US3868449A - Insecticidal o,s-dihydrocarbyl-n-acylphosphoroamidothioates and s,s-dihydrocarbyl-n-acylphosphoroamidodithioates - Google Patents
Insecticidal o,s-dihydrocarbyl-n-acylphosphoroamidothioates and s,s-dihydrocarbyl-n-acylphosphoroamidodithioates Download PDFInfo
- Publication number
- US3868449A US3868449A US432929A US43292974A US3868449A US 3868449 A US3868449 A US 3868449A US 432929 A US432929 A US 432929A US 43292974 A US43292974 A US 43292974A US 3868449 A US3868449 A US 3868449A
- Authority
- US
- United States
- Prior art keywords
- methyl
- alkyl
- carbon atoms
- allyl
- dimethyl
- 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
- 230000000749 insecticidal effect Effects 0.000 title claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 abstract description 13
- 239000001301 oxygen Substances 0.000 abstract description 13
- 239000000460 chlorine Substances 0.000 abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 10
- 239000001257 hydrogen Substances 0.000 abstract description 10
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052801 chlorine Inorganic materials 0.000 abstract description 8
- 239000011737 fluorine Substances 0.000 abstract description 8
- 229910052731 fluorine Inorganic materials 0.000 abstract description 8
- 229910052717 sulfur Inorganic materials 0.000 abstract description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 6
- 239000011593 sulfur Substances 0.000 abstract description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 abstract 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 abstract 1
- -1 2- hexanyl Chemical group 0.000 description 53
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 47
- 125000004432 carbon atom Chemical group C* 0.000 description 28
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 24
- 125000000217 alkyl group Chemical group 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 20
- 238000000034 method Methods 0.000 description 19
- 239000000243 solution Substances 0.000 description 17
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 241000238631 Hexapoda Species 0.000 description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 8
- 231100000167 toxic agent Toxicity 0.000 description 8
- 239000003440 toxic substance Substances 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
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 7
- 229940100198 alkylating agent Drugs 0.000 description 7
- 239000002168 alkylating agent Substances 0.000 description 7
- 125000001246 bromo group Chemical group Br* 0.000 description 7
- 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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000000921 elemental analysis Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 159000000000 sodium salts Chemical class 0.000 description 6
- 238000005917 acylation reaction Methods 0.000 description 5
- 125000003342 alkenyl group Chemical group 0.000 description 5
- RJBIAAZJODIFHR-UHFFFAOYSA-N dihydroxy-imino-sulfanyl-$l^{5}-phosphane Chemical class NP(O)(O)=S RJBIAAZJODIFHR-UHFFFAOYSA-N 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 125000000304 alkynyl group Chemical group 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000004587 chromatography analysis Methods 0.000 description 4
- 229960003390 magnesium sulfate Drugs 0.000 description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 4
- 235000019341 magnesium sulphate Nutrition 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 241000238876 Acari Species 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 241000255993 Trichoplusia ni Species 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- WFFOAQQKQLMGGW-UHFFFAOYSA-N [hydroxy(mercapto)thiophosphoryl]amine Chemical class NP(O)(S)=S WFFOAQQKQLMGGW-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000002917 insecticide Substances 0.000 description 3
- NNKVPIKMPCQWCG-UHFFFAOYSA-N methamidophos Chemical compound COP(N)(=O)SC NNKVPIKMPCQWCG-UHFFFAOYSA-N 0.000 description 3
- 239000012875 nonionic emulsifier Substances 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- JJKWHOSQTYYFAE-UHFFFAOYSA-N 2-methoxyacetyl chloride Chemical compound COCC(Cl)=O JJKWHOSQTYYFAE-UHFFFAOYSA-N 0.000 description 2
- 241001124076 Aphididae Species 0.000 description 2
- 241001600408 Aphis gossypii Species 0.000 description 2
- 241001674044 Blattodea 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
- 241000257159 Musca domestica Species 0.000 description 2
- 241000238675 Periplaneta americana Species 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 2
- 239000012346 acetyl chloride Substances 0.000 description 2
- 150000001263 acyl chlorides Chemical class 0.000 description 2
- 230000010933 acylation Effects 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 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
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 125000004201 2,4-dichlorophenyl group Chemical group [H]C1=C([H])C(*)=C(Cl)C([H])=C1Cl 0.000 description 1
- SYZRZLUNWVNNNV-UHFFFAOYSA-N 2-bromoacetyl chloride Chemical compound ClC(=O)CBr SYZRZLUNWVNNNV-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
- 125000004198 2-fluorophenyl group Chemical group [H]C1=C([H])C(F)=C(*)C([H])=C1[H] 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- 125000004179 3-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(Cl)=C1[H] 0.000 description 1
- WGCICQJXVYFFCA-UHFFFAOYSA-N 3-iodoprop-1-yne Chemical compound ICC#C WGCICQJXVYFFCA-UHFFFAOYSA-N 0.000 description 1
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 description 1
- 125000006283 4-chlorobenzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1Cl)C([H])([H])* 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241000239290 Araneae Species 0.000 description 1
- 241000238421 Arthropoda Species 0.000 description 1
- 241000258920 Chilopoda Species 0.000 description 1
- 240000008067 Cucumis sativus Species 0.000 description 1
- 235000010799 Cucumis sativus var sativus Nutrition 0.000 description 1
- 241000255925 Diptera Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 101001076732 Homo sapiens RNA-binding protein 27 Proteins 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
- 241001465754 Metazoa 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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 102100025873 RNA-binding protein 27 Human genes 0.000 description 1
- 241001454293 Tetranychus urticae Species 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000001266 acyl halides Chemical class 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- HFEHLDPGIKPNKL-UHFFFAOYSA-N allyl iodide Chemical compound ICC=C HFEHLDPGIKPNKL-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000002862 amidating effect Effects 0.000 description 1
- 230000009435 amidation Effects 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 239000005667 attractant Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- KVVXFPNTQJIKNH-UHFFFAOYSA-N bis(prop-2-enyl) sulfate Chemical compound C=CCOS(=O)(=O)OCC=C KVVXFPNTQJIKNH-UHFFFAOYSA-N 0.000 description 1
- WQAQPCDUOCURKW-UHFFFAOYSA-M butane-1-thiolate Chemical compound CCCC[S-] WQAQPCDUOCURKW-UHFFFAOYSA-M 0.000 description 1
- NSXKVMCVAPWBAV-UHFFFAOYSA-N butanethioyl chloride Chemical compound CCCC(Cl)=S NSXKVMCVAPWBAV-UHFFFAOYSA-N 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
- KMGBZBJJOKUPIA-UHFFFAOYSA-N butyl iodide Chemical compound CCCCI KMGBZBJJOKUPIA-UHFFFAOYSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 description 1
- 229940008406 diethyl sulfate Drugs 0.000 description 1
- QUJIVWINNPEYAS-UHFFFAOYSA-N dihexyl sulfate Chemical compound CCCCCCOS(=O)(=O)OCCCCCC QUJIVWINNPEYAS-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000005059 halophenyl group Chemical group 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
- 150000004694 iodide salts Chemical class 0.000 description 1
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 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
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002561 ketenes Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- 238000006263 metalation reaction Methods 0.000 description 1
- RMIODHQZRUFFFF-UHFFFAOYSA-N methoxyacetic acid Chemical compound COCC(O)=O RMIODHQZRUFFFF-UHFFFAOYSA-N 0.000 description 1
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000005648 plant growth regulator Substances 0.000 description 1
- 238000001556 precipitation Methods 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
- 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
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- HJHVQCXHVMGZNC-JCJNLNMISA-M sodium;(2z)-2-[(3r,4s,5s,8s,9s,10s,11r,13r,14s,16s)-16-acetyloxy-3,11-dihydroxy-4,8,10,14-tetramethyl-2,3,4,5,6,7,9,11,12,13,15,16-dodecahydro-1h-cyclopenta[a]phenanthren-17-ylidene]-6-methylhept-5-enoate Chemical compound [Na+].O[C@@H]([C@@H]12)C[C@H]3\C(=C(/CCC=C(C)C)C([O-])=O)[C@@H](OC(C)=O)C[C@]3(C)[C@@]2(C)CC[C@@H]2[C@]1(C)CC[C@@H](O)[C@H]2C HJHVQCXHVMGZNC-JCJNLNMISA-M 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 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
- 229940086542 triethylamine Drugs 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000008096 xylene Substances 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)
-
- 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
- R-Y 0 i 1(0H2)u--XR -N Ra wherein R and R individually are alkyl, alkenyl or alkynyl of up to 6 carbon atoms, Y and X individually are oxygen or sulfur, n is whole number of from 1 to 6, preferably 1 or 2, R is alkyl of 1 to 6 carbon atoms, aryl of up to carbon atoms substituted with up to 2 (0 to 2) fluorine, chlorine or bromine atoms, and R is hydrogen or alkyl of l to 6 carbon atoms.
- Representative alkyl groups which R, R, R and R may represent include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, sec-pentyl and hexyl.
- Representative alkenyl of 3 to 6 carbon atoms which R and R may represent include allyl, 2-butenyl, 2- hexanyl, etc.
- Representative alkynyl of 3 to 6 carbon atoms which R and R may represent include 2- propynyl, 2-butynyl, 2-hexynyl, etc.
- the preferred R groups is hydrogen.
- Representative hydroca'rbyl aryl R groups include phenyl, naphthyl, aralkyl of 7 to 10 carbon atoms, e.g., benzyl, Z-phenylethyl, 3-tolylpropyl, 4-phenylbutyl, and alkaryl of 7 to 10 carbon atoms, e.g., 2- methylphenyl, 3-methylphenyl, 4-methylphenyl, 2,4- dimethylphenyl, 3,5-diethylphenyl and 4-t-butylphenyl.
- phenyl, naphthyl, aralkyl of 7 to 10 carbon atoms e.g., benzyl, Z-phenylethyl, 3-tolylpropyl, 4-phenylbutyl, and alkaryl of 7 to 10 carbon atoms, e.g., 2- methylphenyl, 3-methylphenyl, 4-methylphenyl, 2,4- dimethylphenyl, 3,5-dieth
- halo substituted aryl R group include halophenyl of 1 to 2 fluorine, chlorine or bromine atoms such as 2-fluorophenyl, 3-chlorophenyl, 4- bromophenyl, 2,4-dichlorophenyl, 3,5-dibromophenyl, etc.; and haloaralkyl and haloalkaryl of 7 to 10 carbon atoms and 1 to 2 fluorine, chlorine or bromine atoms such as 2-fiuorobenzyl, 4-chlorobenzyl, 2,4- dibromobenzyl, 2-(4-chlorophenyl)ethyl, 3-(2- fluoraphenyl)propyl, 2-chloro-4-methylphenyl, 3-fluoro-4-methylphenyl, etc.
- thioates of formula (I) are: O-allyl-S-methyl-N- methoxyacetylphosphoroamidothioate, O-propargyl-S:
- O-butyl-S-methyl-N-4-ethoxybutyrylphosphoroamidothioate O-2-butenyl-S-butyl-N-5- methoxypentanoylphosphoroamidothioate, O-methyl- S-methyl-N-S-methoxybutanoylphosphoroamidothioate, O-methyl-Smethyl-N-S-pentoxypentanoylphosphoroamidothioate, O-methyl-S-methyl-N-6- methoxyhexanoylphosphoroamidothioate, O-methyl-S- methyl-N-6-isopropoxyhexanoylphosphoroamidothioate, O-methyl-S-pentyl-N-7-methoxyheptanoylphosphoroamidothioate, and O-methyl-S-methyl-N-7- hexoxyheptanoylphosphoroamidothioate.
- N-alkylthioalkanoylphosphoroamidothioate of formula (I) are: O-methyl-S- allyl-N-methylthioacetylphosphoroamidothioate, O- allyl-S-methyl-N-methyl N-ethylthioacetylphosphoroamidothioate, O-methyl-S-methyl-N- propylthioacetylphosphoroamidothioate, O-propargyl- S-methyl-N-butylthioacetylphosphoroamidothioate, O-rnethyl-S-methyl-N-pentylthioacetylphosphoroamidothioate, O-methyl-S-methyl-N- hexylthioacetylphosphoroamidothioate, O-methyl-S- methyl-N-3-methylthiopropionylphosphoroamidothi- O-allyl-S-allyl
- N-aryloxyalkaonylphosphoroamidothioates of formula (I) are: O-methyl-S-methyl-N-pbromophenoxyacetylphosphoroamidothioate, O- methyl-S-allyl-N-(3-methylphenoxy)acetylphosphoro amidothioate, O-allyl-S-propargyl-N- 3-benzyl-oxypropionylphosphoroamidothioate and O- methyl-S-methyl-N-4-(4-chlorophenoxy)butyrylphosphoroamidothioate.
- N-arylthioalkanoylphosphoroamidothioates of formula (I) are: O-methyl-S-methyl-N-4- chlorophenylthioacetylphosphoroamidothioate, O- propargyl-S-methyl-N-isopropyl-N- benzylthioacetylphosphoroamidothioate, O-ethyl-S- methyl-N-3-(2,4-dichlorophenylthio)propionylphosphoroamidothioate, O-allyl-S-allyl-N-3-(4- methylphenylthio)propionylphosphoroamidothioate and O-isopropyl-S-methyl-N-3-(pchlorobenzylthio)propionylphosphoroamidothioate.
- N-alkoxyalkanoylphosphoroamidodithioates of formula (I) are: S-methyl-S-allyl-N-methyl- N-methoxyacetylphosphoroamidodithioate, S- propargyl-S-methyl-N-ethoxyacetylphosphoroamidodithioate, S-methyl-S-ethyl-N-propoxyacetylphosphoroamidodithioate, S-propyl-S-methyl-N- methoxyacetylphosphoroamidodithioate, S-allyl-S- allyl-N-butoxyacetylphosphoroamidodithioate, S- methyl-Smethyl-N-pentoxyacetylphosphoroamidodithioate, S-methyl-S-methyl-N-hexoxyacetylphosphoroamidodithioate, S-isopropyLS-is
- N-alkylthioalkanoylphosphoroamidodithioate of formula (I) are: S-methyl-S- methyl-N-methylthioacetylphosphoroamidodithioate, S-methyl-S-methyLN-ethylthioacetylphosphoroamidodithioate, S-methyl-S-methyl-N- methyl-N-butylthioacetylphosphoroamidodithioate, S-allyl-S-allyl-N-pentylthioacetylphosphoroamidodithioate, S-methyl-S methyl-N-hexylthioacetylphosphoroamidodithioate, S-methyl-S-methyl-N-3- methylthiopropionylphosphoroamidodithioate, S- methyl-S-methyl-N-3-ethylthiopropionylphosphoroamid
- N-aryloxyalkanoylphos phoroamidodithioates of formula (I) are: S-allyl-S- methyl-N-methyl-N-p-bromophenoxyacetylphosphoroamidodithioate, S-methyl-S-methyl-N-( 3- methylphenoxy)acetylphosphoroamidodithioate, S- ethyl-S-ethyl-3-benzyl0xypropionylphosphoroamidodithioate and S-propargyl-S-methyl-N-4-(4- chlorophenoxy)butyrylphosphoroamidodithioate.
- N-arylthioalkanoylphosphoroamidodithioates of formula (I) are: S-methyl-S- methyl-N-4-chlorophenylthioacetylphosphoroamidodithioate, S-allyl-S-allyl-N-benzylthioacetylphosphoroamidodithioate, S-ethyl-S-methyl-N-3-(2,4- dichlorophenylthio)propionylphosphoroamidodithioate, S-methyl-S-methyl-N-3-(4- methylphenylthio)propionylphosphoroamidodithioate and S-isopropyl-S-propargyl-N-propyl-N-3-(pchlorobenzylthio)propionylphosphoroamidodithioate.
- the preferred compounds of formula (I) are O,S- dialkyl-N-alkoxyalkanoylthiophosphorothioate (Y and X are oxygen).
- the most preferred compounds are 0,- S-dialkyl-N-alkoxyalkanoylphosphoroamidothioates wherein R, R and R are alkyl of l to 3 carbon atoms, n is l or 2, or R is hydrogen.
- the compounds of formula (I) may be prepared by acylating an appropriate O-hydrocarbyl-S- hydrocarbylphosphoroamidothioate or S-hydrocarbyl- S-hydrocarbylphosphoroamidodithioate.
- O-alkyl-S- alkylphosphoroamidothioates and their preparation are disclosed in U.S. Pat. No. 3,309,266.
- O-alkyl-S- unsaturated hydrocarbylphosphoroamidothioates and their preparation are disclosed in U.S. Pat. No. 3,649,723. 7
- acylating agents such as acyl halides, ketenes and acid anhydrides and conventional acylating conditions may be used in this reaction.
- Alkoxyalkanoyl and alkylthioalkanoyl chlorides are preferred acylatingagents.
- This acylation reaction (illustrated with an acyl chloride as the acylating agent) may be represented by the propylthioacetylphosphoroamidodithioate, S-allyl-S- following equation:
- R s 1 be carried out at about to 60C. in the presence of solvents such a methylene chloride, chloroform, tetrahydrofurnn and benzene. Pressure is not critical in this reaction. For convenience, atmospheric or autogenous pressure will be used. Under normal conditions, stoichiometric proportions or a slight deficiency of acylating agent will be used. The acylation will usually take 2 to 24 hours to reach completion.
- the reaction product may be purified by conventional extraction and recrystallization techniques.
- N-acylated phosphoroamidothioates of this invention may also be prepared by acylating an appropriate 0,0- dialkyl phosphoroamidothionate and then isomerizing the resulting N-acylphosphoroamidothionate with an alkylating agents to produce the O-alkyl-S-alkyl-N- acylphosphoroamidothioate.
- This reaction scheme is represented (using an acyl chloride as the acylating wherein R represents an alkylating agent corresponding to R.
- This acylation may be carried out by the same techniques described above for the acylation reaction depicted in equation (1).
- the acylation reaction (2) is also described in applicants U.S. application Ser. No.
- N-acylphosphoroamidothionate and the alkylating agent may be done according to the procedures described in US. Pat. No. 3,309,266 for reacting 0,0- dialkylphosphoroamidothionate with an alkylating agent.
- Suitable alkylating agents represented by R include alkyl, alkenyl, and alkynyl halides, particularly iodides, e.g., methyl iodide, ethyl iodide, allyl iodide, propargyl iodide, butyl iodide, etc. and dialkyl/dialkenyl sulfates, e.g., dimethyl sulfate, diethyl sulfate, diallyl sulfate and dihexyl sulfate.
- iodides e.g., methyl iodide, ethyl iodide, allyl iodide, propargyl iodide, butyl iodide, etc.
- dialkyl/dialkenyl sulfates e.g., dimethyl sulfate, diethyl sulfate, dially
- the 0,0-dihydrocarbyl-N-acylphosphoroamidothioate (VI) can be converted to the O,S- dihydrocarbylphosphoroamidothioate (VII) by treating the 0,0-compound (VI) with a sodium alkyl mercaptide (VIII) to form the S-sodium salt and alkylating the S-sodium salt to form the O,S-compound (VII).
- This reaction scheme is represented by the following equatrons:
- the metalation reaction depicted in equation (4) is conducted by contacting substantially equimolar amounts of the reactants (VI) and (VIII) in the liquid phase in an inert solvent at a temperature of 10-100C. The reaction is complete within 10 hours, more usually in 5 hours or less.
- the sodium salt product (IX) may be used for further reaction without separation.
- the alkylation of the sodium salt (IX) is effected by mixing substantially equimolar amounts of sodium salt (IX) and the alkylating agent R in an inert solvent at a temperature of in the range of 080C, preferably 25-60C.
- the product (VII is isolated by conventional methods, e.g., extraction, chromatography, etc.
- the phosphoroamidothioate compounds may also be prepared by amidating an appropriate 0,0- dihydrocarbylphosphorothiochloridate to obtain an O,- O-dihydrocarbyl-N-acylphosphoroamidothioate and isomerizing said N-acylphosphoroamidothioate with an alkylating agent as described above.
- This reaction scheme is illustrated by the following set of equations:
- T T CI-P-Cl RSH RS-P-CI 1101 The above reactions are preferably carried out in the presence of a weak base, such as the organic amines, for example pyridine, dimethyl aniline, triethyl amine, etc.
- the base is preferably present in an amount at least equal to the moles of mercaptan.
- An inert organic solvent such as diethyl ether, tetrahydrofuran, dioxane, dichloromethane, etc. may be present.
- the reaction temperatures are generally in the range of to 13C., preferably 0 to C.
- the reaction time necessary to complete the addition of the mercaptan to the phosphorous oxychloride will range from about 1 to hours.
- the S-hydrocarbyl-S-hydrocarbylphosphorochloridodithioate product can be purified by distillation, crystallization or chromatography, if desired.
- the second step of the preparation i.e. amidation, is carried out by adding gaseous ammonia or an amine to a solution of the S-hydrocarbyl-S- hydrocarbylphosphorochloridodithioate according to the following equation:
- the reaction is preferably carried out in an inert organic solvent, such as benzene, toluene, xylene and the like, at temperatures in the range of 10 to 75C., preferably 40 to 60c. Completion of the reaction is indicated by cessation of ammonium chloride precipitation.
- the crude product can be isolated by filtration and then separated from ammonium chloride by selective extraction with a solvent, such as acetone, methanol or similar organic materials.
- the 0,0-dihydrocarbylphosphoroamidothioate compounds used to prepare the compounds of the invention are prepared by the following reactions:
- This compound was prepared by the reaction of O,S- dimethylphosphoroamidothioate and bromacetyl chloride in methylene chloride by a procedure similar to that of Example IV.
- the product was purified by chromatography or silica (methylene dichloride/acetone eluants). Elemental analysis on the product is tabulated in Table I.
- UTILITY The compounds of this invention were tested as follows to illustrate their insecticidal activity. Test results An acetone solution of the candidate toxicant containing a small amount of nonionic emulsifier was diluted with water to 30 ppm. cucumber leaves infested with the cotton aphids were dipped in the toxicant soluare reported Table 20 tion. Mortality readings were then taken after 24 hours.
- a 500 ppm acetone solution of the candidate toxicant was placed in a microsprayer (atomizer).
- a random mixture of anesthetized male and female roaches was placed in a container and 55 mg. of the abovedescribed acetone solution was sprayed on them.
- a lid was placed on the container.
- a mortality reading was made after 24 hours.
- a 500 ppm acetone solution of the candidate toxicant was placed in a microsprayer (atomizer).
- a random mixture of anesthetized male and female flies was placed in a container and 55 mg. of the above described acetone solution was sprayed on them.
- a lid was placed on the container.
- a mortality reading was made after 24 hours.
- one or more of the compounds of this invention may be applied in other liquid or solid formulations to the insects, their environment or hosts susceptible to insect attack.
- they may be sprayed or otherwise applied directly to plants or soil so as to effect control of insects 5 coming into contact therewith.
- Formulations of the compounds of this invention will comprise a toxic amount of one or more phosphoroamidothioate and/or phosphoroamidodithioate and a biologically inert carrier. Usually they will also contain a wetting agent. Solid carriers such as silica, clay, talc, sawdust and the like may be used in such formulations. Liquid diluents which may be used with these compounds include water and aromatic solvents. In addition these formulations may contain other compatible pesticides, plant growth regulators, fillers, stabilizers, attractants and the like.
- insecticide and insect refer to their broad and commonlyunderstood 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 lnsecta but also to other related classes of arthropods whose members are segmented invertebrates having more or fewer than six legs, such as spiders, mites, ticks, centipedes, worms and the like.
- An insecticidal composition comprising an insecticidally effective amount of a compound of the formula wherein R and R individually are alkyl, alkenyl or alkynyl of up to 6 carbon atoms, Y and X individually are oxygen or sulfur, n is a whole number of from 1 to 6, R is alkyl of l to 6 carbon atoms, aryl of up to carbon atoms substituted with up to 2 fluorine, chlorine or bromine atoms, and R is hydrogen or alkyl of l to 6 carbon atoms, in a biologically inert carrier.
- alkyl of up to 6 carbon atoms.
- composition of claim 2 wherein R is alkyl of l to 6 carbon atoms and Y and X are oxygen.
- composition of claim 2 wherein R, R and R are alkyl of l to 3 carbon atoms and n is l or 2, and R is hydrogen.
- composition of claim 1 wherein the compound is O,S-dimethyl-N-methoxyacetylphosphoroamidothioate.
- composition of claim 2 wherein R is alkyl of l to 6 carbon atoms, Y is oxygen and X is sulfur.
- composition of claim 6 wherein R, R and R are alkyl of l to 3 carbon atoms, R is hydrogen and n is l, 2 or 3.
- composition of claim 2 wherein R is phenyl substituted with up to 2 fluorine, chlorine or bromine atoms and n is l.
- a method of killing insects which comprises contacting said insects with an insecticidally effective amount of a compound of the formula R-Y o c- (CH2) -X-R2 n P-N wherein R and R individually are alkyl, alkenyl or alkynyl of up to 6 carbon atoms, Y and X individually are oxygen or sulfur, n is a whole number of from l to 6, R is alkyl of l to 6 carbon atoms, aryl of up to 10 carbon atoms substituted with up to 2 fluorine, chlorine or bromine atoms, and R is hydrogen or alkyl of l to 6 carbon atoms.
- R and R individually are alkyl of up to 6 carbon atoms.
- R is alkyl of 1 to 6 carbon atoms and Y and X are oxygen.
- R, R and R are alkyl of l to 3 carbon atoms and n is l or 2, and R is hydrogen.
- R, R and R are alkyl of l to 3 carbon atoms, R is hydrogen and n is l, 2 or 3.
- R is phenyl substituted with up to 2 fluorine, chlorine or bromine atoms and n is 1.
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Abstract
WHEREIN R AND R1 INDIVIDUALLY ARE ALKYL, ALKENYL OR ALKYBYYL OF UP TO 6 CARBON ATOMS, Y AND X INDIVIDUALLY ARE OXYGEN OR SULFUR, N IS A WHOLE NUMBER OF FROM 1 TO 6, R2 IS ALKYL OF 1 TO 6 CARBON ATOMS, ARYL OF UP TO 10 CARBON ATOMS SUBSTITUTED WITH UP TO 2 FLUORINE, CHLORINE OR BROMINE ATOMS, AND R3 IS HYDROGEN OR ALKYL OF 1 TO 6 CARBON ATOMS, IN A BIOLOGICALLY INERT CARRIER.
R-Y-P(=O)(-S-R1)-N(-R3)-CO-(CH2)N-X-R2
1. AN INSECTICIDAL COMPOSITION COMPRISING AN INSECTICIDALLY EFFECTIVE AMOUNT OF A COMPOUND OF THE FORMULA
R-Y-P(=O)(-S-R1)-N(-R3)-CO-(CH2)N-X-R2
1. AN INSECTICIDAL COMPOSITION COMPRISING AN INSECTICIDALLY EFFECTIVE AMOUNT OF A COMPOUND OF THE FORMULA
Description
United States Patent 91 Magee Feb. 25, 1975 INSECTICIDAL O,S-DIHYDROCARBYL-N-ACYLPHOS- PHOROAMIDOTHIOATES AND S,S-DIHYDROCARBYL-N-ACYLPHOS- PHOROAMIDODITHIOATES [76] Inventor: Philip S. Magee, lgnatia, Calif.
[22] Filed: Jan. 14, 1974 [21] Appl. No.: 432,929
Related U.S. Application Data [60] Division ofSer. No. 317,315, Dec.21, 1972, Pat. No. 3,801,680, which is a continuation-in-part of Ser. No. 13,846, Feb. 24, 1970, Pat. No. 3,716,600, which is a continuation-in-part of Ser. No. 810,383, March 25, 1969, abandoned.
[52] U.S. Cl 424/217, 424/216, 424/220 [51] Int. Cl A01n 9/36 [58] Field of Search 424/216, 217, 220
Primary Examiner-Stanley J. Friedman Assistant Examiner-D. W. Robinson Attorney, Agent, or FirmJ. A. Buchanan,- Jr.
20 Claims, No Drawings INSECTICIDAL O,S-DIHYDROCARBYL-N-ACYLPHOS- PHOROAMIDOTHIOATES AND S,S-DII-IYDROCARBYL-N-ACYLPI-IOS- PHOROAMIDODITHIOATES CROSS-REFERENCE TO RELATED APPLICATIONS This application is a division of application Ser. No. 317,315, filed Dec. 21, 1972, now U.S. Pat. No. 3,801,680, issued Apr. 2, 1974, which. in turn is a continuatiomin-part of application Ser. No. 13,846, filed Feb. 24, 1970, now U.S. Pat. No. 3,716,600, which in turn is a continuation-in-part of application Ser. No. 810,383, filed Mar. 25, 1969, now abandoned.
DESCRIPTION OF THE PRIOR ART U.S Pat. No. 3,309,266 teaches that O-alkyl-S-alkyl phosphoroamidothioates are insecticidal. U.S. Pat. No. 3,649,723 teaches that O-alkyl-S-unsaturated hydrocarbylphosphoroamidothioates are insecticidal. U.S. Pat. No. 3,201,446 teaches that 0,0-diethyl-N- trichloroacetylphosphoroamidethioate [N-- (diethoxyphosphinothioyl)-2,2,2-trichloroacetamide] is useful as an insecticide. Russian Pat. No. 253,483, issued on Sept. 30, 1969 to G. V. Protopopova et al., discloses the use of O,S-dialkyl-N- alkylthiocarbonylphosphoroamidothioates, e.g.,
CHSS
as insecticides. L. Almasi et al, Chem. Ber. 100 2626 (1967) and Chem. Ber. 99 3293 (1966), disclose O- ethyl-S-methyl-N-benzoylphosphoroamidothioate, O- ethyl-S-methyl-N-p-chlorobenzoylphosphoroamidothioate and O-ethyl-S-methyl-N-p-methylbenzoylphosphoroamidothioate.
DESCRIPTION OF THE INVENTION The phosphoroamidothioates and phosphoroamidodithioates of this invention are represented by the formula (I):
R-Y 0 i 1(0H2)u--XR -N Ra wherein R and R individually are alkyl, alkenyl or alkynyl of up to 6 carbon atoms, Y and X individually are oxygen or sulfur, n is whole number of from 1 to 6, preferably 1 or 2, R is alkyl of 1 to 6 carbon atoms, aryl of up to carbon atoms substituted with up to 2 (0 to 2) fluorine, chlorine or bromine atoms, and R is hydrogen or alkyl of l to 6 carbon atoms.
Representative alkyl groups which R, R, R and R may represent include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, sec-pentyl and hexyl. Representative alkenyl of 3 to 6 carbon atoms which R and R may represent include allyl, 2-butenyl, 2- hexanyl, etc. Representative alkynyl of 3 to 6 carbon atoms which R and R may represent include 2- propynyl, 2-butynyl, 2-hexynyl, etc. Preferred R, R,
cially methyl. The preferred R groups is hydrogen.
Representative hydroca'rbyl aryl R groups include phenyl, naphthyl, aralkyl of 7 to 10 carbon atoms, e.g., benzyl, Z-phenylethyl, 3-tolylpropyl, 4-phenylbutyl, and alkaryl of 7 to 10 carbon atoms, e.g., 2- methylphenyl, 3-methylphenyl, 4-methylphenyl, 2,4- dimethylphenyl, 3,5-diethylphenyl and 4-t-butylphenyl. Representative halo substituted aryl R group include halophenyl of 1 to 2 fluorine, chlorine or bromine atoms such as 2-fluorophenyl, 3-chlorophenyl, 4- bromophenyl, 2,4-dichlorophenyl, 3,5-dibromophenyl, etc.; and haloaralkyl and haloalkaryl of 7 to 10 carbon atoms and 1 to 2 fluorine, chlorine or bromine atoms such as 2-fiuorobenzyl, 4-chlorobenzyl, 2,4- dibromobenzyl, 2-(4-chlorophenyl)ethyl, 3-(2- fluoraphenyl)propyl, 2-chloro-4-methylphenyl, 3-fluoro-4-methylphenyl, etc.
thioates of formula (I) are: O-allyl-S-methyl-N- methoxyacetylphosphoroamidothioate, O-propargyl-S:
methyl-N-ethoxyacetylphosphoroamidothioate, O- methyl-S-ethyl-N-ethyl-N-propoxyacetylphosphoroamidothioate, O-propyl-S-allyl-N- methoxyacetylphosphoroamidothioate, O-methyl-S- allyl-N-butoxyacetylphosphoroamidothioate, O- methyl-S-methyl-N-pentoXyacetylphosphoroamidothioate, O-methyl-S-methyl-N-hexoxyacetylphosphoroamidothioate, O-isopropyl-S- isopropyl-N-3-methoxypropionylphosphoroamidothioate, O-methyl-S methyl-N- 3-ethoxypropionylphosphoroamidothioate, O-allyl-S-allyl-N- isopropyl-N-3-propoxypropionylphosphoroamidothioate, O-methyl-S-methyl-N-3-isopropoxypropionylphosphoroamidothioate, O-methyl-S-methyl-N-methyl-N-4- methoxybutyrylphosphoroamidothioate, O-methyl-S- methyl-N-4-propoxybutyrylphosphoroamidothioate,
O-butyl-S-methyl-N-4-ethoxybutyrylphosphoroamidothioate, O-2-butenyl-S-butyl-N-5- methoxypentanoylphosphoroamidothioate, O-methyl- S-methyl-N-S-methoxybutanoylphosphoroamidothioate, O-methyl-Smethyl-N-S-pentoxypentanoylphosphoroamidothioate, O-methyl-S-methyl-N-6- methoxyhexanoylphosphoroamidothioate, O-methyl-S- methyl-N-6-isopropoxyhexanoylphosphoroamidothioate, O-methyl-S-pentyl-N-7-methoxyheptanoylphosphoroamidothioate, and O-methyl-S-methyl-N-7- hexoxyheptanoylphosphoroamidothioate.
Representative N-alkylthioalkanoylphosphoroamidothioate of formula (I) are: O-methyl-S- allyl-N-methylthioacetylphosphoroamidothioate, O- allyl-S-methyl-N-methyl N-ethylthioacetylphosphoroamidothioate, O-methyl-S-methyl-N- propylthioacetylphosphoroamidothioate, O-propargyl- S-methyl-N-butylthioacetylphosphoroamidothioate, O-rnethyl-S-methyl-N-pentylthioacetylphosphoroamidothioate, O-methyl-S-methyl-N- hexylthioacetylphosphoroamidothioate, O-methyl-S- methyl-N-3-methylthiopropionylphosphoroamidothi- O-allyl-S-allyl-N-3-ethylthiopropionylphosphoroamidothioate, O-ethyl-S-ethyl-N-3- isopropylthiopropionylphosphoroamidothioate, O- methyl-S-methyl-N-3-propylthiopropionylphosphoroamidothioate, O-4-hexen yl-S-methyl-N-3- butylthiopropionylphosphoroamidothioate, O-methyl- S-methyl-N-4-sec-butylthiobutyrylphosphoroamidothi- 3,5-dibromo-4-ethylphenyl,.
oate, O-propyl-S-isopropyl-N-isopropyl-N-4- methylthiobutyrylphosphoroamidothioate, O-methyl- S-methylN-4-ethylthiobutyrylphosphoroamidothioate, O-allyl-S-methyl-N-S-methylthiopentanoylphosphoroamidothioate, O-allyl-S-methyl-N- ethylthiopentanoylphosphoroamidothioate, O-propyl- S-2-pentenyl-N-6-methyllthiohexanoylphosphoroamidothioate, and O-hexyl-Spentyl-N-7- methylthioheptanoylphosphoroamidothioate.
Representative N-aryloxyalkaonylphosphoroamidothioates of formula (I) are: O-methyl-S-methyl-N-pbromophenoxyacetylphosphoroamidothioate, O- methyl-S-allyl-N-(3-methylphenoxy)acetylphosphoro amidothioate, O-allyl-S-propargyl-N- 3-benzyl-oxypropionylphosphoroamidothioate and O- methyl-S-methyl-N-4-(4-chlorophenoxy)butyrylphosphoroamidothioate.
Representative N-arylthioalkanoylphosphoroamidothioates of formula (I) are: O-methyl-S-methyl-N-4- chlorophenylthioacetylphosphoroamidothioate, O- propargyl-S-methyl-N-isopropyl-N- benzylthioacetylphosphoroamidothioate, O-ethyl-S- methyl-N-3-(2,4-dichlorophenylthio)propionylphosphoroamidothioate, O-allyl-S-allyl-N-3-(4- methylphenylthio)propionylphosphoroamidothioate and O-isopropyl-S-methyl-N-3-(pchlorobenzylthio)propionylphosphoroamidothioate.
Representative N-alkoxyalkanoylphosphoroamidodithioates of formula (I) are: S-methyl-S-allyl-N-methyl- N-methoxyacetylphosphoroamidodithioate, S- propargyl-S-methyl-N-ethoxyacetylphosphoroamidodithioate, S-methyl-S-ethyl-N-propoxyacetylphosphoroamidodithioate, S-propyl-S-methyl-N- methoxyacetylphosphoroamidodithioate, S-allyl-S- allyl-N-butoxyacetylphosphoroamidodithioate, S- methyl-Smethyl-N-pentoxyacetylphosphoroamidodithioate, S-methyl-S-methyl-N-hexoxyacetylphosphoroamidodithioate, S-isopropyLS-isopropyl-N- isopropyl-N-3-methoxypropionylphosphoroamidodithioate, S-methyl-S-methyl-N-3-ethoxypropionylphosphoroamidodithioate, S-methyl-S-methyl-N-3- propoxypropionylphosphoroamidodithioate, S-methyl- S-methyl-N-3-isopropoxypropionylphosphoroamidodithioate, S-2-butenyl-S-methyl-N-4- methoxybutyrylphosphoroamidodithioate, S-methyl-S- methyl-N-4-propoxybutyrylphosphoroamidodithioate, S-butyl-S-methyl-N- 4-ethoxybutyrylphosphoroamidodithioate, S-butyl-S-butyl-N- 5methoxypentanoylphosphoroamidodithioate, S- methyl-S-methyl-N-S-methoxypentanoylphosphoroamidodithioate, S-allyl-S-allyl-N-S- pentoxypentanoylphosphoroamidodithioate, S-methyl- S-methyl-N-6-methoxyhexanoylphosphoroamidodithioate, S-methyl-S-methyl-N-6-isopropoxyhexanoylphosphoroamidodithioate, S-methyl-S-pentyl-N-7- methoxyheptanoylphosphoroamidodithioate. and S- methyl-S-methyl-N-7-hexoxheptanoylphospshoroamidodithioate.
Representative N-alkylthioalkanoylphosphoroamidodithioate of formula (I) are: S-methyl-S- methyl-N-methylthioacetylphosphoroamidodithioate, S-methyl-S-methyLN-ethylthioacetylphosphoroamidodithioate, S-methyl-S-methyl-N- methyl-N-butylthioacetylphosphoroamidodithioate, S-allyl-S-allyl-N-pentylthioacetylphosphoroamidodithioate, S-methyl-S methyl-N-hexylthioacetylphosphoroamidodithioate, S-methyl-S-methyl-N-3- methylthiopropionylphosphoroamidodithioate, S- methyl-S-methyl-N-3-ethylthiopropionylphosphoroamidodithioate S-ethyl-S-ethyl-N-3- isopropylthiopropionylphosphoroamidodithioate, S- methyl-S-methyl-N-3-propylthiopropionylphosphoroamidodithioate, S-methyl-S-methyl-N-3- butylthiopropionylphosphoroamidodithioate, S- methyl-S-methyl-N-4-sec-butylthiobutyrylphosphoroamidodithioate, I S-methyl-S-methyl-N-4- methylthiobutyrylphosphoroamidodithioate, S-methyl- S-methyl-N-4-ethylthiobutyrylphosphoroamidodithioate, S-methyl-S-allyLN-isopropyl-N-5- methylthiopentanoylphosphoroamidodithioate, S- propyl-S-propargyl-N-S-ethylthiopentanoylphosphoroamidodithioate, S-propyl-S-butyl-N-6- methylthiohexanoylphosphoroamidodithioate and S- hexyl-S-pentyl-N-7-methylthioheptanoylphosphoramidodithioate.
Representative N-aryloxyalkanoylphos phoroamidodithioates of formula (I) are: S-allyl-S- methyl-N-methyl-N-p-bromophenoxyacetylphosphoroamidodithioate, S-methyl-S-methyl-N-( 3- methylphenoxy)acetylphosphoroamidodithioate, S- ethyl-S-ethyl-3-benzyl0xypropionylphosphoroamidodithioate and S-propargyl-S-methyl-N-4-(4- chlorophenoxy)butyrylphosphoroamidodithioate.
Representative N-arylthioalkanoylphosphoroamidodithioates of formula (I) are: S-methyl-S- methyl-N-4-chlorophenylthioacetylphosphoroamidodithioate, S-allyl-S-allyl-N-benzylthioacetylphosphoroamidodithioate, S-ethyl-S-methyl-N-3-(2,4- dichlorophenylthio)propionylphosphoroamidodithioate, S-methyl-S-methyl-N-3-(4- methylphenylthio)propionylphosphoroamidodithioate and S-isopropyl-S-propargyl-N-propyl-N-3-(pchlorobenzylthio)propionylphosphoroamidodithioate.
The preferred compounds of formula (I) are O,S- dialkyl-N-alkoxyalkanoylthiophosphorothioate (Y and X are oxygen). The most preferred compounds are 0,- S-dialkyl-N-alkoxyalkanoylphosphoroamidothioates wherein R, R and R are alkyl of l to 3 carbon atoms, n is l or 2, or R is hydrogen.
The compounds of formula (I) may be prepared by acylating an appropriate O-hydrocarbyl-S- hydrocarbylphosphoroamidothioate or S-hydrocarbyl- S-hydrocarbylphosphoroamidodithioate. o-alkyl-S- alkylphosphoroamidothioates and their preparation are disclosed in U.S. Pat. No. 3,309,266. O-alkyl-S- unsaturated hydrocarbylphosphoroamidothioates and their preparation are disclosed in U.S. Pat. No. 3,649,723. 7
Conventional acylating agents, such as acyl halides, ketenes and acid anhydrides and conventional acylating conditions may be used in this reaction. Alkoxyalkanoyl and alkylthioalkanoyl chlorides are preferred acylatingagents.
This acylation reaction (illustrated with an acyl chloride as the acylating agent) may be represented by the propylthioacetylphosphoroamidodithioate, S-allyl-S- following equation:
RY 0 R-Y\(T) PNH R -X(CH2)n Cl PNC(CH2)nX-R HCl R 6 3 R s 1 be carried out at about to 60C. in the presence of solvents such a methylene chloride, chloroform, tetrahydrofurnn and benzene. Pressure is not critical in this reaction. For convenience, atmospheric or autogenous pressure will be used. Under normal conditions, stoichiometric proportions or a slight deficiency of acylating agent will be used. The acylation will usually take 2 to 24 hours to reach completion. The reaction product may be purified by conventional extraction and recrystallization techniques.
N-acylated phosphoroamidothioates of this invention may also be prepared by acylating an appropriate 0,0- dialkyl phosphoroamidothionate and then isomerizing the resulting N-acylphosphoroamidothionate with an alkylating agents to produce the O-alkyl-S-alkyl-N- acylphosphoroamidothioate. This reaction scheme is represented (using an acyl chloride as the acylating wherein R represents an alkylating agent corresponding to R. This acylation may be carried out by the same techniques described above for the acylation reaction depicted in equation (1). The acylation reaction (2) is also described in applicants U.S. application Ser. No. 148,139, filed May 28, 1971. The reaction between the N-acylphosphoroamidothionate and the alkylating agent may be done according to the procedures described in US. Pat. No. 3,309,266 for reacting 0,0- dialkylphosphoroamidothionate with an alkylating agent.
Suitable alkylating agents represented by R include alkyl, alkenyl, and alkynyl halides, particularly iodides, e.g., methyl iodide, ethyl iodide, allyl iodide, propargyl iodide, butyl iodide, etc. and dialkyl/dialkenyl sulfates, e.g., dimethyl sulfate, diethyl sulfate, diallyl sulfate and dihexyl sulfate.
Alternatively, the 0,0-dihydrocarbyl-N-acylphosphoroamidothioate (VI) can be converted to the O,S- dihydrocarbylphosphoroamidothioate (VII) by treating the 0,0-compound (VI) with a sodium alkyl mercaptide (VIII) to form the S-sodium salt and alkylating the S-sodium salt to form the O,S-compound (VII). This reaction scheme is represented by the following equatrons:
(VI) (VIII) wherein R is alkyl.
The metalation reaction depicted in equation (4) is conducted by contacting substantially equimolar amounts of the reactants (VI) and (VIII) in the liquid phase in an inert solvent at a temperature of 10-100C. The reaction is complete within 10 hours, more usually in 5 hours or less. The sodium salt product (IX) may be used for further reaction without separation.
The alkylation of the sodium salt (IX) is effected by mixing substantially equimolar amounts of sodium salt (IX) and the alkylating agent R in an inert solvent at a temperature of in the range of 080C, preferably 25-60C. The product (VII is isolated by conventional methods, e.g., extraction, chromatography, etc.
The phosphoroamidothioate compounds may also be prepared by amidating an appropriate 0,0- dihydrocarbylphosphorothiochloridate to obtain an O,- O-dihydrocarbyl-N-acylphosphoroamidothioate and isomerizing said N-acylphosphoroamidothioate with an alkylating agent as described above. This reaction scheme is illustrated by the following set of equations:
T T CI-P-Cl RSH RS-P-CI 1101 The above reactions are preferably carried out in the presence of a weak base, such as the organic amines, for example pyridine, dimethyl aniline, triethyl amine, etc. The base is preferably present in an amount at least equal to the moles of mercaptan. An inert organic solvent, such as diethyl ether, tetrahydrofuran, dioxane, dichloromethane, etc. may be present. The reaction temperatures are generally in the range of to 13C., preferably 0 to C. The reaction time necessary to complete the addition of the mercaptan to the phosphorous oxychloride will range from about 1 to hours. The S-hydrocarbyl-S-hydrocarbylphosphorochloridodithioate product can be purified by distillation, crystallization or chromatography, if desired.
The second step of the preparation, i.e. amidation, is carried out by adding gaseous ammonia or an amine to a solution of the S-hydrocarbyl-S- hydrocarbylphosphorochloridodithioate according to the following equation:
RS RS wherein R, R and R have the same significance as previously defined.
The reaction is preferably carried out in an inert organic solvent, such as benzene, toluene, xylene and the like, at temperatures in the range of 10 to 75C., preferably 40 to 60c. Completion of the reaction is indicated by cessation of ammonium chloride precipitation. Following the reaction, the crude product can be isolated by filtration and then separated from ammonium chloride by selective extraction with a solvent, such as acetone, methanol or similar organic materials.
The 0,0-dihydrocarbylphosphoroamidothioate compounds used to prepare the compounds of the invention are prepared by the following reactions:
The above reactions 11-13 are conducted by essentially the same procedures described for reactions 8-10.
EXAMPLES The following examples described methods which may be used to prepared the phosphoroamidothioates and phosphoroamidodithioates of this invention. Representative compounds prepared by these methods are tabulated in Table I.
EXAMPLE I Preparation of O,S-dimethyl-N-methoxyacetylphosphoroamidothioate.
A mixture of 45 g (0.5 mole) methoxyacetic acid and g (0.675 mole) thionyl chloride was heated at 50C. for 30 minutes. The reaction mixture was evaporated under reduced pressure to give the crude methoxyacetyl chloride.
A 15.5 g sample of the crude methoxyacetyl chloride was added to 20 g (0.142 mole) O,S-dimethylphosphoroamidothioate in 80 ml methylene dichloride. The reaction mixture was refluxed for 3 hours and then poured into 50 ml of water. The mixture was neutralized with aqueous sodium bicarbonate solution and extracted with methylene dichloride. The methylene dichloride extracts were dried over magnesium sulfate, filtered and evaporated under reduced pressure to give the crude product. The crude was chromatographed on silica (methylene dichloride/acetone eluant) to give the product as an oil. The elemental analysis of this product is tabulated in Table I.
EXAMPLE II Preparation of O,S-dimethyl-N-ethylthioacetylphosphoroamidothioate.
A mixture of 14.1 g (0.1 mole) O,S-dimethylphosphoroamidothioate, 13.8 g (0.1 mole) ethylthioacetyl chloride and 40 ml methylene dichloride was refluxed for 2 hours. The reaction mixture was worked-up and purified by chromatography on silica by a procedure similar to that of Example I. The elemental analysis of this product is tabulated in Table 1.
EXAMPLE Ill EXAMPLE IV Preparation of O,S-dimethyl-N- phenylthioacetylphosphoroamidothioate.
A mixture of 9 g 0,0-dimethyl-N- phenylthioacetylphosphoroamidothioate, 1.8 g dimethyl sulfate and 9 ml chloroform was refluxed for about 3 hours. The crude reaction mixture was chromatographed in silica (methylene dichloride/hexane eluants) to give the product. Elemental analysis on the product is tabulated in Table I.
EXAMPLE V Preparation of O,S-dimethyl-N-bromoacetylphoroamidothioate. 1
This compound was prepared by the reaction of O,S- dimethylphosphoroamidothioate and bromacetyl chloride in methylene chloride by a procedure similar to that of Example IV. The product was purified by chromatography or silica (methylene dichloride/acetone eluants). Elemental analysis on the product is tabulated in Table I.
EXAMPLE VI Preparation of S,S-dimethyl-N-acetylphosphoroamidodithioate.
A solution of 73.2 g (0.48 mole) of phosphorous oxychloride in 300 ml of dry diethyl ether was charged to a 1 liter flask at a temperature of C. A solution of 76.2 g (0.96 mole) of pyridine and 49 g (1.0 mole) of methyl mercaptan in 400 ml. of diethyl ether was added slowly to the flask containing phosphorous oxychloride over a 2-hour period of time, maintaining the temperature from 0C. to 5C. The mixture was then stirred for an additional 6 hours at temperatures of 0 to C. After 18 hours of standing at 0C. the crude reaction product was separated from the solid residue, stripped of solvent and purified to give 31.7 g of a liquid S,S- dimethylphosphorochloridodithioate.
The above S,S-dimethylphosphorochloridodithioate was then charged with 500 ml of toluene to a 1 liter flask and ammonia gas added slowly at a temperature of 50 to C. When the temperature started to drop, ammonia addition was stopped. The reaction was held at 50C. for /2 hour and then cooled to room temperature and filtered. The filtrate was stripped of solvent under vacuum, then purified to give 6.6 g of S,S- dimethylphosphoroamidodithioate. The compound had a melting point of 103-105C., and the following N, S, P analysis:
S,S-dimethylphosphoroamidodithioate was dissolved in 250 ml of dichloromethane and charged to a 500 ml flask. 39.3 g 90.5 mole) of acetylchloride was added. The solution was refluxed for 2 hours and stored at room temperature for 18 hours. The dichloromethane and excess acetylchloride were removed by evaporation and the product dissolved in 250 ml of dichloromethane to which was added 250 ml water containing sufficient calcium hydroxide to give a pH of 7 after thorough mixing. The organic phase was separated from the aqueous phase and the S,S-dimethyl-N- acetylphosphoroamidodithioate recovered from the organic phase as an oil (3.7 g). Analysis was as follows:
LII
(PSC1 at 0-10C. The resulting reaction mixture was cooled in a DRY-lCE/acetone both while 80 g (1 mole) a 50% sodium hydroxide solution was added. After the addition was completed, the reaction mixture was stirred at about 25C forl 1 hours, diluted with 200 ml water and 50 ml chloroform. The organic phase was separate, dried over magnesium-sulfate, filtered and evaporated under reduced pressure. The residue was distilled to 31.3 g of 0,0-diallylphosphorochloridothioate, b.p. 7274C (0.15 mm Hg).
The above 0,0-diallylphosphorochloridothioate (30 g) and 500 ml benzene were then charged to a flask and ammonia (10 g) in 100 m1 benzene was slowly added. A heavy precipitate was formed in an exothermic reaction. The reaction was evaporated to give a cloudy white liquid. The liquid was diluted with 50 ml methylene chloride and refluxed with 10 g of ammonium hydroxide for V2 hour. The organic-layer was washed with water, dried over magnesium sulfate, filtered and evaporated to give 20 g of 0,0-diallylphosphoroamidothioate.
A 10 g (0.0518 mole) sample of the above 0,0- diallylphosphoroamidothioate, 6 g (0.059 mole) acetic anhydride, 40 ml methylene chloride and 1 ml phosphoric acid was refluxed for 3 hours. The reaction mixture was diluted with 50 ml water and 100 ml aqueous saturated ammonium chloride solution. The aqueous solution was extracted with methylene chloride. The methylene chloride extracts were washed with aqueous ammonium chloride solution, dried over magnesium sulfate and evaporated to give 10.4 g of 0,0-dial1yl-N- acetylphosphoroamidothioate.
A mixture of 10 g (0.0425 mole) of the above 0,0- diallyl-N-acetylphosphoroamidothioate, 4.3 g (0.0425 mole) sodium n-butyl mercaptide and 40 ml methanol was refluxed for 4 hours and then evaporated under reduced pressure to give the crude S-sodium-O-allyl-N- 'acetylphosphoroamidothioate salt. The salt, 6 g dimethyl sulfate and 40 ml acetonitrile were then refluxed for 25 hours. A heavy precipitate formed. The reaction mixture was filtered and the filtrate was evapcalculated Found orated under reduced pressure to give 9 g of a yellow liquid residue. The residue was chromatographed on 2 silica (hexane/methylene chloride/acetone eluants) to '72 P 15.52 14.08 give the S-methyl-O-allyl-N-acetylphosphoroamidothioate product as an oil. Elemental analysis for C H NO PS showed: EXAMPLE V11 Preparation of O-allyl-S-methyl-N-acetylphos- Calculmed Found phoroamidothioate.
A 68 g (1.1 mole) sample of allyl alcohol was added g :g-g lg-g dropwise to 84 g (0.5 mole) phosphorous thiochloride TABLE I No. Compound Melting Point Elemental Analysis %P 708 Cale. Found Cale. Found 1 0.S-dimethyl-N-methoxyacetylphosphoroamidothioate 01] 14.53 13.70 6.59 6.25 2 O.S-dimethyl-N-3-methoxypropiony1- phosphoroamidothioate 011 13.61 13.23 6.15 5.85 3 0.5-dimethyl-N-3-hutoxypropionylphosphoroamidothioate 011 11.5 10.5 1 1.9 11.1 4 O.S-dimethyl-N-3-isopropoxypropionylphosphoroamidothioate oil 12.1 1 1.93 12.55 12.13 5 O,S-dimethyl-N-eth lthioacetylphosphoroamidot ioate 011 12.72 11.72 6 O,S-dimethyl-N-3-methylthiopropionylphosphoroamidothioate 133-135 12.7 11.0
TABLE I Continued No. Compound Melting Point Elemental Analysis %P 705 Calc'. Found Calc. Found 7 O,S dimethyl-N-4-methy1thiobutyry1- phosphoroamidothioate 76-78 12.02 12.27 8 O.S-dimethyl-N-phenoxyacetylphosphoroamidothioate oil 11.25 10.82 1 1.62 1 1.68 9 O,S-dimethyl-N-Z,4-dichlorophenoxyacetylphosphoroamidothioate 95100 7.8 9.0 l O,S-dimethyl-N-phenylth ioacetylphosphoroamidothioate oil 10.6 10.15 22.8 20.62 1 l S,S-dimethyl-N-acetylphos horoamidodithioate oil 15.52 14.08 32.1 31.04 12 O-allyl-S-methyl-N'acety1p osphoroamidothioate oil 14.8 14.62 15.4 15.8
UTILITY The compounds of this invention were tested as follows to illustrate their insecticidal activity. Test results An acetone solution of the candidate toxicant containing a small amount of nonionic emulsifier was diluted with water to 30 ppm. cucumber leaves infested with the cotton aphids were dipped in the toxicant soluare reported Table 20 tion. Mortality readings were then taken after 24 hours.
TABLE 11 Compound No. 1 7a Mortality Cabbage Looper Cockroach Housefly Mite Aphid 1 100 100 100 100' 90 2 2O 90 96 70 O 3 30 0 0 96 (30 ppm) 0 4 94 100 (100 ppm) 39 (30 ppm) 0 5 90 100 100 90 22 6 O 100 60 94 7 O 100 60 39 8 100 (625 ppm) 100 100 100 9 100 100 90 39 (30 ppm) 0 I0 100 (625 ppm) 94 30 99 85 l l 0 60 100 97 98 12 90 100 100 85 ppm) 90 TEST PROCEDURES Cabbage lopper (Trichoplusia ni):
An acetone solution of the candidate toxicant containing a small amount of nonionic emulsifier was diluted with water to 500 ppm. Cabbage leaf sections were dipped in the toxicant solution and dried. The sections were then infested with cabbage looper larve. 4
Mortality readings were taken after 24 hours. American Cockroach (Periplaneta americana L.):
A 500 ppm acetone solution of the candidate toxicant was placed in a microsprayer (atomizer). A random mixture of anesthetized male and female roaches was placed in a container and 55 mg. of the abovedescribed acetone solution was sprayed on them. A lid was placed on the container. A mortality reading was made after 24 hours.
Housefiles (Musca domestica L.):
A 500 ppm acetone solution of the candidate toxicant was placed in a microsprayer (atomizer). A random mixture of anesthetized male and female flies was placed in a container and 55 mg. of the above described acetone solution was sprayed on them. A lid was placed on the container. A mortality reading was made after 24 hours.
Two-spotted Mites (Tetramuchus urticae):
An acetone solution of the candidate toxicant containing a small amount of nonionic emulsifier was diluted with water to 100 ppm. Pinto bean leaves which were infested with mites were dipped in the toxicant solution. Mortality readings were taken after 24 hours.
Aphids (Aphis gossypii Glover):
In addition to the specific formulations and application techniques described above, one or more of the compounds of this invention may be applied in other liquid or solid formulations to the insects, their environment or hosts susceptible to insect attack. For example, they may be sprayed or otherwise applied directly to plants or soil so as to effect control of insects 5 coming into contact therewith.
Formulations of the compounds of this invention will comprise a toxic amount of one or more phosphoroamidothioate and/or phosphoroamidodithioate and a biologically inert carrier. Usually they will also contain a wetting agent. Solid carriers such as silica, clay, talc, sawdust and the like may be used in such formulations. Liquid diluents which may be used with these compounds include water and aromatic solvents. In addition these formulations may contain other compatible pesticides, plant growth regulators, fillers, stabilizers, attractants and the like.
The term insecticide and insect as used herein refer to their broad and commonlyunderstood usage rather than to those creatures which in the strict biological sense are classified as insects. Thus, the term insect" is used not only to include small invertebrate animals belonging to the class lnsecta but also to other related classes of arthropods whose members are segmented invertebrates having more or fewer than six legs, such as spiders, mites, ticks, centipedes, worms and the like.
As will be evident to those skilled in the art, various modifications of this invention can be made or followed, in the light of the foregoing disclosure and discussion, without departing from the spirit or scope of the disclosure or from the scope of the following claims.
I claim:
1. An insecticidal composition comprising an insecticidally effective amount of a compound of the formula wherein R and R individually are alkyl, alkenyl or alkynyl of up to 6 carbon atoms, Y and X individually are oxygen or sulfur, n is a whole number of from 1 to 6, R is alkyl of l to 6 carbon atoms, aryl of up to carbon atoms substituted with up to 2 fluorine, chlorine or bromine atoms, and R is hydrogen or alkyl of l to 6 carbon atoms, in a biologically inert carrier.
2. The composition of claim 1 wherein R and R indi-,
vidually are alkyl of up to 6 carbon atoms.
3. The composition of claim 2 wherein R is alkyl of l to 6 carbon atoms and Y and X are oxygen.
4. The composition of claim 2 wherein R, R and R are alkyl of l to 3 carbon atoms and n is l or 2, and R is hydrogen.
5. The composition of claim 1 wherein the compound is O,S-dimethyl-N-methoxyacetylphosphoroamidothioate.
6. The composition of claim 2 wherein R is alkyl of l to 6 carbon atoms, Y is oxygen and X is sulfur.
7. The composition of claim 6 wherein R, R and R are alkyl of l to 3 carbon atoms, R is hydrogen and n is l, 2 or 3.
8. The composition of claim 7 wherein R and R are methyl, R is ethyl, and n is l.
9. The composition of claim 2 wherein R is phenyl substituted with up to 2 fluorine, chlorine or bromine atoms and n is l.
10. The composition of claim 9 wherein R and R are methyl, R is phenyl, Y is oxygen and X is oxygen.
11. A method of killing insects which comprises contacting said insects with an insecticidally effective amount of a compound of the formula R-Y o c- (CH2) -X-R2 n P-N wherein R and R individually are alkyl, alkenyl or alkynyl of up to 6 carbon atoms, Y and X individually are oxygen or sulfur, n is a whole number of from l to 6, R is alkyl of l to 6 carbon atoms, aryl of up to 10 carbon atoms substituted with up to 2 fluorine, chlorine or bromine atoms, and R is hydrogen or alkyl of l to 6 carbon atoms.
12. The method of claim 11 wherein R and R individually are alkyl of up to 6 carbon atoms.
13. The method of claim 12 wherein R is alkyl of 1 to 6 carbon atoms and Y and X are oxygen.
14. The method of claim 12 wherein R, R and R are alkyl of l to 3 carbon atoms and n is l or 2, and R is hydrogen.
15. The method of claim 11 wherein the compound is O,S-dimethyl-N-methoxyacetylphosphoroamidothioate.
16. The method of claim 12 wherein R is alkyl of l to 6 carbon atoms, Y is oxygen and X is sulfur.
17. The method of claim 16 wherein R, R and R are alkyl of l to 3 carbon atoms, R is hydrogen and n is l, 2 or 3.
18. The method of claim 17 wherein R and R are methyl, R is ethyl, and n is l.
19. The method of claim 12 wherein R is phenyl substituted with up to 2 fluorine, chlorine or bromine atoms and n is 1.
20. The method of claim 19 wherein R and R are methyl, R is phenyl, Y is oxygen and X is oxygen.
Claims (1)
1. AN INSECTICIDAL COMPOSITION COMPRISING AN INSECTICIDALLY EFFECTIVE AMOUNT OF A COMPOUND OF THE FORMULA
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4299783A (en) * | 1980-04-28 | 1981-11-10 | Chevron Research Company | 1-Alkylsulfonyl-3-substituted phosphinylthio- or phosphinothioylthio-propenes |
US4900733A (en) * | 1986-09-16 | 1990-02-13 | E. I. Dupont De Nemours & Co. | N-acyl phosphonamidothioates and dithioates |
US20030100604A1 (en) * | 2000-03-28 | 2003-05-29 | Reiner Fischer | Active substance combinations having insecticidal and acaricidal properties |
US6576661B1 (en) | 1999-11-09 | 2003-06-10 | Bayer Aktiengesellschaft | Active ingredient combination having insecticidal and acaricidal characteristics |
US7060692B2 (en) | 2000-08-31 | 2006-06-13 | Bayer Cropscience Ag | Active ingredient combinations comprising insecticidal and acaricidal properties |
-
1974
- 1974-01-14 US US432929A patent/US3868449A/en not_active Expired - Lifetime
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4299783A (en) * | 1980-04-28 | 1981-11-10 | Chevron Research Company | 1-Alkylsulfonyl-3-substituted phosphinylthio- or phosphinothioylthio-propenes |
US4900733A (en) * | 1986-09-16 | 1990-02-13 | E. I. Dupont De Nemours & Co. | N-acyl phosphonamidothioates and dithioates |
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 |
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