CN85107316A - Plant protection agents containing 1, 2, 4-triazole derivatives - Google Patents
Plant protection agents containing 1, 2, 4-triazole derivatives Download PDFInfo
- Publication number
- CN85107316A CN85107316A CN85107316.6A CN85107316A CN85107316A CN 85107316 A CN85107316 A CN 85107316A CN 85107316 A CN85107316 A CN 85107316A CN 85107316 A CN85107316 A CN 85107316A
- Authority
- CN
- China
- Prior art keywords
- alkyl
- group
- formula
- compound
- och
- 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.)
- Granted
Links
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical class C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 title 1
- 239000011814 protection agent Substances 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims abstract description 93
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 62
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 35
- -1 triazole compound Chemical class 0.000 claims abstract description 34
- 125000004414 alkyl thio group Chemical group 0.000 claims abstract description 23
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims abstract description 20
- 230000000694 effects Effects 0.000 claims abstract description 16
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 10
- 150000002367 halogens Chemical class 0.000 claims abstract description 10
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 9
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims abstract description 9
- 125000003302 alkenyloxy group Chemical group 0.000 claims abstract description 5
- 125000000000 cycloalkoxy group Chemical group 0.000 claims abstract description 5
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 5
- 125000000304 alkynyl group Chemical group 0.000 claims abstract description 4
- 125000005133 alkynyloxy group Chemical group 0.000 claims abstract 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 88
- 239000002585 base Substances 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 29
- 238000002360 preparation method Methods 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 21
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 20
- 230000014509 gene expression Effects 0.000 claims description 17
- 239000001301 oxygen Substances 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 125000003282 alkyl amino group Chemical group 0.000 claims description 13
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 11
- 239000000460 chlorine Substances 0.000 claims description 10
- 150000002148 esters Chemical class 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 8
- 239000004009 herbicide Substances 0.000 claims description 8
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 8
- 239000004476 plant protection product Substances 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 6
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical group ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 5
- 125000006310 cycloalkyl amino group Chemical group 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 claims description 4
- 125000006766 (C2-C6) alkynyloxy group Chemical group 0.000 claims description 3
- 241001136616 Methone Species 0.000 claims description 3
- 125000004457 alkyl amino carbonyl group Chemical group 0.000 claims description 3
- BADXJIPKFRBFOT-UHFFFAOYSA-N dimedone Chemical compound CC1(C)CC(=O)CC(=O)C1 BADXJIPKFRBFOT-UHFFFAOYSA-N 0.000 claims description 3
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 2
- 125000003047 N-acetyl group Chemical group 0.000 claims description 2
- 150000008064 anhydrides Chemical class 0.000 claims description 2
- 150000002923 oximes Chemical class 0.000 claims description 2
- 231100000614 poison Toxicity 0.000 claims description 2
- 230000007096 poisonous effect Effects 0.000 claims description 2
- 150000003558 thiocarbamic acid derivatives Chemical class 0.000 claims description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims 4
- 125000006700 (C1-C6) alkylthio group Chemical group 0.000 claims 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims 2
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 claims 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims 2
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 claims 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- GNVMUORYQLCPJZ-UHFFFAOYSA-M Thiocarbamate Chemical compound NC([S-])=O GNVMUORYQLCPJZ-UHFFFAOYSA-M 0.000 claims 1
- 229910052794 bromium Inorganic materials 0.000 claims 1
- 235000013399 edible fruits Nutrition 0.000 claims 1
- 150000004820 halides Chemical class 0.000 claims 1
- 125000005186 naphthyloxy group Chemical group C1(=CC=CC2=CC=CC=C12)O* 0.000 claims 1
- 125000000547 substituted alkyl group Chemical group 0.000 abstract 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 231100000208 phytotoxic Toxicity 0.000 abstract 1
- 230000000885 phytotoxic effect Effects 0.000 abstract 1
- 125000005415 substituted alkoxy group Chemical group 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 39
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 36
- 239000000203 mixture Substances 0.000 description 33
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 32
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 16
- 239000000047 product Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 14
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical class N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 description 13
- 241000196324 Embryophyta Species 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 12
- 238000002425 crystallisation Methods 0.000 description 11
- 230000008025 crystallization Effects 0.000 description 11
- 238000000967 suction filtration Methods 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 239000003643 water by type Substances 0.000 description 10
- 230000002363 herbicidal effect Effects 0.000 description 9
- 238000001953 recrystallisation Methods 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical class Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 8
- 241000209140 Triticum Species 0.000 description 7
- 235000021307 Triticum Nutrition 0.000 description 7
- 150000001263 acyl chlorides Chemical class 0.000 description 7
- 229940017219 methyl propionate Drugs 0.000 description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 229960000583 acetic acid Drugs 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- QIIPQYDSKRYMFG-UHFFFAOYSA-N phenyl hydrogen carbonate Chemical compound OC(=O)OC1=CC=CC=C1 QIIPQYDSKRYMFG-UHFFFAOYSA-N 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000004563 wettable powder Substances 0.000 description 6
- 239000012141 concentrate Substances 0.000 description 5
- 238000007046 ethoxylation reaction Methods 0.000 description 5
- 235000011167 hydrochloric acid Nutrition 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 241000233866 Fungi Species 0.000 description 4
- 240000005979 Hordeum vulgare Species 0.000 description 4
- 235000007340 Hordeum vulgare Nutrition 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
- 239000003995 emulsifying agent Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000008635 plant growth Effects 0.000 description 4
- 229920000151 polyglycol Polymers 0.000 description 4
- 239000010695 polyglycol Substances 0.000 description 4
- RZMGZEJEAAVXRG-UHFFFAOYSA-N 1,2-dihydrotriazole-3-carboxylic acid Chemical compound N1NN(C=C1)C(=O)O RZMGZEJEAAVXRG-UHFFFAOYSA-N 0.000 description 3
- 244000075850 Avena orientalis Species 0.000 description 3
- 235000007319 Avena orientalis Nutrition 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 239000007900 aqueous suspension Substances 0.000 description 3
- 235000013339 cereals Nutrition 0.000 description 3
- 150000001805 chlorine compounds Chemical class 0.000 description 3
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 239000012954 diazonium Substances 0.000 description 3
- 150000001989 diazonium salts Chemical class 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- DBPFRRFGLYGEJI-UHFFFAOYSA-N ethyl glyoxylate Chemical compound CCOC(=O)C=O DBPFRRFGLYGEJI-UHFFFAOYSA-N 0.000 description 3
- 150000002191 fatty alcohols Chemical class 0.000 description 3
- 150000002632 lipids Chemical class 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical class [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- ZEMPKEQAKRGZGQ-AAKVHIHISA-N 2,3-bis[[(z)-12-hydroxyoctadec-9-enoyl]oxy]propyl (z)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCCC(O)C\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CC(O)CCCCCC)COC(=O)CCCCCCC\C=C/CC(O)CCCCCC ZEMPKEQAKRGZGQ-AAKVHIHISA-N 0.000 description 2
- PMZBHPUNQNKBOA-UHFFFAOYSA-N 5-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=CC(C(O)=O)=CC(C(O)=O)=C1 PMZBHPUNQNKBOA-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 235000007320 Avena fatua Nutrition 0.000 description 2
- 241000209764 Avena fatua Species 0.000 description 2
- 125000003601 C2-C6 alkynyl group Chemical group 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- NRYUZBBCZQDOLH-UHFFFAOYSA-N ClC(C1=NC(=NN1)C(=O)O)(Cl)Cl Chemical compound ClC(C1=NC(=NN1)C(=O)O)(Cl)Cl NRYUZBBCZQDOLH-UHFFFAOYSA-N 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical class [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- ODFJOVXVLFUVNQ-UHFFFAOYSA-N acetarsol Chemical compound CC(=O)NC1=CC([As](O)(O)=O)=CC=C1O ODFJOVXVLFUVNQ-UHFFFAOYSA-N 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- HCWYXKWQOMTBKY-UHFFFAOYSA-N calcium;dodecyl benzenesulfonate Chemical compound [Ca].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 HCWYXKWQOMTBKY-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
- 238000007796 conventional method Methods 0.000 description 2
- 125000000118 dimethyl group Chemical class [H]C([H])([H])* 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 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 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 150000002905 orthoesters Chemical class 0.000 description 2
- 235000011091 sodium acetates Nutrition 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000600 sorbitol Substances 0.000 description 2
- 238000009331 sowing Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000006188 syrup Substances 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 235000012222 talc Nutrition 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 1
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 description 1
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 1
- KQCMTOWTPBNWDB-UHFFFAOYSA-N 2,4-dichloroaniline Chemical compound NC1=CC=C(Cl)C=C1Cl KQCMTOWTPBNWDB-UHFFFAOYSA-N 0.000 description 1
- RFVNOJDQRGSOEL-UHFFFAOYSA-N 2-hydroxyethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCO RFVNOJDQRGSOEL-UHFFFAOYSA-N 0.000 description 1
- JJKWHOSQTYYFAE-UHFFFAOYSA-N 2-methoxyacetyl chloride Chemical class COCC(Cl)=O JJKWHOSQTYYFAE-UHFFFAOYSA-N 0.000 description 1
- MSBVBOUOMVTWKE-UHFFFAOYSA-N 2-naphthalen-2-ylnaphthalene Chemical group C1=CC=CC2=CC(C3=CC4=CC=CC=C4C=C3)=CC=C21 MSBVBOUOMVTWKE-UHFFFAOYSA-N 0.000 description 1
- 241000743985 Alopecurus Species 0.000 description 1
- 235000007558 Avena sp Nutrition 0.000 description 1
- KHBQMWCZKVMBLN-UHFFFAOYSA-N Benzenesulfonamide Chemical compound NS(=O)(=O)C1=CC=CC=C1 KHBQMWCZKVMBLN-UHFFFAOYSA-N 0.000 description 1
- 235000016068 Berberis vulgaris Nutrition 0.000 description 1
- 241000335053 Beta vulgaris Species 0.000 description 1
- 241001465180 Botrytis Species 0.000 description 1
- DDZXSPPZDIJNIA-UHFFFAOYSA-N C1=CC=CC2=[S]C(=O)N=C21 Chemical compound C1=CC=CC2=[S]C(=O)N=C21 DDZXSPPZDIJNIA-UHFFFAOYSA-N 0.000 description 1
- RNWSGTDZTJYKTJ-UHFFFAOYSA-N COC(=O)C1C(C=C(CC1(C)C)O)=O Chemical compound COC(=O)C1C(C=C(CC1(C)C)O)=O RNWSGTDZTJYKTJ-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241000771760 Coniosporium <Dothideomycetes incertae sedis> Species 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 241000221785 Erysiphales Species 0.000 description 1
- IYXGSMUGOJNHAZ-UHFFFAOYSA-N Ethyl malonate Chemical compound CCOC(=O)CC(=O)OCC IYXGSMUGOJNHAZ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- PQKBPHSEKWERTG-UHFFFAOYSA-N Fenoxaprop ethyl Chemical group C1=CC(OC(C)C(=O)OCC)=CC=C1OC1=NC2=CC=C(Cl)C=C2O1 PQKBPHSEKWERTG-UHFFFAOYSA-N 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- HHLFWLYXYJOTON-UHFFFAOYSA-N Glyoxylic acid Natural products OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 1
- 244000299507 Gossypium hirsutum Species 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 241000233614 Phytophthora Species 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 241000221535 Pucciniales Species 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 241000209056 Secale Species 0.000 description 1
- 235000007238 Secale cereale Nutrition 0.000 description 1
- 244000046109 Sorghum vulgare var. nervosum Species 0.000 description 1
- 244000098338 Triticum aestivum Species 0.000 description 1
- 241000317942 Venturia <ichneumonid wasp> Species 0.000 description 1
- 241000228452 Venturia inaequalis Species 0.000 description 1
- 208000027418 Wounds and injury Diseases 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
- 239000003377 acid catalyst Substances 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000004647 alkyl sulfenyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 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
- CIZVQWNPBGYCGK-UHFFFAOYSA-N benzenediazonium Chemical class N#[N+]C1=CC=CC=C1 CIZVQWNPBGYCGK-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001784 detoxification Methods 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
- FBCCMZVIWNDFMO-UHFFFAOYSA-N dichloroacetyl chloride Chemical compound ClC(Cl)C(Cl)=O FBCCMZVIWNDFMO-UHFFFAOYSA-N 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- OAMZXMDZZWGPMH-UHFFFAOYSA-N ethyl acetate;toluene Chemical compound CCOC(C)=O.CC1=CC=CC=C1 OAMZXMDZZWGPMH-UHFFFAOYSA-N 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 235000012907 honey Nutrition 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 230000003902 lesion Effects 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229950007687 macrogol ester Drugs 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- BACHBFVBHLGWSL-UHFFFAOYSA-N methyl 2-[4-(2,4-dichlorophenoxy)phenoxy]propanoate Chemical group C1=CC(OC(C)C(=O)OC)=CC=C1OC1=CC=C(Cl)C=C1Cl BACHBFVBHLGWSL-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012875 nonionic emulsifier Substances 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- BGRYSGVIVVUJHH-UHFFFAOYSA-N prop-2-ynyl propanoate Chemical compound CCC(=O)OCC#C BGRYSGVIVVUJHH-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229910052903 pyrophyllite Inorganic materials 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- WIJLMWQGTVECEM-UHFFFAOYSA-N quinoxalin-2-one Chemical compound C1=C[CH]C2=NC(=O)C=NC2=C1 WIJLMWQGTVECEM-UHFFFAOYSA-N 0.000 description 1
- BACHBFVBHLGWSL-JTQLQIEISA-N rac-diclofop methyl Natural products C1=CC(O[C@@H](C)C(=O)OC)=CC=C1OC1=CC=C(Cl)C=C1Cl BACHBFVBHLGWSL-JTQLQIEISA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- KZOJQMWTKJDSQJ-UHFFFAOYSA-M sodium;2,3-dibutylnaphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S([O-])(=O)=O)=C(CCCC)C(CCCC)=CC2=C1 KZOJQMWTKJDSQJ-UHFFFAOYSA-M 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 150000003613 toluenes Chemical class 0.000 description 1
- 229940087291 tridecyl alcohol Drugs 0.000 description 1
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical class COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 description 1
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
A process for preparing a plant protectant of formula I comprising a triazole compound of formula I or a salt thereof, and an inert carrier. Compounds of the formula I in which Z is halogen, nitro, cyano, trifluoromethyl, optionally substituted alkyl, alkoxy, alkylthio, cycloalkyl, phenyl or substituted phenoxy, Y is H, optionally substituted alkyl, alkanyl, alkynyl or cycloalkyl, N is 0, 1, 2 or 3, X is hydroxy, alkyl, cycloalkoxy, phenoxy, alkenyloxy, alkynyloxy, optionally substituted alkoxy and alkylthio or a radical of the formula are suitable for protecting crops from phytotoxic side effects of phytoherbicides.
Description
The present invention has narrated the method for preparing plant protection product, and this plant protection product contains triazole compounds or its salt (when X=OH) of formula 1, and the composition that they can be used as plant protection product is used for agricultural.
Z or identical wherein, perhaps inequality, it represents halogen, nitro, cyano group, trifluoromethyl, alkyl (C1-C4), alkoxyl group (C1-C4) or alkyl sulfenyl (C1-C4), alkyl wherein, alkoxyl group and alkylthio can be replaced by one or more halogen atoms, are particularly replaced by fluorine or chlorine, and Z also represents can be by the cycloalkyl of (C3-C6) of the alkyl of (C1-C4) replacement, or phenyl, phenoxy group, wherein phenyl and phenoxy group can be by halogen lists or polysubstituted, and/or replaced by the trifluoromethyl list;
Y represents hydrogen, can be by the alkyl of (C1-C4) of all or part of replacement of halogen atom, and/or by the alkyl of (C1-C4) of the alkoxyl group of (C1-C4) or the replacement of alkylthio (C1-C4), or alkenyl (C2-C6), (C2-C6) alkynyl, perhaps expression can be by the cycloalkyl of (C3-C6) of the alkyl of (C1-C4) and/or dichloroethylene replacement;
X represents hydroxyl, (C1-C4) alkyl, (C3-C6) cycloalkyloxy, the alkoxyl group of phenyl-(C1-C6), phenoxy group, (C2-C6) alkenyloxy, (C2-C6) alkynyloxy group, (C1-C6) alkoxyl group or alkylthio (C1-C6), wherein alkoxyl group or alkylthio can be by the alkoxyl groups of (C1-C2), alkyl amino-carbonyl singly-(C1-C4), two-[alkyl (C1-C4)] aminocarboxyls, the phenyl amino carbonyl, N-[(C1-C4) alkyl]-N-phenyl-aminocarboxyl, alkylamino singly-(C1-C6), two-(C1-C6) alkylamino, [alkyl (C1-C6)] ketonic oxygen base, (C1-C2) alkylthio, cyano group or fontanel are plain to be replaced, and X also can be the group that is expressed from the next:
Wherein R represents hydrogen or alkyl (C1-C4), perhaps expression single-(C1-C4) alkylamino, two-(C1-C4) alkylamino, cycloalkyl amino (C5-C6), piperidino-(1-position only), morpholino, 2,6-thebaine generation or have formula
Group, R wherein
1And R
2Can be identical or different, the alkyl of their expressions (C1-C4), R
1And R
2Also can form a five-ring alkyl jointly, six-ring alkyl or seven-membered ring alkyl; N represents numeral 0,1,2 or 3.
The example of suitable salt has metal-salt, as basic metal or alkaline earth salt, particularly sodium salt and sylvite, and ammonium salt, list-, two-, three-or four-(C1-C4) alkylammonium salt, single-, two-, three-or the alkanol ammonium salts of four (C1-C4).
Formula I compound is that Y represents by F preferably, the alkyl of (C1-C2) of Cl or all or part of replacement of Br; Z can be identical or different, and Z can represent the fontanel element, (C1-C4) alkoxyl group, alkyl (C1-C4) or CF
3;
X represents the alkoxyl group or the hydroxyl of (C1-C6);
N represents 1,2, or 3.
Good especially representative is that wherein Y is CCl in these compounds
3, CHCl
2, CHF
2CF
2Or CH
3Compound.
Unexpectedly, these compounds of formula I can reduce or eliminate fully the toxic side effect of plant herbicide to crop effectively.Such compound is also referred to as toxicide or safener (safen-ers).
From the science publication [Chem.Ber.94 1868(1961), Chem.Ber.96 3210(1963) and Chem.Ber.98 642(1965)] and German Patent 1,123,321 in can recognize that segment bounds I compound is a known compound.But these documents all do not disclose the detoxification of these compounds.
Most of formula I compound is new, does not promptly report in the past.They are following formula I compound:
Wherein Z can be identical or different, its expression fontanel element, nitro, cyano group, trifluoromethyl, alkyl (C1-C4), alkoxyl group (C1-C4) or (C1-C4) alkylthio, alkyl wherein, alkoxyl group and alkylthio can be replaced by one or more fontanelle atoms (particularly fluorine or chlorine), and Z also can represent by the cycloalkyl of (C3-C6) of the alkyl of (C1-C4) replacement, phenyl or phenoxy group, wherein phenyl and phenoxy group can be undertaken singly or polysubstituted by the fontanel element, and/or are replaced by the trifluoromethyl list;
Y represents hydrogen, can be by all or part of replacement of fontanelle atom and/or by the alkoxyl group of (C1-C4) or the alkyl of alkylthio (C1-C4) mono-substituted (C1-C4) or alkenyl (C2-C6), (C2-C6) alkynyl, or expression can be by the cycloalkyl of (C3-C6) of the alkyl of (C1-C4) and/or dichloroethylene replacement;
X represents hydroxyl, (C1-C4) alkyl, (C3-C6) cycloalkyloxy, the alkoxyl group of phenyl-(C1-C6), phenoxy group, (C2-C6) alkenyloxy, (C2-C6) alkynyloxy group, alkoxyl group (C1-C6) or alkylthio (C1-C6), wherein alkoxyl group or alkylthio can be by the alkoxyl groups of (C1-C2), alkyl amino-carbonyl singly-(C1-C4), two [alkyl (C1-C4)] aminocarboxyl, phenyl amino carbonyl, alkyl N-[(C1-C4)]-N-phenyl-aminocarboxyl, alkylamino singly-(C1-C6), two-(C1-C6) alkylamino, [alkyl (C1-C6)] ketonic oxygen base, alkylthio (C1-C2), cyano group or fontanel are plain to be replaced, and perhaps X represents to have the group of following formula:
Wherein R represents hydrogen, and alkyl (C1-C4) is or single-(C1-C4) alkylamino, two-(C1-C4) alkylamino, cycloalkyl amino (C5-C6), piperidino-(1-position only), morpholino, 2,6-thebaine generation or have formula
Group, R wherein
1And R
2Can be identical or different, the alkyl of their expressions (C1-C4), R
1And R
2Also can form the five-ring alkyl jointly, six-ring alkyl or seven-membered ring alkyl;
N represents numeral 0,1,2 or 3.If X=OH, the salt of formula I also can be used for agricultural so, if X=(C1-C4) alkyl, Y is necessary for CCl so
3Or CHCl
2, except the following formula I compound, wherein
A) Y represents H, and (Z) n represents H, 4-Cl, 4-CH
3, 2-OCH
3, 4-OCH
3Or 4-OC
2H
5, X represents OH, OCH
3Or OC
2H
5;
B) Y represents CH
3, (Z)
nExpression 4-NO
2, 4-OCH
3, 2-Cl, 4-Cl, 2-OCH
3-4-NO
2Or 2-CH
3-4-NO
2, X represents OH or OC
2H
5;
C) Y represents C
2H
5Or CH(CH
3)
2, (Z) n represents H, X represents OCH
3
The method of preparation formula I new compound and salt thereof comprises:
A) with formula II compound:
(X wherein
1Identical with the implication of X, but can not be hydroxyl) with
A1) formula is the compound reaction of Y-CO-Cl; Or with
A2) formula is the anhydride reaction of Y-CO-O-CO-Y; Or with
A3) formula is Y-C(OR
1)
3Ortho ester reaction, R wherein
1The alkyl of expression (C1-C4), perhaps
B) for the compound of preparation Y=H or alkyl (C1-C4), with formula III compound:
With alkali reaction, Y wherein
1Expression H or alkyl (C1-C4), R
3The alkoxyl group or the CH of expression (C1-C4)
3
Heating is at a1) and the compound that a2) obtains under the situation, if suitable words heat in acetic acid.When needing,, the formula I compound that obtains is changed into other compound of formula I by generating the method for derivative.
Unexpectedly, at a1) and a2) in two kinds of methods, be added to acyl chlorides or acid anhydrides on the free amino after, often can observe the direct ring formation of two steps reaction at once, obtain formula I compound.Unexpected also have, at a1) method in, reaction is to take place under the situation that does not add alkali.On the contrary, add alkali and then generate arborescens product (normally will add alkali in other cases).
Formula II compound and acid anhydrides, the reaction of acyl chlorides (YCOCl) or ortho ester is preferably in the organic solvent of inert, no proton and carries out.During with acid anhydrides or ortho ester reaction (method a2 or a3), agents useful for same itself also can be used as solvent.A3) method is particularly carried out in the presence of organic acid (for example right-toluenesulphonic acids) preferably at acid catalyst.
A1), a2) and a3) in the method, suitable inert solvent is best with aromatics especially, for example benzene, toluene, dimethylbenzene and chlorobenzene perhaps are cyclic ether compounds, and for example tetrahydrofuran (THF) is with diox, or ketone compounds, acetone for example, and dipolar, aprotonic solvent, for example dimethyl formamide.According to solvent, temperature of reaction can change between 10 ℃ and reaction mixture boiling point.If a1) use aromatic solvent in the method, then after adding acyl chlorides, the water of generation is removed by water separator under reflux temperature.At a1) or a2) in the method,, under several situations, at first generate intermediate product with formula IV according to (Z) n in the formula II compound and X group:
This product can be separated under certain condition.When using described solvent, if reaction stops at this stage, then subsequent reactions must carry out in acetic acid.About 50 ℃ between the reflux temperature, heating intermediate product IV can be finished this reaction in acetic acid.This subsequent reactions can carry out in a retort, adds before the acetic acid, and the organic solvent distillation that will use the fs is shifted out.
The method b of preparation), substantially with Chem.Ber.96 3120(1963) described method is identical.The mineral alkali that adopts, preferably sodium hydroxide or potassium hydroxide.As described in above-mentioned document,, can make the compound of formula III with kharophen malonic ester or kharophen etheric acid ester cpds and diazonium salt reaction.
According to the reaction of generation derivative commonly used, the above-mentioned formula I compound that obtains can be changed the derivative of accepted way of doing sth I compound.Therefore, the ester of formula I compound is hydrolyzed with acid or alkali, can accesses the formula I compound of X=OH.Adopt usual method, acid of formula I (X=OH) and suitable alkali reaction can access the salt of formula I compound.Adopt usual method, for example make the ester of formula I compound at first generate corresponding acyl chlorides, can obtain other ester class or amides of formula I.
The preparation method of formula II compound is known basically.α-chlorine hydrazone with the formula V:
Can access formula II compound with ammonia react.And phenyl diazonium salt and α-fontanel are reacted for acetylacetic ester or α-fontanel generation-beta-diketon, can preparation formula V compound.J.Chem.Soc.87 1859(1905) and Ber.d.dt.Chem.Ges.50 1482(1917) in this two reactions have been described.
Formula I compound is applicable to that mainly cover crop exempts from the toxic side effect of weedicide.
Formula I compound can use with other weedicide; simultaneously can resist or remove fully the harmful side effect of these weedicides; and not weakening the herbicide action of these weedicides to weeds, this just might further enlarge the use field of plant protection product commonly used.
From the european patent application of having announced 31,938, known safener (Safeners), but these safeners all there is unsuitable effect for phenoxy group phenoxy carboxylic acid ester herbicide.
Formula I compound can reduce the toxic side effect of following weedicide: amino formate; Thiolcarbamates; N-acetyl fontanel phenyl amines; The phenoxy carboxylic acid derivative, naphthyloxy carboxylic acid derivative and the phenoxy group phenoxy carboxylic acid derivative that replace; Heteroaryloxy phenoxy carboxylic acid derivative, quinolyl oxygen base for example, quinoxalinyl oxygen base, pyridyl oxygen base, benzoxazolyl oxygen base, benzothiazolyl oxygen base-phenoxy carboxylic acid ester class and methone 9 oxime derivate.In these compounds, phenoxy group phenoxy carboxylic acid ester class and heteroaryl oxygen phenoxyl carboxylic acid esters are better, and the ester class that is particularly suitable for this respect is low alkyl, alkenyl and alkynyl ester class.
Weedicide cited below is an example, does not plan to limit the kind of weedicide here.
A) alkyl (C1-C4), alkenyl (C2-C4) and (C3-C4) alkynyl phenoxy group phenoxy carboxylic acid ester class and heteroaryl oxygen phenoxyl carboxylic ester type weedicide, for example
2-(4-(2, the 4-dichlorophenoxy)-phenoxy group)-methyl propionate,
2-(4-(4-bromo-2-chlorophenoxy)-phenoxy group)-methyl propionate,
The 2-(4-(4-4-trifluoromethylphenopendant)-phenoxy group)-methyl propionate,
2-(4-(2-chloro-4-4-trifluoromethylphenopendant)-phenoxy group)-methyl propionate,
2-(4-(2, the 4-dichloro benzyl)-phenoxy group)-methyl propionate,
The 4-(4-(4-4-trifluoromethylphenopendant)-phenoxy group)-amylene-[2]-ethyl ester,
2-(4-(3,5-dichloropyridine-2-base oxygen base)-phenoxy group)-ethyl propionate,
2-(4-(3,5-dichloropyridine-2-base oxygen base)-phenoxy group) the propionic acid propargyl ester,
2-(4-(6-Lv benzoxazole-2-base oxygen base)-phenoxy group)-ethyl propionate,
2-(4-(6-chloro benzothiazole-2-base oxygen base)-phenoxy group)-ethyl propionate,
2-(4-(3-chloro-5-trifluoromethyl-2-pyridyl oxygen base)-phenoxy group)-methyl propionate,
2-(4-(5-trifluoromethyl-2-pyridyl oxygen base)-phenoxy group)-butyl propionate,
2-(4-(6-chloro-2-quinoxalinyl oxygen base)-phenoxy group)-ethyl propionate,
2-(4-(6-fluoro-2-quinoxalinyl oxygen base)-phenoxy group)-ethyl propionate,
2-(4-(6-chloro-2-quinolyl oxygen base)-phenoxy group)-ethyl propionate,
B) acetochloroanilide weedicide, for example
N-methoxymethyl-2,6-diethyl-acetochloroanilide,
N-(3 '-methoxy-propyl-2 ')-methyl-6-ethyl-acetochloroanilide,
The N-(3-methyl isophthalic acid, 2,4-oxadiazole-5-ylmethyl)-monochloroacetic acid 2, the 6-xylidine;
C) thiocarbamates, for example
N, N-dipropyl thiocarbamate S-ethyl ester or
N, N-diisobutyl thiocarbamate S-ethyl ester;
D) methone derivatives class, for example
2-(N-oxyethyl group butyryl imino-)-5-(2-ethylenebis dithiocarbamate propyl group)-3-hydroxyl-2-tetrahydrobenzene-1-ketone,
2-(N-oxyethyl group butyryl imino-)-5-(2-phenyl sulfo-propyl group)-3-hydroxyl-2-tetrahydrobenzene-1-ketone, perhaps
2-(1-allyloxy imino-butyl)-and 4-methoxycarbonyl-5,5-dimethyl-3-oxo cyclohexenol.
The ratio of safener and weedicide can change in 1: 10 to 10: 1 wide region, and especially Chang Yong scope is between 2: 1 to 1: 10.In particular case, the optimum amount of weedicide and safener depends on the kind of used weedicide and safener, and the pending properties of doing, and can determine this amount according to various different situations by suitable test.
Safener is mainly used in cereal crop (wheat, rye, barley or oat), rice, corn, Chinese sorghum, and cotton, beet, sugarcane and soybean.According to the character of safener, safener formula I can be used for the pre-treatment (seed dressing) of crop seed, perhaps before sowing safener is put into kind of a sub-trenches, perhaps uses with weedicide before crop germinates or after germinateing.Processing before germinateing comprises the processing of cultural area prior to seeding and has sowed but the plant processing of unerupted cultural area still.Safener preferably uses with weedicide.The preparation of barreled mixture (tank mixtures) or finished product all can be used for this purpose.
Therefore, the present invention has also narrated cover crop, makes its method that exempts from the side effect of weedicide poisonous plant, and this method is included in uses the formula I compound of using significant quantity before or after the weedicide, or the formula I compound of significant quantity is used with weedicide.
Formula I compound has also shown the effect of sterilant, therefore can be used for going out except that phytopathogen, wheat powdery mildew fungi for example, rust fungi and phytophthora (Phytopthora) fungi, Staphlosporonites (Botrytis) fungi, Coniosporium (Piricularia) fungi or venturia inaequalis belong to (Venturia inegualis) fungi.During use, formula I compound can be mixed with pulvis with formulation adjuvant commonly used, wettable powder, and dispersion agent, missible oil etc., these preparations or use as pulvis perhaps dissolve using before or are dispersed in the solvent (water).
In addition, segment bounds I compound also has the effect of coordinate plant growth.Therefore they can influence the regulative mode of plant metabolism, can be used for selectively contained material effect in the plant is improved output, and be used for impelling dry and suppress plant-growth.
Compound of the present invention can be used for conventional formulation, makes wettable powder, missible oil, spray solution, pulvis, Drug coating, granula or microgranules.
The connotation of wettable powder is, this powder can be evenly dispersed in the water when preparation, except active compound, it also contains thinner or inert substance, if need, can add wetting agent, for example the Fatty Alcohol(C12-C14 and C12-C18) of the alkylphenol of many ethoxylations (Polyoxethylated alkylphenols), many ethoxylations (Polyoxethylated fatty alcohols), alkyl sulfonic ester or benzene sulfonamide acid esters; Dispersion agent, wooden sodium sulfonate for example, 2,2 '-dinaphthyl methane-6,6 '-sodium disulfonate, sodium dibutyl naphthalene sulfonate or oleoyl methylamino second sulphonyl sodium (Sodium oleoylmethyltauride).Its preparation can be according to a conventional method, for example grinds and mix each component.
Also can prepare missible oil, for example active compound is dissolved in the inert organic solvents (as butanols, pimelinketone, dimethyl formamide, the aromatic series of dimethyl or higher or varsol), and add one or more emulsifying agents.If active compound is a liquid, can all or part of province desolvate.Exemplify out spendable emulsifying agent below: alkyl aryl sulphonic acid calcium class, for example calcium dodecylbenzene sulphonate; Perhaps nonionic emulsifier, the for example polyoxyethylene sorbitol acid anhydride ester of the sorbitan ester of the macrogol ester of lipid acid, alkylaryl polyglycol ether, fatty alcohol polyglycol ether, propylene oxide/oxirane condensation product, alkyl polyglycol ether, lipid acid, lipid acid, or polyoxyethylene sorbitol ester.
With the solid matter (for example talcum) of active compound and pulverizing, natural clay (as kaolin, wilkinite, pyrophyllite or diatomite) mixes, and can make pulvis.
The preparation of granula is to have on adsorbing, the lightweight granular inert material by active compound is atomised to, perhaps with the concentrate of active compound with tackiness agent (polyvinyl alcohol for example, sodium polyacrylate or mineral oil) be bonded to the surface of carrier (for example sand, kaolin or sticking shape inert material).When making the mixture with fertilizer if desired, suitable active compound also can be granulated according to the ordinary method of producing fertiliser granulates.
In wettable powder, the concentration of active compound is about 10~90% by weight; Remainder can be used conventional recipe ingredient polishing to 100% by weight.In missible oil, the concentration of active compound is about 10~80% by weight.As the prescription of pulvis, in most of the cases contain the active compound of 5% to 20% weight, and the solution that can spray contains the active compound of 1% to 20% weight approximately.For granula, it is liquid or solid that the content of active compound depends in part on active compound, also depends on the granulating assistant of use, weighting agent etc.
In addition, if desired, the prescription of above-mentioned active compound also should contain tackiness agent, wetting agent, and dispersion agent, emulsifying agent, permeate agent, solvent, weighting agent or carrier, these reagent are all used always in concrete prescription.
If desired, the commodity concentrate can be diluted according to a conventional method during use, dilute with water wettable powder for example, missible oil and dispersion agent also carry out the part dilution to minitype particle.For pulvis, granula and the prescription that can spray solution generally further diluted without other inert substance before using.
When formula I compound used as safener, desired applicating ratio will be according to the weedicide of specification sheets and use, and its variation range is very big, and per hectare is used 0.01 to 10 kilogram of active compound generally speaking.
With embodiment the present invention is described below.
A. prepare example
A) the formula I compound of 10 parts of weight and talcum or a kind of inert substance of 90 parts of weight are mixed, in taper pulverizer (beakermill), pulverize this mixture, obtain pulvis.
B) with the formula I compound of 25 parts of weight, 64 parts of weight contain kaolinic quartz (as inert substance), the oleoyl methylamino second sulphonyl sodium (Sodium oleoylmethyltauride) (as lubricant and dispersion agent) of the lignin sulfonic acid potassium of 10 parts of weight and 1 part of weight mixes, in pin type dry pan, grind this mixture, obtain dispersive wettable powder in water easily.
C) the easily preparation of dispersive dispersion concentrate in water: with the formula I compound of 20 parts of weight, the alkyl phenol polyoxyethylene glycol ether of 6 parts of weight (Triton * 207), the different tridecyl alcohol polyglycol ether (8EO) of 3 parts of weight and the paraffin mineral oil of 71 parts of weight (for example boiling range is about 255 ℃ to more than 377 ℃) mix, in ball formula pulverizer, grind this mixture, make granularity less than 5 microns.
D) preparation missible oil: with the formula I compound of 15 parts of weight, the nonyl phenol (as emulsifying agent) of the oxyethyl group of the pimelinketone of 75 parts of weight (as solvent) and 10 parts of weight mixes.
E) in water easily emulsive, by the concentrate that phenoxy carboxylic acid ester and toxicide (10: 1) constitute, prepare by following substances:
The 2-[4-(6-Lv benzoxazole of 12.00% weight-2-base-oxygen base)-and phenoxy group) ethyl propionate,
The formula I compound of 1.20% weight,
The dimethylbenzene of 69.00% weight,
Ten DAADBSA calcium of 7.80% weight,
The nonyl phenol of the ethoxylation of 6.00% weight (10 EO),
The Viscotrol C of the ethoxylation of 4.00% weight (40 EO).
Above-mentioned prescription is pressed a) described method preparation of example.
F) by the 2-[4-(6-Lv benzoxazole-2-base-oxygen base of 4.0% weight)-phenoxy group]-ethyl propionate,
The formula I compound of 40.0% weight,
The dimethyl of 30.0% weight,
The pimelinketone of 20.0% weight,
The calcium dodecylbenzene sulphonate of 4.0% weight and
The Viscotrol C of the ethoxylation of 2.0% weight (40 EO) makes easy emulsive in water, contains the concentrate of phenoxy carboxylic acid ester and toxicide (1: 10).
B. chemical case
Parent compound
1) α-chloro-α-(3-trifluoromethyl hydrazono-)-glyoxalic acid methylester
161.6 gram (1.0 moles) 3-5-trifluoromethylanilines are dissolved in the mixture of 400 ml waters and 326 milliliters of concentrated hydrochloric acids, and at violent stirring and 0 ℃ of following 70 gram Sodium Nitrites solution in 400 ml waters that drips.
The diazonium salt solution that generates is added drop-wise under violent stirring in 165.5 gram α-chloro methyl acetoacetates, 800 ml waters, 444 gram sodium-acetates and the 1000 milliliters of alcoholic acid mixtures, and keeping temperature during dropping is 10 ℃.Further stir after 3 hours, this mixture dilute with water, suction filtration is collected thick product, and extracts with the methyl alcohol boiling.Get 263.6 grams, productive rate: 94%, fusing point: 145 ℃.
2) alpha-amino group-α-(3-trifluoromethyl hydrazono-)-glyoxalic acid methylester
100 gram (0.356 mole) α-chloro-α-(3-trifluoromethyl hydrazono-)-glyoxalic acid methylesters are dissolved in 560 milliliters of tetrahydrofuran (THF)s, and drip 61 grams, 25% strong aqua down at+15 ℃ to+20 ℃.After at room temperature further stirring 5 hours, mixture is poured in the water, suction filtration is collected product, and thick product is with the methyl alcohol extraction of seething with excitement.Get 88.3 grams, productive rate: 95%, fusing point: 138 ℃.
The finished product
3) 1-(3-trifluoromethyl)-and 3-methoxycarbonyl-5-trichloromethyl-1,2, the 4-triazole
A) with toluene be solvent
At first 26.1 gram (0.1 mole) alpha-amino group-α-(3-trifluoromethyl hydrazono-)-glyoxalic acid methylesters are placed 150 milliliters of toluene, under agitation drip 0., 12 moles of trichoroacetic chlorides, make the mixture boiling then, reflux by a water separator, until there not being water to flow out (about 1 hour).
After the cooling, wash toluene solution with water, and under vacuum, steam toluene, remaining thick product recrystallization from methyl alcohol.Get 24 grams, productive rate: 61.7%, product is faint yellow crystallization, fusing point: 92~93 ℃.
B) with the tetrahydrofuran (THF) be solvent
182.8 gram (0.7 mole) alpha-amino group-α-(3-trifluoromethyl hydrazono-)-glyoxalic acid methylesters are dissolved in 1,200 milliliter of tetrahydrofuran (THF), under agitation,, in 10 minutes, splash into 191 gram (1.05 moles) trichoroacetic chlorides without cooling.Mixture at room temperature stirred 30 minutes, refluxed then 15 minutes, at room temperature stirred 5 hours again.Then mixture is put into water, suction filtration is collected the crystallization of separating out, and washes with water, obtains faint yellow crystallization 233.8 grams, productive rate: 86%, and fusing point: 90 ℃.
After the recrystallization, the fusing point of sample is 92~93 ℃ from methyl alcohol.
4) 1-(3-trifluoromethyl)-and 5-trichloromethyl-1,2,4-triazole-3-carboxylic acid
At first with 210 gram (0.54 mole) 1-(3-trifluoromethyls)-3-methoxycarbonyl-5-trichloromethyl-1,2, the 4-triazole places 540 ml methanol, adds 0.57 mole of (22.8 gram) sodium hydroxide again and is dissolved in the solution of 100 ml waters.After at room temperature stirring 5 hours, mixture is poured in 4000 ml waters, filtered and collect undissolved material, the pH value of regulating filtrate with hydrochloric acid is 1, at this moment is settled out clear crystal, and suction filtration is collected, and washes with water.With above-mentioned in water insoluble material (sodium salt of carboxylic acid) be dissolved in the mixed solution of 2,000 ml methanol and 1000 ml waters, with the pH value to 1 of hydrochloric acid conditioning solution, suction filtration is collected the colourless crystallization of separating out, and washes it with water.
The carboxylic acid of merge collecting, and with 1000 milliliters of toluene recrystallizations, 174 restrain productive rate: 84%, fusing point: 133~136 ℃.
5) 1-(3-trifluoromethyl)-and 3-isopropoxy carbonyl-5-trichloromethyl-1,2, the 4-triazole
With 20 gram (0.0534 mole) 1-(3-trifluoromethyls)-5-trichloromethyl-1,2, the vlil of 4-triazole-3-carboxylic acid in 70 milliliters of thionyl chloride 30 minutes removed excessive thionyl chloride then under the vacuum, and thick acyl chlorides was seethed with excitement 60 minutes in 120 milliliters of Virahols.After solution is cooled, inject frozen water, suction filtration is collected colourless crystallization.
Above-mentioned colourless coarse crystallization is in methanol-water=1: in the mixed solution 2(50 milliliter), grind under room temperature, suction filtration is collected once more, and at air drying.Get 19.4 grams, productive rate: 87.3%, molten point: 91 ℃.
6) 1-(3-trifluoromethyl)-and 5-trichloromethyl-1,2,4-triazole-3-carboxylic acid 3 '-5-trifluoromethylaniline.
Similar approach according to example 5 changes into acyl chlorides with 0.0345 moles of carboxylic acids, it is dissolved in 80 milliliters of toluene, and under 15 ℃, drip the mixture that contains 0.0345 mole of (5.56 gram) 3-5-trifluoromethylaniline and 0.0345 mole of (3.5 gram) triethylamine in 20 minutes.Mixture at room temperature stirs after 5 hours and washes with water, and removes toluene under vacuum.Resistates obtains 14.4 gram colourless crystallizations, fusing point with recrystallization in 40 ml methanol: 126 ℃, and productive rate: 81%.
7) 1-(3-trifluoromethyl)-and 3-methoxycarbonyl-5-dichloromethyl-1,2, the 4-triazole
0.1 mole of (26.1 gram) alpha-amino group-α-(3-trifluoromethyl hydrazono-)-glyoxalic acid methylester is dissolved in 150 milliliters of toluene, under stirring and room temperature, drips 0.105 mole of (15.5 gram) dichloroacetyl chloride.Mixture refluxed 60 minutes through water separator, after the cooling, washed mixture with water for several times, removed toluene under the vacuum.Resistates is shallow Honey color slurries, gets 28.2 grams, productive rate: 80%.n
30 D:1.5259。
NMR (Nuclear Magnetic Resonance) spectrum: at CDCI
3In, COOCH
3δ 4.05; CHCI
2δ 6.72; With toluene-ethyl acetate=2: 1 was developping agent, Rf value: 0.52.
8) 1-(2,6-diethyl phenyl)-3-methoxycarbonyl-5-trichloromethyl-1,2, the 4-triazole
0.15 mole of (37.4 gram) alpha-amino group-α-(2,6-diethylbenzene hydrazono-)-glyoxalic acid methylester is dissolved in 165 milliliters of tetrahydrofuran (THF)s, and drips 0.194 mole of (35.4 gram) trichoroacetic chloride.Mixture fully stirs with methylene dichloride at room temperature stirring and falling back in 3 hours, washes organic phase then with water, removes under the vacuum and desolvates, and gets 51.7 grams, productive rate: 91.5%
According to NMR (Nuclear Magnetic Resonance) spectrum and ultimate analysis, the light brown slurries that obtain are the open chain compound of following formula:
18.9 gram (0.047 mole) above-claimed cpds are placed 120 milliliters of Glacial acetic acid, refluxed 1.5 hours; After the cooling, mixture is poured in the water and with ethylene dichloride and is fully stirred.The organic phase water is given a baby a bath on the third day after its birth time then, removes under the vacuum and desolvates.
Remaining faint yellow crystallization is ground with 20 ml methanol, and the suction filtration collection, gets 16.4 grams, productive rate: 91%, and molten point: 76~77 ℃.
9) 1-(3-trifluoromethyl)-and 3-methoxycarbonyl-5-(2,2-dimethyl ethene-1-yl)-1,2, the 4-triazole
26.1 gram (0.1 mole) alpha-amino group-α-(3-trifluoromethyl hydrazono-) glyoxalic acid methylesters are dissolved in 150 milliliters of tetrahydrofuran (THF)s, need not cooling, splash into 15.4 gram (0.13 mole) β in 10 minutes, the beta-dimethyl-acrylate chloride.After reaction mixture under refluxad seethed with excitement 1 hour, distill out most of tetrahydrofuran (THF) under the normal pressure, add excessive water again, stirred reaction mixture.After the water decant gone out, the coarse crystallization recrystallizing methanol, 24 grams, productive rate: 73.7%, fusing point: 143~144 ℃.
10) 1-(4-fluorophenyl)-the 3-methoxycarbonyl)-5-methoxymethyl-1,2, the 4-triazole
21.1 gram (0.1 mole) alpha-amino group-α-(4-fluorophenyl hydrazono-)-glyoxalic acid methylesters are dissolved in 140 milliliters of toluene, need not cooling, drip 14.1 gram (0.13 mole) methoxyacetyl chlorides in 10 minutes.This toluene solution through water separator boiling 1.5 hours, is cooled off then, and washes secondary with water, use 200 milliliters at every turn.Steam toluene under the vacuum, resistates is recrystallization in methyl alcohol.Get 15.2 grams, productive rate: 57.4%, fusing point: 93~94 ℃.
11) 1-(2, the 4-dichlorophenyl)-3-ethoxy carbonyl-5-methyl isophthalic acid, 2, the 4-triazole
11a) α-(2,4 dichloro benzene base azo)-acetamino diethyl malonate
0.2 mole of (33.4 gram) 2,4 dichloro aniline short period of time in 60 ml waters and 75 milliliters of concentrated hydrochloric acids is boiled.Then this suspension is cooled to+5 ℃, and under this temperature, it is carried out diazotization with 0.2 mole of (13.8 gram) Sodium Nitrite solution in 25 ml waters.
With the diazonium salt solution that obtains in 15 minutes, in+5 to+7 ℃ be added drop-wise to by intensively stirred, contain 300 milliliters of ethanol, 200 ml waters are in the mixture of 100 gram sodium-acetates and 0.2 mole of (43.3 gram) acetamino diethyl malonate.After at room temperature further stirring 1 hour, mixture is poured in the water, suction filtration is collected product, and crystallization washes with water.Behind ethanol water recrystallization, the crystalline melt point that obtains is 123~124 ℃, gets 71 grams, productive rate: 91%.
11b) 1-(2, the 4-dichlorophenyl)-the 5-methyl isophthalic acid, 2,4-triazole-3-carboxylic acid
With 39 gram (0.1 mole) example 11a) product that obtains refluxes in 165 ml waters and 24.2 gram potassium hydroxide mixtures and boiled 5 minutes.The solution that generates is cooled to 60 ℃, and uses the concentrated hydrochloric acid acidifying.Suction filtration is collected 1-(2,4-dichlorophenyl)-the 5-methyl isophthalic acid, 2,4-triazole-3-carboxylic acid precipitation, and wash with water until being neutral, get 25.6 grams, productive rate: 94%, fusing point: 163~164 ℃.
11c) 1-(2, the 4-dichlorophenyl)-3-ethoxy carbonyl-5-methyl isophthalic acid, 2, the 4-triazole
With 0.01 mole of 11b) compound in 150 milliliters of thionyl chloride, reflux and boiled 2 hours, under vacuum, remove excessive thionyl chloride then, thick acyl chlorides heated and boiled 30 minutes in 500 milliliters of ethanol.Subsequently mixture is poured in the water, suction filtration is collected the crystallization of separating out, and is washed with water to neutrality.Get 24 grams, productive rate: 80%, fusing point: 131~132 ℃.
After recrystallizing methanol, crystalline melt point is 133~134 ℃.
12) 1-(2, the 4-dichlorophenyl)-3-ethoxy carbonyl-5-methyl isophthalic acid, 2, the 4-triazole
12a) 0.1 mole (27.6 gram) alpha-amino group-α-(2,4 dichloro benzene base hydrazono-) glyoxylic acid ethyl ester refluxed 2 hours in 150 milliliters of acetic anhydride, removed excessive acetic anhydride then under the vacuum, thick product ethyl alcohol recrystallization.Get 21.6 grams, productive rate: 72%, fusing point: 133~134 ℃.
12b) 0.1 mole of (27.6 gram) alpha-amino group-α-(2,4 dichloro benzene base hydrazono-) glyoxylic acid ethyl ester was refluxed 4 hours in 130 milliliters of former acetic acid triethyls, under vacuum, remove excessive ortho-acetate, product ethyl alcohol recrystallization then.Get 18.9 grams, productive rate: 63%, fusing point: 133~134 ℃.
13) 1-(2, the 4-dichlorophenyl)-3-ethoxy carbonyl-1,2, the 4-triazole
0.1 mole of (27.6 gram) alpha-amino group-α-(2,4 dichloro benzene base hydrazono-) glyoxylic acid ethyl ester was refluxed 5 hours in 120 milliliters of trimethyl orthoformates, remove excessive ortho-formiate then under the vacuum, the resistates ethyl alcohol recrystallization.Get 21.4 grams, productive rate: 75%, fusing point: 105~106 ℃.
14) 1-phenyl-3-ethanoyl-5-trichloromethyl-1,2, the 4-triazole
23.6 gram (0.13 mole) trichoroacetic chlorides are under agitation once added in 0.1 mole of (17.7 gram) alpha-amino group-α-phenyl hydrazono-methyl-glyoxal solution in 150 milliliters of tetrahydrofuran (THF)s.After boiling 1 hour under refluxing, mixture is poured in 1 premium on currency, decant goes out to precipitate the water on the thick product subsequently, and thick product recrystallizing methanol gets 21.0 grams, productive rate: 66%, and fusing point: 139~140 ℃.
The formula I compound that exemplifies out in the table I is to prepare according to the method that is similar to example 3 to 14.
Table I instance number (Z) n Y X fusing point (℃) preparation method
n
30 DBy instance number
15 3-Cl CCl
3-OC
2H
576-77 3a
16 3-Cl CCl
3-OH 124-127 4
17 3-Cl CHCl
2-OC
2H
5Sirup 3a
18 2-Cl CCl
3-OC
2H
599-100 3a
19 2-Cl CCl
3-OH 204-205 4
20 2-Cl CCl
3-OCH
3114-115 3b
21 2-Cl CCl
3-OCH
2CH
2CH
390-92 5
22 4-Cl CHCl
2-OCH
3152-153 3a
23 3,5-Cl
2CHCl
2-OCH
31,5809 3a
24 4-NO
2CHCl
2-OCH
3149-150 3a
The table I
Instance number (Z) n Y X fusing point (℃) preparation method
n
30 DBy instance number
25 3,5-Cl
2CCl
3-OCH
3143-145 3b
26 3,5-Cl
2CCl
3-OH 194-195 4
27 2-Cl CHCl
2-OC
2H
5135-136 3a
28 3-Cl CHCl
2-OH 114 4
29 2-Cl CHCl
2-OCH
3158 3a
30 4-NO
2CCl
3-OCH
3201-203 3b
31 H CCl
3-OCH
3103-104 3b
32 H CCl
3-OH 154-156 4
33 4-F CHCl
2-OCH
3168 3a
34 3-CN CCl
3-OH 155 4
35 4-Cl-C
6H
4-O- CCl
3-OH 142 4
36 2,4-Cl
2CCl
3-OC
2H
5111-112 8
37 2,4-Cl
2CCl
3-OH 156 4
38 4-Cl-C
6H
4-O- CCl
3-OCH
31,5925 3b
39 2,4-Cl
2CHCl
2-OCH
3147 3a
40 2-Cl CHCl
2-OH 188-189 4
41
CCl
3-OCH
3Slurry 3b
43 2,4-Cl
2CCl
3-NH-C
6H
5215-217 6
The table I
Instance number (Z) n Y X fusing point (℃) preparation method
n
30 DBy instance number
44 2,4-Cl
2CCl
3-NH-C
6H
4-3-CF
3166-167 6
45 3,5-Cl
2CCl
3″ 160-161 6
46 2,4-Cl
2, CCl
3″ 173 6
5-OCH
3
47 2,4-Cl
2CCl
3-OCH
3162-163 3b
48 2,4-Cl
2CCl
3-OCH
2CH
2CH
2CH
366-67 5
52 3-CF
3CCl
3-OC
2H
564 3a
The table I
Instance number (Z) n Y X fusing point (℃) preparation method
n
30 DBy instance number
56 2,4-Cl
2CCl
3 68-72 6
58 4-Cl CCl
3-OCH
3136-137 3b
59 4-Cl CCl
3-OH 145-147 4
61 3-Cl,4-F CCl
3-OCH
2CH(CH
3)
2122-123 5
63 2,4-Cl
2CCl
3-N(C
2H
5)
2glass-like 6
64 4-CH
3CCl
3-OH 146 4
65 4-CH
3CCl
3-OCH
3132-134 3b
66 4-F CCl
3-OCH
3113-114 3b
67 2-CH
3,4-Cl CCl
3-OC
2H
5117-118 8
68 2-CH
3,4-Cl CCl
3-OCH
3125-126 3b
69 3-CN CCl
3-OCH
3125-126 3b
70 2,4-Cl
2CCl
3-OCH(CH
3)
2154-155 5
71 2,4-Cl
2CCl
3-OCH
2CH
2CH
3129-130 5
The table I
Instance number (Z) n Y X fusing point (℃) preparation method
n
30 DBy instance number
72 4-F CCl
3-OH 131-132 4
73 4-F CCl
3-OCH
2CH
2CH
3120-121 5
74 3-Cl,4-F CCl
3-OCH
3114-115 3b
75 2,6-(C
2H
5)
2CCl
3-OH 193-195 4
76 2,4-Cl
2CCl
3-OCH
2CH(CH
3)
2119-121 5
77 2-Cl CCl
3-OCH(CH
3)
2131-132 5
78 2,4-Cl
2, CCl
3-OCH
3155 3b
5-OCH
3
79 2,4-Cl
2, CCl
3-OH 215 4
5-OCH
3
80 2-CH
3,4-Cl CCl
3-OH 112 4
81 2-Cl CCl
3-OCH
2CH(CH
3)
279-80 5
83 3-Cl,4-F CCl
3-OC
2H
5118-119 8
84 3-Cl,4-F CCl
3-OH 174 4
85 4-F CCl
3-OCH
2CH(CH
3)
2103-104 5
86 2-CH
3,4-Cl CCl
3-OCH
2CH
2CH
2CH
3112 5
87 4-Cl CCl
3-OC
2H
5161-162 8
88 4-CH
3CCl
3-OCH(CH
3)
2154-155 5
89 H CHCl
2-OH 185 4
90 2,4-Cl
2CF
3-OCH
3131 3b
91 4-CH
3CCl
3-OC
2H
5104-105 8
92 4-CH
3CCl
3-OCH
2CH(CH
3)
2125-126 5
94 ″ CCl
3-OCH
2CH
2CH
399 5
The table I
Instance number (Z) n Y X fusing point (℃) preparation method
n
30 DBy instance number
95 4-F CF
3-OCH
387-88 3b
96 4-Cl CCl
3-OCH
2CH(CH
3)
2138-139 5
97 2,6-(C
2H
5)
2CCl
3-OC
2H
596-97 8
98 3,4-Cl
2CCl
3-OCH
3133 3b
99 2,6(C
2H
5)
2CCl
3-ONa 233-234 4
100 2,6(C
2H
5)
2CCl
3-OCH
2CH
2CH
31.5390 5
101 2,6(C
2H
5)
2CCl
3-OCH(CH
3)
283-84 5
102 2,6(C
2H
5)
2CCl
3-OCH
2CH(CH
3)
21,5147 5
103 3,4-Cl
2CCl
3OH 167-168 4
104 2-CF
3,4-Cl CCl
3OCH
3110 3a
105 2-CF
3,4-Cl CCl
3OH 143-145 4
106 2-F,4-Cl-5-OCH
3CCl
3OCH
3177-178 3a
107 2-F,4-Cl,5-OCH
3CCl
3OH 176 4
108 2-CHF
2CF
2O- CCl
3OCH
3116-117 3a
109 3-CHClF-CF
2O- CCl
3OCH
3syrup 3a
110 2-CH
3,3-Cl CCl
3OCH
3144-145 3a
111 2,6-Cl
2CCl
3OCH
3143-144 3a
112 2,5-(OCH
3)
2,4-Cl CCl
3OCH
3149 3a
113 2,5-(OCH
3)
2,4-Cl CCl
3OH 223-224 4
114 3,5-Cl
2,4-OCH
3CCl
3OCH
3148-149 3a
115 3,5-Cl
2-4-OCH
3CCl
3OH 150 4
116 2-Cl,4-Br CCl
3OC
2H
5113-114 3a
117 2-Cl,4-Br CCl
3OH 220 4
118 2-Br CCl
3OCH
3126-127 3a
119 2-Br CCl
3OH 195-196 4
120 2,4-Cl
2CCl
3OCH
2CH
2Cl 88-89 5
121 3-CHClF-CF
2O- CCl
3OH 128-130 4
122 2-CH
3,4-Cl CCl
3CH
3141 14
123 3-CH
3,4-CHF
2CR
2O CCl
3CH
3119-120 14
The table I
Instance number (Z) n Y X fusing point (℃) preparation method
n
30 DBy instance number
124 2,4-Cl
2CCl
3CH
3120-121 14
125 3-OCF
3CCl
3CH
392-93 14
126 3-CHCl
2CF
2O CCl
3CH
3114-115 14
127 H CCl
3CH
3139-140 14
128 2-Cl CCl
3CH
3121-122 14
129 3-CF
2Cl CCl
3CH
3syrup 14
130 4-Cl (CH
3)
2C=CH- OCH
3118-119 9
131 2-CH
3,4-Cl (CH
3)
2C=CH- OCH
3142-143 9
132 2-Cl CH
2Cl OCH
3112-113 10
133 2-CH
3,4-Cl CH
3OCH
373 10
134 3-Cl,4-F (CH
3)
2C=CH- OCH
3185-186 9
135 2,4-Cl
2,5-OCH
3(CH
3)
2C=CH- OCH
3200-201 9
136 3,4-Cl
2CHCl
2-CF
2- OC
2H
5n
30 D:1,5458 9
137 2-CH
3,4-Cl CHCl
2-CF
2- OC
2H
5n
30 D:1,5272 9
138 2-CH
3,4-Cl CHF
2-CF
2- OC
2H
5n
30 D:1.4991 9
139 4-F CHF
2-CF
2- OCH
366-67 9
140 2-Cl (CH
3)
2C=CH- OH 194 4
141 3,4-Cl
2CF
2H-CF
2- OC
2H
5n
30 D:1.5198 9
142 2,4-Cl
2,5-OCH
3CF
2H-CF
2- OCH
3112-113 9
143 2-CH
3,4-Cl CH
3CH=CH- OCH
3175-176 9
145 3-CF
3HCF
2-CF
2-OCH
3Slurry 9
146 2,4-Cl
2HCF
2-CF
2-OC
2H
5Slurry 9
Table I-31-
Instance number (Z) n Y X fusing point (℃) preparation method
n
30 DBy instance number
147 2,4-Cl
2HCF
2-(CF
2)
3-OC
2H
5115-116 9
148 2,4-Cl
2BrCF
2-CF
2- OC
2H
5100-101 9
149 2,4-Cl
2HCF
2-CF
2- OH 123-124 9
150 2-Cl CH
3OH 190 11b
151 2-Cl CH
3OC
2H
5110-111 11c
152 4-Cl CH
3OH 172 11b
153 4-Cl CH
3OC
2H
5115 11c
154 3-Cl,4-F CH
3OH 183 11b
155 4-F CH
3OH 177 11b
156 2-CH
3,4-Cl CH
3OH 177-178 11b
157 2,4-Cl
2,5-OCH
3CH
3OH 193-194 11b
158 2,4-Cl
2CH
3OCH
3180-181 11c
159 3-Cl,4-F CH
3OCH
3140-142 11c
160 3-Cl,4-F CH
3OC
2H
5114-115 11c
161 2,6-(C
2H
5)
2CHF
2-CF
2- OH 222-223 4
162 4-F CH
3OC
2H
5105-106 11c
163 2-CH
3,4-Cl CH
3OC
2H
5153-154 11c
164 2,4-Cl
2H OH 185-186 4
165 2,4-Cl
2H OC
2H
5105-106 13
166 4-CH
3CH
3OC
2H
51,5466 11c
167 4-CH
3CH
3OH 183 11b
168 2-Cl,4-Br CH
3OC
2H
5142-143 11c
169 2-Cl,4-Br CH
3OH 172-173 11b
170 3-CF
3CH
3OH 164-165 11b
171 2,4-Cl
2CH
3OC
2H
5133-134 11c
172 2,4-Cl
2CH
3OH 163-164 11b
*) in toluene, the alcohol of gram molecular weight such as use, triethylamine is as acid binding agent.
C. biological example
Example 1
Wheat up to growing three to four leaf stages, is used weedicide and compound treatment of the present invention in cultivation in the greenhouse then in diameter is 9 centimetres basin.Weedicide and formula I compound are used with the form of aqueous suspension or emulsion, and institute's water consumption is equivalent to 800 liters/hectare.Handle after three weeks, estimate the various infringements that the weedicide use causes plant, will consider the degree of long term inhibition plant-growth especially.
The presentation of results of the present invention compound of table in the I can very effective reduction weedicide grievous injury.
Even quite excessive use weedicide H, i.e. 2.0 kilograms of active substance/hectares, the sign of weedicide infringement also can significantly reduce, and only exists slight permanent lesion.This has illustrated the good action of safener.Certainly, the slight infringement of weedicide is (the seeing example 2) that can eliminate fully.Therefore, the mixture of compound of the present invention and weedicide is suitable for removing selectively the weeds in the cereal crop.
Table 1
The effect of compound amount weedicide, %
H+ instance number a.i. kilogram/hectare TA
H - 2,0 75
H+ 17 2.0+2.5 20
H+ 22 ″ 30
H+ 7 ″ 30
H+ 27 ″ 25
H+ 15 ″ 11
H+ 16 ″ 24
H+ 36 ″ 13
H+ 67 ″ 10
H+ 25 ″ 25
H+ 78 ″ 18
H+ 31 ″ 20
H+ 69 ″ 28
H+ 3 ″ 26
H+ 79 ″ 30
H+ 80 ″ 30
H+ 32 ″ 24
H+ 37 ″ 24
H+ 19 ″ 25
H+ 43 ″ 30
H+ 63 ″ 20
H+ 18 ″ 13
H+ 29 ″ 20
H+ 33 ″ 20
H+ 39 ″ 20
H+ 41 ″ 20
H+ 64 ″ 20
H+ 66 ″ 15
H+ 73 ″ 25
H+ 85 ″ 20
H+ 74 ″ 25
H+ 127 2.0+1.0 30
H+ 89 2.0+2.5 30
H+ 90 ″ 50
H+ 146 ″ 30
H+ 9 ″ 40
H+ 160 ″ 60
H+ 163 ″ 30
H+ 20 ″ 13
H+ 21 ″ 22
H+ 47 ″ 22
H+ 48 ″ 7
H+ 70 ″ 10
H+ 71 ″ 50
H+ 76 ″ 20
H+ 68 ″ 10
H+ 72 ″ 22
H+ 73 ″ 40
H+ 84 ″ 35
H+ 8 ″ 30
H+ 75 ″ 50
H+ 59 ″ 20
H+ 83 ″ 28
H+ 52 ″ 60
H+ 5 ″ 22
H+ 77 ″ 20
H+ 81 ″ 30
H+ 92 ″ 40
H+ 91 ″ 40
H+ 88 ″ 50
H+ 86 ″ 40
H+ 87 ″ 20
H+ 96 ″ 40
H+ 100 ″ 40
H+ 103 ″ 30
H+ 102 ″ 40
H+ 104 2.0+2.5 50
H+ 106 ″ 50
H+ 107 ″ 50
H+ 110 ″ 48
H+ 111 ″ 50
H+ 116 ″ 20
H+ 118 ″ 30
H+ 113 ″ 60
H+ 115 ″ 40
H+ 117 ″ 18
H+ 119 ″ 50
H+ 120 ″ 20
H+ 137 ″ 25
H+ 138 ″ 25
H+ 139 ″ 25
H+ 141 ″ 40
H+ 142 ″ 30
H+ 143 ″ 40
H+ 133 ″ 50
H+ 134 ″ 50
H+ 135 ″ 50
H+ 148 ″ 20
H+ 149 ″ 55
H+ 11c ″ 40
H+ 11b ″ 25
H+ 150 ″ 35
H+ 151 ″ 30
H+ 152 ″ 50
H+ 153 ″ 27
H+ 154 ″ 27
H+ 155 ″ 50
H+ 156 ″ 25
H+ 157 ″ 43
H+ 158 ″ 20
H+ 171 ″ 20
Abbreviation in the table 1
TA=summer wheat (Triticum aestivum)
The a.i.=active princlple
The H=fenoxaprop-ethyl
=2-(4-(6-chlorobenzene thiazole-2-base oxygen base)-phenoxy group)-ethyl propionate
Example 2
Sowing wheat and two kinds of weeds gramineous-Alopecurus myosuroides and wild avena sativa (Avena fatua) in the fertile sandy soil in the basin of 9 cm diameters, and in the greenhouse, cultivate it under the nice and cool condition, tiller up to beginning, use compound treatment of the present invention then, form with aqueous suspension or emulsion is used, use (bucket mixes) with weedicide, water consumption is 300 liters/hectare.
After around the dispenser, estimate the variation and the damage of the plant-growth that is put to the test.
The result of table 2 shows that compound of the present invention has superior safety, can prevent the infringement of weedicide to crop (for example cereal crop) effectively, and don't influence is to the actual herbicide effect of gramineous weeds.
Therefore, the mixture of The compounds of this invention and weedicide can be used for removing selectively weeds.
Table 2 consumption is to the herbicide effect (%) of wheat
Herbicidal compounds active principle kilogram/hectare infringement % for
H+ (instance number) H+ compound (instance number) is ALM AVF (TA)
Weedicide H-0.8 52--
0.4 40 100 100
… 0.2 18 98 100
H + 7 0.8+0.4 2 - -
0.4+0.2 0 100 100
0.2+0.1 0 98 100
H + 27 ″ 2 - -
0 100 100
0 99 99
H + 15 ″ 2 - -
0 100 100
0 100 -
H + 16 ″ 1 - -
0 100 100
0 98 98
H + 18 ″ 3 - -
0 100 100
0 100 97
H + 37 ″ 2 - -
0 100 100
0 99 100
H + 36 ″ 2 - -
0 100 100
0 97 100
Table 2 consumption is to the herbicide effect (%) of wheat
Herbicidal compounds active principle kilogram/public affairs incline the infringement % for
H+ (instance number) H+ compound (instance number) is ALM AVF (TA)
H + 78 0.8+0.4 2 - -
0.4+0.2 0 100 100
…… 0.2+0.1 0 100 100
H + 67 ″ 2 - -
0 100 100
0 100 100
H + 22 ″ 2 - -
0 100 100
0 100 99
H + 79 ″ 3 - -
2 100 100
0 98 98
H + 80 ″ 4 - -
2 100 100
0 98 100
H + 63 0 - -
0 100 100
0 99 97
H + 19 ″ 2 - -
0 100 100
0 100 97
ALM=Alopecurus myocuroides
AVF=wild avena sativa (Avena fatua)
H=sees Table 1
Example 3
In the basin of 13 cm diameters, sow barley (Variety Oriol) in the fertile sandy soil, and under outdoor climate conditions, cultivate, tiller until beginning, use the mixture (bucket mixes) of The compounds of this invention and weedicide to handle then, form with aqueous suspension or emulsion is used, and water consumption is 300 liters/hectare.
After two weeks of dispenser, estimate growth change and other damage of being tried plant.
The result of table 3 shows that compound of the present invention has extraordinary security, can prevent the infringement of weedicide to crop (for example barley) effectively, and not weaken the practical function that it removes gramineous weeds.
Table 3
The compound amount herbicide effect, %
H
1+ instance number (a.i. kilogram/hectare) HV
H
13.0 30
1.5 13
H
1+36 3.0+0.3 15
1.5+1.5 3
Abbreviation: HV=vulgare (Hordeum vulgare)
The H=Diclofop-methyl [(2-(4-(2,4-dichlorophenoxy)-phenoxy group)-methyl propionate]
Claims (7)
1, the method for a kind of plant protection product of preparation, this plant protection contains formula I compound or its salt (when X=OH), and inert support, and said components is mixed the protection that obtains can be used in agricultural,
Wherein Z can be identical or different, and it represents halogen, nitro, cyano group, trifluoromethyl, alkyl (C1-C4), alkoxyl group (C1-C4) or (C1-C4) alkylthio, alkyl wherein, alkoxyl group, alkylthio can be replaced by one or more halogen atoms (particularly fluorine or chlorine), and Z also represents can be by the cycloalkyl of (C3-C6) of the replacement of (C1-C4) alkyl, and phenyl or phenoxy group, wherein phenyl and phenoxy group can be by halogen lists or polysubstituted and/or replaced by the trifluoromethyl list;
Y represents hydrogen, can be by the alkyl all or part of replacement of halogen atom and/or quilt alkoxyl group of (C1-C4) or alkylthio (C1-C4) mono-substituted (C1-C4), (C2-C6) alkenyl or alkynyl (C2-C6), perhaps expression can be by (C3-C6) cycloalkyl of the alkyl of (C1-C4) and/or dichloroethylene replacement; X represents hydroxyl, (C1-C4) alkyl, (C3-C6) cycloalkyloxy, the alkoxyl group of phenyl-(C1-C6), phenoxy group, (C2-C6) alkenyloxy, (C1-C6) alkynyloxy group, alkoxyl group (C1-C6) or (C1-C6) alkylthio, wherein alkoxyl group or alkylthio can be replaced by following radicals: alkoxyl group (C1-C2), alkyl amino-carbonyl singly-(C1-C4), two-[(C1-C4)) alkyl] aminocarboxyls, phenyl amino carbonyl, alkyl N-[(C1-C4)]-N-phenyl-aminocarboxyl, alkylamino singly-(C1-C6), two-[C1-C6] alkylamino, [alkyl of C1-C6] ketonic oxygen base, the alkylthio of [C1-C2], cyano group or halogen, perhaps X represents to have the group of following formula:
Wherein R represents hydrogen or alkyl (C1-C4), or expression alkylamino singly-(C1-C4), two-(C1-C4) alkylamino, cycloalkyl (C5-C6), pyridine subbase.
2, method according to claim 1, wherein plant protection product contains the formula I compound in the claim 1, and wherein represent can be all or part of by F for Y, the alkyl of (C1-C2) that Cl or Br replace.
Z can be identical or different, and it represents halogen, alkoxyl group (C1-C4), alkyl (C1-C4) or CF
3
X represents the alkoxyl group or the hydroxyl of (C1-C6), and n represents 1,2, or 3.
3, method according to claim 2, wherein Y represents CCI
3, CHCI
3, CHF
2, CF
2Or CH
3
4, method according to claim 1, wherein plant protection product and following combinations of herbicides: thiocarbamates, amino formate; N-acetyl halide phenyl amines, phenoxy group-, naphthyloxy-; the phenoxy group phenoxy group-or heteroaryloxy phenoxy group-carboxylic acid esters, or the methone oxime derivatives.
5, cover crop exempts from the method for the poisonous plant side effect of weedicide, and this method comprises the described formula I of claim 1 compound with significant quantity, before using weedicide, handle plant, plant seed or cultural area afterwards or when using weedicide.
6, method according to claim 5, use therein weedicide is a thiocarbamate, carbamate, N-acetyl halide aniline, phenoxy group-, naphthyloxy-, the phenoxy group phenoxy group-or heteroaryloxy phenoxy group-carboxylicesters or methone 9 oxime derivate.
7, the method for preparing generalformula,
Wherein Z can be identical or different, it represents halogen, nitro, cyano group, trifluoromethyl, (C1-C4) alkyl, alkoxyl group (C1-C4) or (C1-C4) alkylthio, wherein alkyl, alkoxyl group and alkylthio can be replaced by one or more halogen atoms (particularly fluorine or chlorine), the cycloalkyl of (C3-C6) that Z or expression can be replaced by (C1-C4) alkyl, and phenyl or phenoxy group, wherein phenyl and phenoxy group can be replaced by the halogen list or be polysubstituted and/or replaced by the trifluoromethyl list.
Y represents hydrogen, can be all or part of that be replaced by halogen atom and/or by the alkyl of the alkoxyl group of (C1-C4) or alkylthio (C1-C4) mono-substituted (C1-C4), (C2-C6) alkenyl or alkynyl (C2-C6), perhaps expression can be by the cycloalkyl of (C3-C6) of the alkyl of (C1-C4) and/or dichloroethylene replacement.
X represents hydroxyl, (C1-C4) alkyl, (C3-C6) cycloalkyloxy, the alkoxyl group of phenyl-(C1-C6), phenoxy group, (C2-C6) alkenyloxy, (C2-C6) alkynyloxy group, (C1-C6) alkoxyl group or (C1-C6) alkylthio, wherein alkoxyl group or alkylthio can be replaced by following radicals: alkoxyl group (C1-C2), single-(C1-C4) alkyl amino-carbonyl, two-(alkyl (C1-C4)) aminocarboxyls, the phenyl amino carbonyl, N-(alkyl (C1-C4))-N-phenyl-amino-carbonyl, alkylamino singly-(C1-C6), two-(C1-C6) alkylamino, (alkyl of C1-C6) ketonic oxygen base, alkylthio (C1-C2), cyano group or halogen or X represent to have the group of following formula:
Wherein R represents hydrogen or alkyl (C1-C4), or expression alkylamino singly-(C1-C4), two-(C1-C4) alkylamino, cycloalkyl amino (C5-C6), pyridine subbase.
Morpholino or 2,6-thebaine generation or have formula
Group, R wherein
1And R
2Can be identical or different, the alkyl of their expressions (C1-C4), R
1And R
2Also can form the five-ring alkyl, six-ring alkyl or seven-membered ring alkyl.
N represents numeral 0,1,2 or 3.
The method that perhaps prepares the salt (when X=OH) of generalformula, this generalformula and its salt all can be used for agricultural, if X=(C1-C4) alkyl, then Y represents CCI
3Or CHCI
2, but following generalformula removes part: wherein
A) Y represents H, and (Z) n represents H, 4-Cl, 4-CH
3, 2-OCH
3, 4-OCH
3Or 4-OC
2H
5, X represents OH, OCH
3Or OC
2H
5
B) Y represents CH
3, (Z) n represents 4-NO
2, 4-OCH
3, 2-Cl, 4-Cl, 2-OCH
3-4-ON
2Or 2-CH
3-4-NO
2, X represents OH or OC
2H
5
C) Y represents C
2H
5Or CH(CH
3)
2, (Z) n represents H, X represents OCH
3,
This preparation method comprises:
A) with formula II compound:
(X wherein
1Identical with the connotation of X, but can not be hydroxyl)
A1) with general formula be the compound reaction of Y-CO-Cl, perhaps
A2) be the anhydride reaction of Y-CO-O-CO-Y with general formula, perhaps
A3) be Y-C(OR with general formula
1)
3Ortho ester reaction, R wherein
1The alkyl of expression (C1-C4), perhaps
B) and the fruit compound in Y=H or alkyl (C1-C4), then with square III compound and alkali reaction,
Y wherein
1Expression hydrogen or alkyl (C1-C4), R
3The alkoxyl group or the CH of expression (C1-C4)
3
If desired, will be at a1) and the compound that a2) obtains under the situation in acetic acid, heat, and the formula I compound that obtains is changed into other compound or its salt with formula I by the method for preparing derivative.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEP3525205.7 | 1985-07-15 | ||
DE19853525205 DE3525205A1 (en) | 1984-09-11 | 1985-07-15 | PLANT PROTECTIVE AGENTS BASED ON 1,2,4-TRIAZOLE DERIVATIVES AND NEW DERIVATIVES OF 1,2,4-TRIAZOLE |
Publications (2)
Publication Number | Publication Date |
---|---|
CN85107316A true CN85107316A (en) | 1987-01-14 |
CN1021789C CN1021789C (en) | 1993-08-18 |
Family
ID=6275800
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN91102410A Expired - Lifetime CN1035326C (en) | 1985-07-15 | 1985-09-30 | Process for preparing derivates of 1,2,4-triazols |
CN 85107316 Expired - Lifetime CN1021789C (en) | 1985-07-15 | 1985-09-30 | Compound containing 1,2,4-triazole derivatives, its preparation and its application used as plant protective agent |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN91102410A Expired - Lifetime CN1035326C (en) | 1985-07-15 | 1985-09-30 | Process for preparing derivates of 1,2,4-triazols |
Country Status (1)
Country | Link |
---|---|
CN (2) | CN1035326C (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103420931A (en) * | 2013-05-02 | 2013-12-04 | 范国煌 | Pentacyclic compound capable of adjusting polarization of macrophages and resisting diabetes and application thereof |
CN104755467A (en) * | 2012-10-26 | 2015-07-01 | 杜邦公司 | Substituted triazoles as herbicides |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1060650C (en) * | 1994-06-07 | 2001-01-17 | 张贵发 | Brain marrow source |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5188968A (en) * | 1975-02-04 | 1976-08-04 | Toriazoorujudotaino shinkiseiho |
-
1985
- 1985-09-30 CN CN91102410A patent/CN1035326C/en not_active Expired - Lifetime
- 1985-09-30 CN CN 85107316 patent/CN1021789C/en not_active Expired - Lifetime
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104755467A (en) * | 2012-10-26 | 2015-07-01 | 杜邦公司 | Substituted triazoles as herbicides |
CN103420931A (en) * | 2013-05-02 | 2013-12-04 | 范国煌 | Pentacyclic compound capable of adjusting polarization of macrophages and resisting diabetes and application thereof |
CN103420931B (en) * | 2013-05-02 | 2015-07-08 | 范国煌 | Pentacyclic compound capable of adjusting polarization of macrophages and resisting diabetes and application thereof |
Also Published As
Publication number | Publication date |
---|---|
CN1021789C (en) | 1993-08-18 |
CN1054595A (en) | 1991-09-18 |
CN1035326C (en) | 1997-07-02 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1024794C (en) | Oxa-or thia-zoline derivative and preparaiton thereof | |
CN100335466C (en) | Pyrimidine compounds and their use as pesticides | |
CN1052379C (en) | Quinazoline derisatives | |
CN1052308A (en) | Different azoles quinoline, its preparation method and as the application of plant protection product | |
CN1052115A (en) | The pyrazoline compounds of protection preventing crop from detriment of herbicides | |
CN1159278C (en) | Fungicidal methods, compounds and compositions contg. benzophenones | |
CN1148358C (en) | 1-substituted-4-carbamoyl-1,2,4-triazol-5-one derivatives and herbicide | |
CN1235600A (en) | 4-hetaroylpyrazol derivatives | |
CN1038643A (en) | Band heterocyclic 2-alcoxyl phenoxy group sulfonyl ureas and they application as weedicide or plant-growth regulator | |
CN1133038A (en) | Substituted isoxazolines, process for producing them, agents containing them and their use as safeners | |
CN1075952A (en) | Parasiticidal phenylhydrazine derivatives | |
CN1027069C (en) | Oxazolidinedione deriv., processes for preparation thereof and the deriv.-contg. herbicide | |
CN1017678B (en) | Contain the Herbicidal combinations of pyrazole derivatives as active component | |
CN1413990A (en) | Epimino substituted benzene derivative | |
CN1028714C (en) | Pyrimidine derivatives their production and use | |
CN1048386A (en) | Novel thiazole base alkoxy acrylic ester, they the preparation method, do the purposes of mycocide and prepare the intermediate of this compounds | |
CN1054063A (en) | Heterogeneous ring compound | |
CN1014240B (en) | Process for preparing pyridazinone derivatives and insecticidal compositions | |
CN1030419A (en) | 6,7-dihydro-pyrazolo [1,5-a] [1,3,5] triazine-2-sulphonamide its preparation method and with its purposes as weedkiller and plant-growth regulator | |
CN1052769A (en) | The protective mixture of sulfonylurea and monoacetylaniline class weed killer herbicide | |
CN1149927C (en) | 3-hydroxy-5-methyl-isoxazole pesticide composition and using method | |
CN87100152A (en) | The compound of weeding | |
CN1058968A (en) | Plant protection product, its preparation method and application | |
CN1129893A (en) | Herbicidal compositions | |
CN1021789C (en) | Compound containing 1,2,4-triazole derivatives, its preparation and its application used as plant protective agent |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
C53 | Correction of patent of invention or patent application | ||
COR | Change of bibliographic data |
Free format text: CORRECT: PATENTEE; FROM: HOECHST SCHERING CO. LTD,. TO: AVENTIS CROPSCIENCE GMBH |
|
C17 | Cessation of patent right |