US3845172A - N-hydrocarboyl phosphoroamido-thioates and phosphoroamidodithioates - Google Patents
N-hydrocarboyl phosphoroamido-thioates and phosphoroamidodithioates Download PDFInfo
- Publication number
- US3845172A US3845172A US00317478A US31747872A US3845172A US 3845172 A US3845172 A US 3845172A US 00317478 A US00317478 A US 00317478A US 31747872 A US31747872 A US 31747872A US 3845172 A US3845172 A US 3845172A
- Authority
- US
- United States
- Prior art keywords
- methyl
- allyl
- hours
- carbon atoms
- alkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- WFFOAQQKQLMGGW-UHFFFAOYSA-N [hydroxy(mercapto)thiophosphoryl]amine Chemical class NP(O)(S)=S WFFOAQQKQLMGGW-UHFFFAOYSA-N 0.000 title description 3
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 9
- 239000001257 hydrogen Substances 0.000 abstract description 9
- 229910052717 sulfur Chemical group 0.000 abstract description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 239000011593 sulfur Chemical group 0.000 abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 80
- -1 trichloroacetylphosphoroamidothioate [N- (diethoxyphosphinothioyl) 2,2,2 trichloroacetamide] Chemical compound 0.000 description 69
- 239000000203 mixture Substances 0.000 description 30
- 239000000047 product Substances 0.000 description 27
- 239000000243 solution Substances 0.000 description 25
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 24
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 19
- 125000004432 carbon atom Chemical group C* 0.000 description 18
- 239000003921 oil Substances 0.000 description 17
- 235000019198 oils Nutrition 0.000 description 17
- 125000000217 alkyl group Chemical group 0.000 description 16
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 14
- 231100000167 toxic agent Toxicity 0.000 description 14
- 239000003440 toxic substance Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 238000002360 preparation method Methods 0.000 description 12
- 239000011541 reaction mixture Substances 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 11
- 241000238631 Hexapoda Species 0.000 description 11
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 11
- 239000007787 solid Substances 0.000 description 10
- 125000003342 alkenyl group Chemical group 0.000 description 9
- 238000000921 elemental analysis Methods 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 238000009472 formulation Methods 0.000 description 8
- 230000000749 insecticidal effect Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000002168 alkylating agent Substances 0.000 description 7
- 229940100198 alkylating agent Drugs 0.000 description 7
- 125000000304 alkynyl group Chemical group 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 7
- 239000002270 dispersing agent Substances 0.000 description 7
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 7
- 235000019341 magnesium sulphate Nutrition 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000004480 active ingredient Substances 0.000 description 6
- 238000005917 acylation reaction Methods 0.000 description 6
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- 159000000000 sodium salts Chemical class 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 241000238876 Acari Species 0.000 description 5
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 5
- 239000012346 acetyl chloride Substances 0.000 description 5
- 239000008346 aqueous phase Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- 231100000419 toxicity Toxicity 0.000 description 5
- 230000001988 toxicity Effects 0.000 description 5
- 241001124076 Aphididae Species 0.000 description 4
- 241001674044 Blattodea Species 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 239000002917 insecticide Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 241000255925 Diptera Species 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 241000607479 Yersinia pestis Species 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- RJBIAAZJODIFHR-UHFFFAOYSA-N dihydroxy-imino-sulfanyl-$l^{5}-phosphane Chemical class NP(O)(O)=S RJBIAAZJODIFHR-UHFFFAOYSA-N 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 description 3
- 231100001225 mammalian toxicity Toxicity 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000000361 pesticidal effect Effects 0.000 description 3
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 241001600408 Aphis gossypii Species 0.000 description 2
- 240000007124 Brassica oleracea Species 0.000 description 2
- 235000003899 Brassica oleracea var acephala Nutrition 0.000 description 2
- 235000011301 Brassica oleracea var capitata Nutrition 0.000 description 2
- 235000001169 Brassica oleracea var oleracea Nutrition 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 150000001266 acyl halides Chemical class 0.000 description 2
- 230000010933 acylation Effects 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004495 emulsifiable concentrate Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 235000014666 liquid concentrate Nutrition 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000012875 nonionic emulsifier Substances 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 150000003871 sulfonates Chemical class 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 1
- 125000000069 2-butynyl group Chemical group [H]C([H])([H])C#CC([H])([H])* 0.000 description 1
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 1
- 125000000474 3-butynyl group Chemical group [H]C#CC([H])([H])C([H])([H])* 0.000 description 1
- WGCICQJXVYFFCA-UHFFFAOYSA-N 3-iodoprop-1-yne Chemical compound ICC#C WGCICQJXVYFFCA-UHFFFAOYSA-N 0.000 description 1
- ISULZYQDGYXDFW-UHFFFAOYSA-N 3-methylbutanoyl chloride Chemical compound CC(C)CC(Cl)=O ISULZYQDGYXDFW-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 125000006042 4-hexenyl group Chemical group 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
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- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 241000255967 Helicoverpa zea Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000500891 Insecta Species 0.000 description 1
- 241000257159 Musca domestica Species 0.000 description 1
- 241000377938 Mycobacterium phage Pinto Species 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
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- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- DUFXJOMADJUMJK-UHFFFAOYSA-N [amino(hydroxy)phosphinothioyl] acetate Chemical compound CC(=O)OP(N)(O)=S DUFXJOMADJUMJK-UHFFFAOYSA-N 0.000 description 1
- NYGXYXSBRYGEEM-UHFFFAOYSA-N [amino(hydroxy)phosphinothioyl] hexanoate Chemical compound CCCCCC(=O)OP(=S)(N)O NYGXYXSBRYGEEM-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- ORWKVZNEPHTCQE-UHFFFAOYSA-N acetic formic anhydride Chemical compound CC(=O)OC=O ORWKVZNEPHTCQE-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
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- 238000005804 alkylation reaction Methods 0.000 description 1
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 1
- HFEHLDPGIKPNKL-UHFFFAOYSA-N allyl iodide Chemical compound ICC=C HFEHLDPGIKPNKL-UHFFFAOYSA-N 0.000 description 1
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- KVVXFPNTQJIKNH-UHFFFAOYSA-N bis(prop-2-enyl) sulfate Chemical compound C=CCOS(=O)(=O)OCC=C KVVXFPNTQJIKNH-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- WQAQPCDUOCURKW-UHFFFAOYSA-M butane-1-thiolate Chemical compound CCCC[S-] WQAQPCDUOCURKW-UHFFFAOYSA-M 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
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- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- QUJIVWINNPEYAS-UHFFFAOYSA-N dihexyl sulfate Chemical compound CCCCCCOS(=O)(=O)OCCCCCC QUJIVWINNPEYAS-UHFFFAOYSA-N 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000002561 ketenes Chemical class 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical class [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 235000011160 magnesium carbonates Nutrition 0.000 description 1
- 238000006263 metalation reaction Methods 0.000 description 1
- NNKVPIKMPCQWCG-UHFFFAOYSA-N methamidophos Chemical compound COP(N)(=O)SC NNKVPIKMPCQWCG-UHFFFAOYSA-N 0.000 description 1
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 1
- DRFWNARXWNRANJ-UHFFFAOYSA-N n-[methoxy(methylsulfanyl)phosphoryl]butanamide Chemical compound CCCC(=O)NP(=O)(OC)SC DRFWNARXWNRANJ-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 230000001069 nematicidal effect Effects 0.000 description 1
- 239000005645 nematicide Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000005648 plant growth regulator Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- SUVIGLJNEAMWEG-UHFFFAOYSA-N propane-1-thiol Chemical compound CCCS SUVIGLJNEAMWEG-UHFFFAOYSA-N 0.000 description 1
- YORCIIVHUBAYBQ-UHFFFAOYSA-N propargyl bromide Chemical compound BrCC#C YORCIIVHUBAYBQ-UHFFFAOYSA-N 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052903 pyrophyllite Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 235000001508 sulfur Nutrition 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- WQYSXVGEZYESBR-UHFFFAOYSA-N thiophosphoryl chloride Chemical compound ClP(Cl)(Cl)=S WQYSXVGEZYESBR-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000002110 toxicologic effect Effects 0.000 description 1
- 231100000723 toxicological property Toxicity 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical class [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 229940086542 triethylamine Drugs 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- 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 Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/22—Amides of acids of phosphorus
- C07F9/24—Esteramides
- C07F9/2454—Esteramides the amide moiety containing a substituent or a structure which is considered as characteristic
- C07F9/2479—Compounds containing the structure P(=X)n-N-acyl, P(=X)n-N-heteroatom, P(=X)n-N-CN (X = O, S, Se; n = 0, 1)
- C07F9/2487—Compounds containing the structure P(=X)n-N-acyl, P(=X)n-N-heteroatom, P(=X)n-N-CN (X = O, S, Se; n = 0, 1) containing the structure P(=X)n-N-C(=X) (X = O, S, Se; n = 0, 1)
Definitions
- N-acyl derivatives of O hydrocarbyl S hydrocarbyl phosphoroamidothioates and S hydrocarbyl S hydrocarbyl phosphoroamidodithioates combine a high degree of insecticidal activity with relatively low mammalian toxicity. This finding is especially surprising since structural modifications which decrease mammalian toxicity normally also decrease insecticidal activity proportionately. This unique combination may permit these novel acylated derivatives to be used to control insects in environments in which the corresponding non-acylated compounds could not be used.
- the phosphoroamidothioates and phosphoroamidodithioates of this invention are represented by the formula Patented Oct. 29, 1974 o R-Y o i l-nu wherein R and R individually are alkyl, alkenyl or alkynyl of up to 6 carbons, R is hydrogen, alkyl of l to 18 carbon atoms, cycloalkyl of 3 to 8 carbon atoms, alkenyl of 2 to 18 carbon atoms or alkynyl of 3 to 18 carbon atoms, R is hydrogen or alkyl of 1 to 6 carbon atoms, and Y is oxygen or sulfur.
- Representative alkyl groups which 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, Z-butenyl, isobutenyl, 3-heXenyl, etc.
- Representative alkynyl of 3 to 6 carbon atoms which R and R may represent include 2-propynyl, 2-butynyl, 3hexynyl, etc.
- Preferred R and R groups are alkyl of 1 to 3 carbon atoms, especially methyl.
- the preferred R group is hydrogen.
- Representative alkyl R groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, amyl, heptyl, 3-ethylamyl, Z-methylhexyl, n-hexyl, n-octyl, 4methylheptyl, n-nonyl, n-decyl, S-ethyloctyl, n-undecyl, n-dodecyl, 8- methyldecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, and n-octadecyl.
- Representative cycloalkyl groups are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, Z-methylcyclohexyl, cycloheptyl and cyclooctyl.
- Representative alkenyl R groups are vinyl, propenyl, 3-butenyl, 2-butenyl, 4-pentenyl, 4-hexenyl, S-hexenyl, S-heptenyl, 3-heptenyl, 4-octenyl, 7-octenyl, S-nonenyl, 4-nonenyl, 7-nonenyl, 9-decenyl, 6-decenyl, ll-dodecenyl, 8-undecenyl, 8-pentadecenyl, 8-heptadecenyl, S-heptadecenyl, 10-heptadecenyl.
- Representative alkynyl R groups are propargyl, 3-butynyl, S-hexynyl, 7-decynyl, 8-octadecynyl, etc.
- the preferred R groups have up to 11 carbon atoms.
- the most preferred R groups are alkyl, particularly n-alkyl.
- N alkanoylphosphoroamidothioates of formula (I) are:
- O-methyl-S-methyl-N-formylphosphoroamidothioate O-methyl-S-allyl-N-acetylphosphoroamidothioate, 'O-methyl-S-methyl-N-methyl-N-acetylphosphoroamidothioate, O-allyl-S-allyl-N-propionylphosphoroamidothioate, O-methyl-S-methyl-N-butyrylphosphoroamidothioate, O-ethyl-S-hexyl-N-isobutyrylphosphoroamidothioate, O-methyl-S-methyl-N-pentanoylphosphoroamidothioate, O-propargyl-S-propargyl-N-hexanoylphosphoroamidothioate, 0-methyl-S-methyl-N-heptanoylphosphoroamidothioate, O-methyl-S-methyl-N-isoprop
- N-alkenoylphosphoroamidothioates of formula (I) are:
- N alkynoylphosphoroamidothioates of formula (I) are:
- N-formylphosphoroamidothioates of formula (I) are:
- O-methyl-S-methyl-N-isopropyl-N-formylphosphoroamidothioate O-allyl-S-allyl-N-formylphosphoroamidothioate, O-propargyl-S-methyl-N-formylphosphoroamidothioate, O-ethyl-S-ethyl-N-ethyl-N-formylphosphoroarnidothioate, O-isopropyl-S-isopropyl-N-formylphosphoroamidothioate, O-allyl-S-propargyl-N-forrnylphosphoroamidothioate,
- N-alkanoylphosphoroamidodithioates of formula (I) are:
- N-cycloalkylcarbonylphosphoroamidodithioates of formula (I) are:
- N-alkenoylphosphoroamidodithioates of formula (I) are:
- N-alkynoylphosphoroamidodithioates of formula (I) are:
- N-formylphosphoroamidodithioates of formula (I) are:
- the preferred compounds of formula (I) are O,S-dialkyl-N-alkanoylphosphoroarnidothioates wherein R and R are alkyl of 1 to 3 carobn atoms, R is lower n-alkyl of 1 to 6 carbon atoms, and 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-a'lkyl-S-a1kylphosphoroamidothioates and their preparation are disclosed in US. Pat. No. 3,309,266.
- O-alkyl-S-unsaturated hydrocarbyl phosphoroarnidothioates and their preparation are disclosed in US. 3,649,723.
- acylating agents such as acyl halides, ketenes and acid anhydrides and conventional acylating conditions may be used in this reaction.
- This acylation reaction (illustrated with an acyl halide as the acylating agent) may be represented by the following equation:
- R, R ,R R and Y have the same significance as previously defined.
- the acylation reaction (1) will usually be carried out at about 0 to 60 C. in the presence of solvents such as methylene chloride, chloroform, tetrahydrofuran 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-dihydrocarbylphosphoroamidothionate and then isomerizing the resulting N-acylphosphoroamidothionate with an alkylating agent to produce the O-hydrocarbyl-S-hydrocarbyl N acylphosphoroamidothioate.
- This reaction scheme is represented (using an acyl chloride as the acylating agent) by the following equations:
- 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. 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. 3,309,266 for reacting an QO-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 and dialkenyl sulfates, e.g., dimethyl sulfate, diethyl sulfate, diallyl sulfate and dihexyl sulfate.
- iodides e.g., methyl iodide, ethyl iodide, allyl iodide, propargyl iodide, butyl iodide, etc.
- dialkyl and dialkenyl sulfates e.g., dimethyl sulfate, diethyl sulfate, diallyl
- 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 (R SNa) to form the S-sodium salt and alkylating the S-sodium salt to form the O,S-compound (VII).
- Ths reaction scheme is represented by the following equations:
- 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 10-100" C. 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 (D0 is effected by mixing substantially equimolar amounts of the sodium salt (IX) and the alkylating agent R in an inert solvent at a temperature in the range of 0-80" C., preferably 25-60 C.
- the product (VII) is isolated by conventional methods, e.g., extraction, chromatography, etc.
- 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 0 to 15 C., preferably 0 to 5 C.
- the reaction time necessary to complete the addition of the mercaptan to the phosphorous oxychloride will range from about 1 to 10 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 reacting gaseous ammonia or an amine with the S-hydrocarbyl-S-hydrocarbylphosphorochloridodithioate according to the following equation:
- 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 75 C., preferably 40 to 60 C. Completion of the reaction is indicated by cessation of ammonium chloride amine hydrochloride precipitation.
- the crude product can be isolated by conventional techniques such as filtration, extraction, distillation, chromatography, etc.
- the 0,0 dihydrocarbylphosphoroamidothioate compounds used to prepare the compounds of the invention are prepared by the following reactions:
- Example 1 14.1 g. (0.1 mole) of O-methyl-S-methylphosphoroamidothioate was dissolved in 100 ml. benzene in a flask. 7.85 g. (0.1 mole) acetylchloride was added to this solution. This mixture was brought to refluxHCl being evolved at that point. This mixture was then stirred overnight at ambient temperature. Supernatant liquid was decanted and the solvent was stripped off at 3040 C., 12 mm. Hg. An oil remained which solidified on standing. This solid was filtered and washed with ether to yield 7 g. of impure O-methyl-S-methyl-N-acetylphosphoroamidothioate. This material melted at 64-68 C. and had the following analysis:
- Example 2 176 g. (1.25 moles) of O-methyl-S-methyl phosphoroamidothionate was dissolved in 300 ml. of dichloromethane and charged to a 1 liter flask. 98 g. (1.25 moles) of acetylchloride dissolved in 100 ml. of dichloromethane was added. The solution was stirred, warmed to 33 C., held at that temperature for 4 hours, then an additional 98 g. (1.25 moles) of acetylchloride was added. The mixture was held at room temperature for 18 hours and then added to 500 ml. of ice water. The phases were separated and the aqueous phase was extracted with four 200 ml.
- Example 3 6 g. of 0,0 diethyl N acetylphosphoroamidothionate was mixed with 10 ml. ethyl iodide in a flask. This mixture was refluxed for hours. The resulting reaction mixture was stripped at 80 C., 30 mm. Hg, leaving 4.5 g. oil which crystallized on standing.
- Example 4 30 g. of 0,0-dimethylphosphoroamidothioate and 41 g. of n-decanoyl chloride were dissolved in 120 ml. of methylene chloride and refluxed for 2 hours. After treatment with water to remove acidic by-products, the solution was dried over magnesium sulfate and stripped to give 60.4 g. of 0,0-dimethyl N decanoyl phosphoroamidothioate (96% yield).
- Example 7 Preparation of O,S-dimethyl-N-formylphosphoroamidothioate.A 10 ml. sample of 98% formic acid was added slowly to 20 ml. of acetic anhydride at C. To the resulting formic acetic anhydride containing solution was added 21.2 g. (0.15 mole) 0,0-dimethylphosphoroamidothioate, 30 ml. methylene dichloride and 0.5 ml. phosphoric acid. The resulting reaction mixture was stirred at about 25 C. for 23 hours, then mixed with 15 g. ice and 30 ml. saturated ammonium chloride solution. The aqueous mixture was neutralized with 15% ammonium hydroxide solution.
- the aqueous phase was extracted with methylene chloride.
- the methylene chloride extract and the organic phase were combined, washed with saturated ammonium chloride solution, dried over magnesium sulfate and evaporated under reduced pressure to give 25 g. of 0,0-dimethyl-N formylphosphoroamidothioate product.
- the nuclear magnetic resonance spectrum showed that the product contained about 0,0-dimethyl-N-acetylphosphoroamidothioate.
- Analysis for C H NO PS showed:
- Example 8 Preparation of S-sodium-O-methyl N hexanoylphosphoroamidothioate.0,0 dimethyl-N-hexanoylphosphoroamidothioate, 69 g. (0.28 mol), was dissolved in 100 m1. methanol. To this solution was added 23 g. (0.29 mol) of 50% aqueous sodium hydroxide. The resulting solution was stirred for minutes, then 26.3 g. (0.29
- Example 9 Preparation of S-allyl-O-methyl-N-hexanoylphosphoroamidothioate.--A mixture of 7 g. S-sodium-O-methyl-N- hexanoylphosphoroamidothioate (prepared as described in Example 8) and 30 g. allyl bromide was refluxed for 3.5 hours and allowed to stand at about 25 C. for about 16 hours. The solids in the reaction mixture were filtered and washed with methylene dichloride. The filtrate and methylene dichloride washes were evaporated under reduced pressure to give the product as a viscous oil. Elemental analysis on the product is tabulated in Table I.
- Example 10 Preparation of S-propargyl-O-methyl-N-hexanoylphosphoroamidothioate.
- a mixture of 7 g. S-sodium-O-methyl-N-hexanoylphosphoroamidothioate (prepared as described in Example 8) and 30 g. propargyl bromide was refluxed for 3 hours and then allowed to stand at about 25 C. for about 17 hours.
- the reaction mixture was diluted with methylene dichloride and filtered.
- the filtrate was evaporated under reduced pressure and the residue was dissolved in benzene and filtered. Hexane was then added to benzene solution to precipitate 5.7 g. of the product, m.p. 6365 C. Elemental analysis on the product is tabulated in Table I.
- Example 11 Preparation of O,S-dimethyl-N-octadecanoylphosphoroamidothioate-A mixture of 7.8 g. 0,0-dimethyl-N-octadecanoylphosphoroamidothioate, 1.8 g. dimethyl sulfate and 20 ml. chloroform was refluxed for 3 hours. The reaction mixture was cooled and then filtered. The filtrate was evaporated under reduced pressure to give a solid. The solid was recrystallized from methylene dichloride to give the product as fine white crystals, m.p. 5762 C. Elemental analysis on the product is tabulated in Table I.
- Example 12 Preparation of O,S dimethyl-N-isovaleroylphosphoroamidothioate.-A mixture of 35 g. O,S-dimethylphosphoroamidothioate, 21.7 g. isovaleroyl chloride, ml. methylene dichloride and 8 g. magnesium sulfate was refluxed for 2 hours. Large amounts of hydrochloric acid were evolved. The reaction mixture was diluted with 200 ml. water and neutralized with aqueous sodium carbonate solution. The aqueous phase was separated and extracted with methylene dichloride. The organic layers were combined, washed with Water, dried over magnesium sulfate, and filtered. The crude product separated out as a viscous oil. The oil was crystallized from methylene dichloride/ hexane to give the product, m.p. 7578 C. Elemental analysis on the product is tabulated in Table 1.
- Example 13 Preparation of O,S-dimethyl-N-undecynoylphosphoroamidothioate.
- the crude reaction mixture was chromatographed on silica gel (hexane/ methylene chloride/ acetone eluants) to give the product, m.p. 34-40 C. Elemental analysis on the product is tabulated in Table I.
- Example 14 Preparation of O,S-dimethyl N cyclohexylcarbonylphosphoroamidothioate.--The product was prepared by acylating 14.1 g. (0.1 mole) O,S-dimethylphosphoro- 12 1 placed in a rnicrosprayer (atomizer). A random mixture of anesthetized male and female roaches 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.
- UTILITY 60 male and female flies was placed in a container and 55
- the compounds of this invention were tested as follows to illustrate their insecticidal activity. Test results are reported in Table 11.
- Two-spotted mites (Tetramuchus urticae): An acetone solution of the candidate toxicant containing a small amount of nonionic emulsifier was diluted with water to p.p.m. 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): An acetone solution of the candidate toxicant containing a small amount of nonionic emulsifier was diluted with Water to 30 p.p.m. Cucumber leaves infested with the cotton aphids were dipped in the toxicant solution. Mortality readings were then taken after 24 hours.
- O-methyl-S-methyl-N- acetylphosphoroamidothioate showed excellent activity 40 against the following insects:
- Toxicity index is a measure of a compounds safety relative to its insecticidal activity. It is defined here as:
- LD insects p.p.m.
- LD rats-oral mg/kg.
- LD insects is the least dosage that will provide mortality of the test insect. It is determined by testing the toxicants at various concentrations by the above-described 50 testing and plotting the results. LD rats-ora is the lowest dosage that will kill 50% of the test rodents in standard oral application tests.
- the toxicity indexes of O- methyl-S-methyl-N-acetylphosphoroamidothioate and its non-acylated analog O-methyl-S-methylphosphoroamidothioate, determined as above, are reported in Table III below. Also reported are the toxicity indexes of other 0- methyl-S-methyl-N-acylphosphoroamidothioates.
- the compounds of this invention are toxic to a variety of crop and household pests, in addition to the typical pests exemplified above. Like most agricultural chemicals, they are not usually applied full strength, but are generally incorporated with conventional biologically inert extenders or carriers normally employed for facilitating dispersion of active ingredients for agricultural chemical applications, recognizing the accepted fact that the formulation and mode of application may affect the activity of a material.
- the toxicants of this invention may be applied as sprays, dusts, or granules to the insects, their environment or hosts susceptible to insect attack. They may be formulated as granules of large particle size, as powdery dusts, as wettable powders, as emulsifiable concentrates, as solutions, or as any of several other known types of formulations, depending on the desired mode of application.
- Wettable powders are in the form of finely divided particles which disperse readily in water or other dispersant. These compositions normally contain from 80% toxicant and the rest inert material which includes dispersing agents, emulsifying agents, and wetting agents. The powder may be applied to the soil as a dry dust or preferably as a suspension in water. Typical carriers include fullers earth, kaolin clays, silicas, and other highly absorbent, readily wet, inorganic diluents.
- Typical wetting, dispersing, or emulsifying agents used in agricultural formulations include, for example, the alkyl and alkylaryl sulfonates and sulfonates and their sodium salts; alkylamide sulfonates, including fatty methyl taurides; alkylaryl polyether alcohols, sulfated higher alcohols, and polyvinyl alcohols; polyethylene oxides; sulfonated animal and vegetable oils; sulfonated petroleum oils; fatty acid esters of polyhydric alcohols and the ethylene oxide addition products of such esters; and the addition products of long chain mercaptans and ethylene oxide.
- the surface active agent when used, normally comprises from one percent to fifteen percent by weight of the pesticidal composition.
- Dusts are freely flowing admixtures of the active ingredient with finely divided solids such as talc, natural clays, kieselguhr, pyrophyllite, chalk, diatomaceous earths, calcium phosphates, calcium and magnesium carbonates, sulfur, lime, flours, and other organic and inorganic solids which act as dispersants and carriers for the toxicant. These finely divided solids have an average particle size of less than about fifty microns.
- a typical dust formulation useful herein contains 75% silica and 25% of the toxicant.
- Useful liquid concentrates include the emulsifiable concentrates, which are homogeneous liquid or paste compositions which are readily dispersed in water or other dispersant, and may consist entirely of the toxicant with a liquid or solid emulsifying agent, or may also contain a liquid carrier, such as xylene, heavy aromatic naphthas, isophorone, and other non-volatile organic solvents.
- emulsifiable concentrates which are homogeneous liquid or paste compositions which are readily dispersed in water or other dispersant, and may consist entirely of the toxicant with a liquid or solid emulsifying agent, or may also contain a liquid carrier, such as xylene, heavy aromatic naphthas, isophorone, and other non-volatile organic solvents.
- a liquid carrier such as xylene, heavy aromatic naphthas, isophorone, and other non-volatile organic solvents.
- compositions for insecticidal applications include simple solutions of the active ingredient in a dispersant in which it is completely soluble at the desired concentration, such as acetone, alkylated naphthalenes, xylene, or other organic solvents.
- Granular formulations, wherein the toxicant is carried on relatively coarse particles, are of particular utility for aerial distribution or for penetration of cover crop canopy.
- Baits, prepared by mixing solid or liquid concentrates of the toxican with a suitable food, such as a mixture of cornmeal and sugar, are useful formulations for control of insect pests.
- Pressurized sprays typically aerosols wherein the active ingredient is dispersed in finely divided form as a result of vaporization of a low-boiling dispersant solvent carrier, such as the Freons, may also be used. All of these techniques for formulating and applying the active ingredient are well known in the art.
- the percentages by weight of the toxicant may vary according to the manner in which the composition is to be applied and the particular type of formulation, but in general comprises 0.5 to of the toxicant by weight of the pesticidal composition.
- the pesticidal compositions may be formulated and applied with other active ingredients, including other nematocides, insecticides, fungicides, bactericides, plant growth regulators, fertilizers, etc.
- other active ingredients including other nematocides, insecticides, fungicides, bactericides, plant growth regulators, fertilizers, etc.
- an effective amount and concentration of the toxicants of this invention is, of course, employed.
- insecticide and insect refer to their broad and commonly understood usage rather than to those creatures which in the strict biological sense are classified as insects.
- insect is used not only to include small invertebrate animals belonging to the class Insecta, 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.
- R is alkenyl or alkynyl of up to 6 carbon atoms
- R is alkyl, alkenyl or alkynyl of up to 6 carbon atoms
- R is hydrogen or alkyl of 1 to 6 carbon atoms
- R is hydrogen, alkyl of 1 to 18 carbon atoms, cycloalkyl of 3 to 8 carbon atoms, alkenyl of 2 to 18 carbon atoms or alkynyl of 3 to 18 carbon atoms
- Y is oxygen or sulfur.
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Abstract
1. A COMPOUND OF THE FORMULA
R1-S-P(=O)(-Y-R)-N(-R3)-CO-R3
WHEREIN R IS ALKENYL OR ALKYNYL OF UP TO 6 CARBON ATOMS, R1 IS ALKYL, ALKENYL OR ALKYNYL OF UP TO 6 CARBON ATOMS, R3 IS HYDROGEN OR ALKYL OF 1 TO 6 CARBON ATOMS AND R2 IS HYDROGEN, ALKYL OF 1 TO 18 CARBON ATOMS, CYCLOALKYL OF 3 TO 8 CARBON ATOMS, ALKENYL OF 2 TO 18 CARBON ATOMS OR ALKYNYL OF 3 TO 18 CARBON ATOMS AND Y IS OXYGEN OR SULFUR.
R1-S-P(=O)(-Y-R)-N(-R3)-CO-R3
WHEREIN R IS ALKENYL OR ALKYNYL OF UP TO 6 CARBON ATOMS, R1 IS ALKYL, ALKENYL OR ALKYNYL OF UP TO 6 CARBON ATOMS, R3 IS HYDROGEN OR ALKYL OF 1 TO 6 CARBON ATOMS AND R2 IS HYDROGEN, ALKYL OF 1 TO 18 CARBON ATOMS, CYCLOALKYL OF 3 TO 8 CARBON ATOMS, ALKENYL OF 2 TO 18 CARBON ATOMS OR ALKYNYL OF 3 TO 18 CARBON ATOMS AND Y IS OXYGEN OR SULFUR.
Description
United States Patent O 3,845,172 N HYDROCARBOYL PHOSPHOROAMIDO- THIOATES AND PHOSPHOROAMIDODI- THIOATES Philip S. Magee, Ignatio, Calif., assignor to Chevron Research Company, San Francisco, Calif.
No Drawing. Continuation-impart of application Ser. No. 148,139, May 28, 1971, which is a Continuation-impart of application Ser. No. 13,846, Feb. 24, 1970, now Patent No. 3,716,600, which in turn is a continuationin-part of abandoned application Ser. No. 810,383, Mar. 25, 1969. This application Dec. 21, 1972, Ser. No. 317,478 The term of this patent subsequent to Feb. 13, 1990,
has been disclaimed Int. Cl. A01n 9/36; C07f 9/24 US. Cl. 260-956 8 Claims ABSTRACT OF THE DISCLOSURE N-hydrocarboyl derivatives of 0,8 dihydrocarbylphosphoroamidothioates and 8,8 dihydrocarbylphosphoroamidodithioates have a high degree of insecticidal activity with relatively low mammalian toxicity.
CROSS-REFERENCE TO RELATED APPLICATIONS This application is a continuation-in-part of US. Ser. No. 148,139, filed May 28, 1971, which is a continuationin-part of US. Ser. No. 13,846, filed Feb. 24, 1970, now US. Pat 3,716,600, which, in turn, is a continuation-inpart of US. Ser. No. 810,383, filed Mar. 25, 1969, now abandoned.
DESCRIPTION OF THE PRIOR ART US. 3,309,266 teaches that O-alkyl S alkyl phosphoromidothioates are insecticidal. US. 3,649,723 teaches that O alkyl S unsaturated hydrocarbylphosphoromidothioates are insecticidal. US. 3,201,446 teaches that 0,0- diethyl N trichloroacetylphosphoroamidothioate [N- (diethoxyphosphinothioyl) 2,2,2 trichloroacetamide] is useful as an insecticide. Russian Pat. 253,483, issued on Sept. 30, 1969 to G. V. Protopopova et al., discloses the use of 0,8 dialkyl N alkylthiocarbonylphosphoroamidothioates, e.g.,
CHaO\(T) O PNH--S C2115 CHaS as insecticides. L. Almasi et al., Chem. Berg, 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 According to this invention it has been generally found that N-acyl derivatives of O hydrocarbyl S hydrocarbyl phosphoroamidothioates and S hydrocarbyl S hydrocarbyl phosphoroamidodithioates combine a high degree of insecticidal activity with relatively low mammalian toxicity. This finding is especially surprising since structural modifications which decrease mammalian toxicity normally also decrease insecticidal activity proportionately. This unique combination may permit these novel acylated derivatives to be used to control insects in environments in which the corresponding non-acylated compounds could not be used.
The phosphoroamidothioates and phosphoroamidodithioates of this invention are represented by the formula Patented Oct. 29, 1974 o R-Y o i l-nu wherein R and R individually are alkyl, alkenyl or alkynyl of up to 6 carbons, R is hydrogen, alkyl of l to 18 carbon atoms, cycloalkyl of 3 to 8 carbon atoms, alkenyl of 2 to 18 carbon atoms or alkynyl of 3 to 18 carbon atoms, R is hydrogen or alkyl of 1 to 6 carbon atoms, and Y is oxygen or sulfur.
Representative alkyl groups which 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, Z-butenyl, isobutenyl, 3-heXenyl, etc. Representative alkynyl of 3 to 6 carbon atoms which R and R may represent include 2-propynyl, 2-butynyl, 3hexynyl, etc. Preferred R and R groups are alkyl of 1 to 3 carbon atoms, especially methyl. The preferred R group is hydrogen.
Representative alkyl R groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, amyl, heptyl, 3-ethylamyl, Z-methylhexyl, n-hexyl, n-octyl, 4methylheptyl, n-nonyl, n-decyl, S-ethyloctyl, n-undecyl, n-dodecyl, 8- methyldecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, and n-octadecyl. Representative cycloalkyl groups are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, Z-methylcyclohexyl, cycloheptyl and cyclooctyl.
Representative alkenyl R groups are vinyl, propenyl, 3-butenyl, 2-butenyl, 4-pentenyl, 4-hexenyl, S-hexenyl, S-heptenyl, 3-heptenyl, 4-octenyl, 7-octenyl, S-nonenyl, 4-nonenyl, 7-nonenyl, 9-decenyl, 6-decenyl, ll-dodecenyl, 8-undecenyl, 8-pentadecenyl, 8-heptadecenyl, S-heptadecenyl, 10-heptadecenyl. Representative alkynyl R groups are propargyl, 3-butynyl, S-hexynyl, 7-decynyl, 8-octadecynyl, etc.
The preferred R groups have up to 11 carbon atoms. The most preferred R groups are alkyl, particularly n-alkyl.
Representative N alkanoylphosphoroamidothioates of formula (I) are:
O-methyl-S-methyl-N-formylphosphoroamidothioate, O-methyl-S-allyl-N-acetylphosphoroamidothioate, 'O-methyl-S-methyl-N-methyl-N-acetylphosphoroamidothioate, O-allyl-S-allyl-N-propionylphosphoroamidothioate, O-methyl-S-methyl-N-butyrylphosphoroamidothioate, O-ethyl-S-hexyl-N-isobutyrylphosphoroamidothioate, O-methyl-S-methyl-N-pentanoylphosphoroamidothioate, O-propargyl-S-propargyl-N-hexanoylphosphoroamidothioate, 0-methyl-S-methyl-N-heptanoylphosphoroamidothioate, O-methyl-S-methyl-N-isopropyl-N-octanoylphosphoroamidothioate, O-methyl-S-pentyl-N-decanoylphosphoroamidothioate, O-methyl-S-methyl-N-dodecanoylphosphoroamidothioate. Representative N cycloalkylcarbonylphosphoroamidothioates of formula (I) are:
O-methyl-S-methyl-N-cyclopropylcarbonylphosphoroamidothioate,
O-methyl-S-allyl-N-cyclohexylcarbonylphosphoroamidothioate,
O-propargyl-S-propargyl-N-methyl-N-cyclooctylcarbonylphosphoroamidothioate,
etc.
Representative N-alkenoylphosphoroamidothioates of formula (I) are:
O-methyl-S-methyl-N-acrylylphosphoroamidothioate, O-methyl-S-methyl-N-3-butenoylphosphoroamidothioate, O-methyl-S-methyl-N-isobuteno-ylphosphoroamidothioate, O-allyl-S-allyl-N-methyl-N-3-pentenoylphosphoroamidothioate, 'O-propargyl-S-methyl-N-4-pentenoylphosphoroamidothioate, O-methyl-S-methyl-N-6-heptenoylphosphoroamidothioate, O-methyl-S-methyl-N-7-octenoylphosphoroamidothioate, O-methyl-S-methyl-N-l 1-dodecenoylphosphoroamidothioate,
etc.
Representative N alkynoylphosphoroamidothioates of formula (I) are:
O-methyl-S-propyl-N-isopropyl-N-propynoylphosphoroamiclothioate, O-allyl-S-allyl-N-2-butynoylphosphoroamidothioate, O-propargyl-S-hexyl-N-9-decynoylphosphoroamidothioate, O-propyl-S-allyl-N-6-dodecynoylphosphoroamidothioate,
etc.
Representative N-formylphosphoroamidothioates of formula (I) are:
O-methyl-S-methyl-N-isopropyl-N-formylphosphoroamidothioate, O-allyl-S-allyl-N-formylphosphoroamidothioate, O-propargyl-S-methyl-N-formylphosphoroamidothioate, O-ethyl-S-ethyl-N-ethyl-N-formylphosphoroarnidothioate, O-isopropyl-S-isopropyl-N-formylphosphoroamidothioate, O-allyl-S-propargyl-N-forrnylphosphoroamidothioate,
etc.
Representative N-alkanoylphosphoroamidodithioates of formula (I) are:
S-methyl-S-methyl-N-formylphosphoroamidodithioate, S-methyl-S-allyl-N-acetylphosphoroamidodithioate, S-methyl-S-methyl-N-methyl-N-acetylphosphoroamidodiothioate, S-allyl-S-allyl-N-propionyl-phosphoroamidodithioate, S-methyl-S-methyl-N-butyrylphosphoroamidodithioate, S-ethyl-S-heXyl-N-isobutyrylphosphoroamidodithioate, S-methyl-S-methyl-N-pentanoylphosphoroamidodithioate, S-propargyl-S-propargyl-N-hexanoylphosphoroamido dithioate, S-methyl-S-methyl-N-heptanoylphosphoroamidodithioate, S-methyl-S-rnethylN-isopropyl-N-octanoylphosphoroamidodithioate, S-methyl-S-pentyl-N-decanoylphosphoroamidodithioate, S-methyl-S-methyl-N-dodecanoylphosphoroamidodithioate,
etc.
Representative N-cycloalkylcarbonylphosphoroamidodithioates of formula (I) are:
S-methyl-S-methyl-N-cyclopropylcarbonylphosphoroamidodithioate,
S-methyl-S-a1lyl-N-cyclohexylcarbonylphosphoroamidodithioate,
S-progaryl-S-propargyl-N-methyl-N-cyclooctylcarbonylphosphoroamidodithioate,
etc.
Representative N-alkenoylphosphoroamidodithioates of formula (I) are:
S-propargyl-S-propargyl-N-methyl-Ncyclooctylcarbonyl- S-methyl-S-methyl-N-3-butenoylphosphoroamidodithioate,
S-methyl-S-methyl-N-isobutenoylphosphoroamidodithioate,
S-allyl-S-allyl-N-methyl-N-3-pentenoylphosphoroamidodithioate,
S-propargyl-S-methyl-N-4-pentenoylphosphoroamidodithioate,
S-methyl-S-methyl-N-6-heptenoylphosphoroamidodithioate,
S-methyl-S-methyl-N-7-octenoylphosphoroamidodithioate,
S-methyl-S-methyl-N-l l-dodecenoylphosphoroamidodi thioate,
etc.
Representative N-alkynoylphosphoroamidodithioates of formula (I) are:
S-rnethyl-S-propyl-N-isopropyl-N-propynoylphosphoroamidodithioate,
S-allyl-S-allyl-N-2-butynoylphosphoroarnidodithioate,
S-propargyl-S-hexyl-N*9-decynoylphosphoroamidodithioate,
S-propyl-S-allyl-N-6-dodecynoylphosphoroamidodithioate,
etc.
Representative N-formylphosphoroamidodithioates of formula (I) are:
S-methy1S-methyl-N-isopropyl-N-formylphosphoroarnidodithioate, S-allyl-S-allyl-N-formylphosphoroamidodithioate, S-propargyl-S-methyl-N-formylphosphoroamidodithioate, S-ethyl-S-ethyl-N-ethy1-N-formylphosphoroamidodithioate, S-isopropyl-S-isopropyl-N-formylphosphoroamidodithioate, S-allylS-propargyl-N-formylphosphoroarnidodithioate,
etc.
The preferred compounds of formula (I) are O,S-dialkyl-N-alkanoylphosphoroarnidothioates wherein R and R are alkyl of 1 to 3 carobn atoms, R is lower n-alkyl of 1 to 6 carbon atoms, and 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-a'lkyl-S-a1kylphosphoroamidothioates and their preparation are disclosed in US. Pat. No. 3,309,266. O-alkyl-S-unsaturated hydrocarbyl phosphoroarnidothioates and their preparation are disclosed in US. 3,649,723.
Conventional acylating agents, such as acyl halides, ketenes and acid anhydrides and conventional acylating conditions may be used in this reaction.
This acylation reaction (illustrated with an acyl halide as the acylating agent) may be represented by the following equation:
wherein R, R ,R R and Y have the same significance as previously defined.
The acylation reaction (1) will usually be carried out at about 0 to 60 C. in the presence of solvents such as methylene chloride, chloroform, tetrahydrofuran 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-dihydrocarbylphosphoroamidothionate and then isomerizing the resulting N-acylphosphoroamidothionate with an alkylating agent to produce the O-hydrocarbyl-S-hydrocarbyl N acylphosphoroamidothioate. This reaction scheme is represented (using an acyl chloride as the acylating agent) by the following equations:
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. 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. 3,309,266 for reacting an QO-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 and 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 (R SNa) to form the S-sodium salt and alkylating the S-sodium salt to form the O,S-compound (VII). Ths reaction scheme is represented by the following equations:
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 10-100" C. 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 (D0 is effected by mixing substantially equimolar amounts of the sodium salt (IX) and the alkylating agent R in an inert solvent at a temperature in the range of 0-80" C., preferably 25-60 C. The product (VII) is isolated by conventional methods, e.g., extraction, chromatography, etc.
If the acylating agent, e.g.,
is weak it may be desirable to prepare the compounds of this invention by amidating an appropriate 0,0-dihydrocarbylphosphorothiochloridate to obtain an 0,-0-dihydrocarbyl-N-acylphosphoroamidothioate and reacting said N- acylphosphoroamidothioate with an alkylating agent as 6 described above. This reaction scheme is illustrated by the following set of equations:
C1 Cl 1 T P c l RS HCl 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 0 to 15 C., preferably 0 to 5 C. The reaction time necessary to complete the addition of the mercaptan to the phosphorous oxychloride will range from about 1 to 10 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 reacting gaseous ammonia or an amine with the S-hydrocarbyl-S-hydrocarbylphosphorochloridodithioate according to the following equation:
P-Cl R NHz P-NHPJ E01 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 75 C., preferably 40 to 60 C. Completion of the reaction is indicated by cessation of ammonium chloride amine hydrochloride precipitation. Following the reaction, the crude product can be isolated by conventional techniques such as filtration, extraction, distillation, chromatography, etc.
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 describe methods which may be used to prepare the phosphoroamidothioates and phosphoroamidodithioates of this invention. Representative compounds prepared by these methods are tabulated in Table I.
Example 1 14.1 g. (0.1 mole) of O-methyl-S-methylphosphoroamidothioate was dissolved in 100 ml. benzene in a flask. 7.85 g. (0.1 mole) acetylchloride was added to this solution. This mixture was brought to refluxHCl being evolved at that point. This mixture was then stirred overnight at ambient temperature. Supernatant liquid was decanted and the solvent was stripped off at 3040 C., 12 mm. Hg. An oil remained which solidified on standing. This solid was filtered and washed with ether to yield 7 g. of impure O-methyl-S-methyl-N-acetylphosphoroamidothioate. This material melted at 64-68 C. and had the following analysis:
Calculated (percent): P, 16.93; S, 17.48. Found (percent): P, 18.28; S, 18.05.
Example 2 176 g. (1.25 moles) of O-methyl-S-methyl phosphoroamidothionate was dissolved in 300 ml. of dichloromethane and charged to a 1 liter flask. 98 g. (1.25 moles) of acetylchloride dissolved in 100 ml. of dichloromethane was added. The solution was stirred, warmed to 33 C., held at that temperature for 4 hours, then an additional 98 g. (1.25 moles) of acetylchloride was added. The mixture was held at room temperature for 18 hours and then added to 500 ml. of ice water. The phases were separated and the aqueous phase was extracted with four 200 ml. portions of dichloromethane. The extracts were combined with the separated organic phase and the solvent removed by gentle heating under vacuum to give 50 g. of product. The aqueous phase after batch extraction was further extracted continuously for 18 hours in a liquid-liquid extraction apparatus using 2 liters of dichloromethane as the extractant. Evaporation of the dichloromethane gave an additional 110 g. of product, giving a total yield of 87%. Upon purification, the product, O-methyl-S-methyl- N-acetylphosphoroamidothioate, gave the following analysis:
Calculated (percent): N, 7.65; S, 17.48. Found (percent): N, 7.28; S, 17.88.
Example 3 6 g. of 0,0 diethyl N acetylphosphoroamidothionate was mixed with 10 ml. ethyl iodide in a flask. This mixture was refluxed for hours. The resulting reaction mixture was stripped at 80 C., 30 mm. Hg, leaving 4.5 g. oil which crystallized on standing. This material, O-ethyl- S ethyl N acetylphosphoroamidothioate, had the following analysis:
Calculated (percent): P, 14.68; S, 15.19. Found (percent): P, 14.02; S, 15.15.
8 Example 4 30 g. of 0,0-dimethylphosphoroamidothioate and 41 g. of n-decanoyl chloride were dissolved in 120 ml. of methylene chloride and refluxed for 2 hours. After treatment with water to remove acidic by-products, the solution was dried over magnesium sulfate and stripped to give 60.4 g. of 0,0-dimethyl N decanoyl phosphoroamidothioate (96% yield).
20 g. of the above 0,0-dimethyl-N-decanoyl phosphoro amidothioate was then mixed with 4 g. dimethyl sulfate and held at 60 C. for 1 hour. O-methyl-S-methyl-N- decanoyl phosphoroamidothioate was recovered by chromatographic means giving a yield of 9.5 g. This material had the following analysis:
Calculated (percent): P, 10.50; S, 10.85. Found (percent): P, 10.67; S, 10.47.
Example 5 S,S-dimethyl-N-acetylphosphoroamidodithioate was preprepared as follows.
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 0 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 0 C. to 5 C. The mixture was then stirred for an additional 6 hours at temperatures of 0 to 10 C. After 18 hours of standing at 0 C. 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 55 C. When the temperature started to drop, ammonia addition was stopped. The reaction was held at 50 C. 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 l03105 C. and the following N, S, P analysis:
Calculated (percent): N, 8.9; S, 41.0; P, 19.7. Found (percent): N, 9.65; S, 38.1; P, 19.2.
S,S-dimethylphosphoroamidodithioate was dissolved in 250 m1. dichloromethane and charged to a 500 ml. flask. 39.3 g. (0.5 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 suflicient 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:
Calculated (percent): N, 7.03; S, 32.1; P, 15.52. Found (percent): N, 6.48; S, 31.05; P, 14.08.
Example 6 Preparation of 0 allyl-S-methyl-N-acetylphosphoroamidothioate.A 68 g. (1.1 mol) sample of allyl alcohol was added dropwise to 84 g. (0.5 mol) phosphorous thiochloride (PSCl at 0-10 C. The resulting reaction mixture was cooled in a Dry-Ice/acetone bath while g. (1 mol) of a 50% sodium hydroxide solution was added. After the addition was completed, the reaction mixture was stirred at about 25 C. for 1% hours, diluted with 200 ml. water and 50 ml. chloroform. The organic phase was separated, dried over magnesium sulfate, filtered and evaporated under reduced pressure. The residue was distilled to 31.3 g. of 0,0-diallylphosphorochloridothioate, b.p. 72-74 C. (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 ml. 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 /2 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 mol) sample of the above 0,0-diallylphosphoroamidothioate, 6 g. (0.059 mol) 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-diallyl-N-acetylphosphoroamidothioate.
A mixture of 10 g. (0.0425 mol) of the above 0,0- diallyl-N-acetylphosphoroamidothioate, 4.3 g. (0.0425 mol) 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 evaporated under reduced pressure to give 9 g. of a yellow liquid residue. The residue was chromatographed on silica (hexane/methylene chloride/acetone eluants) to give the S-methyl-O-allyl-N- acetylphosphoroamidothioate product as an oil. Elemental analysis for C H NO PS showed:
Calculated (percent): P, 14.8; S, 15.4. Found (percent): P, 14.62; S, 15.8.
Example 7 Preparation of O,S-dimethyl-N-formylphosphoroamidothioate.A 10 ml. sample of 98% formic acid was added slowly to 20 ml. of acetic anhydride at C. To the resulting formic acetic anhydride containing solution was added 21.2 g. (0.15 mole) 0,0-dimethylphosphoroamidothioate, 30 ml. methylene dichloride and 0.5 ml. phosphoric acid. The resulting reaction mixture was stirred at about 25 C. for 23 hours, then mixed with 15 g. ice and 30 ml. saturated ammonium chloride solution. The aqueous mixture was neutralized with 15% ammonium hydroxide solution. The aqueous phase was extracted with methylene chloride. The methylene chloride extract and the organic phase were combined, washed with saturated ammonium chloride solution, dried over magnesium sulfate and evaporated under reduced pressure to give 25 g. of 0,0-dimethyl-N formylphosphoroamidothioate product. The nuclear magnetic resonance spectrum showed that the product contained about 0,0-dimethyl-N-acetylphosphoroamidothioate. Analysis for C H NO PS showed:
Calculated (percent): N, 8.28; P, 18.32. Found (percent): N, 7.83; P, 17.08. A 13 g. sample of 0,0'-dimethyl-N-formylphosphoroamidothioate and 2.5 g. dimethyl sulfate were heated at 70-80 C. for 6 hours. The crude reaction mixture was chromatographed on silica gel (methylene chloride/acetone eluants) to give the O,S-dimethyl-N-formylphosphoroamidothioate product as an oil. Anlysis on the product is tabulated in Table I.
Example 8 Preparation of S-sodium-O-methyl N hexanoylphosphoroamidothioate.0,0 dimethyl-N-hexanoylphosphoroamidothioate, 69 g. (0.28 mol), was dissolved in 100 m1. methanol. To this solution was added 23 g. (0.29 mol) of 50% aqueous sodium hydroxide. The resulting solution was stirred for minutes, then 26.3 g. (0.29
mol) of n-propyl mercaptan was added. This mixture was refluxed for 4 hours, and then held at 25 C. for about 17 hours. The precipitated solid was removed by filtration, washed with methylene dichloride and then dried under vacuum to give 38 g. of product, m.p. 105-108 C. Elemental analysis showed:
Calc. (percent): S, 17.2; P, 16.6. Found (percent): S, 16.5; P, 16.2.
Example 9 Preparation of S-allyl-O-methyl-N-hexanoylphosphoroamidothioate.--A mixture of 7 g. S-sodium-O-methyl-N- hexanoylphosphoroamidothioate (prepared as described in Example 8) and 30 g. allyl bromide was refluxed for 3.5 hours and allowed to stand at about 25 C. for about 16 hours. The solids in the reaction mixture were filtered and washed with methylene dichloride. The filtrate and methylene dichloride washes were evaporated under reduced pressure to give the product as a viscous oil. Elemental analysis on the product is tabulated in Table I.
Example 10 Preparation of S-propargyl-O-methyl-N-hexanoylphosphoroamidothioate.A mixture of 7 g. S-sodium-O-methyl-N-hexanoylphosphoroamidothioate (prepared as described in Example 8) and 30 g. propargyl bromide was refluxed for 3 hours and then allowed to stand at about 25 C. for about 17 hours. The reaction mixture was diluted with methylene dichloride and filtered. The filtrate was evaporated under reduced pressure and the residue was dissolved in benzene and filtered. Hexane was then added to benzene solution to precipitate 5.7 g. of the product, m.p. 6365 C. Elemental analysis on the product is tabulated in Table I.
Example 11 Preparation of O,S-dimethyl-N-octadecanoylphosphoroamidothioate-A mixture of 7.8 g. 0,0-dimethyl-N-octadecanoylphosphoroamidothioate, 1.8 g. dimethyl sulfate and 20 ml. chloroform was refluxed for 3 hours. The reaction mixture was cooled and then filtered. The filtrate was evaporated under reduced pressure to give a solid. The solid was recrystallized from methylene dichloride to give the product as fine white crystals, m.p. 5762 C. Elemental analysis on the product is tabulated in Table I.
Example 12 Preparation of O,S dimethyl-N-isovaleroylphosphoroamidothioate.-A mixture of 35 g. O,S-dimethylphosphoroamidothioate, 21.7 g. isovaleroyl chloride, ml. methylene dichloride and 8 g. magnesium sulfate was refluxed for 2 hours. Large amounts of hydrochloric acid were evolved. The reaction mixture was diluted with 200 ml. water and neutralized with aqueous sodium carbonate solution. The aqueous phase was separated and extracted with methylene dichloride. The organic layers were combined, washed with Water, dried over magnesium sulfate, and filtered. The crude product separated out as a viscous oil. The oil was crystallized from methylene dichloride/ hexane to give the product, m.p. 7578 C. Elemental analysis on the product is tabulated in Table 1.
Example 13 Preparation of O,S-dimethyl-N-undecynoylphosphoroamidothioate.A mixture of 20.9 g. (0.685 mole) 0,0- dimethyl-N-undecynoylphosphoroamidothioate (prepared by acylating 0,0-dimethylphosphoroamidothioate with undecynoyl chloride) and 7 g. (0.055 mole) dimethyl sulfate was heated for 2 hours at 70-75 C. The crude reaction mixture was chromatographed on silica gel (hexane/ methylene chloride/ acetone eluants) to give the product, m.p. 34-40 C. Elemental analysis on the product is tabulated in Table I.
1 1 Example 14 Preparation of O,S-dimethyl N cyclohexylcarbonylphosphoroamidothioate.--The product was prepared by acylating 14.1 g. (0.1 mole) O,S-dimethylphosphoro- 12 1 placed in a rnicrosprayer (atomizer). A random mixture of anesthetized male and female roaches 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.
amidothioate with 14.7 g. (0.1 mole) cyclohexanecarbox- 5 ylic acid chloride in methylene dichloride by a procedure Hqllsefiles (Musca A 500 P-P- acetone similar to those heretofore described. Elemental analysis Solutlon of the candldate tQXlcant Was Placed In a mlcfoon the product is tabulated in Table I. sprayer (atomizer). A random mixture of anesthetized TABLE I Compounds of the formula BY o \T ll P-N-C-R l 11 8 R Elemental analysis, percent Melting P S point, Y R R1 R R3 Cale. Found Cale. Found 0 CH3 CH3 H H 011 18. 32 19. 47 0 CH; CH; H CH1 64-58 15. 93 18. 28 17. 48 18. 05 o C2H OH; H CH5 67-75 15. 70 15.35 15. 24 15. 95 0 CH1 CH1 H C2H5 on 15. 65 14. 52 16. 25 16. 22 0 CH: OH; H (CHsCHz): 011 13. 42 14. 68 14. 79 15. 18 0 CH3 OH; H (CHmCH 011 14. 68 12. 15. 18 13. 65 0 CH OH; H 11-01 11 011 12.95 12.48 13.42 11.88 0 CH3 OH; H t-C1H1 0 1 13. 76 11. 90 14. 13. 68 0 CH CH3 H n-C1H11 011 10. 10. 57 10. 85 10. 47 O CQHE C Hs H CH3 179-183 14. 68 14.02 15. 19 15. 15 s CH1 OH; H CH3 011 15. 52 14. 08 32. 1 31. 05 o C H CHECCHZ H CH1 011 14. 05 13. 81 14.85 15.58 0 CH3 CH2=CHCH2 H CzH5 14. 38 14. 05 0 CH3 CH CCH2 H CzHs 14. 50 14. 22 0 CH3 CH1=CHCH1 H n-O H11 .13 12. 09 12. 10 0 CH3 CHECCH: H n-C5H11 63-65 11.77 11.60 12.18 11.82 0 CH3 CH1 CH3 CH1 Oil 15.70 13. 50 16. 27 14. 80 0 CH3 CH1=CHCH1 H sec-C1111 on 12.33 12. 15 12. 75 12. 1 0 CH CH: C CH1 H sec-0.1m 83-85 12. 43 12. 5 12. 87 12. 99 0 CH CH3 H 11-C111H11 58-51 10. 0 0 CH1 3 H D-C12H15 -61 9. 6 0 CH3 CH3 H Il-C11H85 51-62 7. 6 0 CH3 OH; H sec-01H Oil 13. 0 CH1 CH1 H 114311115 011 11.5 0 CH1 CH3 H n-CnHza 49-50 9. 58 0 CH3 CH3 H n-C18H11 59-61 8. 8 9. 12 0 CH3 CH3 CH3 11-C5H11 Oil 12. 24 0 CH3 CH3 H sec-C5. 11 011 12.10 0 CH OH; H CH1CH=CHCH1 011 0 CH1 OH; H C 1: H Oil 15.99 0 CH3 CH3 H n-oleoyl Oil 7. 64 0 CH3 CH1 H (GH3)2C=OH 75-78 13. CH1 CH H CH2=CH(CH2)8 Oil 10.07 CH CH3 H CH=C(CH1)1 34-40 10. 14 7.14 10.5 11. 93
CH1 CH1 H 95-100 12 33 12.18 12. 76 13. 40
35 0 CH1 CH1 E Q Oil 14.8 13. 75 15.3 14.82
37 O CH1=CHCH1 CH3 H CH3 Oil 14.8 14.6 15.4 15.8
UTILITY 60 male and female flies was placed in a container and 55 The compounds of this invention were tested as follows to illustrate their insecticidal activity. Test results are reported in Table 11.
Test Procedures 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 p.p.m. 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): An acetone solution of the candidate toxicant containing a small amount of nonionic emulsifier was diluted with Water to 30 p.p.m. Cucumber leaves infested with the cotton aphids were dipped in the toxicant solution. Mortality readings were then taken after 24 hours.
TABLE II [Percent mortality] American Cabbage looper cockroach Housefly Mite Aphid Number (500 p.p.m.). (500 p.p.m.) (500 p.p.m.) (100 p.p.m.) p.p.m.)
70 100 (250 p.p.m.) 100 (100 ppm)... 76 p.p.m.).- 68 (10 p.p.m.).
2 100 (250 ppm)... 100 (100 p.p.m.)* 100 (250 p.p.1n)
90 (250 p.p.m.) 100 (100 p.p.m.)* 100 (250 pp 90 (100 p.p.m.)*-. 106 (100 p m 100.. 10 .m.) 26 (250 p.p.m.)*
.p 39 pm 0 97.. 98.
93 (125 p.p.rn.)- 30--.
72 I00 9 60. 100 78. 22 78. 100 50. 39 0 0. 22 98 (30 p.p.m.) 39. 100 100 (30 p.p.n1.)- 22. 60 100 100 94. so 20(100 p.p.m.) 100 2 7? 92 60 99-- 100 99 100 70. 39 100 100 (16 p.p.m.) 0. 100.-. 100 100 78.
27 n 0 0 96 (200 ppm.)
28 50 (625 p.p.m.) 0 7 31 70 (625 p.p.m.)..
' German cockroaches.
In tests carried out in the field, O-methyl-S-methyl-N- acetylphosphoroamidothioate showed excellent activity 40 against the following insects:
Corn earworm Corn.
As previously indicated the toxicological properties of the compounds of this invention are unexpectedly better than corresponding non-acylated compounds. This feature may be illustrated by comparing the toxicity index of a representative compound of this invention with that of its corresponding non-acylated analog. Toxicity index is a measure of a compounds safety relative to its insecticidal activity. It is defined here as:
LD insects (p.p.m.) LD rats-oral (mg/kg.)
LD insects is the least dosage that will provide mortality of the test insect. It is determined by testing the toxicants at various concentrations by the above-described 50 testing and plotting the results. LD rats-ora is the lowest dosage that will kill 50% of the test rodents in standard oral application tests. The toxicity indexes of O- methyl-S-methyl-N-acetylphosphoroamidothioate and its non-acylated analog O-methyl-S-methylphosphoroamidothioate, determined as above, are reported in Table III below. Also reported are the toxicity indexes of other 0- methyl-S-methyl-N-acylphosphoroamidothioates.
TABLE III LD50 LDao LDuo LDno Toxicity index 10 rats cabbage german LDnu LDQO cotton oral looper roaches flies mites aphids Cabbage German Compound (mg/kg.) (p.p.m.) (p.p.m.) (p.p.m.) (p.p.m.) (p.p.m) looper roaches Flies Mites Aphids O-methy1-S-methyl-N-acetylphosphoroamidothioate 700 20. 5 21. 5 14. 3 2. 9 3. 1 O-methyl-S-methyl-N-propionyl phosphoroamidothioate 1,000 18 8.5 2.7 0-methyl-S-methyl-N-butyrylphosphoroamidothioate 19. 6 O-methyl-S-methyl-N-isobutyrylphosphoroamidothioate 500 2.9 1.1 O-methyl-S-methylphosphoroamidothioate 16 92 15.2 -10 9.5 7.5 575 95 62.5 59.3 47
The compounds of this invention are toxic to a variety of crop and household pests, in addition to the typical pests exemplified above. Like most agricultural chemicals, they are not usually applied full strength, but are generally incorporated with conventional biologically inert extenders or carriers normally employed for facilitating dispersion of active ingredients for agricultural chemical applications, recognizing the accepted fact that the formulation and mode of application may affect the activity of a material. The toxicants of this invention may be applied as sprays, dusts, or granules to the insects, their environment or hosts susceptible to insect attack. They may be formulated as granules of large particle size, as powdery dusts, as wettable powders, as emulsifiable concentrates, as solutions, or as any of several other known types of formulations, depending on the desired mode of application.
Wettable powders are in the form of finely divided particles which disperse readily in water or other dispersant. These compositions normally contain from 80% toxicant and the rest inert material which includes dispersing agents, emulsifying agents, and wetting agents. The powder may be applied to the soil as a dry dust or preferably as a suspension in water. Typical carriers include fullers earth, kaolin clays, silicas, and other highly absorbent, readily wet, inorganic diluents. Typical wetting, dispersing, or emulsifying agents used in agricultural formulations include, for example, the alkyl and alkylaryl sulfonates and sulfonates and their sodium salts; alkylamide sulfonates, including fatty methyl taurides; alkylaryl polyether alcohols, sulfated higher alcohols, and polyvinyl alcohols; polyethylene oxides; sulfonated animal and vegetable oils; sulfonated petroleum oils; fatty acid esters of polyhydric alcohols and the ethylene oxide addition products of such esters; and the addition products of long chain mercaptans and ethylene oxide. Many other types of useful surface active agents are available in commerce. The surface active agent, when used, normally comprises from one percent to fifteen percent by weight of the pesticidal composition.
Dusts are freely flowing admixtures of the active ingredient with finely divided solids such as talc, natural clays, kieselguhr, pyrophyllite, chalk, diatomaceous earths, calcium phosphates, calcium and magnesium carbonates, sulfur, lime, flours, and other organic and inorganic solids which act as dispersants and carriers for the toxicant. These finely divided solids have an average particle size of less than about fifty microns. A typical dust formulation useful herein contains 75% silica and 25% of the toxicant.
Useful liquid concentrates include the emulsifiable concentrates, which are homogeneous liquid or paste compositions which are readily dispersed in water or other dispersant, and may consist entirely of the toxicant with a liquid or solid emulsifying agent, or may also contain a liquid carrier, such as xylene, heavy aromatic naphthas, isophorone, and other non-volatile organic solvents. For application these concentrates are dispersed in water or other liquid carrier, and normally applied as a spray to the area to be treated.
Other useful formulations for insecticidal applications include simple solutions of the active ingredient in a dispersant in which it is completely soluble at the desired concentration, such as acetone, alkylated naphthalenes, xylene, or other organic solvents. Granular formulations, wherein the toxicant is carried on relatively coarse particles, are of particular utility for aerial distribution or for penetration of cover crop canopy. Baits, prepared by mixing solid or liquid concentrates of the toxican with a suitable food, such as a mixture of cornmeal and sugar, are useful formulations for control of insect pests. Pressurized sprays, typically aerosols wherein the active ingredient is dispersed in finely divided form as a result of vaporization of a low-boiling dispersant solvent carrier, such as the Freons, may also be used. All of these techniques for formulating and applying the active ingredient are well known in the art.
The percentages by weight of the toxicant may vary according to the manner in which the composition is to be applied and the particular type of formulation, but in general comprises 0.5 to of the toxicant by weight of the pesticidal composition.
The pesticidal compositions may be formulated and applied with other active ingredients, including other nematocides, insecticides, fungicides, bactericides, plant growth regulators, fertilizers, etc. In applying the chemical an effective amount and concentration of the toxicants of this invention is, of course, employed.
The term insecticide and insect as used herein refer to their broad and commonly understood 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 Insecta, 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 on this invention can be made or followed, in the light of the foregoing disclosure and discussion, with out departing from the spirit or scope of the disclosure or from the scope of the following claims.
What is claimed is:
1. A compound of the formula wherein R is alkenyl or alkynyl of up to 6 carbon atoms, R is alkyl, alkenyl or alkynyl of up to 6 carbon atoms, R is hydrogen or alkyl of 1 to 6 carbon atoms and R is hydrogen, alkyl of 1 to 18 carbon atoms, cycloalkyl of 3 to 8 carbon atoms, alkenyl of 2 to 18 carbon atoms or alkynyl of 3 to 18 carbon atoms and Y is oxygen or sulfur.
2. The compound of Claim 1 wherein R is hydrogen and Y is oxygen.
3. The compound of Claim 2 wherein R is alkyl.
4. The compound of Claim 3 wherein R is n-alkyl of up to 11 carbon atoms.
5. The compound of Claim 4 wherein R is methyl or ethyl.
6. The compound of Claim 5 wherein R is methyl, ethyl or allyl.
7. The compound of Claim 6 wherein R and R are methyl and R is allyl.
8. The compound of Claim 1 wherein R is alkenyl.
References Cited UNITED STATES PATENTS 2/1973 Magee 260-959 8/1965 Tolkmith 260959 US. Cl. X.R.
Claims (1)
1. A COMPOUND OF THE FORMULA
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
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US00317478A US3845172A (en) | 1971-05-28 | 1972-12-21 | N-hydrocarboyl phosphoroamido-thioates and phosphoroamidodithioates |
US484912A US3914417A (en) | 1972-12-21 | 1974-07-11 | Insectidical N-hydrocarboyl phosphoroamidothioates and phosphoroamidodithioates |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US14813971A | 1971-05-28 | 1971-05-28 | |
US00317478A US3845172A (en) | 1971-05-28 | 1972-12-21 | N-hydrocarboyl phosphoroamido-thioates and phosphoroamidodithioates |
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US3845172A true US3845172A (en) | 1974-10-29 |
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US00317478A Expired - Lifetime US3845172A (en) | 1971-05-28 | 1972-12-21 | N-hydrocarboyl phosphoroamido-thioates and phosphoroamidodithioates |
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US4315870A (en) * | 1979-01-24 | 1982-02-16 | Rohm And Haas Company | Phosphorodiamidothioates |
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US4544553A (en) * | 1981-06-24 | 1985-10-01 | Rohm And Haas Company | Pesticidal phosphoroamido (di) thioates |
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US5298501A (en) * | 1991-03-25 | 1994-03-29 | Valent U.S.A. Corporation | Chemically stable granules containing insecticidal phosphoroamidothioates |
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US4218444A (en) * | 1978-06-05 | 1980-08-19 | Chevron Research Company | Insecticidal formulation |
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US4315870A (en) * | 1979-01-24 | 1982-02-16 | Rohm And Haas Company | Phosphorodiamidothioates |
US4299783A (en) * | 1980-04-28 | 1981-11-10 | Chevron Research Company | 1-Alkylsulfonyl-3-substituted phosphinylthio- or phosphinothioylthio-propenes |
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US4614734A (en) * | 1981-06-24 | 1986-09-30 | Rohm And Haas Company | Pesticidal phosphoroamido(di)thioates |
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EP0415609A2 (en) * | 1989-08-18 | 1991-03-06 | CHEVRON U.S.A. Inc. | Pelletized insecticidal composition |
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US5298501A (en) * | 1991-03-25 | 1994-03-29 | Valent U.S.A. Corporation | Chemically stable granules containing insecticidal phosphoroamidothioates |
US5352674A (en) * | 1991-03-25 | 1994-10-04 | Valent U.S.A. | Chemically stable granules containing insecticidal phosphoroamidothioates |
US5369100A (en) * | 1991-03-25 | 1994-11-29 | Valent U.S.A. Corporation | Chemically stable compacted particles containing insecticidal phosphoroamidothioates and methods for the manufacture and use thereof |
US5449667A (en) * | 1993-08-10 | 1995-09-12 | Sumitomo Chemical Company, Limited | Amidothiophosphate derivative and insecticide, nematocide and acaricide containing the same as active ingredient |
US5698540A (en) * | 1994-02-10 | 1997-12-16 | Sumitomo Chemical Company, Limited | Stabilized pesticidal composition containing acephate |
US5914105A (en) * | 1994-06-17 | 1999-06-22 | Ecolab Inc. | Petroleum based pest bait |
US5464613A (en) * | 1994-06-17 | 1995-11-07 | Ecolab, Inc. | Fat-based pest bait |
US5614203A (en) * | 1995-01-30 | 1997-03-25 | Environmentally Safe Systems, Inc. | Environmentally safe pesticide and plant growth accelerator |
WO1997009882A1 (en) * | 1995-09-14 | 1997-03-20 | Valent U.S.A. Corporation | Phosphoroamidothioate coated sand and method |
US6337323B2 (en) | 1996-12-19 | 2002-01-08 | Valent U.S.A. Corporation | Chemically stable, insecticidally active phosphoromidothioate pellet compositions and methods for their manufacture |
US20040259847A1 (en) * | 1996-12-19 | 2004-12-23 | Valent U.S.A. Corporation | Chemically stable, insecticidally active phosphoroamidothioate pellet compositions and methods for their manufacture |
US6013272A (en) * | 1996-12-19 | 2000-01-11 | Valent U.S.A. Corporation | Chemically stable, insecticidally active phosphoroamidothioate pellet compositions and methods for their manufacture |
US7919482B2 (en) | 1996-12-19 | 2011-04-05 | Arysta Lifescience North America, Llc | Chemically stable, insecticidally active phosphoroamidothioate pellet compositions and methods for their manufacture |
US6761897B2 (en) | 1996-12-19 | 2004-07-13 | Valent U.S.A. Corporation | Chemically stable, insecticidally active phosphoroamidothioate pellet compositions and methods for their manufacture |
WO2000072680A1 (en) * | 1999-05-28 | 2000-12-07 | Valent U.S.A. Corporation | Insecticidal composition and method for the use thereof |
US6177412B1 (en) | 1999-05-28 | 2001-01-23 | Valent U.S.A. Corporation | Insecticidal composition and method for the use thereof |
AU776762C (en) * | 1999-05-28 | 2005-07-07 | Valent U.S.A. Corporation | Insecticidal composition and method for the use thereof |
AU776762B2 (en) * | 1999-05-28 | 2004-09-23 | Valent U.S.A. Corporation | Insecticidal composition and method for the use thereof |
BG65268B1 (en) * | 1999-10-29 | 2007-11-30 | Aventis Cropscience S.A. | Novel pesticide and/or growth regulating compositions with particular non-ionic surfactant |
US6576661B1 (en) | 1999-11-09 | 2003-06-10 | Bayer Aktiengesellschaft | Active ingredient combination having insecticidal and acaricidal characteristics |
US6818670B2 (en) | 1999-11-09 | 2004-11-16 | Bayer Aktiengesellschaft | Active ingredient combination having insecticidal and acaricidal characteristics |
US20030100604A1 (en) * | 2000-03-28 | 2003-05-29 | Reiner Fischer | Active substance combinations having insecticidal and acaricidal properties |
US6900190B2 (en) | 2000-03-28 | 2005-05-31 | Bayer Aktiengesellschaft | Active substance combinations having insecticidal and acaricidal properties |
US7060692B2 (en) | 2000-08-31 | 2006-06-13 | Bayer Cropscience Ag | Active ingredient combinations comprising insecticidal and acaricidal properties |
US6831104B2 (en) | 2000-10-02 | 2004-12-14 | Tommy G. Taylor | Insect pest eradication system |
US20060255490A1 (en) * | 2001-03-09 | 2006-11-16 | Granulated Active Ingredients | Granulated active ingredients |
US7157094B2 (en) | 2001-03-09 | 2007-01-02 | Arysta Lifescience North America Group | Granulated active ingredients |
US7473685B2 (en) | 2001-12-18 | 2009-01-06 | United Phosphorus, Ltd. | Process for preparation of chemically stable, dry-flow, low compact, dust free, soluble granules of phosphoroamidothioates |
US6875381B2 (en) | 2001-12-18 | 2005-04-05 | United Phosphorus, Ltd. | Process for preparation of chemically stable, dry-flow, low compact, dust free, soluble granules of phosphoroamidothioates |
US20030127761A1 (en) * | 2001-12-18 | 2003-07-10 | Jadhav Prakash Mahadeo | Process for preparation of chemically stable, dry-flow, low compact, dust free, soluble granules of phosphoroamidothioates |
US20030153484A1 (en) * | 2002-02-08 | 2003-08-14 | Masking Agent For Agrichemicals | Masking agent for agrichemicals |
US7407927B2 (en) | 2002-02-08 | 2008-08-05 | Arysta Lifescience North America, Llc | Masking agent for agrichemicals |
US6752943B1 (en) | 2002-12-31 | 2004-06-22 | United Phosphorus, Ltd. | Apparatus and process for granulating dry powder materials |
US8222234B1 (en) | 2006-05-19 | 2012-07-17 | Sander William A | Phosphoroamidothioate granules and methods of manufacture thereof |
US8221776B1 (en) | 2006-05-19 | 2012-07-17 | Sander William A | Phosphoroamidothioate granules and methods of manufacture thereof |
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