CA1053233A - Dithiophosphate esters of cyclic pyridine carbamates or thiocarbamates - Google Patents
Dithiophosphate esters of cyclic pyridine carbamates or thiocarbamatesInfo
- Publication number
- CA1053233A CA1053233A CA180,783A CA180783A CA1053233A CA 1053233 A CA1053233 A CA 1053233A CA 180783 A CA180783 A CA 180783A CA 1053233 A CA1053233 A CA 1053233A
- Authority
- CA
- Canada
- Prior art keywords
- formula
- compound according
- parts
- alkyl
- compound
- 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
Links
- -1 cyclic pyridine carbamates Chemical class 0.000 title claims description 7
- 150000002148 esters Chemical class 0.000 title 1
- 150000003558 thiocarbamic acid derivatives Chemical class 0.000 title 1
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 241000607479 Yersinia pestis Species 0.000 claims abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 5
- 239000001257 hydrogen Substances 0.000 claims abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- 239000001301 oxygen Substances 0.000 claims abstract description 5
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 4
- 150000002367 halogens Chemical class 0.000 claims abstract description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000005864 Sulphur Substances 0.000 claims abstract description 3
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 3
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims abstract 4
- 150000001875 compounds Chemical class 0.000 claims description 31
- 239000000460 chlorine Substances 0.000 claims description 15
- 239000000654 additive Substances 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 241000238876 Acari Species 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 239000000969 carrier Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 241001465754 Metazoa Species 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 241000500891 Insecta Species 0.000 claims 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims 1
- 229910019142 PO4 Inorganic materials 0.000 abstract 1
- 235000021317 phosphate Nutrition 0.000 abstract 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 abstract 1
- 239000013543 active substance Substances 0.000 description 27
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- 241000196324 Embryophyta Species 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 241000233866 Fungi Species 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 6
- 239000008187 granular material Substances 0.000 description 6
- 230000000749 insecticidal effect Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000005995 Aluminium silicate Substances 0.000 description 5
- 235000012211 aluminium silicate Nutrition 0.000 description 5
- 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 5
- 239000002689 soil Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 230000000895 acaricidal effect Effects 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 4
- 235000013399 edible fruits Nutrition 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 241000426497 Chilo suppressalis Species 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 3
- 241000238631 Hexapoda Species 0.000 description 3
- 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 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 241000244206 Nematoda Species 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 3
- 235000019993 champagne Nutrition 0.000 description 3
- 235000013601 eggs Nutrition 0.000 description 3
- 239000004495 emulsifiable concentrate Substances 0.000 description 3
- 230000003032 phytopathogenic effect Effects 0.000 description 3
- 229920000151 polyglycol Polymers 0.000 description 3
- 239000010695 polyglycol Substances 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- 241001425390 Aphis fabae Species 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 241000219146 Gossypium Species 0.000 description 2
- 206010061217 Infestation Diseases 0.000 description 2
- 241000258916 Leptinotarsa decemlineata Species 0.000 description 2
- 241000243784 Meloidogyne arenaria Species 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 2
- 244000046052 Phaseolus vulgaris Species 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 241000238680 Rhipicephalus microplus Species 0.000 description 2
- 244000061456 Solanum tuberosum Species 0.000 description 2
- 241000256250 Spodoptera littoralis Species 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 241001454293 Tetranychus urticae Species 0.000 description 2
- 240000008042 Zea mays Species 0.000 description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 229920005610 lignin Polymers 0.000 description 2
- 238000004452 microanalysis Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 210000002784 stomach Anatomy 0.000 description 2
- 230000009885 systemic effect Effects 0.000 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
- 239000008158 vegetable oil Substances 0.000 description 2
- QFBDCSDDHUBEGG-UHFFFAOYSA-N 1,2-dibutylnaphthalene;sodium Chemical compound [Na].C1=CC=CC2=C(CCCC)C(CCCC)=CC=C21 QFBDCSDDHUBEGG-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 241001124076 Aphididae Species 0.000 description 1
- 241001600407 Aphis <genus> Species 0.000 description 1
- 241000235349 Ascomycota Species 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 241000221198 Basidiomycota Species 0.000 description 1
- 241000537222 Betabaculovirus Species 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 241000238660 Blattidae Species 0.000 description 1
- 241000283690 Bos taurus Species 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 241000907223 Bruchinae Species 0.000 description 1
- 241001260012 Bursa Species 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241000257161 Calliphoridae Species 0.000 description 1
- 241001124134 Chrysomelidae Species 0.000 description 1
- 241001414835 Cimicidae Species 0.000 description 1
- 241000255749 Coccinellidae Species 0.000 description 1
- 241000254173 Coleoptera Species 0.000 description 1
- 241001466044 Delphacidae Species 0.000 description 1
- 241001481702 Dermanyssidae Species 0.000 description 1
- 241000131287 Dermestidae Species 0.000 description 1
- 241001414830 Diaspididae Species 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 240000002024 Gossypium herbaceum Species 0.000 description 1
- 235000004341 Gossypium herbaceum Nutrition 0.000 description 1
- 241000238816 Gryllidae Species 0.000 description 1
- 241001243087 Gryllotalpidae Species 0.000 description 1
- 241000256244 Heliothis virescens Species 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 241000238889 Ixodidae Species 0.000 description 1
- 235000007688 Lycopersicon esculentum Nutrition 0.000 description 1
- 241000257226 Muscidae Species 0.000 description 1
- 208000031888 Mycoses Diseases 0.000 description 1
- 241000256259 Noctuidae Species 0.000 description 1
- 241000233654 Oomycetes Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 241001415279 Pseudococcidae Species 0.000 description 1
- 241000258921 Pulicidae Species 0.000 description 1
- 241000255893 Pyralidae Species 0.000 description 1
- 241001124072 Reduviidae Species 0.000 description 1
- 241000949016 Rhipicephalus bursa Species 0.000 description 1
- 240000003768 Solanum lycopersicum Species 0.000 description 1
- 241000254107 Tenebrionidae Species 0.000 description 1
- 241000896028 Tettigoniidae Species 0.000 description 1
- 241000130767 Tineidae Species 0.000 description 1
- 241000221561 Ustilaginales Species 0.000 description 1
- 240000006677 Vicia faba Species 0.000 description 1
- 235000010749 Vicia faba Nutrition 0.000 description 1
- 240000006365 Vitis vinifera Species 0.000 description 1
- 235000014787 Vitis vinifera Nutrition 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 description 1
- 239000000642 acaricide Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229940115440 aluminum sodium silicate Drugs 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- FHIVAFMUCKRCQO-UHFFFAOYSA-N diazinon Chemical compound CCOP(=S)(OCC)OC1=CC(C)=NC(C(C)C)=N1 FHIVAFMUCKRCQO-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical compound OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 235000009973 maize Nutrition 0.000 description 1
- 125000005394 methallyl group Chemical group 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 230000001069 nematicidal effect Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- RBXVOQPAMPBADW-UHFFFAOYSA-N nitrous acid;phenol Chemical class ON=O.OC1=CC=CC=C1 RBXVOQPAMPBADW-UHFFFAOYSA-N 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000006072 paste Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000429 sodium aluminium silicate Substances 0.000 description 1
- 235000012217 sodium aluminium silicate Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000009331 sowing Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000004563 wettable powder Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
- A01N57/16—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing heterocyclic radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- 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
- C07F9/6561—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing systems of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring or ring system, with or without other non-condensed hetero rings
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Dentistry (AREA)
- Engineering & Computer Science (AREA)
- Plant Pathology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
- Agronomy & Crop Science (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Abstract of the Disclosure Dithi?phosphates of the formula
Description
The present invention relates to dithiophosphates, to processes for their preparation, and to their use in pest control.
The said dithiophosphates correspond to the formula ~ C=X (I) I ~ 11 ~C)R2 P~SR
wherein - 3 Rl represents hydrogen, halogen or nitro, ~2 represents Cl-C5-alkyl, R represen~s Cl-C5-alkyl, C3-C5-alkenyl, C3-C5-alkynyl, Cl-c5-alkoxy-cl-c5-alkyl or cl-~5-alkylthio-Cl C5 alkyl, and X represents oxygen or sulphur.
i~ _ i~ By halogen is meant fluorine, chlorine, bromine and/or ~ iodine. The Cl-C5-alkyl, C3-C5-alkenyl, C3-Cs-alkynyl, 1. .~
Cl-C5-alkoxy-Cl-C5-alkyl and Cl-C~-alkylthio-Cl-C5-alkyl i groups denoted by R2 and R3 can be straight-chain or branched. Examples of such groups are: methyl, methoxy, methoxymethyl, ethyl, ethoxyethyl, ethylthioethyl, propyl, isopropyl, n-butyl, i-, sec.-, tert.-butyl, n pentyl, isopentyl, allyl, methallyl, propargyl and isobutinyl.
Preferred compounds of formula I because of their action are those wherein
The said dithiophosphates correspond to the formula ~ C=X (I) I ~ 11 ~C)R2 P~SR
wherein - 3 Rl represents hydrogen, halogen or nitro, ~2 represents Cl-C5-alkyl, R represen~s Cl-C5-alkyl, C3-C5-alkenyl, C3-C5-alkynyl, Cl-c5-alkoxy-cl-c5-alkyl or cl-~5-alkylthio-Cl C5 alkyl, and X represents oxygen or sulphur.
i~ _ i~ By halogen is meant fluorine, chlorine, bromine and/or ~ iodine. The Cl-C5-alkyl, C3-C5-alkenyl, C3-Cs-alkynyl, 1. .~
Cl-C5-alkoxy-Cl-C5-alkyl and Cl-C~-alkylthio-Cl-C5-alkyl i groups denoted by R2 and R3 can be straight-chain or branched. Examples of such groups are: methyl, methoxy, methoxymethyl, ethyl, ethoxyethyl, ethylthioethyl, propyl, isopropyl, n-butyl, i-, sec.-, tert.-butyl, n pentyl, isopentyl, allyl, methallyl, propargyl and isobutinyl.
Preferred compounds of formula I because of their action are those wherein
2 -~'~ ,~ . .
, , , ~ .,,,,;.. :.. , ;.. ...
1(~5;3'233 Rl represents hydrogen or chlorine, R2 represents methyl or ethyl, R3 represents n-propyl, iso-propyl, iso-~utyl, methoxyethyl or ethoxyethyl, and X represents oxygen.
The compounds of formula I are prepared by methods known per se, e.g. as follows:
- a) l ~ \C_X + HS- ~ ~ acid-binding ~ I
~/ ~ agent (II) 2 ~l (III) -. . .
b) O
R ~ \ ll ~ if necessary C=X ~ MeS-P< . . . > I
~\N~ N/ ~ acld-bLndlng agent (II) CH2-Cl (IV) i 10 In formulae II, III and IV, the symbols Rl to R3 and X have the meanings given for formula I, and Me stands for a monovalent metal, particularly for an alkali metal such as sodium or potassium. Suitable acid-binding l agents are: tertiary amines, e.g. trialkylamines, pyridine or '~ 15 dialkylanilines; inorganic bases such as hydroxides; carbonates and bicarbonates of alkali metals and alkaline-earth metals.
It is sometimes necessary to use catalysts in the reactions, such as, e.g. copper or copper chloride.
, _ 3 _ . .
, ~(J5;~ 3 The reactions a) and b) are perform~d at a temperature of 0-120C, preferably between 10 and 70~C, at normal pressure and in solvents or diluents that are inert to the reactants. The following, for example, are suitable as solvents or diluents: ethers and ethereal compounds, such as diethyl ether, dipropyL ether, dioxane, dimethoxyethane or tetrahydrofuran; amides such as N,N-di-allcylated carboxylic acid amides; aliphatic, aromatic as well as halogenated hydrocarbons, especially benzene, toluene, xylenes, chloroform or chlorobenzene;
nitriles such as acetonitrlles; DMS0; ketones such as acetone, methyl ethyl ketone, or mixtures of such solvents with water.
The starting ma~erials of formulae II, III and IV
are known, and can be prepared my methods analogous to known methods.
- ' ' ,.
.
.
.
, .
.
~S3Z33 The compounds of formula I have ~ broa~ biocidal action an~ are there~ore suitable for the control of diverse plant and animal pests. They possess however, in particular, insecticidal and acaricidal properties, and can be used against all development stages, such as, e.g. eggs, larvae, pupae, nymphs and adults of insects and members of the order acarina~ such as, e.g.
against insects of the families: Tettigoniidae, Gryllidae, P f ~-h ocor; d oc e Gryllotalpidae, Blattidae, Reduviidae, ~ ~ rrhocorid~c, Cimicidae, Delphacidae, Aphididae, Diaspididae, 5ca~abe ~ da~
Pseudococcidae, ~car~Q~id~c, Dermestidae, Coccinellidae, Tenebrionidae, Chrysomelidae, Bruchidae, Tineidae ~ r,`i dae Noctuidae, L~matri~dae-, Pyralidae, Culcidae, Tripulidaes Stomoxydae, Trype~idae, Muscidae, Calliphoridae and ; 15 Pulicidae, as well as acarids of the families: Ixodidae, .. ~rgasidae,- Tetxanychidae and Dermanyssidae.
The insecticidal or acaricidal action can be appreciably broadened and adapted to suit the given circùmstances by the addition of other insecticides and/or acaricides.
Suitable additives are, for example:
organic phosphorus compounds, deriva~ives of nitrophenols, - formamidines, ureas, carbamates, and - chlorinated hydrocarbons.
_ 5 _ .
.
1053~33 The active substances of ormula I are suitable also for the control of members of the division thallophyta, such as, e.g. viruses, bacteria and fungi. They thus have fungicidal properties rendering them effective against phytopathogenic fungi in various cultivated crops, such as corn, maize, rice, vegetables, ornamental plants, fruit trees, grape vines, field fruits, etc..
With the new active substances, fungi occurring on fruits, blossom, follage, stalks, tubers and roots can be checked or destro~ed, whereby parts of plants subse~uently growing remain immune against such fungus infestation.
The active substances of formula I are effective especially against phytopathogenic fungi belonging to the following classes: Oomycetes, Zy~omycetes, Ascomycetes, Basidiomycetes and Denteromycetes.
Furthermore, the new active substances are used ~or the treatment of seed~ fruits, tubers, etc. for protection against fungus infections due to, for example, smut fungus of all varieties, such as Ustilaginales, and for the ~ontrol oi phytopathogenic nematodes, .~ . , .
- . .
:
., , ~
.
. . .
1(~53Z33 The compounds o~ formula X can bc ~1sed on their own or together with suitable carriers and/or additives.
Suitable carriers and additives may be solid or licluid, and correspond to the substances co~non in ormulation practice, such as, e.g. natural and regenerated substances, solvents, dispersi.ng agents, wetting agents~ adhesives, thickeners, binders and/or fer~ilisers.
For application, the compounds of formula I can be processed into the form of dusts, emulsion concentrates, granulates) dispersions, sprays~ or solutions, the ~ -formulation of these preparations being effected in a manner commonl)7 known in practice. Also to be mentioned ;~
are cattle dips and spray races, in ~hich aqueous preparations are used.
The agents according to the invention are produced in a manner kno~7n per se by the -intimate mixing and/or grinding o~-active substances of formula I with t11e suitable carri.ers, optionally with the addition of dispersing agents or solvents ~hic11 are inert to the active substances.
The active substances can be obtained and used ~n the i iollowing preparation forms:
~rA~ solid preparations: dusts, scattering agents, granulates~
( coated granulates, impregnated granulates and homogeneous granuiate3;
liquid preparations:
a) water di.spersible active substance concentrates:
wettable powders, pastes, emulsions;
b) solutions.
' .
~ - .. . . : : . : .
. . , . . . . :
105;~Z33 The content of active substance in the described agents is between 0.1 and 95%; it is to be mentioned in this connection that in the case of application from an aeroplane, or by means of other suitable devices, S concentrations of up to 99.5% can be employed, or even the pure active substance.
The active substances of formula I can be prepared, for example, as follows:
~ Dusts:
The ollowing substances are used in the preparation of a) a 5% dust, and b~ a 2% dust:
q a)5 parts of active substance, 95 parts of ~alcum;
b)2 parts of active substance, 1 part of highly dispersed silicic acid, 97 parts of talcum.
The active substances are mixed and ground with the c-rriers.
`' ' ' ' . ' .'~ .
:~ .
. .
1~53~ 33 Granulate-.
The ~ollo~Jing substances are used to produce a 5% granulate:
5 parts of active substance, 0.25 parts of epichlorhydrin, 0.25 parts of cetyl polyglycol ether,
, , , ~ .,,,,;.. :.. , ;.. ...
1(~5;3'233 Rl represents hydrogen or chlorine, R2 represents methyl or ethyl, R3 represents n-propyl, iso-propyl, iso-~utyl, methoxyethyl or ethoxyethyl, and X represents oxygen.
The compounds of formula I are prepared by methods known per se, e.g. as follows:
- a) l ~ \C_X + HS- ~ ~ acid-binding ~ I
~/ ~ agent (II) 2 ~l (III) -. . .
b) O
R ~ \ ll ~ if necessary C=X ~ MeS-P< . . . > I
~\N~ N/ ~ acld-bLndlng agent (II) CH2-Cl (IV) i 10 In formulae II, III and IV, the symbols Rl to R3 and X have the meanings given for formula I, and Me stands for a monovalent metal, particularly for an alkali metal such as sodium or potassium. Suitable acid-binding l agents are: tertiary amines, e.g. trialkylamines, pyridine or '~ 15 dialkylanilines; inorganic bases such as hydroxides; carbonates and bicarbonates of alkali metals and alkaline-earth metals.
It is sometimes necessary to use catalysts in the reactions, such as, e.g. copper or copper chloride.
, _ 3 _ . .
, ~(J5;~ 3 The reactions a) and b) are perform~d at a temperature of 0-120C, preferably between 10 and 70~C, at normal pressure and in solvents or diluents that are inert to the reactants. The following, for example, are suitable as solvents or diluents: ethers and ethereal compounds, such as diethyl ether, dipropyL ether, dioxane, dimethoxyethane or tetrahydrofuran; amides such as N,N-di-allcylated carboxylic acid amides; aliphatic, aromatic as well as halogenated hydrocarbons, especially benzene, toluene, xylenes, chloroform or chlorobenzene;
nitriles such as acetonitrlles; DMS0; ketones such as acetone, methyl ethyl ketone, or mixtures of such solvents with water.
The starting ma~erials of formulae II, III and IV
are known, and can be prepared my methods analogous to known methods.
- ' ' ,.
.
.
.
, .
.
~S3Z33 The compounds of formula I have ~ broa~ biocidal action an~ are there~ore suitable for the control of diverse plant and animal pests. They possess however, in particular, insecticidal and acaricidal properties, and can be used against all development stages, such as, e.g. eggs, larvae, pupae, nymphs and adults of insects and members of the order acarina~ such as, e.g.
against insects of the families: Tettigoniidae, Gryllidae, P f ~-h ocor; d oc e Gryllotalpidae, Blattidae, Reduviidae, ~ ~ rrhocorid~c, Cimicidae, Delphacidae, Aphididae, Diaspididae, 5ca~abe ~ da~
Pseudococcidae, ~car~Q~id~c, Dermestidae, Coccinellidae, Tenebrionidae, Chrysomelidae, Bruchidae, Tineidae ~ r,`i dae Noctuidae, L~matri~dae-, Pyralidae, Culcidae, Tripulidaes Stomoxydae, Trype~idae, Muscidae, Calliphoridae and ; 15 Pulicidae, as well as acarids of the families: Ixodidae, .. ~rgasidae,- Tetxanychidae and Dermanyssidae.
The insecticidal or acaricidal action can be appreciably broadened and adapted to suit the given circùmstances by the addition of other insecticides and/or acaricides.
Suitable additives are, for example:
organic phosphorus compounds, deriva~ives of nitrophenols, - formamidines, ureas, carbamates, and - chlorinated hydrocarbons.
_ 5 _ .
.
1053~33 The active substances of ormula I are suitable also for the control of members of the division thallophyta, such as, e.g. viruses, bacteria and fungi. They thus have fungicidal properties rendering them effective against phytopathogenic fungi in various cultivated crops, such as corn, maize, rice, vegetables, ornamental plants, fruit trees, grape vines, field fruits, etc..
With the new active substances, fungi occurring on fruits, blossom, follage, stalks, tubers and roots can be checked or destro~ed, whereby parts of plants subse~uently growing remain immune against such fungus infestation.
The active substances of formula I are effective especially against phytopathogenic fungi belonging to the following classes: Oomycetes, Zy~omycetes, Ascomycetes, Basidiomycetes and Denteromycetes.
Furthermore, the new active substances are used ~or the treatment of seed~ fruits, tubers, etc. for protection against fungus infections due to, for example, smut fungus of all varieties, such as Ustilaginales, and for the ~ontrol oi phytopathogenic nematodes, .~ . , .
- . .
:
., , ~
.
. . .
1(~53Z33 The compounds o~ formula X can bc ~1sed on their own or together with suitable carriers and/or additives.
Suitable carriers and additives may be solid or licluid, and correspond to the substances co~non in ormulation practice, such as, e.g. natural and regenerated substances, solvents, dispersi.ng agents, wetting agents~ adhesives, thickeners, binders and/or fer~ilisers.
For application, the compounds of formula I can be processed into the form of dusts, emulsion concentrates, granulates) dispersions, sprays~ or solutions, the ~ -formulation of these preparations being effected in a manner commonl)7 known in practice. Also to be mentioned ;~
are cattle dips and spray races, in ~hich aqueous preparations are used.
The agents according to the invention are produced in a manner kno~7n per se by the -intimate mixing and/or grinding o~-active substances of formula I with t11e suitable carri.ers, optionally with the addition of dispersing agents or solvents ~hic11 are inert to the active substances.
The active substances can be obtained and used ~n the i iollowing preparation forms:
~rA~ solid preparations: dusts, scattering agents, granulates~
( coated granulates, impregnated granulates and homogeneous granuiate3;
liquid preparations:
a) water di.spersible active substance concentrates:
wettable powders, pastes, emulsions;
b) solutions.
' .
~ - .. . . : : . : .
. . , . . . . :
105;~Z33 The content of active substance in the described agents is between 0.1 and 95%; it is to be mentioned in this connection that in the case of application from an aeroplane, or by means of other suitable devices, S concentrations of up to 99.5% can be employed, or even the pure active substance.
The active substances of formula I can be prepared, for example, as follows:
~ Dusts:
The ollowing substances are used in the preparation of a) a 5% dust, and b~ a 2% dust:
q a)5 parts of active substance, 95 parts of ~alcum;
b)2 parts of active substance, 1 part of highly dispersed silicic acid, 97 parts of talcum.
The active substances are mixed and ground with the c-rriers.
`' ' ' ' . ' .'~ .
:~ .
. .
1~53~ 33 Granulate-.
The ~ollo~Jing substances are used to produce a 5% granulate:
5 parts of active substance, 0.25 parts of epichlorhydrin, 0.25 parts of cetyl polyglycol ether,
3.50 parts of polyethylene glycol, - 91 parts o~ kaolin ~ particle si~e 0.3 - 0.8 mm).
The active su~stance is mixed ~ith epichlorhydrin and dissolved with 6 parts of acetone, the polyethylene glycol and cetyl polyglycol ether are then added. The solution thus obtained is sprayed on to kaolin, and the acetone subsequen~ly evaporated off ;n vacuo, Wet~abl~ owder:
... . .
. The following constituents are used or the preparation of a) a 40%, b) and c) a 25%, and d) a 10% wettable powder:
a) 40 parts of active substance, ! 5 parts of sodium lignin sulphon~te, 1 part of sodium dibutyl-naph~halene sulphonate, 54 parts of silicic acid.
~ , .
20 b) 25 parts of active substance J
The active su~stance is mixed ~ith epichlorhydrin and dissolved with 6 parts of acetone, the polyethylene glycol and cetyl polyglycol ether are then added. The solution thus obtained is sprayed on to kaolin, and the acetone subsequen~ly evaporated off ;n vacuo, Wet~abl~ owder:
... . .
. The following constituents are used or the preparation of a) a 40%, b) and c) a 25%, and d) a 10% wettable powder:
a) 40 parts of active substance, ! 5 parts of sodium lignin sulphon~te, 1 part of sodium dibutyl-naph~halene sulphonate, 54 parts of silicic acid.
~ , .
20 b) 25 parts of active substance J
4.5 parts o calcium lignin sulphonate 1.9 parts of Champagne challc/hydroxycthyl cellulose mixture (1~
.
1.5 parts of sodium dibutyl naphthalene sulphonate, 19.5 parts of silicic acicl, "~
g _ , .
. . : . . :.
.
1.5 parts of sodium dibutyl naphthalene sulphonate, 19.5 parts of silicic acicl, "~
g _ , .
. . : . . :.
5;~ 3 . , 19.5 parts of Champagne cllalk, 28.1 parts o~ kaolin.
c) 25 parts o~ ac~ive sub.s~ance, .5 parts of isooctylpherloY~y-polyoxyethylene-etllanolf 1.7 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1), 8.3 parts of sodium aluminium silicate, 16.5 parts of kieselguhr9 46 parts o~ kaolin.
d) 10 parts of active substance, 3 parts of a mixture of tlle sodium salts of saturated ~atty alcohol sulphates, S parts of naphthalenesulphonic acid/formaldeh~de condensate, lS 82 parts of kaolin.
The active substances are întimately mixed, in suitable mixers, ~ith the additives, the mixture being then ground in the appropriate mills and rollers; Wett~ble po~ders are obtained which can be diluted ~ith water to give suspensions of any desired concentration.
.~ - .
Em~11sifiable concentrates:
The following substances are used to produce a) a 10%
and b) a 25% emulsifiable concentrate:
a) lO parts of active substance, 3.4 parts of epoxidised vegetable oil, ,, , , - 10_ .
. .
~os3~33 7r par~s o~ a combination emulsifier consisting of fatty alcohol polygl~Tcol cther and alkylaryl-sulphonate calcium salt, . 40 parts of dimethyl~ormamide, 43.2 parts of xylene~
b) 25 parts of ac~ive substance, 2.5 parts of epoxidised vegetable oil, 10 parts of an alky~arylsulphonate/fatty alcohol-polyglycol e~her mi~ture 5 parts of dimethylformamide, 57.5 parts of xylene.
From these concentrates it is possible to produce, by diluti.on with water, emulsions of any desired concentration.
'`; ~:
The follo~7ing constituents are used to prepare a . 5/O spray ~ 5 parts of active substance, .; 1 part of epichlorhydrin, I 94 parts of ligroin (boiling limits 160-190C).
;
~, ' -, ; . :
:,. - 11 -... ~...................................... .
- . :' .' ' ' .
. . .
1C~53233 Example 1 Pre~ration of 0,S-dimethyl-_-[6-chloro-oxazolo(4,5-b) pyridin-2(3H~-on-3-yl-methyl~-dithiophosphate 22 g of 3-chloromethyl-6-chloro-oxazolo(4,5-b)-pyridin-2(3H~-one, 24 g of potassium salt of 0,S-dimethyl-~ 5 dithiophosphoric acid and 50 ml of methanol are heatedfor 5 minutes at 65C. The methanol is then distilled off . and 100 ml of water added to the residue; the precipitated oil is isolated by extraction with ether to ob~ain the compound CH~jO\ 11 ~ C~
~.P-S-CH2-N 0 10 CH3$/ N
as pale brown, non-distillable oil.
Cal.: C 31.7 H 3.0 N 8.2 P 9.1 S 18.8 Cl 10.4 %
Found: 31.4 3.1 7.8 8.8 18.7 10.7 %
~' ' ' .
~: . ' . ' ' .
;3Z;~
:
.
Also the following compounds were prepared in an analogous manner: :
R ~ \
1 11 C=X ' ~\N ~ N / o il /0~2 ~ 2 ~ SR
.~ Rl R2 ~ X _croanalys,i s .
H CM3 (n)~C3H7- o a) H C2H5 C2H5- O b) H C2 5 (n)-C3H7- O c) . ~ C2~15 (iso)-C3H7~ O d) H C21I5 (n)-C4H9- O e) : .
, 10 ~I C2~15 (iso)-C4~19~ O f) H C2~15 CH30C2~ O g) ~ C2~15 C2H50C2H4- O h) ., . }~ C2}15 CH2=CH CH2- O i) . Cl CH3 (n)-C3H7 O i) : 15 Cl C2M5 C2H5- O k) Cl - C21I5 (n)~C3}I7_ O l) . Gl C2H5 (iso)-C3H7- m~
i Cl C2 5 ~n) C~}19- O n) . Cl C2~15 (iso)-C~H9- O _ _ ,, , . _ .
.. ' ' ~ ' , , ' 5~233 R R R ~ ----- X _______________ 1 2 3 . Microanalysis l __ ~ __ ~
Cl C2HS CH30C2H4- 0M.P, 69-71~G
Cl C~H5 C2H50C2H4- 0'- P) .
¦Cl ¦ C2115 l Ch2 Cll _~ I
:
Microanalysis S a) Cal. C 3~,5 H4,5 N 8,4 P 9,3S 19,2 %
-Fnd. 39,2 4,7 8,0 9,419,5 %
-b) Cal. C 3g,$ H4,5 N 8,4 P 9,3S 19,2 %
Fnd. 39,5 . 4,6 8,3 9,219,0 %
c) Cal- C 41,3 H4,g N 8,0 P 8,9S 18,4 %
10 Fnd. 41,0 5,1 8,0 8,918,2 %
.
: d) Cal. C 41,3 H4,9 N 8,0 P 8,9S 18,4 %
Fnd. 41,3 5,1 8,1 8,818,1 %
e) Cal.. C 43,1 H 5,3 N 7,7 P 8,6 S 17,7 %
FndO 42,8 5,3 7,7 8,617,3 %
15 f) Cal. C 43,1 H5,3 N 7,7 P 8,6S 17,7 %
Fnd, 43,0 5,3 7~7 8,717,6 %
., .
Cal. = Calcula~ed Fnd. = Found .. .. .
., .
~ .. . .. ... . . ... .. ..
- . .
. . ..
3~33 g) Cal. C 39,6 H 4,7 N 7,7 P 8,5 S 17,6 ~/0 Fnd. 39,5 4,97,5 8,6 17,6 %
h) Cal. C 41,2H S>lN 7,4 P 8,2S 17,0 %
Fnd. 41,1 5,17,3 8,3 16,7 %
5i) Cal. C 41,6 H 4,4 N 8,1 P 9,0S 18,5 %
Fnd. 41,4 4,58,1 9,0 18,4 %
' j) Cal. C 35,8H 3,8 Cl 9,6 N 7,6 P 8,4 S 17,4 %
Fnd. 35,9 4,0 9,8 7,3 8,5 17,4 %
' k) Cal. C 35,8H 3,8Cl 9,6N 7,6P 8,4 S 17,4 %
.Fnd. 36,0 3,8 10,0 7,9 8,1 17,0 %
1) Cal. C 37,6 H 4,2 N 7,3 P 8,1 S 16~7 Cl 9,3 % :
Fnd. 37,6 4,1 7,4 7,8 16,4 9,6 ~/0 m) Cal. C 37,6 H 4,2Cl 9,3 N 7,3P 8,1 S 16,7 %
Fnd. 37,4 4,1 9,S 7,5 7,9 16,5 %
.
15n) Cal.C 39,4 H 4,6Cl 8,9N 7,1 P 7,8 S16,2 %
Fnd. 39,1 4,5 9,3 6,8 7,7 16,5 %
o) Cal.C 39,4 H 4,6 Cl 8,9 N 7,1 P 7,8 S 16,2 %
Fnd. 39,1 4,6 9,2 7,2 7,7 16,0 %
p) Cal.C 37,8H 4,4Cl 8,6 N 6,8 P 7,5 S15,5 %
20Fnd. 38,0 4,38,9 6~8 7,4 lS,l %
.
,/ q) Cal.C 37,9H 3,7Cl 9,3 N 7,4 P 8,2 S16,8 %
Fnd. 38,1 3,89,6 7,6 8,1 16,5 %
- 15 - .
..
- ~ . ' , .. : .
Example 2 ~Q53Z33 A) Insecticidal stomach poison action Cotton and potato plants were sprayed with a o.o5% aqueous active-substance emulsion (obtained from a 10% emulsifiable concentrate).
After the drying of the obtained coating, Spodoptera littoralis or Heliothis virescens larvae L3 were placed onto the cotton plants~ and Colorada beetle larvae (Leptinotarsa decemlineata) onto the potato plants. The test was carried out at 24C with 60% relative humidity.
The compounds according to Example 1 e~hibited in the above test a good insecticidal stomach poison action against Spodoptera littoralis, ~eliothis and Leptinotarsa decemlineata larvae.
B) SystemQ;c insecticidal action In order to determine the systemic action, rooted bean plants (Vicia faba) were placed into a 0.01% aqueous a~ti~e~substance solution (obtained from a 10% emulsifiable concentrate). After a period of 24 hours~ bean aphids (Aphis fabea) were placed onto the parts of the plants above the soil. The insects were proteated by a special device from the effects of ContaGt and of gas. The test was carried out at 24C with 70% relative humidity.
In the above test, the compounds according to Example 1 exhibited a systemic action against Aphis fabae.
Action a~ainst Chilo suppressalis Rice plants of the type Caloro were planted, 6 plants per pot, in plastic pots having a top diameter of 17 cm, and grown to a height of ca. 60 cm. Infestation with Chilo suppressalis larvae (Ll, 3-4~mm long~ was carried out 2 days after application of the active substance in granular form (amount applied = 8 kg of active substance per hectare) to the paddy water. The eval~
uation of the insecticidal action was made 10 days after application of the granules.
1(~5;~
.. .
The compounds according to Example 1 were effective against Chilo suppressalis in the above test.
Example 4 Action a~a_nst ticks A) ipicephalus bursa In each case, 5 adult ticks or 50 tick larvae were placed into a small glass test tube~ and the test tubes then immersed for 1 to 2 minutes in 2 ml of an aqueous emulsion from a dilution series of 100~ 10~ 1 and 0.1 ppm of test substance. The tubes were then sealed with a standardised cotton plug, and inverted so that ~he active substance emulsion could be absorbed by the cotton wool.
An evaluation in the case of the adults was made after 2 weeks, and in the case of the larvae after 2 days. There were two repeats for each test. -B) Boophilus microplus (larvae) With a dilution series analogous to that in Test A~ tests were car-ried out with 20 sensitive larvae and OP-resistant larvae, respectively (re-sistance is with respect to diazinon compatibility).
Compounds according to Example 1 were effecti~e in these tests again-st adults and larvae of Rhipicephalus bursa and against sensitive and OP-re-. .
sistant larvae, respectively~ of Boophilus microplus.Example 5 Acarioidal aotion Phaseolus vulgaris (plants) were infested, 12 hours before the test for acaricidal action, with an infested piece of leaf from a mass culture of Tetranychus urticae. The transferred mobile stages were sprayed with the emul-sified test preparations from a chromatography-sprayer in a manner ensuring no running off of the spray liquor. An assessment was made after 2 to 7 days~ by examination under a binocular, of the living and of the dead larvae, adults and eggs, and the results expressed in percentages. The treated plants were ~l~S3;~33 kept during the l'holding time" in greenhouse compartments at 25 C.
The compounds according to Example 1 were effective in the above test against adults, larvae and eggs of Tetranychus urticae.
Example 6 Action a~ainst soil nematodes In order ~o test the action against soil nematodes the active sub-stances were added~ in the concentration stated in each case, to soil in-fested with root-gall-nematodes (Meloidogyne arenaria), and the whole intim-ately mixed. In the one test series~ tomato seedlings were planted immediat-ely afterwards in the thus prepared soil, and in the other test series to-matoes were planted after a waiting time of 8 days.
Far~an assessment of the nematicidal action~ the galls present on the roots were counted 28 days after planting and sowing, respectively.
Active substances accordlng to Example 1 exhibited in this test a good action against Meloidogyne arenaria.
I
!
'':~
~' , ' ' : ' ' , .
,~
,- , - , : , ,: . . . . .
:: . - , , , ., , . ' ,, , .: ., '
c) 25 parts o~ ac~ive sub.s~ance, .5 parts of isooctylpherloY~y-polyoxyethylene-etllanolf 1.7 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1), 8.3 parts of sodium aluminium silicate, 16.5 parts of kieselguhr9 46 parts o~ kaolin.
d) 10 parts of active substance, 3 parts of a mixture of tlle sodium salts of saturated ~atty alcohol sulphates, S parts of naphthalenesulphonic acid/formaldeh~de condensate, lS 82 parts of kaolin.
The active substances are întimately mixed, in suitable mixers, ~ith the additives, the mixture being then ground in the appropriate mills and rollers; Wett~ble po~ders are obtained which can be diluted ~ith water to give suspensions of any desired concentration.
.~ - .
Em~11sifiable concentrates:
The following substances are used to produce a) a 10%
and b) a 25% emulsifiable concentrate:
a) lO parts of active substance, 3.4 parts of epoxidised vegetable oil, ,, , , - 10_ .
. .
~os3~33 7r par~s o~ a combination emulsifier consisting of fatty alcohol polygl~Tcol cther and alkylaryl-sulphonate calcium salt, . 40 parts of dimethyl~ormamide, 43.2 parts of xylene~
b) 25 parts of ac~ive substance, 2.5 parts of epoxidised vegetable oil, 10 parts of an alky~arylsulphonate/fatty alcohol-polyglycol e~her mi~ture 5 parts of dimethylformamide, 57.5 parts of xylene.
From these concentrates it is possible to produce, by diluti.on with water, emulsions of any desired concentration.
'`; ~:
The follo~7ing constituents are used to prepare a . 5/O spray ~ 5 parts of active substance, .; 1 part of epichlorhydrin, I 94 parts of ligroin (boiling limits 160-190C).
;
~, ' -, ; . :
:,. - 11 -... ~...................................... .
- . :' .' ' ' .
. . .
1C~53233 Example 1 Pre~ration of 0,S-dimethyl-_-[6-chloro-oxazolo(4,5-b) pyridin-2(3H~-on-3-yl-methyl~-dithiophosphate 22 g of 3-chloromethyl-6-chloro-oxazolo(4,5-b)-pyridin-2(3H~-one, 24 g of potassium salt of 0,S-dimethyl-~ 5 dithiophosphoric acid and 50 ml of methanol are heatedfor 5 minutes at 65C. The methanol is then distilled off . and 100 ml of water added to the residue; the precipitated oil is isolated by extraction with ether to ob~ain the compound CH~jO\ 11 ~ C~
~.P-S-CH2-N 0 10 CH3$/ N
as pale brown, non-distillable oil.
Cal.: C 31.7 H 3.0 N 8.2 P 9.1 S 18.8 Cl 10.4 %
Found: 31.4 3.1 7.8 8.8 18.7 10.7 %
~' ' ' .
~: . ' . ' ' .
;3Z;~
:
.
Also the following compounds were prepared in an analogous manner: :
R ~ \
1 11 C=X ' ~\N ~ N / o il /0~2 ~ 2 ~ SR
.~ Rl R2 ~ X _croanalys,i s .
H CM3 (n)~C3H7- o a) H C2H5 C2H5- O b) H C2 5 (n)-C3H7- O c) . ~ C2~15 (iso)-C3H7~ O d) H C21I5 (n)-C4H9- O e) : .
, 10 ~I C2~15 (iso)-C4~19~ O f) H C2~15 CH30C2~ O g) ~ C2~15 C2H50C2H4- O h) ., . }~ C2}15 CH2=CH CH2- O i) . Cl CH3 (n)-C3H7 O i) : 15 Cl C2M5 C2H5- O k) Cl - C21I5 (n)~C3}I7_ O l) . Gl C2H5 (iso)-C3H7- m~
i Cl C2 5 ~n) C~}19- O n) . Cl C2~15 (iso)-C~H9- O _ _ ,, , . _ .
.. ' ' ~ ' , , ' 5~233 R R R ~ ----- X _______________ 1 2 3 . Microanalysis l __ ~ __ ~
Cl C2HS CH30C2H4- 0M.P, 69-71~G
Cl C~H5 C2H50C2H4- 0'- P) .
¦Cl ¦ C2115 l Ch2 Cll _~ I
:
Microanalysis S a) Cal. C 3~,5 H4,5 N 8,4 P 9,3S 19,2 %
-Fnd. 39,2 4,7 8,0 9,419,5 %
-b) Cal. C 3g,$ H4,5 N 8,4 P 9,3S 19,2 %
Fnd. 39,5 . 4,6 8,3 9,219,0 %
c) Cal- C 41,3 H4,g N 8,0 P 8,9S 18,4 %
10 Fnd. 41,0 5,1 8,0 8,918,2 %
.
: d) Cal. C 41,3 H4,9 N 8,0 P 8,9S 18,4 %
Fnd. 41,3 5,1 8,1 8,818,1 %
e) Cal.. C 43,1 H 5,3 N 7,7 P 8,6 S 17,7 %
FndO 42,8 5,3 7,7 8,617,3 %
15 f) Cal. C 43,1 H5,3 N 7,7 P 8,6S 17,7 %
Fnd, 43,0 5,3 7~7 8,717,6 %
., .
Cal. = Calcula~ed Fnd. = Found .. .. .
., .
~ .. . .. ... . . ... .. ..
- . .
. . ..
3~33 g) Cal. C 39,6 H 4,7 N 7,7 P 8,5 S 17,6 ~/0 Fnd. 39,5 4,97,5 8,6 17,6 %
h) Cal. C 41,2H S>lN 7,4 P 8,2S 17,0 %
Fnd. 41,1 5,17,3 8,3 16,7 %
5i) Cal. C 41,6 H 4,4 N 8,1 P 9,0S 18,5 %
Fnd. 41,4 4,58,1 9,0 18,4 %
' j) Cal. C 35,8H 3,8 Cl 9,6 N 7,6 P 8,4 S 17,4 %
Fnd. 35,9 4,0 9,8 7,3 8,5 17,4 %
' k) Cal. C 35,8H 3,8Cl 9,6N 7,6P 8,4 S 17,4 %
.Fnd. 36,0 3,8 10,0 7,9 8,1 17,0 %
1) Cal. C 37,6 H 4,2 N 7,3 P 8,1 S 16~7 Cl 9,3 % :
Fnd. 37,6 4,1 7,4 7,8 16,4 9,6 ~/0 m) Cal. C 37,6 H 4,2Cl 9,3 N 7,3P 8,1 S 16,7 %
Fnd. 37,4 4,1 9,S 7,5 7,9 16,5 %
.
15n) Cal.C 39,4 H 4,6Cl 8,9N 7,1 P 7,8 S16,2 %
Fnd. 39,1 4,5 9,3 6,8 7,7 16,5 %
o) Cal.C 39,4 H 4,6 Cl 8,9 N 7,1 P 7,8 S 16,2 %
Fnd. 39,1 4,6 9,2 7,2 7,7 16,0 %
p) Cal.C 37,8H 4,4Cl 8,6 N 6,8 P 7,5 S15,5 %
20Fnd. 38,0 4,38,9 6~8 7,4 lS,l %
.
,/ q) Cal.C 37,9H 3,7Cl 9,3 N 7,4 P 8,2 S16,8 %
Fnd. 38,1 3,89,6 7,6 8,1 16,5 %
- 15 - .
..
- ~ . ' , .. : .
Example 2 ~Q53Z33 A) Insecticidal stomach poison action Cotton and potato plants were sprayed with a o.o5% aqueous active-substance emulsion (obtained from a 10% emulsifiable concentrate).
After the drying of the obtained coating, Spodoptera littoralis or Heliothis virescens larvae L3 were placed onto the cotton plants~ and Colorada beetle larvae (Leptinotarsa decemlineata) onto the potato plants. The test was carried out at 24C with 60% relative humidity.
The compounds according to Example 1 e~hibited in the above test a good insecticidal stomach poison action against Spodoptera littoralis, ~eliothis and Leptinotarsa decemlineata larvae.
B) SystemQ;c insecticidal action In order to determine the systemic action, rooted bean plants (Vicia faba) were placed into a 0.01% aqueous a~ti~e~substance solution (obtained from a 10% emulsifiable concentrate). After a period of 24 hours~ bean aphids (Aphis fabea) were placed onto the parts of the plants above the soil. The insects were proteated by a special device from the effects of ContaGt and of gas. The test was carried out at 24C with 70% relative humidity.
In the above test, the compounds according to Example 1 exhibited a systemic action against Aphis fabae.
Action a~ainst Chilo suppressalis Rice plants of the type Caloro were planted, 6 plants per pot, in plastic pots having a top diameter of 17 cm, and grown to a height of ca. 60 cm. Infestation with Chilo suppressalis larvae (Ll, 3-4~mm long~ was carried out 2 days after application of the active substance in granular form (amount applied = 8 kg of active substance per hectare) to the paddy water. The eval~
uation of the insecticidal action was made 10 days after application of the granules.
1(~5;~
.. .
The compounds according to Example 1 were effective against Chilo suppressalis in the above test.
Example 4 Action a~a_nst ticks A) ipicephalus bursa In each case, 5 adult ticks or 50 tick larvae were placed into a small glass test tube~ and the test tubes then immersed for 1 to 2 minutes in 2 ml of an aqueous emulsion from a dilution series of 100~ 10~ 1 and 0.1 ppm of test substance. The tubes were then sealed with a standardised cotton plug, and inverted so that ~he active substance emulsion could be absorbed by the cotton wool.
An evaluation in the case of the adults was made after 2 weeks, and in the case of the larvae after 2 days. There were two repeats for each test. -B) Boophilus microplus (larvae) With a dilution series analogous to that in Test A~ tests were car-ried out with 20 sensitive larvae and OP-resistant larvae, respectively (re-sistance is with respect to diazinon compatibility).
Compounds according to Example 1 were effecti~e in these tests again-st adults and larvae of Rhipicephalus bursa and against sensitive and OP-re-. .
sistant larvae, respectively~ of Boophilus microplus.Example 5 Acarioidal aotion Phaseolus vulgaris (plants) were infested, 12 hours before the test for acaricidal action, with an infested piece of leaf from a mass culture of Tetranychus urticae. The transferred mobile stages were sprayed with the emul-sified test preparations from a chromatography-sprayer in a manner ensuring no running off of the spray liquor. An assessment was made after 2 to 7 days~ by examination under a binocular, of the living and of the dead larvae, adults and eggs, and the results expressed in percentages. The treated plants were ~l~S3;~33 kept during the l'holding time" in greenhouse compartments at 25 C.
The compounds according to Example 1 were effective in the above test against adults, larvae and eggs of Tetranychus urticae.
Example 6 Action a~ainst soil nematodes In order ~o test the action against soil nematodes the active sub-stances were added~ in the concentration stated in each case, to soil in-fested with root-gall-nematodes (Meloidogyne arenaria), and the whole intim-ately mixed. In the one test series~ tomato seedlings were planted immediat-ely afterwards in the thus prepared soil, and in the other test series to-matoes were planted after a waiting time of 8 days.
Far~an assessment of the nematicidal action~ the galls present on the roots were counted 28 days after planting and sowing, respectively.
Active substances accordlng to Example 1 exhibited in this test a good action against Meloidogyne arenaria.
I
!
'':~
~' , ' ' : ' ' , .
,~
,- , - , : , ,: . . . . .
:: . - , , , ., , . ' ,, , .: ., '
Claims (16)
1. Compounds of the formula wherein R1 represents hydrogen, halogen or nitro, R2 represents C1-C5-alkyl, R3 represents C1-C5-alkyl, C3-C5-alkenyl, C3-C5-alkynyl, C1-C5-alkoxy-C1-C5-alkyl or C1-C5-alkylthio-C1-C5-alkyl, and X represents oxygen or sulphur.
2. Compounds according to Claim 1, wherein R1 represents hydrogen or chlorine, R2 represents methyl or ethyl, R3 represents n-propyl, iso-propyl, iso-butyl, methoxyethyl or ethoxyethyl, and X represents oxygen.
3. Compounds according to Claim 2 of the formula.
.
.
4. Compound according to Claim 2 of the formula .
5. Compound according to Claim 2 of the formula .
6. Compound according to Claim 2 of the formula .
7. Compound according to Claim 2 of the formula .
8. Compound according to Claim 2 of the formula .
9. Compound according to Claim 2 of the formula .
10. Compound according to Claim 2 of the formula .
11. Compound according to Claim 2 of the formula .
12. Compound according to Claim 2 of the formula
13. Compound according to Claim 2 of the formula
14. Process for the preparation of a compound according to Claim 1, in which process a compound of the formula is reacted with a compound of the formula in the presence of an acid-binding agent, or with a compound of the formula wherein R1 to R3 and X have the meanings given in Claim 1, and Me stands for a monovalent metal.
15. A method of combating various plant and animal pests at a locus, which method comprises applying to the locus a compound as claimed in Claim 1 on its own or together with suitable carriers and/or additives.
16. A method according to Claim 15 wherein the pests are of the class Insecta or of the order Acarina.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH1469672A CH571814A5 (en) | 1972-10-06 | 1972-10-06 | 3-(Thiophosphorylthiomethyl)-oxazolo (4,5-b) pyridine-2(3H)-(thi)ones - with biocidal (esp insecticidal and acaricidal) activity |
CH1130173 | 1973-08-02 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1053233A true CA1053233A (en) | 1979-04-24 |
Family
ID=25708090
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA180,783A Expired CA1053233A (en) | 1972-10-06 | 1973-09-11 | Dithiophosphate esters of cyclic pyridine carbamates or thiocarbamates |
Country Status (9)
Country | Link |
---|---|
JP (1) | JPS4969841A (en) |
CA (1) | CA1053233A (en) |
DD (1) | DD108448A5 (en) |
DE (1) | DE2349746A1 (en) |
FR (1) | FR2202101B1 (en) |
GB (1) | GB1439067A (en) |
IL (1) | IL43191A0 (en) |
IT (1) | IT1054145B (en) |
NL (1) | NL7313349A (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114560873B (en) * | 2021-12-27 | 2023-02-28 | 浙江日出药业有限公司 | Preparation method of 3-chloromethyl-6-chloro-oxazole [4,5-b ] pyridine-2 (3H) ketone |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CH536071A (en) * | 1970-06-26 | 1973-04-30 | Agripat Sa | Insecticidal and acaricidal agents |
-
1973
- 1973-09-10 IL IL43191A patent/IL43191A0/en unknown
- 1973-09-11 CA CA180,783A patent/CA1053233A/en not_active Expired
- 1973-09-27 NL NL7313349A patent/NL7313349A/xx unknown
- 1973-10-03 DE DE19732349746 patent/DE2349746A1/en active Pending
- 1973-10-04 DD DD173881A patent/DD108448A5/xx unknown
- 1973-10-05 FR FR7335691A patent/FR2202101B1/fr not_active Expired
- 1973-10-05 IT IT29800/73A patent/IT1054145B/en active
- 1973-10-05 GB GB4666573A patent/GB1439067A/en not_active Expired
- 1973-10-05 JP JP48112211A patent/JPS4969841A/ja active Pending
Also Published As
Publication number | Publication date |
---|---|
FR2202101A1 (en) | 1974-05-03 |
DD108448A5 (en) | 1974-09-20 |
JPS4969841A (en) | 1974-07-05 |
IL43191A0 (en) | 1973-11-28 |
DE2349746A1 (en) | 1974-04-11 |
GB1439067A (en) | 1976-06-09 |
FR2202101B1 (en) | 1977-08-12 |
NL7313349A (en) | 1974-04-09 |
IT1054145B (en) | 1981-11-10 |
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