalntr prior to admitting the anesthetized flies. The caged flies were allowed to feed on the bait for twenty four hours, at a temperature of 80 + 50F. and the relative humidity of 50 # 5 percent. Flies which showd no sign of movement on prodding were considered dead. Adults and nymphal stages of the two-spotted mite (Tetranvchus urticae Koch). reared on Tendergreen bean plants at 80 4 sor and SOt 5 percent relative humidity were the test organisms. Infested leaves from a stock culture were placed on the primary leaves of two bean plants six to eight inches in height, growing in a two-and-a- half inch clay pot. 150-200 Mires, a sufficient number for testing. transferred from the excised leaves to the fresh plants in a period of twenty-four hours. Hollowing the twenty-four hour transfer period, the excised leaves were removed from the infested plants. The test compounds were formulated by diluting the stock suspension with water to give a suspension containing 500 parts of test co=pound per million parts of final formulation. The potted plants (one pot per compound) were placed on 3 revolving turntable and'sprayed with 100-110 milliliters of test compound formulation by use of a DeVilbiss spray gun set at 60 psig. air pressure. This application, which lasted 25 seconds. was sufficient to wet the plants to run-off. As a control. 100-110 milliliters of water solution containing acetone and emulsifier in the same concentration as the test compound formulation, but containing no test compound. were also sprayed on infested plants. The sprayed plants were held at 80 + 5 F and 50 + 5 percent relative humidity for six days, aftcr which a mortality count of motile forms was made. Microscopic examination for motile forms was made on the leaves of the test plants. Any individual which uas cnpable of locomotion upon prodding was considered living. Infective migratory larvae of the foot-knot nematode, Heloidogyne incognita ver. acritz, reared in the greenhouse on roots of tomato (Florida N-l) and cucumber (National pickling), constituted the test organism. This particular nematode incites distinct galls or knots on the roots of certain plants. Infected roots, containing egg masses, vere removed.from the stock culture and cleaned of soil by shaking and washing with tap water. Roots were finely chopped. then vigorously shaken in a 0.5 percent NaOCf solution for 4 minutes. To separate the nematode eggs from root tissue, the mixture was poured rhrough a 32-mesh sieve nestled in a 500-mesh sieve followed by a gentle stream of water to remove any trace of NaOCf. The trapped eggs were rinsed with water into a 50-inC beaker. Samples of the egg suspension were counted with the aid of a stereoscopic microscope. 4000 to 6000 eggs were added to a series of pint mason jars, each containing 180 cc. of soil. The jars were capped and mixed thoroughly to insure uniform infestation of the soil. The test compounds were formulated by diluting the stock suspension with water to give a suspension containing 3.3 mg of test compound per 10 ml of final formulation which when added to the jar of soil was approximately equal to a rate of 28 kilogram of test compound per acre. Following addition of formulation, the jars there tightly capped, and the contents were thoroughly mixed on a ball mill for five minutes. The jars remained capped for 48 hours after which the contents were transferred to three inch diameter pots. The coil was then planted uith cucumber seeds, and since cucumber is susceptible to root-knot nematode attack, it served as an indicator crop. The pots were then placed in a greenhouse. After 4-6 weeks, the cucumber plants were removed from the pots, the roots were washed free of adhering soil, and directly compared with the roots of similar plants grown in infested but untreated soil. The averaged degree of gall formation on the roots of the cucumber plants was the basis for ascertaining nematode control. The results of these tests are set forth in Table II below. In these tests the pesticidal activity of the compounds at the indicated dosage rate against aphid, mite, Southern ArmN-orm, Bean Beetle house fly and root-knot nematode was rated as follows: A = excellent concrol B - partial control. C = no control Dashes indicate no test conducted. TABLE II Revan Mite Mite Southern Mexican Been Mouse Root-Knot Example Aphid Adult Egg Army Worm Beetle Fly Hematode 1 A A C A C A A 2 A A C A C A 3 A A C A C A 4 A A C A A A A 5 C C C C C C 6 A A C A A A A 7 B C C C C B A 8 A A C A B A A 9 A A C A A A 10 C C C A C A 11 C C C C C C 12 C C C C C A 13 A A C A C A A TABLE II (continued) Revan Mite Mite Southern Mexican Been Mouse Root-Knot Example Aphid Adult Egg Army Worm Beetle Fly Hematode 14 A A C A C A 15 A A C A A A 16 A A C A C A A 17 A A C B B B 18 A A C C C A 19 A A C A C A 20 A A C A C A 21 A A C A C A 22 A A C A C A 23 A A C A C A 24 A A B A C A 25 A A A A A A 26 A A A A C A 27 C A C C C C - TABLE II (continued) Revan Mite Mite Southern Mexican Been Mouse Root-Knot Example Aphid Adult Egg Army Worm Beetle Fly Hematode 28 A A C C C A 29 A A A A B A 30 A A A A A A 31 C A C A B B 32 C C C C C C 33 C C C C C C 34 A A A A A A 35 A A B A A A 36 A C C C C A 37 A A C A C A 38 A A A A C A 39 A A A A A A 40 A A C A A A - TABLE II (continued) Revan Mite Mite Southern Mexican Been Mouse Root-Knot Example Aphid Adult Egg Army Worm Beetle Fly Hematode 41 A A C A C A 42 A A A A B A 43 A A C A A A 44 A A A A C A 45 A A C A C A - It will be understood that the pect species employed in the above testis are merely representative of a wide variety of plant pests that can be controlled by the use of the compounds of ti4s invention. The- compounds contemplated in this invention may be applied as mite ovicides and miticides according to methods known to those skilled in the art. Moreover it has been found that the compoun.ds- of the instant invention are useful as fumigants for grain insects. have soil insecticidal activity against the corn root worm, and also possess systemic activity. Pesticidal compositions contanning the compounds as the active toxicant will usually comprise a carrier and/or diluent. either liquid or sold. Suitable liquid diluents or carriers include water, petroleum distillates. or other liquid carriers with or without surface active agents. Liquid concentrates may be prepared by dissolving one of these com pounds with a nonpbytotoxic solvent such as acetone, xylene, or nitrobenzene and dispersing the toxicants in water with- the aid of suitable surface active emulsifying and dispersing agents The. choice of dispersing and emulsifying agents and the. amount employed is dictated by the nature of the composition and the ability of the agent to facilitate the dispersion of the toxicant. Generally, it is desirab.le- to use as little- of the agent as is possible, consistent with the desired dispersion of the toxicant in the spray so that rain does not reemulsify the toxicant after it is applied to the plant and wash it off the plant. Nonionic, anioniC, amphoteric or cationic dispersing and emulsifying agents may be empoloyed; for example, the condensation products of alkylene oxides uitb phenol tnd organic ncids, alkyl aryl sulfonates, complex ether alcohols, questernary ammonium compounds, and the like. In the preparation of vettable powder or dust or granulated compositions, the active ingredient is dispersed in and on an appropriately divided solid carrier such as clay, talc, bentonite, diatomaceous earth. fullers earth. and the like. In the formulation of the wettable powders the aforementioned dispersing agents as well as lignosulfonates can be included. The required amount of the toxicants conter- plated herein may be applied per acre treated in fror 1 to 20D gallons or mort of liquid carrier and/or- diluent or in from about 5 to 500 pounds of inert solid carrier andlor diluent. The concentrÅation in the liquid concentrate will usually vary from about 10 to 95 percent by weight and in the solid formulations from about 0.5 to about 90 percent by weight. Satisfactory sprays. dusts. or granules for general use contain from about 114 to 15 pounds of active toxicant per acre. The pesticides contemplated herein prevent attack by insects, mites and nenatodes upon plants or other material to which the pesticides are applied. and they have relatively high residual toxicity. With respect to plants. they have a high margin of safety in that when used in sufficient amount to kill or repel the insects, they do not burn or injure the plant, and they resist weathering which includes wash-off caused by rain, decomposition by ultraviolet light, oxidation, or hydrolysis in the presence of moisture oz, at lent such decomposition. oxidation, and hydrolysis as would materially decrease the desirable pesticidal characterictic of the toxitants or impart undesirable characteristic for instance, phytotoxicity, to the toxicants. The toxicants are so chemically inert that they are compatible with substantially any other constituents of the spray schedule, and they may be used in the soil, upon the seeds, or the roots of plants without injuring either the seeds or roots of plants. They may also be used in combination with other pesticidally active compounds. When used as miticides they will normally be applied to the foliage of the plants to be treated. It will ge appreciated that the compounds of this invention can also be used in combination with other biologically active compounds.

Claims: CLAIMS: 1. A phosphorous ester of a cyanohdrin of the general iormula: EMI50.1 wherein X is O or S; R and R1 are the same or different and are independently hydrogen, lower alkyl CC1-C15). whereby C3-c15 can be branched or unbranched, and wherein the alkyl chain can be substituted or unsubstituted with alkylthio, alkoxy, or one or, more halo; cycloalkyl (C3-C8), alkenyl, phenyl. benzyl, pyridinyl, pyrimidinyl, furanyl, pyranyl. naphthalene, thiophene, all of which may be optionally substituted with one or more halogen, nitro, eyano,allylcxy trihalomethyl, alkyl, alkylthio, alkoxy, or aryloxy, aryloxy alkyl. which can be further substituted with alkoxy. halogen, alkyl, or tribalomethyl groups; taken together R and R1 may form a 5 or 6 membered carbocyclic ring. R2 and R3 can be the same or different and are independently: a) alkyl (C1-C10), b) alkylthio (C1-C8), c) haloalkyl (C1-C8), d) alkoxy (C1-C8) with the proviso that and R3 may not be alkoxy at the same time, c) alkyl or dialkyl amino (C1-C8) f) phenyl or benzyl which crn be optionally substituted with one or more nitro. cyano. halogen, trihalomethyl. alkyl, alkoxy, alkylthio or aryloxy. g) thioaromatic radicals, and h) oxyaromatic radicals. 2. A11 aster as claimed in claim 1 wherein X is o. 3. An ester as claimed in claim 2 wherein R and R1 are the same or different and are independently hydrogen, lower alkyl (C1-C6), phenyl substituted with aryloxy, further substituted with halogen. 4 An ester as claimed in claim 3 wherein R2 and R3 can be the same or different and are independently alkylthio and alkoxy (C1-Cg) with the proviso that R2 and R3 may not be alkoxy at the same time. 5. O-(d -Cyanobenzyl)-O-ethyl-S-n- propylthiophosphate. 6. O-(2-Cyano-2-propyl)-O-ethyl-5-npropylthiophosphate. 7. O-(2-Methyl-1-cyanopropyl)-O-ethyl S-propylthiophosphate. 8. O-(&alpha;-Cyano-3-[2',4'-dichlorophenoxy- benzyl)-O-ethyl-5-n-propylthiophosphate. 9. O-(1-Cyanoethyl)-O-ethyl-S-propylthiophosphate 10. A pesticidal composition comprising an acceptable carrier and as the active toxic ant a pesticidally effective amount of an ester as claimed in any one of the preceding claims. 11. A method of controlling nematodes, insects and mites which comprises subjecting them to a nematocidally, insecticidally or miticidally effective amount of an ester as claimed in any one of claims 1 to 9.

Inventors: AYAD, HAFEZ MOHAMMED, HODAKOWSKI, LEONARD EDWARD
Applicants: UNION CARBIDE CORPORATION
Application year: 1981
Main classification: C07F9
IPC codes: A01P7, A01N25, A01N57, C07F9