WO2015000392A1 - N-(芳基烷基)芳氧苯氧羧酸酰胺类化合物及其制备方法与应用 - Google Patents
N-(芳基烷基)芳氧苯氧羧酸酰胺类化合物及其制备方法与应用 Download PDFInfo
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- WO2015000392A1 WO2015000392A1 PCT/CN2014/081211 CN2014081211W WO2015000392A1 WO 2015000392 A1 WO2015000392 A1 WO 2015000392A1 CN 2014081211 W CN2014081211 W CN 2014081211W WO 2015000392 A1 WO2015000392 A1 WO 2015000392A1
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- Prior art keywords
- group
- oxy
- phenoxy
- ylmethyl
- formula
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- -1 aryloxy phenoxy carboxylic acid amide compound Chemical class 0.000 title claims abstract description 93
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 125
- 230000002363 herbicidal effect Effects 0.000 claims abstract description 14
- 230000000749 insecticidal effect Effects 0.000 claims abstract description 7
- 230000000895 acaricidal effect Effects 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 50
- 125000004432 carbon atom Chemical group C* 0.000 claims description 41
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 32
- 125000003118 aryl group Chemical group 0.000 claims description 31
- 125000001072 heteroaryl group Chemical group 0.000 claims description 31
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 27
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 22
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 17
- 125000001424 substituent group Chemical group 0.000 claims description 16
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine group Chemical group NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 15
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 15
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 14
- 125000000304 alkynyl group Chemical group 0.000 claims description 13
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 13
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 claims description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 125000006319 alkynyl amino group Chemical group 0.000 claims description 12
- 239000002585 base Substances 0.000 claims description 12
- 125000003342 alkenyl group Chemical group 0.000 claims description 11
- 229910052736 halogen Inorganic materials 0.000 claims description 11
- 150000002367 halogens Chemical class 0.000 claims description 11
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 claims description 10
- 230000000844 anti-bacterial effect Effects 0.000 claims description 10
- 125000004541 benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 claims description 10
- 229940080818 propionamide Drugs 0.000 claims description 10
- 125000004076 pyridyl group Chemical group 0.000 claims description 10
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 claims description 10
- 125000000335 thiazolyl group Chemical group 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- 125000006310 cycloalkyl amino group Chemical group 0.000 claims description 8
- 125000005843 halogen group Chemical group 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000003282 alkyl amino group Chemical group 0.000 claims description 6
- 125000005110 aryl thio group Chemical group 0.000 claims description 6
- 239000003814 drug Substances 0.000 claims description 6
- 229940079593 drug Drugs 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 239000012312 sodium hydride Substances 0.000 claims description 6
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 6
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 5
- 239000004480 active ingredient Substances 0.000 claims description 5
- 150000004982 aromatic amines Chemical class 0.000 claims description 5
- 125000004104 aryloxy group Chemical group 0.000 claims description 5
- 230000004071 biological effect Effects 0.000 claims description 5
- 125000001188 haloalkyl group Chemical group 0.000 claims description 5
- 125000005368 heteroarylthio group Chemical group 0.000 claims description 5
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- 125000005418 aryl aryl group Chemical group 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 125000005366 cycloalkylthio group Chemical group 0.000 claims description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 4
- 125000005553 heteroaryloxy group Chemical group 0.000 claims description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 4
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 4
- 125000006799 (C2-C6) alkenylamino group Chemical group 0.000 claims description 3
- 125000006766 (C2-C6) alkynyloxy group Chemical group 0.000 claims description 3
- 125000003601 C2-C6 alkynyl group Chemical group 0.000 claims description 3
- 125000004414 alkyl thio group Chemical group 0.000 claims description 3
- 125000005109 alkynylthio group Chemical group 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 125000004438 haloalkoxy group Chemical group 0.000 claims description 3
- 125000005241 heteroarylamino group Chemical group 0.000 claims description 3
- 125000005842 heteroatom Chemical group 0.000 claims description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- 125000005133 alkynyloxy group Chemical group 0.000 claims description 2
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 claims description 2
- 125000004604 benzisothiazolyl group Chemical group S1N=C(C2=C1C=CC=C2)* 0.000 claims description 2
- 125000004603 benzisoxazolyl group Chemical group O1N=C(C2=C1C=CC=C2)* 0.000 claims description 2
- 125000004619 benzopyranyl group Chemical group O1C(C=CC2=C1C=CC=C2)* 0.000 claims description 2
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 claims description 2
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- OILAIQUEIWYQPH-UHFFFAOYSA-N cyclohexane-1,2-dione Chemical compound O=C1CCCCC1=O OILAIQUEIWYQPH-UHFFFAOYSA-N 0.000 claims description 2
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 125000002541 furyl group Chemical group 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 125000002883 imidazolyl group Chemical group 0.000 claims description 2
- 239000011630 iodine Substances 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 125000001786 isothiazolyl group Chemical group 0.000 claims description 2
- 125000000842 isoxazolyl group Chemical group 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- ZNPKAOCQMDJBIK-UHFFFAOYSA-N nitrocyanamide Chemical group [O-][N+](=O)NC#N ZNPKAOCQMDJBIK-UHFFFAOYSA-N 0.000 claims description 2
- 125000002971 oxazolyl group Chemical group 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 2
- 125000003367 polycyclic group Chemical group 0.000 claims description 2
- 125000004309 pyranyl group Chemical group O1C(C=CC=C1)* 0.000 claims description 2
- 125000003373 pyrazinyl group Chemical group 0.000 claims description 2
- 125000003226 pyrazolyl group Chemical group 0.000 claims description 2
- 125000000714 pyrimidinyl group Chemical group 0.000 claims description 2
- 125000000168 pyrrolyl group Chemical group 0.000 claims description 2
- 125000005493 quinolyl group Chemical group 0.000 claims description 2
- 235000009518 sodium iodide Nutrition 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 125000001544 thienyl group Chemical group 0.000 claims description 2
- 125000003320 C2-C6 alkenyloxy group Chemical group 0.000 claims 3
- 239000003513 alkali Substances 0.000 claims 3
- 125000003277 amino group Chemical group 0.000 claims 3
- 125000005264 aryl amine group Chemical group 0.000 claims 3
- 125000000000 cycloalkoxy group Chemical group 0.000 claims 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims 2
- 150000001408 amides Chemical class 0.000 claims 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 2
- XIHRUFOQGSWNFW-CYBMUJFWSA-N (2R)-N-[(6-chloropyridin-3-yl)methyl]-2-[4-[5-(trifluoromethyl)pyridin-2-yl]oxyphenoxy]propanamide Chemical compound O([C@H](C)C(=O)NCC=1C=NC(Cl)=CC=1)C(C=C1)=CC=C1OC1=CC=C(C(F)(F)F)C=N1 XIHRUFOQGSWNFW-CYBMUJFWSA-N 0.000 claims 1
- 125000006552 (C3-C8) cycloalkyl group Chemical group 0.000 claims 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims 1
- JTZSFNHHVULOGJ-UHFFFAOYSA-N 3-(trifluoromethyl)pyridine Chemical compound FC(F)(F)C1=CC=CN=C1 JTZSFNHHVULOGJ-UHFFFAOYSA-N 0.000 claims 1
- 241000282330 Procyon lotor Species 0.000 claims 1
- 125000003172 aldehyde group Chemical group 0.000 claims 1
- 150000001345 alkine derivatives Chemical class 0.000 claims 1
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- 125000005597 hydrazone group Chemical group 0.000 claims 1
- 230000007062 hydrolysis Effects 0.000 claims 1
- 238000006460 hydrolysis reaction Methods 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 125000002098 pyridazinyl group Chemical group 0.000 claims 1
- 125000001113 thiadiazolyl group Chemical group 0.000 claims 1
- 125000004149 thio group Chemical group *S* 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 28
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- 238000000034 method Methods 0.000 description 15
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/60—1,4-Diazines; Hydrogenated 1,4-diazines
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- A—HUMAN NECESSITIES
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
- A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
- A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/62—Oxygen or sulfur atoms
- C07D213/63—One oxygen atom
- C07D213/64—One oxygen atom attached in position 2 or 6
- C07D213/643—2-Phenoxypyridines; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
- C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
- C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
Definitions
- the present invention relates to an N-arylsulfonyl group having herbicidal, bactericidal, insecticidal activity; an aryloxyphenoxycarboxylic acid amide compound, a process for the preparation thereof, and the use of these compounds for controlling harmful weeds, harmful germs, pests and the like method. ⁇ Background technique ⁇
- the aryloxyphenoxycarboxylic acid compound has activity against grass weeds, and a plurality of such active compounds have been successfully developed into herbicides, such as clodinafop-propargyl US represented by formula (P-1).
- 4505743 is an aryloxyphenoxypropionate herbicide developed by Syngenta Crop Protection Co., Ltd., which is used at a dose of 40 ⁇ 60 g active ingredient per hectare for some varieties of wheat field to control malignant grass weeds;
- the cyhalofop-butyl EP 0302203 represented by formula (P-2) was developed and produced by Dow Agrotech in 1987 and used in rice fields with a dose of 50 to 100 grams of active ingredient per hectare.
- a phenoxyphenoxypropionate herbicide a phenoxyphenoxypropionate herbicide
- the oxazolamide Metalifop WO 200005956A1 represented by the formula (P-3) is a therapeutic component developed by the Korea Institute of Chemical Technology and used at a dose of 90 to 120 g.
- Another special aryloxyphenoxypropionate herbicide in the rice field of the hectare/heterophylline, other aryloxyphenoxycarboxylic acid herbicides can not be directly used in the gramineous crop field control without adding a safener. grass.
- the aryloxyphenoxycarboxylic acid herbicides are active against grass weeds, and some have very excellent activities. It is insufficient that these herbicides are mostly unsafe for grass crops (such as wheat, rice, etc.).
- the acetylene ester shown in (P-1) although highly active against grass weeds, is safe only for some wheat varieties and not safe for rice; cyanoflufenate of formula (P-2)
- the oxazolamide shown by formula (P-3) although safe for rice, has much lower activity against grass weeds than acetylene ester shown in (P-1), and does not Safety.
- aryloxyphenoxycarboxylic acid compound for grass crops, especially rice and wheat
- the inventors introduced 0-chain unsaturated hydroxylamine into the structure of aryloxyphenoxycarboxylic acid, and designed and synthesized A/- Unsaturated chain aryl aryl oxy oxy carboxylic acid amide compound (CN 201010221128.2 ), and found that acetylene oxalate shown by (P-1) and cyhalofoprin (P-2) and (P) -3)
- the shown oxazolamide has a broader spectrum of activity and higher activity such as (P-4), etc., and compared with the acetylene ester shown by (P-1), we invented (P-4) It is safer for wheat, and -1) and (P-4) are not safe for rice, so it cannot be used for the control of weeds in paddy fields.
- the present invention provides an N-arylnonylaryloxyphenoxycarboxylic acid amide compound having a biological activity such as weeds, harmful bacteria, pests and the like and an isomer thereof represented by the formula (I):
- Ar 1 and Ar 2 are the same or different and represent a C 6 -C 12 aryl group or a heteroaryl group having up to 10 carbon atoms, and
- a) a C 3 -C 12 aryl group or a hydrogen atom in a heteroaryl group having up to 10 carbon atoms is partially or wholly substituted with the same or different substituents selected from the group consisting of halogen, nitro, cyano, amine Base, hydroxyl group, thiol group, carboxyl group, leave group, thiol group, fluorenyl group.
- substituents selected from the group consisting of halogen, nitro, cyano, amine Base, hydroxyl group, thiol group, carboxyl group, leave group, thiol group, fluorenyl group.
- R 1 and R 2 , R 3 are the same or different and represent hydrogen, CrCs fluorenyl, C 2 -C 6 chain; J: Hirsch, C 2 -C 6 alkynyl, C 3 -C 8- cyclodecyl, C 6 -C 12 aryl or heteroaryl having up to 10 carbon atoms;
- n 1 or 2, 3;
- alkyl, cyclodecyl, alkenyl, alkynyl, aryl, heteroaryl groups in la) and II. are unsubstituted or fluorenyl or cyclodecyl groups described in la) and II.
- the alkenyl, alkynyl, aryl, heteroaryl group is partially or wholly substituted with a substituent selected from the group consisting of the same or different substituents: halogen, C r C 6 fluorenyl, C r C 6 fluorenyl oxygen group, C r C 6 alkyl with thio, CC 6 alkyl with an amine, di (CC 6) alkylamino, C 2 -C ⁇ 3 ⁇ 4 alkenyl, C 2 -C 6 alkenyl group, C 2 -C 6 alkenylthio, c 2 -c 6 alkenylamino, di c 2 -c 6 alkenylamino, c 2 -c 6 alkynyl, c 2 -c 6 alkynyloxy , c 2 -c 6 alkynylthio, c 2 -c 6 alkynylamino, di c 2 -c 6 alkynylamino,
- Halogen means fluorine, chlorine, bromine, iodine
- ⁇ base refers to a straight or branched chain thiol
- Cyclodecyl group refers to a saturated or unsaturated cyclic fluorenyl group
- Alkenyl means straight or branched and may have a double bond at any position
- Alkenyl means straight or branched and may have a triple bond at any position
- Haloalkyl a straight or branched alkyl group in which a hydrogen atom is partially or completely substituted by a halogen atom; a halogenated cycloalkyl group: a saturated or unsaturated cycloalkyl group, and a hydrogen atom moiety thereof Or all substituted by a halogen atom; haloalkenyl: refers to a straight or branched chain and may have a double bond at any position, and a part or all of the hydrogen atom thereof is substituted by a halogen atom;
- Haloalkynyl group means a straight chain or a branched chain and may have a triple bond at any position, and a part or all of the hydrogen atom thereof is substituted by a halogen atom;
- aryl means phenyl and a cyclic aryl or polycyclic aryl derived therefrom, such as naphthyl, biphenyl, etc.; heteroaryl with up to 10 carbon atoms means a heterocyclic An aryl or polycyclic heteroaryl group having at least one N and/or 0, S, P, such as pyridyl, thiazolyl, quinoxalinyl, benzoxazolyl, pyrazolyl, thiadiazole Base, thienyl, benzothienyl, furyl, benzofuranyl, pyrrolyl, benzopyrrolyl, imidazolyl, benzimidazolyl, quinolyl, pyranyl, pyrazinyl, pyrimidinyl, anthracene Azinyl, benzopyranyl, benzopyrimidinyl, oxazolyl, isoxazolyl, benzisoxazolyl
- Preferred compounds of the invention are: In formula (I):
- a " 1 and Ar 2 are the same or different and represent phenyl, pyridyl, thiazolyl, quinoxalinyl, benzoxazolyl, and phenyl, pyridyl, thiazolyl, quinoxalinyl
- the hydrogen atom in the benzoxazolyl group is partially or completely substituted by the same or different substituents selected from the group consisting of halogen, cyano, dC 6 alkyl, dC 6 decyloxy, dC 6 decylthio, CrC 6 mercaptoamine, C r C 6 halodecyl, dC 6 halodecyloxy;
- R 1 and R 2 , R 3 are the same or different and represent hydrogen, C r C 6 fluorenyl, C r C 6 halogenated fluorenyl;
- n stands for 1.
- a " 1 and Ar 2 are the same or different and represent pyridyl, thiazolyl, quinoxalinyl, benzoxazolyl, and pyridyl, thiazolyl, quinoxalinyl, benzoxazolyl Part or all of the hydrogen atom is substituted with the same or different substituents selected from the group consisting of: halogen, CC 3 fluorenyl, CC 3 decyloxy, C r C 3 halodecyl, CC 3 haloalkoxy;
- R 1 and R 2 , R 3 are the same or different and represent hydrogen, d-Cs fluorenyl;
- n stands for 1.
- Particularly preferred compounds of formula (I) according to the invention are mixtures of the following compounds in a ratio of the R isomer and the S isomer:
- the compounds of the invention may exist in the form of one or more isomers. Isomers include enantiomers, diastereomers, geometric isomers.
- a compound represented by the formula (I) of the present invention may form a geometric isomer (a different configuration is represented by Z and E, respectively) due to a carbon-carbon double bond in which a different substituent is bonded, and the present invention includes Z-isomers and E-isomers and mixtures thereof in any ratio.
- the compound of the formula (I) of the present invention forms a stereoisomer due to the attachment of four different substituents on the same carbon atom (respectively represented by R and S, respectively, the present invention includes the R-type isomer And S-isomers and mixtures of them in any ratio.
- the invention further relates to a biologically effective amount of a compound of formula (I) and at least one additional composition selected from the group consisting of surfactants, solid diluents and liquid diluents for controlling harmful weeds, harmful pathogens, pests.
- the invention also relates to a method for controlling harmful weeds, harmful germs, pests, comprising contacting a biologically effective amount of a compound of formula (I) with harmful weeds, harmful germs, pests or their environment. It also relates to such a harmful weed, harmful pathogen, pest control method, harmful weeds, harmful bacteria, pests or their environment, biologically effective amount of the compound of formula (I) to prevent harmful weeds, harmful bacteria, pests .
- the compounds of formula (I) according to the invention have a broad spectrum of activity: some compounds are useful for controlling harmful weeds and for controlling harmful germs or pests. Moreover, some compounds have high biological activity against certain harmful weeds, so that good results can be obtained at very low doses.
- compositions of the invention are compositions containing the preferred compounds described above.
- a preferred method is the method of using the above preferred compounds.
- the invention will be further illustrated by the following formula (I), which is listed in Tables 1 to 2, but does not limit the invention.
- the melting points given in the present invention are uncorrected; when the compound of the formula (I) synthesized by the present invention is a viscous solid, some of the viscous solid refrigerators will solidify into a non-tacky solid after being placed; all the compounds in Table 1 are in LC-MS (APCI).
- the compound of the formula (I) of the present invention can be obtained by the reaction formula 1 shown below; (II) in the reaction formula 1 can be obtained by the reaction formula 2 shown below; (III) in the reaction formula 1 can be passed
- the reaction formula 3 or the reaction formula 4 shown below is obtained, and Z in the reaction formula 1 to the reaction formula 4 is a leaving group such as chlorine, bromine, sulfonate or the like, and other substituents are as previously described unless otherwise specified. limited.
- the compound of the formula (I) can be produced by the following reaction (Reaction formula 1): in a suitable solvent such as dichloromethane or dichloroacetic acid, toluene at -10 to 110 ° C, in a suitable base such as triethylamine In the presence of pyridine, a compound of the formula (II) and a compound of the formula (III) are reacted to obtain a compound of the formula (I), and a suitable catalyst such as 4-dimethylaminopyridine (DMAP) is added. Or sodium iodide can speed up the reaction or increase the reaction yield.
- reaction formula 1 reaction (Reaction formula 1): in a suitable solvent such as dichloromethane or dichloroacetic acid, toluene at -10 to 110 ° C, in a suitable base such as triethylamine
- a compound of the formula (II) and a compound of the formula (III) are reacted to obtain a compound of the formula (I), and a suitable catalyst such
- the compound of formula (II) can be prepared by the following reaction (reaction formula 2): in a suitable solvent such as hydrazine, hydrazine-dimethylformamide (DMF) or toluene, tetrahydrofuran, ethanol, in a suitable base such as potassium carbonate or hydrogen.
- a suitable solvent such as hydrazine, hydrazine-dimethylformamide (DMF) or toluene, tetrahydrofuran, ethanol
- a suitable base such as potassium carbonate or hydrogen.
- the compound of the formula (IV) and the compound of the formula (V) are reacted in the presence of potassium oxide, sodium carbonate, sodium hydroxide or sodium hydride at 25 to 15 CTC to obtain a compound of the formula (VI).
- a compound represented by the formula (VI) with an acid halide reagent such as thionyl chloride or oxalyl chloride
- the compound represented by the formula (II) is
- a compound of the formula (VIII) is reacted with a compound of the formula (VIII) to give a compound of the formula (III) 4) addition of a suitable phase transfer catalyst such as benzyltriethylammonium chloride (of TEBA) or tetrabutylammonium bromide, tetrabutylammonium chloride or the like to accelerate the reaction to improve the reaction yield.
- a suitable phase transfer catalyst such as benzyltriethylammonium chloride (of TEBA) or tetrabutylammonium bromide, tetrabutylammonium chloride or the like to accelerate the reaction to improve the reaction yield.
- the compound of the formula (I) provided by the invention has a broad spectrum biological activity at a dosage of 15 to 2250 g of active ingredient per hectare, and can be used for controlling harmful weeds, and can also be used for controlling harmful bacteria or pests, and some compounds have good properties. Harmful weed control can achieve good results at very low doses.
- the compound of the formula (I) provided by the present invention is biologically active and has a good biological activity. In particular, it exhibits activity in the control of agricultural, horticultural, flower and hygienic harmful weeds, harmful germs, and pests.
- the pests described here include, but are not limited to:
- Gramineous weeds crabgrass, valerian, foxtail, hard grass, valerian, brome, amethyst, stalked wheat, sodic grass, star grass, wild oats, ryegrass;
- weeds Broadleaf weeds: ramie, sorghum, sylvestris, scorpion, scorpion scorpion, scorpion scorpion, hedgehog, etc.
- Harmful pathogens Phytophthora species, white genus, genus Gibberella, species of genus, genus Sclerotinia, genus Rhizoctonia, species of Botrytis, species of Pythium, species of Fusarium
- rice blast Pyricularia oryzae
- wheat stripe rust Puccinia striiformis
- leaf rust Pieris oryzae
- barley stripe rust Pieris
- leaf attractor Pierinia recondita
- barley Erysiphe graminis Sphaerotheca fuligenea, Podosphaera leucotrichar and Podosphaera leucotrichar
- Orthoptera such as striata, pteridopterus such as cotton scorpion horse, rice scorpion horse, melon scorpion horse, Homoptera such as spider mites, locusts, locusts, lepidoptera such as oriental armyworm, Spodoptera litura, side dish Moth, beet armyworm, Spodoptera litura, Pieris rapae, Hymenoptera such as leaf bee larvae, Diptera such as Aedes, Culex, fly, scorpion, such as orange scorpion, cotton leaf scorpion.
- the compound of the formula (I) of the present invention When used alone, it is effective for controlling harmful weeds, harmful germs, and pests, and they can also be used together with other substances.
- the agricultural preparation containing the compound of the formula (I) of the present invention as an active ingredient can be prepared into any desired dosage form.
- the invention is further illustrated by the following examples in which the yields in the examples are not optimized.
- 2-chlorothiazol-5-methylamine 100 mL three-necked vial, hydrazine-dimethylformamide (40 mL), phthalimide (0.05 mol) and potassium hydroxide (0.05 mol), After stirring at room temperature, 2-chloro-5-chloromethylthiazole (0.05 mol) was added dropwise and stirred at room temperature overnight. The reaction was poured into ice water (250 mL). The solid was added to a 250 mL three-necked flask and ethanol (150 ml) was added.
- 2-Chloropyridine-5-methylamine 100 mL three-necked flask was charged with hydrazine, hydrazine-dimethylformamide (DMF) (40 mL), phthalimide (0.05 mol) and potassium hydroxide (0.05) Mol), dissolved by stirring at room temperature, 2-chloro-5-chloromethylpyridine (0.05 mol) was added dropwise, and stirred at room temperature overnight. The reaction was poured into ice water (250 mL). The solid was added to a 250 mL three-necked flask and ethanol (150 ml) was added.
- DMF hydrazine-dimethylformamide
- phthalimide 0.05 mol
- potassium hydroxide 0.05) Mol
- the synthesized compounds were tested for herbicidal, bactericidal and insecticidal activity, and some of the experimental results are as follows.
- the method is as follows: (1) Quantitatively compacting the soil in a plastic pot with a cross-sectional area of 64 cm 2 and placing it in a stainless steel pot. Select seeds with full grain size and uniform size, and divide the monocot weeds [Digitaria sanguinalis, Echinochloa crus-galli, Setaria viridis, Abutilon theophrasti, Amaranthus spinosus, Chenopodium album, seeding, each area 1/3, covered with 1 cm thick fine soil, water is added from the bottom of the plastic pot to the upper layer of soil infiltration, placed in the greenhouse for cultivation, and the test material is grown to the required leaf age for testing; (2) Weighing the appropriate amount Compound of formula (I), dissolved in N, N-dimethylformamide, added a small amount of Tween 80 emulsifier, stirred evenly, added with quantitative water, formulated into a The concentration is required, and the corresponding solvent and clean water are used as the control; (3) Treatment method: The soil material before the seedling is
- the method is as follows: The test compound is dissolved in a suitable solvent such as hydrazine, hydrazine-dimethylformamide (DMF), and further contained at 0.1 °/. Dilute the Tween80 emulsifier to the desired concentration with sterile water; pipette 3 mL of the solution into 27 mL of potato agar medium (PDA) cooled to 45 ° C and shake well, then pour into the Petri dish; After cooling, use the inoculation needle to take a 6 mm diameter hyphae from the edge of the colony of Sclerotinia sclerotiorum that was cultured for 7 days, and move it to the center of the culture dish with the hyphae facing down, and set a blank containing no test compound as a control.
- a suitable solvent such as hydrazine, hydrazine-dimethylformamide (DMF)
- DMF hydrazine-dimethylformamide
- the activity is divided into four grades A, B, C, and D with respect to the blank control, 100 ° / ( ⁇ inhibition rate ⁇ 90 ° /. is grade A, 90% > inhibition rate 70% is grade B, 70 °
- the inhibition rate is 50% for class C, 50%> inhibition rate ⁇ 0% for class D.
- Sclerotinia sclerotiorum such as compounds 32 and 48, 67 at 25 mg/L. At the concentration, the S. sclerotiorum has C or higher activity.
- the activity of the compound of the formula (I) of the present invention against Botrytis cinerea was determined, and the results showed that the compound of the present invention is active against Botrytis cinerea, such as Compound 03. And 05, 20, 22, etc. at 25 mg / L concentration of Cucumber gray mold bacteria have C or higher activity.
- Example 8 against Rhizoctonia solani (in vitro leaf culture method) is as follows: The test compound is dissolved in a suitable solvent such as hydrazine, hydrazine-dimethylformamide (DMF), and then used. Contains 0.1 ° /.
- the Tween80 emulsifier is diluted with sterile water to the required concentration; the leaves of the fresh and young broad bean seedlings are treated with a certain concentration of the drug and placed in a petri dish with aqueous filter paper, and the homemade perforated iron for the leaves and filter paper. The shelves are separated. After drying the leaves, connect the fresh hyphae with a diameter of 6 mm and culture for 2 to 3 days.
- Example 9 bactericidal activity against wheat powdery mildew (Erisiphe griminis) (potted method)
- the method is as follows: The test compound is dissolved in a suitable solvent such as hydrazine, hydrazine-dimethylformamide (DMF), and 0.1 °/. Dilute the emulsifier of Tween80 emulsifier to the required concentration; take a pot of about 15 cm of straight stem, and soak 20 full and healthy seeds of wheat per stalk, and wait for the second leaf to grow for test. Take the prepared wheat. The seedling plants are sprayed with a certain concentration of the drug, and the harmful bacteria are inoculated one day later. Each treatment was repeated 3 times, and the blank containing no test compound was used as a control.
- a suitable solvent such as hydrazine, hydrazine-dimethylformamide (DMF), and 0.1 °/.
- DMF hydrazine-dimethylformamide
- the compound of the present invention has a control effect on wheat powdery mildew, for example, compound 03 has an effect of more than 80% on wheat powdery mildew at a concentration of 500 mg/L.
- the method is as follows: Weigh an appropriate amount of the compound of the formula (I) provided by the present invention, dissolve it in a suitable solvent such as N, N-dimethylformamide, add a small amount of Tween 80 emulsifier, stir evenly, add quantitative water, and prepare the preparation. The concentration is required, and the water is set as the control.
- a suitable solvent such as N, N-dimethylformamide
- the soybean meal is attached to the newly unearthed bean seedlings, and each plant is connected to more than 20 heads, and then the bean seedlings are immersed together with the test insects in the liquid solution of the compound of the formula (I) provided by the present invention, and taken out after 5 seconds, sucking Remove the excess liquid, insert it into the absorbent sponge, cover it with a glass tube, and check the number of surviving and dead insects after 24 hours. Repeat 3 times and the results are averaged. Relative blank pair According to the percentage.
- the results indicate that the compound of the present invention is active against soybean meal. For example, at a concentration of 500 mg/L, the activities (mortality) of the compounds 13 and 20, 22 against the broad bean meal are more than 50%.
- Example 11 Acaricidal activity against cotton red spider (Tetranychus urticae)
- the method is as follows: Weigh an appropriate amount of the compound of the formula (I) provided by the present invention, dissolve it in a suitable solvent such as N, N-dimethylformamide, add a small amount of Tween 80 emulsifier, stir evenly, add quantitative water, and prepare the preparation. The concentration is required, and the water is set as the control. Choose a good bean sprout to inoculate red spider. After the spider is colonized, cut the bean seedlings into the prepared liquid for 10 seconds. Remove the excess liquid from the filter paper and insert it into the water beaker. In the observation room culture, the number of survival and death sputum was checked after 24 hours, and there were 100-200 cockroaches per bean seedling. The experiment was repeated three times. The results were averaged.
- a suitable solvent such as N, N-dimethylformamide
- the activity is divided into four levels A, B, C, and D relative to the blank control, 100% ⁇ mortality ⁇ 90% for grade A, and 90% > mortality ⁇ 70°/.
- grade B 70%> mortality ⁇ 50% for grade C, 50% > mortality ⁇ 0% for grade D.
- the results indicate that the compound of the present invention is active against cotton spider mites, for example, at a concentration of 500 mg/L, the activity (mortality) of compound 48 against cotton spider mites is greater than 50%.
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Abstract
本发明公开了式(I)所示N-(芳基烷基)芳氧苯氧羧酸酰胺类化合物及其制备方法与应用。式(I)式中Ar1和Ar2、R1、R2、R3、n具有说明书中所给定义。本发明式(I)化合物具有除草和/或杀菌、杀虫、杀螨生物活性,有的化合物具有很高的除草活性,在15~75克有效成分/公顷用量下就可以获得很好的效果。
Description
N- (芳基浣基)芳氧苯氧羧酸酰胺类化合物及其制备方法与应用
【技术领域】
本发明涉及具有除草、 杀菌、 杀虫生物活性的 N 芳基垸基;)芳氧苯氧羧酸酰胺类化合 物及其制备方法、 以及用这些化合物控制有害杂草、 有害病菌、 害虫的用途与方法。 【背景技术】
芳氧苯氧羧酸类化合物具有防除禾本科杂草的活性, 并有多个该类活性化合物被成功 开发为除草剂, 如式(P-1 )所示的炔草酯(clodinafop-propargyl US 4505743)是瑞士先 正达作物保护有限公司开发的使用剂量为 40〜60 克有效成分 /公顷,用于某些品种小麦田 防除恶性禾本科杂草的芳氧苯氧丙酸酯类除草剂; 而式 (P-2 ) 所示的氰氟草酯 (cyhalofop-butyl EP 0302203) 是由美国陶氏益农公司于 1987年开发生产的使用剂量为 50〜100 克有效成分 /公顷的水稻田专用的苯氧苯氧丙酸酯类除草剂; 式(P-3)所示的噁 唑酰草胺 (Metamifop WO 200005956A1 )则是由韩国化工技术研究院开发的使用剂量为 90〜120 克有效成分 /公顷的水稻田另一专用的芳氧苯氧丙酸酯类除草剂, 其它芳氧苯氧 羧酸类除草剂在不添加安全剂的情况下基本上不能直接用于禾本科作物田防治杂草。
芳氧苯氧羧酸类除草剂对禾本科杂草具有活性, 有的还具有非常优异的活性, 不足的 是这些除草剂对禾本科作物 (如小麦、 水稻等) 大多不安全。 如 (P-1 ) 所示的炔草酯尽 管对禾本科杂草活性很高, 但它只对部分小麦品种安全, 对水稻都不安全; 式 (P-2) 所 示的氰氟草酯和式 (P-3) 所示的噁唑酰草胺尽管对水稻安全, 但它对禾本科杂草的活性 又远低于 (P-1 ) 所示的炔草酯, 且对小麦也不安全。
为获得对禾本科作物特别是水稻、 小麦安全的高活性芳氧苯氧羧酸类化合物, 发明人 将 0-链式不饱和羟胺引入芳氧苯氧羧酸结构中, 设计并合成 A/-不饱和链氧基芳氧苯氧羧 酸酰胺类化合物 (CN 201010221128.2 ), 并从中发现较 (P-1 ) 所示的炔草酯和 (P-2) 所示的氰氟草酯以及 (P-3) 所示的噁唑酰草胺具有更广的活性谱和更高活性的化合物如 ( P-4) 等, 且与 (P-1 ) 所示的炔草酯相比, 我们发明的 (P-4) 对小麦更安全, 不足的 -1 ) 和 (P-4) 对水稻都不安全, 因而不能用于水稻田杂草的防治。
为进一步提高(P-4) 的除草活性和 /或对作物特别是水稻的安全性, 我们又将芳基垸 基引入芳氧苯氧羧酸酰胺类结构中, 设计并合成一系列具有广谱活性的化合物, 并获得一 批除草活性高于(P-2)和(P-3)的化合物,且有的化合物对水稻安全, 从而解决了(P-1 )
和 (P-4) 不能用于水稻田的不足。 同时有的化合物还显示出明显的杀菌或杀虫活性。
【发明内容】
巾:
I . Ar1和 Ar2是相同的或不同的,并代表 C6-C12芳基或带多至 10个碳原子的杂芳基, 且
a) C3-C12芳基或带多至 10个碳原子的杂芳基中的氢原子部分或全部被选自下列中相 同或不同的取代基取代: 卤素、 硝基、 氰基、 胺基、 羟基、 巯基、 羧基、 酵基、 肼基、 腙 基、。1-。6焼基、。1 -。6烧基氧基、。1 -。6焼基硫基、。1-。6焼基胺基、二 (。1 -。6)烧基胺基、
C2-C6链烯基、 C2-C3链烯基氧基、 C2-C6链烯基硫基、 C2-C6链烯基胺基、 二 C2-C6链烯 基胺基、 02 6链炔基、 C2-C6链炔基氧基、 C2-C6链炔基硫基、 02-06链炔基胺基、二 c2-c6 链炔基胺基、 ( 3-08环垸基、 c3-c8环垸基氧基、 c3-c8环垸基硫基、 c3-c8环垸基胺基、 二 C3-C8环烷基胺基、 C6-C12芳基或带多至 10个碳原子的杂芳基、 c6-c12芳基氧基或带 多至 10个碳原子的杂芳基氧基、 C6-C12芳基硫基或带多至 10个碳原子的杂芳基硫基、 C6-C12芳基胺基或带多至 10个碳原子的杂芳基胺基;
II. R1和 R2, R3是相同的或不同的, 并代表氢、 CrCs垸基、 C2-C6链; J:希基、 C2-C6 链炔基、 C3-C8环垸基、 C6-C12芳基或带多至 10个碳原子的杂芳基;
III. n代表 1或 2、 3; 且
1 ) l.a)和 II. 中所述烷基、环垸基、链烯基、链炔基、芳基、杂芳基为未取代的或 l.a) 和 II.中所述垸基、 环垸基、 链烯基、 链炔基、 芳基、 杂芳基中氢原子部分或全部被选自下 列中相同或不同的取代基取代:卤素、 CrC6垸基、 CrC6垸基氧基、 CrC6垸基硫基、 C C6 垸基胺基、 二 (C C6)烷基胺基、 C2-C^¾烯基、 C2-C6链烯基氧基、 C2-C6链烯基硫基、 c2-c6链烯基胺基、 二 c2-c6链烯基胺基、 c2-c6链炔基、 c2-c6链炔基氧基、 c2-c6链炔 基硫基、 c2-c6链炔基胺基、二 c2-c6链炔基胺基、 c3-c8环烷基、 c3-c8环垸基氧基、 c3-c8 环垸基硫基、 C3-C3环垸基胺基、二 C3-C8环烷基胺基、 C6-C12芳基或带多至 10个碳原子 的杂芳基、 C6-C12芳基氧基或带多至 10个碳原子的杂芳基氧基、 06-012芳基硫基或带多 至 10个碳原子的杂芳基硫基、 C6-C12芳基胺基或带多至 10个碳原子的杂芳基胺基、 二
C6-C12芳基胺基或带多至 10个碳原子的二杂芳基胺基、 C6-C12芳基芳基或带多至 10个碳 原子的杂芳基芳基、 C6-C12芳基杂芳基或带多至 10个碳原子的杂芳基杂芳基; 且 1 )中所 述垸基、 环垸基、 链烯基、 链炔基、 芳基、 杂芳基中氢原子部分或全部被选自下列中相同 或不同的取代基取代: 氢、 卤素、 CrCs烷基、 C C6垸基氧基、 d-Cs烷基硫基、 C C6 垸基胺基、 二 (C Ce)烷基胺基、 C2-C3链烯基、 C2-C6链烯基氧基、 C2-C6链烯基硫基、 C2-C6链烯基胺基、 二 C2-C6链烯基胺基、 C2-C6链炔基、 C2-C6链炔基氧基、 C2-C6链炔 基硫基、 c2-c6链炔基胺基、二 c2-c6链炔基胺基、 c3-c8环垸基、 c3-c8环垸基氧基、 c3-c8 环烷基硫基、 C3-C3环垸基胺基、 = C3-C8环垸基胺基、 C6-C12芳基或带多至 10个碳原子 的杂芳基、 C6-C12芳基氧基或带多至 10个碳原子的杂芳基氧基、 c6-c12芳基硫基或带多 至 10个碳原子的杂芳基硫基、 C6-C12芳基胺基或带多至 10个碳原子的杂芳基胺基、 二 C6-C12芳基胺基或带多至 10个碳原子的二杂芳基胺基、 C6-C12芳基芳基或带多至 10个碳 原子的杂芳基芳基、 C6-C12芳基杂芳基或带多至 10个碳原子的杂芳基杂芳基;
上面给出的化合物(I)的定义中, 所用术语不论单独使用还是用在复合词中, 代表如 下取代基:
卤素: 指氟、 氯、 溴、 碘;
垸基: 指直链或支链垸基;
环垸基: 指饱和或不饱和的环垸基;
链烯基; 指直链或支链并可在任何位置上存在有双键;
链炔基; 指直链或支链并可在任何位置上存在有三键;
卤代烷基: 指直链或支链烷基, 在这些烷基上的氢原子部分或全部被卤原子取代; 卤代环垸基: 指饱和或不饱和的环垸基, 且其中的氢原子部分或全部被卤原子取代; 卤代链烯基: 指直链或支链并可在任何位置上存在有双键, 且其中的氢原子部分或全 部被卤原子取代;
卤代炔基: 指直链或支链并可在任何位置上存在有三键, 且其中的氢原子部分或全部 被卤原子取代;
c6-c12芳基指苯基和由它派生出的一环芳基或多环芳基, 如萘基, 联苯基等; 带多至 10个碳原子的杂芳基指一环杂芳基或多环杂芳基, 式中至少有 1个 N和 /或 0, S, P, 如吡啶基、 噻唑基、 喹喔啉基、 苯并噁唑基、 吡唑基、 噻二唑基、 噻吩基、 苯 并噻吩基、 呋喃基、 苯并呋喃基、 吡咯基、 苯并吡咯基、 咪唑基、 苯并咪唑基、 喹啉基、 吡喃基、 吡嗪基、 嘧啶基、 哒嗪基、 苯并吡喃基、 苯并嘧啶基、 噁唑基、 异噁唑基、 苯并 异噁唑基、 苯并噻唑基、 异噻唑基、 苯并异噻唑基、 嘧啶并三唑基等;
C6-C12芳基和带多至 10个碳原子的杂芳基可以部分或全部氢化,其中 1个或 2个 CH2 被 CO取代, 如环已烯基, 环已二酮基等。
本发明优选的化合物为: 式 (I) 中:
I. A「1和 Ar2是相同或不同的, 并代表苯基、 吡啶基、 噻唑基、 喹喔啉基、 苯并噁唑 基, 且苯基、 吡啶基、 噻唑基、 喹喔啉基、 苯并噁唑基中的氢原子部分或全部被选自下列 中相同或不同的取代基取代: 卤素、氰基、 d-C6烷基、 d-C6垸基氧基、 d-C6垸基硫基、 CrC6垸基胺基、 CrC6卤代垸基、 d-C6卤代垸氧基;
II. R1和 R2, R3是相同的或不同的, 并代表氢、 CrC6垸基、 CrC6卤代垸基;
III. n代表 1。
本发明进一步优选的化合物为: 式 (I ) 中-
I. A「1和 Ar2是相同或不同的, 并代表吡啶基、 噻唑基、 喹喔啉基、 苯并噁唑基, 且 吡啶基、 噻唑基、 喹喔啉基、 苯并噁唑基中的氢原子部分或全部被选自下列中相同或不同 的取代基取代: 卤素、 C C3垸基、 C C3垸氧基、 CrC3卤代垸基、 C C3卤代烷氧基;
II. R1禾卩 R2, R3是相同的或不同的, 并代表氢、 d-Cs垸基;
III. n代表 1。
本发明特别优选的式( I )化合物是下述化合物 R型异构体和 S型异构体任何比例的 混合物:
N-(2-氯噻唑 -5-基甲基 )-2-(4-((5-氯 -3-氟吡啶 -2-基)氧基)苯氧基)丙酰胺;
N-甲基 -N-(2-氯噻唑 -5-基甲基 )-2-(4-((5-氯 -3-氟吡啶 -2-基)氧基)苯氧基)丙酰胺; N-乙基 -N-(2-氯噻唑 -5-基甲基 )-2-(4-((5-氯 -3-氟吡啶 -2-基)氧基)苯氧基)丙酰胺;
N-(2-氯噻 P坐 -5-基甲基 )-2-(4-((3-氯 -5-三氟甲基吡啶 -2-基)氧基)苯氧基)丙酰胺; N-甲基 -N-(2-氯噻睡 -5-基甲基 )-2-(4-((3-氯 -5-三氟甲基吡啶 -2-基)氧基)苯氧基)丙酰胺; N-乙基 -N-(2-氯噻唑 -5-基甲基 )-2-(4-((3-氯 -5-三氟甲基吡啶 -2-基)氧基)苯氧基)丙酰胺; N-(2-氯噻唑 -5-基甲基 )-2-(4-((5-三氟甲基吡啶 -2-基)氧基)苯氧基)丙酰胺;
N-(2-氯噻唑 -5-基甲基 )-2-(4-((2-氟 -4-氰基苯基)氧基)苯氧基)丙酰胺;
N-(2-氯吡啶 -5-基甲基 )-2-(4-((5-氯 -3-氟吡啶 -2-基)氧基)苯氧基)丙酰胺;
N-(2-氯吡啶 -5-基甲基 )-2-(4-((3-氯 -5-三氟甲基吡啶 -2-基)氧基)苯氧基)丙酰胺; N-(2-氯吡啶 -5-基甲基 )-2-(4-((5-三氟甲基吡啶 -2-基)氧基)苯氧基)丙酰胺;
N-(2-氯吡啶 -5-基甲基 )-2-(4-((2-氟 -4-氰基苯基)氧基)苯氧基)丙酰胺;
N-(2-氯噻 P坐 -5-基甲基 )-2-(4-((6-氯喹喔啉 -2-基)氧基)苯氧基)丙酰胺;
N-(2-氯吡啶 -5-基甲基 )-2-(4-((6-氯喹喔啉 -2-基)氧基)苯氧基)丙酰胺;
N-(2-氯噻唑 -5-基甲基 )-2-(4-((6-氯苯并 [d]噁唑 -2-基)氧基)苯氧基)丙酰胺;
N-(2-氯吡啶 -5-基甲基 )-2-(4-((6-氯苯并 [d]噁唑 -2-基)氧基)苯氧基)丙酰胺。
本发明进一步特别优选的式 ( I ) 化合物是下述化合物 R型异构体:
(R)-N-(2-氯噻唑 -5-基甲基 )-2-(4-((5-氯 -3-氟吡啶 -2-基)氧基)苯氧基)丙酰胺;
(R)-N-甲基 -N-(2-氯噻唑 -5-基甲基 )-2-(4-((5-氯 -3-氟吡啶 -2-基)氧基)苯氧基)丙酰胺;
(R)-N-乙基 -N-(2-氯噻唑 -5-基甲基 )-2-(4-((5-氯 -3-氟吡啶 -2-基)氧基)苯氧基)丙酰胺; (R)-N-(2-氯吡啶 -5-基甲基 )-2-(4-((5-氯 -3-氟吡啶 -2-基)氧基)苯氧基)丙酰胺;
(R)-N-(2-氯噻唑 -5-基甲基 )-2-(4-((3-氯 -5-三氟甲基吡啶 -2-基)氧基)苯氧基)丙酰胺; (R)— N-甲基— N-(2-氯噻唑—5—基甲基 )-2-(4-((3-氯 -5-三氟甲基吡啶 -2-基)氧)苯氧基)丙酰胺; (R)-N-乙基 -N-(2-氯噻唑 -5-基甲基 )-2-(4-((3-氯 -5-三氟甲基吡啶 -2-基)氧)苯氧基)丙酰胺;
(R)-N-(2-氯吡啶 -5-基甲基 )-2-(4-«3-氯 -5-三氟甲基吡啶 -2-基)氧基)苯氧基)丙酰胺; (R)-N-(2-氯噻唑 -5-基甲基 )-2-(4-((5-三氟甲基吡啶 -2-基)氧基)苯氧基)丙酰胺; (R)-N-(2-氯吡啶 -5-基甲基 )-2-(4-((5-三氟甲基吡啶 -2-基)氧基)苯氧基)丙酰胺; (R)-N-(2-氯噻唑 -5-基甲基 )-2-(4-((2-氟 氰基苯基)氧基)苯氧基)丙酰胺;
(R)-N-(2-氯吡啶 -5-基甲基 )-2-(4-((2-氟 氰基苯基)氧基)苯氧基)丙酰胺;
(R)-N-(2-氯噻唑 -5-基甲基 )-2-(4-((6-氯苯并 [d]噁唑 -2-基)氧基)苯氧基)丙酰胺; (R)-N-(2-氯吡啶 -5-基甲基 )-2-(4-((6-氯苯并 [d]噁唑 -2-基)氧基)苯氧基)丙酰胺; (R)-N-(2-氯噻唑 -5-基甲基 )-2-(4-((6-氯喹喔啉 -2-基)氧基)苯氧基)丙酰胺;
(R)-N-(2-氯吡啶 -5-基甲基 )-2-(4-((6-氯喹喔啉 -2-基)氧基)苯氧基)丙酰胺。
本发明的化合物可以一种或多种异构体的形式存在。 异构体包括对映异构体、 非对映 异构体、 几何异构体。 如本发明的式(I )所示的化合物, 由于其中的碳一碳双键连接不同 的取代基而可以形成几何异构体 (分别以 Z和 E来表示不同的构型), 本发明包括 Z型异构 体和 E型异构体以及它们任何比例的混合物。本发明的式(I )所示的化合物, 由于其中同 一碳原子上连接四个不同的取代基而形成立体异构体(分别以 R和 S来表示不同的构型 本发明包括 R型异构体和 S型异构体以及它们任何比例的混合物。
本发明还涉及一种防治有害杂草、 有害病菌、 害虫的含有生物有效量的式 (I )化合物 和至少一种另外的选自表面活性剂、 固体稀释剂和液体稀释剂的组合物。
本发明还涉及一种防治有害杂草、有害病菌、害虫的方法,包括将生物有效量的式(I ) 化合物接触有害杂草、 有害病菌、 害虫或其环境。 同时也涉及这样一种有害杂草、 有害病 菌、 害虫防治方法, 有害杂草、 有害病菌、 害虫或其环境用生物有效量的式(I )化合物进 行接触来防治有害杂草、 有害病菌、 害虫。
本发明的式 (I)化合物具有广谱活性: 有的化合物可用于防治有害杂草, 还可用于防 治有害病菌或害虫。 而且有的化合物对某些有害杂草具有很高的生物活性, 使得在很低的 剂量下就可以获得很好的效果。
本发明优选的组合物是含有上述优选化合物的组合物。 优选的方法是使用上述优选化 合物的方法。
下面用表 1〜表 2中列出的部分式(I)化合物来进一歩说明本发明, 但并不限定本发 明。 本发明中所给熔点均未经校正; 本发明所合成的式(I )化合物为粘性固体时, 有些粘 性固体冰箱放置后会固化为非粘性固体;表 1中所有化合物在 LC-MS (APCI, Pos) (Agilent 1100 Series LC/MSD)中均可观察到其分子离子峰; 表 1 中化合物的 1H NMR (Varian INOVA-300 spectrometer)以 tetramethylsilane (TMS)作内标, 氘代氯仿 (CDCI3) 或氘 代二甲基亚砜 (DMSO) 作溶剂。
表 1
'ZZV^ (Z/UJ (+ΙΛΙ sod)SIA!-。,: (H 3|0ΖΕ!μ丄 'ΗΙ· 's) ζ γ L '(Η Md 'HZ '山) L2V L '(HN+H Md9 Ή9 'UJ) 〜 0999 '(HO 'ΗΙ· '^Η 9·9=Γ 'b) 069 '(JHO 'HZ 'ω) 8/9 〜0017 '(εΗΟ 'HS 'ZH 9·9=Γ 'Ρ) 1 (εΙ〇α〇)9 y^MN H d 996- 6 ^^ ZZ
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'Η2 '山) 1>6S 〜 '(εΗΟ 'HS 'ZH 69=Γ 'Ρ) Ζ09 - (εΙθαθ)9 dl/MN HL QZ
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■gog uno;
'90S:o|BO (z/ J (+ΙΛΙ sod)SIA|-On : (H ' 's) PLZ l '(H &d 'ΗΙ· 'ZH ζ=Γ 'Ρ) 8161 '(Η S|。ze!L|丄 'HI 's) OlVl '(H Md 'HZ 'ZH 0·6=Γ 'Ρ) 990 Ζ '(Η Md 'H3 'ZH 0·6=Γ 'Ρ) '(ΗΟ
' 'ΖΗ 9·9=Γ ' ) ριβ ρ '(Ζ Ο Ήζ '山) 1^9 〜 S81? '(ΕΗ〇 Ήε 's) ι,εΐ- ε '(ΕΗΟ Ήε 'ΖΗ 9·9=Γ 'Ρ) 109 (ειοαο)9 am HLO。 Ο ½-9217 ^WHgf葛^ QZ : puncy '26^:0|60 (Z/UJ (+|/\| sod)SIAI-0"l '(
'HI 's) P9Z8 '(H ' 'ΖΗΙ· =Γ 'Ρ) 9867 '(H 3|0ze!L|丄 Ήΐ 's) S/S7 '(Η Md ' Ζ 'ZH 0·6=Γ 'Ρ) £601 '(ΗΝ + Η Ήε 'ω) 696.9〜0 6.9 '(Η。 ' 'ZH 6.9=Γ 'b) 80Ζ '(¾0 'H2 'ω) 06S 〜 S9S '(εΗΟ Ήε 'ΖΗ 6·9=Γ 'Ρ) 9891 (εΙ0α〇)9 ^ΙΛΙΝ Η 0。 6 £Η ΐ?¾ '斜園 惠¾ Zi
ΟΙΡ: Punoj Olt :O|BO (Z/UJ (+ sod)SIAI-〇"l (H d 'HI 'ZH YZ=? 'P) V2LL '(H八 d 'ΗΙ· '^H YZ=Z? '^H 0·6= Γ 'ΡΡ) 869Z '(H-9|。ze!L|丄 ' 's) 92€7 '(H Md 'H2 'ZH ε·6=Γ 'Ρ) 9 '(H Md 'H 'ZH £ 6=Γ 'Ρ) SW9 '(HO ' 'ΖΗ 9.9=Γ 'b) 9S9f '(¾0 'Η2 '山) SWfr〜09t^ '( ◦ 'Η2 '山) 06fS〜 '(ΕΗΟ 'HS 'ZH 9·9=Γ 'Ρ) '(εΗΟ 'HS '^Η 2 Ζ=Γ Ί) 8601 (εΙθαθ)δ dl/MN Η 3。 0017-669 90
9 17: punoj '99f :。|eo (Z/UJ (+^\| s。d)SIAI-0"l: (H 'Hl'^H fr =「 'P) 0191 '(H八 d 'HI 'ZH YZ=Z? 'ZH 06= 'ΡΡ) mYL '(H 9|0ze!L|丄 'ΗΙ· 's) 0^7 '(H 4d 'HZ '^H 0·6=Γ 'Ρ) /807 '(H d 'HZ 'ZH 0·6=Γ 'Ρ) 91.6 '(HO 'HI '^Η 6·9=Γ 'b) 296 '( 〇 'H2 '山) 0S9 〜 991^ '(εΗ〇 'H€ 's) Ζ ζ '(εΗ〇 Ήε 'ΖΗ 9·9=Γ 'Ρ) 176 :(εΙ〇α〇)9 dlAIN Ht εο ΐ7ΐ7: punoi '2t7i7 :O|BO (Z/UJ (+|/\| sod)SIAI-。"l: (H 'HI 'ZH 1· =Γ 'Ρ) 199 I '(H Ad 'ΗΙ· 'ZH Z=z 'ZH 06=L「 'PP) 2097 '(Η 9|0ΖΒ!μ丄 'ΗΙ· 's) 1?8€7 '(H Md 'H3 '^Η€ 6=Γ 'Ρ) 60" '(ΗΝ +Η d Ήε 'ω) 6Ζ6·9〜868·9 '(Η。 'ΗΙ· '^Η 6·9=Γ 'b) 269 '( 〇 'ΗΖ '山) fr6S 〜SSS'17 '(εΗΟ Ήε 'ΖΗ 6·9=「 'Ρ) LL 1 (εΙθαθ)9 Ή^ΙΝ Ό。 6·00Ι·-|·Ό0Ι· 10
01
TlZl80/l7l0ZN3/X3d Z6C000/ST0Z OAV
4.600 (m, 2H, CH2), 4.730 (q, J=6.6 Hz, 1 H, CH), 6.923-6.977 (m, 3H, 2Ph H + NH), 7.231—7.450 (m, 6H, Thiazole H + Benzoxazole H + 2Ph H); LC-MS(Pos +) m/z) calc:464, found:464.
72 白色固体 熔点: 143.0-144.1 °C . 1 H NMR 5(CDCI3) 1 .600 (d, J=6.9 Hz, 3H, CH3), 4.469- 4.500 (m, 2H, CH2), 4.757 (q, J=6.9 Hz, 1 H, CH), 6.860〜6.992 (m, 3H, 2Ph H + NH), 7.240—7.544 (m, 8H, 3Py H + 3Benzoxazole-H + 2Ph H); LC-MS(Pos M+) m/z) calc:458, found:458.
本发明式 (I) 所示的化合物可以通过下面所示的反应式 1得到; 反应式 1中的 (II) 可以通过下面所示的反应式 2得到; 反应式 1中的 (III)可以通过下面所示的反应式 3或 反应式 4得到, 反应式 1至反应式 4中的 Z为离去基团, 如氯、 溴、 磺酸酯等, 其它取代 基除特别指明外均如前所限定。
1 :
式 (I) 的化合物可以这样来制备 (反应式 1 ): 在合适的溶剂如二氯甲垸或二氯乙垸、 甲苯中, 于 -10〜110°C, 在合适的碱如三乙胺或吡啶存在下, 用式 (II) 所示的化合物和 式(III)所示的化合物反应, 得式(I)所示的化合物, 加入合适的催化剂如 4-二甲胺基吡 啶 (DMAP) 或碘化钠可加快反应或提高反应收率。
式(II)的化合物可以这样来制备(反应式 2):在合适的溶剂如 Ν,Ν-二甲基甲酰胺(DMF) 或甲苯、 四氢呋喃、 乙醇中, 在合适的碱如碳酸钾或氢氧化钾、 碳酸钠、 氢氧化钠、 氢化 钠存在下, 于 25〜15CTC条件下, 用式 (IV) 所示的化合物和式 (V) 所示的化合物反应 得式 (VI) 所示的化合物, 式 (VI) 所示的化合物与酰卤化试剂如氯化亚砜或草酰氯、 三
氯化磷等反应即得式 (II) 所示化合物。
式(III) 的化合物可以这样来制备(反应式 3或反应式 4): 在合适的溶剂如 Ν,Ν-二甲 基甲酰胺 (DMF) 或四氢呋喃、 乙醇、 二氯甲垸中, 在合适的碱如氢氧化钠、 氢氧化钾、 碳酸钠、 碳酸钾、 氢化钠、 三乙胺、 吡啶存在下, 于 25〜120 °C条件下, 用式(VII) 所 示的化合物和式(VIII)所示的化合物反应得式(IX)所示的化合物, 式(IX)所示的化合 物在合适的溶剂如乙醇或甲醇中, 用合适的试剂如水合肼水解即得式 (III R2=H) 所示的 化合物; 式 (III R2=H ) 所示的化合物与 R2Z垸基化反应得式 (III ) 所示的化合物 (反应 式 3); 或在合适的溶剂如三氯甲垸和水或四氢呋喃、 乙醇中, 在合适的碱如氢氧化钠、 氢 氧化钾、 碳酸钾、 碳酸钠、 氢化钠等存在下, 于 0〜100 Ό条件下, 用式(X)所示的化合 物和式 (VIII) 所示的化合物反应得式 (III) 所示的化合物 (反应式 4), 加入合适的相转 移催化剂如苄基三乙基氯化铵 (TEBA) 或四丁基溴化铵、 四丁基氯化铵等可加快反应 或提高反应收率。
具体合成方法在下面的实施例中有更详细的阐述。
本发明提供的式 (I) 化合物在 15〜2250克有效成分 /公顷用量下具有广谱生物活性, 既可用于防治有害杂草, 还可用于防治有害病菌或害虫, 有的化合物具有很好的有害杂草 防治作用, 在很低的剂量下就可以获得很好的效果。
本发明提供的式(I)化合物, 具有生物活性且有的化合物具有很好的生物活性. 特别 是在农业、 园艺、 花卉和卫生有害杂草、 有害病菌、 害虫的防治方面表现出活性。 这里所 述的有害生物包括, 但不仅限于此:
禾本科杂草: 马唐、 稗草、 狗尾草、 硬草、 茼草、 雀麦、 看麦娘、 节节麦、 碱茅、 星 星草、 野燕麦、 黑麦草;
阔叶杂草: 苘麻、 繁缕、 龙葵、 藜、 凹头苋、 反枝苋、 刺苋等。
有害病原菌: 疫霉属种类, 白粉属种类, 赤霉属种类, 黑星菌属种类, 核盘菌属种类, 丝核菌属种类, 葡萄孢属种类, 梨孢属种类, 镰孢属种类,如水稻稻瘟病 (Pyricularia oryzae); 小麦条锈病 ( Puccinia striiformis)> 叶锈病 ( Puccinia recondita) 禾口其它锈病; 大麦条锈病 (Puccinia striiformis)、 叶诱病 (Puccinia recondita)禾卩其它诱病; 大麦禾口小 麦白粉病 (Erysiphe graminis )、 黄瓜白粉病 ( Sphaerotheca fuligenea )、 苹果白粉病 (Podosphaera leucotrichar)和葡萄白粉病 (Podosphaera leucotrichar); 小麦纹枯病禾口颖枯 病 (Septoria nodorum ) 谷物上的长蠕孢、 嘴孢霉、 壳针孢属病、 核球壳菌属病、 Pseudocercosporella herpotrichoides禾口小麦全烛病 (Gaeumannomyces graminis)。 花 生褐斑病 (Cercospora arachidicola) 禾口花生黑斑病 (Cercosporidium personata); 苹果
轮纹有害病菌 ( Botryosphaeria berengriana f.sp pi「icola)、苹果腐烂有害病菌 ( Cytospora sp. ); 甜菜、大豆和稻谷上的其尾孢霉属病。番茄、黄瓜、葡萄灰霉病(Botrytis cinerea)。 蔬菜 (如黄瓜) 上的铰链孢属病。 黄瓜上的炭疽病, 苹果黑星病, 黄瓜霜霉病, 葡萄霜霉 病, 马铃薯和番茄上的疫病, 稻谷上的单子菌 Thanatephorus cucumeris以及其他宿主如 小麦和大麦、 蔬菜上的其它丝核菌; 油菜菌核病(Sclerotonia sclerotiorum); 小麦赤霉病 (Gibberella zeae); 辣椒疫霉病 (Phytophytho「a capsici)等等。
害虫: 直翅目如蜚蠊, 缨翅目如棉蓟马、 稻蓟马、 瓜蓟马, 同翅目如叶蝉、 飞虱、 蚜 虫, 鳞翅目如东方粘虫、 斜纹夜蛾、 小菜蛾、 甜菜夜蛾、 粉纹夜蛾, 菜青虫, 膜翅目如叶 蜂幼虫, 双翅目如伊蚊、 库蚊、 蝇, 蜱螨目如桔全爪螨、 棉叶螨。
单独使用本发明的式(I)化合物时, 对控制有害杂草、 有害病菌、 害虫是有效的, 它 们也可以与其他物质一起使用。
以本发明式 (I) 化合物作为有效成份的农用制剂, 可以制成所希望的任何一种剂型。 以下结合实施例对本发明作进一步说明, 实施例中的收率均未经优化。
【具体实施方式】
实施例 1
(R)-2-(4-((5-氯 -3-氟吡啶 -2-基)氧基)苯氧基)丙酸 在配有磁力搅拌器、 温度计和冷凝 管的 100 mL三口瓶中加入 Ν,Ν-二甲基甲酰胺 (DMF)(40 mL), (R)2-(4-羟基苯氧基)丙酸 (0.02 mol),搅拌溶解后, 分批加入碳酸钾 (0.04 mol), 升温至 60〜8CTC搅拌 0.5〜1.0 hr。 逐滴加入 2,3-二氟 -5-氯吡啶 (0.02 mol), 继续搅拌反应 6〜8 hr。将反应物冷却至室温, 倒 入冰水 (250 mL)中, 再向混合物中缓慢加入稀盐酸, 调节至 pH=4〜5, 过滤, 水洗, 干燥 得白色固体的标题化合物 5.92 g。
2-氯噻唑 -5-基甲胺 100 mL三口瓶中加入 Ν, Ν-二甲基甲酰胺 (40 mL),邻苯二甲酰亚 胺 (0.05 mol)和氢氧化钾 (0.05 mol),室温搅拌溶解后,滴加 2-氯 -5-氯甲基噻唑 (0.05 mol), 室温搅拌过夜。将反应物倒入冰水 (250 mL)中,过滤,水洗得白色固体。将固体加入到 250 mL三口瓶中, 加入乙醇 (150 ml)。 加热溶解后, 滴加水合肼 (18 g, 80%), 搅拌回流条件 下反应 3〜4 hr, 冷却, 过滤, 取滤液, 脱溶得到黄色的油状物, 倒入饱和氯化钠溶液中, 乙酸乙酯萃取, 干燥, 脱溶得标题化合物 2.90 g。
(R)-N-(2-氯噻唑 -5-基甲基 )-2-(4-((5-氯 -3-氟吡啶 -2-基)氧基)苯氧基)丙酰胺 (表 1 中化 合物 01 ) 100 mL单口瓶中加入甲苯 (40 mL),(R)-2-(4-«3-氟 -5-氯吡啶 -2-基)氧基)苯氧基) 丙酸(3.3 mmol)和二氯亚砜 (10 mmol)。 反应物回流 3〜5 hr后脱去甲苯得 (R)-2-(4-((3- 氟 -5-氯吡啶 -2-基)氧基)苯氧基)丙酰氯。 酰氯中加入二氯甲浣 (40 mL), 2-氯噻唑 -5-基甲胺 (3.3 mmol)和催化量的 4-二甲基氨基吡啶 (DMAP), 冰浴冷却条件下搅拌 10〜15 min, 逐 滴滴入三乙胺 (10 mmol)。 反应物继续搅拌 2〜3 hr, 倒入 100〜200 mL冰水中, 用二氯 甲烷萃取。 有机相水洗 (100 mL *2), 无水硫酸钠干燥, 脱溶。 所得粗产品经柱层析(薄层 色谱硅胶 V 5«/V «Μ.=5 1 ) 得淡黄色固体的标题化合物 0.36 g, 收率 25 %, 熔点 100.1 -100.9 °C。
实施例 2
Ν-甲基 -(2-氯噻唑 -5-基)甲胺 200 mL单口瓶中加入 2-氯 -5-氯甲基噻唑 (0.05 mol), CHCI3(50 mL) , 搅拌均匀后滴加甲胺水溶液 (25 g, 25-30%)和氢氧化钠水溶液 (25 ml,
10%), 并加入少量相转移催化剂四丁基溴化铵, 25〜30 °C搅拌反应过夜。 稀盐酸调 pH 至弱碱性, 分液, 有机相水洗两次后无水硫酸钠干燥, 脱溶得 6.67 g淡桔黄色液体的标题 化合物。
(R)-N-甲基 -N-(2-氯噻唑 -5-基甲基 )-2-(4-((5-氯 -3-氟吡啶 -2-基)氧基)苯氧基)丙酰胺 (表 1中化合物 03) 100 mL单口瓶中加入甲苯 (40 mL), (R)-2-(4-((3-氟 -5-氯吡啶 -2-基)氧基) 苯氧基)丙酸 (3.3 mmol)和二氯亚砜 (10 mmol)。 反应物回流 3〜5 hr后脱去甲苯得其酰 氯。 酰氯中加入二氯甲垸 (40 mL), N-甲基 -(2-氯噻唑 -5-基)甲胺(3.3 mmol)和催化量的 4- 二甲基氨基吡啶 (DMAP), 冰浴冷却条件下搅拌 5〜10 min, 逐滴滴入三乙胺 (10 mmol)。 反应物继续搅拌 2〜3 hr后倒入 100〜200 mL冰水中,二氯甲垸萃取。有机相用水洗 (100 mL *2), 无水硫酸钠干燥, 脱溶。所得粗产品经柱层析(薄层色谱硅胶 V e/V « =5/1 ) 得淡黄色粘性液体的标题化合物 0.73 g, 收率 48 %。
(R 2-(4-«3-氯 -5-三氟甲基吡啶 -2-基)氧基)苯氧基)丙酸 在配有磁力搅拌器、 温度计
和冷凝管的 100 mL三口瓶中加入 Ν,Ν-二甲基甲酰胺 (DMF)(40 mL), (R)-2-(4-羟基苯氧) 丙酸 ( [α]58920 Ό=+59.5ο (丙酮)) (0.02 mol), 搅拌溶解后, 分批加入碳酸钾 (0.04 mol), 升温至 60〜80 °C搅拌 1 .0〜1 .5 hr。 逐滴加入 2,3-二氯 -5-三氟甲基吡啶 (0.02 mol), 继续 搅拌反应 8〜10 hr。 将反应物冷却至室温, 倒入冰水 (250 mL)中, 再向混合物中缓慢加入 稀盐酸,调节至 pH=4〜5,过滤,水洗,干燥得白色固体的标题化合物 6.56 g, [α]58920 c=+37.9° (丙酮)。
2-氯吡啶 -5-基甲胺 100 mL三口烧瓶中加入 Ν,Ν-二甲基甲酰胺 (DMF)(40 mL), 邻苯 二甲酰亚胺 (0.05 mol)和氢氧化钾 (0.05 mol),室温搅拌溶解,滴加 2-氯 -5-氯甲基吡啶 (0.05 mol), 室温搅拌过夜。 将反应物倒入冰水 (250 mL)中, 过滤, 水洗得白色固体。 将固体加 入到 250 mL三口瓶中, 加入乙醇 (150 ml)。 加热溶解后, 滴加水合肼 (18 g, 80%), 搅拌 条件下回流反应 4-6 hr, 冷却, 过滤, 取滤液, 脱溶得到黄色的油状物, 倒入饱和氯化钠 溶液中, 乙酸乙酯萃取, 干燥, 脱溶得淡黄色标题化合物 2.96 g。
(R)-2-(4-((3-氯 -5-三氟甲基吡啶 -2-基)氧基)苯氧基)丙酰氯 100 mL 单口瓶中加入甲 苯 (40 mL), (R)-2-(4-((3-氯 -5-三氟甲基吡啶 -2-基)氧基)苯氧基)丙酸(3.3 mmol)和氯化亚 砜 (10 mmol)。 反应物回流 4〜6 hr后脱去溶剂和过量的氯化亚砜得标题物。
(R)-N-(2-氯吡啶 -5-基甲基 )-2-(4-((3-氯 -5-三氟甲基吡啶 -2-基)氧基)苯氧基)丙酰胺 (表 1中化合物 42) 100 mL单口瓶中加入二氯甲烷 (40 mL), (R)-2-(4-((3-氯 -5-三氟甲基吡啶 -2-基)氧基)苯氧基)丙酰氯 (3.3 mmol), 2-氯吡啶 -5-基甲胺(3.3 mmol)和催化量的 4-二甲 基氨基吡啶 (DMAP), 冰浴冷却下搅拌 10〜15 min后, 逐滴滴入三乙胺 (10 mmol)。 反应 物继续搅拌 2〜3 hr后, 倒入 200 mL冰水中, 用二氯甲垸萃取。 有机相水洗, 无水硫酸 钠干燥, 脱溶。 所得粗产品经柱层析(薄层色谱硅胶 V 5«/V ««=3/1 )得类白色固体的 标题化合物 0.42 g, [α]58920 =+ 9.4° (丙酮), ee%=99.0%, 熔点 109.6-112.0 °C。
(R/S)-2-(4-羟基苯氧基)丙酸 在 15〜25'C条件下,将 2-溴丙酸缓慢加入到 50°/。NaOH
(0.1 mol )溶液中, 搅拌溶解后加入 30 ml水, 继续搅拌 5〜10 min, 备用。在 15〜25°C 条件下,反应瓶中加入对苯二酚(0.4 mol )禾口水 50 ml,搅拌下加入 50% NaOH (0.8 mol ), 再加入上述 2-溴丙酸的 NaOH溶液, 50〜60 'C反应 4〜6 hr,冷却,稀盐酸调 PH 至 4.0〜 4.5, 用乙酸乙酯萃取, 稀盐酸调 pH至 1 .0〜1.5, 乙酸异丙酯萃取, 有机相加水共沸除去
乙酸异丙酯, 水溶液用 50°/。NaOH溶液调 PH至 2.0〜2.5, 冷却, 用乙酸乙酯萃取, 无水 硫酸钠干燥, 脱溶得 (R,S)-2-(4-羟基苯氧基)丙酸 16.5 g, [a]589 2。'c=-0.1〜+0.1 ° (丙酮)。
(R/S)-2-(4-((3-氯 -5-三氟甲基吡啶 -2-基)氧基)苯氧基)丙酸 在配有磁力搅拌器、 温度 计和冷凝管的 100 mL三口瓶中加入 Ν,Ν-二甲基甲酰胺 (DMF)(40 mL), (R/S)-2-(4-羟基苯 氧基)丙酸 (0.02 mol), 搅拌溶解后, 分批加入碳酸钾 (0.04 mol), 升温至 60〜80 °C搅拌 0〜 5 hr后, 逐滴加入 2,3-二氯 -5-三氟甲基吡啶 (0.02 mol), 继续搅拌反应 8〜10 hr。 将反应物冷却至室温, 倒入冰水 (250 mL)中, 再向混合物中缓慢加入稀盐酸, 调节至 pH=4〜5, 过滤, 水洗, 干燥得白色固体的标题化合物 7.02 g, [a]5S9 2Q O=-0.2〜+0.2° (丙 酮)。
(R/S)-2-(4-«3-氯 -5-三氟甲基吡啶 -2-基)氧基)苯氧基)丙酰氯 100 mL单口瓶中加入 甲苯 (40 mL), (R/S)-2-(4-((3-氯 -5-三氟甲基吡啶 -2-基)氧基)苯氧基)丙酸([α]589 2。 ϋ=-0.2〜 +0.2° (丙酮) ) (3.3 mmol)和氯化亚砜 (10 mmol)。 反应物回流 4〜6 hr后脱去溶剂和过 量的氯化亚砜得标题化合物。
(R/S)-N-(2-氯吡啶 -5-基甲基 )-2-(4-«3-氯 -5-三氟甲基吡啶 -2-基)氧基)苯氧基)丙酰胺 (表 1中化合物 43) 100 mL单口瓶中加入二氯甲烷 (40 mL),(R/S)-2-(4-(3-氯 -5-三氟甲基 吡啶 -2-基氧基)苯氧基)丙酰氯 (3.3 mmol), 2-氯吡啶 -5-基甲胺 (3.3 mmol)和催化量的 4- 二甲基氨基吡啶 (DMAP), 冰浴冷却下搅拌 10〜15 min后, 逐滴滴入三乙胺 (10 mmol)。 反应物继续搅拌 2〜3 hr后,倒入 200ml冰水中,用二氯甲垸萃取。有机相水洗 (100 mL *2), 无水硫酸钠干燥, 脱溶。 所得产品经柱层析 (薄层色谱硅胶 ν 5¾βίΑ/ =3/1 )得类白色 固体的标题化合物 0.37 g, 收率 22.6 %, [a]589 2Q e=-0.3° (丙酮), ee%=0.15% , 熔点 109.0-110.5 °C。
生测实施例
对所合成化合物进行了除草、 杀菌和杀虫活性试验, 部分实验结果如下。
实施例 5 除草活性评价
方法如下: (1 )在截面积 64cm2的塑料盆钵中定量装土压平, 置于不锈钢盆中, 选取 籽粒饱满、 大小一致的种子, 分单子叶杂草 【马唐 (Digitaria sanguinalis )、 稗草 ( Echinochloa crus-galli )、 狗尾草 ( Setaria viridis)】禾口双子叶杂草【苘麻 (Abutilon theophrasti ), 刺鬼 (Amaranthus spinosus ), 藜(Chenopodium album)】分钵播种, 各 占钵面积的 1/3, 覆 1 cm厚细土, 从塑料盆钵底部加水至上层土壤浸润, 置于温室培养, 待试材长至所需叶龄进行试验处理; (2 ) 称取适量本发明提供的式 (I ) 化合物, 以 N, N-二甲基甲酰胺溶解, 再加入少量吐温 80乳化剂, 搅拌均匀, 加入定量清水, 配制成所
需浓度, 设相应溶剂和清水为对照; (3) 处理方式: 试材播种次日进行苗前土壤处理, 单 子叶试材长至 1叶 1心期、双子叶试材长至 2片真叶期进行苗后茎叶处理; (4)按设置剂 量定量移取药液进行茎叶喷雾和土壤喷雾处理, 分别以喷雾溶剂和清水为对照; (5)处理 试材置于温室培养; (6)处理 15-25天后目测地上部生长情况, 根据调查结果, 按以下公 式计算各化合物对杂草的防效: 防效 (%) =100χ (对照株高 -处理株高) I对照株高。 结 果表明本发明化合物对杂草具有显著活性。 部分结果如表 3〜表 4。 鉴于表 3和表 4的结 果, 测试了部分化合物对水稻和小麦的安全性(结果见表 5), 同时比较了部分化合物与同 类商品对照药剂噁唑酰草胺和氰氟草酯对水稻田重要杂草千金子和稗草的除草活性, 结果 见表 6。结果表明化合物 42对水稻具有安全性,且对水稻田重要杂草千金子和稗草具有优 异活性, 化合物 42对其它禾本科杂草也具有优异活性。
表 3 部分化合物在 2250克 /公顷剂量下的除草活性
*/表示未测试。
实施例 6 对油菜菌核病菌 (Sclerotonia sclerotiorum) 的杀菌活性
方法如下: 待测化合物溶于适宜溶剂如 Ν,Ν-二甲基甲酰胺 (DMF) 中, 再用含 0.1 °/。 Tween80乳化剂的无菌水稀释至所需浓度; 用移液管取 3 mL药液加入冷却至 45°C的 27 mL 的马铃薯琼脂培养基 (PDA) 中并充分摇匀后倒入培养皿; 冷却后用接种针从培养 7 天的油菜菌核病菌菌落边缘取 6 mm直径菌丝块, 移至培养皿中央, 菌丝面朝下, 同时设 不含待测化合物的空白为对照,每处理 4次重复;处理完毕后将培养皿置于 28°C的恒温生
化培养箱中培养, 4天后测量菌丝生长直径, 采用 EXCEL统计软件进行分析并计算菌丝 生长抑制率(%)。 活性相对于空白对照以百分比计, 分为 A、 B、 C、 D四级, 100°/ (^抑 制率 ^90°/。为 A级, 90%>抑制率 70%为 B级, 70°/。>抑制率 50%为 C级, 50%> 抑制率 ^ 0%为 D级。结果表明本发明的化合物对油菜菌核病菌具有活性, 如化合物 32和 48, 67等在 25 mg/L浓度下对油菜菌核病菌均具有 C级以上的活性。
实施例 7对黄瓜灰霉病菌 (Botrytis cinerea) 的杀菌活性
采用实施例 6对油菜菌核病菌的杀菌活性的测定方法, 测定了本发明式 ( I )化合物 对黄瓜灰霉病菌的活性, 结果表明本发明的化合物对黄瓜灰霉病菌具有活性,如化合物 03 和 05, 20, 22等在 25 mg/L浓度下对黄瓜灰霉病菌均具有 C级以上的活性。
实施例 8对水稻纹枯病菌 (Rhizoctonia solani) 的杀菌活性 (离体叶片培养法) 方法如下: 待测化合物溶于适宜溶剂如 Ν,Ν-二甲基甲酰胺 (DMF) 中, 再用含 0.1 °/。 Tween80乳化剂的无菌水稀释至所需浓度;取新鲜、幼嫩的蚕豆幼苗植株叶片经一定浓度 的药剂处理后平放在铺有含水滤纸的培养皿内, 叶片与滤纸用自制打孔铁架相隔。 叶片晾 干后接上直径为 6 mm, 培养 2~3天的新鲜菌丝块。 每处理 3次重复, 另设不含待测化合 物的空白为对照, 保湿适温培养至空白对照发病后, 检查病斑面积, 计算药剂防效。 活性 相对于空白对照以百分比计。 结果表明本发明的化合物对水稻纹枯病具有防治效果, 如化 合物 01在 500 mg/L浓度下对水稻纹枯病的防效达 50%以上。
实施例 9对小麦白粉病 (Erisiphe griminis) 的杀菌活性 (盆栽法)
方法如下: 待测化合物溶于适宜溶剂如 Ν,Ν-二甲基甲酰胺 (DMF) 中, 再用含 0.1 °/。 Tween80乳化剂的无菌水稀释至所需浓度; 取直茎 15 cm左右的盆钵, 每钵播种小麦饱 满健壮的种子 20粒, 待长出二叶一心后供试验用; 取准备好的小麦幼苗植株经一定浓度 的药剂喷雾处理, 一天后进行有害病菌接种。 每处理 3次重复, 另设不含待测化合物的空 白为对照, 保湿适温培养至空白对照发病后, 检査病斑面积, 计算药剂防效。 活性相对于 空白对照以百分比计。结果表明本发明的化合物对小麦白粉病具有防治效果,如化合物 03 在 500 mg/L浓度下对小麦白粉病的防效达 80%以上。
实施例 10对豆蚜 (Aphis fabae) 的杀虫活性评价
方法如下: 称取适量本发明提供的式(I)化合物, 以合适溶剂如 N, N-二甲基甲酰胺 溶解, 再加入少量吐温 80乳化剂, 搅拌均匀, 加入定量清水, 配制成所需浓度, 设清水 为对照。 将豆岈接于刚出土的豆苗上, 每株接 20头以上, 然后将豆苗连同试虫一起浸于 本发明提供的式(I)化合物的药液中, 5秒钟后取出, 吸去多余药液, 插入吸水的海棉中, 用玻管罩住, 24小时后检査存活和死亡虫数。重复 3次, 结果取平均值。活性相对空白对
照以百分比计。 结果表明本发明的化合物对豆蚜具有活性, 如在 500 mg/L浓度下, 化合 物 13和 20, 22等对蚕豆岈的活性 (死亡率) 均大于 50%。
实施例 11 对棉红蜘蛛 (Tetranychus urticae) 的杀螨活性
方法如下: 称取适量本发明提供的式(I)化合物, 以合适溶剂如 N, N-二甲基甲酰胺 溶解, 再加入少量吐温 80乳化剂, 搅拌均匀, 加入定量清水, 配制成所需浓度, 设清水 为对照。 选择长势良好的豆苗接种红蜘蛛, 待红蜘蛛定殖后, 将带螨豆苗剪下于配制好的 药液中浸渍 10秒, 取出用滤纸吸去多余的药液, 插于盛水烧杯中, 于观察室内培养, 24 小时后检查存活和死亡螨数,每株豆苗上有 100-200个螨。实验重复 3次。结果取平均值。 活性相对于空白对照以百分比计, 分为 A、 B、 C、 D四级, 100%≥死亡率≥ 90%为 A级, 90% >死亡率≥ 70°/。为 B级, 70%>死亡率≥50%为 C级, 50%>死亡率≥0%为 D级。 结果表明本发明的化合物对棉红蜘蛛具有活性, 如在 500 mg/L浓度下,化合物 48等对棉 红蜘蛛的活性 (死亡率) 大于 50%。
Claims
1、 N- (芳基浣基)芳氧苯氧羧酸酰胺类化合物及其异构体, 其特征在于用通式(I)表
其中:
I. Ar1和 Ar2是相同的或不同的,并代表 C6-C12芳基或带多至 10个碳原子的杂芳基, 且
a) C6-C12芳基或带多至 10个碳原子的杂芳基中的氢原子部分或全部被选自下列中相 同或不同的取代基取代: 素、 硝基、 氰基、 胺基、 羟基、 巯基、 羧基、 醛基、 肼基、 腙 基、。τ〇6嫁基、 Ci-〇6院基氧基、 Ci_C6嫁基硫基、 CTCS焼基胺基、二 (〇τ。6)嫁基胺基、
C2-C6链烯基、 C2-C6链烯基氧基、 C2-C6链烯基硫基、 C2-C6链烯基胺基、 二 C2-C6链烯 基胺基、 c2-c6链炔基、 c2-c6链炔基氧基、 c2-c6链炔基硫基、 c2-c6链炔基胺基、二 c2-c6 链炔基胺基、 c3-c8环烷基、 c3-c8环垸基氧基、 c3-c8环烷基硫基、 c3-c8环垸基胺基、 二 C3-C8环烷基胺基、 C6-C12芳基或带多至 10个碳原子的杂芳基、 c6-c12芳基氧基或带 多至 10个碳原子的杂芳基氧基、 C6-C12芳基硫基或带多至 10个碳原子的杂芳基硫基、 c6-c12芳基胺基或带多至 10个碳原子的杂芳基胺基;
II. R1和 R2, R3是相同的或不同的, 并代表氢、 CpCe烷基、 C2-C6链稀基、 C2-C6 链炔基、 C3-C8环垸基、 C6-C12芳基或带多至 10个碳原子的杂芳基;
III. n代表 1或 2、 3; 且
1) l.a)和 II. 中所述烷基、环烷基、链烯基、链炔基、芳基、杂芳基为未取代的或 l.a) 和 II.中所述烷基、 环垸基、 链烯基、 链炔基、 芳基、 杂芳基中氢原子部分或全部被选自下 列中相同或不同的取代基取代:卤素、 CrC6烷基、 CrC6烷基氧基、 CrC6烷基硫基、 Ci-C6 烷基胺基、 二(d-C6)烷基胺基、 C2-C6链烯基、 C2-C6链烯基氧基、 C2-C6链烯基硫基、 c2-c6链烯基胺基、 二 c2-c6链烯基胺基、 c2-c6链炔基、 c2-c6链炔基氧基、 c2-c6链炔 基硫基、 c2-c6链炔基胺基、二 c2-c6链炔基胺基、 -08环烷基、 c3-c8环垸基氧基、 c3-c8 环烷基硫基、 C3-C8环垸基胺基、二 C3-C8环烷基胺基、 C6-C12芳基或带多至 10个碳原子 的杂芳基、 C6-C12芳基氧基或带多至 10个碳原子的杂芳基氧基、 c6-c12芳基硫基或带多 至 10个碳原子的杂芳基硫基、 C6-C12芳基胺基或带多至 10个碳原子的杂芳基胺基、 二
c6-c12芳基胺基或带多至 10个碳原子的二杂芳基胺基、 C6-C12芳基芳基或带多至 10个碳 原子的杂芳基芳基、 C6-C12芳基杂芳基或带多至 10个碳原子的杂芳基杂芳基; 且 1 )中所 述烷基、 环烷基、 链烯基、 链炔基、 芳基、 杂芳基中氢原子部分或全部被选自下列中相同 或不同的取代基取代: 氢、 卤素、 d-C6烷基、 CrC6烷基氧基、 d-C6烷基硫基、 d-C6 垸基胺基、 二(CrC6)烷基胺基、 C2-C6链烯基、 C2-C6链烯基氧基、 C2-C6链烯基硫基、 C2-C6链烯基胺基、 二 C2-C6链烯基胺基、 02-06链炔基、 C2-C6链炔基氧基、 C2-C6链炔 基硫基、 c2-c6链炔基胺基、二 c2-c6链炔基胺基、 c3-c8环烷基、 c3-c8环烷基氧基、 c3-c8 环烷基硫基、 C3-C8环垸基胺基、二 C3-C8环烷基胺基、 C6-C12芳基或带多至 10个碳原子 的杂芳基、 C6-C12芳基氧基或带多至 10个碳原子的杂芳基氧基、 c6-c12芳基硫基或带多 至 10个碳原子的杂芳基硫基、 C6-C12芳基胺基或带多至 10个碳原子的杂芳基胺基、 二 C6-C12芳基胺基或带多至 10个碳原子的二杂芳基胺基、 C6-C12芳基芳基或带多至 10个碳 原子的杂芳基芳基、 c6-c12芳基杂芳基或带多至 10个碳原子的杂芳基杂芳基;
上面给出的化合物(I)的定义中, 所用术语不论单独使用还是用在复合词中, 代表如 下取代基:
卤素: 指氟、 氯、 溴、 碘;
烷基: 指直链或支链烷基;
环烷基: 指饱和或不饱和的环烷基;
链烯基; 指直链或支链并可在任何位置上存在有双键;
链炔基; 指直链或支链并可在任何位置上存在有三键;
卤代烷基: 指直链或支链烷基, 在这些烷基上的氢原子部分或全部被卤原子取代; 卤代环烷基: 指饱和或不饱和的环烷基, 且其中的氢原子部分或全部被卤原子取代; 卤代链烯基: 指直链或支链并可在任何位置上存在有双键, 且其中的氢原子部分或全 部被卤原子取代;
卤代炔基: 指直链或支链并可在任何位置上存在有三键, 且其中的氢原子部分或全部 被卤原子取代;
c6-c12芳基指苯基和由它派生出的一环芳基或多环芳基;
带多至 10个碳原子的杂芳基指一环杂芳基或多环杂芳基, 环中含有 1-5个下列中相 同或不同的杂原子: N, 0, S, P;
C6-C12芳基和带多至 10个碳原子的杂芳基可以部分或全部氢化,其中 1个或 2个 CH2 被 CO取代, 如环已烯基, 环已二酮基等。
2、根据权利要求 1所述的 N- (芳基烷基)芳氧苯氧羧酸酰胺类化合物及其异构体,其特
征在于通式 (I)所示化合物中:
c6-c12芳基指苯基和由它派生出的萘基或联苯基;
带多至 10个碳原子的杂芳基指吡啶基、 噻唑基、 喹喔啉基、 苯并噁唑基、 吡唑基、 噻二唑基、 噻吩基、 苯并噻吩基、 呋喃基、 苯并呋喃基、 吡咯基、 苯并吡咯基、 咪唑基、 苯并咪唑基、 喹啉基、 吡喃基、 吡嗪基、 嘧啶基、 哒嗪基、 苯并吡喃基、 苯并嘧啶基、 噁 唑基、异噁唑基、苯并异噁唑基、 苯并噻唑基、 异噻唑基、苯并异噻唑基、 嘧啶并三唑基。
3、 根据权利要求 1或 2所述的 N- (芳基垸基)芳氧苯氧羧酸酰胺类化合物及其异构体, 其特征在于通式 (I)所示化合物中-
I. Ar1和 Ar2是相同或不同的, 并代表苯基、 吡啶基、 噻唑基、 喹喔啉基、 苯并噁唑 基, 且苯基、 吡啶基、 噻唑基、 喹喔啉基、 苯并噁唑基中的氢原子部分或全部被选自下列 中相同或不同的取代基取代: 卤素、氰基、 d-C6烷基、 d-C6烷基氧基、 d-C6垸基硫基、 Ci-C6烷基胺基、 d-C6卤代垸基、 d-Cs卤代垸氧基;
II. R1和 R2, R3是相同的或不同的, 并代表氢、 d-C6烷基、 d-C6卤代垸基;
III. n代表 1。
4、 根据权利要求 1或 2所述的 N- (芳基烷基)芳氧苯氧羧酸酰胺类化合物及其异构体, 其特征在于通式 (I)所示化合物中-
I. Ar1和 Ar2是相同或不同的, 并代表吡啶基、 噻唑基、 喹喔啉基、 苯并噁唑基, 且 吡啶基、 噻唑基、 喹喔啉基、 苯并噁唑基中的氢原子部分或全部被选自下列中相同或不同 的取代基取代: 卤素、 d-C3烷基、 d-C3烷氧基、 d-Cs卤代烷基、 d-C3卤代烷氧基;
II. R1和 R2, R3是相同的或不同的, 并代表氢、 d-C3浣基;
III. n代表 1。
5、 根据权利要求 1或 2所述的 N- (芳基垸基)芳氧苯氧羧酸酰胺类化合物及其异构体, 其特征在于通式 (I)所示化合物是下述化合物 R型异构体和 S型异构体任何比例的混合 物-
N-(2-氯噻唑 -5-基甲基 )-2-(4-((5-氯 -3-氟吡啶 -2-基)氧基)苯氧基)丙酰胺;
N-甲基 -N-(2-氯噻唑 -5-基甲基 )-2-(4-((5-氯 -3-氟吡啶 -2-基)氧基)苯氧基)丙酰胺;
N-乙基 -N-(2-氯噻唑 -5-基甲基 )-2-(4-((5-氯 -3-氟吡啶 -2-基)氧基)苯氧基)丙酰胺;
N-(2-氯噻唑 -5-基甲基 )-2-(4-((3-氯 -5-三氟甲基吡啶 -2-基)氧基)苯氧基)丙酰胺;
N-甲基 -N-(2-氯噻唑 -5·¾甲基) -2-(Φ((3-氯 -5·三氟甲基吡啶 -2~¾)氧基)苯氧基)丙酰胺;
Ν-乙基 -Ν-(2-氯噻唑 -5·*甲基) -2-(Φ((3-氯 -5·三氟甲基吡啶 -2~¾)氧基)苯氧基)丙酰胺;
Ν-(2-氯噻唑 -5-基甲基 )-2-(4-((5-三氟甲基吡啶 -2-基)氧基)苯氧基)丙酰胺;
N-(2-氯噻唑 -5-基甲基 )-2_(4_((2-氟 -4-氰基苯基)氧基)苯氧基)丙酰胺; N-(2-氯吡啶 -5-基甲基 )-2-(4-((5-氯 -3-氟吡啶 -2-基)氧基)苯氧基)丙酰胺;
N-(2-氯吡啶 -5-基甲基 )-2-(4-((3-氯 -5-三氟甲基吡啶 -2-基)氧基)苯氧基)丙酰胺;
N-(2-氯吡啶 -5-基甲基) -2-(4-((5-三氟甲基吡啶 -2-基)氧基)苯氧基)丙酰胺;
N-(2-氯吡啶 -5-基甲基 )-2-(4-((2-氟 -4-氰基苯基)氧基)苯氧基)丙酰胺;
N-(2-氯噻唑 -5-基甲基 )-2-(4-((6-氯喹喔啉 -2-基)氧基)苯氧基)丙酰胺;
N-(2-氯吡啶 -5-基甲基 )-2-(4-((6-氯喹喔啉 -2-基)氧基)苯氧基)丙酰胺;
N-(2-氯噻唑 -5-基甲基 )-2-(4-((6-氯苯并 [d]噁唑 -2-基)氧基)苯氧基)丙酰胺;
N-(2-氯吡啶 -5-基甲基 )-2-(4-((6-氯苯并 [d]噁唑 -2-基)氧基)苯氧基)丙酰胺。
6、 根据权利要求 1或 2所述的 N- (芳基烷基)芳氧苯氧羧酸酰胺类化合物及其异构体, 其特征在于通式 (I)所示化合物是:
(R)-N-(2-氯噻唑 -5-基甲基 )-2-(4-((5-氯 -3-氟吡啶 -2-基)氧基)苯氧基)丙酰胺;
(R)-N-甲基 -N-(2-氯噻挫 -5-基甲基 )-2-(4-((5-氯 -3-氟吡啶 -2-基)氧基)苯氧基)丙酰胺; (R)-N-乙基 -N-(2-氯噻唑 -5-基甲基 )-2-(4-((5-氯 -3-氟吡啶 -2-基)氧基)苯氧基)丙酰胺; (R)-N-(2-氯吡啶 -5-基甲基 )-2-(4-((5-氯 -3-氟吡啶 -2-基)氧基)苯氧基)丙酰胺;
(R)-N-(2-氯噻唑 -5-基甲基 )-2-(4-((3-氯 -5-三氟甲基吡啶 -2-基)氧基)苯氧基)丙酰胺; (R)-N-甲基 -N-(2-氯噻唑 -5"¾甲基) ·2-(4-((3-氯 "5-三氟甲基吡啶 -2-基)氧)苯氧基)丙酰胺; (R)-N-乙基 -N-(2-氯噻唑 -5"¾甲基) ·2-(4-((3-氯 "5-三氟甲基吡啶 -2-基)氧)苯氧基)丙酰胺; (R)-N-(2-氯吡啶 -5-基甲基 )-2-(4-((3-氯 -5-三氟甲基吡啶 -2-基)氧基)苯氧基)丙酰胺; (R)-N-(2-氯噻唑 -5-基甲基 )-2-(4-((5-三氟甲基吡啶 -2-基)氧基)苯氧基)丙酰胺;
(R)-N-(2-氯吡啶 -5-基甲基 )-2-(4-((5-三氟甲基吡啶 -2-基)氧基)苯氧基)丙酰胺;
(R)-N-(2-氯噻唑 -5-基甲基 )-2-(4-((2-氟 -4-氰基苯基)氧基)苯氧基)丙酰胺;
(R)-N-(2-氯吡啶 -5-基甲基 )-2-(4-((2-氟 -4-氰基苯基)氧基)苯氧基)丙酰胺;
(R)-N-(2-氯噻唑 -5-基甲基 )-2-(4-((6-氯苯并 [d]噁唑 -2-基)氧基)苯氧基)丙酰胺;
(R)-N-(2-氯吡啶 -5-基甲基 )-2-(4-((6-氯苯并 [d]噁唑 -2-基)氧基)苯氧基)丙酰胺;
(R)-N-(2-氯噻唑 -5-基甲基 )-2-(4-((6-氯喹喔啉 -2-基)氧基)苯氧基)丙酰胺;
(R)-N-(2-氯吡啶 -5-基甲基 )-2-(4-((6-氯喹喔啉 -2-基)氧基)苯氧基)丙酰胺。
7、根据权利要求 1或 2所述的 N- (芳基烷基)芳氧苯氧羧酸酰胺类化合物及其异构体的 制备方法, 其特征在于式(I)所示的化合物通过下面所示的反应制备得到,
反应式 1 :
在溶剂二氯甲烷或二氯乙烷、 甲苯中, 于 -io〜iicrc, 在碱三乙胺或吡啶存在下, 用 式 (II) 所示的化合物和式(III) 所示的化合物反应, 得式 (I) 所示的化合物, 加入催化 剂 4-二甲胺基吡啶或碘化钠可加快反应或提高反应收率 (反应式 1 );
在溶剂 N,N-二甲基甲酰胺 (DMF)或甲苯、 四氢呋喃、 乙醇中, 在碱碳酸钾或氢氧化 钾、 碳酸钠、 氢氧化钠、 氢化钠存在下, 于 25〜150°C条件下, 用式(IV) 所示的化合物 和式(V) 所示的化合物反应得式(VI) 所示的化合物, 式 (VI ) 所示的化合物与酰卤化 试剂氯化亚砜或草酰氯、 三氯化磷反应即得式 (II)所示化合物(反应式 2);
在溶剂 N,N-二甲基甲酰胺或四氢呋喃、乙醇、二氯甲院中,在碱氢氧化钠、氢氧化钾、 碳酸钠、 碳酸钾、 氢化钠、 三乙胺、 吡啶存在下, 于 25〜120 Ό条件下, 用式(VII) 所 示的化合物和式(VIII)所示的化合物反应得式(IX)所示的化合物, 式(IX)所示的化合 物在溶剂乙醇或甲醇中, 用水合肼水解即得式 (III R2=H) 所示的化合物, 式(III R2=H) 所示的化合物与 R2Z烷基化反应得式 ( III ) 所示的化合物(反应式 3); 或在溶剂三氯甲 烷和水或四氢呋喃、 乙醇中, 在碱氢氧化钠或氢氧化钾、碳酸钾、碳酸钠、氢化钠存在下, 于 0〜100 条件下, 用式 (X) 所示的化合物和式(VIII) 所示的化合物反应得式(III) 所示的化合物, 加入相转移催化剂苄基三乙基氯化铵或四丁基溴化铵、 四丁基氯化铵可 加快反应或提高反应收率 (反应式 4);
式中 Ar1和 Ar\ R1, R2、 R3、 n具有权利要求 1中所给定义, Z为离去基团氯或溴、 磺酸酯。
8、根据权利要求 1或 2所述的 N- (芳基烷基)芳氧苯氧羧酸酰胺类化合物及其异构体的
用途, 其特征在于在 15〜2250克有效成分 /公顷用量下具除草和 /或杀菌、 杀虫、 杀螨生物 活性。
9、根据权利要求 1或 2所述的 N- (芳基烷基)芳氧苯氧羧酸酰胺类化合物及其异构体用 于制备具有除草活性和 /或杀菌活性、 杀虫活性、 杀螨活性的药物的用途。
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DATABASE REGISTRY SOURCE: CHEMICAL LIBRARY, SUPPLIER: FCH GROUP; 1 May 2011 (2011-05-01), accession no. 287844-32-9 * |
DATABASE REGISTRY SOURCE: CHEMICAL LIBRARY, SUPPLIER: FCH GROUP; May 2011 (2011-05-01), accession no. 300300-39-3 25 * |
DATABASE REGISTRY SUPPLIER: FCH GROUP, SOURCE: CHEMICAL LIBRARY; 10 April 2011 (2011-04-10), accession no. 277890-56-8 * |
DATABASE REGISTRY SUPPLIER: FCH GROUP, SOURCE: CHEMICAL LIBRARY; 10 April 2011 (2011-04-10), accession no. 277972-18-5 * |
DATABASE REGISTRY SUPPLIER: FCH GROUP, SOURCE: CHEMICAL LIBRARY; 12 May 2011 (2011-05-12), accession no. 293775-94-6 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2017213137A1 (ja) * | 2016-06-09 | 2017-12-14 | アグロカネショウ株式会社 | 新規化合物およびこれを有効成分とする農園芸用薬剤 |
CN107382896A (zh) * | 2017-08-02 | 2017-11-24 | 张建华 | 苯并噁唑‑2‑氧基苯氧基丙酰亚胺类化合物及其合成方法与应用 |
CN107382896B (zh) * | 2017-08-02 | 2019-07-09 | 张建华 | 苯并噁唑-2-氧基苯氧基丙酰亚胺类化合物及其合成方法与应用 |
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CN104277033A (zh) | 2015-01-14 |
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