US3057774A - Carbamoylalkyl phosphonothioates - Google Patents
Carbamoylalkyl phosphonothioates Download PDFInfo
- Publication number
- US3057774A US3057774A US14193A US1419360A US3057774A US 3057774 A US3057774 A US 3057774A US 14193 A US14193 A US 14193A US 1419360 A US1419360 A US 1419360A US 3057774 A US3057774 A US 3057774A
- Authority
- US
- United States
- Prior art keywords
- ethyl
- methylphosphonodithioate
- water
- weight
- phosphonothioates
- 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
- -1 Carbamoylalkyl phosphonothioates Chemical class 0.000 title description 66
- FUWGSUOSJRCEIV-UHFFFAOYSA-N phosphonothioic O,O-acid Chemical class OP(O)=S FUWGSUOSJRCEIV-UHFFFAOYSA-N 0.000 description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 28
- 241000607479 Yersinia pestis Species 0.000 description 27
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 26
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 24
- 241000238631 Hexapoda Species 0.000 description 24
- 150000001875 compounds Chemical class 0.000 description 24
- 239000000203 mixture Substances 0.000 description 23
- DXVBUJOATHQUCY-UHFFFAOYSA-N hydroxy-methyl-sulfanyl-sulfanylidene-$l^{5}-phosphane Chemical compound CP(O)(S)=S DXVBUJOATHQUCY-UHFFFAOYSA-N 0.000 description 22
- 239000004094 surface-active agent Substances 0.000 description 20
- 238000000034 method Methods 0.000 description 19
- 125000004432 carbon atom Chemical group C* 0.000 description 18
- 239000003795 chemical substances by application Substances 0.000 description 18
- 239000007787 solid Substances 0.000 description 18
- 239000007788 liquid Substances 0.000 description 17
- 230000000749 insecticidal effect Effects 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 14
- 239000012141 concentrate Substances 0.000 description 14
- 235000008504 concentrate Nutrition 0.000 description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 12
- 239000000725 suspension Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000000839 emulsion Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 8
- 239000007921 spray Substances 0.000 description 8
- 239000002917 insecticide Substances 0.000 description 7
- GYPNJSBBOATUPK-UHFFFAOYSA-N 2-chloro-n-propan-2-ylacetamide Chemical compound CC(C)NC(=O)CCl GYPNJSBBOATUPK-UHFFFAOYSA-N 0.000 description 6
- 241000238876 Acari Species 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000003995 emulsifying agent Substances 0.000 description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- WXJXBKBJAKPJRN-UHFFFAOYSA-N Methanephosphonothioic acid Chemical compound CP(O)(O)=S WXJXBKBJAKPJRN-UHFFFAOYSA-N 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- KVYMNPHHMZSJCI-UHFFFAOYSA-N ethoxy-methyl-sulfanyl-sulfanylidene-$l^{5}-phosphane Chemical compound CCOP(C)(S)=S KVYMNPHHMZSJCI-UHFFFAOYSA-N 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 239000002736 nonionic surfactant Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000000080 wetting agent Substances 0.000 description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000000443 aerosol Substances 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000000344 soap Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 231100000331 toxic Toxicity 0.000 description 4
- 230000002588 toxic effect Effects 0.000 description 4
- 238000005292 vacuum distillation Methods 0.000 description 4
- HOZLOOPIXHWKCI-UHFFFAOYSA-N 2-chloro-n-methylacetamide Chemical compound CNC(=O)CCl HOZLOOPIXHWKCI-UHFFFAOYSA-N 0.000 description 3
- XZIIFPSPUDAGJM-UHFFFAOYSA-N 6-chloro-2-n,2-n-diethylpyrimidine-2,4-diamine Chemical compound CCN(CC)C1=NC(N)=CC(Cl)=N1 XZIIFPSPUDAGJM-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 241001521235 Spodoptera eridania Species 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 125000002877 alkyl aryl group Chemical group 0.000 description 3
- 239000003945 anionic surfactant Substances 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000003892 spreading Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 2
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 241000239290 Araneae Species 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004338 Dichlorodifluoromethane Substances 0.000 description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 239000004264 Petrolatum Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000000440 bentonite Substances 0.000 description 2
- 229910000278 bentonite Inorganic materials 0.000 description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 2
- 229940042935 dichlorodifluoromethane Drugs 0.000 description 2
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- TZIRZWKKHSEPPT-UHFFFAOYSA-N ethyl-propan-2-yloxy-sulfanyl-sulfanylidene-$l^{5}-phosphane Chemical compound CCP(S)(=S)OC(C)C TZIRZWKKHSEPPT-UHFFFAOYSA-N 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 239000000417 fungicide Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000004009 herbicide Substances 0.000 description 2
- ITIDSNKGTOBPBD-UHFFFAOYSA-N hydroxy-phenyl-sulfanyl-sulfanylidene-$l^{5}-phosphane Chemical compound OP(S)(=S)C1=CC=CC=C1 ITIDSNKGTOBPBD-UHFFFAOYSA-N 0.000 description 2
- 239000011872 intimate mixture Substances 0.000 description 2
- 231100000518 lethal Toxicity 0.000 description 2
- 230000001665 lethal effect Effects 0.000 description 2
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 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
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229940066842 petrolatum Drugs 0.000 description 2
- 235000019271 petrolatum Nutrition 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 239000008247 solid mixture Substances 0.000 description 2
- 229940035044 sorbitan monolaurate Drugs 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000000271 synthetic detergent Substances 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical group CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 description 1
- NFAOATPOYUWEHM-UHFFFAOYSA-N 2-(6-methylheptyl)phenol Chemical compound CC(C)CCCCCC1=CC=CC=C1O NFAOATPOYUWEHM-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- YMQRPXBBBOXHNZ-UHFFFAOYSA-N 2-chloro-1-morpholin-4-ylethanone Chemical compound ClCC(=O)N1CCOCC1 YMQRPXBBBOXHNZ-UHFFFAOYSA-N 0.000 description 1
- AZOOMRDAGOXGNJ-UHFFFAOYSA-N 2-chloro-n-prop-2-enylacetamide Chemical compound ClCC(=O)NCC=C AZOOMRDAGOXGNJ-UHFFFAOYSA-N 0.000 description 1
- YQIGLEFUZMIVHU-UHFFFAOYSA-N 2-methyl-n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C(C)=C YQIGLEFUZMIVHU-UHFFFAOYSA-N 0.000 description 1
- 241000256118 Aedes aegypti Species 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 241000238421 Arthropoda Species 0.000 description 1
- 241000258920 Chilopoda Species 0.000 description 1
- 241000254173 Coleoptera Species 0.000 description 1
- 241000255925 Diptera Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 241000258937 Hemiptera Species 0.000 description 1
- 241000257303 Hymenoptera 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
- 240000007049 Juglans regia Species 0.000 description 1
- 235000009496 Juglans regia Nutrition 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 241000131095 Oniscidea Species 0.000 description 1
- 231100000674 Phytotoxicity Toxicity 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 241000256248 Spodoptera Species 0.000 description 1
- 206010043268 Tension Diseases 0.000 description 1
- 241001454293 Tetranychus urticae Species 0.000 description 1
- 241000254113 Tribolium castaneum Species 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003899 bactericide agent 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
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 150000001723 carbon free-radicals Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- VXIVSQZSERGHQP-UHFFFAOYSA-N chloroacetamide Chemical compound NC(=O)CCl VXIVSQZSERGHQP-UHFFFAOYSA-N 0.000 description 1
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 1
- 229960001231 choline Drugs 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000007799 cork Substances 0.000 description 1
- 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
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- NAKDJXIEBCHXIZ-UHFFFAOYSA-N dihydroxy-phenyl-sulfanylidene-$l^{5}-phosphane Chemical compound OP(O)(=S)C1=CC=CC=C1 NAKDJXIEBCHXIZ-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- GFTATZBXSYXGRK-UHFFFAOYSA-N ethyl-hydroxy-sulfanyl-sulfanylidene-$l^{5}-phosphane Chemical compound CCP(O)(S)=S GFTATZBXSYXGRK-UHFFFAOYSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910000286 fullers earth Inorganic materials 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 150000004820 halides Chemical class 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
- IPCSVZSSVZVIGE-UHFFFAOYSA-M hexadecanoate Chemical compound CCCCCCCCCCCCCCCC([O-])=O IPCSVZSSVZVIGE-UHFFFAOYSA-M 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
- 239000003906 humectant Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- ZVTUXDLIMYIOGQ-UHFFFAOYSA-N hydroxy-propan-2-yl-sulfanyl-sulfanylidene-$l^{5}-phosphane Chemical compound CC(C)P(O)(S)=S ZVTUXDLIMYIOGQ-UHFFFAOYSA-N 0.000 description 1
- FLQUDUCNBDGCRI-UHFFFAOYSA-N hydroxy-sulfanyl-sulfidophosphanium Chemical compound SP(S)=O FLQUDUCNBDGCRI-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 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
- 239000003350 kerosene Substances 0.000 description 1
- 235000014666 liquid concentrate Nutrition 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000005394 methallyl group Chemical group 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000002757 morpholinyl group Chemical group 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
- 230000001473 noxious effect Effects 0.000 description 1
- 239000002674 ointment Substances 0.000 description 1
- 239000003883 ointment base Substances 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000005936 piperidyl group Chemical group 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 150000003141 primary amines Chemical group 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229910052903 pyrophyllite Inorganic materials 0.000 description 1
- PWZUUYSISTUNDW-VAFBSOEGSA-N quinestrol Chemical compound C([C@@H]1[C@@H](C2=CC=3)CC[C@]4([C@H]1CC[C@@]4(O)C#C)C)CC2=CC=3OC1CCCC1 PWZUUYSISTUNDW-VAFBSOEGSA-N 0.000 description 1
- 230000000284 resting effect Effects 0.000 description 1
- 239000003128 rodenticide Substances 0.000 description 1
- 150000003335 secondary amines Chemical group 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- COITVVSLPILCRT-UHFFFAOYSA-M sodium ethoxy-oxido-phenyl-sulfanylidene-lambda5-phosphane Chemical compound C1(=CC=CC=C1)P(OCC)([O-])=S.[Na+] COITVVSLPILCRT-UHFFFAOYSA-M 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- RLJSXMVTLMHXJS-UHFFFAOYSA-M sodium;4-decylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCC1=CC=C(S([O-])(=O)=O)C=C1 RLJSXMVTLMHXJS-UHFFFAOYSA-M 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 230000009885 systemic effect Effects 0.000 description 1
- 125000004568 thiomorpholinyl group Chemical group 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 229940078499 tricalcium phosphate Drugs 0.000 description 1
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 1
- 235000019731 tricalcium phosphate Nutrition 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 235000020234 walnut Nutrition 0.000 description 1
- 239000002023 wood 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
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6536—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having nitrogen and sulfur atoms with or without oxygen atoms, as the only ring hetero atoms
- C07F9/6544—Six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4075—Esters with hydroxyalkyl compounds
-
- 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
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
- C07F9/576—Six-membered rings
- C07F9/59—Hydrogenated pyridine rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6527—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having nitrogen and oxygen atoms as the only ring hetero atoms
- C07F9/6533—Six-membered rings
Definitions
- This invention relates to new and useful phosphonothioates and to methods of making same. Additionally this invention relates to insecticidal compositions containing the new phosphonothioates as an active ingredient.
- the new compounds of this invention can be termed carbamoylalkyl phosphonothiates and can be represented by the structure wherein R is phenyl or an alkyl radical containing from 1 to carbon atoms (i.e. methyl, ethyl, propyl, butyl, amyl, and the various isomeric forms thereof); wherein R is an alkyl radical containing from 1 to 4 carbon atoms (i.e. methyl, ethyl, propyl, butyl, and the various isomeric forms thereof); wherein X is a chalkogen of atomic weight less than 40 (i.e.
- A is a divalent aliphatic hydrocarbon radical having the empirical formula C T-I wherein n is a whole number from 1 to 3; and wherein N is (1) NH or (2) a primary amine residue NHR" wherein R is a hydrocarbon radical containing not more than 7 carbon atoms or (3) a secondary amine residue NRR" wherein R" and R are hydrocarbon radicals containing not more than 7 carbon atoms or (4) a saturated single ring heterocyclic secondary amine residue containing not more than 5 carbon atoms (e.g. morpholinyl, C H ON, thiamorpholinyl, C H SN, piperidyl, C H N, pyrrolidyl, C H N, etc.).
- N is (1) NH or (2) a primary amine residue NHR" wherein R is a hydrocarbon radical containing not more than 7 carbon atoms or (3) a secondary amine residue NRR" wherein R" and R are hydrocarbon radicals containing not more than 7 carbon atoms or
- hydrocarbon radicals containing not more than 7 carbon atoms is meant to include the aryl, alkaryl, aralkyl, cycloalkyl, alkenyl and alkyl radicals as exemplified by phenyl, tolyl, benzyl, cyclohexyl, methylcyclohexyl, allyl, methallyl, methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, and the various isomeric hydrocarbon forms thereof containing not more than 7 carbon radicals.
- R" and R' be aliphatic hydrocarbon radicals containing not more than 3 carbon atoms (i.e.
- R and R be alkyl radicals containing not more than 3 carbon atoms (i.e., methyl, ethyl, n-propyl, or isopropyl).
- the phosphonothioates of this invention can be prepared by reacting a salt (i.e. ammonium or alkali metal such as sodium, potassium, or lithium) of a phosphonothioic acid of the structure RO X wherein X, R and R have the aforedescribed significance in an anhydrous system with a substantially equimolecular amount of an amide of the structure wherein A and N have the aforedescribed significance and wherein the term halogen means a halogen having an atomic number above 9 but not higher than 35 in the presence of an inert organic liquid or solvent (e.g.
- Example ll CH3 i H PSCHrC-NHCH 031150 Employing the procedure of Example I but replacing 2-chloro-N-isopropylacetamide with an equimolecular amount of 2-chloro-N-methylacetamide there is obtained ethyl S (N methylcarbamoylmethyl) methylphosphonodithioate, a brown solid soluble in chloroform but insoluble in water.
- Example II Employing the procedure of Example I but replacing 2-chloro-N-isopropylacetamide with an equimolecular amount of 2-chloro-N-methylacetamide and replacing ammonium O-ethyl methylphosphonodithioate with an equimolecular amount of ammonium O-methyl methylphosphonodithioate there is obtained O-methyl S-(N- methylcarbamoylmethyl) methylphosphonodithioate, an oil soluble in chloroform but insoluble in water.
- Example IV CH3 S CgHsO Employing the procedure of Example I but replacing 2-chloro-N-isopropylacetamide with an equimolecular amount of N-allyl-2-chloroacetamide there is obtained O-ethyl S-(N-allyl-carbamoylmethyl) methylphosphonodithioate which is soluble in chloroform and isopropyl alcohol but insoluble in water.
- Example V CH ISI Employing the procedure of Example I but replacing 2-ch1oro-N-isopropylacetamide with an equimolecular amount of 2-chloro-acetamide there is obtained O-ethyl S-(carbamoylmethyl) methylphosphonodithioate which is soluble in chloroform but insoluble in water.
- Example IX Employing the procedure of Example I but replacing ammonium O-ethyl methylphosphonodithioate With an equimolecular amount of ammonium O-ethyl methylphosphonothioate there is obtained O-ethyl S-(N-isopropylcarbamoylmethyl) methylphosphonothioate which is soluble in ethanol, carbon tetrachloride and chloroform but insoluble in water.
- the phosphonothioates of this invention can also be prepared by reacting a phosphonothioic acid of the structure Kit P-SH
- R, R and X have the aforedescribed significance in an anhydrous system with a substantially equimolecular amount of an acrylamide of the structure wherein a and b are unlike integers from 0 to 1, inclusive, and wherein N has the aforedescribed significance in the presence of an inert organic liquid or solvent (e.g. acetone, methyl ethyl ketone, dioxane, benzene, toluene, xylene, etc.) at a temperature above the freezing point of the system and up to and including the boiling point of the system, but preferably in the range of 20 C. to C.
- a catalyst e.g.
- a tertiary organic amine such as pyridine, triethylamine, choline and their equivalents.
- Any catalytic amount can be employed which amount usually will be in the range of 0.1 to 2.5% by Weight based on the total weight of the respective reactants. Because of the tendency of acrylamides to polymerize the reaction is most advantageously carried out in the presence of a polymerization inhibitor, e.g. hydroquinone.
- a polymerization inhibitor e.g. hydroquinone.
- this means of preparing the compounds of this invention is the following:
- the residue is then taken up with methylene chloride and the organic solution washed first with aqueous sodium carbonate and then twice with water and the washings discarded.
- the so-washed organic solution is then subjected to vacuum distillation to remove the solvent.
- the residue (21.0 parts by weight) is S-(Z-carbamoylethyl) O-ethyl methylphosphonodithioate, which is soluble in acetone, ethanol and chloroform but insoluble in water.
- any inert organic liquid or mixture of inert organic liquids can be used provided at least one of the reactants is soluble therein.
- the methods by which the phosphonothioates of this invention are isolated will vary slightly with the reactants employed and the product produced. Further purification by selective solvent extraction or by absorptive agents such as activated carbon or clays can precede the removal of the inert organic liquid or solvent. Additionally an inert organic solvent can be added to and in the purification by absorptive agents. However, the product is generally satisfactory for insecticidal purposes without further purification.
- insect and insecticide are used herein in their broad common useage to include spiders, mites, ticks, and like pests which are not in the strict biological sense classed as insects.
- useage herein conforms to the definitions provided by Congress in Public Law 104, the Federal Insecticide, Fungicide, and Rodenticide Act of 1947, Section 2, subsection h, wherein the term insect is used to refer not only to those small invertebrate animals belonging mostly to the class Insecta, comprising six-legged, usually winged forms, as beetles, bugs, bees, flies, and so forth, but also to other allied classes of arthropods Whose members are Wingless and usually have more than six legs, as spiders, mites, ticks, centipedes, and wood lice.
- the phosphonothiates of this invention are effective against a wide variety of insect pests.
- As illustrative of the activity but not lirnitative thereof is the following:
- O-ethyl S-(N-isopropylcarbamoylmethyl) methylphosphonodithioate was dissolved in sufficient acetone to make a concentrate solution thereof.
- Approximately 0.1 co. of sorbitan monolaurate polyoxyethylene derivative (a commercial water-soluble nonionic emulsifying agent containing 20 moles of ethylene oxide per mole of sorbitan monolaurate) is then mixed with the concentrate.
- the phosphonothioates of this invention are useful per se in controlling a wide variety of insect pests, it is preferable that they be supplied to the pests or to the environment of the pest or pests in a dispersed form in a suitable extending agent.
- dispersed is used in its widest possible sense.
- particles of the phosphonothioates of this invention may be molecular in size and held in true solution in a suitable organic solvent. It means further, that the particles may be colloidal in size and distributed throughout a liquid phase in the form of suspensions or emulsions or in the form of particles held in suspension by wetting agents.
- It also includes particles which are distributed in a semi-solid viscous carrier such as petrolatum or soap or other ointment base in which they may be actually dissolved in the semi-solid or held in suspension in the semi-solid with the aid of suitable wetting or emulsifying agents.
- a semi-solid viscous carrier such as petrolatum or soap or other ointment base
- dispersed also means that the particles may be mixed with and distributed throughout a solid carrier providing a mixture in particulate form, e.g. pellets, granules, powders, or dusts.
- dispersed also includes mixtures which are suitable for use as aerosols including solutions, suspensions, or emulsions of the phosphonothioates of this invention in a carrier such as dichloro-difluoromethane and like fluorochloroalkanes which boil below room temperature at atmos pheric pressure.
- a carrier such as dichloro-difluoromethane and like fluorochloroalkanes which boil below room temperature at atmos pheric pressure.
- the expression extending agent includes any and all of those substances in which the phosphonothioates of this invention are dispersed. It includes, therefore, the solvents of a true solution, the liquid phase of suspensions, emulsions or aerosols, the semi-solid carrier of ointments and the solid phase of particulate solids, e.g. pellets, granules, dusts and powders.
- concentration of the phosphonothioates of this invention employed in combatting or controlling insect pests can vary considerably provided the required dosage (i.e., toxic or lethal amount) thereof is supplied to the pests or to the environment of the pests.
- the extending agent is a liquid or mixture of liquids (e.g. as in solutions, suspensions, emulsions, or aerosols) the concentration of the phosphonothioate employed to supply the desired dosage generally will be in the range of 0.001 to 50 percent by weight.
- concentration of the phosphonothioate employed to supply the desired dosage generally will be in the range of 0.1 to 25 percent by weight.
- the manufacturer must supply the agriculturist with a low-cost concentrate or spray base or particulate solid base in such form that, by merely mixing with water or solid extender (e.g., powdered clay or talc) or other low-cost material available to the agriculturist at the point of use, he will have an easily prepared insecticidal spray or particulate solid.
- a low-cost concentrate or spray base or particulate solid base in such form that, by merely mixing with water or solid extender (e.g., powdered clay or talc) or other low-cost material available to the agriculturist at the point of use, he will have an easily prepared insecticidal spray or particulate solid.
- the phosphonothioate generally will be present in a concentration of 5 to 95 percent by weight, the residue being any one or more of the well known insecticidal adjuvants, such as the various surface active agents (e.g., detergents, a soap or other emulsifying or wetting agent), surfaceactive clays, solvents, diluents, carrier media, adhesives, spreading agents, humectants, and the like.
- the various surface active agents e.g., detergents, a soap or other emulsifying or wetting agent
- surfaceactive clays e.g., solvents, diluents, carrier media, adhesives, spreading agents, humectants, and the like.
- organic liquids which can be used for the preparation of solutions, suspensions or emulsions of the phosphonothioates of this invention.
- organic liquids for example, isopropyl ether, acetone, methyl ethyl ketone, dioxane, cyclohexanone, carbon tetrachloride, ethylene dichloride, tetrachloroethane, hexane, heptane and like higher liquid alkanes, hydrogenated naphthalenes, solvent naphtha, benzene, toluene, xylene, petroleum fractions (e.g. those boiling almost entirely under 400 F.
- organic liquid extending agent at atmospheric pressure and having a flash point above about F., particularly kerosene), mineral oils having an unsulfonatable residue above about 80 percent and preferably above about percent.
- organic liquid extending agent a portion of same can be replaced by such low molecular weight aliphatic hydrocarbons as dipentene, diisobutylene, propylene trimer, and the like or suitable polar organic liquids such as the aliphatic ethers and the aliphatic ketones containing not more than about 10 carbon atoms as exemplified by acetone, methyl ethyl ketone, diisobutyl ketone, dioxane, isopropyl ether, and the like.
- the phosphonothioates of this invention are to be supplied to the insect pests or to the environment of the pests as aerosols, it is convenient to dissolve them in a suitable solvent and disperse the resulting solution in dichlorodifluoromethane or like chlorofluoroalkane which boils below room temperature at atmospheric pressure.
- the phosphonothioates of this invention are preferably supplied to the insect pests or to the environment of the insect pests in the form of emulsions or suspensions.
- Emulsions or suspensions are prepared by dispersing the phosphonothioate of this invention either per se or in the form of an organic solution thereof in water with the aid of a water-soluble surfactant.
- surfactant as employed here and in the appended claims is used as in volume II of Schwartz, Perry and Berchs Surface Active Agents and Detergents (1958, Interscience Publishers, Inc., New York) in place of the expression emulsifying agent to connote generically the various emulsifying agents, dispersing agents, wetting agents and spreading agents that are adapted to be admixed with the active compounds of this invention in order to secure better wetting and spreading of the active ingredients in the water vehicle or carrier in which they are insoluble through lowering the surface tension of the water (see also Frear, Chemistry of Insecticides, Fungicides and Herbicides, second edition page 280).
- surfactants include the well-known capillary-active substances which may be anion-active (or anionic), cation active (or cationic), or non-ionizing (or non-ionic) which are described in detail in volumes I and II of Schwartz, Perry and Berchs Surface Active Agents and Detergents (1958, Interscience Publishers, Inc., New York), and also in the November 1947 issue of Chemical Industries (pages 811-824) in an article entitled Synthetic Detergents, by John W. McCutcheon, and also in the July, August, September and October 1952 issues of Soap and Sanitary Chemicals under the title Synthetic Detergents. The disclosures of these articles with respect to surfactants, i.e.
- the anion-active, cation-active and non-ionizing capillary active substances are incorporated in this specification by reference in order to avoid unnecessary enlargement of this specification.
- the preferred surfactants are the water-soluble anionic surface-active agents and the water soluble non-ionic surface-active agents set forth in US. 2,846,398 (issued August 5, 1958). In general it is preferred that a mixture of water-soluble anionic and water-soluble non-ionic surfactants be employed.
- the phosphonothioate's of this invention can be dispersed by suitable methods (e.g., tumbling or grinding) in solid extending agents either of organic or inorganic nature and supplied to theinsect pests environment in particulate form.
- suitable methods e.g., tumbling or grinding
- solid extending agents either of organic or inorganic nature and supplied to theinsect pests environment in particulate form.
- Such solid materials include for example, tricalcium phosphate, calcium carbonate, kaolin, bole, kieselguhr, talc, bentonite, fullers earth, pyrophyllite, diatomaceous earth, calcined magnesia, volcanic ash, sulfur and the like inorganic solid materials, and include for example, such materials of organic nature as powdered cork, powdered wood, and powdered walnut shells.
- the preferred solid carriers are the adsorbent clays, e.g.
- the phosphonothioates of this invention can be dispersed in a semi-solid extending agent such as petrolatum or soap (e.g., sodium stearate or oleate or palmitate or mixtures thereof) with or without the aid of solubility promoters and/or surfactants or dispersing agents.
- a semi-solid extending agent such as petrolatum or soap (e.g., sodium stearate or oleate or palmitate or mixtures thereof) with or without the aid of solubility promoters and/or surfactants or dispersing agents.
- the dispersions can be provided ready for use in combatting insect pests or they can be provided in a concentrated form suitable for mixing with or dispersing in other extending agents.
- a particularly useful concentrate is an intimate mixture of phosphonothioate of this invention with a water-soluble surfactant which lowers the surface ten sion of water in the weight proportions of 0.1 to 15 parts of surfactant with sufficient of the phosphonothioate of this invention to make 100 parts by weight.
- Such a concentrate is particularly adapted to be made into a spray for combatting various forms of insect pests (particularly mites) by the addition of water thereto.
- Such a concentrate is an intimate mixture of 95 parts by weight of O-ethyl S-(N-methylcarbamoylmethyl) methylphosphonodithioate and parts by weight of a water-soluble non-ionic surfactant such as the polyoxyethylene derivative of sorbitan monolaurate.
- Another useful concentrate adapted to be made into a spray for combatting insect pests (particularly mites) is a solution (preferably as concentrated as possible) of a phosphonothioate of this invention in an organic solvent therefor.
- the said liquid concentrate preferably contains dissolved therein a minor amount (e.g., 0.5 to percent by weight of the weight of the new insecticidal agent) of a surfactant (or emulsifying agent), which surfactant is also water-soluble.
- Such a concentrate is a solution of O-ethyl S-(N-isopropylcarbamoylmethyl) methylphosphonodithioate in benzene which solution contains dissolved therein a water-soluble polyoxyethylene glycol non-ionic surfactant and a watersoluble alkylaryl sulfonate anionic surfactant.
- anionic and nonionic surfactants are preferred.
- anionic surfactants the particularly preferred are the well known watersoluble alkali metal alkylaryl sulfonates as exemplified by sodium decylbenzene sulfonate and sodium dodecylbenzene sulfonate.
- non-ionic surfactants the particularly preferred are the water-soluble polyoxyethylene derivatives of alkylphenols (particularly isooctylphenol) and the water-soluble polyoxyethylene derivatives of the mono-higher fatty acid esters of sorbitan containing 15 to 30 moles of ethylene oxide per mole of sorbitan monoester or alkylphenol.
- the active ingredient can be one or more of the compounds of this invention.
- the compounds of this invention can also be advantageously employed in combination with other pesticides, including, for example, nematocides, bactericides, and herbicides. In this manner it is possible to obtain mixtures which are effective against a wide variety of pests and other forms of noxious life.
- the O-aryl phosphonothioates of this invention either per se or compositions comprising same are supplied to the insect pests or to their environment in a lethal or toxic amount.
- This can be done by dispersing the new insecticidal agent or insecticidal composition comprising same in, on or over an infested environment or in, on or over an environment the insect pests frequent, e.g. agricultural soil or other growth media or other media infested with insect pests or attractable to the pests for habitational or sustenance or propagational purposes, in any conventional fashion which permits contact between the insect pests and the phosphonothioates of this invention.
- Such dispersing can be brought about by applying sprays or particulate solid compositions to a surface infested with the insect pests or attractable to the pests, as for example, the surface of an agricultural soil or other media such as the above ground surface of plants by any of the conventional methods, e.g. power clusters, boom and hand sprayers, and spray dusters. Also for sub-surface application such dispersing can be carried out by simply mixing the new insecticidal agent per se or insecticidal spray or particulate solid compositions comprising same with the infested environment or with the environment the insect pests frequent, or by employing a liquid carrier for the new insecticidal agent to accomplish sub-surface penetration and impregnation therein.
- R and R are alkyl radicals containing not more than 3 carbon atoms and wherein R" is an aliphatic hydrocarbon radical containing not more than 3 carbon atoms and selected from the group consisting of alkyl and alkenyl radicals.
- R, R and X have the same significance as in claim 1 with a substantially equimolar amount of a halide of the structure I halogen-AO-N wherein halogen means a halogen having an atomic number above 9 but not higher than 35 and wherein A and N have the same significance as in claim 1 in the presence of an inert organic liquid.
- the method of making compounds of claim 1 WhlCh comprises reacting in an anhydrous system a phosphonothioic acid of the structure R O INC P-SH 12 wherein R, R and X have the same significance as in claim 1 with a substantially equimolecular amount of an amide of the structure wherein a and b are unlike integers from 0 to 1 and wherein N has the same significance as in claim 1 in the presence of an inert organic liquid and a catalytic amount of a tertiary organic amine.
- An insecticidal composition comprising a compound of claim 1 dispersed in an extending agent.
- An insecticidal composition comprising a compound of claim 1 dispersed in an extending agent, the composition containing 0.1 to 25 percent by weight of said compound of claim 1, the extending agent being selected from the group consisting of solid and semi-solid extending agents.
- An insecticidal composition comprising a compound of claim 1 dispersed in a liquid extending agent, the composition containing 0.001 to percent by weight of said compound of claim 1.
- An insecticidal composition comprising a compound of claim 2 dispersed in an adsorbent clay, the composition containing 0.1 to 25 percent by weight of said compound of claim 2.
- An insecticidal concentrate comprising a compound of claim 2 and an insecticidal adjuvant, said concentratc containing from 5 to percent by weight of the compound of claim 2.
- An insecticidal concentrate comprising a compound of claim 1 dispersed in an organic solvent therefor and having dissolved therein a minor amount of a surfactant, said concentrate forming an emulsion with water upon agitation therewith.
- An insecticidal concentrate adapted to be made into a sprayable composition by the addition of water comprising a compound of claim 2 in admixture with a watersoluble surfactant in the weight proportion of 0.1 to 15 parts of surfactant and suflicient of said compound of claim 2 to make parts by weight.
- the method of controlling insects which comprises contacting the insects with a toxic amount of a compound of claim 1.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
United States Pater O 3,057,774 CARBAMOYLALKYL PHOSPHONOTHIOATES Joseph W. Baker and John P. Chupp, Kirkwood, and
Peter E. Newallis, Crestwood, Mo., assignors to Monsanto Chemical Company, St. Louis, Mo., :1 corporation of Delaware No Drawing. Filed Mar. 11, 1960, Ser. No. 14,193 19 Claims. (Cl. 167-22) This invention relates to new and useful phosphonothioates and to methods of making same. Additionally this invention relates to insecticidal compositions containing the new phosphonothioates as an active ingredient.
The new compounds of this invention can be termed carbamoylalkyl phosphonothiates and can be represented by the structure wherein R is phenyl or an alkyl radical containing from 1 to carbon atoms (i.e. methyl, ethyl, propyl, butyl, amyl, and the various isomeric forms thereof); wherein R is an alkyl radical containing from 1 to 4 carbon atoms (i.e. methyl, ethyl, propyl, butyl, and the various isomeric forms thereof); wherein X is a chalkogen of atomic weight less than 40 (i.e. sulfur or oxygen); wherein A is a divalent aliphatic hydrocarbon radical having the empirical formula C T-I wherein n is a whole number from 1 to 3; and wherein N is (1) NH or (2) a primary amine residue NHR" wherein R is a hydrocarbon radical containing not more than 7 carbon atoms or (3) a secondary amine residue NRR" wherein R" and R are hydrocarbon radicals containing not more than 7 carbon atoms or (4) a saturated single ring heterocyclic secondary amine residue containing not more than 5 carbon atoms (e.g. morpholinyl, C H ON, thiamorpholinyl, C H SN, piperidyl, C H N, pyrrolidyl, C H N, etc.).
By the expression hydrocarbon radicals containing not more than 7 carbon atoms is meant to include the aryl, alkaryl, aralkyl, cycloalkyl, alkenyl and alkyl radicals as exemplified by phenyl, tolyl, benzyl, cyclohexyl, methylcyclohexyl, allyl, methallyl, methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, and the various isomeric hydrocarbon forms thereof containing not more than 7 carbon radicals. In general it is preferred that R" and R' be aliphatic hydrocarbon radicals containing not more than 3 carbon atoms (i.e. methyl, ethyl, n-propyl, isopropyl, and allyl) and it is preferred that R and R be alkyl radicals containing not more than 3 carbon atoms (i.e., methyl, ethyl, n-propyl, or isopropyl).
The phosphonothioates of this invention can be prepared by reacting a salt (i.e. ammonium or alkali metal such as sodium, potassium, or lithium) of a phosphonothioic acid of the structure RO X wherein X, R and R have the aforedescribed significance in an anhydrous system with a substantially equimolecular amount of an amide of the structure wherein A and N have the aforedescribed significance and wherein the term halogen means a halogen having an atomic number above 9 but not higher than 35 in the presence of an inert organic liquid or solvent (e.g. acetone, methyl ethyl ketone, benzene, toluene, xylene, etc.), at a temperature above the freezing point of the system and "ice up to and including the boiling point of the system, but preferably at a temperature in the range of 20 C. to 120 C.
As illustrative of the phosphonothioates of this invention is the following:
O-methyl S-(carbamoylmethyl) methylphosphonodithioate O-ethyl S-(carbamoylmethyl) methylphosphonodithioate O-ethyl S-(carbamoylmethyl) methylphosphonothiate O-ethyl S-(carbamoylmethyl) isopropylphosphonothioate O-ethyl S-(carbamoylmethyl) phenylphosphonodithioate O-isopropyl S[2-(carbamoyl)ethyl] ethy-lphosphonodithioate V O-n-butyl S-[3-(carbamoyl)propyl] methylphosphonodithioate O-methyl S-(N-methylcarbamoylmethyl) phonothioate O-ethyl S-(N-ethylcarbamoylmethyl) methylphosphono thioate O-ethyl S-(N-allylcarbamoylmethyl) isopropylphosphonodithioate O-ethyl S-(N-isopropylcarbamoylmethyl) phenylphosphonodithioate O -ethyl S- (N-isoamylcarbamoylmethyl) methylphosphonodithioate O-ethyl S-(N-phenylcarbamoylmethyl) methylphosphonodithioate O ethyl S (N-cyclohexylcarbamoylmethyl) ethylphosphonodithioate Omethyl S-(N,N-dimethylcarbamoylmethyl) methylphosphonothioate O-methyl S-(N,N-dimethylcarbamoylmethyl) methylphosphonodithioate O-ethyl S-(N,N-dimethylcarbamoylmethyl) methylphosphonodithioate O-ethyl S-[2-(N,N-diethylcarbamoyl)ethyl] ethylphosphonodithioate O-ethyl S-(N,N-diallylcarbamoylmethyl) methylphosphonodithioate O- ethyl S-(N,N-diallylcarbamoylmethyl) phenylphosphonodithioate O -isopropyl S-(N,N-diisopropylcarbamoylrnethyl) methylphosphonothioate O-methyl S-(N,N-diphenylcarbamoylmethyl) methylphosphonodithioate O-methyl S-(N-ethyl-N-phenylcarbamoylmethyl) ethylphosphonothioate O-methyl S-(4-morpholinylcarbonylmethyl) methylphosphonodithioate O-methyl S-(1-piperidinylcarbonylmethyl) methylphosphonodithioate O-ethyl S-(4-thiamorph0linylcarbonylmethyl) phosphonodithioate O-methyl S-(N-methyl-N- phenylcarbamoylmethyl) methylphosphonothioate methyl-phosmethyl- As illustrative of the preparation of the compounds of this invention is the following:
To a suitable reaction vessel equipped with a thermometer, agitator and reflux condenser is charged parts by weight of acetone, 13.5 parts by weight (substantially 0.10 mol) of 2-chloro-N-isopropylacetamide, and 19.0 parts by Weight (substantially 0.11 mol) of ammonium O-ethyl methylphosphonodithioate and the mass refluxed for 4 hours. The reaction mass is then cooled to room temperature and filtered. The filter cake is then washed with acetone and the washings combined with the original filtrate. The liquid mass is then subjected to vacuum distillation to remove the acetone. The residue is then taken up with 75 parts by weight of methylene chloride and the organic solution washed first with aqueous sodium carbonate and then twice with water and the washings discarded. The so-washed organic solution is then subjected to vacuum distillation to remove the solvent. The residue, an amber oil, is O-ethyl S-(N-isopropylcarbamoylmethyl) methylphosphonodithioate which is soluble in ethanol and chloroform but insoluble in water. Analysis.--Theory: 5.6% N, 11.9% P, 24.6% S. Found: 5.5% N, 12.1% P, 25.1% S.
Example ll CH3 i H PSCHrC-NHCH 031150 Employing the procedure of Example I but replacing 2-chloro-N-isopropylacetamide with an equimolecular amount of 2-chloro-N-methylacetamide there is obtained ethyl S (N methylcarbamoylmethyl) methylphosphonodithioate, a brown solid soluble in chloroform but insoluble in water.
Employing the procedure of Example I but replacing 2-chloro-N-isopropylacetamide with an equimolecular amount of 2-chloro-N-methylacetamide and replacing ammonium O-ethyl methylphosphonodithioate with an equimolecular amount of ammonium O-methyl methylphosphonodithioate there is obtained O-methyl S-(N- methylcarbamoylmethyl) methylphosphonodithioate, an oil soluble in chloroform but insoluble in water.
Example IV CH3 S CgHsO Employing the procedure of Example I but replacing 2-chloro-N-isopropylacetamide with an equimolecular amount of N-allyl-2-chloroacetamide there is obtained O-ethyl S-(N-allyl-carbamoylmethyl) methylphosphonodithioate which is soluble in chloroform and isopropyl alcohol but insoluble in water.
Example V CH ISI Employing the procedure of Example I but replacing 2-ch1oro-N-isopropylacetamide with an equimolecular amount of 2-chloro-acetamide there is obtained O-ethyl S-(carbamoylmethyl) methylphosphonodithioate which is soluble in chloroform but insoluble in water.
Example VI OH; S
CzHsO Employing the procedure of Example I but replacing 2-chloro-N-isopropylacetamide with an equimolecular amount of N,N-diallyl alpha-chloro acetamide there is obtained S-(N,N-diallyl-carbamoylmethyl) O-ethyl methylphosphonodithioate which oil is soluble in chloroform but insoluble in water.
Employing the procedure of Example I but replacing ammonium O-ethyl methylphosphonodithioate with an equimolecular amount of sodium O-ethyl phenylphosphonothioate there is obtained O-ethyl S-(N-isopropylcarbamoylmethyl) phenylphosphonothioate which is soluble in chloroform but insoluble in water.
Example IX Employing the procedure of Example I but replacing ammonium O-ethyl methylphosphonodithioate With an equimolecular amount of ammonium O-ethyl methylphosphonothioate there is obtained O-ethyl S-(N-isopropylcarbamoylmethyl) methylphosphonothioate which is soluble in ethanol, carbon tetrachloride and chloroform but insoluble in water.
Example X CH3 0 O l 'SCEhi'JNHC/H;
Employing the procedure of Example I but replacing ammonium O-ethyl methylphosphonodithioate with an equimolecular amount of ammonium O-ethyl methylphosphonothioate and replacing 2-chloro-N-isopropylacetarnide with an equimolecular amount of 2-chloro-N-methylacetamide there is obtained O-ethyl S-(N-methylcarbamoylmethyl) methylphosphonothioate which is insoluble in water, but soluble in chloroform, ethanol and butanone.
The phosphonothioates of this invention can also be prepared by reacting a phosphonothioic acid of the structure Kit P-SH
wherein R, R and X have the aforedescribed significance in an anhydrous system with a substantially equimolecular amount of an acrylamide of the structure wherein a and b are unlike integers from 0 to 1, inclusive, and wherein N has the aforedescribed significance in the presence of an inert organic liquid or solvent (e.g. acetone, methyl ethyl ketone, dioxane, benzene, toluene, xylene, etc.) at a temperature above the freezing point of the system and up to and including the boiling point of the system, but preferably in the range of 20 C. to C. This reaction can be accelerated by the use of a catalyst, e.g. a tertiary organic amine such as pyridine, triethylamine, choline and their equivalents. Any catalytic amount can be employed which amount usually will be in the range of 0.1 to 2.5% by Weight based on the total weight of the respective reactants. Because of the tendency of acrylamides to polymerize the reaction is most advantageously carried out in the presence of a polymerization inhibitor, e.g. hydroquinone. As illustrative of this means of preparing the compounds of this invention is the following:
EXAMPLE XI CH3 S H il P SOHzOHzCNHz To a suitable reaction vessel equipped with a thermometer, agitator and reflux condenser and containing approximately 80 parts by weight of dioxane, approximately 15.6 parts by weight (substantially 0.10 mole) of O-ethyl methylphosphonodithioic acid approximately 0.3 part by weight of triethylamine and approximately 0.2 part by weight of hydroquinone is added slowly with external cooling approximately 6.4 parts by weight (substantially 0.09 mole) of acrylamide. The temperature is raised slowly to the refluxing temperature and held there for ten hours. The resulting organic solution is then subjected to vacuum distillation to remove the dioxane. The residue is then taken up with methylene chloride and the organic solution washed first with aqueous sodium carbonate and then twice with water and the washings discarded. The so-washed organic solution is then subjected to vacuum distillation to remove the solvent. The residue, (21.0 parts by weight) is S-(Z-carbamoylethyl) O-ethyl methylphosphonodithioate, which is soluble in acetone, ethanol and chloroform but insoluble in water.
EXAMPLE XII CH3 S Employing the procedure of Example XI but replacing acrylamide with an equimolar quantity of methacrylamide there is obtained S-(Z-carbamoylpropyl) O-ethyl methylphosphonodithioate which is soluble in acetone, carbon tetrachloride and methanol, but insoluble in water.
EXAMPLE XIII PSCHzOH-CNHGH(GH5)2 CzHsQ H3 Employing the procedure of Example XI but replacing acrylamide with an equimolar quantity of N-isopropylmethacrylamide there is obtained O-ethyl S-(Z-N-isopropylcarbamoylpropyl) methylphosphonodithioate which is soluble in chloroform and acetone but insoluble in water.
EXAMPLE XIV \fi l PSOHOHz-(iNHz O2H O H3 Employing the procedure of Example XI but replacing acrylamide with an equimolar amount of crotonamide there is obtained O-ethyl S-(Z-carbamoylisopropyl) methylphosphonodithioate which is insoluble in water.
EXAMPLE XV (CH3)2GEO Employing the procedure of Example XI but replacing O-ethyl methylphosphonodithioic acid with an equimolar quantity of O-isopropyl ethylphosphonodithioic acid there is 7 obtained s-(carbamoylethyl) O-isopropyl ethylphosphonodithioate which is soluble in chloroform and acetone but insoluble in water.
EXAMPLE XVI onmono s i -SGHB( iNHCHa CH3 OHQCHZ Employing the procedure of Example I but replacing 2-chloro-N-isopropylacetamide with an equimolar amount of 4-morpholinylcarbonylmethyl chloride there is obtained O-ethyl S(4-rnorpholinylcarbonylmethyl) methylphosphonodithioate which is insoluble in Water.
In the processes of this invention any inert organic liquid or mixture of inert organic liquids can be used provided at least one of the reactants is soluble therein. The methods by which the phosphonothioates of this invention are isolated will vary slightly with the reactants employed and the product produced. Further purification by selective solvent extraction or by absorptive agents such as activated carbon or clays can precede the removal of the inert organic liquid or solvent. Additionally an inert organic solvent can be added to and in the purification by absorptive agents. However, the product is generally satisfactory for insecticidal purposes without further purification.
It will be understood that the terms insect and insecticide are used herein in their broad common useage to include spiders, mites, ticks, and like pests which are not in the strict biological sense classed as insects. Thus the useage herein conforms to the definitions provided by Congress in Public Law 104, the Federal Insecticide, Fungicide, and Rodenticide Act of 1947, Section 2, subsection h, wherein the term insect is used to refer not only to those small invertebrate animals belonging mostly to the class Insecta, comprising six-legged, usually winged forms, as beetles, bugs, bees, flies, and so forth, but also to other allied classes of arthropods Whose members are Wingless and usually have more than six legs, as spiders, mites, ticks, centipedes, and wood lice.
The phosphonothiates of this invention are effective against a wide variety of insect pests. As illustrative of the activity but not lirnitative thereof is the following:
One gram of O-ethyl S-(N-isopropylcarbamoylmethyl) methylphosphonodithioate was dissolved in sufficient acetone to make a concentrate solution thereof. Approximately 0.1 co. of sorbitan monolaurate polyoxyethylene derivative (a commercial water-soluble nonionic emulsifying agent containing 20 moles of ethylene oxide per mole of sorbitan monolaurate) is then mixed with the concentrate. To this mixture and with agitation is added sufficient Water to provide an aqueous emulsion A having a concentration of 0.004% by Weight of O-ethyl 7 sults against the mobile, resting and ova stages of the same mite were obtained employing instead of O-ethyl S-(N- isopropylcarbamoylmethyl) methylphosphonodithioate the following:
O-methyl S- (N-methylcarbamoylmethyl) methylphosphonodithioate, and O-ethyl S-(N-methylcarbamoylmethyl) methylphosphonodithioate at like concentrations.
Contact activity was also observed employing the compounds of this invention against the red flour beetle, e.g. a 100% kill was observed employing O-ethyl S-(N-methylcarbamoylmethyl) methylphosphonodithioate at a concentration of 0.25% by weight.
Employing O-ethyl S (N methylcarbamoylmethyl) methylphosphonodithioate at a concentration of 2.5 p.p.m. against yellow fever mosquito larvae, Ades aegypti, 100% kill was observed.
Contact activity was also observed against the southern armyworm, Prodenia eridania, employing the compounds of this invention.
Systemic activity was also observed against a wide variety of insects. For example against the two-spotted spider mite, Tezranychus telarius (L.), a 100% kill was observed employing O-ethyl S-(N-isopropylcarbamoylmethyl) methylphosphonodithioate at a concentration of 0.004% by weight. Also for example against the southern armyworm, Prodenia cridania, a 100% kill was observed employing O-ethyl S-(N-rnethylcarbamoylmethyl) methylphosphonodithioate at a concentration of 0.016% by weight.
Although the phosphonothioates of this invention are useful per se in controlling a wide variety of insect pests, it is preferable that they be supplied to the pests or to the environment of the pest or pests in a dispersed form in a suitable extending agent.
In the instant specification and appended claims it is to be understood that the term dispersed is used in its widest possible sense. When it is said that the phosphonothioates of this invention are dispersed, it means that particles of the phosphonothioates of this invention may be molecular in size and held in true solution in a suitable organic solvent. It means further, that the particles may be colloidal in size and distributed throughout a liquid phase in the form of suspensions or emulsions or in the form of particles held in suspension by wetting agents. It also includes particles which are distributed in a semi-solid viscous carrier such as petrolatum or soap or other ointment base in which they may be actually dissolved in the semi-solid or held in suspension in the semi-solid with the aid of suitable wetting or emulsifying agents. The term dispersed also means that the particles may be mixed with and distributed throughout a solid carrier providing a mixture in particulate form, e.g. pellets, granules, powders, or dusts. The term dispersed also includes mixtures which are suitable for use as aerosols including solutions, suspensions, or emulsions of the phosphonothioates of this invention in a carrier such as dichloro-difluoromethane and like fluorochloroalkanes which boil below room temperature at atmos pheric pressure.
In the instant specification and appended claims it is to be understood that the expression extending agent" includes any and all of those substances in which the phosphonothioates of this invention are dispersed. It includes, therefore, the solvents of a true solution, the liquid phase of suspensions, emulsions or aerosols, the semi-solid carrier of ointments and the solid phase of particulate solids, e.g. pellets, granules, dusts and powders.
The exact concentration of the phosphonothioates of this invention employed in combatting or controlling insect pests can vary considerably provided the required dosage (i.e., toxic or lethal amount) thereof is supplied to the pests or to the environment of the pests. When the extending agent is a liquid or mixture of liquids (e.g. as in solutions, suspensions, emulsions, or aerosols) the concentration of the phosphonothioate employed to supply the desired dosage generally will be in the range of 0.001 to 50 percent by weight. When the extending agent is a semi-solid or solid, the concentration of the phosphonothioate employed to supply the desired dosage generally will be in the range of 0.1 to 25 percent by weight. From a practical point of view, the manufacturer must supply the agriculturist with a low-cost concentrate or spray base or particulate solid base in such form that, by merely mixing with water or solid extender (e.g., powdered clay or talc) or other low-cost material available to the agriculturist at the point of use, he will have an easily prepared insecticidal spray or particulate solid. In such a concentrate composition, the phosphonothioate generally will be present in a concentration of 5 to 95 percent by weight, the residue being any one or more of the well known insecticidal adjuvants, such as the various surface active agents (e.g., detergents, a soap or other emulsifying or wetting agent), surfaceactive clays, solvents, diluents, carrier media, adhesives, spreading agents, humectants, and the like.
There are a large number of organic liquids which can be used for the preparation of solutions, suspensions or emulsions of the phosphonothioates of this invention. For example, isopropyl ether, acetone, methyl ethyl ketone, dioxane, cyclohexanone, carbon tetrachloride, ethylene dichloride, tetrachloroethane, hexane, heptane and like higher liquid alkanes, hydrogenated naphthalenes, solvent naphtha, benzene, toluene, xylene, petroleum fractions (e.g. those boiling almost entirely under 400 F. at atmospheric pressure and having a flash point above about F., particularly kerosene), mineral oils having an unsulfonatable residue above about 80 percent and preferably above about percent. In those instances wherein there may be concern about the phytotoxicity of the organic liquid extending agent a portion of same can be replaced by such low molecular weight aliphatic hydrocarbons as dipentene, diisobutylene, propylene trimer, and the like or suitable polar organic liquids such as the aliphatic ethers and the aliphatic ketones containing not more than about 10 carbon atoms as exemplified by acetone, methyl ethyl ketone, diisobutyl ketone, dioxane, isopropyl ether, and the like. In certain instances, it is advantageous to employ a mixture of organic liquids as the extending agent.
When the phosphonothioates of this invention are to be supplied to the insect pests or to the environment of the pests as aerosols, it is convenient to dissolve them in a suitable solvent and disperse the resulting solution in dichlorodifluoromethane or like chlorofluoroalkane which boils below room temperature at atmospheric pressure.
The phosphonothioates of this invention are preferably supplied to the insect pests or to the environment of the insect pests in the form of emulsions or suspensions. Emulsions or suspensions are prepared by dispersing the phosphonothioate of this invention either per se or in the form of an organic solution thereof in water with the aid of a water-soluble surfactant. The term surfactant as employed here and in the appended claims is used as in volume II of Schwartz, Perry and Berchs Surface Active Agents and Detergents (1958, Interscience Publishers, Inc., New York) in place of the expression emulsifying agent to connote generically the various emulsifying agents, dispersing agents, wetting agents and spreading agents that are adapted to be admixed with the active compounds of this invention in order to secure better wetting and spreading of the active ingredients in the water vehicle or carrier in which they are insoluble through lowering the surface tension of the water (see also Frear, Chemistry of Insecticides, Fungicides and Herbicides, second edition page 280). These surfactants include the well-known capillary-active substances which may be anion-active (or anionic), cation active (or cationic), or non-ionizing (or non-ionic) which are described in detail in volumes I and II of Schwartz, Perry and Berchs Surface Active Agents and Detergents (1958, Interscience Publishers, Inc., New York), and also in the November 1947 issue of Chemical Industries (pages 811-824) in an article entitled Synthetic Detergents, by John W. McCutcheon, and also in the July, August, September and October 1952 issues of Soap and Sanitary Chemicals under the title Synthetic Detergents. The disclosures of these articles with respect to surfactants, i.e. the anion-active, cation-active and non-ionizing capillary active substances, are incorporated in this specification by reference in order to avoid unnecessary enlargement of this specification. The preferred surfactants are the water-soluble anionic surface-active agents and the water soluble non-ionic surface-active agents set forth in US. 2,846,398 (issued August 5, 1958). In general it is preferred that a mixture of water-soluble anionic and water-soluble non-ionic surfactants be employed.
The phosphonothioate's of this invention can be dispersed by suitable methods (e.g., tumbling or grinding) in solid extending agents either of organic or inorganic nature and supplied to theinsect pests environment in particulate form. Such solid materials include for example, tricalcium phosphate, calcium carbonate, kaolin, bole, kieselguhr, talc, bentonite, fullers earth, pyrophyllite, diatomaceous earth, calcined magnesia, volcanic ash, sulfur and the like inorganic solid materials, and include for example, such materials of organic nature as powdered cork, powdered wood, and powdered walnut shells. The preferred solid carriers are the adsorbent clays, e.g. bentonite. These mixtures can be used for insecticidal purposes in the dry form, or, by addition of water-soluble surfactants or wetting agents the dry particulate solids can be rendered wettable by water so as to obtain stable aqueous dispersions or suspensions suitable for use as sprays.
For special purposes the phosphonothioates of this invention can be dispersed in a semi-solid extending agent such as petrolatum or soap (e.g., sodium stearate or oleate or palmitate or mixtures thereof) with or without the aid of solubility promoters and/or surfactants or dispersing agents.
In all of the forms described above the dispersions can be provided ready for use in combatting insect pests or they can be provided in a concentrated form suitable for mixing with or dispersing in other extending agents. As illustrative of a particularly useful concentrate is an intimate mixture of phosphonothioate of this invention with a water-soluble surfactant which lowers the surface ten sion of water in the weight proportions of 0.1 to 15 parts of surfactant with sufficient of the phosphonothioate of this invention to make 100 parts by weight. Such a concentrate is particularly adapted to be made into a spray for combatting various forms of insect pests (particularly mites) by the addition of water thereto. As illustrative of such a concentrate is an intimate mixture of 95 parts by weight of O-ethyl S-(N-methylcarbamoylmethyl) methylphosphonodithioate and parts by weight of a water-soluble non-ionic surfactant such as the polyoxyethylene derivative of sorbitan monolaurate.
Another useful concentrate adapted to be made into a spray for combatting insect pests (particularly mites) is a solution (preferably as concentrated as possible) of a phosphonothioate of this invention in an organic solvent therefor. The said liquid concentrate preferably contains dissolved therein a minor amount (e.g., 0.5 to percent by weight of the weight of the new insecticidal agent) of a surfactant (or emulsifying agent), which surfactant is also water-soluble. As illustrative of such a concentrate is a solution of O-ethyl S-(N-isopropylcarbamoylmethyl) methylphosphonodithioate in benzene which solution contains dissolved therein a water-soluble polyoxyethylene glycol non-ionic surfactant and a watersoluble alkylaryl sulfonate anionic surfactant.
Of the surfactants aforementioned in preparing the various emulsifiable, wettable or dispersible compositions or concentrates of this invention, the anionic and nonionic surfactants are preferred. Of the anionic surfactants, the particularly preferred are the well known watersoluble alkali metal alkylaryl sulfonates as exemplified by sodium decylbenzene sulfonate and sodium dodecylbenzene sulfonate. Of the non-ionic surfactants, the particularly preferred are the water-soluble polyoxyethylene derivatives of alkylphenols (particularly isooctylphenol) and the water-soluble polyoxyethylene derivatives of the mono-higher fatty acid esters of sorbitan containing 15 to 30 moles of ethylene oxide per mole of sorbitan monoester or alkylphenol.
In all of the various dispersions described hereinbefore for insecticidal purposes, the active ingredient can be one or more of the compounds of this invention. The compounds of this invention can also be advantageously employed in combination with other pesticides, including, for example, nematocides, bactericides, and herbicides. In this manner it is possible to obtain mixtures which are effective against a wide variety of pests and other forms of noxious life.
In controlling or combatting insect pests the O-aryl phosphonothioates of this invention either per se or compositions comprising same are supplied to the insect pests or to their environment in a lethal or toxic amount. This can be done by dispersing the new insecticidal agent or insecticidal composition comprising same in, on or over an infested environment or in, on or over an environment the insect pests frequent, e.g. agricultural soil or other growth media or other media infested with insect pests or attractable to the pests for habitational or sustenance or propagational purposes, in any conventional fashion which permits contact between the insect pests and the phosphonothioates of this invention. Such dispersing can be brought about by applying sprays or particulate solid compositions to a surface infested with the insect pests or attractable to the pests, as for example, the surface of an agricultural soil or other media such as the above ground surface of plants by any of the conventional methods, e.g. power clusters, boom and hand sprayers, and spray dusters. Also for sub-surface application such dispersing can be carried out by simply mixing the new insecticidal agent per se or insecticidal spray or particulate solid compositions comprising same with the infested environment or with the environment the insect pests frequent, or by employing a liquid carrier for the new insecticidal agent to accomplish sub-surface penetration and impregnation therein.
While this invention has been described with respect to certain'embodiments, it is to be understood that it is not so limited and that variations and modifications thereof obvious to those skilled in the art can be made without departing from the spirit and scope thereof.
What is claimed is:
1. Carbamoylalkyl phosphonothioates of the structure RO X o hsautn wherein R is selected from the group consisting of phenyl and alkyl radicals containing from 1 to 5 carbon atoms; wherein R is an alkyl radical containing from 1 to 4 carbon atoms; wherein X is a chalkogen of atomic weight less than 40; wherein A is a divalent aliphatic hydrocarbon radical having the empirical formula C H wherein n is a whole number from 1 to 3; and wherein N is selected from the group consisting of (l) NH (2) NHR wherein R" is a hydrocarbon radical containing from 1 to 7 carbon atoms and are selected from the group consisting of aryl, alkaryl, aralkyl, cycloalkyl, alkenyl and alkyl radicals, (3) NR"R wherein R" and R are hydrocarbon radicals containing from 1 to 7 carbon atoms, and (4) saturated single ring heterocyclic secondary amine residues containing not more than carbon atoms in the ring.
2. Carbamoylalkyl phosphonothioates of the structure r t P S- CH2CNRR wherein R and R are alkyl radicals containing not more than 3 carbon atoms wherein R" and R are aliphatic hydrocarbon radicals containing not more than 3 carbon atoms and selected from the group consisting of alkyl and alkenyl radicals.
3. Canbamoylalkyl phosphonothioates of the structure wherein R and R are alkyl radicals containing not more than 3 carbon atoms and wherein R" is an aliphatic hydrocarbon radical containing not more than 3 carbon atoms and selected from the group consisting of alkyl and alkenyl radicals.
4. O-ethyl S-(N-isopropylcarbamoylmethyl) methylphosphonodithioate.
5. O-ethyl S-(N-methylcarbarnoylmethyl) methylphosphonondithioate.
6. O-ethyl S-(N,N-diallylcarbamoyalmethyl) methylphosphonodithioate.
7. O-ethyl S-(N-isopropylcarbamoylmethyl) methylphosphonothioate.
8. O-ethyl S-(carbamoylmethyl) methylphosphonodithioate.
9. The method of making the compounds of claim 1 which comprises reacting in an anhydrous system a salt selected from the class consisting of ammonium and alkali metals of a phosphonothioic acid of the structure.
where R, R and X have the same significance as in claim 1 with a substantially equimolar amount of a halide of the structure I halogen-AO-N wherein halogen means a halogen having an atomic number above 9 but not higher than 35 and wherein A and N have the same significance as in claim 1 in the presence of an inert organic liquid.
10. The method of making compounds of claim 1 WhlCh comprises reacting in an anhydrous system a phosphonothioic acid of the structure R O INC P-SH 12 wherein R, R and X have the same significance as in claim 1 with a substantially equimolecular amount of an amide of the structure wherein a and b are unlike integers from 0 to 1 and wherein N has the same significance as in claim 1 in the presence of an inert organic liquid and a catalytic amount of a tertiary organic amine.
11. An insecticidal composition comprising a compound of claim 1 dispersed in an extending agent.
12. An insecticidal composition comprising a compound of claim 1 dispersed in an extending agent, the composition containing 0.1 to 25 percent by weight of said compound of claim 1, the extending agent being selected from the group consisting of solid and semi-solid extending agents.
13. An insecticidal composition comprising a compound of claim 1 dispersed in a liquid extending agent, the composition containing 0.001 to percent by weight of said compound of claim 1.
14. An insecticidal composition comprising a compound of claim 2 dispersed in an adsorbent clay, the composition containing 0.1 to 25 percent by weight of said compound of claim 2.
15. An insecticidal concentrate comprising a compound of claim 2 and an insecticidal adjuvant, said concentratc containing from 5 to percent by weight of the compound of claim 2.
16. An insecticidal concentrate comprising a compound of claim 1 dispersed in an organic solvent therefor and having dissolved therein a minor amount of a surfactant, said concentrate forming an emulsion with water upon agitation therewith.
17. An insecticidal concentrate adapted to be made into a sprayable composition by the addition of water comprising a compound of claim 2 in admixture with a watersoluble surfactant in the weight proportion of 0.1 to 15 parts of surfactant and suflicient of said compound of claim 2 to make parts by weight.
18. The method of controlling insects which comprises contacting the insects with a toxic amount of a compound of claim 1.
19. The method of controlling insects which comprises contacting the insects with a toxic amount of a compound of claim 2.
References Cited in the file of this patent UNITED STATES PATENTS 2,668,831 Tolkrnith Feb. 9, 1954 2,712,029 Winkle June 28, 1955 2,864,849 Schrader Dec. 16, 1958 2,912,452 Schrader Nov. 10, 1959 2,915,429 Scherer Dec. 1, 1959 2,920,993 Fairchild Jan. 12, 1960 :UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,057,774 October 9, 1962 Joseph W. Baker et a1.
It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.
Column 10, line 75, after "atoms, insert and are selected from the group consisting of aryl, alkaryl, aralkyl, cycloa l kyl, alkenyl and alkyl radicals Signed and sealed this 26th day of February 1963,
(SEAL) Attest:
ESTON co JOHNSON I DAVID L. LADD Commissioner of Patents Attesting Officer
Claims (1)
1. A CARBAMOYLAKYL PHOSPHONOTHIOATES OF THE STRUCTURE
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US14193A US3057774A (en) | 1960-03-11 | 1960-03-11 | Carbamoylalkyl phosphonothioates |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US14193A US3057774A (en) | 1960-03-11 | 1960-03-11 | Carbamoylalkyl phosphonothioates |
Publications (1)
Publication Number | Publication Date |
---|---|
US3057774A true US3057774A (en) | 1962-10-09 |
Family
ID=21764042
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US14193A Expired - Lifetime US3057774A (en) | 1960-03-11 | 1960-03-11 | Carbamoylalkyl phosphonothioates |
Country Status (1)
Country | Link |
---|---|
US (1) | US3057774A (en) |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3233010A (en) * | 1959-10-02 | 1966-02-01 | Bayer Ag | Dithiophosphonic acid esters and process for their production |
US3238202A (en) * | 1961-05-02 | 1966-03-01 | Montedison Spa | Amides of o, o-dialkyldithiophos-phorylacetic acids |
US3351679A (en) * | 1964-08-07 | 1967-11-07 | Stauffer Chemical Co | Substituted (nu-formyl-nu-alkylcarbamoyl methyl) phosphonothioates |
US3401220A (en) * | 1964-08-07 | 1968-09-10 | Stauffer Chemical Co | Methods of killing pests selected from the group consisting of mites and insects with phosphonothioates |
US3691163A (en) * | 1970-08-03 | 1972-09-12 | Exxon Research Engineering Co | Certain phosphorus-containing thiomorpholinones |
US4016266A (en) * | 1975-06-02 | 1977-04-05 | Stauffer Chemical Company | N-Alkylthiomethylacetamidephosphorodithioate insecticides |
DE2604224A1 (en) * | 1976-02-04 | 1977-08-11 | Hoechst Ag | HERBICIDAL AGENTS |
FR2361067A1 (en) * | 1976-04-23 | 1978-03-10 | Hoechst Ag | ORGANOPHOSPHORUS COMPOUNDS WITH ANILIDE GROUPS AND PESTICIDE PRODUCTS WHICH CONTAIN IT |
US4162279A (en) * | 1977-09-28 | 1979-07-24 | Stauffer Chemical Company | Phosphonoxycarboxamides |
US4223028A (en) * | 1979-04-30 | 1980-09-16 | Stauffer Chemical Company | Butynylamide phosphate and phosphonates and method for controlling insects |
US4283395A (en) * | 1980-03-24 | 1981-08-11 | Stauffer Chemical Company | S-Alkyl and alkenyl-thiophenylacetamido thiophosphates and phosphonates and method of controlling insects |
US4356022A (en) * | 1980-03-24 | 1982-10-26 | Stauffer Chemical Company | S-Alkyl and alkenyl-thiophenylacetamido thiophosphates and phosphonates as plant growth regulants |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2668831A (en) * | 1953-04-21 | 1954-02-09 | Dow Chemical Co | O-ethyl s-(ethylxanthoyl) n, n-diethylamidothiophosphate |
US2712029A (en) * | 1953-07-20 | 1955-06-28 | Shell Dev | Monoamides of trihalomethanephosphonic acid monoesters |
US2864849A (en) * | 1955-09-07 | 1958-12-16 | Bayer Ag | Thiophosphoric acid esters and their production |
US2912452A (en) * | 1956-04-21 | 1959-11-10 | Bayer Ag | Thiophosphoric acid esters and their production |
US2915429A (en) * | 1957-09-17 | 1959-12-01 | Hoechst Ag | O, o'-diethyl-dithiophosphoric acid-s-(dimethyl-thiocarbamyl-mercaptomethyl)-ester insecticides |
US2920993A (en) * | 1957-12-09 | 1960-01-12 | Du Pont | Insecticidal composition and method of destroying insects |
-
1960
- 1960-03-11 US US14193A patent/US3057774A/en not_active Expired - Lifetime
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2668831A (en) * | 1953-04-21 | 1954-02-09 | Dow Chemical Co | O-ethyl s-(ethylxanthoyl) n, n-diethylamidothiophosphate |
US2712029A (en) * | 1953-07-20 | 1955-06-28 | Shell Dev | Monoamides of trihalomethanephosphonic acid monoesters |
US2864849A (en) * | 1955-09-07 | 1958-12-16 | Bayer Ag | Thiophosphoric acid esters and their production |
US2912452A (en) * | 1956-04-21 | 1959-11-10 | Bayer Ag | Thiophosphoric acid esters and their production |
US2915429A (en) * | 1957-09-17 | 1959-12-01 | Hoechst Ag | O, o'-diethyl-dithiophosphoric acid-s-(dimethyl-thiocarbamyl-mercaptomethyl)-ester insecticides |
US2920993A (en) * | 1957-12-09 | 1960-01-12 | Du Pont | Insecticidal composition and method of destroying insects |
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3233010A (en) * | 1959-10-02 | 1966-02-01 | Bayer Ag | Dithiophosphonic acid esters and process for their production |
US3238202A (en) * | 1961-05-02 | 1966-03-01 | Montedison Spa | Amides of o, o-dialkyldithiophos-phorylacetic acids |
US3351679A (en) * | 1964-08-07 | 1967-11-07 | Stauffer Chemical Co | Substituted (nu-formyl-nu-alkylcarbamoyl methyl) phosphonothioates |
US3401220A (en) * | 1964-08-07 | 1968-09-10 | Stauffer Chemical Co | Methods of killing pests selected from the group consisting of mites and insects with phosphonothioates |
US3691163A (en) * | 1970-08-03 | 1972-09-12 | Exxon Research Engineering Co | Certain phosphorus-containing thiomorpholinones |
US4016266A (en) * | 1975-06-02 | 1977-04-05 | Stauffer Chemical Company | N-Alkylthiomethylacetamidephosphorodithioate insecticides |
DE2604224A1 (en) * | 1976-02-04 | 1977-08-11 | Hoechst Ag | HERBICIDAL AGENTS |
FR2340047A1 (en) * | 1976-02-04 | 1977-09-02 | Hoechst Ag | HERBICIDE PRODUCTS BASED ON ORGANOPHOSPHORIC COMPOUNDS |
US4278461A (en) * | 1976-02-04 | 1981-07-14 | Hoechst Aktiengesellschaft | Herbicidal agents |
FR2361067A1 (en) * | 1976-04-23 | 1978-03-10 | Hoechst Ag | ORGANOPHOSPHORUS COMPOUNDS WITH ANILIDE GROUPS AND PESTICIDE PRODUCTS WHICH CONTAIN IT |
US4152428A (en) * | 1976-04-23 | 1979-05-01 | Hoechst Aktiengesellschaft | Pesticidal agents |
US4162279A (en) * | 1977-09-28 | 1979-07-24 | Stauffer Chemical Company | Phosphonoxycarboxamides |
US4223028A (en) * | 1979-04-30 | 1980-09-16 | Stauffer Chemical Company | Butynylamide phosphate and phosphonates and method for controlling insects |
US4283395A (en) * | 1980-03-24 | 1981-08-11 | Stauffer Chemical Company | S-Alkyl and alkenyl-thiophenylacetamido thiophosphates and phosphonates and method of controlling insects |
US4356022A (en) * | 1980-03-24 | 1982-10-26 | Stauffer Chemical Company | S-Alkyl and alkenyl-thiophenylacetamido thiophosphates and phosphonates as plant growth regulants |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US3057774A (en) | Carbamoylalkyl phosphonothioates | |
US3065125A (en) | Alkynyl phosphonothioates | |
US3149143A (en) | O-ethyl s-(4-chlorophenyl) methylphosphonodithioate | |
US3106565A (en) | Organophosphorus esters | |
US3205238A (en) | Thenyl phosphorothioates | |
US3099597A (en) | Halophenyl arylphosphonothioates | |
US3131120A (en) | O-cyanoaryl alkylphosphonothioates | |
US3279983A (en) | Halophenyl phosphonothioates | |
US3077431A (en) | Phosphinothioates | |
US3102019A (en) | Method for inhibiting germination and preemergent growth of plants using s(n-aryl, n-aliphatic carbamoylmethyl) phosphorothiate triesters | |
US3028302A (en) | Haloalkenyloxyalkyl phosphorothioates | |
US3165441A (en) | Methylphosphonothioate insecticide | |
US3078212A (en) | O-(cyanoaryl) phosphonothioates | |
US3082147A (en) | Insecticidal o-(aryl) phosphonothioates | |
US3168436A (en) | S-[alpha-(4-nitrobenzoyloxy)benzyl] o, o-diethyl phosphorodithioate | |
US3061613A (en) | O-(coumarinyl)-dialkylphosphinothioates | |
US3077432A (en) | Aliphatic phosphonothioates | |
US3351682A (en) | Omicron-aryl dialkylphosphinothioates | |
US3413318A (en) | 2-oxo-tetrahydrofuranyl compounds | |
US3037904A (en) | Phosphorodithioates | |
US3082148A (en) | Insecticidal phosphonothioates | |
US3070489A (en) | Phosphinates | |
US3052596A (en) | Phosphino compounds, compositions and methods of destroying arachnids | |
US3096238A (en) | Omicron-(halophenyl) phosphonothioates | |
US3058878A (en) | Phosphonothioates |