IL31339A - Imidazolinedione,oxazolidinedione and thiazolidinedione phosphorothioic acid esters and their use as insecticides - Google Patents

Imidazolinedione,oxazolidinedione and thiazolidinedione phosphorothioic acid esters and their use as insecticides

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IL31339A
IL31339A IL31339A IL3133968A IL31339A IL 31339 A IL31339 A IL 31339A IL 31339 A IL31339 A IL 31339A IL 3133968 A IL3133968 A IL 3133968A IL 31339 A IL31339 A IL 31339A
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methyl
dimethyl
phosphorodithioate
oxazolidinedione
diethyl
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IL31339A
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IL31339A0 (en
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Hercules Inc
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
    • C07D263/30—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D263/34—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D263/44—Two oxygen atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
    • A01N57/16—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing heterocyclic radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D233/72—Two oxygen atoms, e.g. hydantoin
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D233/72—Two oxygen atoms, e.g. hydantoin
    • C07D233/74—Two oxygen atoms, e.g. hydantoin with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to other ring members
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D233/72—Two oxygen atoms, e.g. hydantoin
    • C07D233/80—Two oxygen atoms, e.g. hydantoin with hetero atoms or acyl radicals directly attached to ring nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
    • C07F9/5537—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom the heteroring containing the structure -C(=O)-N-C(=O)- (both carbon atoms belong to the heteroring)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/645—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having two nitrogen atoms as the only ring hetero atoms
    • C07F9/6503—Five-membered rings
    • C07F9/6506—Five-membered rings having the nitrogen atoms in positions 1 and 3
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6527—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07F9/653—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6527—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07F9/6533—Six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6536—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having nitrogen and sulfur atoms with or without oxygen atoms, as the only ring hetero atoms
    • C07F9/6539—Five-membered rings

Description

31339/3 'Ύ' Imidazolinedione,' oxazolidinedione and thiazolidinedione phpephorothioic acid esters and their use as insecticides HERCULES INCORPORATED C. 29604 This invention relates to organophosphorous compounds and to insecticidal compositions containing them.
The organophosphorous compounds of this invention are represented by the general formula; wherein Y is 0 or S, A is 0, S, R3N or R6C0N, R1 is CH. or C?H_, J ^ 5 R6 is CH3, C2H5 or C3H7 and R2 , R3 , R4 and R5 are H or CH3 , pro's 2 "¾ vided (1) when A is RJN, at least one of R and R is CH3 , and at least one of R4 and R5 is H, and (2) when A is R6C0N, R2 is H.
The compounds of this invention are toxic to various insects. All of the compounds have contact toxicity to certain insects. A number of the compounds of this invention, moreover, have systemic toxicity to certain insects being readily absorbed by plants through root systems, in many cases also through foliage, and transported through the plant to growing tips where their toxicity is exerted on sucking insects and the like, that attack the plants. Consequently, the compounds of. this invention have utility as insecticides.
The compounds of this invention and reactions for making them are illustrated by the following examples in which all percentages are by weight.
Example 1 0 , O-Dimethyl S- ( 1-methyl) -2 , 4-imidazolidinedione-3-yl) methyl phosphorodithioate A mixture of 285 g. of l-methyl-2 , 4-imidazolidinedione , 80 g. of paraformaldehyde and 1.0 g. of barium hydroxide was'" · r of phosphorous pentachloride at 0°C. After 18 hours at room temperature, the solvent was removed and the crude mixture distilled to give 30.14 g. of 3-chloromethyl-l-methyl-2 , 4-imidazolidinedione b.p. 155°C./4.0 mm. Analysis found: CI, 21.7% (21.8% Cl = theory) .
A mixture of 9.8 g. of 3-chloromethyl-l-methyl-2 , 4- imidazolidinedione and 11.0 g. of ammonium 0,0-dimethyl phosphoro- dithioate in 50 ml. acetonitrile was stirred for 10 hours at 25°C. , and then for 3 hours at 60°C. The mixture was then poured into 0 200 ml. water. The organic layer was taken up in 100 ml. benzene, and the benzene solution was washed with 5% aqueous sodium Bicarbonate solution and then with water and dried. After distilling off the benzene, there was obtained as residue 16.1 g. oily 0,0-dimethyl S- ( l-methyl-2 , 4-imidazolidinedione-3-yl) methyl phos- phorodithioate , which analyzed 11.0% P (10.9% P = theory).
Example 2 0 ,0-Diethyl S- (1-methyl) -2 , 4-imidazolidinedione-3-yl) methyl phos- phorodithioate The ethyl ester corresponding to the product of Example 1 0 was prepared using the procedure of Example 1, and the corresponding ammonium 0,0-diethyl phosphorodithioate as reagent.
Example 3 0, 0-Dimethyl S- E- ( 1 ' -methyl-21 , 4 ' -imidazolidinedione-3 ' -yjj., ethyj, phosphorodithioate A mixture of 57 g. of l-methyl-2 , 4-imidazolidinedione , 46.2 g. of ethylene carbonate and 0.3 g. sodium bicarbonate was heated to 150-200°C. until C02 evolution ceased. The product mixture was cooled, diluted with 300 ml. of pyridine and treated with 60 g. of acetic anhydride. After heating this mixture at 30 100°C. for four hours , it was stripped of solvent, and the crude l-methyl-3- ( 21 -acetoxyethyl) -2 , 4-imidazolidinedione was distilled l-methyl-3- ( 2 ' -acetoxyethyl) -2 , 4-imidazolidinedione (60 g.) was added at 0.5 ml. /minute to a 12' x 1" packed tube at 550°C. The crude pyrolysate was distilled to give 18 g. of l-methyl-3-vinyl-2 , 4-imidazolidinedione , b.p. 86-89°C./0.3 mm.
To a solution of 7.6 g. l-methyl-3-vinyl-2 , 4-imidazolidinedione in 10 ml. benzene was added dropwise 10.3 g. 0,0-dimethyl phosphorodithioic acid at 25°C. , with air cooling over an 18-hour period. The resulting solution was diluted with 50 ml. benzene and washed with two 50 ml. portions of a 5% aqueous sodium bicarbonate solution and then with water and dried. The benzene was distilled off, and 15.7 g. oily 0,0-dimethyl S (11 -methyl-21 , 41 -imidazolidinedione-3 ' -yl) ethyl phosphorodithioate was recovered. It analyzed 10.9% P (10.4% P = theory) .
Example 4 0 , 0-Diethyl S-(L- ( 1 ' -methyl-2 ' , 4 ' -imidazolidinedione-3 ' -yl^ ethyjj? phosphorodithioate This compound was prepared as in Example 3 using 0,0-diethyl phosphorodithioic acid as reagent. The product analyzed 9.9% P (9.5% P = theory).
Example 5 0, 0-Diethyl S- ( l-methyl-2 , 4-imidazolidinedione-3-yl) methyl phosphorothioate To a solution of 20.6 g. ammonium 0,0-diethyl phosphorothioate in 100 ml. dimethylsulfoxide was gradually added 16.2 g. 3-chloromethyl-l-methyl-2 , 4-imidazolidinedione (prepared as in Example 1) at 25-37°C. After 18 hours at 25°C. , the solution was heated at 60°C. for 3 hours, and then cooled. The product was worked up by diluting with 1,000 ml. water and extracting with methylene chloride. The organic layer was washed with water and dried, and the 0,0-diethyl S- ( l-methyl-2 , 4-imidazolidinedione-3-yl) r Example 6 0,0-Dimethyl S- ( l-methyl-2 , 4-imidazolidinedione-3-yl) methyl phosphorothioate Following the procedure of Example 5 using ammonium 0,0-dimethyl phosphorothioate as reagent, there was obtained a 96% of theoretical yield of 0,0-dimethyl S- ( l-methyl-2 , 4-imida-zolidinedione-3-yl) methyl phosphorothioate analyzing 11.8% P, 10.2% N (11.6% P, 10.4% N = theory).
Example 7 0,0-Dimethyl S- ( 1 , 5-dimethyl-2 , 4-imidazolidinedione-3-yl) methyl phosphorodithioate 1 , 5-Dimethyl-3-chloromethyl-2 , 4-imidazolidinedione was prepared in the same way as 3-chloromethyl-l-methyl-2 , 4-imidazolidinedione described above using 1 , 5-dimethyl-2 , 4-imidazolidinedione in place of l-methyl-2 , 4-imidazolidinedione. The product distilled at 109°C./2.0 mm.
A. mixture of 11.6 g. 1 , 5-dimethyl-3-chloromethyl-2 , 4- imidazolidinedione and 11.5 g. ammonium 0,0-dimethyl phosphoro- dithioate in 100 ml. acetonitrile was heated at 60°C. for 8 hours. The acetonitrile was distilled off, and the product was diluted with 100 ml. ether and washed with 5% aqueous sodium bicarbonate solution and then with water and dried. On distilling off the ether, there was obtained 11.0 g. 0,0-dimethyl S- ( 1 , 5-dimethyl-2 , 4-imidazolidinedione-3-yl) methyl phosphorodi- thioate which analyzed 11.9% P (10.4% P = theory).
Example 8. 0,0-Dimethyl S- (jL- ( 2 ' , 4 ' -imidazolidinedione-3 ' -ylj ethyj phos-phorodithioate 3-vinyl-2 , 4-imidazolidinedione was prepared in the same way as l-methyl-3-vinyl—2 , 4-imidazolidinedione described above using 2 , 4-imidazolidinedione in place of l-methyl-2 , 4-imidazoli° A mixture of 2.3 g. 3-vinyl-2 , 4-imidazolidinedione and^ 5 ml. 0,0-dimethyl phosphorodithioic acid was heated cautiously and gradually to 95 °C. with precautions for cooling to control the exothermic reaction. The reaction was then continued for 3 hours at 80-90 °C. The reaction mixture was cooled, diluted with 40 ml. benzene, washed with 5% aqueous sodium bicarbonate and water and then dried. The benzene was distilled off and 5.6 g. solid 0,0-dimethyl S- {l- ( 21 , 41 -imidazolidinedione-3 ' -yl) ethy^ phosphorodithioate was recovered. This solid after recrystalli-zation from isopropyl alcohol melted at 110-112°C. It analyzed 10.9% P (10.9% P = theory).
Example 9 0,0-Diethyl S- .- ( 2 ', 4 ' -imidazolidinedione-31 -yl) ethyj phosphorodithioate Using 0,0-diethyl phosphorodithioic acid in Example 8, there was obtained 0,0-diethyl S- [l- (21 , 4 ' -imidazolidinedione-3 ' -yl) ethyTj phosphorodithioate as an oil which analyzed 11.0% P (10.0% P = theory) .
Example 10 0,0-Dimethyl S- ( 2 , 4-oxazolidinedione-3-yl) methyl phosphorodithioate A mixture of 17.2 g. of 2 , 4-oxazolidinedione , 6.0 g. paraformaldehyde and 0.1 g. Ba(0H)2 was melted and heated at 90 °C. for one hour. The melt was taken into methylene chloride (100 ml.) and treated with 36 g. phosphorous pentachloride . The mixture was let stand overnight at 25 °C. and the solvent removed. The residue was treated with cold water and recrystallized from isopropanol to give 16.3 g. of 3-chloromethyl-2 , 4-oxazolidinedione m.p. 68-69°C. , which analyzed 23.7% chlorine (theory: 22. i%) . ' A mixture of 7.5 g. 3-chloromethyl-2 , 4-oxazolidinedione and 9.6 g. ammonium 0,0-dimethyl phosphorodithioate in 40 ml. of - ° and water and then dried. On removal of the solvent, there remained 12.2 g. 0,0-dimethyl S- ( 2 , 4-oxazolidinedione-3-yl) methyl phosphorodithioate as a colorless oil which analyzed 11.5% P. (11.4% P. , theory) .
Example 11 0,0-Diethyl S- (2 , 4-oxazolidinedione-3-yl) methyl phosphorodithioat Following the procedure of Example 10,11.8 g. of ammoniu 0,0-diethyl phosphorodithioate was reacted with 7.5 g. 3-chloro-methyl-2 , 4-oxazolidinedione , and 14.4 g. 0,0-diethyl S-(2,4-oxa-zolidinedione-3-yl) methyl phosphorodithioate was recovered as a colorless oil which analzyed 9.8% P. (10.3% P., theory).
Example 12 0,0-Dimethyl S- ( 5-methyl-2 , 4-oxazolidinedione-3-yl) methyl phosphorodithioate Following the procedure of Example 10, 12.3 g. of 3-chloromethyl-5-methyl-2 , 4-oxazolidinedione prepared in an analogous manner was reacted with 14.4 g. ammonium 0,0-dimethyl phosphorodithioate , and 17.4 g. 0,0-dimethyl S- (5-methyl-2 , 4-oxa-zolidinedione-3-yl) methyl phosphorodithioate was recovered as an oil which analyzed 11.2% P. (10.9% P., theory).
Example 13 0,0-Diethyl S- ( 5-methyl-2 , 4-oxazolidinedione-3-yl) methyl phosphorodithioate Following the procedure of Example 10, 12.3 g. of 3-chloromethyl-5-methyl-2 , 4-oxazolidinedione prepared in analogous manner was reacted with 17.6 g. of ammonium 0,0-diethyl phosphorodithioate and 18.8 g. 0,0-diethyl S- ( 5-methyl-2 , 4-oxazoli-dinedione-3-yl) methyl phosphorodithioate was obtained as an oil which analyzed 9.9% P. (9.1%P., theory).
Example 14 0,0-dimethyl S-Q- ( 5 ' -methyl-2 ' , 4 ' -oxazolidinedione-3 ' -yl) ethyQ A solution of 11.5 g. of 0,0-dimethyl phosphorodithioic^ acid and 8.4 g. 3-vinyl-5-methyl-2 , 4-oxazolidinedione in 50" ml. benzene was heated at 50°C. for 3 hours, and the benzene was distilled off with final heating for 3 hours at 90°C. The product was redissolved in benzene, washed with 5% aqueous sodium bicarbonate and water and dried. On removal of the benzene, there remained 15.3 g. Ο,Ο-dimethyl S- ^l- (51 -methyl-2 ' , 4 ' -oxazolidinedione-3 ' -yl) ethy^ phosphorodithioate which was an oil analyzing 11.2% P (10.4% P., theory).
Example 15 0,0-Diethyl S-Q- ( 5 ' -methyl-21 , 4 ' -oxazolidinedione-3 ' -yl) ethyl} phosphorodithioate Following the procedure of Example 14, 13.5 g. 0,0-diethy phosphorodithioic acid was reacted with 8.4 g. 3-vinyl-5-methyl-2 , 4-oxazolidinedione and 17.5 g. 0,0-diethyl S-Q-( 5 ' -methyl-2 ' , 4 ' -oxazolidinedione-31 -yl) ethyl] phosphorodithioate which was an oil analyzing 9.9% P. (9.5% P., theory) was obtained.
Example 16 0,0-Dimethyl S- ( 2 , 4-oxazolidinedione-3-yl) methyl phosphorothioate A mixture of 20.2 g. of 2 , 4-oxazolidinedione , 6.6 g. of paraformaldehyde and .1 g Ba(0H)2 was melted and heated at 90°C. for one hour. The melt was taken into 100 ml. methylene chloride and 18.2 g. phosphorous tribromide added at 0-10 °C. The mixture was let stand at 25 °C. overnight, the methylene chloride solution decanted and the solvent removed. The residue was washed with water and recrystallized to give 16.7 g. of 3-bromomethyl-2 , 4-oxazolidinedione ; m.p. 63-64°C. An NMR spectrum was consistent with its structure.
A mixture of 15.0 g. 3-bromomethyl-2 , 4-oxazolidinedione and 13.0 g. ammonium 0,0-dimethyl phosphorothioate in 100 ml. acetonitrile was heated at 25 °C. for 48 hours, and at 60 °C. for methylene chloride solution was filtered, and the filtrate was freed of solvent by heating under reduced pressure. The residue from this treatment was 15.3 g. 0 , O-dimethyl S- ( 2 , 4-oxazolidine-dione-3yl) methyl phosphorothiate which analyzed 12.6% P. (12.2% P. , theory) .
Example 17 0,0-Diethyl S- ( 2 , 4-oxazolidinedione-3-yl) methyl phosphorothioate A mixture of 15.0 g. 3-chloromethyl-2 , 4-oxazolidine-dione and 20.4 g. ammonium 0,0-diethyl phosphorothioate in 100 ml dimethyl sulfoxide was heated at 25°C. for 48 hours, and at 60°C. for 3 hours. The mixture was diluted with 400 ml. water, and extracted with methylene chloride. The methylene chloride extract was dried and freed of solvent to obtain 18.3 g. 0,0-diethyl S- ( 2 , 4-oxazolidinedione-3-yl) methyl phosphorothioate which analyzed 11.1% P. (10.9% P., theory).
Example 18 0,0-Dimethyl S-Q- ( 2 ' , 4 ' -oxazolidinedione-3 ' -yl) ethyj phosphorodithioate A mixture of 202 g. of 2 , 4-oxazolidinedione , 185 g. of ethylene carbonate and 1.0 g. of sodium bicarbonate was heated to 155-160°C. for three hours. The melt was cooled, dissolved in 500 ml pyridine and treated with 220 g. of acetic anhydride. This mixture was heated to 100°C. for three hours, the pyridine removed and the residue distilled at 3-8 mm. Hg pressure to give 148.0 g. 3- ( 21 -acetoxyethyl) -2 , 4-oxazolidinedione , b.p. 144-150°C, which analyzed 7.8% nitrogen (theory: 7.5%).
This acetate was added to a tube packed with stainless steel helices which was heated to 580°C. The pyrolyzate was distilled to give 51.1 g. 3-vinyl-2 , 4-oxazolidinedione , b.p. 100-105°C./0.2 mm., which analyzed 10.8% nitrogen (theory: 10.8%).
A mixture of 17.0 g. of 0,0-dimethyl phosphorodithioic of the benzene, there remained 14.2 g. 0,0-dimethyl S- | 1- (2 ' , 4 ' - , oxazolidinedione-3 ' -yl) phosphorodithioate which was an oil analyzing 10.4% P. (10.9% P., theory).
Example 19 0,0-Diethyl S-Q.- ( 2 ', 4 ' -oxazolidinedione-3 ' -yl) ethyl] phosphorodithioate Following the procedure of Example 18, 20.0 g. 0,0-diethyl phosphorodithioic acid was reacted with 9.0 g. 3-vinyl 2 , 4-oxazolidinedione and 21.9 g. 0,0-diethyl S- 1- (2 ' , 41 -oxazo-lidinedione-3 ' -yl) ethy^ phosphorodithioate which was an oil analyzing 10.6% P. (9.9% P., theory) was obtained.
Example 20 0,0-Dimethyl S- ( 2 , 4-thiazolidinedione-3-yl) methyl phosphorodithioate A mixture of 225 g. of 3-chloromethyl-2 , 4-thiazolidine-dione and 290 g. of ammonium 0,0-dimethyl phosphorodithioate in 1500 ml of water was stirred at 50°C. for eight hours, the organic layer taken into 1000 ml of benzene, and the benzene solution was. washed with two 100 ml. portions of 5% aHC03, two 100 ml. portions of water and dried. Removal of the benzene gave 323.3 g. of a pale yellow oil which was 0,0-diemthyl S- ( 2 , 4-thiazolidine-dione-3-yl) methyl phosphorodithioate and which analyzed for 11.5% phosphorous , the theoretical value for phosphorous being 10.8%.
Example 21 0,0-Diethyl S- ( 2 , 4-thiazolidinedione-3-yl) methyl phosphorodithioate Following the procedure of Example 20, 16.5 g. of 3-chloromethyl-2 , 4-thiazolidinedione and 30 g. of ammonium diethyl phosphorodithioate gave 0,0-diethyl S- (2 , 4-thiazolidinedione-3-yl) methyl phosphorodithioate which analyzed 10.1% phosphorous.
Example 22 0 ,Ο-Dimethyl S- ( 5-methyl-2 , 4-thiazolidinedione-3-yl) methyl phosphorodithioate Following the procedure of Example 20, 9.0 g. of 3-chloromethyl-5-methyl-2 , 4-thiazolidinedione and 10.5 g. of ammonium 0,0-dimethyl phosphorodithioate gave 10.8 g. of an oil which was 0,0-dimethyl S- (5-methyl-2 , 4-thiazolidinedione-3-yl) methyl phosphorodithioate and which analyzed 9.7% phosphorous.
The theoretical value for phosphorous is 10.3%.
Example 23 0,0-Diethyl S- (5-methyl-2 , 4-thiazolidinedione-3-yl) methyl phosphorodithioate Following the procedure of Example 20, 9.0 g. of 3-chloromethyl-5-methyl-2 , 4-thiazolidinedione and 12.5 g. of ammonium 0,0-diethyl phosphorodithioate, gave 11.8 g. of an oil which was 0,0-diethyl S- ( 5-methyl-2 , 4-thiazolidinedione-3-yl) methy phosphorodithioate. It analyzed 9.4% phosphorous. The theoretical value for phosphorous is 9.4%.
Example 24 0 , O-dimethyl S- (5 , 5-dimethyl-2 , 4-thiazolidinedione-3-yl) methyl phosphorodithioate Following the procedure of Example 20, 15.5 g. of , 5-dimethyl-3-chloromethyl-2 , 4-thiazolidinedione and 16.5 g. of ammonium 0 , O-dimethyl . phosphorodithioate gave 21.4 g. of an oil which was 0,0-dimethyl S- ( 5 , 5-dimethyl-2 , 4-thiazolidinedione-3-yl) methyl phosphorodithioate. It analyzed 8.5% phosphorous. The theoretical value for phosphorous is 9.9%.
Example 25 0,0-Diethyl S- ( 5 , 5-dimethyl-2 , 4-thiazolidinedione-3-yl) methyl phosphorodithioate By the procedure of Example 20, substituting 19.5 g.
It analyzed 9.5% phosphorous. The theoretical value for phos- | phorous is 9.1%.
Example 26 0 ,0-Dimethyl S- ( 2 , 4-thiazolidinedione-3-yl) methyl phosphorodithioate A mixture of 16.6 g. of 3-chloromethyl-2 , 4-thiazoli-dinedione and 17.7 g. ammonium 0,0-dimethyl phos phorothioate in 100 ml. water were reacted at 50°C. for 8 hours to obtain 6.8 g. 0 ,0-dimethyl s-( 2 , 4-thiazolidinedione-3-yl) methyl phos-phorodithioate which was recovered by extracting with benzene, washing with aqueous sodium bicarbonate, and distilling off the benzene. It was an oil analyzing 10.0% P. and 4.6% N. (11.4% P. and 5.1% N. , theory).
Example 27 0,0-Dimethyl S-Q- ( 2 ' , 4 ' -thiazolidinedione-3-yl) ethyj? phosphorodithioate A mixture of 7.2 g. of 3-vinyl-2 , 4-thiazolidinedione and 15.8 g. of 0,0-dimethyl phosphorodithioic acid was heated at 50-60°C. for 12 hrs. (Cautions when heated to 90°C. , the mixture exothermically decomposed.) The mixture was diluted with 50 ml. of benzene, washed twice with 50 ml. of 5% aHC03 , H2O and dried. The benzene was removed to give 15.0 g. of an oil which was 0,0-dimethyl s- .-( 2 ' , 4 ' -thiazolidinedione-3-yl) ethyl] phosphorodithioate and which analyzed 11.4% phosphorous. The theoretical value for phosphorous in this product is 10.3%.
Example 28 0,0-Diethyl S- [1,-( 2 ' , 4 ' -thiazolidinedione-31 -yl) ethyl] phosphorodithioate By the procedure of Example 27, substituting 18.6 g. of 0,0-diethyl phosphorodithioic acid for the 0,0-dimethyl acid, 17.6 g. of an oil was obtained which was 0,0-diethyl ( 2 ' , 4 ' - - ' - Ο,Ο-Dimethyl S- ( l-acetylhydantoin-3-yl) methyl phosphorodi-thioate Preparation of 1-Acetylhydantoin - A solution of 300 g. of hydantoin and 300 g. of acetic anhydride was refluxed for 3 hours. Excess anhydride was removed by distillation to a pot temperature of 80°C./18 mm. The residue was heated to reflux with 600 ml of water. On cooling 211.3 g. of white crytals formed m.p. 92-141°C. , N 17.3% (theory for 1-acetylhydan-toin ·Η20 is 17.5%). Recrystallization from alcohol gave 156 g. product m.p. 146-148°C. , N 19.5% (theory 19.7%).
Preparation of l-Acetyl-3-Hydroxymethylhydantoin - A suspension of 59 g. of 1-acetylhydantoin in 88 ml. of water containing 44 g. of 37% aqueous formaldehyde was heated until homogeneous (about 60°C. in 15 minutes). On cooling, 30 g. of white crystals formed m.p. 103-104°C. , N 16.2% and OH (Zerewitinoff) 10.4% (theory is 16.4 and 9.9%, respectively).
Preparation of l-Acetyl-3-Chlorometh lhydantoin - To a suspension of 28.3 g. of l-acetyl-3-hydroxymethylhydantoin in 51 ml of methylene chloride was cooled to 10-15°C. and 34.4 g. of PClg was added over 30 minutes. After standing overnight at room temperature, the methylene chloride was removed at room temperature under aspirator vacuum. Cold water was added to the residue, and the solid removed by filtration weighed 25.2 g., m.p. 108-110°C, CI 18.7% (theory 18.7%).
Preparation of 0,0-Dimethyl S- ( l-Acetylhydantoin-3-yl) methyl Phosphorodithioate - A solution of 12.5 g. of 1-acetyl-3-chloromethylhydantoin and 13.4 g. of ammonium dimethyl phosphorodithioate in 100 ml. acetone was refluxed for 8 hours during which time NH4CI precipitated. The cooled suspension was poured into water, and the organic layer was extracted with ether. residue was topped at 80°C./5 mm. to leave 14.2 g. of yellow viscous liquid, N 8.6% and P 10.8% (theory is 9.0 and 10.0%, respectively) . MR and Infrared absorption spectra were consistent with the proposed structure.
Example 30 0,O-Dimethyl S- ( l-acetyl-5 , 5-dimethylhydantoin-3-yl) methyl phosphorodithioate Following the procedure of Example 29, 11.8 g. 1-acetyl-3-chloromethyl-5 , 5-dimethylhydantoin m.p. 103-105°C. was reacted with 9.2 g. ammonium dimethyl phosphorodithioate and 12.6 g. 0,O-dimethyl S- ( l-acetyl-5 , 5-dimethylhydantoin-3-yl) methyl phosphorodithioate was obtained. It analyzed 8.6% PT' Example 31 0, O-Dimethyl S- ( 1-acetylhydantoin-3-yl) methyl phosphorothioate A mixture of 10 g. of 1-acety1-3-chloromethylhydantoin , 9 g. of ammonium dimethyl monothiophosphate in 50 ml. acetonitrile was refluxed for 8 hours. The cooled reaction mixture was filtere and solvent removed from the filtrate at 80°C./18 mm. The residue was dissolved in hot acetone, the solution cooled and decanted from sludge. Removal of solvent and topping at 80°C./0.5 mm.' left 12 g. of a yellow viscous liquid, P 10.3% and N 10.1% (theory is 10.4 and 9.44%, respectively).
Example 32 0,O-Dimethyl S- (l-acetyl-5 , 5-dimethylhydantoin-3-yl) methyl phosphorothioate Following the procedure of Example 31, 21 g. 1-acetyl-3-chloromethyl-5 , 5-dimethylhydantoin m.p. 103-105°C. was reacted with 17 g. ammonium dimethyl monothiophosphate, and 19.6 g. 0, O-dimethyl S- ( l-acetyl-5 , 5-dimethylhydantoin-3-yl) methyl phosphorothioate was obtained which analyzed 9.9% P. 0 , O-Dimethyl S- ( l-butyrylhydantoin-3-yl) methyl phosphorothioate Following the procedure of Example 31, 15 g. 1-butyryl-3-chloromethylhydantoin was reacted with 11 g. ammonium dimethyl monothiophosphate in acetonitrile reaction medium and 20.8 g. 0,0-dimethyl S- ( l-butyrylhydantoin-3-yl) methyl phosphorothioate was obtained .
Example 34 0,0-Diethyl S- ( l-acetylhydantoin-3-yl) methyl phosphorothiate Following the procedure of Example 31, 10 g. l-acetyl-3-chloromethylhydantoin was reacted with 11 g. ammonium diethyl monothiophosphate in acetonitrile reaction medium and 11.7 g. 0,0-dieth S- ( l-acetylhydantoin-3-yl) methyl phosphorothioate was obtained.
Example 35 0,0-Diethyl S- ( l-acetyl-5 , 5-dimethylhydantoin-3-yl) methyl phos-phorodithioate Following the procedure of Example 31, 11.8 g. 1-acetyl-3-chloromethyl-5 , 5-dimethylhydantoin m.p. 103-105 °C. was reacted with 11.0 g. ammonium diethyl dithiophosphate and 3.6 g. 0,0-diethy S- ( l-acetyl-5 , 5-dimethylhydantoin-3-yl) methyl phosphorodithioate was obtained which analyzed 8.6% P.
The compounds of this invention are used in the impure condition or in a purified condition as essential components of toxic dispersible compositions for control of insects. A dis-pers.ible composition of this type is a concentrate comprising the compound and an effective amount of a dispersing agent.
In the case of a solid dispersible composition, the dispersing agent is a finely divided dispersible inert solid such as is well known in the insecticides art. A typical dis-persible solid of this type is clay. A typical dispersible concentrate contains 10-50% of active toxicant and 50-90% dispersing agent. In the case of a liquid dispersible composition, the emulsifying composition comprising an effective amount of an emul sifying surface active agent and an organic solvent, the latter being present in a concentration sufficient to render the composition fluid.
The solid dispersible compositions are usually also water dispersible, in which case the composition contains toxicant, dispersible solid, and an emulsifying agent in amounts sufficient to bring about a stable dispersion of the toxicant and solid in water. A composition of this type is the well-known dispersible powder.
Suitable dispersing and emulsifying agents are well-known in the art and many are disclosed in Frear, Chemistry of Insecticides, Fungicides, and Herbicides. Suitable solid dispersing agents are inorganic and include talc, attapulgite, prophylite, diatomaceous earth, kaolin, aluminum and magnesium silicates, mont morillonite, Fuller's earth, and their equivalents.
Dispersing agents which are useful in such concentrates are the well-known surface active agents of the anionic, cationic, or nonionic type, and include alkali metal (sodium or potassium) oleates and similar soaps, amine salts of long chain fatty acids (oleates) , sulfonated animal and vegetable oils (fish oils and castor oil) , sulfonated petroleum oils, sulfonated acyclic hydrocarbons, sodium salts of lignin sulfonic acids, alkylnaphthalene sodium sulfonates, sodium lauryl sulfonate, disodium monolauryl-phosphates, sorbitol laurate, pentaerythritol monostearate , glycerol monostearate, polyethylene oxides, ethylene oxide condensates of stearic acid, stearyl alcohol, stearyl amine, rosin amines, dehydroabietyl amine and the like, lauryl amine salts, dehydroabietyl amine salts, lauryl pyridinium bromide, stearyl trimethyi ammonium bromide, cetyl dimethylbenzylammonium chloride, and the like. The aqueous dispersions may thus be made from the The preferred compositions, for spraying on plants infested with insects are those in which water is used as the major component, and a compound of this invention is a minor component. Such aqueous dispersions are usually prepared in the field so as to have a content of 0.5 to 10% by weight of active agent by dispersing a concentrate made up of about 10-90% by weight active agent, about 0.5-10% by weight dispersing agent, and 0-90% by weight inert diluent.
The toxicant compounds of this invention are also adapted to application by low volume aerial spraying by dissolving one or more of said compounds alone or in admixture with a minor amount of another toxicant such as, for example, toxaphene, in sufficient solvent up to a quantity equal to the weight of the total toxic material to produce a solution having a viscosity at 25°C. of 10-50 centipoises, preferably 20-30 centipoises, said solvent consisting essentially of xylene and containing sufficient isophorone, when necessary, to effect complete solubility of the toxicants at the desired viscosity.
The systemically active compounds of this invention are applied to the roots of plants for absorption through the roots, or to the foliage of plants for absorption through the foliage. These compounds are generally applied or used in admixture with a granular solid carrier or a wettable powder or as an aqueous emulsion of the compound itself or of the compound dissolved in an organic solvent or adsorbed on a wettable powder. The composition of a systemically toxic compound of this invention absorbed on a granular solid can be applied along with seeds at planting. In such case, a mixture of the composition and seeds are planted together. The systemi-cally active compounds of this invention also can be applied to the seeds themselves in wettable powders, in aqueous emulsions, seeds germinate. The systemically active compounds can also be added to the soil after the plants to be protected have sprouted. This can be done by directing an aqueous emulsion comprising a systemically active compound of this invention with or without a solid carrier to the locus of the roots in the soil, the toxic compound being carried into the soil by rain or by artificial watering .
The toxicities of the compounds of this invention are illustrated by the data set forth in the following tables. These data relative to each compound were obtained as follows. An emul-sifiable concentrate was made from each of the compounds indicated in the tables by dissolving 1.5 parts of compound in 3 parts of benzene and adding three parts of Tween 20 sorbitol monolaurate polyoxyethylene derivative. The concentrate thus obtained was then dispersed in 150 ml. of water to produce a 1% aqueous emulsion. Emulsions of lower concentrations were obtained by diluting aliquot portions of this emulsion with appropriate quantities of water. These aqueous emulsions were then tested for toxicity relative to selected insects, the test procedure for a specific insect being the same for each compound tested. The test results are summarized in the following tables. The insect mortality values are reported as "%/%" or "%/ppm" . The abbreviation "%/%" refers to the percentage of insects killed by the test compound in aqueous emulsion at the concentration indicated by the second percent sign, which concentration is percent by weight of the emulsion. The abbreviation "%/ppm" refers to the percentage of insects killed by the test compound in aqueous emulsion at the concentration indicated by "ppm" , which concentration is in parts by weight per million parts by weight of emulsion.
Table 1 - Insect Toxicity of Compounds of the Fo MBB PA Ex. R2 R3 R4 R5 Y .:%/% %/% 1 CH3 H CH3 H H S 100/.0025 100/.0025 2 C2H5 H CH3 H H S 100/.001 100/.001 3 CH3 CH3 CH3 H H S 100/.005 100/.005 4 C2H5 CH3 CH3 H H S 100/.001 100/.001 C2H5 H CH3 H H 0 80/.005 100/.001 6 CH3 H CH3 H H 0 100/.001 100/.001 7 CH3 H CH3 CH3 H s 100/.005 100/.005 8 CH3 CH3 H H H s 70/.01 100/.005 9 C2H5 CH3 H H H s 90/.005 100/.005 MBB = Mexican Bean Beetle PA = Pea Aphid R-TSM = Resistant Two-spotted Mite PA-S = Pea Aphid - Systemic TSM-S = Two-spotted Mite - Systemic Table 2 - Insect Toxicity of Compounds of the Formula Compound of •4 ,5 - Example R1 R2 R' R Y Two-spotted Mite - Systemic CH H H H s 100/10 3 11 C2H5 H H H s 100/50 12 CH H CH3 H s 100/10 3 13 C2H5 H CH H s 40/50 3 14 CH3 CH3 CH3 H s 100/50 C2H5 CH3 CH3 H s 80/50 19 C2H5 CH3 H H s 100/50 Table 3 - Insect Toxicity of Compounds of th Formula: H H S 100/.01 100/.005 100/.0025 100 H H s 40/.025 100/.005 100/.005 0 CH3 H s 100/.05 100/.005 100/.005 0 CH3 H s 100/.05 100/.01 0/.D1. 0 CH CH3 s 100/.05 100/.005 100/.01 0 3 CH3 CH3 s 60/.05 100/.005 100/.01 0 H H 0 100/.05 100/.005 100/.005 70 H H s 40/.05 90/.0025 100/.005 0/ H H s 80/.05 100/.005 100/.005 0/ HF House Fly PC MBB - Mexican Bean Beetle CRW PA - Pea Aphid PA-S SAW - Southern Army Worm TSM-S R-TSM - Resistant two -spotted Mite Table 4 - Insect Toxicity of Compounds of the Form Compound of HF MBB PA SAW Example R1 R6 R4 Y % / % % / % % / % % 1 % 29 CH3 CH3 H H S 92/05 30/005 100/005 100/05 CH3 • CH3 CH3 CH3 S 24/05 100/005 80/005 100/05 31 CH3 CH3 H H 0 · 48/05 100/005 100/005 0/. 1 32 CH3 CH3 CH3 C¾ 0 100/05 100/001 100/005 70/05 33 CH3 C3H7 H H 0 100/05 100/005 100/01 100/025 34 CH3 C2H5 H H 0 88/05 100/005 100/001 90/05 C2H5 CH3 CH3 CH3 s 40/025 100/005 100/01 100/.1 Legend: 005 = .005, 05 = .05, 01 = .01 HF - House Fly; MBB - Mexican Bean Beetle; PA - Pea Aphid; SAW - Southern Ar TSM - Two-spotted Mite; PC - Plum Curculio; CRW - Corn Root Worm; PA-S - Pea TSM-S - Two-spotted Mite-Systemic.
From these data, it can be seen that the compounds of this invention have selective contact toxicity for insects. Moreover, it can be seen that the compounds of Examples 1-21,24 and 26-35 have systemic toxicity for the pea aphid.
Thus, this invention provides new and useful insecticides .

Claims (1)

1. C2H5' r6 is CH3' C2H5 or C3H7 and r2' r3 ' r and r5 are H or CH3 , provided (1) when A is R^N, at least one of R2 and RJ is CH3 , and at least one of R and R is H, and (2) when A is R6C0N, R2 is H. * 3. A water dispersible composition according to claim 2, which comprises a dispersing agent therefor. 4. A water dispersible composition according to claim 2, wherein said dispersing agent is an inorganic finely divided surface active solid. 5. A water dispersible composition according to claim 2, wherein said dispersing agent is an organic surface active agent, and said composition comprises an organic solven
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