NO140979B - PYRAZOLE DERIVATIVES WITH HERBICID ACTIVITY - Google Patents
PYRAZOLE DERIVATIVES WITH HERBICID ACTIVITY Download PDFInfo
- Publication number
- NO140979B NO140979B NO743388A NO743388A NO140979B NO 140979 B NO140979 B NO 140979B NO 743388 A NO743388 A NO 743388A NO 743388 A NO743388 A NO 743388A NO 140979 B NO140979 B NO 140979B
- Authority
- NO
- Norway
- Prior art keywords
- methyl
- water
- pyrazolium
- cyclopropyl
- mixture
- Prior art date
Links
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical class C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 title description 19
- 230000000694 effects Effects 0.000 title description 4
- 150000001875 compounds Chemical class 0.000 claims description 21
- 230000002363 herbicidal effect Effects 0.000 claims description 10
- 150000001450 anions Chemical class 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 150000003217 pyrazoles Chemical class 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims 1
- 125000000753 cycloalkyl group Chemical group 0.000 claims 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims 1
- 241000196324 Embryophyta Species 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- -1 3,5-disubstituted pyrazole Chemical class 0.000 description 17
- 239000000203 mixture Substances 0.000 description 17
- 239000007787 solid Substances 0.000 description 16
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- 239000011541 reaction mixture Substances 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 239000012141 concentrate Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 239000007921 spray Substances 0.000 description 9
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000004094 surface-active agent Substances 0.000 description 8
- 239000004009 herbicide Substances 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 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 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000035784 germination Effects 0.000 description 5
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 5
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 5
- 239000012022 methylating agents Substances 0.000 description 5
- 239000002689 soil Substances 0.000 description 5
- NCMXQGJXACFGRX-UHFFFAOYSA-M 3-cyclopropyl-1,2-dimethyl-5-phenylpyrazol-1-ium;methyl sulfate Chemical compound COS([O-])(=O)=O.C[N+]=1N(C)C(C=2C=CC=CC=2)=CC=1C1CC1 NCMXQGJXACFGRX-UHFFFAOYSA-M 0.000 description 4
- 240000005979 Hordeum vulgare Species 0.000 description 4
- 235000007340 Hordeum vulgare Nutrition 0.000 description 4
- 240000007594 Oryza sativa Species 0.000 description 4
- 235000007164 Oryza sativa Nutrition 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 125000005594 diketone group Chemical group 0.000 description 4
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 4
- 239000000428 dust Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 235000019198 oils Nutrition 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 4
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical class [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- ZEPXXRGMHZRBKL-UHFFFAOYSA-N 1-cyclopropyl-3-phenylpropane-1,3-dione Chemical compound C1CC1C(=O)CC(=O)C1=CC=CC=C1 ZEPXXRGMHZRBKL-UHFFFAOYSA-N 0.000 description 3
- GTEZIVSIRGDAEX-UHFFFAOYSA-N 3-cyclopropyl-1-methyl-5-phenylpyrazole Chemical compound CN1N=C(C2CC2)C=C1C1=CC=CC=C1 GTEZIVSIRGDAEX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 241000209761 Avena Species 0.000 description 3
- 235000007319 Avena orientalis Nutrition 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 241000209504 Poaceae Species 0.000 description 3
- 229920001213 Polysorbate 20 Polymers 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 3
- 244000062793 Sorghum vulgare Species 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 235000021307 Triticum Nutrition 0.000 description 3
- 241000209140 Triticum Species 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 150000004694 iodide salts Chemical class 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- JZMJDSHXVKJFKW-UHFFFAOYSA-N methyl sulfate Chemical compound COS(O)(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-N 0.000 description 3
- 238000007069 methylation reaction Methods 0.000 description 3
- 235000019713 millet Nutrition 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920000151 polyglycol Polymers 0.000 description 3
- 239000010695 polyglycol Substances 0.000 description 3
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000012312 sodium hydride Substances 0.000 description 3
- 229910000104 sodium hydride Inorganic materials 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 2
- FTYFVWHJQIWRMZ-UHFFFAOYSA-N 5-cyclopropyl-1-methyl-3-phenylpyrazole Chemical compound CN1N=C(C=2C=CC=CC=2)C=C1C1CC1 FTYFVWHJQIWRMZ-UHFFFAOYSA-N 0.000 description 2
- 240000006995 Abutilon theophrasti Species 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 244000078127 Eleusine coracana Species 0.000 description 2
- 235000013499 Eleusine coracana subsp coracana Nutrition 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000000370 acceptor Substances 0.000 description 2
- 125000002877 alkyl aryl group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000000010 aprotic solvent Substances 0.000 description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
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- 150000002576 ketones Chemical class 0.000 description 2
- ICIHDUSPYJNBRL-UHFFFAOYSA-N methyl sulfate;1h-pyrazol-1-ium Chemical class [NH2+]1C=CC=N1.COS([O-])(=O)=O ICIHDUSPYJNBRL-UHFFFAOYSA-N 0.000 description 2
- 230000001035 methylating effect Effects 0.000 description 2
- 230000011987 methylation Effects 0.000 description 2
- HDZGCSFEDULWCS-UHFFFAOYSA-N monomethylhydrazine Chemical compound CNN HDZGCSFEDULWCS-UHFFFAOYSA-N 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 2
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- 239000007858 starting material Substances 0.000 description 2
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- HIMLFYUFZYQSDE-UHFFFAOYSA-N 1,3-dicyclohexylpropane-1,3-dione Chemical compound C1CCCCC1C(=O)CC(=O)C1CCCCC1 HIMLFYUFZYQSDE-UHFFFAOYSA-N 0.000 description 1
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- 150000002334 glycols Chemical class 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000004970 halomethyl group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- VUQUOGPMUUJORT-UHFFFAOYSA-N methyl 4-methylbenzenesulfonate Chemical compound COS(=O)(=O)C1=CC=C(C)C=C1 VUQUOGPMUUJORT-UHFFFAOYSA-N 0.000 description 1
- CAAULPUQFIIOTL-UHFFFAOYSA-N methyl dihydrogen phosphate Chemical compound COP(O)(O)=O CAAULPUQFIIOTL-UHFFFAOYSA-N 0.000 description 1
- MNRGFUBMMILKAL-UHFFFAOYSA-N methyl phenylmethanesulfonate Chemical compound COS(=O)(=O)CC1=CC=CC=C1 MNRGFUBMMILKAL-UHFFFAOYSA-N 0.000 description 1
- 150000005451 methyl sulfates Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 235000010460 mustard Nutrition 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920000053 polysorbate 80 Polymers 0.000 description 1
- 150000003109 potassium Chemical class 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000003586 protic polar solvent Substances 0.000 description 1
- 239000008262 pumice Substances 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000035943 smell Effects 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 229920005552 sodium lignosulfonate Polymers 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 description 1
- SNOOUWRIMMFWNE-UHFFFAOYSA-M sodium;6-[(3,4,5-trimethoxybenzoyl)amino]hexanoate Chemical compound [Na+].COC1=CC(C(=O)NCCCCCC([O-])=O)=CC(OC)=C1OC SNOOUWRIMMFWNE-UHFFFAOYSA-M 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000004563 wettable powder Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
- C07C45/455—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation with carboxylic acids or their derivatives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/29—Saturated compounds containing keto groups bound to rings
- C07C49/313—Saturated compounds containing keto groups bound to rings polycyclic
- C07C49/317—Saturated compounds containing keto groups bound to rings polycyclic both carbon atoms bound to the keto group belonging to rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
- Cosmetics (AREA)
Description
Foreliggende oppfinnelse gjelder herbicid-aktive pyrazoliumforbindelser med nedenstående formel I: The present invention relates to herbicide-active pyrazolium compounds with the following formula I:
hvor where
R3 betyr C3-C7-cykloalkyl, fenyl eller C^-C^-alkyl, R4 betyr C3-C7~cykloalkyl, C^-C^-alkyl eller benzyl X betyr et anion med en ladning på fra 1 til 3, og m er et helt tall fra 1 til 3. R3 means C3-C7-cycloalkyl, phenyl or C^-C^-alkyl, R4 means C3-C7-cycloalkyl, C^-C^-alkyl or benzyl X means an anion with a charge of from 1 to 3, and m is an integer from 1 to 3.
Diketonforløperne som anvendes ved fremstilling av pyrazoliumsaltene med formel I med strukturen: The diketone precursors used in the preparation of the pyrazolium salts of formula I with the structure:
hvor , , m og X er som beskrevet ovenfor, fremstilles ved å omsette et metylketon (II) med en alkylkarboksylsyreester (III), where , , m and X are as described above, is prepared by reacting a methyl ketone (II) with an alkylcarboxylic acid ester (III),
fortrinnsvis metyl- eller etylesteren, i nærvær av et alkalimetall-hydrid, fortrinnsvis natriumhydrid, og et aprotisk organisk løsningsmiddel, som f.eks. dimetylsulfoksyd (DMSO), dimetylformamid (DMF), xylen, toluen, benzen eller lignende. Reaksjonen utføres fortrinnsvis ved en temperatur mellom 0 og 40°C, og mest foretrukket mellom 0 og 25°C. Reaksjonen gir det (3-diketon som tilsvarer de anvendte reaktanter. Metylketonet og karboksylsyreesteren reagerer i ekvimolare mengder. Det er imidlertid vanligvis ønskelig å anvende et lite overskudd, dvs. opp til ca. 10% overskudd, av karboksylsyreesteren i reaksjonsblandingen. Reaksjonen kan illustreres som følger: preferably the methyl or ethyl ester, in the presence of an alkali metal hydride, preferably sodium hydride, and an aprotic organic solvent, such as e.g. dimethylsulfoxide (DMSO), dimethylformamide (DMF), xylene, toluene, benzene or the like. The reaction is preferably carried out at a temperature between 0 and 40°C, and most preferably between 0 and 25°C. The reaction gives the (3-diketone which corresponds to the reactants used. The methyl ketone and the carboxylic acid ester react in equimolar amounts. However, it is usually desirable to use a small excess, i.e. up to approx. 10% excess, of the carboxylic acid ester in the reaction mixture. The reaction can be illustrated as follows:
hvor R^ og R^ er som ovenfor definert. where R^ and R^ are as defined above.
Fremgangsmåten ifølge oppfinnelsen for fremstilling av forbindelsene med formel I omfatter først, kondensasjon av diketonet med formel IV med enten hydrazin eller et metyl-hydrazin for å gi den tilsvarende 3,5-disubstituerte pyrazol som metyleres for å gi det ønskede pyrazoliumsalt med formel I. Disse reaksjoner angis nedenfor. The process according to the invention for the preparation of the compounds of formula I comprises first, condensation of the diketone of formula IV with either hydrazine or a methyl-hydrazine to give the corresponding 3,5-disubstituted pyrazole which is methylated to give the desired pyrazolium salt of formula I. These reactions are listed below.
hvor R^/ R^f m og X er som ovenfor definert. Symbolet' , / angir alternative festepunkter for metyl-substituenten. Eksempler på anioner som er egnet for anvendelse i foreliggende oppfinnelse, er halogenider, som f.eks. klorid, bromid og jodid, sulfat, hydrogensulfat, metylsulfat, benzen-sulfonat, perklorat, C^-C^-alkylbenzensulfonat, fortrinnsvis p-toluensulfonat, fosfat, C^-C^-alkansulfonat, where R^/ R^f m and X are as defined above. The symbol' , / denotes alternative attachment points for the methyl substituent. Examples of anions which are suitable for use in the present invention are halides, such as e.g. chloride, bromide and iodide, sulfate, hydrogen sulfate, methyl sulfate, benzene sulfonate, perchlorate, C 2 -C 3 -alkylbenzene sulfonate, preferably p-toluenesulfonate, phosphate, C 3 -C 4 -alkanesulfonate,
hvor R,- er halogen, metyl, halogenmetyl eller dihalogenmety 1, where R,- is halogen, methyl, halomethyl or dihalomethyl 1,
Rg og R^ er halogen, Rg er hydrogen eller metyl og Rg er klor Rg and R^ are halogen, Rg is hydrogen or methyl and Rg is chlorine
eller metyl. or methyl.
Diketonet og hydrazinet reagerer i ekvimolare mengder. The diketone and hydrazine react in equimolar amounts.
Et lite overskudd opp til ca. 10% av en av reaktantene kan imidlertid brukes med fordel. Denne reaksjonen utføres vanligvis i nærvær av et løsningsmiddel, enten protisk eller aprotisk, ved en temperatur mellom 70 og 150°C og fortrinnsvis mellom 80 og 120°C. Foretrukne løsningsmidler for disse reaksjoner er protiske løsnings-midler, som f.eks. lavere alkanoler inkludert metanol, etanol, n-propanol, isopropanol, n-butanol og isobutanol. Aprotiske.. løsningsmidler som er egnet for bruk i disse reaksjoner omfatter xylen, toluen, benzen, dimetylsulfoksyd, dimetylformamid og pyridin. Innføringen av en sur katalysator, som f.eks. p-toluensulfonsyre, øker kondensasjons-cykliseringsreaksjonens hastighet og kan med fordel brukes om reaksjonen går langsomt. A small surplus of up to approx. However, 10% of one of the reactants can be used with advantage. This reaction is usually carried out in the presence of a solvent, either protic or aprotic, at a temperature between 70 and 150°C and preferably between 80 and 120°C. Preferred solvents for these reactions are protic solvents, such as e.g. lower alkanols including methanol, ethanol, n-propanol, isopropanol, n-butanol and isobutanol. Aprotic solvents suitable for use in these reactions include xylene, toluene, benzene, dimethylsulfoxide, dimethylformamide and pyridine. The introduction of an acidic catalyst, such as p-toluenesulfonic acid, increases the speed of the condensation-cyclization reaction and can be used with advantage if the reaction is slow.
Når hydrazin anvendes ved opprinnelig kondensasjon When hydrazine is used in initial condensation
av diketonet, gjennomføres metyleringen av det resulterende pyrazol med fordel ved hjelp av et kjent metyleringsmiddel, fortrinnsvis i nærvær av en syreakseptor, som f.eks. et alkalimetallhydroksyd, of the diketone, the methylation of the resulting pyrazole is advantageously carried out by means of a known methylating agent, preferably in the presence of an acid acceptor, such as e.g. an alkali metal hydroxide,
et alkalimetallalkoksyd eller et tertiært organisk amin. Foretrukne syreakseptorer omfatter natrium- eller kaliumhydroksyd, natrium- eller kaliummetoksyd, -etoksyd, -propoksyd eller -t-butoksyd, trimetylamin, trietylamin og pyridin. an alkali metal alkoxide or a tertiary organic amine. Preferred acid acceptors include sodium or potassium hydroxide, sodium or potassium methoxide, -ethoxide, -propoxide or -t-butoxide, trimethylamine, triethylamine and pyridine.
Metyleringen av pyrazolen utføres fortrinnsvis i nærvær The methylation of the pyrazole is preferably carried out in the presence of
av et løsningsmiddel ved en temperatur mellom 50 og 200°C, fortrinnsvis mellom 90 og- 120°C. Foretrukne løsningsmidler omfatter aromatiske hydrokarboner som f.eks. toluen, xylen og klorbenzen, ketoner med 4 til 7 karbonatomer som f.eks. metylisobutylketon (MIBK) og metylbutylketon (MBK), C2-C5-alkoholer, dipolare aprotiske løsningsmidler som f.eks. dimetylsulfoksyd (DMSO), of a solvent at a temperature between 50 and 200°C, preferably between 90 and -120°C. Preferred solvents include aromatic hydrocarbons such as toluene, xylene and chlorobenzene, ketones with 4 to 7 carbon atoms such as methyl isobutyl ketone (MIBK) and methyl butyl ketone (MBK), C2-C5 alcohols, dipolar aprotic solvents such as e.g. dimethyl sulfoxide (DMSO),
dimetylformamid (DMF), acetonitril, nitrobenzen og N,N-dimetyl-acetamid og cykliske etere som f.eks. dioksan og tetrahydrofuran. dimethylformamide (DMF), acetonitrile, nitrobenzene and N,N-dimethylacetamide and cyclic ethers such as e.g. dioxane and tetrahydrofuran.
Eksempler på metyleringsmidler er: metylhalogenider, dimetylsulfat, metylfosfat, metylhydrogensulfat og metyltoluensulfonat. Examples of methylating agents are: methyl halides, dimethyl sulphate, methyl phosphate, methyl hydrogen sulphate and methyl toluene sulphonate.
Mens de 3,5-disubstituerte pyrazoler kombineres med ekvimolare mengder metyleringsmiddel, er det vanlig praksis å anvende et overskudd metyleringsmiddel. Molforhold mellom metyleringsmiddel og pyrazol innenfor området fra 1:1 til 1,5:1 While the 3,5-disubstituted pyrazoles are combined with equimolar amounts of methylating agent, it is common practice to use an excess of methylating agent. Molar ratio between methylating agent and pyrazole in the range from 1:1 to 1.5:1
er foretrukket. Selvsagt kreves det dobbelt mengde metyleringsmiddel når det anvendes hydrazin. is preferred. Of course, double the amount of methylating agent is required when hydrazine is used.
I disse metyleringsreaksjoner er det ofte funnet at In these methylation reactions it is often found that
ved avkjøling av reaksjonsblandingen utskilles det faste eller oljeaktige pyrazoliumsaltet, som renses ved separasjon fra det organiske skiktet. I noen tilfeller, særlig når og R^ er meget lipofile (f.eks. 3,5-dicykloheksyl-, 3-cykloheksyl-5-fenyl- upon cooling the reaction mixture, the solid or oily pyrazolium salt is separated, which is purified by separation from the organic layer. In some cases, especially when and R^ are very lipophilic (e.g. 3,5-dicyclohexyl-, 3-cyclohexyl-5-phenyl-
og 3-dodecyl-5-fenylforbindelser), kan imidlertid ikke separasjonen av pyrazoliumsaltet fra den organiske fase foretas enkelt. I slike tilfeller kan produktet oppnås ved fordampning av løsningsmidlet og oppløsning av residuet i kloroform, vann- and 3-dodecyl-5-phenyl compounds), however, the separation of the pyrazolium salt from the organic phase cannot be carried out easily. In such cases, the product can be obtained by evaporating the solvent and dissolving the residue in chloroform, water
vasking av kloroformskiktet og fordampning av kloroformen for å oppnå pyrazoliumsaltet som rest. washing the chloroform layer and evaporating the chloroform to obtain the pyrazolium salt as a residue.
Når metyltoluensulfonat eller metylsulfat anvendes som metyleringsmidler oppnås ofte urene eller hygroskopiske materialer på grunn av anionforurensninger (som f.eks. HSO^ eller S0^_). I slike tilfeller renses det blandede anion ved å føre en vandig løsning av denne blanding gjennom en anionvekslerkolonne. Alternativt kan den vandige løsning av blandede anioner omdannes til et jodid ved å anvende vandig mettet kaliumjodid- eller natriumjodidløsning. Den sistnevnte behandling gir det relativt vannuløselige jodidet. Perklorater fremstilles ved tilsetning av fortynnet vandig perklorsyre til en vandig pyrazoliumsaltløsning for å gi det vannuløselige perkloratet. Ytterligere rene pyrazoliumsalter, f.eks. CH^SC^ , HSO^ , SO^- eller Cl kan omdannes ved den ovennevnte fremgangsmåte med anionveksler-kromatografi til nye pyrazoliumsalter, og til jodider og perklorater som ovenfor definert. Pyrazoliumhalogenider fremstilles som ovenfor beskrevet, bortsett fra at reaksjonen utføres i et forseglet kar eller en glassforet bombe som holdes ved en temperatur på ca. 100°C. When methyltoluenesulfonate or methylsulfate are used as methylating agents, impure or hygroscopic materials are often obtained due to anionic impurities (such as HSO^ or SO^_). In such cases, the mixed anion is purified by passing an aqueous solution of this mixture through an anion exchange column. Alternatively, the aqueous solution of mixed anions can be converted to an iodide by using aqueous saturated potassium iodide or sodium iodide solution. The latter treatment yields the relatively water-insoluble iodide. Perchlorates are prepared by adding dilute aqueous perchloric acid to an aqueous pyrazolium salt solution to give the water-insoluble perchlorate. Further pure pyrazolium salts, e.g. CH^SC^ , HSO^ , SO^- or Cl can be converted by the above-mentioned method with anion-exchange chromatography into new pyrazolium salts, and into iodides and perchlorates as defined above. Pyrazolium halides are prepared as described above, except that the reaction is carried out in a sealed vessel or glass-lined bomb maintained at a temperature of approx. 100°C.
Et annet aspekt ved foreliggende oppfinnelse er å anvende en herbicid effektiv mengde av forbindelsen med formel I som aktivt stoff i et herbicid preparat for behandling av bladene på uønskede planter. Den aktive forbindelse anvendes i en mengde av mellom 0,028 og 1,12 g/m 2 og fortrinnsvis i mengder mellom 0,056 og 0,56 g/m 2. Overraskende kan disse forbindelser også benyttes som melduggbekjempelsesmidler når de påføres på bladene hos planter i mengder mellom 0,02 8 og 1,12 kg/m<2>. Another aspect of the present invention is to use a herbicidally effective amount of the compound of formula I as active substance in a herbicidal preparation for treating the leaves of unwanted plants. The active compound is used in an amount of between 0.028 and 1.12 g/m 2 and preferably in amounts between 0.056 and 0.56 g/m 2 . Surprisingly, these compounds can also be used as mildew control agents when applied to the leaves of plants in amounts between 0.02 8 and 1.12 kg/m<2>.
Pyrazoliumsalter med formel I hvor er fenyl, Pyrazolium salts of formula I where is phenyl,
R^ er C^-C^-alkyl (fortrinnsvis C5~c^^) og m og X er som R 1 is C 1 -C 4 -alkyl (preferably C 5 -C 4 ) and m and X are as
ovenfor definert, oppviser utmerket selektiv bekjempelse av bredbladede planter efter spiring i nærvær av små kornplanter, som f.eks. bygg, hvete og ris. Dette er spesielt overraskende siden de lavere homologene, dvs. hvor R^ er metyl, er ineffektive som herbicid middel i alle testede doseringer. Disse forbindelser oppviser også overraskende herbicid aktivitet før spiring. defined above, exhibits excellent selective control of broad-leaved plants after germination in the presence of small cereal plants, such as e.g. barley, wheat and rice. This is particularly surprising since the lower homologues, i.e. where R 1 is methyl, are ineffective as herbicides in all dosages tested. These compounds also exhibit surprising herbicidal activity before germination.
Som det vil bli observert senere er de pyrazoliumsalter med formel I som er mest uvanlige i sin herbicide effektivitet de hvor R^ betyr en C^-C^-alkylgruppe og R^, m og X er som ovenfor definert. Foretrukne forbindelser er de hvor R^ er C^-C^-cykloalkyl eller fenyl, R^ er C^-C^-cykloalkyl As will be observed later, the pyrazolium salts of formula I which are most unusual in their herbicidal effectiveness are those where R 1 is a C 1 -C 4 alkyl group and R 1 , m and X are as defined above. Preferred compounds are those where R 1 is C 1 -C 3 -cycloalkyl or phenyl, R 3 is C 3 -C 4 -cycloalkyl
og X og m er som ovenfor definert. Disse forbindelser er meget effektive som herbicider. De er spesielt effektive når de påføres på bladene til uønskede planter og er effektive både mot bredbladede ugressplanter og mot uønskede gressplanter. Videre kan de anvendes for selektiv bekjempelse av floghavre, bredbladet ugress og uønskede gressplanter, spesielt fingerhirse, i nærvær av små kornplanter som f.eks. bygg, hvete og ris. Enda mer overraskende er det at nevnte forbindelser også oppviser aktivitet før spiring. and X and m are defined as above. These compounds are very effective as herbicides. They are particularly effective when applied to the leaves of unwanted plants and are effective against both broadleaf weeds and unwanted grasses. Furthermore, they can be used for the selective control of field oats, broad-leaved weeds and unwanted grass plants, especially finger millet, in the presence of small cereal plants such as e.g. barley, wheat and rice. Even more surprising is that said compounds also exhibit activity before germination.
Det er en fordel at mange av pyrazoliumsaltene med formel I oppviser en høy grad av vannløselighet og gjør det derved mulig å fremstille vannkonsentrater av dem. Blant de foretrukne saltene er metylsulfåtene, hydrogensulfåtene, sulfatene, kloridene og bromidene. I praksis kan de vandige konsentratene påføres di- It is an advantage that many of the pyrazolium salts of formula I exhibit a high degree of water solubility and thereby make it possible to prepare water concentrates from them. Among the preferred salts are the methyl sulfates, hydrogen sulfates, sulfates, chlorides and bromides. In practice, the aqueous concentrates can be applied di-
rekte som en væskespray på bladene til uønskede bredbladede ugressplanter og uønskede gressplanter. Alternativt kan de fortynnes ytterligere med vann og påføres som fortynnet vandig spray på disse uønskede planter. directly as a liquid spray on the leaves of unwanted broadleaf weeds and unwanted grasses. Alternatively, they can be further diluted with water and applied as a diluted aqueous spray to these unwanted plants.
Vannblandbare konsentrater fremstilles ved å løse Water-miscible concentrates are prepared by dissolving
fra 15 til 95% av forbindelsen i 85 til S% av et vann-blandbart løsningsmiddel som for eksempel vann eller et annet polart vann-blandbart løsningsmiddel, som for eksempel 2-metoksy-etanol, metanol, propylenglykol, dietylenglykol, dietylenglykolmonoetyleter, forma- from 15 to 95% of the compound in 85 to 50% of a water-miscible solvent such as water or another polar water-miscible solvent such as 2-methoxyethanol, methanol, propylene glycol, diethylene glycol, diethylene glycol monoethyl ether, forma-
mid og dimetylformamid. Påføringen utføres ved å tilsette en på forhånd bestemt mengde av det vann-blandbare konsentratet til en spraytank og påføre blandingen som sådan eller i kombinasjon med et passende fortynningsmiddel, som for eksempel en ytterligere mengde vann eller et av de andre løsningsmidlene. mid and dimethylformamide. The application is carried out by adding a predetermined amount of the water-miscible concentrate to a spray tank and applying the mixture as such or in combination with a suitable diluent, such as an additional amount of water or one of the other solvents.
Ytelsen av produktet i alle de ovenfor nevnte sammensetninger som anvendes i form av væskespray, forbedres uventet ved å tilsette et overflateaktivt middel eller en blanding av slike midler. Konvensjonelle anioniske, kationiske og anionisk-ikkeioniske overflateaktive midler kan anvendes. The performance of the product in all the above-mentioned compositions used in the form of liquid spray is unexpectedly improved by adding a surfactant or a mixture of such agents. Conventional anionic, cationic and anionic-nonionic surfactants can be used.
Eksempler på ikke-ioniske overflateaktive midler Examples of non-ionic surfactants
er: alkylpolyoksyetylenetere, polyoksyetylen(20)sorbitanmonolaurat, polyoksyetylen(20)sorbitanmonooleat, alkylarylpolyglykoletere, alkylfenoletoksylater, trimetylnonylpolyetylénglykoletere, alkyl-fenoletylenoksydkondensater, oktylfenoksypolyetoksyetanoler, nonylfenylpolyetylenglykoletere, kondensater av polyoksyetylener, polyoksypropylener, alifatiske polyetere, alifatiske polyestere, alkylarylpolyoksyetylenglykoler og liknende. are: alkyl polyoxyethylene ethers, polyoxyethylene (20) sorbitan monolaurate, polyoxyethylene (20) sorbitan monooleate, alkyl aryl polyglycol ethers, alkyl phenol ethoxylates, trimethylnonyl polyethylene glycol ethers, alkyl phenol ethylene oxide condensates, octylphenoxy polyethoxyethanols, nonylphenyl polyethylene glycol ethers, condensates of polyoxyethylenes, polyoxypropylenes, aliphatic polyethers, aliphatic polyesters, alkylarylpolyoxyethylene glycols and the like.
Eksempler på anioniske overflateaktive midler er: natriumdodecylbenzensulfonat og dioktylesteren av natriumsulforav-syre. Examples of anionic surfactants are: sodium dodecylbenzenesulphonate and the dioctyl ester of sodium sulphoraic acid.
Egnede kationiske overflateaktive midler omfatter dikokosdimetylammoniumklorid, stearamidopropyldimetyl-betahydroksy-etylammoniumnitrat og liknende. Suitable cationic surfactants include dicocosdimethylammonium chloride, stearamidopropyldimethyl-betahydroxy-ethylammonium nitrate and the like.
Disse overflateaktive midler tilsettes fortrinnsvis til spray-tanken i en mengde av 0,1 til 5 volum! for å skaffe en These surfactants are preferably added to the spray tank in an amount of 0.1 to 5 volumes! to obtain one
god fuktning av sprayløsning på plantenes blader. good wetting of the spray solution on the leaves of the plants.
Herbicide konsentrater inneholdende overflateaktive midler lages fortrinnsvis som vandige sprayløsninger inneholdende ca. 30 vekt! av det passende pyrazoliumsaltet, fra 25 til 50 vekt! vann og resten av blandingen (25 - 45 vekt!) av et valgt overflateaktivt middel. Overflateaktive midler som er spesielt nyttige ved fremstilling av egnede konsentrater med slike midler omfatter oktyl-fenol-etylenoksydkondensatet, en etanolisk løsning av et alkylfenol-etoksylat, et polyglykol-eterkondensat fremstilt fra etylenoksyd og en alkylarylpolyglykoleter. Herbicide concentrates containing surfactants are preferably made as aqueous spray solutions containing approx. 30 weight! of the appropriate pyrazolium salt, from 25 to 50 wt! water and the rest of the mixture (25 - 45 weight!) of a selected surfactant. Surfactants which are particularly useful in preparing suitable concentrates with such agents include the octyl phenol ethylene oxide condensate, an ethanolic solution of an alkylphenol ethoxylate, a polyglycol ether condensate prepared from ethylene oxide and an alkyl aryl polyglycol ether.
Andre blandinger som med fordel kan anvendes med forbindelsen fremstilt ifølge oppfinnelsen omfatter støv, støvkon-sentraterog fuktbare pulvere. Other mixtures which can be advantageously used with the compound produced according to the invention include dust, dust concentrates and wettable powders.
Støv fremstilles vanligvis ved å male sammen ca. Dust is usually produced by grinding together approx.
1 til 25 vekt! av det aktive midlet med fra 99 til 25 vekt! av et fast fortynningsmiddel som for eksempel kaolin, attapulgitt, talk, pimpesten, diatomejord, fullers jord, tremel eller liknende. 1 to 25 weight! of the active agent with from 99 to 25 weight! of a solid diluent such as kaolin, attapulgite, talc, pumice stone, diatomaceous earth, fuller's earth, wood flour or the like.
Støvkonsentrater fremstilles på liknende måte bortsett fra at 25 til 95 vekt! av det aktive stoffet males med 75 til 5 vekt! av fortynningsmidlet. Dust concentrates are prepared in a similar manner except that 25 to 95 wt! of the active substance is ground with 75 to 5 weight! of the diluent.
Fuktbare pulvere fremstilles på samme måte som stø\ konsentrater bortsett fra at 1 til 5 vekt! av et dispergeringsmiddel som for eksempel kalsiumsaltet av en polymerisert alkylarylsulfon-syre, natriumlignosulfonat eller natriumsaltet av konsensert nafta-lensulfonsyre blandes med blandingen og 1 til 5 vekt! av et overflateaktivt middel som for eksempel polyoksyetylert vegetabilsk olje, alkylfenoksypolyoksyetylenetanol, eller natriumalkyl-naftalensulfonat også blandes inn. Wettable powders are prepared in the same manner as solid concentrates except that 1 to 5 wt! of a dispersing agent such as the calcium salt of a polymerized alkylaryl sulfonic acid, sodium lignosulfonate or the sodium salt of concentrated naphthalene sulfonic acid is mixed with the mixture and 1 to 5 wt. of a surface-active agent such as, for example, polyoxyethylated vegetable oil, alkylphenoxypolyoxyethylene ethanol, or sodium alkyl naphthalene sulfonate is also mixed in.
I praksis dispergeres det fuktbare pulveret i vann og påføres som en væskespray på bladene til de uønskede plantene. Påføringsmengden skal være tilstrekkelig til å skaffe 0,028 til In practice, the wettable powder is dispersed in water and applied as a liquid spray to the leaves of the unwanted plants. The amount of application must be sufficient to obtain 0.028 to
1,12 g/m 2 av pyrazoliumsaltet og, selv om 0,056 til 0,56 g/m 2 av nevnte salt vanligvis er tilstrekkelig for bekjempelse av uønsket bredbladet ugress og uønskede gressplanter, skal det forstås at mengder som overstiger Ijl2 g/m 2 og så stor som 2,24 g/m 2 kan brukes. Disse store mengder vil naturligvis bli brukt på slike områder som for eksempel veikanter, under kraftlinjer og langs hekkrader på grensen av eiendomslinjer og åkre. 1.12 g/m 2 of the pyrazolium salt and, although 0.056 to 0.56 g/m 2 of said salt is usually sufficient for control of unwanted broadleaf weeds and grasses, it should be understood that amounts exceeding Ijl2 g/m 2 and as large as 2.24 g/m 2 can be used. These large quantities will naturally be used in areas such as roadsides, under power lines and along hedgerows on the border of property lines and fields.
For å gjøre forståelsen av oppfinnelsen lettere gis de følgende eksempler, hovedsakelig for å illustrere visse mere spesielle detaljer ved den og også for å illustrere fremstillingen av utgangsmaterialene som er anvendbare herfor. Dersom intet annet er angitt er alle deler og prosenter angitt som vektdeler og -prosenter. In order to make the understanding of the invention easier, the following examples are given, mainly to illustrate certain more special details of it and also to illustrate the production of the starting materials which are applicable for this. If nothing else is stated, all parts and percentages are stated as parts and percentages by weight.
Eksempel A Example A
Fremstilling av 1, 3- dicykloheksyl- l, 3- propandion. Preparation of 1,3-dicyclohexyl-1,3-propanedione.
Natriumhydrid (39,5 g av 54!-ig, 0,889 mol) av-kjøles med et isbad til 18°C i en passende kolbe utstyrt med om-rører, kjøler, tørkerør, dråpetrakt og termometer. Dimetylsulfoksyd (700 ml), tørket over 4A molekylærsikt, tilsettes langsomt. Etter at tilsetningen er avsluttet omrøres reaksjonsblandingen i 0,5 time ved romstemperatur. Isbadet byttes og en blanding av cykloheksan-karboksylsyre-etylester (138,8 g, 0,889 mol) og cykloheksylmetyl-keton (101,9 g, 0,80 mol) tilsettes dråpevis. Det ble ikke observert noen eksoterm. Reaksjonsblandingen får lysere farge og det observeres noen bobler. Etter at tilsetningen er avsluttet fjernes isbadet og reaksjonsblandingen omrøres over natten ved romstemperatur. Den tykke, mørkfargede reaksjonsblandingen helles over .is Sodium hydride (39.5 g of 54 µg, 0.889 mol) is cooled with an ice bath to 18°C in a suitable flask equipped with a stirrer, condenser, drying tube, dropping funnel and thermometer. Dimethyl sulfoxide (700 ml), dried over 4A molecular sieve, is added slowly. After the addition has ended, the reaction mixture is stirred for 0.5 hour at room temperature. The ice bath is changed and a mixture of cyclohexane-carboxylic acid ethyl ester (138.8 g, 0.889 mol) and cyclohexylmethyl ketone (101.9 g, 0.80 mol) is added dropwise. No exotherm was observed. The reaction mixture becomes lighter in color and some bubbles are observed. After the addition is finished, the ice bath is removed and the reaction mixture is stirred overnight at room temperature. The thick, dark colored reaction mixture is poured over ice
(8 liter) inneholdende fosforsyre (50 ml) og ekstraheres med eter. Eteren vaskes med vann, tørkes og fordampes i vakuum for å gi en gyldengul olje (204 g) som lukter sterkt av esteren. Produktet kan renses ved reaksjon med kopperkomplekser ifølge konvensjonelle frem-gangsmåter om ønsket. Når den er ren forekommer den i form av hvite krystaller med smeltepunkt på 50-52°C. (8 liters) containing phosphoric acid (50 ml) and extracted with ether. The ether is washed with water, dried and evaporated in vacuo to give a golden yellow oil (204 g) which smells strongly of the ester. The product can be purified by reaction with copper complexes according to conventional methods if desired. When it is pure, it occurs in the form of white crystals with a melting point of 50-52°C.
Anal. Beregnet for C15H2402: C, 76,22, H, 10,24 Anal. Calculated for C15H24O2: C, 76.22, H, 10.24
Funnet: C, 76,20, H, 10,03 Found: C, 76.20, H, 10.03
Andre g-diketoner kan fremstilles fra estere og ketoner inneholdende R, og R^ som tidligere definert. Således er 1-cyklopropyl-3-fenyl-l,3-propandion rapportert fremstilt i fast form med smp. 36-37°C fra etylbenzoat og cyklopropylmetylketon i nærvær av natriumamid. Alternativt er det funnet at samme forbindelse med smp. 3'8-40°C kan fremstilles fra etylcyklopropankarboksylat, acetonfenon og natriumhydrid. Ennvidere er en serie l-alkyl-3-fenyl-1,3-propandioner fremstilt fra karboksylsyreetylestere og acetonfenon i nærvær av natriumamid. Illustrerende eksempler er angitt i tabellen som er fremstilt ifølge reaksjonen: hvor R^ og R4 er angitt i tabell I nedenfor. Other g-diketones can be prepared from esters and ketones containing R, and R^ as previously defined. Thus, 1-cyclopropyl-3-phenyl-1,3-propanedione has been reported to be produced in solid form with m.p. 36-37°C from ethyl benzoate and cyclopropyl methyl ketone in the presence of sodium amide. Alternatively, it has been found that the same compound with m.p. 3'8-40°C can be prepared from ethyl cyclopropane carboxylate, acetone phenone and sodium hydride. Furthermore, a series of 1-alkyl-3-phenyl-1,3-propanediones has been prepared from carboxylic acid ethyl esters and acetonephenone in the presence of sodium amide. Illustrative examples are given in the table prepared according to the reaction: where R 1 and R 4 are given in Table I below.
Eksempel B Example B
Fremstilling av 3-cyklopropyl-l-metyl-5-fenylpyrazol og 5-cyklopropyl- l- metyl- 3- fenylpyrazol. Preparation of 3-cyclopropyl-1-methyl-5-phenylpyrazole and 5-cyclopropyl-1-methyl-3-phenylpyrazole.
l-Cyklopropyl-3-fenyl-1,3-propandion (37,6 g, 0,2 mol) og 2-propanol (250 ml) oppvarmes til tilbakeløp. Metylhydrazin (10,2 g, 0,22 mol) tilsettes så dråpevis og løsningen får stå 1-Cyclopropyl-3-phenyl-1,3-propanedione (37.6 g, 0.2 mol) and 2-propanol (250 ml) are heated to reflux. Methylhydrazine (10.2 g, 0.22 mol) is then added dropwise and the solution is allowed to stand
under tilbakeløp inntil reaksjonen er avsluttet (2,5 timer). Løsningen filtreres så og fordampes i vakuum for å gi en gul olje (39,2 g, 99%). Undersøkelse av produktet på en tynnskiktskromato-grafiplate av silikagel utviklet med kloroform og jod viste at det var en forurensning tilstede. Produktet kromatograferes på silikagel med kloroform ag gir en hvit, tåket olje. Isomerene kan anvendes som en blanding eller isoleres ved konvensjonell kjemisk separasjons-teknikk som for eksempel fraksjonert krystallisasjon. under reflux until the reaction is complete (2.5 hours). The solution is then filtered and evaporated in vacuo to give a yellow oil (39.2 g, 99%). Examination of the product on a thin layer chromatography plate of silica gel developed with chloroform and iodine showed that a contaminant was present. The product is chromatographed on silica gel with chloroform and gives a white, cloudy oil. The isomers can be used as a mixture or isolated by conventional chemical separation techniques such as fractional crystallization.
Anal. Beregnet for <C>13<H>14<N>2<:> C, 77,68, H, 7,26, N, 13,52 Anal. Calculated for <C>13<H>14<N>2<:> C, 77.68, H, 7.26, N, 13.52
Funnet : C, 77,92, H, 7,33, N, 13,56. Found: C, 77.92, H, 7.33, N, 13.56.
De følgende pyrazoler med strukturen: The following pyrazoles with the structure:
fremstilles ved fremgangsmåten ifølge dette eksempel ved å anvende det passende 1,3-propandion som substitutt for l-cyklopropyl-3-fenyl-1,3-propandion. Resultatene av fremgangsmåten angis i tabell II nedenfor. Symbolet angir alternative stillinger for feste av metylsubstituenten. is prepared by the method according to this example by using the appropriate 1,3-propanedione as a substitute for 1-cyclopropyl-3-phenyl-1,3-propanedione. The results of the procedure are set out in Table II below. The symbol indicates alternative positions for attachment of the methyl substituent.
Eksempel i Example i
Fremstilling av 3-cykloheksyl-l,2-dimetyl-5£enylpyrazolium-metylsulfat. Preparation of 3-cyclohexyl-1,2-dimethyl-5£enylpyrazolium methyl sulfate.
I et passende reaksjonskar oppløses l-metyl-3(5)-cykloheksyl-5(3)-fenylpyrazol (8,0 g, 0,033 mol) i tørt toluen og oppvarmes til ca. 65°C. Dimetylsulfat (4,5 g, 0,035 mol) tilsettes så og blandingen oppvarmes til tilbakeløp. Tic (benzen) etter 1\ In a suitable reaction vessel, 1-methyl-3(5)-cyclohexyl-5(3)-phenylpyrazole (8.0 g, 0.033 mol) is dissolved in dry toluene and heated to approx. 65°C. Dimethyl sulfate (4.5 g, 0.035 mol) is then added and the mixture is heated to reflux. Tic (benzene) after 1\
timer viser en liten rest av pyrazol. Etter 2 timer begynner reaksjonsblandingen å mørkne og oppvarmingen avbrytes. Ved av- hours shows a small residue of pyrazole. After 2 hours, the reaction mixture begins to darken and heating is discontinued. By off-
kjøling dannes et hvitt fast stoff som frafiltreres og vaskes med tørt toluen. Dette klebrige, hvite, faste stoff vakuumtørkes ved romstemperatur og gir et sprøtt fast stoff. Heksan tilsettes så cooling, a white solid is formed which is filtered off and washed with dry toluene. This sticky white solid is vacuum dried at room temperature to a brittle solid. Hexane is then added
og det f asteyétof f et brytes opp og oppsamles ved filtrering. Det faste stoffet (6,3 g, 50! utbytte) har smeltepunkt 48-51°C. Ved å and the solid is broken up and collected by filtration. The solid (6.3 g, 50% yield) has a melting point of 48-51°C. By
bli utsatt for luft blir det klebrig (hygroskopisk). Ved analyse bemerkes følgende: Analyse. Beregnet for C18H26<N>2S04-H20: C, 56,24, H, 7,34, N, 7,29 exposed to air it becomes sticky (hygroscopic). When analyzing, the following is noted: Analysis. Calculated for C18H26<N>2SO4-H2O: C, 56.24, H, 7.34, N, 7.29
Funnet : C, 56,91, H, 7,33, N, 7,12 Found: C, 56.91, H, 7.33, N, 7.12
Eksempel 2 Example 2
Fremstilling av 5-cyklopropyl-l,2-dimetyl-3-fenylpyrazolium-metylsulfat. Preparation of 5-cyclopropyl-1,2-dimethyl-3-phenylpyrazolium methyl sulfate.
En blanding av 3-cyklopropyl-l-metyl-5-fenylpyrazol og 5-cyklopropyl-l-metyl-3-fenylpyrazol (33,1 g, 0,167 mol) og tørt toluen (250 ml) oppvarmes til tilbakeløp og ca. 25 ml løsningsmiddel fjernes med en Dean Stark-felle. Løsningen avkjøles så og dimetylsulfat (18 mlj 0,193 mol) tilsettes. Reaksjonsblandingen holdes ved 100°C i 2,5 timer. Det dannes en gulbrun olje som blir fast ved avkjøling. Det faste stoffet fjernes ved filtrering og tørkes under vakuum slik at det oppnås et kremfarget fast stoff (49,5 g, 91,5!) A mixture of 3-cyclopropyl-1-methyl-5-phenylpyrazole and 5-cyclopropyl-1-methyl-3-phenylpyrazole (33.1 g, 0.167 mol) and dry toluene (250 ml) is heated to reflux and approx. 25 ml of solvent is removed with a Dean Stark trap. The solution is then cooled and dimethyl sulfate (18 mL/0.193 mol) is added. The reaction mixture is kept at 100°C for 2.5 hours. A yellow-brown oil is formed which solidifies on cooling. The solid is removed by filtration and dried under vacuum to give a cream-colored solid (49.5 g, 91.5!)
med et smeltepunkt på 163-170°C, hvis analyse er som følger: with a melting point of 163-170°C, whose analysis is as follows:
Beregnet for C15H2()<N>2S04: C, 55 , 54 , H, 6,22, N, 8,64 S, 9,89 Calculated for C15H2()<N>2S04: C, 55 , 54 , H, 6.22, N, 8.64 S, 9.89
Funnet : C, 55,27, H, 6,23, N, 9,48, S, 9,99. Found : C, 55.27, H, 6.23, N, 9.48, S, 9.99.
Ved å følge fremgangsmåten i ovenstående eksempel fremstilles forbindelsene i tabell III nedenfor ved å erstatte 3-cyklopropyl-l-metyl-5-fenylpyrazol med et passende 1-metylpyrazol med den generelle formel VII: Following the procedure in the above example, the compounds in Table III below are prepared by replacing 3-cyclopropyl-1-methyl-5-phenylpyrazole with an appropriate 1-methylpyrazole of the general formula VII:
De følgende pyrazoler gir når de omsettes med dimetylsulfat ifølge ovenstående metode, produkter som er en blanding av metylsulfat- og hydrogensulfatsalter. I slike tilfeller omdannes produktene fullstendig til jodider og/eller perkloratsalter ved oppløsning i vann og behandling med mettet kalium- (eller natrium-) jodid eller fortynnet perklorsyre respektive. Ved for eksempel å anvende enten: The following pyrazoles, when reacted with dimethyl sulfate according to the above method, give products which are a mixture of methyl sulfate and hydrogen sulfate salts. In such cases, the products are completely converted to iodides and/or perchlorate salts by dissolution in water and treatment with saturated potassium (or sodium) iodide or dilute perchloric acid, respectively. For example, by applying either:
hvor R4 er n~ cnii23' ^H3)3C~> cykloheptyl-, eller where R4 is n~ cnii23' ^H3)3C~> cycloheptyl-, or
utskilles ikke metylsulfat-/hydrogensulfatsaltene når undecyl- og cykloheptylgruppene anvendes, ved avkjøling av reaksjonsblandingen. the methyl sulfate/hydrogen sulfate salts are not separated when the undecyl and cycloheptyl groups are used, upon cooling the reaction mixture.
I disse tilfeller vakuurafordampes reaksjonsblandingen, residuet In these cases, the reaction mixture, the residue, is evaporated in vacuo
løses i vann og anvendes for fremstilling av jodidet og/eller perkloratet uten noen løsningsmiddelekstraksjon. is dissolved in water and used for the preparation of the iodide and/or perchlorate without any solvent extraction.
Eksempel 3 Example 3
Fremstilling av 5-cyklopropyl-l,2-dimetyl-3-fenylpyrazolium- Preparation of 5-cyclopropyl-1,2-dimethyl-3-phenylpyrazolium-
perklorat. perchlorate.
En vandig løsning (500 ml) inneholdende 10 g 5-cyklopropyl-1,2-dimetyl-3-fenylpyrazolium-metylsulfat ekstraheres med eter. Det vandige skiktet avskilles og behandles med fortynnet perklorsyre (10 ml) for å gi et fast stoff. Etter omrøring i en time fjernes det faste stoffet ved filtrering og tørkes for å gi et kremfarget, fast stoff (6,1 g, 60!) med smeltepunkt 160-161°C. An aqueous solution (500 ml) containing 10 g of 5-cyclopropyl-1,2-dimethyl-3-phenylpyrazolium methyl sulfate is extracted with ether. The aqueous layer is separated and treated with dilute perchloric acid (10 ml) to give a solid. After stirring for one hour, the solid is removed by filtration and dried to give a cream colored solid (6.1 g, 60!) mp 160-161°C.
Ved analyse oppnås følgende: By analysis, the following is achieved:
Beregnet for C14H17C1N204: C, 53,75, H, 5,48, N, 8,96, Cl, 11,34 Calculated for C14H17C1N2O4: C, 53.75, H, 5.48, N, 8.96, Cl, 11.34
Funnet: C, 54,0, H, 5,40, N, 8,90, Cl, 11,48. Found: C, 54.0, H, 5.40, N, 8.90, Cl, 11.48.
Som angitt i tabell IV nedenfor fremstilles mange eksempler på perklorater som fremstilles ifølge fremgangsmåten i eksempel 3 ovenfor ved å anvende passende ren, teknisk eller rå 1,2-dimetyl-3,5-substituert pyrazolium-metylsulfatsalt som start-materiale med strukturen: As indicated in Table IV below, many examples of perchlorates are prepared according to the method of Example 3 above by using the appropriate pure, technical or crude 1,2-dimethyl-3,5-substituted pyrazolium methyl sulfate salt as starting material with the structure:
Eksempel 4 Example 4
Fremstilling av 5- cyklopropyl- l, 2- dimetyl- 3- fenylpyrazoliumjodid. Preparation of 5-cyclopropyl-1,2-dimethyl-3-phenylpyrazolium iodide.
En løsning av 5-cyklopropyl-l,2-dimetyl-3-fenylpyra-zoliummetylsulfat (12,3 g) oppløst i vann (100 ml) ekstraheres med eter. Det vandige skiktet avskilles og behandles med en mettet vandig løsning av kaliumjodid. Etter omrøring i 0,5 time avskilles det faste stoffet ved filtrering og tørkes foiyå gi et strå-farget fast stoff (4,7 g, 36!) med smeltepunkt 150-152°C. Ved analyse noteres følgende: A solution of 5-cyclopropyl-1,2-dimethyl-3-phenylpyrazolium methyl sulfate (12.3 g) dissolved in water (100 ml) is extracted with ether. The aqueous layer is separated and treated with a saturated aqueous solution of potassium iodide. After stirring for 0.5 hour, the solid is separated by filtration and dried to give a straw-colored solid (4.7 g, 36!) with a melting point of 150-152°C. During analysis, the following is noted:
Beregnet for C14H17N2I: C, 49,42, H, 5,04, N, 8,24 Calculated for C14H17N2I: C, 49.42, H, 5.04, N, 8.24
Funnet : C ,49,07, H, 5,06, N, 8,16. Found: C, 49.07, H, 5.06, N, 8.16.
Illustrerende jodider i tabell V nedenfor fremstilles ved fremgangsmåten som beskrevet ovenfor i eksempel 4 ved å erstatte 5-cyklopropyl-l,2-dimetyl-3-fenyl-pyrazolium-metylsulfat med et passende pyrazolium-metylsulfatsalt med strukturene: Illustrative iodides in Table V below are prepared by the method described above in Example 4 by replacing 5-cyclopropyl-1,2-dimethyl-3-phenyl-pyrazolium methyl sulfate with an appropriate pyrazolium methyl sulfate salt with the structures:
Den selektive etterspiringsherbicide aktiviteten for forbindelsene ifølge oppfinnelsen demonstreres med følgende tester hvor forskjellige en- og tofrøbladede planter behandles med testforbindelsene dispergert i vandige acetonblandinger. I testene dyr-kes frøplantene i jiffyplater i ca. to uker. Testforbindelsene dispergeres i 50/50 aceton/vann-blandinger inneholdende 0,51 av et polyoksyetylensorbitanmonolaurat overflateaktivt middel tilstrekkelig mengde til å gi ca. 0,056 til 0,45 g/m av aktiv forbindelse når de påføres plantene gjennom en spraydyse som arbeider med 2,8 kg/cm trykk i en på forhånd bestemt tid. Etter spraying plasseres plantene på drivhusbenker og behandles på vanlig måte. Fem uker etter behandlingen undersøkes frøplantene og graderes etter det nedenfor anførte graderingssystem. De oppnådde data er gjengitt i tabellene VI og VII nedenfor, hvor det kan sees at forbindelsene er meget effektive for bekjempelse av mange bredbladede ugressplanter og uønskede gressplanter. The selective post-emergence herbicidal activity of the compounds according to the invention is demonstrated with the following tests where different monocotyledonous and dicotyledonous plants are treated with the test compounds dispersed in aqueous acetone mixtures. In the tests, the seedlings are grown in jiffy plates for approx. two weeks. The test compounds are dispersed in 50/50 acetone/water mixtures containing 0.51 of a polyoxyethylene sorbitan monolaurate surfactant sufficient to give approx. 0.056 to 0.45 g/m of active compound when applied to the plants through a spray nozzle operating at 2.8 kg/cm pressure for a predetermined time. After spraying, the plants are placed on greenhouse benches and treated in the usual way. Five weeks after the treatment, the seedlings are examined and graded according to the grading system listed below. The data obtained are reproduced in Tables VI and VII below, where it can be seen that the compounds are very effective in controlling many broadleaf weeds and unwanted grass plants.
Plantenavns forkortelse: Plant name abbreviation:
MU - Sennep ( Brassica kaber) MU - Mustard (Brassica kaber)
PI - Perumelde ( Amaranthus retroflexus) BA - Hønsehirse ( Echinochloa crusgalli) CR - Fingerhirse ( Digitaria sanguinalis) WO - Floghavre (Avena fatua) PI - Sweet millet ( Amaranthus retroflexus) BA - Chickpea millet ( Echinochloa crusgalli) CR - Finger millet ( Digitaria sanguinalis) WO - Oats (Avena fatua)
WH - Hvete ( Tritisum aestivum) WH - Wheat ( Tritisum aestivum)
MG - Ormevindel ( Ipomoea purpurea) MG - Wormwort (Ipomoea purpurea)
Bygg " ( Hordeum vulgare) Barley" (Hordeum vulgare)
VL - "Velvetleaf" ( Abutilon theophrasti) FO - Grønn busthirse ( Setaria viridis) RI - Ris ( Oryza sativa) VL - "Velvetleaf" ( Abutilon theophrasti) FO - Green bush millet ( Setaria viridis) RI - Rice ( Oryza sativa)
Førspiringsaktiviteten for forbindelsene ifølge oppfinnelsen demonstreres ved følgende tester hvor en 50/50 aceton/vann-blanding inneholdende 0,5 volum! av et overflateaktivt middel be-stående av polyoksyetylensorbitanmonolaurat og tilstrekkelig test-forbindelse til å gi 1,12 g/m 2 av nevnte forbindelse når blandingen påføres potter som det er sådd frø av testplanteartene i. The pre-germination activity of the compounds according to the invention is demonstrated by the following tests where a 50/50 acetone/water mixture containing 0.5 volume! of a surface-active agent consisting of polyoxyethylene sorbitan monolaurate and sufficient test compound to give 1.12 g/m 2 of said compound when the mixture is applied to pots in which seeds of the test plant species have been sown.
Pottene prepareres samme dag de herbicidbehandles ved The pots are prepared on the same day they are treated with herbicide
å helle 100 ml jord i hver plastpotte som basis, så plasseres frø to pour 100 ml of soil into each plastic pot as a base, then place seeds
av ormevindel, tomat, floghavre og "nutsedge" på denne basis og de dekkes med 50 ml jord (1,0 til 1,3 cm). Frø av hver av de andre 8 planteartene som er angitt nedenfor blandes separat med jord og 50 ml av jord-frøblandingen tilsettes til potten. Pottene stampes så for å jevne jorden og jorden forhåndsfuktes med vann før herbi-cidpåføringen. Denne forhåndsfukting sikrer at herbicidbehandlings-løsningen spres jevnt over pottens overflate og beskytter ugressfrø-ene fra å bli skadet av aceton. Hver av de 12 ugressartene inneholdes i en separat potte. Pottene plasseres så på 25,4x30,5cm store pla-ter før kjemisk behandling. of wormwood, tomato, field oats and nutsedge on this basis and they are covered with 50 ml of soil (1.0 to 1.3 cm). Seeds of each of the other 8 plant species listed below are mixed separately with soil and 50 ml of the soil-seed mixture is added to the pot. The pots are then tamped to level the soil and the soil is pre-moistened with water before the herbicide application. This pre-moistening ensures that the herbicide treatment solution is spread evenly over the surface of the pot and protects the weed seeds from being damaged by acetone. Each of the 12 weed species is contained in a separate pot. The pots are then placed on 25.4x30.5cm plates before chemical treatment.
De utsådde pottene behandles med 5 ml av testløsningen og plasseres så på benker i drivhuset. Pottene vannes etter behandlingen og holdes i drivhuset i tre uker. Resultatene av behandlingen nedtegnes så og verdiene er angitt i tabell VIII. The sown pots are treated with 5 ml of the test solution and then placed on benches in the greenhouse. The pots are watered after treatment and kept in the greenhouse for three weeks. The results of the treatment are then recorded and the values are given in Table VIII.
Plantearter som anvendes ved bestemmelse av herbicidets virkning før spiring. Plant species used to determine the effect of the herbicide before germination.
Graderingssytemet som anvendes i disse tester er det samme som er beskrevet i eksempel 7 ovenfor. The grading system used in these tests is the same as described in example 7 above.
Claims (2)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US39978473A | 1973-09-21 | 1973-09-21 | |
US399785A US3907825A (en) | 1973-09-21 | 1973-09-21 | 1,2-Dialkyl-3,5-disubstituted pyrazolium salts and the use thereof as herbicidal agents |
US399655A US3929451A (en) | 1973-09-21 | 1973-09-21 | Pre-emergence 1,2-dialkyl-3,5-disubstituted herbicidal compounds and method for using same |
Publications (3)
Publication Number | Publication Date |
---|---|
NO743388L NO743388L (en) | 1975-04-14 |
NO140979B true NO140979B (en) | 1979-09-10 |
NO140979C NO140979C (en) | 1979-12-19 |
Family
ID=27410350
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
NO743388A NO140979C (en) | 1973-09-21 | 1974-09-20 | PYRAZOLE DERIVATIVES WITH HERBICID ACTIVITY |
Country Status (23)
Country | Link |
---|---|
JP (1) | JPS6029681B2 (en) |
AR (1) | AR226406A1 (en) |
BG (1) | BG24952A3 (en) |
BR (1) | BR7407854D0 (en) |
CA (1) | CA1037958A (en) |
CH (1) | CH596186A5 (en) |
CS (1) | CS188926B2 (en) |
DD (1) | DD116744A5 (en) |
DE (1) | DE2441498C2 (en) |
DK (1) | DK139771B (en) |
ES (1) | ES430278A1 (en) |
FI (1) | FI58120C (en) |
FR (1) | FR2278686A1 (en) |
GB (1) | GB1435639A (en) |
HU (1) | HU170660B (en) |
IE (1) | IE40743B1 (en) |
IL (1) | IL45377A (en) |
IT (1) | IT1050243B (en) |
NL (1) | NL7412302A (en) |
NO (1) | NO140979C (en) |
RO (1) | RO64924A (en) |
SE (1) | SE416549B (en) |
TR (1) | TR18379A (en) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5531050U (en) * | 1978-08-23 | 1980-02-28 | ||
JPS5543704A (en) * | 1978-09-20 | 1980-03-27 | Toshiba Corp | Exposing device |
AU727325B2 (en) | 1996-02-01 | 2000-12-07 | Rhone-Poulenc Agro | Process for preparing diketone compounds |
DE19645313A1 (en) * | 1996-11-04 | 1998-05-07 | Basf Ag | Substituted 3-benzylpyrazoles |
GB9714305D0 (en) | 1997-07-07 | 1997-09-10 | Rhone Poulenc Agrochimie | Chemical process |
US6392099B1 (en) | 1998-11-19 | 2002-05-21 | Eagleview Technologies, Inc. | Method and apparatus for the preparation of ketones |
US6369276B1 (en) | 1998-11-19 | 2002-04-09 | Eagleview Technologies, Inc. | Catalyst structure for ketone production and method of making and using the same |
US6545185B1 (en) | 2001-03-29 | 2003-04-08 | Eagleview Technologies, Inc. | Preparation of ketones from aldehydes |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
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DE2260485C2 (en) * | 1971-12-17 | 1983-12-29 | American Cyanamid Co., Wayne, N.J. | 1,2-dialkyl-3,5-diphenylpyrazolium salts and herbicidal agents containing them |
-
1974
- 1974-07-31 IL IL45377A patent/IL45377A/en unknown
- 1974-08-15 GB GB3603674A patent/GB1435639A/en not_active Expired
- 1974-08-22 CA CA207,576A patent/CA1037958A/en not_active Expired
- 1974-08-22 AR AR226406A patent/AR226406A1/en active
- 1974-08-30 DE DE2441498A patent/DE2441498C2/en not_active Expired
- 1974-09-05 TR TR18379A patent/TR18379A/en unknown
- 1974-09-11 FI FI2664/74A patent/FI58120C/en active
- 1974-09-12 DD DD181066A patent/DD116744A5/xx unknown
- 1974-09-12 RO RO7479967A patent/RO64924A/en unknown
- 1974-09-17 NL NL7412302A patent/NL7412302A/en not_active Application Discontinuation
- 1974-09-19 IE IE1941/74A patent/IE40743B1/en unknown
- 1974-09-20 HU HUAE425A patent/HU170660B/hu unknown
- 1974-09-20 FR FR7431874A patent/FR2278686A1/en active Granted
- 1974-09-20 IT IT53123/74A patent/IT1050243B/en active
- 1974-09-20 NO NO743388A patent/NO140979C/en unknown
- 1974-09-20 CH CH1276074A patent/CH596186A5/xx not_active IP Right Cessation
- 1974-09-20 DK DK496574AA patent/DK139771B/en not_active IP Right Cessation
- 1974-09-20 SE SE7411889A patent/SE416549B/en not_active IP Right Cessation
- 1974-09-20 BR BR7854/74A patent/BR7407854D0/en unknown
- 1974-09-21 BG BG027748A patent/BG24952A3/en unknown
- 1974-09-21 JP JP49109427A patent/JPS6029681B2/en not_active Expired
- 1974-09-21 ES ES430278A patent/ES430278A1/en not_active Expired
- 1974-09-23 CS CS746526A patent/CS188926B2/en unknown
Also Published As
Publication number | Publication date |
---|---|
JPS6029681B2 (en) | 1985-07-12 |
RO64924A (en) | 1980-01-15 |
DD116744A5 (en) | 1975-12-12 |
FI58120C (en) | 1980-12-10 |
AR226406A1 (en) | 1982-07-15 |
FR2278686A1 (en) | 1976-02-13 |
CA1037958A (en) | 1978-09-05 |
HU170660B (en) | 1977-08-28 |
DK139771B (en) | 1979-04-17 |
NO140979C (en) | 1979-12-19 |
CS188926B2 (en) | 1979-03-30 |
SE7411889L (en) | 1975-03-24 |
FI266474A (en) | 1975-03-22 |
DE2441498C2 (en) | 1986-04-24 |
NL7412302A (en) | 1975-03-25 |
DE2441498A1 (en) | 1975-03-27 |
GB1435639A (en) | 1976-05-12 |
FI58120B (en) | 1980-08-29 |
IL45377A (en) | 1979-11-30 |
AU7187174A (en) | 1976-02-05 |
SE416549B (en) | 1981-01-19 |
TR18379A (en) | 1977-05-01 |
CH596186A5 (en) | 1978-03-15 |
JPS5076071A (en) | 1975-06-21 |
ES430278A1 (en) | 1977-02-16 |
FR2278686B1 (en) | 1978-11-03 |
IT1050243B (en) | 1981-03-10 |
DK496574A (en) | 1975-05-20 |
BR7407854D0 (en) | 1975-07-15 |
DK139771C (en) | 1979-09-24 |
NO743388L (en) | 1975-04-14 |
BG24952A3 (en) | 1978-06-15 |
IL45377A0 (en) | 1974-11-29 |
IE40743L (en) | 1975-03-21 |
IE40743B1 (en) | 1979-08-15 |
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