CA1092127A - Tricyclopentyltin compounds and pesticidal compositions containing same - Google Patents
Tricyclopentyltin compounds and pesticidal compositions containing sameInfo
- Publication number
- CA1092127A CA1092127A CA284,768A CA284768A CA1092127A CA 1092127 A CA1092127 A CA 1092127A CA 284768 A CA284768 A CA 284768A CA 1092127 A CA1092127 A CA 1092127A
- Authority
- CA
- Canada
- Prior art keywords
- carbon atoms
- alkoxy
- tin
- carbon
- alkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000000203 mixture Substances 0.000 title abstract description 39
- DWZUHANLQLDURV-UHFFFAOYSA-N tricyclopentyltin Chemical class C1CCCC1[Sn](C1CCCC1)C1CCCC1 DWZUHANLQLDURV-UHFFFAOYSA-N 0.000 title description 4
- 230000000361 pesticidal effect Effects 0.000 title description 2
- 150000001875 compounds Chemical class 0.000 claims abstract description 60
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 29
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 26
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 12
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 11
- 239000001301 oxygen Substances 0.000 claims abstract description 11
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 10
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical group [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 10
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 10
- 239000011737 fluorine Chemical group 0.000 claims abstract description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 9
- GNVMUORYQLCPJZ-UHFFFAOYSA-M Thiocarbamate Chemical group NC([S-])=O GNVMUORYQLCPJZ-UHFFFAOYSA-M 0.000 claims abstract description 9
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 9
- 239000011593 sulfur Substances 0.000 claims abstract description 9
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical group NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 claims abstract description 8
- JCXJVPUVTGWSNB-UHFFFAOYSA-N Nitrogen dioxide Chemical compound O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims abstract description 8
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical group [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims abstract description 8
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 8
- 150000002367 halogens Chemical class 0.000 claims abstract description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 8
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 8
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Chemical group SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 claims abstract description 7
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical group [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 claims abstract description 5
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims abstract description 5
- 150000007942 carboxylates Chemical group 0.000 claims abstract description 3
- 150000002431 hydrogen Chemical class 0.000 claims abstract 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 7
- 125000001153 fluoro group Chemical group F* 0.000 claims description 7
- 239000010452 phosphate Chemical group 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical group [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 7
- 230000001747 exhibiting effect Effects 0.000 claims description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 5
- 150000001408 amides Chemical group 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 102000027528 liver X receptor-like Human genes 0.000 claims 2
- 108091008780 liver X receptor-like Proteins 0.000 claims 2
- 102000034570 NR1 subfamily Human genes 0.000 claims 1
- 108020001305 NR1 subfamily Proteins 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- -1 hydrocarbon radicals Chemical class 0.000 abstract description 17
- 241000238631 Hexapoda Species 0.000 abstract description 15
- 241000233866 Fungi Species 0.000 abstract description 12
- 239000000460 chlorine Substances 0.000 abstract description 11
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 abstract description 7
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052794 bromium Inorganic materials 0.000 abstract description 7
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 5
- 229910052801 chlorine Inorganic materials 0.000 abstract description 5
- 229930195733 hydrocarbon Natural products 0.000 abstract description 5
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical group FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract description 3
- 238000009472 formulation Methods 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 3
- 206010061217 Infestation Diseases 0.000 abstract description 2
- 231100000674 Phytotoxicity Toxicity 0.000 abstract description 2
- 125000001309 chloro group Chemical group Cl* 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 65
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 59
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 54
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 33
- 229910052718 tin Inorganic materials 0.000 description 33
- 241000196324 Embryophyta Species 0.000 description 27
- 239000007787 solid Substances 0.000 description 24
- 239000002253 acid Substances 0.000 description 23
- 238000004458 analytical method Methods 0.000 description 23
- 239000007788 liquid Substances 0.000 description 23
- 239000002904 solvent Substances 0.000 description 23
- 238000000034 method Methods 0.000 description 22
- 239000000047 product Substances 0.000 description 22
- 238000009835 boiling Methods 0.000 description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 19
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 19
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 17
- 241000255993 Trichoplusia ni Species 0.000 description 16
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 15
- 241000220225 Malus Species 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 235000011430 Malus pumila Nutrition 0.000 description 14
- 235000015103 Malus silvestris Nutrition 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 14
- 235000013601 eggs Nutrition 0.000 description 14
- 239000011541 reaction mixture Substances 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000012074 organic phase Substances 0.000 description 12
- IYHVUMHJYLPTQF-UHFFFAOYSA-M tricyclopentylstannanylium;hydroxide Chemical compound C1CCCC1[Sn](C1CCCC1)(O)C1CCCC1 IYHVUMHJYLPTQF-UHFFFAOYSA-M 0.000 description 12
- 239000013078 crystal Substances 0.000 description 11
- 150000004820 halides Chemical class 0.000 description 11
- 239000002689 soil Substances 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 230000004071 biological effect Effects 0.000 description 10
- 238000002844 melting Methods 0.000 description 10
- 230000008018 melting Effects 0.000 description 10
- 239000012071 phase Substances 0.000 description 10
- 231100000167 toxic agent Toxicity 0.000 description 10
- 239000003440 toxic substance Substances 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 9
- 241000221785 Erysiphales Species 0.000 description 9
- 229910052783 alkali metal Inorganic materials 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 8
- 241001635274 Cydia pomonella Species 0.000 description 7
- 235000009754 Vitis X bourquina Nutrition 0.000 description 7
- 235000012333 Vitis X labruscana Nutrition 0.000 description 7
- 240000006365 Vitis vinifera Species 0.000 description 7
- 235000014787 Vitis vinifera Nutrition 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000011369 resultant mixture Substances 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000012141 concentrate Substances 0.000 description 6
- 235000008504 concentrate Nutrition 0.000 description 6
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 6
- 241000239290 Araneae Species 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 244000061176 Nicotiana tabacum Species 0.000 description 5
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 5
- 244000046052 Phaseolus vulgaris Species 0.000 description 5
- 150000001340 alkali metals Chemical class 0.000 description 5
- 239000000969 carrier Substances 0.000 description 5
- 239000012043 crude product Substances 0.000 description 5
- 201000010099 disease Diseases 0.000 description 5
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 229910052740 iodine Inorganic materials 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000003822 preparative gas chromatography Methods 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 241000233679 Peronosporaceae Species 0.000 description 4
- 206010039509 Scab Diseases 0.000 description 4
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 230000000855 fungicidal effect Effects 0.000 description 4
- 239000000417 fungicide Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- DNENLKYRLFOCFN-UHFFFAOYSA-M tricyclopentyl(fluoro)stannane Chemical compound C1CCCC1[Sn](C1CCCC1)(F)C1CCCC1 DNENLKYRLFOCFN-UHFFFAOYSA-M 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- 241000238876 Acari Species 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 241000255967 Helicoverpa zea Species 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 241000256247 Spodoptera exigua Species 0.000 description 3
- 241001454293 Tetranychus urticae Species 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- HARHCBUPLVDQNZ-UHFFFAOYSA-M chloro(tricyclopentyl)stannane Chemical compound C1CCCC1[Sn](C1CCCC1)(Cl)C1CCCC1 HARHCBUPLVDQNZ-UHFFFAOYSA-M 0.000 description 3
- MDDMXCXXMJTDMK-UHFFFAOYSA-M chloro-tris(cyclopentylmethyl)stannane Chemical compound C1CCCC1C[Sn](CC1CCCC1)(Cl)CC1CCCC1 MDDMXCXXMJTDMK-UHFFFAOYSA-M 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000002917 insecticide Substances 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 3
- 235000019341 magnesium sulphate Nutrition 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- RKRGLFVHHICLSP-UHFFFAOYSA-N tetrakis(cyclopentylmethyl)stannane Chemical compound C1(CCCC1)C[Sn](CC1CCCC1)(CC1CCCC1)CC1CCCC1 RKRGLFVHHICLSP-UHFFFAOYSA-N 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- 150000003606 tin compounds Chemical class 0.000 description 3
- UENSMKBMMVUEQJ-UHFFFAOYSA-M tricyclopentylstannyl acetate Chemical compound CC([O-])=O.C1CCCC1[Sn+](C1CCCC1)C1CCCC1 UENSMKBMMVUEQJ-UHFFFAOYSA-M 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- 241001124076 Aphididae Species 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 241000254173 Coleoptera Species 0.000 description 2
- 241000256113 Culicidae Species 0.000 description 2
- 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 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- 101100400378 Mus musculus Marveld2 gene Proteins 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000007900 aqueous suspension Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- PXHPYTPPLJAGEW-UHFFFAOYSA-M bromo-tris(2-cyclopentylethyl)stannane Chemical compound C1(CCCC1)CC[Sn](CCC1CCCC1)(CCC1CCCC1)Br PXHPYTPPLJAGEW-UHFFFAOYSA-M 0.000 description 2
- BRTFVKHPEHKBQF-UHFFFAOYSA-N bromocyclopentane Chemical compound BrC1CCCC1 BRTFVKHPEHKBQF-UHFFFAOYSA-N 0.000 description 2
- KGZMNQXFVZRDCX-UHFFFAOYSA-N butyl(tricyclopentyl)stannane Chemical compound C1CCCC1[Sn](C1CCCC1)(CCCC)C1CCCC1 KGZMNQXFVZRDCX-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000003776 cleavage reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000002274 desiccant Substances 0.000 description 2
- 239000012990 dithiocarbamate Substances 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- CUPFNGOKRMWUOO-UHFFFAOYSA-N hydron;difluoride Chemical compound F.F CUPFNGOKRMWUOO-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- SHYJMQIXEOODJK-UHFFFAOYSA-N methyl-tris(2-methylcyclopentyl)stannane Chemical compound C[Sn](C1C(CCC1)C)(C1C(CCC1)C)C1C(CCC1)C SHYJMQIXEOODJK-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- ZHPWRIMJTIXQIA-UHFFFAOYSA-N pentyltin Chemical compound CCCCC[Sn] ZHPWRIMJTIXQIA-UHFFFAOYSA-N 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 238000003918 potentiometric titration Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000007017 scission Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 208000024891 symptom Diseases 0.000 description 2
- LTSUHJWLSNQKIP-UHFFFAOYSA-J tin(iv) bromide Chemical compound Br[Sn](Br)(Br)Br LTSUHJWLSNQKIP-UHFFFAOYSA-J 0.000 description 2
- YFRLQYJXUZRYDN-UHFFFAOYSA-K trichloro(methyl)stannane Chemical compound C[Sn](Cl)(Cl)Cl YFRLQYJXUZRYDN-UHFFFAOYSA-K 0.000 description 2
- HFSRERHKQBMBEC-UHFFFAOYSA-N tris(cyclopentylmethyl)-methylstannane Chemical compound C[Sn](CC1CCCC1)(CC1CCCC1)CC1CCCC1 HFSRERHKQBMBEC-UHFFFAOYSA-N 0.000 description 2
- 239000010455 vermiculite Substances 0.000 description 2
- 229910052902 vermiculite Inorganic materials 0.000 description 2
- 235000019354 vermiculite Nutrition 0.000 description 2
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical class OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 1
- SXVRSCIZJBGJGB-UHFFFAOYSA-N 1-chloropropan-2-ylbenzene Chemical compound ClCC(C)C1=CC=CC=C1 SXVRSCIZJBGJGB-UHFFFAOYSA-N 0.000 description 1
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical compound N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 description 1
- VXRDAMSNTXUHFX-UHFFFAOYSA-N 2,3-dihydroxybutanedioic acid;n,n-dimethyl-2-[6-methyl-2-(4-methylphenyl)imidazo[1,2-a]pyridin-3-yl]acetamide Chemical compound OC(=O)C(O)C(O)C(O)=O.N1=C2C=CC(C)=CN2C(CC(=O)N(C)C)=C1C1=CC=C(C)C=C1.N1=C2C=CC(C)=CN2C(CC(=O)N(C)C)=C1C1=CC=C(C)C=C1 VXRDAMSNTXUHFX-UHFFFAOYSA-N 0.000 description 1
- KPIVDNYJNOPGBE-UHFFFAOYSA-N 2-aminonicotinic acid Chemical compound NC1=NC=CC=C1C(O)=O KPIVDNYJNOPGBE-UHFFFAOYSA-N 0.000 description 1
- LBPSXTQMIHEQSO-UHFFFAOYSA-M 2-aminopyridine-3-carboxylate tricyclopentylstannanylium Chemical compound NC1=C(C(=O)[O-])C=CC=N1.C1(CCCC1)[Sn+](C1CCCC1)C1CCCC1 LBPSXTQMIHEQSO-UHFFFAOYSA-M 0.000 description 1
- HLBOAQSKBNNHMW-UHFFFAOYSA-N 3-(3-methoxyphenyl)pyridine Chemical compound COC1=CC=CC(C=2C=NC=CC=2)=C1 HLBOAQSKBNNHMW-UHFFFAOYSA-N 0.000 description 1
- QCXJEYYXVJIFCE-UHFFFAOYSA-N 4-acetamidobenzoic acid Chemical compound CC(=O)NC1=CC=C(C(O)=O)C=C1 QCXJEYYXVJIFCE-UHFFFAOYSA-N 0.000 description 1
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 1
- 241000256118 Aedes aegypti Species 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- SJGMTMJJUBKJDE-UHFFFAOYSA-M Br[Mg]CCC1CCCC1 Chemical compound Br[Mg]CCC1CCCC1 SJGMTMJJUBKJDE-UHFFFAOYSA-M 0.000 description 1
- 240000007124 Brassica oleracea Species 0.000 description 1
- 235000003899 Brassica oleracea var acephala Nutrition 0.000 description 1
- 235000011301 Brassica oleracea var capitata Nutrition 0.000 description 1
- 235000001169 Brassica oleracea var oleracea Nutrition 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- BYGYPYYTXNGRGK-UHFFFAOYSA-M C(C)(=O)NC1=CC=C(C(=O)[O-])C=C1.C1(CCCC1)[Sn+](C1CCCC1)C1CCCC1 Chemical compound C(C)(=O)NC1=CC=C(C(=O)[O-])C=C1.C1(CCCC1)[Sn+](C1CCCC1)C1CCCC1 BYGYPYYTXNGRGK-UHFFFAOYSA-M 0.000 description 1
- ZVOBLGXLBIUMFY-UHFFFAOYSA-N C1(CCCC1)CC[Sn](CCC1CCCC1)CCC1CCCC1 Chemical compound C1(CCCC1)CC[Sn](CCC1CCCC1)CCC1CCCC1 ZVOBLGXLBIUMFY-UHFFFAOYSA-N 0.000 description 1
- LZKVSSFNDRMSAD-UHFFFAOYSA-M C1CCCC1C[Sn](CC1CCCC1)(Br)CC1CCCC1 Chemical compound C1CCCC1C[Sn](CC1CCCC1)(Br)CC1CCCC1 LZKVSSFNDRMSAD-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 240000008067 Cucumis sativus Species 0.000 description 1
- 235000010799 Cucumis sativus var sativus Nutrition 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 241000489973 Diabrotica undecimpunctata Species 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- 241001057636 Dracaena deremensis Species 0.000 description 1
- 241000896222 Erysiphe polygoni Species 0.000 description 1
- 240000002024 Gossypium herbaceum Species 0.000 description 1
- 235000004341 Gossypium herbaceum Nutrition 0.000 description 1
- 244000299507 Gossypium hirsutum Species 0.000 description 1
- 241000257232 Haematobia irritans Species 0.000 description 1
- 229920003091 Methocel™ Polymers 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- GENQXANMPQDDQH-UHFFFAOYSA-N OP(O)(O)=O.OP(O)(O)=O.Br Chemical compound OP(O)(O)=O.OP(O)(O)=O.Br GENQXANMPQDDQH-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 241000233629 Phytophthora parasitica Species 0.000 description 1
- 241001281803 Plasmopara viticola Species 0.000 description 1
- 241001337928 Podosphaera leucotricha Species 0.000 description 1
- 229920003171 Poly (ethylene oxide) Chemical class 0.000 description 1
- 241000220324 Pyrus Species 0.000 description 1
- 229910009027 Sn—OH Inorganic materials 0.000 description 1
- 229910009053 Sn—O—Sn Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 244000186561 Swietenia macrophylla Species 0.000 description 1
- 241001454294 Tetranychus Species 0.000 description 1
- 241000228452 Venturia inaequalis Species 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- WKSUJUKGSZTRCB-UHFFFAOYSA-M [Br-].CC1CCCC1[Mg+] Chemical compound [Br-].CC1CCCC1[Mg+] WKSUJUKGSZTRCB-UHFFFAOYSA-M 0.000 description 1
- LEEWRICIBNMZRW-UHFFFAOYSA-M [Br-].[Mg+]CC1CCCC1 Chemical compound [Br-].[Mg+]CC1CCCC1 LEEWRICIBNMZRW-UHFFFAOYSA-M 0.000 description 1
- OCZPOJZKHCBXPQ-UHFFFAOYSA-N [Mg]C1CCCC1 Chemical compound [Mg]C1CCCC1 OCZPOJZKHCBXPQ-UHFFFAOYSA-N 0.000 description 1
- NYWPNCCXLCIBIR-UHFFFAOYSA-M [OH-].C1(CCCC1)CC[Sn+](CCC1CCCC1)CCC1CCCC1 Chemical compound [OH-].C1(CCCC1)CC[Sn+](CCC1CCCC1)CCC1CCCC1 NYWPNCCXLCIBIR-UHFFFAOYSA-M 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910000318 alkali metal phosphate Inorganic materials 0.000 description 1
- 229910052936 alkali metal sulfate Inorganic materials 0.000 description 1
- 229910052977 alkali metal sulfide Inorganic materials 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229940094070 ambien Drugs 0.000 description 1
- 229940095564 anhydrous calcium sulfate Drugs 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 235000021016 apples Nutrition 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000005228 aryl sulfonate group Chemical group 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 230000003190 augmentative effect Effects 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- BAMCOYQQDPMILS-UHFFFAOYSA-M benzenethiolate tricyclopentylstannanylium Chemical compound [S-]C1=CC=CC=C1.C1(CCCC1)[Sn+](C1CCCC1)C1CCCC1 BAMCOYQQDPMILS-UHFFFAOYSA-M 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- LUZSPGQEISANPO-UHFFFAOYSA-N butyltin Chemical compound CCCC[Sn] LUZSPGQEISANPO-UHFFFAOYSA-N 0.000 description 1
- SHZIWNPUGXLXDT-UHFFFAOYSA-N caproic acid ethyl ester Natural products CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- OYIYZYBQAKULCH-UHFFFAOYSA-N cyanic acid Chemical compound N#CO.N#CO OYIYZYBQAKULCH-UHFFFAOYSA-N 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 235000005911 diet Nutrition 0.000 description 1
- 230000037213 diet Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000004495 emulsifiable concentrate Substances 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- AWYFNIZYMPNGAI-UHFFFAOYSA-L ethylenebis(dithiocarbamate) Chemical compound [S-]C(=S)NCCNC([S-])=S AWYFNIZYMPNGAI-UHFFFAOYSA-L 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 210000003608 fece Anatomy 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000005826 halohydrocarbons Chemical class 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 231100000636 lethal dose Toxicity 0.000 description 1
- 235000014666 liquid concentrate Nutrition 0.000 description 1
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 description 1
- 229910001623 magnesium bromide Inorganic materials 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000003129 miticidal effect Effects 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 231100000194 ovacidal Toxicity 0.000 description 1
- 230000003151 ovacidal effect Effects 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 244000052769 pathogen Species 0.000 description 1
- 230000001717 pathogenic effect Effects 0.000 description 1
- 235000021017 pears Nutrition 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- ZYHDBGZTUIIXNE-UHFFFAOYSA-K pentyltin(3+) trihydroxide Chemical compound [OH-].C(CCCC)[Sn+3].[OH-].[OH-] ZYHDBGZTUIIXNE-UHFFFAOYSA-K 0.000 description 1
- 238000003359 percent control normalization Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 229910052903 pyrophyllite Inorganic materials 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000012056 semi-solid material Substances 0.000 description 1
- CBXWGGFGZDVPNV-UHFFFAOYSA-N so4-so4 Chemical compound OS(O)(=O)=O.OS(O)(=O)=O CBXWGGFGZDVPNV-UHFFFAOYSA-N 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- KRACNPWSAAYFIV-UHFFFAOYSA-N tetrakis(2-cyclopentylethyl)stannane Chemical compound C1(CCCC1)CC[Sn](CCC1CCCC1)(CCC1CCCC1)CCC1CCCC1 KRACNPWSAAYFIV-UHFFFAOYSA-N 0.000 description 1
- QERYCTSHXKAMIS-UHFFFAOYSA-N thiophene-2-carboxylic acid Chemical compound OC(=O)C1=CC=CS1 QERYCTSHXKAMIS-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- DBGVGMSCBYYSLD-UHFFFAOYSA-N tributylstannane Chemical compound CCCC[SnH](CCCC)CCCC DBGVGMSCBYYSLD-UHFFFAOYSA-N 0.000 description 1
- CCCDVPNBEHCRRA-UHFFFAOYSA-K trichloro(pentyl)stannane Chemical compound CCCCC[Sn](Cl)(Cl)Cl CCCDVPNBEHCRRA-UHFFFAOYSA-K 0.000 description 1
- MOOVAXSYAVJCKG-UHFFFAOYSA-M tricyclopentylstannanylium;bromide Chemical compound C1CCCC1[Sn](C1CCCC1)(Br)C1CCCC1 MOOVAXSYAVJCKG-UHFFFAOYSA-M 0.000 description 1
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/22—Tin compounds
- C07F7/2284—Compounds with one or more Sn-N linkages
-
- 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
- A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
- A01N55/02—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur containing metal atoms
- A01N55/04—Tin
-
- 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
- A01N57/12—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing acyclic or cycloaliphatic 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/22—Tin compounds
- C07F7/2208—Compounds having tin linked only to carbon, hydrogen and/or halogen
-
- 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/22—Tin compounds
- C07F7/2224—Compounds having one or more tin-oxygen linkages
-
- 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/22—Tin compounds
- C07F7/226—Compounds with one or more Sn-S linkages
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Pyridine Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Abstract of the Disclosure - Trioirganotin compounds of the general formula or effectively control fungi an various types insects when incorporated into formulations that are applied directly to these organisms or to substrates, particularly plants, that are susceptible to infestation with these types of organisms.
The present compounds are particularly advantageous due to their considerably lower phytotoxicity relative to homologous triorfanotin compounds wherein the hydrocarbon radicals are linear and contain from 5 to 7 carbon atoms. In the foregoing formulae R is selected from the group consisting of hydrogen and alkyl containing from 1 to 3 carbon atoms, n is 0, 1 or 2, X is selected from the group consisting of chlorine, bromine, fluorine, hydroxyl, nitrate, cyanate, thiocyanate, carbamate, thiocarbamate, nitrate, carboxylate , phenoxy, alkoxy (-OR2), dithiocarbamoyl , mercaptide (-SR1) and dialkyldithiophosphate wherein R1 represents alkyl containing from 1 to 12 carbon atoms wherein Z is hydrogen, halogen, 1-3 carbon alkyl, 1-3 carbon alkoxy or nitro (-NO2), R1 is alkyl containing from 1 to 12 carbon atoms and Y is oxygen,, wherein m is an integer from 2 to 10, inclusive,
The present compounds are particularly advantageous due to their considerably lower phytotoxicity relative to homologous triorfanotin compounds wherein the hydrocarbon radicals are linear and contain from 5 to 7 carbon atoms. In the foregoing formulae R is selected from the group consisting of hydrogen and alkyl containing from 1 to 3 carbon atoms, n is 0, 1 or 2, X is selected from the group consisting of chlorine, bromine, fluorine, hydroxyl, nitrate, cyanate, thiocyanate, carbamate, thiocarbamate, nitrate, carboxylate , phenoxy, alkoxy (-OR2), dithiocarbamoyl , mercaptide (-SR1) and dialkyldithiophosphate wherein R1 represents alkyl containing from 1 to 12 carbon atoms wherein Z is hydrogen, halogen, 1-3 carbon alkyl, 1-3 carbon alkoxy or nitro (-NO2), R1 is alkyl containing from 1 to 12 carbon atoms and Y is oxygen,, wherein m is an integer from 2 to 10, inclusive,
Description
I RS(1183 )MS
~ 9Z127' NOVEL TRICYCLOPENTYI,TIN COMPOUMDS AND
PESTICIDAL COMPOSITIONS CONTAINING SAME
_ , .. . . . . .
BACKGROUND
Thls invention relates to compositions for selectively controlling ~ungi and pestiferous insects, including mites using a specified class of triorganotin compounds. The organisms against which the present compounds are effective are responsible for a considerable portion of the annual damage to agricultural crops. Many tri- alkyl ~erivatives particularly tri-n butyltin and tri-n-amyltin derivatives may effectively control these organisms, however, these compound I are sufficiently non selective toward desirable plant crops in that while the fungus or insect attacking the plant may be controlled, any plant to which the organotin compound is applied may be killed or severely damaged.
It is therefore an objective of this invention to provide a class of triorganotin compounds that can effecti~ely I control both fungi and insects on living plants without ¦ significantly damaging the plant. Many triorganotin compounds ¦¦ are active against either fungi or insects but not both of these classes of organisms. Surprisingly it has been found ¦~ that certain triorganotin compounds wherein the hydrocarbon 1¦ groups bonded to the tin atom contain a cyclopentyl structure I satisfy this ob~ective.
j ..
I
iO~21'~7 SUMMARY OF THR INVRNTION
This lnvention provides novel tricyclopentyl- and tricyclopentylalkyltin compounds of the general formulae ~ (CH~)n t 5nX and ¦ ~ (CH~)n ~ ~S ¦
wherein R is selected from the group consisting of hydrogen 5and alkyl containing from 1 to 3 carbon atoms, n is O, 1 or 2, : I X is selected from the group consisting of fluorine, nitrate, : cyanate, thiocycanate, carbamate, thiocarbamate, nitrate, -O-C ~ NH2~ ~ alkoxy (-OR ), " R~
~I dithiocarbamoyl ~SCN /~ ~ , mercaptide t-SR~ ) 10~ and dialkyldithiophosphate (SP~ ~ whereln R
~ 9Z127' NOVEL TRICYCLOPENTYI,TIN COMPOUMDS AND
PESTICIDAL COMPOSITIONS CONTAINING SAME
_ , .. . . . . .
BACKGROUND
Thls invention relates to compositions for selectively controlling ~ungi and pestiferous insects, including mites using a specified class of triorganotin compounds. The organisms against which the present compounds are effective are responsible for a considerable portion of the annual damage to agricultural crops. Many tri- alkyl ~erivatives particularly tri-n butyltin and tri-n-amyltin derivatives may effectively control these organisms, however, these compound I are sufficiently non selective toward desirable plant crops in that while the fungus or insect attacking the plant may be controlled, any plant to which the organotin compound is applied may be killed or severely damaged.
It is therefore an objective of this invention to provide a class of triorganotin compounds that can effecti~ely I control both fungi and insects on living plants without ¦ significantly damaging the plant. Many triorganotin compounds ¦¦ are active against either fungi or insects but not both of these classes of organisms. Surprisingly it has been found ¦~ that certain triorganotin compounds wherein the hydrocarbon 1¦ groups bonded to the tin atom contain a cyclopentyl structure I satisfy this ob~ective.
j ..
I
iO~21'~7 SUMMARY OF THR INVRNTION
This lnvention provides novel tricyclopentyl- and tricyclopentylalkyltin compounds of the general formulae ~ (CH~)n t 5nX and ¦ ~ (CH~)n ~ ~S ¦
wherein R is selected from the group consisting of hydrogen 5and alkyl containing from 1 to 3 carbon atoms, n is O, 1 or 2, : I X is selected from the group consisting of fluorine, nitrate, : cyanate, thiocycanate, carbamate, thiocarbamate, nitrate, -O-C ~ NH2~ ~ alkoxy (-OR ), " R~
~I dithiocarbamoyl ~SCN /~ ~ , mercaptide t-SR~ ) 10~ and dialkyldithiophosphate (SP~ ~ whereln R
-2-~z~z~ l represents alkyl containing from l to 12 carbon atom~ or phenyl Z
erein Z 1s nydrogen, ~a~oeen,_1,3 oarbon alkyl, 1-3 carbon alkoxy .or nitro (-NO2), R is alkyl containing ,0, 0 from l to 12 carbon atoms and Y is oxygen,-OC(CH2jmC-O- , O ' 5wherein m is an integer fr~m 2 to lO, inclusive, -OC
sulfur, sulfate or carbonate.
These compounds are particularly effective as control agents for fungi and insects yet do not exhibit the high level of phytotoxicity characteristic of tri-n-alkyltin compounds.
., .
.
.
2~27 The present invention provides a triorganotin compound exhibiting a formula selected from the group consisting of I ~ ~CII2) - r~ SnX and ~ (C~I2)n ~ Sn wherein R is hydrogen or alkyl of from 1 to 3 carbon atoms; N is O, 1 or 2;
X is selected from the group consisting of fluorine, hydroxyl, nitrate, cyanate, thiocyanate, carbamate, thiocarbamate, phosphate, carbonate, amide (NH2), amino (NR2 or NRlH), -O-C ~_NH2, H2N ~ , ~3_ C O ~ ~
~ S /R ~
phenoxy, alkoxy (-OR ), dithiocarbamoyl, ~SCN J , mercaptide (SR ), dialkyldithiophosphate ~SP ~ provided that X is not hydroxyl when ~ \OR J
R is hydrogen and n is O; wherein Rl represents alkyl containing from 1 to 12 carbon atoms or ~ Z wherein Z is hydrogen, halogen, alkyl containing 1 to 3 carbon atoms, alkoxy containing 1 to 3 carbon atoms, or nitro (-NO2) J
R is alkyl containing from 1 to 12 carbon atoms and Y is oxygen, O O
-OC(CH2)m C-O- wherein m is an integer from 2 to 10 inclusive, O O
-OC { >- CO -, sulfur, sulfate, phosphate or carbonate.
~B 3a -1, ~09ZlZ7 ¦; DRTAILED DESCRIPTION OF THE INVENTION
The hydrocarbon groups of the present triorganotin compounds contain a cyclopentyl group either bond:~d directly ¦~ to the tin atom or separated from the tin atom by one or two ! ~ethylene groups. The cyclopentyl group may have as a ~I substituent an alkyl group contain~ng from 1 to 3 carbon ~toms.
l Tri(cyclopentyl~tin and tri(cyclopentylalkyl)tin halides wherein the halogen is chlorine, bromine or iodine ` can be prepared by reacting at least three moles of the i corresponding cyclopentyl or cyclopentylalkyl magnesium halide, CypMgZ or Cyp(CH2)nZ ~ wherein Cyp represents a cyclopentyl i ring, for every mole of an alkyltin trihalide R SnZ 3 wherein !~ 3 R is lower alkyl and preferably contains from 1 to 4 carbon ¦~ atoms. The resultant tetraorgano~in compound, Cyp3SnR , is reacted witn an equimolar amount of a stannic halide 3 SnZ 4 . During the reaction the lower alkyl group R
present on the tetraorganotin compound is replaced by a halogen atom from the stannic halide. The reactions involved in the formation of the present triorganotin compound~ can be ~0 , represented by the following two equations where Z , Z and Z
,~ !
are individually selected from the group consisting of chlorine, bromine and iodine.
1~ , ~t ` . I
I
I
1~ 1 ~L09ZlL7 1 ~) 2 3 ~ 2
erein Z 1s nydrogen, ~a~oeen,_1,3 oarbon alkyl, 1-3 carbon alkoxy .or nitro (-NO2), R is alkyl containing ,0, 0 from l to 12 carbon atoms and Y is oxygen,-OC(CH2jmC-O- , O ' 5wherein m is an integer fr~m 2 to lO, inclusive, -OC
sulfur, sulfate or carbonate.
These compounds are particularly effective as control agents for fungi and insects yet do not exhibit the high level of phytotoxicity characteristic of tri-n-alkyltin compounds.
., .
.
.
2~27 The present invention provides a triorganotin compound exhibiting a formula selected from the group consisting of I ~ ~CII2) - r~ SnX and ~ (C~I2)n ~ Sn wherein R is hydrogen or alkyl of from 1 to 3 carbon atoms; N is O, 1 or 2;
X is selected from the group consisting of fluorine, hydroxyl, nitrate, cyanate, thiocyanate, carbamate, thiocarbamate, phosphate, carbonate, amide (NH2), amino (NR2 or NRlH), -O-C ~_NH2, H2N ~ , ~3_ C O ~ ~
~ S /R ~
phenoxy, alkoxy (-OR ), dithiocarbamoyl, ~SCN J , mercaptide (SR ), dialkyldithiophosphate ~SP ~ provided that X is not hydroxyl when ~ \OR J
R is hydrogen and n is O; wherein Rl represents alkyl containing from 1 to 12 carbon atoms or ~ Z wherein Z is hydrogen, halogen, alkyl containing 1 to 3 carbon atoms, alkoxy containing 1 to 3 carbon atoms, or nitro (-NO2) J
R is alkyl containing from 1 to 12 carbon atoms and Y is oxygen, O O
-OC(CH2)m C-O- wherein m is an integer from 2 to 10 inclusive, O O
-OC { >- CO -, sulfur, sulfate, phosphate or carbonate.
~B 3a -1, ~09ZlZ7 ¦; DRTAILED DESCRIPTION OF THE INVENTION
The hydrocarbon groups of the present triorganotin compounds contain a cyclopentyl group either bond:~d directly ¦~ to the tin atom or separated from the tin atom by one or two ! ~ethylene groups. The cyclopentyl group may have as a ~I substituent an alkyl group contain~ng from 1 to 3 carbon ~toms.
l Tri(cyclopentyl~tin and tri(cyclopentylalkyl)tin halides wherein the halogen is chlorine, bromine or iodine ` can be prepared by reacting at least three moles of the i corresponding cyclopentyl or cyclopentylalkyl magnesium halide, CypMgZ or Cyp(CH2)nZ ~ wherein Cyp represents a cyclopentyl i ring, for every mole of an alkyltin trihalide R SnZ 3 wherein !~ 3 R is lower alkyl and preferably contains from 1 to 4 carbon ¦~ atoms. The resultant tetraorgano~in compound, Cyp3SnR , is reacted witn an equimolar amount of a stannic halide 3 SnZ 4 . During the reaction the lower alkyl group R
present on the tetraorganotin compound is replaced by a halogen atom from the stannic halide. The reactions involved in the formation of the present triorganotin compound~ can be ~0 , represented by the following two equations where Z , Z and Z
,~ !
are individually selected from the group consisting of chlorine, bromine and iodine.
1~ , ~t ` . I
I
I
1~ 1 ~L09ZlL7 1 ~) 2 3 ~ 2
3 CypMgZ ~ R Sn~3 -~ Cyp3SnR + 3MgZ Z
9 3 ~ 3 3 Cyp3SnR + SnZ~ ) Cyp3SnZ + R SnZ3 3 2 The aforementioned alkyltin trihalide R SnZ 3 can, in turn, be prepared by reacting the corresponding alkyl halide, R Z , with a stannous halide SnZz as described in ¦ United States Patent 3,340,283~ issued September 5, 1967 to ' Carl R. Glosk~y assigned to M ~ T Chemicals Inc.
The reaction between the stannic halide and tetra-1~ organotin compound should be performed under ar~ydrous ji conditions at temperatures from about -25 to 80C., preferably from +25 to 80C.~ in a hydrocarbon solvent. Prererred solvents include pentane, hexane and cyclohexane.
Preferably the stannic halide is dissolved in an I organic solvent and the resultant solution added dropwise to 1' a second solution containing the tetraorganotin compound in I~
the same solvent. The temperature of the reaction mixture ~s preferably maintained below about 30C. during the addition, which requires about one hour, after which the mixture is heated to a temperature from 35 to 80C. Preferably the temperature employed is the reflux temperature of the reaction mixture. Heating is continued for from about 15 to 60 minutes to ensure complete reaction. The reaction mixture is then allowed to cool to ambient temperature, and extracted with one or more portions of water or aqueous mineral acid. The by-il 3 3 product of the reaction, a monoorganotin trihalide, R SnZ3, i3 " soluble in the aqueous phase of the reaction mixture. Thedesired product remains in the organic phase, and is readily ,1 jl I
1~9Z~LZ7 lsolated by bolllng o~f the hydrocarbon solvent. No rurther puri~ication is usually requiréd, however the product can be distilled if desired. The organic layer is preferably freed of any dlssolved water following the extracting step.
Any of the conventional chemical dehydrating agents are suitable, provided that they wlll not react with either the triorganotin halide or the hydrocarbon solvent. Preferred drying agents include anhydrous magnesium sulfate, anhydrous I sodium sulfate and anhydrous calcium sulfate.
l Tri(cyclopentylalkyl)tin bromides can be prepared by ¦ the gradual addition of bromine to a solution containing the corresponding tetra(cyclopentylalkyl)tin compound. The tetraorganotin compound is, in turn, prepared by reacting a cyclopentylalkyl magnesium halide with a stannic halide in a ~1 molar ratio of 4:1, respectively.
¦ The present triorganotin halides are solids or liquidsl ll at ambient temperature. The halides can readily be converted to' ¦ other derivatives such as the oxide, acetate and sulfate 1i using known reactions. The desired anionic radical can be !! introduced by react~ng the corresponding triorganotin halide, hydroxide or bis(trior~anotin~ oxide Tith the reagent indioated ln tne following table.
109Z~'~7 OR~lANOTIN DERIVATIVE + REAGENT DESIRED PRODUCT
Chloride, Bromide Carboxylic acid + carboxylake, or Iodide acid acceptor, e.K. e.g. acetate an amine " alkali metal salt of "
a carboxylic acid " aqueous solution of oxide tor alkali metal hydroxide hydroxide) " alkali metal alkoxide alkoxlde or alcohol + acid acceptor (e.g. an amine) " alkali metal phenoxide phenoxide or phenol + acid acceptor " potassium fluoride or fluoride hydrofluoric acid " alkali metal sulfide sulfide " alkali metal sulfate sulfate " mercaptan + acid mercaptide acceptor " alkali metal cyanate cyanate " alkali metal khiocyanate thiocyanate " alkali metal thiocarbamate khiocarbamate " alkali metal dithiocarbamate dithiocarbamate 1~921%7 ORGANOTIN DERIVATIVE ~ REAGENT DESIRED PRODUCT
. . . _ _ _ Chloride, Bromide phosphoric acid phosphate or Iodide or alkali metal phosphate .~ alkali metal dialkyldithio-dialkyldithio- phosphate phosphate Oxide or ~ydroxide carboxylic acid or carboxylate anhydride " alcohol ~or phenol) alkoxide (or l - phenoxide) : " hydrofluoric acid fluoride " dilute (10-25 weight sulfate %) aqueous sulfuric " hydrogen sulfide sulfide alkyl or aryl mercaptide mercaptan " carbon dioxide carbonate Hydroxide heat to remove oxide water ;
: .
.
I
I
I
I I
The reactlon condltion~ such as preferred solvents, temperatures and reaction tlmes for preparing the derivatives summarized in the preceding table are known ln the art and, I therefore, do not require a detailed description in the present I specification. A comprehensive treatment o~ this sub~ect matter together wlth numerous literature references is j contained in an article by R. K. Ingham et al. that appeared in the October, 1960 issue of CHEMICAL RE~-IEWS (pp. 459-539).
The aforementioned derivatives may be liquids or solids at ¦ ambient temperature, depending upon the type of substituents represented by X or Y.
The present tricyclopentyltin and tricyclopentyl-¦ alkyltin compounds effectively control many types of undesirable ll fungi and insects, particularly mites, when applied to living ¦1 plants that are susceptible to infestations of these organismsO
!~ The combination of fungicidal and miticidal activity is not i common for a single organotin compound. A single application !' f these compounds to living plants or other substrates provides ~I residual and extended control o~ many varieties of ~ungi and 1~ insects for a considerable period of time, the duration of which s dep_ndent to some extent upor mechanical and j biological influences, including weather. Formulations containing the present organotin compounds can be applied directly to the organism to be controlled.
I
I
. I
_ 9 _ ~z~
In preparing compositions ~or application to plants the organotin compound is often augmented or modified by combining it with one or more commonly employed pesticide additives or adjuvants includ:Lng organic solvents, water or other liquid carriers, surfactants to aid in dispersing or emulsi-fying the organotin compound and rinely comminuted solid carriers. Depending upon the concentration of triorganotin compound in these compositions, they can be employed either without additional diluents or as liquid concentrates which are subsequently diluted with one or more additional inert liquids to produce the ultimate treating compositions. In compositions employed as concen-trates, the triorganotin compound can be present at concentrations of from about 5 to about 98% by weight. Other biologically active agents that are chemically compatible with-the present triorganotin compounds can also be added.
The optimum effective concentration of tin compound . ; to be employed as toxicant in a composition is dependant upon whether the organism is contacted with or, as in the case Of insects~ ingests the toxicant. The actual weight of compound constituting an effecti~e dose is primarily dependent upon the susceptibility of the particular organism to a given triorganoti n compound. For control of insects, good results are obtai~ned with liquid or dust compositions containing as little as one part per million by weight of toxicant. Compositions contain-ing up to 90 percent by weight of toxicant can be employed to treat a heavily infested area.
~O~ZIZ7 In the preparatlon of dust composition~, the organo-tin compound can be blended with many commonly employed finely dlvlded solid carriers such as ~uller's earth, attapulgite, bentonite, pyrophyllite, vermiculite, diatomaceou3 earth, talc, chalkg gypsum a~d wood flour. The carrier, usually ln a ~inely divided form, is ground or mixed with the toxicant or wetted wlth a dispersion o~ the toxicant in a volatile liquid. Depending upon the relative proportions of toxicant and carrier, these compositions can be employed as concentrates that are subsequently diluted with additional solid carrier to obtain the desired amount of active ingredient.
Alternatively, such concentrate dust compositions can be employed in combination with various known anionic, cationlc or non-ionic surfactants as emulsifying or dispersing agents to lorm spray concentrates. Such concentrates are readily disper~lble ln liquid carriers to form spray composltions or llquld formulations contalning ~he toxicants in any desired amount. Th~ choice and concentration of surfactant are ; determlned by the abillty of the material to facilitate ~he dlspersi.ng o~ the concentrate in the liquld carrier to produce ~he desired liquid compositlon. Suitable liquid carriers include water, methanol, ethanol, isopropanol, methyl ethyl ketone, acetone, methylene chloride, chlorobenzene, toluene, xylene and petroleum distlllates. Among the pre~erred petrolleum distlllates are those boiling under 400F. at ~¦ atmospher1 pressure and hav~ng a flash po~nt abo~e aoou~ ôOF.
I
~'.)!~21;',~ ~
Ll~uid compositions can also be prepared by dissolvlng one of the present triorganotin compounds in a mixture containing a water-immisci.ble organic llquid and a surface active dispersing agent. The resultant emulsifiable concentrate is then further diluted wikh water and an oil to form spray m~i~x~res in the form of oll-in-wa~er emulslons.
In such compo~ltion~l the carrier comprises an aqueous emulsion, i.e. a mixture of water-lmmiscible solvent, emulsifying agent and water. Preferred dispersing agents for these composltions are oil-soluble and include the condensation products of alkylene oxides with phenols and organic and inorganic acids, polyoxyethylene derivatives of sorbitan esters, alky~arylsulfonates~ complex ether alcohols, . . mahogany soaps and the like. Suitable organic liquids to be: 15 . employed in the compositions include petroleum distillates, hexanol, llquid halohydrocarbons.and synthetic organic olls.
The surface active dispersing agents .are usually employed in - the liquid dispersions and aqueous emulsions in the amount Or from about 1 to about 20 percent by weighk of the combined .
~3 ~r~ight o~ ~he dlspersing agent and the active toxicant.
When operating in accordance with the present .
. lnventio~? the organotin compound or a composition cont~.inin~
the co~pound can be applied directly onto the organism to be controlled or to the site to be protected, particularly plants and trees. Application to the follage of plants is convenlently carried out using power dusters, boom sprayers and spray dusters;`~~When employed in this manner the composltion : should ~ot contain any significant amounts o~ phytotoxlc dlluenks. In large scale operations, dusts or low volume sprays may be appl:Led from an aircraft.
1 09Zi.27 ¦¦ The following examples represent prererred embodiments of the present compounds anA their use as fungicides and insecticides, and are not intended to limit the ~I scope of the accompanying claims. All parts and percentages 1 are by weight unless otherwise specified.
EXAMPLES
EXAMPLE 1 - Preparation of Tricyclopentyltin Chloride , and Derivatives Thereof j~ A. Prepara~ tric~clopentyltin ,~
o ! To 24.3 g. (1 g. atom) of magnesium chips heated to a temperature of 40C. under a nitrogen atmosphere was added a 25 cc. portlon of a solution containing 149 g.
(1 mole) of bromocyclopentane dissolved in 750 cc. o~
anhydrous tetrahydrofuran. The reaction was initiated using .i , ~ a few drops of ethylene dibromide. The remaining portion of the bromocyclopentane solution was gradually added during a period of 2 hours while the reaction mixture was heated to the boiling point. Heating was continued for an addltional 1.5`
hours, during which time 15 cc. o~ a 3 normal solution o~
butylmagneslum bromide in tetrahydrofl-~ran was added to react wiih any impurities which could prevent or inhibit the formation of the cyclopentylmagnesium bro~ide. A small particle Or iodine was also added as an initiator for the ~ reaction. The reaction mixture was allowed to cool to ambient temperature and remain at this temperature for about 16 hours, during which time stirring of the mixture was continued. At the end of this period all of the magnesium appeared to have reacted. A 100 cc. portion of tetrahydrofuran !
i! !
- ~1 ,. . . . I
iu~32~ z7 ~I was added to compensate for solvent loss resulting from ,~ evaporation, after which the reaction mixture was heated to the bolllng point for two hours. A 500 cc. portion of this solution containing o.66 mole of cyclopentyl magnesium bromide ¦
, was added dropwlse to a stirred solution of butyltin trichlorld~
56.4 g.~ 0.2 mole) dissolved in 250 cc. of dry benzene. The addition required one hour and was conducted under a nitrogen atmosphere. During the addition the temperature of the 1, reaction mixture was maintained below 45OC. Following completion of the addition the reaction mixture was heated to ~ the boiling point for one hour, then allowed to cool to 'i ambien~ temperature and stirred for 18 hours. To the resultant mixture was added a solution containing 200 cc. water and 35 g.
of citric acid. The organic phase of the resultant two phase ~5 liquid was separated and the water ~resent therein removed " using a portion of anhydrous magnesium sulfate, which was subse~uently removed by filtration. The solvent was evaporated~
under reduced pressure to yield 72.25 g. (94% yield) of a l!iquid, butyltricyclopentyltin, exhibiting a refractive .' Z7 index (n D) of 1.5220. This liquid was extracted 1 time with methanol. Analysis by yapor phase chromatography indicated that ihe product was 96.7% pure. The product was ~ound to contain 30.24% tin. The calculated value for butyltricyclo-;! pentyltin is 30.98%.
Ii I
i, I
.
Il l Zl.~7 B. Cleavage of Butyltricyclopentyltin to ~! T icyclopentyltin Chloride 'i A 19.2 g. (0.05 mole) portion of the butyltricyclo- ¦
Il pentyltin prepared as described in part A of this example ~, was dlssolved ln 75 cc. of heptane. To this solution was added a solution containing 13.0 g. ~0.05 mole) of anhydrou~
stannic chloride and 75 cc. heptane. The addition required 20 minutes3 following whlch the resultant mixture was heated to the boiling point for 30 minutes and then allowed to - I
1~ cool to ambient temperature. A solution obtained by combining ¦
9 3 ~ 3 3 Cyp3SnR + SnZ~ ) Cyp3SnZ + R SnZ3 3 2 The aforementioned alkyltin trihalide R SnZ 3 can, in turn, be prepared by reacting the corresponding alkyl halide, R Z , with a stannous halide SnZz as described in ¦ United States Patent 3,340,283~ issued September 5, 1967 to ' Carl R. Glosk~y assigned to M ~ T Chemicals Inc.
The reaction between the stannic halide and tetra-1~ organotin compound should be performed under ar~ydrous ji conditions at temperatures from about -25 to 80C., preferably from +25 to 80C.~ in a hydrocarbon solvent. Prererred solvents include pentane, hexane and cyclohexane.
Preferably the stannic halide is dissolved in an I organic solvent and the resultant solution added dropwise to 1' a second solution containing the tetraorganotin compound in I~
the same solvent. The temperature of the reaction mixture ~s preferably maintained below about 30C. during the addition, which requires about one hour, after which the mixture is heated to a temperature from 35 to 80C. Preferably the temperature employed is the reflux temperature of the reaction mixture. Heating is continued for from about 15 to 60 minutes to ensure complete reaction. The reaction mixture is then allowed to cool to ambient temperature, and extracted with one or more portions of water or aqueous mineral acid. The by-il 3 3 product of the reaction, a monoorganotin trihalide, R SnZ3, i3 " soluble in the aqueous phase of the reaction mixture. Thedesired product remains in the organic phase, and is readily ,1 jl I
1~9Z~LZ7 lsolated by bolllng o~f the hydrocarbon solvent. No rurther puri~ication is usually requiréd, however the product can be distilled if desired. The organic layer is preferably freed of any dlssolved water following the extracting step.
Any of the conventional chemical dehydrating agents are suitable, provided that they wlll not react with either the triorganotin halide or the hydrocarbon solvent. Preferred drying agents include anhydrous magnesium sulfate, anhydrous I sodium sulfate and anhydrous calcium sulfate.
l Tri(cyclopentylalkyl)tin bromides can be prepared by ¦ the gradual addition of bromine to a solution containing the corresponding tetra(cyclopentylalkyl)tin compound. The tetraorganotin compound is, in turn, prepared by reacting a cyclopentylalkyl magnesium halide with a stannic halide in a ~1 molar ratio of 4:1, respectively.
¦ The present triorganotin halides are solids or liquidsl ll at ambient temperature. The halides can readily be converted to' ¦ other derivatives such as the oxide, acetate and sulfate 1i using known reactions. The desired anionic radical can be !! introduced by react~ng the corresponding triorganotin halide, hydroxide or bis(trior~anotin~ oxide Tith the reagent indioated ln tne following table.
109Z~'~7 OR~lANOTIN DERIVATIVE + REAGENT DESIRED PRODUCT
Chloride, Bromide Carboxylic acid + carboxylake, or Iodide acid acceptor, e.K. e.g. acetate an amine " alkali metal salt of "
a carboxylic acid " aqueous solution of oxide tor alkali metal hydroxide hydroxide) " alkali metal alkoxide alkoxlde or alcohol + acid acceptor (e.g. an amine) " alkali metal phenoxide phenoxide or phenol + acid acceptor " potassium fluoride or fluoride hydrofluoric acid " alkali metal sulfide sulfide " alkali metal sulfate sulfate " mercaptan + acid mercaptide acceptor " alkali metal cyanate cyanate " alkali metal khiocyanate thiocyanate " alkali metal thiocarbamate khiocarbamate " alkali metal dithiocarbamate dithiocarbamate 1~921%7 ORGANOTIN DERIVATIVE ~ REAGENT DESIRED PRODUCT
. . . _ _ _ Chloride, Bromide phosphoric acid phosphate or Iodide or alkali metal phosphate .~ alkali metal dialkyldithio-dialkyldithio- phosphate phosphate Oxide or ~ydroxide carboxylic acid or carboxylate anhydride " alcohol ~or phenol) alkoxide (or l - phenoxide) : " hydrofluoric acid fluoride " dilute (10-25 weight sulfate %) aqueous sulfuric " hydrogen sulfide sulfide alkyl or aryl mercaptide mercaptan " carbon dioxide carbonate Hydroxide heat to remove oxide water ;
: .
.
I
I
I
I I
The reactlon condltion~ such as preferred solvents, temperatures and reaction tlmes for preparing the derivatives summarized in the preceding table are known ln the art and, I therefore, do not require a detailed description in the present I specification. A comprehensive treatment o~ this sub~ect matter together wlth numerous literature references is j contained in an article by R. K. Ingham et al. that appeared in the October, 1960 issue of CHEMICAL RE~-IEWS (pp. 459-539).
The aforementioned derivatives may be liquids or solids at ¦ ambient temperature, depending upon the type of substituents represented by X or Y.
The present tricyclopentyltin and tricyclopentyl-¦ alkyltin compounds effectively control many types of undesirable ll fungi and insects, particularly mites, when applied to living ¦1 plants that are susceptible to infestations of these organismsO
!~ The combination of fungicidal and miticidal activity is not i common for a single organotin compound. A single application !' f these compounds to living plants or other substrates provides ~I residual and extended control o~ many varieties of ~ungi and 1~ insects for a considerable period of time, the duration of which s dep_ndent to some extent upor mechanical and j biological influences, including weather. Formulations containing the present organotin compounds can be applied directly to the organism to be controlled.
I
I
. I
_ 9 _ ~z~
In preparing compositions ~or application to plants the organotin compound is often augmented or modified by combining it with one or more commonly employed pesticide additives or adjuvants includ:Lng organic solvents, water or other liquid carriers, surfactants to aid in dispersing or emulsi-fying the organotin compound and rinely comminuted solid carriers. Depending upon the concentration of triorganotin compound in these compositions, they can be employed either without additional diluents or as liquid concentrates which are subsequently diluted with one or more additional inert liquids to produce the ultimate treating compositions. In compositions employed as concen-trates, the triorganotin compound can be present at concentrations of from about 5 to about 98% by weight. Other biologically active agents that are chemically compatible with-the present triorganotin compounds can also be added.
The optimum effective concentration of tin compound . ; to be employed as toxicant in a composition is dependant upon whether the organism is contacted with or, as in the case Of insects~ ingests the toxicant. The actual weight of compound constituting an effecti~e dose is primarily dependent upon the susceptibility of the particular organism to a given triorganoti n compound. For control of insects, good results are obtai~ned with liquid or dust compositions containing as little as one part per million by weight of toxicant. Compositions contain-ing up to 90 percent by weight of toxicant can be employed to treat a heavily infested area.
~O~ZIZ7 In the preparatlon of dust composition~, the organo-tin compound can be blended with many commonly employed finely dlvlded solid carriers such as ~uller's earth, attapulgite, bentonite, pyrophyllite, vermiculite, diatomaceou3 earth, talc, chalkg gypsum a~d wood flour. The carrier, usually ln a ~inely divided form, is ground or mixed with the toxicant or wetted wlth a dispersion o~ the toxicant in a volatile liquid. Depending upon the relative proportions of toxicant and carrier, these compositions can be employed as concentrates that are subsequently diluted with additional solid carrier to obtain the desired amount of active ingredient.
Alternatively, such concentrate dust compositions can be employed in combination with various known anionic, cationlc or non-ionic surfactants as emulsifying or dispersing agents to lorm spray concentrates. Such concentrates are readily disper~lble ln liquid carriers to form spray composltions or llquld formulations contalning ~he toxicants in any desired amount. Th~ choice and concentration of surfactant are ; determlned by the abillty of the material to facilitate ~he dlspersi.ng o~ the concentrate in the liquld carrier to produce ~he desired liquid compositlon. Suitable liquid carriers include water, methanol, ethanol, isopropanol, methyl ethyl ketone, acetone, methylene chloride, chlorobenzene, toluene, xylene and petroleum distlllates. Among the pre~erred petrolleum distlllates are those boiling under 400F. at ~¦ atmospher1 pressure and hav~ng a flash po~nt abo~e aoou~ ôOF.
I
~'.)!~21;',~ ~
Ll~uid compositions can also be prepared by dissolvlng one of the present triorganotin compounds in a mixture containing a water-immisci.ble organic llquid and a surface active dispersing agent. The resultant emulsifiable concentrate is then further diluted wikh water and an oil to form spray m~i~x~res in the form of oll-in-wa~er emulslons.
In such compo~ltion~l the carrier comprises an aqueous emulsion, i.e. a mixture of water-lmmiscible solvent, emulsifying agent and water. Preferred dispersing agents for these composltions are oil-soluble and include the condensation products of alkylene oxides with phenols and organic and inorganic acids, polyoxyethylene derivatives of sorbitan esters, alky~arylsulfonates~ complex ether alcohols, . . mahogany soaps and the like. Suitable organic liquids to be: 15 . employed in the compositions include petroleum distillates, hexanol, llquid halohydrocarbons.and synthetic organic olls.
The surface active dispersing agents .are usually employed in - the liquid dispersions and aqueous emulsions in the amount Or from about 1 to about 20 percent by weighk of the combined .
~3 ~r~ight o~ ~he dlspersing agent and the active toxicant.
When operating in accordance with the present .
. lnventio~? the organotin compound or a composition cont~.inin~
the co~pound can be applied directly onto the organism to be controlled or to the site to be protected, particularly plants and trees. Application to the follage of plants is convenlently carried out using power dusters, boom sprayers and spray dusters;`~~When employed in this manner the composltion : should ~ot contain any significant amounts o~ phytotoxlc dlluenks. In large scale operations, dusts or low volume sprays may be appl:Led from an aircraft.
1 09Zi.27 ¦¦ The following examples represent prererred embodiments of the present compounds anA their use as fungicides and insecticides, and are not intended to limit the ~I scope of the accompanying claims. All parts and percentages 1 are by weight unless otherwise specified.
EXAMPLES
EXAMPLE 1 - Preparation of Tricyclopentyltin Chloride , and Derivatives Thereof j~ A. Prepara~ tric~clopentyltin ,~
o ! To 24.3 g. (1 g. atom) of magnesium chips heated to a temperature of 40C. under a nitrogen atmosphere was added a 25 cc. portlon of a solution containing 149 g.
(1 mole) of bromocyclopentane dissolved in 750 cc. o~
anhydrous tetrahydrofuran. The reaction was initiated using .i , ~ a few drops of ethylene dibromide. The remaining portion of the bromocyclopentane solution was gradually added during a period of 2 hours while the reaction mixture was heated to the boiling point. Heating was continued for an addltional 1.5`
hours, during which time 15 cc. o~ a 3 normal solution o~
butylmagneslum bromide in tetrahydrofl-~ran was added to react wiih any impurities which could prevent or inhibit the formation of the cyclopentylmagnesium bro~ide. A small particle Or iodine was also added as an initiator for the ~ reaction. The reaction mixture was allowed to cool to ambient temperature and remain at this temperature for about 16 hours, during which time stirring of the mixture was continued. At the end of this period all of the magnesium appeared to have reacted. A 100 cc. portion of tetrahydrofuran !
i! !
- ~1 ,. . . . I
iu~32~ z7 ~I was added to compensate for solvent loss resulting from ,~ evaporation, after which the reaction mixture was heated to the bolllng point for two hours. A 500 cc. portion of this solution containing o.66 mole of cyclopentyl magnesium bromide ¦
, was added dropwlse to a stirred solution of butyltin trichlorld~
56.4 g.~ 0.2 mole) dissolved in 250 cc. of dry benzene. The addition required one hour and was conducted under a nitrogen atmosphere. During the addition the temperature of the 1, reaction mixture was maintained below 45OC. Following completion of the addition the reaction mixture was heated to ~ the boiling point for one hour, then allowed to cool to 'i ambien~ temperature and stirred for 18 hours. To the resultant mixture was added a solution containing 200 cc. water and 35 g.
of citric acid. The organic phase of the resultant two phase ~5 liquid was separated and the water ~resent therein removed " using a portion of anhydrous magnesium sulfate, which was subse~uently removed by filtration. The solvent was evaporated~
under reduced pressure to yield 72.25 g. (94% yield) of a l!iquid, butyltricyclopentyltin, exhibiting a refractive .' Z7 index (n D) of 1.5220. This liquid was extracted 1 time with methanol. Analysis by yapor phase chromatography indicated that ihe product was 96.7% pure. The product was ~ound to contain 30.24% tin. The calculated value for butyltricyclo-;! pentyltin is 30.98%.
Ii I
i, I
.
Il l Zl.~7 B. Cleavage of Butyltricyclopentyltin to ~! T icyclopentyltin Chloride 'i A 19.2 g. (0.05 mole) portion of the butyltricyclo- ¦
Il pentyltin prepared as described in part A of this example ~, was dlssolved ln 75 cc. of heptane. To this solution was added a solution containing 13.0 g. ~0.05 mole) of anhydrou~
stannic chloride and 75 cc. heptane. The addition required 20 minutes3 following whlch the resultant mixture was heated to the boiling point for 30 minutes and then allowed to - I
1~ cool to ambient temperature. A solution obtained by combining ¦
4 cc. of 12N aqueous hydrochloric acid and 96 cc. water was then added to the reaction .nixture with vigorous stirring Ij both durlng the addition and f'or five minutes thereafter.
il The organic layer of the resultant two-phase liquid was . .
~I combined with an aqueous hydrochloric acid solution prepared as described hereinabove. I'he organic layer was isolated and the water therein removed using a quantity of anhydrous ~ !' !
magnesium sulfate. The heptane was then evaporated under reduced pressure to yield 17.8 g. of pale yellow crystals l~ exhibiting a melting range of 41-44C. Upon analysis by vapor phase chromatography the product was found to be 97.2%
pure. Following a recrystalization from pentane at -7~C., the~
product melted between 44 and 45C. and was 99.6% pure, as `
determined by vapor phase chromatography.
~ Tricyclopentyltin hydroxide was prepared by adding I a solution of the corresponding chloride (18.1 g. of the chlorlde in 40 cc. of tetrahydro~uran) to a solution containing, 3.0 g. o~ sodium hydroxide, 12 cc. water and 12 cc. methanol. I
" The addition was gradual and required 20 minutes, at which time !
ii . I
il The organic layer of the resultant two-phase liquid was . .
~I combined with an aqueous hydrochloric acid solution prepared as described hereinabove. I'he organic layer was isolated and the water therein removed using a quantity of anhydrous ~ !' !
magnesium sulfate. The heptane was then evaporated under reduced pressure to yield 17.8 g. of pale yellow crystals l~ exhibiting a melting range of 41-44C. Upon analysis by vapor phase chromatography the product was found to be 97.2%
pure. Following a recrystalization from pentane at -7~C., the~
product melted between 44 and 45C. and was 99.6% pure, as `
determined by vapor phase chromatography.
~ Tricyclopentyltin hydroxide was prepared by adding I a solution of the corresponding chloride (18.1 g. of the chlorlde in 40 cc. of tetrahydro~uran) to a solution containing, 3.0 g. o~ sodium hydroxide, 12 cc. water and 12 cc. methanol. I
" The addition was gradual and required 20 minutes, at which time !
ii . I
5- 1 l! I
Il 1' ` . I
~V~Z~
I!
~l ~
, 12 cc. of water were added. The resultant slurry was stirred i:
for 0.5 hour, at which time 150 cc. of water were added to I completely precipitate the product. The solid was isolated I and washed with deionized water until no detectible amount 1, of chloride ion was present in the water. The solid was then 'l dried in a circulating air oven maintained at a temperature , i I
of 40 C. Analysis by potentiometric titration indicated that the hydroxide was between 98.6 and 99.1% pure.
¦, C. TricycloPentyltin Fluoride 10r~ Tricyclopentyltin fluoride was prepared from the corresponding hydroxide. A solution containing 300 g. of i - ~` tricyclopentyltin hydroxide and 3600 cc. of tetrahydrofuran wasi ; clarified by filtration. To this solution was gradually I added a solution obtained by combining 50 g. of a 48~ aqueous " hydrofluoric acid solution with 150 cc. of water. The resultant mixture, which contained a white precipitate, was heated to the boiling point (64C.) for 0.25 hour, then cooled to ambient temperature filtered, and washed sequentially with 1 liter of a 0.1% aqueous hydrofluoric acid solution, 2Q ~ lter deionized water and 500 cc. methanol. After being dried under reduced pressure at a temperature of 50~C. the white solid (280 g.) melted from 275 to 280C. with evidence of decom~osition. The solid was found to contain ~, 34.05% tin and 5.32% fluorine. The calculated values for ' tri(cyclopentyl)tin fluoride are 34.40% tin and 5.51% fluorine.
~i i , ll i !l - ,¦ D. Tricyclopentyltin Acetate To a suspension of 17.15 g. tricyclopentyltin hydroxide in 100 cc. o~ dlethyl ether was added dropwise over 0.25 hour, a solution of 3.15 g. acekic acid (glacial) in 'l 100 cc. diethyl ether. The solids dissolved and the solution was stirred for 0.25 hour at 25C. About 15 g. of anhydrous magnesium sulfate were added to the solution and the mixture stirred for 1 hour to remove water formed during reaction.
~ The mixture was then filtered and solvent removed on a rotary .~ 10 i! evaporator to yield 20 g. of a white solid. The solid was placed in a desiccator over sodium hydroxide pellets and held ~ under reduced pressure for 48 hours to remove excess unreacted ; ,; acetic acid. The product, a white solid, weighed 18.7 g~ and il melted from 52 to 54C.
l~ Analysis: Found: Tin, 30.65%; Acid No. 160 , Calculated: Tln, 30.82%; Acid No. 146 li ¦I E. Tricyclo~entyltin ?-Ethylhexanoate A 17.1 g. portion of tricyclopentyltin hydroxide !~ and 7.2 g. of 2-ethylhexanoic acid in 200 cc. benzene were heated to the boiling point and the ~y-product water (o.84 cc.) removed using a Dean-Stark trap. The benzene was evaporated ~i under reduced pressure to yield 23.5 g. of a yellow liquid, n D = 1.5068.
~Analysis: Found: Sn, 25.14%; Acid No. 123.6.
,iCalculated: Sn, 25.29%; Acid No. 119.5. ~
; 1! 17- !
'11 1 ; -I
., I ",, .. ~............. . I
z~
¦l F. Tricyclopent;yltin Benzoate j The benzoate was prepared using the procedure , described for the 2-ethylhexanoate using 17.1 g. tricyclo- ¦
,' pentyltin hydroxide and 6.1 g. benzoic acid. The product, ~ recrystallized once from n-hexane at -70C., weighed 19.6 g.
and melted from 37 to 38.5C.
Analysis: Found: Tin, 26.42%; Acid No. 131.
,~ Calculated: Tin, 26.54%, Acid No. 125.
G. Bis[tricyclopentyltin] Oxide i, ¦¦ By heating a sample of the hydroxide for 6 hours at ~ 100C. under a pressure o O.5 to 1.0 mm. Hg., a sample of '~ the bls-oxide was prepared which showed a strong absorption in the infra-red spectrum at 785 cm. , attributable to the ~ Sn-O-Sn linkage. No absorption character stic of the Sn-OH
linkage was evident, indicating that the com~ound had been entirely dehydrated to the bis-oxide.
~5 H- Tricyclopentyltin Phenoxide i The phenoxide was prepared by heating to the boiling point a solution containing '7.15 g. t~~cyolopentyltin ~ hydroxide, 4.71 g. phenol and 200 cc. benzene. The by-product i~ I
water ~10.8 ccO) was removed during the reaction.
Evaporation o~ the solvent yielded 21.05 g. of a yellow oil, 1, 25 '' n D = 1.~627.
` Analysis: Found: Sn, 28.04; -OC6H~ residue, 2400%.
Calculated: Sn9 28.32; -OC6H5 residue, 22.2%.
~l -18-3Z~LZ7 I Tricyclope--nt~lt-l-n--c-hloride (from the h~droxlde) I
To a suspension of 17.15 g. tricyclopentyltin hydroxide in 100 cc. of pentane was added 6cc. of ¦¦ a 36% aqueous hydrochloric acid solution with stirring. The organic phase was separated and dried over magneslum sulfate after adding 3 g. sodium sulfate and 100 cc.
ether to break up the emulsion. After filterlng, the pentane ,' phase was stripped of solvent to yield 17.05 g. of white ~- crystals, melting from 39.5 to 42.5C.
1, Analysis: Found: Sn, 32.60; Cl, 9.82%.
Zli Calculated: Sn, 32083; Cl, 9.81%.
' Analysis by vapor phase chromatography indicated that ,~ the product was over 95% pure.
!;
Z,l J. Tricyclopentyltin Dimethy'l'dithioc'arb'ama'te . ,1 - 1, ~ To a solution containing sodium dimethyldithiocar-'' bamate dihydrate t5.38 g.) and 50 cc. water was added a ' solution containing 10.84 g. tricyclopentyltin chloride and ~! 50 cc. acetone. The mixture was stirred ~or 1 hour., then , .
~ poured into a separatory funnel. The lower phase was added to Z, - lG0 cc. of acetone. The aqueous phase was extracted once ~ with 50 cc. hexane, the hexane added to the acetone solution and the mixture dried using anhydrous magnesium sulfate for l l/2 hours. After filtering, the solvent was removed under reduced pressure to yield 13.15 g. of a beige solid, that Z
j melted from 55 to 57C.
Analysis: Found: Sn, 26.67; S total 14.48%.
il Calculated: Sn, 26.60; S total 14.30%. 3 - I, 109Z~ 7 , K. Tricyclopentyltin 4-Acetylaminobenzoate Il .
A mixture containing 17.15 g. tricyclopentyltln ' hydroxide, 9.0 g. 4-acetylaminobenzoic acid and 250 cc. benzene ,I were heated to the boiling point using a Dean-Stark trap to ,t isolate the water formed. A o.8 cc. portion of water was 5 I' collected over a 1.5 hour period. The hot solution was filtered and allowed to cool to room temperature as crystals were deposited. The crystals were filtered and dried under vacuum.
Yield=21.49 g. of white crystals melting from 169 to 174C.
j Analysis: Found: Sn, 23.87%; Acid No. 113.
' Calculated: Sn, 23.54%; Acid No. lll.
L. Tricyclopentyltin 2-Aminonicotinate ~) A mix~ure containing 17.2 g. tricyclopentYltin - hydroxide, 5.90 g. 2-aminonicotinic acid and 250 cc. benzene ``
was heated to the boiling point using a Dean-Stark trap to collect the water (0.9 cc.) ~ormed as a by-product~ The hot ' solution was filtered and allowed to cool to room temperature, during which time it deposited 22.26 g. of yellow solids melting from 92 to 98C. The crude product was recrystallized ~rom 250 cc. heptane to yield 11.48 g. of ~hite crystals melting t.i from lOl to 103C. When evaporated to 1/2 o~ the original volume under reduced pressure a~d cooled to 0C. the heptane ' solution deposited another 7.5 g. of white crystals melting from 99 to 101C. Both crops were combined and analyzed.
Analysis: Found: Sn, 26.29%; Acid No. 123.
~ Calculated: Sn, 25.63%; Acid No. 121.
1~ -i ~l 20- l ~', 11 .
: , 11 . I
I! l i! . - !
1~)92 1 Z~
I
: I! M. Bis~tric,yclopent~ltin] Su~lr~de To an aqueous solution contalning 12.1 g. o~ disodium I ¦ ethylenebis(dithiocarbamate) in 150 cc. water was added dropwise over 1/4 hour a solution containing 25 g. tricyclo-1; pentyltin chloride and 150 cc. acetone. Sollds initially formed, however during l hour of stirring the solid changed to Il a yellow oil suspended in a viscous liquid. The mixture was poured lnto a separatory funnel and 75 cc. of ether were added.
~ The aqueous phase was removed and the organic phase added to lO0 cc. acetone. The organic phase was dried over anhydrous magnesium sulfate. Evaporation of the solvent yielded 31.19 g.
i of a mixture of yellow viscous liquid and solids. A 200 cc.
;
portion of benzene was added and the mixtur-e heated. The .
crude product was then cooled to 25C. and filtered. The - 15 filtrate was stripped of solvent to give 24.25 g. of a yellow liquid plus solids. This mixture was filtered and over a period of four days the filtrate partially solidified. The resultant mixture was recrystallized from 100 cc. isopropanol to yield ` 6.6 g. of yellow crystals melting from 70 to 72C.
Analysis: ~ound: -Sn, 34.87; S total3 4.39%~
Calculated for [~C,Hg)gSn]2 S
Sn, 34.70, S total, 4.69%.
j.
I~ N. Tricyclo~entyltin 2-ThioE~ e Carboxylate A 18.8 g. portion of tricyclopentyltin hydroxide and 6.4 g. 2-thiophene carboxylic acid were heated to the boiling ; , point for 2 hours in 200 cc. benzene, during which time 0.6 cc.
~ water collected in the Dean Stark trap. The hot reaction mixturè
.~ ij . I
,~ I
109ZlZ7 i I, ~
was filtered9 then freed of solvent under reduced pressure to ¦ yield 24.54 g. of a whlte solid meltlng ~rom 58 to 62C.
'~! Analysis: Found: Sn, 26.43%, Acld No. 118.
~i Calculated: Sng 26.20%; Acid No. 124.
I 0. Bis[tricyclopentyltln] Adi~ate The adlpic acid derivative was prepared ln a manner similar to the foregoing procedure N using 18.8 g. tricyclopentyl-tin hydroxide and 3.65 g. adiplc acid. A o.85 cc. portion ~ of water was collected during the reaction. On removing the benzene, 20.63 g. of a white solld were isolated and melted from 61 to 65C. Recrystallization from 100 cc. methanol ; ~ yielded 18.55 g. of white crystalæ that melted from 66 to 69C.
-~ Analysis: Found: Sn, 29.46%; Acid No. 142.
~; Calculated: Sn, 29.81%; Acid No. 141.
i, ..
~ P. Tricyclopentyltin Thiophenoxide ~t .
` A mixture containing 18.8 g. tricyclopentyltin hydroxide, 5.5 g. thiophenol and 200 cc. benzene was heated to the boiling point. A total of o.84 cc. of water was collected }
' over a 1.5 bour period. The resultant solution was flltered and solvQnt evaporated to yield 22.9 g. of yellow liquid ;: 2 ~
product~ ~ D = 1.5885.
Analysis: Found: Sn, 29.25; S~ 6.68%.
` Calculated: Sn, 25.29; S, 6.82%.
`ti~ !
,~ 1i il -22-,.~
;I t 1()~21~7 Q. Trlcyclopentyltin ]~2,4-Triazole A mixture containing 18.8 g. tricyclopentyltin hydroxide, 3.45 g. 1,2,4-triazole and 200 cc. toluene was ~I heated to the boiling point for 1 hour during which time 0.82 cc. of water was collected using a Dean-Stark trap.
A 100 cc~ of toluene was then distilled off and the hot solution filtered. On cooling, crystals were deposited which when isolated and dried, weighed 19.1 g. One recrystallization ij from boiling toluene yielded 17.9 g. of product melting from I, 204.5 to 210C.
¦¦ Analysis: Found: Sn, 30.16, N, 11.37%.
Calculated: Sn, 30.12; N, 10.66%.
EXAMPLE 2 - Preparation of Tri(2-cyclopentylethyl)tin Bromide l and Derivatives Thereof l A. Tetra(2-cyclopentylethyl)tin ¦¦ To a solution containing 0.5 mole of cyclopentylethyl magnesium bromide prepared in the conventional manner from 0.5 mole 2-cyclopentyl-1-bromoethanel 0.5 g.-atom magnesium chips and 250 cc. tetrahydrofuran was added a solution containing 26.0 g. (0.1 mole) stannic chloride and 100 cc.
benzene. The addition was gradual and required 0.5 hour to complete, at which time the reaction mixture was heated to the ¦
boiling point for 2 hours then allowed to cool to ambient Il temperature. The product was then hydrolyzed using a solution 1i containing 15 g. of citric acid and ?50 cc. of water. The organic portion of the resultant two-phase liquid was isolated ~ and the water therein removed usin~ anhydrous magnesium sulfate ¦I The solvent was evaporated under reduced pressure to yield ¦ 59.3 g. of a semi-solid material which was comblned with 100 cc~
of isopropanol and stirred for one hour. The resultant slurry ¦
li ~
~.~9z~z7 was flltered, washed wlth cold (0C.) methanol and dried 'co ! yield 49.15 g. of a whlte solld that melted from 74 to 77C.
I Analysis: Found: Sn, 22.41%; Cl, 0.13%.
!I Calculated: Sn, 23.40%; Cl, 0.0%.
i1 l, B. Cleavage of Tetra(?-cvclopentyleth~l)tin I
~ o a solution containing 40.6 g. tetra(2-cyclopentyl-j ethyl)tin, 90 cc. chloroform and 35 cc. methanol maintained at 0C. was added dropwise over 5 hours a solution containing "
I, 12.8 g. br~mine in a mixture of 50 cc. methanol and 50 cc.
chloroform. When the addition was complete, the mixture was !~ I
allowed to warm to 25C. then the solvents were evaporated under reduced pressure to yield 41.7 g. of white solids. These were ,'' t recrystalllzed from 150 cc. methanol by cooling to -20 C.
The crystals were filtered, washed wikh methanol at a temperature f -600C and dried under reduced pressure. The first crop i of crystals weighed 24.4 g. and melted from 55 to 58OC. The mother liquor solution was evaporated to 1/3 of the original volume then cooled to 0 C. whereupon it deposited a second crop of cr~stals which were filtered and dried. This crop ~0 weighed 7 9 g. and melted from 58 to 60. The two crops when combined weighed 32.3 g.
Analysis: Found: Sn, 23.90%; Br, 15.22%.
Calculated for tri(cyclopentylethyl)tin bromlde:
i Sn, 24.22%; Br, 16.31%.
`~ _z4_ %~
l C. BisCtri(cycloventylethyl)tin; Oxlde ll I To a solution contalning 1.6 g. (0.04 mole) of sodium ,i hydroxide, 50 cc. methanol and 50 cc. water was added a I~ solution containing 9.8 g. trl(cyclopentylethyl)tin bromide, 1 5 !. loo cc . methanol and 40 cc.~acetone. The additlon was gradual and required 10 minutes. Following completlon of the addition the reaction mixture was heated to the boiling point (670C.) for two hours, then cooled to ambient temperature, at whlch ,~ time 150 cc. of water and 100 cc. of diethyl ether were added and the resultant mixture stirred vigorously for five minutes. The organic phase of the resultant two-phase liquid was isolated and freed of water using anhydrous ; magnesium sulfate. The drying agent was removed after two hours and the solvent evaporated under reduced pressure to yield 8.2 g. of a yellow oil which was found to contain 27.33%
ii tin. The tin content of pure bis[tri(cyclopentylethyl)tin]
oxide is 28.38. Analysis by vapor phase chromatography demonstrated that the compound was 91.4% pure.
.. i;
EXAMPLE 3 - Preparation of tri(2-cyclopentylmethyl)tin Bromide lZ Tetra(cyclopentylmethyl)tin was prepared using the procedure described in Example 2 from cyclopentylmethyl- ¦
magnesium bromide and stannic chloride. The product was a ! ~
solid melting from 63 to 66~C. and contained 27.86% tin.
The calculated tin content Of tetra(cyclopentylmethyl)tin ' is 26.30%.
'I
i~1, , .
il -25-, .
lO~ .Z~
I
Tetra(cyclopentylmethyl)tin was cleaved by reactlng the compound with bromine uslng the procedure described in li the preceding example. Following one recrystallization ~rom ~ methanol the product melted from 32 to 340C. and was found !~ to contain 26.34% tin and 17.84% bromine. The calculated values for tritcyclopentylmethyl)tin bromide are 26.49% for tin and 17.84% ~or bromine.
EXAMPLE 4 - Preparation of Tri(cyclopentylmethyl)tin Chloride and the Corresponding Oxide i( I
l,~ Methyltri(cyclopentylmethyl)tin was prepared by reacting 0.425 mole of cyclopentylmethylmagnesium bromide with i 30.5 g. methyltin trichloride in 150 cc. of benzene. The , crude product was isolated from the reaction mixture as a ~`
yellow~oil (48.3 g.) of refractive index 1.5192 at 24 and in 85% purity. After washing twice with methanol (75 cc. and 25 cc ) and distillation under reduced pressure 33.8 g. of product boiling at 140QC. under 0.3 mm. Hg were obtained~ i j. 24 n D = 1.5230. Vapor phas~ chrom~tography showe~ ~he material to be 95.6% pure.
1l To a solution o~ methyltri(cyclopentylmethyl)tin (26.8 g.) in 100 cc. of pentane, was added dropwise a solution !, . ' - _. I
of stannic chloride (18.2 g.) in 100 cc. pentane over 20 minutes. The resultant yellow solution was heated to the ` boiling point for 0.5 hour then cooled to room temperature.
~ The mixture was combine_ with a solution containing 2 cc. 12N
hydrochloric acid and 98 cc. water, following which the organic phase was separated and washed with another portion of ,j 11 ~
1109ZlZ7 1~ ~
2 cc 12N hydrochloric acid and 98 cc water. The organic phase was again separated and the water therein removed using anhydrous magnesium sulfate. After filtration, the ,~ solvent was removed under reduced pressure to yield 28.20 g.
5 Il, of a white solid that melted from 88 to 90C-Analysis: Found: Sn, 29.21; Cl, 8.87%.
~t Calculated for tri(cyclopentylmethyl)tin chloride:
Sn, 29.41; Cl, 8.80%.
~j Vapor phase chromatography indicated the compound to be i 98.3% pure.
., ~
is[tri(cyclopentylmethyl)tin] Oxide To a solution containing 1.8 g. sodium hydroxide,10 cc. water and 10 cc. methanol was added dropwise a solution containine 12.11 g. tris(cyclopentylmethyl)tin chloride and , ' , 25 cc tetr2hydrofuran over 15 minutes. An oil formed initiall~
and dissol~ed as the addition proceeded. When the addition was complete, the solution was stirred at 25C. ~or 0.5 hour. ¦
A 300 cc. portion of cold (10C.) water was added followed by 200 cc. of diethyl ether with vigorous stirring. The organic ~ phase was isolated and the water therein removed using anhydrous ~agnesium sulfate. After filtratlon the solvent was removed under reduced pressure to yield 11.28 g. of a waxy solid melting from 59 to 630. The crude product was purified b~ adding 60 cc. methanol and cooling to 0~C.
whereupon a small amount of solid material precipitated. The '~ solid was removed and the ~iltrate evaporated under reduced pressure to yield 11.35 g. of yellow liquid, n D = 1.5296.
Analysis: Found: Sn, 30.16.
Caleulated for bis[tri(cyclopentylmethyl)tin] oxide:
ji Sn, 31.56. `
Assay by potentiornetric titration = 92.6% purity.
lO~Zl'~q I ~' EXAMPLE 5 - Preparation of Tr1(2-methylcyclopenkyl)tin Chlorlde and the Corresponding Oxide.
A. Methyltri(2-methylcyclopent~l)tin To a solution contalning 0.31 mole of 2-methyl-cyclopentylmagnesium bromide in 15C cc. of tetrahydrofuran was , added a solution containing 21.6 g. methyltin trichloride in 150 cc. dry toluene over a period of l hour. When the ~! addition was complete, the mixture was heated to the boiling l~ point ~or 2 hours and then stirred at 25C. for 16 hours. The I
reaction mixture was then hydrolyzed uslng a solution containing 25 g. cltric acid and 250 cc. water. The organic phase was `` separated and the water therein removed using anhydrous i/
' magnesium sulfate. The liquid phase was then evaporated under I
, .
reduced pressure to yield 25.45 g. of crude product. Low i boiling impurities were distilled off at from 25 to 75C. under¦
1~
IJ a pressure of 0.1 mm. Hg. The residue, which contained the i desired product, weighed 33.85 g. and exhibited a refractive index of 1.5192 at 24C.
Analysis: Found: Sn, 30.11.
,~ Calculated for methyl tri(2-methylcyclopentyl)tin: ,3 Sn9 30.98.
9. T~i(2-methylcyclcpentjl)tin Chloride To a solutlon containing 13.4 g. of methyl tri(2-methylcyclopentyl)tin and 50 cc. of hexane was added over a 0.5 hour period a solution containing 9.1 g. of stannic , chloride and 50 cc. of hexane. Following completion of the ;, addition the resultant mixture was heated to the boiling point ¦¦ for 15 minutes then cooled to 25C. The reaction mixture was 5,~' then hydrolyzed by addition of a solution containing 2 cc.
, il ~ 28-3' ~ I
., . I
i 1~3Z~Z7 1' concentrated (12N) hydrochlorlc acid and 100 cc. of water The organic phase of the resultant two-phase liquld was ''I isolated and combined wlth a second portion of the afore-ll mentioned hydrochloric acid solution. The organic phase was ', again isolated and the water therein removed using a portion of anhydrous magnesium sulfate. The liquid phase was then evaporated under reduced pressure to yield 14 g. of a yellow oil that exhibited a refractive index (~ D) of 1.5333 and was found to contain 28.48% tin and 8.61% chlorine. The calculated values for the desired chloride are 29.4% tin and 8.78% chlorine.
! I
C. Bis~trit2-methylcyclopentyl)tin] Oxide ' Bis[tri(2-methylcyclopentyl)tin~ oxide was prepared by gradually adding a solution containing ~.l g. of the !~ corresponding chloride (prepared as described in the foregoing ., , ; paragraph) 25 cc. methanol and 15 cc. acetone to a solution containing l.2 g. of sodium hydroxide, 20 cc. water and 50 cc. I
methanol. The addition required 0.5 hourg following which the ¦
'I
~ 'I resultant solution was heated to the boiling point for 10 .. !
~ 20 ; minutes, then cooled to 15C., during which time 300 cc. of .. , ~
water were gradually added. The resultant mixture was stirred for l hour while the temperature was maintained at 15C. A
~I 50 cc. portion of diethyl ether was then added while the mixturè
; ~ was stirred at high speed. The organic phase of the resultant !
25 ~ `' two-phase liquid was isolated and the water therein removed using anhydrous magnesium sulfate. The liquid was then evaporated under reduced pressure to yield 7.6 g. of a pale j~ -29-i i i~ 1.
g~Q9~LZ7 yellow oil which was found to contain 30.54% tin. The calculated tln content of bis~tri(2-methylcyclopentyl)tin~
oxide is 31.56%. A potentiometric titration of the product indicated that it was 98% pure.
Biological Activity o~ Trlcyclopentyltin and Tri(cyclopentylalkyl)tin Compounds ; The following procedures were employed to evaluate the efficacy of the present triorganotin compounds in I controlling a number of representative fungi and insects.
~ Procedure 1 - Employed Using Two-spotted Spider Mite (Tetranychus urticae), Beet Army Worm (Spodoptera exigua) and Cabbage Looper (Trichoplusia ni).
A cotton plant with two fully expanded leaves is ¦l dipped into an aqueous dispersion of the tesk compound. An ¦~ additional portion is in~ected into the soil at the root zone.
Lepidopterous insect larvae are dipped into the water dispersion and placed in petri dish cages clamped around the ~treated foliage. When using the two-spot~ed spider mite as the test insect the dipping step is not performed since the ,~ mites are on the leaf before the plant is treated. A mortality count is taken six days after treatment.
Procedure 2 - Employed Using Tobacco Black Shank Fungus (phytophthora parasitica var.- nicotiane)O
¦I Tobacco plants are transplanted into soil infested ll wlth the test organism. Immediately after transplanting the soil is drenched with a solution o~ test chemical. The test ¦1 is graded on the basis of plant survival.
. I
lO~)Z1~7 Procedure 3 - Ernployed Using Bean Mildew (Erysiphe polygoni).
Bean seeds are planted in fumigated soil which is then drenched with a solution of the test compound. When the plants reach a suitable size they are inoculated with the fungus. After 7 days the relative number of healthy plants is noted.
Procedure 4 - Employed Using Grape Downy Mildew (Plasmopara viticola) Rice Blast (Pericularia oryzae) and ! Apple Powdery Mildew (Podosphaera leucotricha).
~ost plants, (grape, rice or apple, depending upon the fungus) are sprayed with a water suspension of the test compound and then inoculated with the pathogen. After disease ¦
symptoms are well developed on untreated control plants the 1i test plants are graded for disease control.
Procedure 5 - Secondary Evaluation of Activity In Combatting Two-spotted Spider Mite (Tetranychus bimaculatis) I l¦ and Aphid.
¦I Bean plants infested with the organism are sprayed ll with a water disperslon containing the test compound. The , percent mortality is observed three days after spraying ~¦ Procedure 6 - Employed Using Codling Moth ~arvae (Carpocapra pomonella).
I Codling moth eggs are placed on a paraffin surface ¦I that has previously been treated with a water dispersion of ~ the test compound. The paraffin is perforated, allowing the li newly hatched larva ~o feed on an underlay of food. After ¦~ six days a mortality count is made.
109Zl'7 Procedure 7 - Employed Using bollworm Larvae Five third instar bollworm larvae are placed in petri plates containing a layer of semi-synthetic diet. These ~ larvae are sprayed with 3 cc. of a 400 ppm solution or I suspension of the chemlcal from a distance Or 15 inches using a Spraying Systems Company nozzle 40100-120. After spraying, ~I the petri dish cover is replaced with a fiber brewer lid to il permit limited air exchange. Following a holding period of ll up to 3 days, mortality counts are made.
Ij Procedure 8 - Employed Using Apple Scab (Venturia inaequalis).
Apple seedlings are infected with the fungus. The seedlings are then sprayed with an aqueous solution or sus-pension of the test chemical. After a period of incubation ~, the plants are rated for disease control.
¦I Procedure 9 - Employed Using Hornfly Larvae The test compound is mixed with caIf feces and horn~ly eggs are introduced. After 2 days observation is made to determine the presence of fly larvae.
¦, Procedure 10 - Employed Using Cabbage Looper ,ll (Trichoplusia ni) To Determine Sllstems Activity.
A water dispersion of the test compound is injected into the root zone of a bean plant that is infested with the ~ cabbage looper. Mortality counts are made 3 to 6 days after I treatment.
ll -32-109Z~ 7 Procedure 11 - Employed Using Cabbage Looper (Trichoplusia ni).
A bean plant is sprayed with a water dispersion of ~est compound and a number of cabbage loopers are placed on the treated foliage. A check for mortality is made after 3 days.
Procedure 12 - Employed Using Cabbage Looper To ¦ Determine Ovicical Activity.
The test chemlcal is dissolved in a suitable water-ll miscible solvent and diluted with water to the desired concentration. Eggs of the cabbage looper, having been deposited by the adult insects on paper toweling or other 3 ~ ~ substrate~ are fastened to the underside of a test plant leaf ; I~ with methocel or other appropriate adhesive. Egg sheets are 1 selected having 25-50 eggs per plant. Cotton or other 3 ¦l appropriate host plants are used. The leaf of the plant to I~ which eggs are attached is dipped in the solution containing 5 ~¦ the test chemical. Ovicidal observations are recorded 3-5 Il days after treatment. Inactive materials show large areas of l foliage consumed by freshly emerged larvae.
[J9Z~
Procedure 13 - Employed Using Western Spotted j Cucumber Beetle Larvae.
¦ Seventy-five grams o~ air-dried soil are placed in 1 236 cc. capaciky round bottle and treated with sufficient ,' volume of a solution containing 400 ppm of the chemical to give 25 ppm of toxicant on an air-dried soil basis. The ~ treated soil after being allowed to air dry is mixed by j! shaking and rolllng.
1~ Eggs of the western spotted cucumber beetle (laid over a period Or 3 or 4 days) are collected and a measured , quantity of eggs are suspended in water. The egg concentration i is 70-80 eggs/0.5 cc. of solution. A portion of the suspension ' conkaining about 50 eggs is pipetted into the bottom of a clear ii , plastic medicinal vial. An amount of treated soil sufficient - 15 ` to cover the eggs is added, a corn seed is placed on the soil and covered with additional treated soil.
i' The soil3 eggs and seed mix is watered and additional water is added as necessary to maintain growth of the seedling I ~ corn plant. Care must be ~aken not to add too much water or ~ the larvae will drown. After a period of from 6-9 days an observation ls made to determine the presence of larvae both on top of the soil and at the roots of the seedling.
1, _34 !i ~
~11 ' ",, Il . .' ., . , . ~, lO~Z1~7 Procedure 14 - Employed Using Codling Moth Larvae To Determine Ovlcidal Activity And Control Of Newly Hatched Larvae The test chemical is dissolved in a small amount of a suitable water-miscible solvent and diluted with water to achieve the desired concentration. The chemical solution is I applied to apples or pears which are then covered with eggs ¦ of the codling moth. The fruit is then incubated for from ii eight to ten days ln a greenhouse. The number of living and ~i dead larvae are then counted and compared with a sample of untreated ~ru1t used as a control.
¦ Procedure 15 - Employed Using Mosquito Larvae ¦ Third or early fourth instar larvae of Aedes aegypti are used for the test organiem. Twenty to twenty-five larvae ~/ are placed in distilled water containing the candidate chemical.
Activity I8 recorded as the concentration (p.p.m.) constituting ¦ a lethal dose ~or 95 percent o~ the population (LDg~).
¦ Procedure 16 - Employed Using Apple Powdery Mildew I ~ ¦! Aqueous solutions or suspensions of the experimental 20~ chemical are poured into cups of vermiculite in which plants are gro~7ing.~ The aqueous system usua'ly contains acetone and a wettlng agent, both in non~toxic amounts. Two to four days after the compound is appl~ed the leaves are wet with a 1l spore suspension of apple powdery mildew. The plants are ' then put in a greenhouse. When disease symptoms are clear, ~I the plan~s are graded. Untreated plants are rated as "0%
!~ control" and the disease ~ree plants are rated as 100% control.
I . .. ..
Il .. , ..,':"' ', :' " ,,,' I
~19~ 7 The accompanying ~ables summarize the data obtalned uslng the aforementioned procedures with representative compounds encompassed by the accompanying claims.
I TABLE I
Biologlcal Activity of Tricyclopentyltin Hydroxide Again~t - Fungi Organism Proc.No. Concentration Control Rating : (p.p.m.) (%) - Tobacco Black Shank 2 25 100 l 2 6.3 100 j Bean Mildew 3 25 100 Grape Downy Milaew 4 100 100 4 6.2 95 Rice Blast 4 100 93 ~l ~ 4 25 67 , .l Apple Powdery Mildew 4 loo loo TABLE II
Biological Activity of Tricyclopentyltin Hydroxide Against Insects Organism Proc. No. Concentration Control Rating Spider Mite 5 400 100 i 5 100 100 :: ~25 1 5 25 86 ~ li Beet Army Worm 1 400 100 ;1 ~ Cabbage Looper 1 100 100 Codling Moth Larvae 6 400 loo Bollworm Larvae 7 4bo loo I Aphid 5 400 100 ! -11 ' lO~Z:1.27 TABLE III
Blological Activity Or Trlcyclopentyltin Chloride A~ A
Fungicide Or~anism Proc. No. Concentration Control Rating Apple Scab 8 100 90 I Rice Blast 4 400 95 I Apple Powdery Mildew 16 - 100 70 ¦ TABLE IV
¦ Biological Activity of Tricyclopentyltin Chloride As An Insectic~de Or~anismProc. No. Concentration Control Ratin~ ¦
! (p,p.m.) ¦I Cabbage Looper1 400 100 Codling Moth Larvae 14 400 100 TABLE V
,I Biological Activity of Tricyclopentyltin Acetate As A
Il Fungicide ', Or~ ismProc. No. Concentration Control Rating i (p.P.m.) Grape Downy Mildew 4 400 100 ~1 100 90 ¦, Apple Powdery Mildew 4 100 90 li , 1~ Biological Activity of Tricyclopentyltin Acetate As An jj Insecticide ; Organism Pro~ No. Con(centration Control Ratin~
ll Cabbage Looper 12 400 90 Cucumùer Beetle Larvae 13 25 100 11 .
lO~lZl'~7 iTABLE VII
. .. .
; Biological Activity of Tricyclopentyltin Fluoride As An Insecticide And Fungicide Organism Proc. No. Concentration Control Ratln (P~P.-m.-) Spider Mite 1 400 99 li Cabbage Looper 1 400 100 - !I Codling Moth Larvae 14 400 100 j, Grape Downy Mildew4 400 100 I , 100 94 ~ 50 80 Rice Blast 4 400 96 ' Apple Powdery Mildew 4 100 90 TABLE ~III !
Biological Activity of Tricyclopentyltin Bromide iI Pr~ No. Conc~ntration Controlr~R)ating l Spider Mite 1 400 100 Cabbage Looper 1 400 1803 Mosquito Larvae 15 1 100 , Tobacco Black Shank 2 25 100 25.... ', ~rape nowny~.r~ildew4 400 97 : !l loo loo '' Apple Powdery Mildew 4 400 90 i' 100 97 1 6.3 75 ; -38-I
l . l lZiZ'7 TABLE IX
Biological Activity of Tri(cYCloPentYlethYl)tin Hydroxide . Organism Proc. No. Concentration Control Ratin~
Spider Mite 5 400 95 . 100 98 Grape Downy Mildew 4 400 1~0 ~ . 100 55 Apple Scab 8 400 100 TABLE X
Biological Activity of Tri(cyclopentylethyl)tin Bromide 'I Or~anism Proc. No. Concentration Control Rating Cabbage Looper 1 400 83 Horn~ly Larva 9 100 100 : I Tobacco Black Shank 2 25 100 ~ Apple Powdery Mildew 4 400 75 Il , I
¦¦ TABLE XI
,j Biological Activity of Tri(2-methylcyclopentyl~tin Chloride Organism Proc~ No. Concentration ControL Ratin~ ¦
il Cabbage Looper 1 400 100 ¦i Grape Downy Mildew 4 400 100 !j Apple Scab 8 400 100 loo 60
Il 1' ` . I
~V~Z~
I!
~l ~
, 12 cc. of water were added. The resultant slurry was stirred i:
for 0.5 hour, at which time 150 cc. of water were added to I completely precipitate the product. The solid was isolated I and washed with deionized water until no detectible amount 1, of chloride ion was present in the water. The solid was then 'l dried in a circulating air oven maintained at a temperature , i I
of 40 C. Analysis by potentiometric titration indicated that the hydroxide was between 98.6 and 99.1% pure.
¦, C. TricycloPentyltin Fluoride 10r~ Tricyclopentyltin fluoride was prepared from the corresponding hydroxide. A solution containing 300 g. of i - ~` tricyclopentyltin hydroxide and 3600 cc. of tetrahydrofuran wasi ; clarified by filtration. To this solution was gradually I added a solution obtained by combining 50 g. of a 48~ aqueous " hydrofluoric acid solution with 150 cc. of water. The resultant mixture, which contained a white precipitate, was heated to the boiling point (64C.) for 0.25 hour, then cooled to ambient temperature filtered, and washed sequentially with 1 liter of a 0.1% aqueous hydrofluoric acid solution, 2Q ~ lter deionized water and 500 cc. methanol. After being dried under reduced pressure at a temperature of 50~C. the white solid (280 g.) melted from 275 to 280C. with evidence of decom~osition. The solid was found to contain ~, 34.05% tin and 5.32% fluorine. The calculated values for ' tri(cyclopentyl)tin fluoride are 34.40% tin and 5.51% fluorine.
~i i , ll i !l - ,¦ D. Tricyclopentyltin Acetate To a suspension of 17.15 g. tricyclopentyltin hydroxide in 100 cc. o~ dlethyl ether was added dropwise over 0.25 hour, a solution of 3.15 g. acekic acid (glacial) in 'l 100 cc. diethyl ether. The solids dissolved and the solution was stirred for 0.25 hour at 25C. About 15 g. of anhydrous magnesium sulfate were added to the solution and the mixture stirred for 1 hour to remove water formed during reaction.
~ The mixture was then filtered and solvent removed on a rotary .~ 10 i! evaporator to yield 20 g. of a white solid. The solid was placed in a desiccator over sodium hydroxide pellets and held ~ under reduced pressure for 48 hours to remove excess unreacted ; ,; acetic acid. The product, a white solid, weighed 18.7 g~ and il melted from 52 to 54C.
l~ Analysis: Found: Tin, 30.65%; Acid No. 160 , Calculated: Tln, 30.82%; Acid No. 146 li ¦I E. Tricyclo~entyltin ?-Ethylhexanoate A 17.1 g. portion of tricyclopentyltin hydroxide !~ and 7.2 g. of 2-ethylhexanoic acid in 200 cc. benzene were heated to the boiling point and the ~y-product water (o.84 cc.) removed using a Dean-Stark trap. The benzene was evaporated ~i under reduced pressure to yield 23.5 g. of a yellow liquid, n D = 1.5068.
~Analysis: Found: Sn, 25.14%; Acid No. 123.6.
,iCalculated: Sn, 25.29%; Acid No. 119.5. ~
; 1! 17- !
'11 1 ; -I
., I ",, .. ~............. . I
z~
¦l F. Tricyclopent;yltin Benzoate j The benzoate was prepared using the procedure , described for the 2-ethylhexanoate using 17.1 g. tricyclo- ¦
,' pentyltin hydroxide and 6.1 g. benzoic acid. The product, ~ recrystallized once from n-hexane at -70C., weighed 19.6 g.
and melted from 37 to 38.5C.
Analysis: Found: Tin, 26.42%; Acid No. 131.
,~ Calculated: Tin, 26.54%, Acid No. 125.
G. Bis[tricyclopentyltin] Oxide i, ¦¦ By heating a sample of the hydroxide for 6 hours at ~ 100C. under a pressure o O.5 to 1.0 mm. Hg., a sample of '~ the bls-oxide was prepared which showed a strong absorption in the infra-red spectrum at 785 cm. , attributable to the ~ Sn-O-Sn linkage. No absorption character stic of the Sn-OH
linkage was evident, indicating that the com~ound had been entirely dehydrated to the bis-oxide.
~5 H- Tricyclopentyltin Phenoxide i The phenoxide was prepared by heating to the boiling point a solution containing '7.15 g. t~~cyolopentyltin ~ hydroxide, 4.71 g. phenol and 200 cc. benzene. The by-product i~ I
water ~10.8 ccO) was removed during the reaction.
Evaporation o~ the solvent yielded 21.05 g. of a yellow oil, 1, 25 '' n D = 1.~627.
` Analysis: Found: Sn, 28.04; -OC6H~ residue, 2400%.
Calculated: Sn9 28.32; -OC6H5 residue, 22.2%.
~l -18-3Z~LZ7 I Tricyclope--nt~lt-l-n--c-hloride (from the h~droxlde) I
To a suspension of 17.15 g. tricyclopentyltin hydroxide in 100 cc. of pentane was added 6cc. of ¦¦ a 36% aqueous hydrochloric acid solution with stirring. The organic phase was separated and dried over magneslum sulfate after adding 3 g. sodium sulfate and 100 cc.
ether to break up the emulsion. After filterlng, the pentane ,' phase was stripped of solvent to yield 17.05 g. of white ~- crystals, melting from 39.5 to 42.5C.
1, Analysis: Found: Sn, 32.60; Cl, 9.82%.
Zli Calculated: Sn, 32083; Cl, 9.81%.
' Analysis by vapor phase chromatography indicated that ,~ the product was over 95% pure.
!;
Z,l J. Tricyclopentyltin Dimethy'l'dithioc'arb'ama'te . ,1 - 1, ~ To a solution containing sodium dimethyldithiocar-'' bamate dihydrate t5.38 g.) and 50 cc. water was added a ' solution containing 10.84 g. tricyclopentyltin chloride and ~! 50 cc. acetone. The mixture was stirred ~or 1 hour., then , .
~ poured into a separatory funnel. The lower phase was added to Z, - lG0 cc. of acetone. The aqueous phase was extracted once ~ with 50 cc. hexane, the hexane added to the acetone solution and the mixture dried using anhydrous magnesium sulfate for l l/2 hours. After filtering, the solvent was removed under reduced pressure to yield 13.15 g. of a beige solid, that Z
j melted from 55 to 57C.
Analysis: Found: Sn, 26.67; S total 14.48%.
il Calculated: Sn, 26.60; S total 14.30%. 3 - I, 109Z~ 7 , K. Tricyclopentyltin 4-Acetylaminobenzoate Il .
A mixture containing 17.15 g. tricyclopentyltln ' hydroxide, 9.0 g. 4-acetylaminobenzoic acid and 250 cc. benzene ,I were heated to the boiling point using a Dean-Stark trap to ,t isolate the water formed. A o.8 cc. portion of water was 5 I' collected over a 1.5 hour period. The hot solution was filtered and allowed to cool to room temperature as crystals were deposited. The crystals were filtered and dried under vacuum.
Yield=21.49 g. of white crystals melting from 169 to 174C.
j Analysis: Found: Sn, 23.87%; Acid No. 113.
' Calculated: Sn, 23.54%; Acid No. lll.
L. Tricyclopentyltin 2-Aminonicotinate ~) A mix~ure containing 17.2 g. tricyclopentYltin - hydroxide, 5.90 g. 2-aminonicotinic acid and 250 cc. benzene ``
was heated to the boiling point using a Dean-Stark trap to collect the water (0.9 cc.) ~ormed as a by-product~ The hot ' solution was filtered and allowed to cool to room temperature, during which time it deposited 22.26 g. of yellow solids melting from 92 to 98C. The crude product was recrystallized ~rom 250 cc. heptane to yield 11.48 g. of ~hite crystals melting t.i from lOl to 103C. When evaporated to 1/2 o~ the original volume under reduced pressure a~d cooled to 0C. the heptane ' solution deposited another 7.5 g. of white crystals melting from 99 to 101C. Both crops were combined and analyzed.
Analysis: Found: Sn, 26.29%; Acid No. 123.
~ Calculated: Sn, 25.63%; Acid No. 121.
1~ -i ~l 20- l ~', 11 .
: , 11 . I
I! l i! . - !
1~)92 1 Z~
I
: I! M. Bis~tric,yclopent~ltin] Su~lr~de To an aqueous solution contalning 12.1 g. o~ disodium I ¦ ethylenebis(dithiocarbamate) in 150 cc. water was added dropwise over 1/4 hour a solution containing 25 g. tricyclo-1; pentyltin chloride and 150 cc. acetone. Sollds initially formed, however during l hour of stirring the solid changed to Il a yellow oil suspended in a viscous liquid. The mixture was poured lnto a separatory funnel and 75 cc. of ether were added.
~ The aqueous phase was removed and the organic phase added to lO0 cc. acetone. The organic phase was dried over anhydrous magnesium sulfate. Evaporation of the solvent yielded 31.19 g.
i of a mixture of yellow viscous liquid and solids. A 200 cc.
;
portion of benzene was added and the mixtur-e heated. The .
crude product was then cooled to 25C. and filtered. The - 15 filtrate was stripped of solvent to give 24.25 g. of a yellow liquid plus solids. This mixture was filtered and over a period of four days the filtrate partially solidified. The resultant mixture was recrystallized from 100 cc. isopropanol to yield ` 6.6 g. of yellow crystals melting from 70 to 72C.
Analysis: ~ound: -Sn, 34.87; S total3 4.39%~
Calculated for [~C,Hg)gSn]2 S
Sn, 34.70, S total, 4.69%.
j.
I~ N. Tricyclo~entyltin 2-ThioE~ e Carboxylate A 18.8 g. portion of tricyclopentyltin hydroxide and 6.4 g. 2-thiophene carboxylic acid were heated to the boiling ; , point for 2 hours in 200 cc. benzene, during which time 0.6 cc.
~ water collected in the Dean Stark trap. The hot reaction mixturè
.~ ij . I
,~ I
109ZlZ7 i I, ~
was filtered9 then freed of solvent under reduced pressure to ¦ yield 24.54 g. of a whlte solid meltlng ~rom 58 to 62C.
'~! Analysis: Found: Sn, 26.43%, Acld No. 118.
~i Calculated: Sng 26.20%; Acid No. 124.
I 0. Bis[tricyclopentyltln] Adi~ate The adlpic acid derivative was prepared ln a manner similar to the foregoing procedure N using 18.8 g. tricyclopentyl-tin hydroxide and 3.65 g. adiplc acid. A o.85 cc. portion ~ of water was collected during the reaction. On removing the benzene, 20.63 g. of a white solld were isolated and melted from 61 to 65C. Recrystallization from 100 cc. methanol ; ~ yielded 18.55 g. of white crystalæ that melted from 66 to 69C.
-~ Analysis: Found: Sn, 29.46%; Acid No. 142.
~; Calculated: Sn, 29.81%; Acid No. 141.
i, ..
~ P. Tricyclopentyltin Thiophenoxide ~t .
` A mixture containing 18.8 g. tricyclopentyltin hydroxide, 5.5 g. thiophenol and 200 cc. benzene was heated to the boiling point. A total of o.84 cc. of water was collected }
' over a 1.5 bour period. The resultant solution was flltered and solvQnt evaporated to yield 22.9 g. of yellow liquid ;: 2 ~
product~ ~ D = 1.5885.
Analysis: Found: Sn, 29.25; S~ 6.68%.
` Calculated: Sn, 25.29; S, 6.82%.
`ti~ !
,~ 1i il -22-,.~
;I t 1()~21~7 Q. Trlcyclopentyltin ]~2,4-Triazole A mixture containing 18.8 g. tricyclopentyltin hydroxide, 3.45 g. 1,2,4-triazole and 200 cc. toluene was ~I heated to the boiling point for 1 hour during which time 0.82 cc. of water was collected using a Dean-Stark trap.
A 100 cc~ of toluene was then distilled off and the hot solution filtered. On cooling, crystals were deposited which when isolated and dried, weighed 19.1 g. One recrystallization ij from boiling toluene yielded 17.9 g. of product melting from I, 204.5 to 210C.
¦¦ Analysis: Found: Sn, 30.16, N, 11.37%.
Calculated: Sn, 30.12; N, 10.66%.
EXAMPLE 2 - Preparation of Tri(2-cyclopentylethyl)tin Bromide l and Derivatives Thereof l A. Tetra(2-cyclopentylethyl)tin ¦¦ To a solution containing 0.5 mole of cyclopentylethyl magnesium bromide prepared in the conventional manner from 0.5 mole 2-cyclopentyl-1-bromoethanel 0.5 g.-atom magnesium chips and 250 cc. tetrahydrofuran was added a solution containing 26.0 g. (0.1 mole) stannic chloride and 100 cc.
benzene. The addition was gradual and required 0.5 hour to complete, at which time the reaction mixture was heated to the ¦
boiling point for 2 hours then allowed to cool to ambient Il temperature. The product was then hydrolyzed using a solution 1i containing 15 g. of citric acid and ?50 cc. of water. The organic portion of the resultant two-phase liquid was isolated ~ and the water therein removed usin~ anhydrous magnesium sulfate ¦I The solvent was evaporated under reduced pressure to yield ¦ 59.3 g. of a semi-solid material which was comblned with 100 cc~
of isopropanol and stirred for one hour. The resultant slurry ¦
li ~
~.~9z~z7 was flltered, washed wlth cold (0C.) methanol and dried 'co ! yield 49.15 g. of a whlte solld that melted from 74 to 77C.
I Analysis: Found: Sn, 22.41%; Cl, 0.13%.
!I Calculated: Sn, 23.40%; Cl, 0.0%.
i1 l, B. Cleavage of Tetra(?-cvclopentyleth~l)tin I
~ o a solution containing 40.6 g. tetra(2-cyclopentyl-j ethyl)tin, 90 cc. chloroform and 35 cc. methanol maintained at 0C. was added dropwise over 5 hours a solution containing "
I, 12.8 g. br~mine in a mixture of 50 cc. methanol and 50 cc.
chloroform. When the addition was complete, the mixture was !~ I
allowed to warm to 25C. then the solvents were evaporated under reduced pressure to yield 41.7 g. of white solids. These were ,'' t recrystalllzed from 150 cc. methanol by cooling to -20 C.
The crystals were filtered, washed wikh methanol at a temperature f -600C and dried under reduced pressure. The first crop i of crystals weighed 24.4 g. and melted from 55 to 58OC. The mother liquor solution was evaporated to 1/3 of the original volume then cooled to 0 C. whereupon it deposited a second crop of cr~stals which were filtered and dried. This crop ~0 weighed 7 9 g. and melted from 58 to 60. The two crops when combined weighed 32.3 g.
Analysis: Found: Sn, 23.90%; Br, 15.22%.
Calculated for tri(cyclopentylethyl)tin bromlde:
i Sn, 24.22%; Br, 16.31%.
`~ _z4_ %~
l C. BisCtri(cycloventylethyl)tin; Oxlde ll I To a solution contalning 1.6 g. (0.04 mole) of sodium ,i hydroxide, 50 cc. methanol and 50 cc. water was added a I~ solution containing 9.8 g. trl(cyclopentylethyl)tin bromide, 1 5 !. loo cc . methanol and 40 cc.~acetone. The additlon was gradual and required 10 minutes. Following completlon of the addition the reaction mixture was heated to the boiling point (670C.) for two hours, then cooled to ambient temperature, at whlch ,~ time 150 cc. of water and 100 cc. of diethyl ether were added and the resultant mixture stirred vigorously for five minutes. The organic phase of the resultant two-phase liquid was isolated and freed of water using anhydrous ; magnesium sulfate. The drying agent was removed after two hours and the solvent evaporated under reduced pressure to yield 8.2 g. of a yellow oil which was found to contain 27.33%
ii tin. The tin content of pure bis[tri(cyclopentylethyl)tin]
oxide is 28.38. Analysis by vapor phase chromatography demonstrated that the compound was 91.4% pure.
.. i;
EXAMPLE 3 - Preparation of tri(2-cyclopentylmethyl)tin Bromide lZ Tetra(cyclopentylmethyl)tin was prepared using the procedure described in Example 2 from cyclopentylmethyl- ¦
magnesium bromide and stannic chloride. The product was a ! ~
solid melting from 63 to 66~C. and contained 27.86% tin.
The calculated tin content Of tetra(cyclopentylmethyl)tin ' is 26.30%.
'I
i~1, , .
il -25-, .
lO~ .Z~
I
Tetra(cyclopentylmethyl)tin was cleaved by reactlng the compound with bromine uslng the procedure described in li the preceding example. Following one recrystallization ~rom ~ methanol the product melted from 32 to 340C. and was found !~ to contain 26.34% tin and 17.84% bromine. The calculated values for tritcyclopentylmethyl)tin bromide are 26.49% for tin and 17.84% ~or bromine.
EXAMPLE 4 - Preparation of Tri(cyclopentylmethyl)tin Chloride and the Corresponding Oxide i( I
l,~ Methyltri(cyclopentylmethyl)tin was prepared by reacting 0.425 mole of cyclopentylmethylmagnesium bromide with i 30.5 g. methyltin trichloride in 150 cc. of benzene. The , crude product was isolated from the reaction mixture as a ~`
yellow~oil (48.3 g.) of refractive index 1.5192 at 24 and in 85% purity. After washing twice with methanol (75 cc. and 25 cc ) and distillation under reduced pressure 33.8 g. of product boiling at 140QC. under 0.3 mm. Hg were obtained~ i j. 24 n D = 1.5230. Vapor phas~ chrom~tography showe~ ~he material to be 95.6% pure.
1l To a solution o~ methyltri(cyclopentylmethyl)tin (26.8 g.) in 100 cc. of pentane, was added dropwise a solution !, . ' - _. I
of stannic chloride (18.2 g.) in 100 cc. pentane over 20 minutes. The resultant yellow solution was heated to the ` boiling point for 0.5 hour then cooled to room temperature.
~ The mixture was combine_ with a solution containing 2 cc. 12N
hydrochloric acid and 98 cc. water, following which the organic phase was separated and washed with another portion of ,j 11 ~
1109ZlZ7 1~ ~
2 cc 12N hydrochloric acid and 98 cc water. The organic phase was again separated and the water therein removed using anhydrous magnesium sulfate. After filtration, the ,~ solvent was removed under reduced pressure to yield 28.20 g.
5 Il, of a white solid that melted from 88 to 90C-Analysis: Found: Sn, 29.21; Cl, 8.87%.
~t Calculated for tri(cyclopentylmethyl)tin chloride:
Sn, 29.41; Cl, 8.80%.
~j Vapor phase chromatography indicated the compound to be i 98.3% pure.
., ~
is[tri(cyclopentylmethyl)tin] Oxide To a solution containing 1.8 g. sodium hydroxide,10 cc. water and 10 cc. methanol was added dropwise a solution containine 12.11 g. tris(cyclopentylmethyl)tin chloride and , ' , 25 cc tetr2hydrofuran over 15 minutes. An oil formed initiall~
and dissol~ed as the addition proceeded. When the addition was complete, the solution was stirred at 25C. ~or 0.5 hour. ¦
A 300 cc. portion of cold (10C.) water was added followed by 200 cc. of diethyl ether with vigorous stirring. The organic ~ phase was isolated and the water therein removed using anhydrous ~agnesium sulfate. After filtratlon the solvent was removed under reduced pressure to yield 11.28 g. of a waxy solid melting from 59 to 630. The crude product was purified b~ adding 60 cc. methanol and cooling to 0~C.
whereupon a small amount of solid material precipitated. The '~ solid was removed and the ~iltrate evaporated under reduced pressure to yield 11.35 g. of yellow liquid, n D = 1.5296.
Analysis: Found: Sn, 30.16.
Caleulated for bis[tri(cyclopentylmethyl)tin] oxide:
ji Sn, 31.56. `
Assay by potentiornetric titration = 92.6% purity.
lO~Zl'~q I ~' EXAMPLE 5 - Preparation of Tr1(2-methylcyclopenkyl)tin Chlorlde and the Corresponding Oxide.
A. Methyltri(2-methylcyclopent~l)tin To a solution contalning 0.31 mole of 2-methyl-cyclopentylmagnesium bromide in 15C cc. of tetrahydrofuran was , added a solution containing 21.6 g. methyltin trichloride in 150 cc. dry toluene over a period of l hour. When the ~! addition was complete, the mixture was heated to the boiling l~ point ~or 2 hours and then stirred at 25C. for 16 hours. The I
reaction mixture was then hydrolyzed uslng a solution containing 25 g. cltric acid and 250 cc. water. The organic phase was `` separated and the water therein removed using anhydrous i/
' magnesium sulfate. The liquid phase was then evaporated under I
, .
reduced pressure to yield 25.45 g. of crude product. Low i boiling impurities were distilled off at from 25 to 75C. under¦
1~
IJ a pressure of 0.1 mm. Hg. The residue, which contained the i desired product, weighed 33.85 g. and exhibited a refractive index of 1.5192 at 24C.
Analysis: Found: Sn, 30.11.
,~ Calculated for methyl tri(2-methylcyclopentyl)tin: ,3 Sn9 30.98.
9. T~i(2-methylcyclcpentjl)tin Chloride To a solutlon containing 13.4 g. of methyl tri(2-methylcyclopentyl)tin and 50 cc. of hexane was added over a 0.5 hour period a solution containing 9.1 g. of stannic , chloride and 50 cc. of hexane. Following completion of the ;, addition the resultant mixture was heated to the boiling point ¦¦ for 15 minutes then cooled to 25C. The reaction mixture was 5,~' then hydrolyzed by addition of a solution containing 2 cc.
, il ~ 28-3' ~ I
., . I
i 1~3Z~Z7 1' concentrated (12N) hydrochlorlc acid and 100 cc. of water The organic phase of the resultant two-phase liquld was ''I isolated and combined wlth a second portion of the afore-ll mentioned hydrochloric acid solution. The organic phase was ', again isolated and the water therein removed using a portion of anhydrous magnesium sulfate. The liquid phase was then evaporated under reduced pressure to yield 14 g. of a yellow oil that exhibited a refractive index (~ D) of 1.5333 and was found to contain 28.48% tin and 8.61% chlorine. The calculated values for the desired chloride are 29.4% tin and 8.78% chlorine.
! I
C. Bis~trit2-methylcyclopentyl)tin] Oxide ' Bis[tri(2-methylcyclopentyl)tin~ oxide was prepared by gradually adding a solution containing ~.l g. of the !~ corresponding chloride (prepared as described in the foregoing ., , ; paragraph) 25 cc. methanol and 15 cc. acetone to a solution containing l.2 g. of sodium hydroxide, 20 cc. water and 50 cc. I
methanol. The addition required 0.5 hourg following which the ¦
'I
~ 'I resultant solution was heated to the boiling point for 10 .. !
~ 20 ; minutes, then cooled to 15C., during which time 300 cc. of .. , ~
water were gradually added. The resultant mixture was stirred for l hour while the temperature was maintained at 15C. A
~I 50 cc. portion of diethyl ether was then added while the mixturè
; ~ was stirred at high speed. The organic phase of the resultant !
25 ~ `' two-phase liquid was isolated and the water therein removed using anhydrous magnesium sulfate. The liquid was then evaporated under reduced pressure to yield 7.6 g. of a pale j~ -29-i i i~ 1.
g~Q9~LZ7 yellow oil which was found to contain 30.54% tin. The calculated tln content of bis~tri(2-methylcyclopentyl)tin~
oxide is 31.56%. A potentiometric titration of the product indicated that it was 98% pure.
Biological Activity o~ Trlcyclopentyltin and Tri(cyclopentylalkyl)tin Compounds ; The following procedures were employed to evaluate the efficacy of the present triorganotin compounds in I controlling a number of representative fungi and insects.
~ Procedure 1 - Employed Using Two-spotted Spider Mite (Tetranychus urticae), Beet Army Worm (Spodoptera exigua) and Cabbage Looper (Trichoplusia ni).
A cotton plant with two fully expanded leaves is ¦l dipped into an aqueous dispersion of the tesk compound. An ¦~ additional portion is in~ected into the soil at the root zone.
Lepidopterous insect larvae are dipped into the water dispersion and placed in petri dish cages clamped around the ~treated foliage. When using the two-spot~ed spider mite as the test insect the dipping step is not performed since the ,~ mites are on the leaf before the plant is treated. A mortality count is taken six days after treatment.
Procedure 2 - Employed Using Tobacco Black Shank Fungus (phytophthora parasitica var.- nicotiane)O
¦I Tobacco plants are transplanted into soil infested ll wlth the test organism. Immediately after transplanting the soil is drenched with a solution o~ test chemical. The test ¦1 is graded on the basis of plant survival.
. I
lO~)Z1~7 Procedure 3 - Ernployed Using Bean Mildew (Erysiphe polygoni).
Bean seeds are planted in fumigated soil which is then drenched with a solution of the test compound. When the plants reach a suitable size they are inoculated with the fungus. After 7 days the relative number of healthy plants is noted.
Procedure 4 - Employed Using Grape Downy Mildew (Plasmopara viticola) Rice Blast (Pericularia oryzae) and ! Apple Powdery Mildew (Podosphaera leucotricha).
~ost plants, (grape, rice or apple, depending upon the fungus) are sprayed with a water suspension of the test compound and then inoculated with the pathogen. After disease ¦
symptoms are well developed on untreated control plants the 1i test plants are graded for disease control.
Procedure 5 - Secondary Evaluation of Activity In Combatting Two-spotted Spider Mite (Tetranychus bimaculatis) I l¦ and Aphid.
¦I Bean plants infested with the organism are sprayed ll with a water disperslon containing the test compound. The , percent mortality is observed three days after spraying ~¦ Procedure 6 - Employed Using Codling Moth ~arvae (Carpocapra pomonella).
I Codling moth eggs are placed on a paraffin surface ¦I that has previously been treated with a water dispersion of ~ the test compound. The paraffin is perforated, allowing the li newly hatched larva ~o feed on an underlay of food. After ¦~ six days a mortality count is made.
109Zl'7 Procedure 7 - Employed Using bollworm Larvae Five third instar bollworm larvae are placed in petri plates containing a layer of semi-synthetic diet. These ~ larvae are sprayed with 3 cc. of a 400 ppm solution or I suspension of the chemlcal from a distance Or 15 inches using a Spraying Systems Company nozzle 40100-120. After spraying, ~I the petri dish cover is replaced with a fiber brewer lid to il permit limited air exchange. Following a holding period of ll up to 3 days, mortality counts are made.
Ij Procedure 8 - Employed Using Apple Scab (Venturia inaequalis).
Apple seedlings are infected with the fungus. The seedlings are then sprayed with an aqueous solution or sus-pension of the test chemical. After a period of incubation ~, the plants are rated for disease control.
¦I Procedure 9 - Employed Using Hornfly Larvae The test compound is mixed with caIf feces and horn~ly eggs are introduced. After 2 days observation is made to determine the presence of fly larvae.
¦, Procedure 10 - Employed Using Cabbage Looper ,ll (Trichoplusia ni) To Determine Sllstems Activity.
A water dispersion of the test compound is injected into the root zone of a bean plant that is infested with the ~ cabbage looper. Mortality counts are made 3 to 6 days after I treatment.
ll -32-109Z~ 7 Procedure 11 - Employed Using Cabbage Looper (Trichoplusia ni).
A bean plant is sprayed with a water dispersion of ~est compound and a number of cabbage loopers are placed on the treated foliage. A check for mortality is made after 3 days.
Procedure 12 - Employed Using Cabbage Looper To ¦ Determine Ovicical Activity.
The test chemlcal is dissolved in a suitable water-ll miscible solvent and diluted with water to the desired concentration. Eggs of the cabbage looper, having been deposited by the adult insects on paper toweling or other 3 ~ ~ substrate~ are fastened to the underside of a test plant leaf ; I~ with methocel or other appropriate adhesive. Egg sheets are 1 selected having 25-50 eggs per plant. Cotton or other 3 ¦l appropriate host plants are used. The leaf of the plant to I~ which eggs are attached is dipped in the solution containing 5 ~¦ the test chemical. Ovicidal observations are recorded 3-5 Il days after treatment. Inactive materials show large areas of l foliage consumed by freshly emerged larvae.
[J9Z~
Procedure 13 - Employed Using Western Spotted j Cucumber Beetle Larvae.
¦ Seventy-five grams o~ air-dried soil are placed in 1 236 cc. capaciky round bottle and treated with sufficient ,' volume of a solution containing 400 ppm of the chemical to give 25 ppm of toxicant on an air-dried soil basis. The ~ treated soil after being allowed to air dry is mixed by j! shaking and rolllng.
1~ Eggs of the western spotted cucumber beetle (laid over a period Or 3 or 4 days) are collected and a measured , quantity of eggs are suspended in water. The egg concentration i is 70-80 eggs/0.5 cc. of solution. A portion of the suspension ' conkaining about 50 eggs is pipetted into the bottom of a clear ii , plastic medicinal vial. An amount of treated soil sufficient - 15 ` to cover the eggs is added, a corn seed is placed on the soil and covered with additional treated soil.
i' The soil3 eggs and seed mix is watered and additional water is added as necessary to maintain growth of the seedling I ~ corn plant. Care must be ~aken not to add too much water or ~ the larvae will drown. After a period of from 6-9 days an observation ls made to determine the presence of larvae both on top of the soil and at the roots of the seedling.
1, _34 !i ~
~11 ' ",, Il . .' ., . , . ~, lO~Z1~7 Procedure 14 - Employed Using Codling Moth Larvae To Determine Ovlcidal Activity And Control Of Newly Hatched Larvae The test chemical is dissolved in a small amount of a suitable water-miscible solvent and diluted with water to achieve the desired concentration. The chemical solution is I applied to apples or pears which are then covered with eggs ¦ of the codling moth. The fruit is then incubated for from ii eight to ten days ln a greenhouse. The number of living and ~i dead larvae are then counted and compared with a sample of untreated ~ru1t used as a control.
¦ Procedure 15 - Employed Using Mosquito Larvae ¦ Third or early fourth instar larvae of Aedes aegypti are used for the test organiem. Twenty to twenty-five larvae ~/ are placed in distilled water containing the candidate chemical.
Activity I8 recorded as the concentration (p.p.m.) constituting ¦ a lethal dose ~or 95 percent o~ the population (LDg~).
¦ Procedure 16 - Employed Using Apple Powdery Mildew I ~ ¦! Aqueous solutions or suspensions of the experimental 20~ chemical are poured into cups of vermiculite in which plants are gro~7ing.~ The aqueous system usua'ly contains acetone and a wettlng agent, both in non~toxic amounts. Two to four days after the compound is appl~ed the leaves are wet with a 1l spore suspension of apple powdery mildew. The plants are ' then put in a greenhouse. When disease symptoms are clear, ~I the plan~s are graded. Untreated plants are rated as "0%
!~ control" and the disease ~ree plants are rated as 100% control.
I . .. ..
Il .. , ..,':"' ', :' " ,,,' I
~19~ 7 The accompanying ~ables summarize the data obtalned uslng the aforementioned procedures with representative compounds encompassed by the accompanying claims.
I TABLE I
Biologlcal Activity of Tricyclopentyltin Hydroxide Again~t - Fungi Organism Proc.No. Concentration Control Rating : (p.p.m.) (%) - Tobacco Black Shank 2 25 100 l 2 6.3 100 j Bean Mildew 3 25 100 Grape Downy Milaew 4 100 100 4 6.2 95 Rice Blast 4 100 93 ~l ~ 4 25 67 , .l Apple Powdery Mildew 4 loo loo TABLE II
Biological Activity of Tricyclopentyltin Hydroxide Against Insects Organism Proc. No. Concentration Control Rating Spider Mite 5 400 100 i 5 100 100 :: ~25 1 5 25 86 ~ li Beet Army Worm 1 400 100 ;1 ~ Cabbage Looper 1 100 100 Codling Moth Larvae 6 400 loo Bollworm Larvae 7 4bo loo I Aphid 5 400 100 ! -11 ' lO~Z:1.27 TABLE III
Blological Activity Or Trlcyclopentyltin Chloride A~ A
Fungicide Or~anism Proc. No. Concentration Control Rating Apple Scab 8 100 90 I Rice Blast 4 400 95 I Apple Powdery Mildew 16 - 100 70 ¦ TABLE IV
¦ Biological Activity of Tricyclopentyltin Chloride As An Insectic~de Or~anismProc. No. Concentration Control Ratin~ ¦
! (p,p.m.) ¦I Cabbage Looper1 400 100 Codling Moth Larvae 14 400 100 TABLE V
,I Biological Activity of Tricyclopentyltin Acetate As A
Il Fungicide ', Or~ ismProc. No. Concentration Control Rating i (p.P.m.) Grape Downy Mildew 4 400 100 ~1 100 90 ¦, Apple Powdery Mildew 4 100 90 li , 1~ Biological Activity of Tricyclopentyltin Acetate As An jj Insecticide ; Organism Pro~ No. Con(centration Control Ratin~
ll Cabbage Looper 12 400 90 Cucumùer Beetle Larvae 13 25 100 11 .
lO~lZl'~7 iTABLE VII
. .. .
; Biological Activity of Tricyclopentyltin Fluoride As An Insecticide And Fungicide Organism Proc. No. Concentration Control Ratln (P~P.-m.-) Spider Mite 1 400 99 li Cabbage Looper 1 400 100 - !I Codling Moth Larvae 14 400 100 j, Grape Downy Mildew4 400 100 I , 100 94 ~ 50 80 Rice Blast 4 400 96 ' Apple Powdery Mildew 4 100 90 TABLE ~III !
Biological Activity of Tricyclopentyltin Bromide iI Pr~ No. Conc~ntration Controlr~R)ating l Spider Mite 1 400 100 Cabbage Looper 1 400 1803 Mosquito Larvae 15 1 100 , Tobacco Black Shank 2 25 100 25.... ', ~rape nowny~.r~ildew4 400 97 : !l loo loo '' Apple Powdery Mildew 4 400 90 i' 100 97 1 6.3 75 ; -38-I
l . l lZiZ'7 TABLE IX
Biological Activity of Tri(cYCloPentYlethYl)tin Hydroxide . Organism Proc. No. Concentration Control Ratin~
Spider Mite 5 400 95 . 100 98 Grape Downy Mildew 4 400 1~0 ~ . 100 55 Apple Scab 8 400 100 TABLE X
Biological Activity of Tri(cyclopentylethyl)tin Bromide 'I Or~anism Proc. No. Concentration Control Rating Cabbage Looper 1 400 83 Horn~ly Larva 9 100 100 : I Tobacco Black Shank 2 25 100 ~ Apple Powdery Mildew 4 400 75 Il , I
¦¦ TABLE XI
,j Biological Activity of Tri(2-methylcyclopentyl~tin Chloride Organism Proc~ No. Concentration ControL Ratin~ ¦
il Cabbage Looper 1 400 100 ¦i Grape Downy Mildew 4 400 100 !j Apple Scab 8 400 100 loo 60
Claims (11)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A triorganotin compound exhibiting a formula selected from the group consisting of and wherein R is hydrogen or alkyl of from 1 to 3 carbon atoms;
N is O, 1 or 2;
X is selected from the group consisting of fluorine, hydroxyl, nitrate, cyanate, thiocyanate, carbamate, thiocarbamate, phosphate, carbonate, amide (NH2), amino (NR? or NR1?), , , phenoxy, alkoxy (-OR2), dithiocarbamoyl, , mercaptide (SR1), dialkyldithiophosphate provided that X is not hydroxyl when R is hydrogen and n is 0;
wherein R1 represents alkyl containing from 1 to 12 carbon atoms or wherein Z is hydrogen, halogen, alkyl containing 1 to 3 carbon atoms, alkoxy containing 1 to 3 carbon atoms, or nitro (-NO2), R2 is alkyl containing from 1 to 12 carbon atoms and Y is oxygen wherein m is an integer from 2 to 10 inclusive , sulfur, sulfate, phosphate or carbonate.
N is O, 1 or 2;
X is selected from the group consisting of fluorine, hydroxyl, nitrate, cyanate, thiocyanate, carbamate, thiocarbamate, phosphate, carbonate, amide (NH2), amino (NR? or NR1?), , , phenoxy, alkoxy (-OR2), dithiocarbamoyl, , mercaptide (SR1), dialkyldithiophosphate provided that X is not hydroxyl when R is hydrogen and n is 0;
wherein R1 represents alkyl containing from 1 to 12 carbon atoms or wherein Z is hydrogen, halogen, alkyl containing 1 to 3 carbon atoms, alkoxy containing 1 to 3 carbon atoms, or nitro (-NO2), R2 is alkyl containing from 1 to 12 carbon atoms and Y is oxygen wherein m is an integer from 2 to 10 inclusive , sulfur, sulfate, phosphate or carbonate.
2. A triorganotin compound exhibiting a formula selected from the group consisting of and wherein R is hydrogen or alkyl of from 1 to 3 carbon atoms n is 0, 1 or 2 and X is selected from the group consisting of fluorine, nitrate, cyanate, carba-mate, thiocarbamate, amide (NH2), amino (NR? or NR1H), , , alkoxy (-OR2), and dialkyldithiophosphate wherein R1 represents alkyl containing from 1 to 12 carbon atoms or phenyl wherein Z is hydrogen, halogen, 1-3 carbon alkyl, 1-3 carbon alkoxy or nitro (-NO2), R2 is alkyl containing from 1 to 12 carbon atoms and Y is oxygen, , wherein m is an integer from 2 to 10, inclusive, , sulfur, sulfate or carbonate.
3. A triorganotin compound exhibiting a formula selected from the group consisting of and wherein X is selected from the group consisting of fluorine, nitrate, cyanate, carbamate, thiocarbamate, amide (NH2), amino (NR? or NR1H), , , alkoxy (-OR2), dithiocarbamoyl and dialkyldithiophosphate wherein R1 represents alkyl containing from 1 to 12 carbon atoms or phenyl wherein Z is hydrogen, halogen, 1-3 carbon alkyl, 1-3 carbon alkoxy or nitro (-NO2), R2 is alkyl containing from 1 to 12 carbon atoms and Y is oxygen, , wherein m is an integer from 2 to 10, inclusive, , sulfur, sulfate or carbonate.
4. A triorganotin compound according to claim 3 wherein Y is oxygen.
5. A triorganotin compound according to claim 3 wherein X is , or .
6. A triorganotin compound according to claim 3 wherein Y is sulfur, or .
7. A triorganotin compound of the formula or wherein m is 1 or 2, X is selected from the group consisting of fluorine, hydroxyl, nitrate, cyanate, thiocyanate, carbamate, thiocarbamate, phosphate, carbonate, , , , , phenoxy, alkoxy (-OR2), dithiocarbamoyl , mercaptide (-SR1) and dialkyldithiophosphate wherein R1 represents alkyl containing from 1 to 12 carbon atoms or wherein Z is hydrogen, halogen, 1-3 carbon alkyl, 1-3 carbon alkoxy or nitro (-NO2), R2 is alkyl containing from 1 to 12 carbon atoms and Y is oxygen, , , sulfur, sulfate or phosphate.
8. A triorganotin compound according to claim 7 wherein X is hydroxyl.
9. A triorganotin compound according to claim 7 wherein Y is oxygen.
10. A triorganotin compound of the formula or wherein R is alkyl and contains from 1 to 3 carbon atoms, X is selected from the group consisting of fluorine, hydroxyl, nitrate, cyanate, carbamate, thiocarbamate, phosphate, carbonate, carboxylate , , , , , phenoxy, alkoxy (-OR2), dithiocarbamoyl mercaptide (-SR1) dialkyldithiophosphate wherein R1 represents alkyl containing from 1 to 12 carbon atoms or wherein Z is hydrogen, halogen, 1-3 carbon alkyl, 1-3 carbon alkoxy or nitro (-NO2), R2 is alkyl containing from 1 to 12 carbon atoms and .gamma. is oxygen, , , sulfur, sulfate or carbonate.
11. A triorganotin compound according to claim 10 wherein .gamma. is oxygen and R is methyl or ethyl.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US71511476A | 1976-08-17 | 1976-08-17 | |
US715,114 | 1976-08-17 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1092127A true CA1092127A (en) | 1980-12-23 |
Family
ID=24872720
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA284,768A Expired CA1092127A (en) | 1976-08-17 | 1977-08-16 | Tricyclopentyltin compounds and pesticidal compositions containing same |
Country Status (6)
Country | Link |
---|---|
JP (1) | JPS5340749A (en) |
BE (1) | BE857839A (en) |
CA (1) | CA1092127A (en) |
DE (1) | DE2737032C2 (en) |
FR (1) | FR2362149A1 (en) |
GB (1) | GB1581269A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105579461A (en) * | 2013-09-26 | 2016-05-11 | 旭化成化学株式会社 | Alkyl tin compound |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AR243195A1 (en) * | 1985-09-03 | 1993-07-30 | Shionogi & Co Ltd Y Nitto Kase | Tri-organo-tin compounds and pesticide compounds that contain them. |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3790611A (en) * | 1972-10-05 | 1974-02-05 | M & T Chemicals Inc | Tris(cyclohexylalkyl)tin or hexakis(cyclohexylalkyl)tin compounds |
-
1977
- 1977-08-10 GB GB33599/77A patent/GB1581269A/en not_active Expired
- 1977-08-16 JP JP9755377A patent/JPS5340749A/en active Granted
- 1977-08-16 BE BE180219A patent/BE857839A/en not_active IP Right Cessation
- 1977-08-16 CA CA284,768A patent/CA1092127A/en not_active Expired
- 1977-08-17 DE DE2737032A patent/DE2737032C2/en not_active Expired
- 1977-08-17 FR FR7725125A patent/FR2362149A1/en active Granted
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105579461A (en) * | 2013-09-26 | 2016-05-11 | 旭化成化学株式会社 | Alkyl tin compound |
US9844775B2 (en) | 2013-09-26 | 2017-12-19 | Asahi Kasei Kabushiki Kaisha | Alkyl tin compound |
CN105579461B (en) * | 2013-09-26 | 2020-02-14 | 旭化成株式会社 | Alkyl tin compound |
Also Published As
Publication number | Publication date |
---|---|
JPS6137277B2 (en) | 1986-08-22 |
DE2737032C2 (en) | 1987-04-02 |
FR2362149B1 (en) | 1983-07-08 |
FR2362149A1 (en) | 1978-03-17 |
GB1581269A (en) | 1980-12-10 |
DE2737032A1 (en) | 1978-02-23 |
BE857839A (en) | 1977-12-16 |
JPS5340749A (en) | 1978-04-13 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CA1092127A (en) | Tricyclopentyltin compounds and pesticidal compositions containing same | |
KR920002887B1 (en) | Process for the organotin compound | |
US4222950A (en) | Method for preparing triorganotin halide | |
EP0086826A1 (en) | Alpha-branched alkylthiophosphate pesticides. | |
US4191698A (en) | Tricyclopentyltin fluoride | |
US3790611A (en) | Tris(cyclohexylalkyl)tin or hexakis(cyclohexylalkyl)tin compounds | |
JPS6270383A (en) | S,s-di-(tertiary-alkyl)thiophosphonate insecticide | |
EP0049643B1 (en) | Improvements in or relating to bis(substituted phenyl) alkyltin compounds | |
US3281321A (en) | Acetamidido-(thio)-phosphoric or phosphonic acid esters as rodenticides | |
US3892863A (en) | Fungicidal and miticidal method containing triorganotin compounds | |
US4535077A (en) | O-ethyl S,S-dialkyl phosphorodithioates for use as pesticides | |
US4010276A (en) | Certain triorganotin compounds used to combat mites | |
US4343815A (en) | Method for combating fungi and mites using certain triorganotin compounds | |
CA1097651A (en) | Triorganotin compounds and method for combatting fungi and insects using same | |
US3892862A (en) | Composition and method for combatting fungi and mites containing triorganotin compounds | |
US4584317A (en) | Pesticidal tin amidoximes | |
US4565812A (en) | Fungicidal tin salts of thienyl and furyl hydroxamic acids, compositions, and method of use therefor | |
CA1048928A (en) | Method for combating fungi and mites using certin triorganotin compounds | |
US4465675A (en) | Insecticidal and fungicidal 1-alkyl-5-alkylsulfonyl-4-chloropyrazole-3-yl-(thio)phosphates and (thio)phosphonates | |
US4732894A (en) | Fungicidal insecticidal and acaricidal tin salts of heterocyclic hydroxamic acids | |
US3151022A (en) | Omicron, omicron-dimethyl-omicron-(4-methylmercaptophenyl) phosphate and pesticidal use | |
US4678804A (en) | Fungicidal benzylthiostannanes | |
US4112083A (en) | Pesticidal O,S-dialkyl O-sulfonyloxyphenyl phosphorothiolates and phosphorodithioates | |
US3965218A (en) | Phosphoroamidothioates | |
US3524869A (en) | Triorganotin (substituted phenoxides) |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
MKEX | Expiry |