CN100409748C - 取代苯基异噁唑类除草剂 - Google Patents
取代苯基异噁唑类除草剂 Download PDFInfo
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- CN100409748C CN100409748C CNB2005101197573A CN200510119757A CN100409748C CN 100409748 C CN100409748 C CN 100409748C CN B2005101197573 A CNB2005101197573 A CN B2005101197573A CN 200510119757 A CN200510119757 A CN 200510119757A CN 100409748 C CN100409748 C CN 100409748C
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- 239000004009 herbicide Substances 0.000 title claims abstract description 29
- 230000002363 herbicidal effect Effects 0.000 title claims description 16
- ZBRDJMFLJXFIGJ-UHFFFAOYSA-N 3-phenyl-1,2-oxazole Chemical class O1C=CC(C=2C=CC=CC=2)=N1 ZBRDJMFLJXFIGJ-UHFFFAOYSA-N 0.000 title abstract description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 15
- 125000001309 chloro group Chemical group Cl* 0.000 claims abstract description 5
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 5
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 45
- YZHUMGUJCQRKBT-UHFFFAOYSA-M sodium chlorate Chemical compound [Na+].[O-]Cl(=O)=O YZHUMGUJCQRKBT-UHFFFAOYSA-M 0.000 claims description 11
- 229910052801 chlorine Inorganic materials 0.000 claims description 10
- 239000000460 chlorine Substances 0.000 claims description 10
- QZJWWOFPJIBHDC-UHFFFAOYSA-N benzene;1,2-oxazole Chemical class C=1C=NOC=1.C1=CC=CC=C1 QZJWWOFPJIBHDC-UHFFFAOYSA-N 0.000 claims description 8
- 125000000842 isoxazolyl group Chemical group 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 7
- 241000196324 Embryophyta Species 0.000 abstract description 5
- 125000001424 substituent group Chemical group 0.000 abstract description 4
- 230000004927 fusion Effects 0.000 abstract 1
- CTAPFRYPJLPFDF-UHFFFAOYSA-N isoxazole Chemical group C=1C=NOC=1 CTAPFRYPJLPFDF-UHFFFAOYSA-N 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 49
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 36
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 22
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 20
- 239000007787 solid Substances 0.000 description 19
- -1 phenyl heterocyclic compound Chemical class 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 15
- 239000000376 reactant Substances 0.000 description 15
- 238000001035 drying Methods 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000002253 acid Substances 0.000 description 12
- 230000002194 synthesizing effect Effects 0.000 description 12
- 238000007254 oxidation reaction Methods 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 11
- 238000010792 warming Methods 0.000 description 11
- 238000005406 washing Methods 0.000 description 11
- 230000003647 oxidation Effects 0.000 description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 235000019441 ethanol Nutrition 0.000 description 9
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 7
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 229940117975 chromium trioxide Drugs 0.000 description 6
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 6
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000005711 Benzoic acid Substances 0.000 description 5
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Natural products OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 230000029936 alkylation Effects 0.000 description 5
- 238000005804 alkylation reaction Methods 0.000 description 5
- 238000013459 approach Methods 0.000 description 5
- 235000010233 benzoic acid Nutrition 0.000 description 5
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 238000001953 recrystallisation Methods 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical group CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 150000001263 acyl chlorides Chemical class 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- 238000005815 base catalysis Methods 0.000 description 4
- 150000003935 benzaldehydes Chemical class 0.000 description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzenecarboxaldehyde Natural products O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 230000032050 esterification Effects 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 4
- 229940072033 potash Drugs 0.000 description 4
- 235000015320 potassium carbonate Nutrition 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000010189 synthetic method Methods 0.000 description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 3
- ZSSRSUBTIJYIOJ-UHFFFAOYSA-N 2-chloro-5-[4-chloro-1-methyl-5-(trifluoromethyl)pyrazol-3-yl]-4-fluorobenzaldehyde Chemical compound ClC1=C(C(F)(F)F)N(C)N=C1C1=CC(C=O)=C(Cl)C=C1F ZSSRSUBTIJYIOJ-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YUXAFWCMLUALCL-UHFFFAOYSA-N acetic acid;benzaldehyde Chemical class CC(O)=O.CC(O)=O.O=CC1=CC=CC=C1 YUXAFWCMLUALCL-UHFFFAOYSA-N 0.000 description 3
- 230000002152 alkylating effect Effects 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 150000008048 phenylpyrazoles Chemical class 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 235000011181 potassium carbonates Nutrition 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 238000009333 weeding Methods 0.000 description 3
- 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 description 2
- CNSFDKCCOAEGRL-UHFFFAOYSA-N 3-(4-chloro-2-fluoro-5-methoxyphenyl)-1-methyl-5-(trifluoromethyl)pyrazole Chemical class C1=C(Cl)C(OC)=CC(C2=NN(C)C(=C2)C(F)(F)F)=C1F CNSFDKCCOAEGRL-UHFFFAOYSA-N 0.000 description 2
- DBALFNGUWGSGFU-UHFFFAOYSA-N 4-chloro-3-(4-chloro-2-fluoro-5-methoxyphenyl)-1-methyl-5-(trifluoromethyl)pyrazole Chemical class C1=C(Cl)C(OC)=CC(C=2C(=C(N(C)N=2)C(F)(F)F)Cl)=C1F DBALFNGUWGSGFU-UHFFFAOYSA-N 0.000 description 2
- 240000006995 Abutilon theophrasti Species 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Natural products CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 2
- 244000058871 Echinochloa crus-galli Species 0.000 description 2
- JGWYSVOCJHJVAG-UHFFFAOYSA-N N-[[2-chloro-5-[4-chloro-1-methyl-5-(trifluoromethyl)pyrazol-3-yl]-4-fluorophenyl]methylidene]hydroxylamine Chemical compound CN1C(=C(C(=N1)C2=C(C=C(C(=C2)C=NO)Cl)F)Cl)C(F)(F)F JGWYSVOCJHJVAG-UHFFFAOYSA-N 0.000 description 2
- JRNVZBWKYDBUCA-UHFFFAOYSA-N N-chlorosuccinimide Chemical compound ClN1C(=O)CCC1=O JRNVZBWKYDBUCA-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 240000003461 Setaria viridis Species 0.000 description 2
- 235000002248 Setaria viridis Nutrition 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- STSCVKRWJPWALQ-UHFFFAOYSA-N TRIFLUOROACETIC ACID ETHYL ESTER Chemical compound CCOC(=O)C(F)(F)F STSCVKRWJPWALQ-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 150000008062 acetophenones Chemical class 0.000 description 2
- 238000007171 acid catalysis Methods 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 150000001350 alkyl halides Chemical class 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000017858 demethylation Effects 0.000 description 2
- 238000010520 demethylation reaction Methods 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 230000002140 halogenating effect Effects 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 230000003389 potentiating effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 125000003226 pyrazolyl group Chemical group 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000547 substituted alkyl group Chemical group 0.000 description 2
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 2
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- WBYWAXJHAXSJNI-VOTSOKGWSA-N trans-cinnamic acid Chemical class OC(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-N 0.000 description 2
- SZUVGFMDDVSKSI-WIFOCOSTSA-N (1s,2s,3s,5r)-1-(carboxymethyl)-3,5-bis[(4-phenoxyphenyl)methyl-propylcarbamoyl]cyclopentane-1,2-dicarboxylic acid Chemical compound O=C([C@@H]1[C@@H]([C@](CC(O)=O)([C@H](C(=O)N(CCC)CC=2C=CC(OC=3C=CC=CC=3)=CC=2)C1)C(O)=O)C(O)=O)N(CCC)CC(C=C1)=CC=C1OC1=CC=CC=C1 SZUVGFMDDVSKSI-WIFOCOSTSA-N 0.000 description 1
- QFLWZFQWSBQYPS-AWRAUJHKSA-N (3S)-3-[[(2S)-2-[[(2S)-2-[5-[(3aS,6aR)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoylamino]-3-methylbutanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-4-[1-bis(4-chlorophenoxy)phosphorylbutylamino]-4-oxobutanoic acid Chemical compound CCCC(NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@@H](NC(=O)CCCCC1SC[C@@H]2NC(=O)N[C@H]12)C(C)C)P(=O)(Oc1ccc(Cl)cc1)Oc1ccc(Cl)cc1 QFLWZFQWSBQYPS-AWRAUJHKSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- WAXPDQIRCFAGFY-UHFFFAOYSA-N 2-chloro-3-(4-chloro-2-fluoro-5-methoxyphenyl)-1-methyl-5-(trifluoromethyl)-3H-pyrazole Chemical class CN1C(=CC(N1Cl)C2=CC(=C(C=C2F)Cl)OC)C(F)(F)F WAXPDQIRCFAGFY-UHFFFAOYSA-N 0.000 description 1
- ADLKIFMMWOYQLL-UHFFFAOYSA-N 2-chloro-5-[2-chloro-1-methyl-5-(trifluoromethyl)-3H-pyrazol-3-yl]-4-fluorophenol Chemical class CN1C(=CC(N1Cl)C2=CC(=C(C=C2F)Cl)O)C(F)(F)F ADLKIFMMWOYQLL-UHFFFAOYSA-N 0.000 description 1
- JKVPDGYQAOBXJO-UHFFFAOYSA-N 2-chloro-5-[4-chloro-1-methyl-5-(trifluoromethyl)pyrazol-3-yl]-N,N-diethyl-4-fluorobenzamide Chemical compound CCN(CC)C(=O)C1=C(C=C(C(=C1)C2=NN(C(=C2Cl)C(F)(F)F)C)F)Cl JKVPDGYQAOBXJO-UHFFFAOYSA-N 0.000 description 1
- DIOWSFPKIDPEBF-UHFFFAOYSA-N 3-(4-chloro-2-fluoro-5-methoxyphenyl)-5-(trifluoromethyl)-1,2-oxazole Chemical compound C1=C(Cl)C(OC)=CC(C2=NOC(=C2)C(F)(F)F)=C1F DIOWSFPKIDPEBF-UHFFFAOYSA-N 0.000 description 1
- QBWKPGNFQQJGFY-QLFBSQMISA-N 3-[(1r)-1-[(2r,6s)-2,6-dimethylmorpholin-4-yl]ethyl]-n-[6-methyl-3-(1h-pyrazol-4-yl)imidazo[1,2-a]pyrazin-8-yl]-1,2-thiazol-5-amine Chemical compound N1([C@H](C)C2=NSC(NC=3C4=NC=C(N4C=C(C)N=3)C3=CNN=C3)=C2)C[C@H](C)O[C@H](C)C1 QBWKPGNFQQJGFY-QLFBSQMISA-N 0.000 description 1
- NDQDSZLEZCMONY-UHFFFAOYSA-N 3-[2-chloro-5-[4-chloro-1-methyl-5-(trifluoromethyl)pyrazol-3-yl]-4-fluorophenyl]prop-2-enoic acid Chemical compound ClC1=C(C(F)(F)F)N(C)N=C1C1=CC(C=CC(O)=O)=C(Cl)C=C1F NDQDSZLEZCMONY-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- 241000448435 Acalypha australis Species 0.000 description 1
- 240000001592 Amaranthus caudatus Species 0.000 description 1
- 235000009328 Amaranthus caudatus Nutrition 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- 241000981770 Buddleja asiatica Species 0.000 description 1
- JINPTJBSENHUPN-UHFFFAOYSA-N CN(C(C(F)(F)F)=C1Cl)N=C1C(C=C(CN)C(Cl)=C1)=C1F Chemical class CN(C(C(F)(F)F)=C1Cl)N=C1C(C=C(CN)C(Cl)=C1)=C1F JINPTJBSENHUPN-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical group CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 229940087098 Oxidase inhibitor Drugs 0.000 description 1
- 235000011999 Panicum crusgalli Nutrition 0.000 description 1
- 235000010086 Setaria viridis var. viridis Nutrition 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
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- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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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
- A01N43/72—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
- A01N43/80—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 1,2
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Abstract
本发明提供了一类取代苯基异噁唑结构的除草剂，即在苯环上，1-位连接的是异噁唑环，2，4-位碳原子上的氢原子分别被氟原子、氯原子取代，5-位上连接不同的取代基。对合成的化合物分别测定了它们的熔点，并对其结构通过MS和′H-NMR确认。除草剂对禾本科杂草稗草、狗尾草和阔叶杂草苘麻、苋菜进行了除草活性测试，获得很好的效果。
Description
技术领域
本发明涉及取代苯基异噁唑类除草剂。
背景技术
由于人类对环保问题的重视，对农药的毒性及其对环境的影响提出了更高的要求，因此，化学农药的开发研制将进入“超高效、无毒、无污染”的新时期。取代苯基杂环类化合物是潜在的原卟啉原氧化酶抑制剂，许多公司对这类化合物进行了大量的研究，开发出了很多高效除草剂。例如：1991年日本农药公司申请了欧洲专利(EP443059)，介绍了除草剂ET-751，它的化学结构是：
1988年日本组合化学公司也申请了欧洲专利(EP 273417)，开发了KIH-9201除草剂：
1986和1987年，日本科研制药公司相继申请了世界专利(WO 86/26930和WO 87/02357)，报导了除草剂KPP-300和KPP-314，它们的结构为：
该类除草剂的分子结构中，在苯环上的苯1，2，4，5-位上均有取代基，2，4-位为卤素，1-位与杂环相连。研究表明，苯环上的2-位为氟，4-位为氯取代的化合物，活性较高。
本发明就是在保留化合物活性部分的基础上，改变其它基团，开发一类新结构的高效除草剂。
发明内容
本发明除草剂为取代苯基异噁唑衍生物，苯环上1-位连接的是异噁唑环，2，4-位碳原子上的氢原子分别被氟原子、氯原子取代，5-位上连接不同的取代基，异噁唑环上的5位为三氟甲基取代，4位为氢或氯原子，除草剂的分子结构通式为：
其中：
R1＝H时，R2＝-OCH2COOCH3，-OCH2COOC2H5，-OCH2CON(C2H5)2，-OCH2C(CH3)＝CH2，-OCOOC2H5，-OCH3，-CH(OCOCH3)2，-CHO；
R1＝Cl时，R2＝-CH(OCOCH3)2，-CHO，-COOCH3，-COOC2H5，-COOCH(CH3)2，-CON(C2H5)2，-CONHC6H5。
取代苯基异噁唑类除草剂(A)的制备方法，包括异噁唑环的合成和苯环上5-位取代基的引入两部分，合成上可参照取代苯基吡唑衍生物(B)的合成。
其中：
R3＝-CH3，R1＝H时，R2＝-OCH2COOCH3，-OCH2COOC2H5，-OCH2COOCH(CH3)2，-OCH2CON(C2H5)2，-OCH2C(CH3)＝CH2，-OCH2OC2H5；
R3＝-CH3，R1＝Cl时，R2＝-OCH2CON(C2H5)2，-OCH2C(CH3)＝CH2，-CH＝NOCH3，-CH＝NOC2H5，-CH＝NOCH2COOCH3，-CH＝NOCH2COOCH(CH3)2，-CH＝NOH，-CH(OCOCH3)2，-CON(C2H5)2，-CONHC6H5，-CONH(p-CH3C6H4)，-CONH(p-FC6H4)，-CH＝CHCOOC2H5，-CH＝CHCOOCH(CH3)2，-CH＝CHCON(C2H5)2，-CH＝CHCONHC6H5，-CH＝CHCONH(p-CH3C6H4)，-CH＝CHCONH(p-FC6H4)；
R3＝-CH3，R1＝Br时，R2＝-OCH2COOCH3，-OCH2COOC2H5，-OCH2COOCH(CH3)2，-OCH2CON(C2H5)2；
R3＝-C2H5，R1＝Cl时，R2＝-OCH2COOCH3，-OCH2COOC2H5，-OCH2COOCH(CH3)2，-OCH2CON(C2H5)2。
取代苯基五元氮杂环类除草剂(A)和(B)的制备方法，包括氮杂环的合成和苯环上5-位取代基的引入两部分：
(一)氮杂环的合成
(1)吡唑环结构由取代苯乙酮为起始原料，通过a.缩合，b.闭环，c.烷基化，d.卤代，可以制备取代苯基吡唑类除草剂(V)。
其中：R1＝Cl或Br；R2＝-CH3或-OCH3；R3＝-CH3。
具体合成方法如下：
(a)缩合取代苯乙酮(I)与三氟乙酸乙酯在碱性条件下进行缩合反应，制得1-取代苯基-4，4，4-三氟甲基-1，3一丁二酮(II)。反应所用的碱为醇钠，醇或醚为溶剂(如：甲醇、乙醇、乙醚、异丙醚等)，反应温度为室温至回流，反应时间为45分钟-20小时。
(b)闭环1-取代苯基-4，4，4-三氟甲基-1，3一丁二酮与水合肼进行闭环反应，可以得到取代苯基吡唑环化合物(III)。反应中溶剂可以是苯、甲苯、乙酸等隋性溶剂，反应时间30-60分钟。反应所得产物为不同异构体的混合物，即吡唑环上的氢原子可以存在于两个不同位置的氮原子上。
(c)烷基化化合物(III)在苯、甲苯、丙酮等惰性溶剂中，与烷基化试剂硫酸酯(如：硫酸二甲酯或硫酸二乙酯)、卤代烷(如碘甲烷、溴乙烷等)，反应在室温至回流温度下进行，反应时间为0.5-6.0小时，制得1-甲基-3-取代苯基-5-三氟甲基-1H-吡唑化合物(IV)。
烷基化反应可采用碱催化或不加碱催化下进行。
(d)卤代化合物(IV)与卤化剂进行卤化可制得化合物(V)。卤化剂可以直接用氯、溴卤素，也可用卤代琥珀酰亚胺、氯化硫酰、溴化钠/次氯酸钠等。反应使用的溶剂为乙酸、N，N-二甲基甲酰胺等，反应温度为70-110℃。
(2)异噁唑结构：
由取代苯基取代丁二酮出发，经过(e)、闭环，(f)脱水，可以制得取代苯基异噁唑类化合物(VIII)，如下所示：
其中：R1＝H，Cl；R2＝-CH3，-OCH3。
R1为氯的取代丁二酮，可由R1为氢的相应化合物氯化制得。
具体合成方法如下：
(e)闭环化合物(VI)与盐酸羟胺发生闭环反应，得到取代苯基异噁唑结构化合物(VII)。反应在丙酮、乙酸、甲苯等溶剂中进行，反应时间15-45分钟。
(f)脱水取代苯基异噁唑(VII)在浓硫酸中脱水，得到取代苯基异噁唑(VIII)，反应温度80-120℃，反应时间1-6小时。
(二)苯环5位取代基的转化：
(1)苯环5位的甲氧基可以经过(g)脱甲基转化为羟基，(h)烷基化，引入不同的取代基团，如下所示：
其中，Het代表前面所述的吡唑环或异噁唑环；R4为烷基或取代烷基、烯基等。
具体合成方法如下：
(g)脱甲基具有杂环结构的取代苯甲醚(化合物IX)在酸催化下脱去甲基，可以把甲氧基转化为羟基，得到化合物X。反应所用酸可以是质子酸，如硫酸、氢溴酸，也可以是非质子酸，如三氟化硼等。
(h)烷化化合物X的羟基可以用不同的试剂烷基化，得到目的产物(化合物XI)。所用烷基化试剂，依据所合成的目的化合物不同可以为卤代烷、硫酸酯、氯乙酸酯等。反应在惰性溶剂中进行，如苯、甲苯、丙酮、氯仿等，碱催化一般是必须的，所用碱可以是碳酸钾、氢氧化钠、三乙胺等。在部分化合物的合成中，加入相转移催化剂(如四丁基溴化胺等)可以明显加快反应进行。除少数活性较高的烷基化试剂可以室温下反应外，反应一般在回流下进行，反应时间根据所用试剂活泼性和反应条件不同从1小时至10小时不等。
(2)苯环5位的甲基可以通过(i)乙酐保护下用三氧化铬氧化，(j)水解转化为醛基。醛基可以(k)肟化，并进一步(1)烷基化取代；或者，(m)缩合转化为丙烯酸，再进一步(n)酯化或酰胺化，得到不同结构的化合物。如下所示：
其中：R5为烷基或取代烷基；R5为烷氧基或胺基。
苯环5位的甲基还可以(o)氧化为羧基，再(p)酯化或酰胺化，得到不同结构的化合物。如下所示：
其中：R7为烷氧基或胺基。
具体合成方法如下：
(i)氧化
化合物(XII)的甲基在乙酐保护下，用三氧化铬氧化，得到取代苯甲醛二乙酸酯(化合物XIII)。苯环侧链的甲基很容易被三氧化铬氧化，氧化先生成醛，很快进一步氧化成酸，一般说来反应很难停留在醛的阶段。但是，当反应体系存在乙酐时，生成的中间产物与乙酐反应生成苯甲醛二乙酸酯而被保护起来，避免了进一步氧化。实际上，反应中进一步的氧化反应是不可能完全避免的，因此总有少量的取代苯甲酸生成。反应在乙酸/乙酐混合溶剂中进行，乙酸与乙酐的体积比1-3，当乙酐量不足时，会有较多的进一步氧化产物取代苯甲酸生成。反应在室温下进行为宜，温度过高有发生燃烧的危险。反应中生成的少量取代苯甲酸和未反应完的原料，可以通过重结晶的方法很容易的除去。
(j)水解
取代苯甲醛二乙酸酯(化合物XIII)水解得到取代苯甲醛(化合物XIV)。水解反应在酸或碱催化下进行，所用酸可以是盐酸、硫酸、乙酸等，所用碱可以是碳酸钾、碳酸氢钠、氨水等。当反应在碱性较强的碳酸钾催化下进行时，苯环上的氟原子会被溶剂乙醇的乙氧基取代，当使用碱性较弱的碳酸氢钠时，则可以避免这一副反应的发生。
(k)肟化
取代苯甲醛(化合物XIV)与盐酸羟胺反应得到取代苯甲醛肟时(化合物XV)。反应所用溶剂为乙酸、乙醇等，反应温度70-110℃。反应中可以加入碱(如碳酸钾、碳酸氢钠等)作缚酸剂，也可以不加。
(1)烷基化
将取代苯甲醛肟(化合物XV)的羟基烷基化，可以得到不同的目的产物(XVI)。此步骤与步骤(h)相似，此处不再重复。
(m)缩合
取代苯甲醛(化合物XIV)与丙二酸反应，得到取代苯基丙烯酸(化合物XVII)。反应时，丙二酸的活泼亚甲基与取代苯甲醛的醛基首先发生亲核加成，然后脱水、脱羧，得到产物。反应在胺催化下进行，如：二乙胺、吡啶、六氢吡啶、喹啉等。反应温度50-100℃，反应时间0.5-2小时。
(n)酯化或酸胺化
取代苯基丙烯酸(化合物XVII)可以进一步转化为不同的酯或酰胺(化合物XVIII)。反应分两步进行：首先，取代苯基丙二酸与氯化亚砜作用，生成相应的酰氯；然后，酰氯再与不同的酵或胺反应，得到相应的酯或酰胺。第一步反应在苯、甲苯、二氯乙烷等惰性溶剂中进行，反应结束后，蒸出未反应完的氯化亚砜和生成的氯化氢、二氧化硫，生成的酰氯留在反应器中直接用于下一步反应。第二步反应：当目的产物为酯时，可以在相应的醇中进行；当目的产物为酰胺时，一般在苯、甲苯、氯仿等非质子溶剂中进行，反应中可以加入三乙胺作缚酸剂。
(o)氧化
化合物XII的甲基用三氧化铬氧化，得到取代苯甲酸(化合物XIX)。此步骤与步骤(i)相似，只是所用溶剂为乙酸，而不是乙酸/乙酐混合溶剂。
(P)酯化或酰胺化
取代苯甲酸可以进一步转化为不同的酯或酰胺(化合物XX)。此步骤与步骤(n)相似，此处不再重复。
能过以上所描述的方法，本发明合成了以下化合物，取代基及物性如表1所示。
表1化合物的结构与物性
以上化合物的结构均通过MS和′H NMR确认正确。
以上化合物的除草活性见表2所示。
表2化合物的除草活性
具体实施方式
实施例1
1-(4-氯-2-氟-5-甲氧基苯基)-4，4，4-三氟-1，3-丁二酮的合成；
在250ml三口烧瓶中加入13g4-氯-2-氟-5-甲氧基苯乙酮，60ml甲醇，13.5g三氟乙酸乙酯和26ml质量分数为25％的甲醇钠甲醇溶液。升温至回流，反应45min。反应结束后，将反应物倒入含有盐酸的冰水中，抽滤，水洗，干燥，得白色固体18.6g，产率97.2％。
实施例2
3(5)-(4-氯-2-氟-5-甲氧基苯基)-5(3)-三氟甲基吡唑的合成：
100ml三口烧瓶中加入2gl-(4-氯-2-氟-5-甲氧基苯基)-4，4，4-三氟-1，3-丁二酮，20ml乙酸和1ml质量分数为50％的水合肼，升温至110℃反应1h。降温，有固体析出，将反应物倒入水中，过滤，水洗，干燥，得淡黄色固体2g，产率100％。
实施例3
3-(4-氯-2-氟-5-甲氧基苯基)-1-甲基-5-三氟甲基-1H-吡唑的合成：
在100ml三口烧瓶中加入3(5)-(4-氯-2-氟-5-甲氧基苯基)-5(3)-三氟甲基吡唑2g，20ml甲苯和2ml硫酸二甲酯。升温至回流反应2h。反应结束后，反应液用2mol/L氢氧化钠溶液10ml洗，水洗，无水硫酸镁干燥，蒸出甲苯。加入少量乙醇重结晶，得到了白色固体1.9g，产率90.5％。m.p.115.5-116℃。
实施例4
4-氯-3-(4-氯-2-氟-5-甲氧基苯基)-1-甲基-5-三氟甲基-1H-吡唑的合成：
3-(4-氯-2-氟-5-甲氧基苯基)-1-甲基-5-三氟甲基-1H-吡唑15g、N-氯代琥珀酰亚胺20g、N，N-二甲基甲酰胺125ml，升温至80℃反应2h，将反应液倒入水中，30ml乙酸乙酯萃取两遍。合并有机层，15ml水洗两遍，干燥，蒸出乙酸乙酯，得白色固体。乙醇重结晶，得到了白色固体14.0g，产率83.2％.m.p.72-72.5℃。
实施例5
2-氯-5-(4-氯-1-甲基-5-三氟甲基-1H-吡唑-3-基)-4-氟苯甲醛二乙酸酯(化合物14)合成：
4-氯-3-(4-氯-2-氟-5-甲氧基苯基)-1-甲基-5-三氟甲基-1H-吡唑15g、冰乙酸40ml、乙酐110ml、浓硫酸13.6ml。稍稍冷却，控制温度15-20℃，搅拌下，分批加入三氧化铬约8g，HPLC控制反应终点。原料转化完全后，将反应液倒入水中，过滤，得白色固体。15ml乙酸重结晶，得白色固体14.8g，收率75.0％。
化合物40、42可按类似方法合成。
实施例6
2-氯-5-(4-氯-1-甲基-5-三氟甲基-1H-吡唑-3-基)-4-氟苯甲醛的合成：
2-氯-5-(4-氯-1-甲基-5-三氟甲基-1H-吡唑-3-基)-4-氟苯甲醛二乙酸酯6.8g、乙醇45ml、水8ml、碳酸氢钠7g，搅拌下回流反应1.5h。反应结束后，将反应物倒入水中，过滤，干燥，得白色固体5.0g，收率95.5％。m.p.71～72.5℃。
化合物41、43可按类似方法合成。
实施例7
3-[2-氯-5-(4-氯-1-甲基-5-三氟甲基-1H-吡唑-3-基)-4-氟苯基]丙烯酸(化合物25)的合成：
2-氯-5-(4-氯-1-甲基-5-三氟甲基-1H-吡唑-3-基)-4-氟苯甲醛11g、丙二酸10g、吡啶80ml，升温至85℃反应1.5h。将反应液倒入水中，用盐酸调节pH值至酸性，过滤，得白色固体12.5g，收率100％。
实施例8
2-氯-5-(4-氯-1-甲基-5-三氟甲基-1H-吡唑-3-基)-4-氟苯甲醛肟(化合物11)的合成：
2-氯-5-(4-氯-1-甲基-5-三氟甲基-1H-吡唑-3-基)-4-氟苯甲醛10g、无水碳酸钾10g、乙醇100ml、盐酸羟胺5g，升温至回流反应20min。将反应液倒入水中，过滤，得白色固体10.2g，收率97.7％。
实施例9
2-氯-5-(4-氯-1-甲基-5-三氟甲基-1H-吡唑-3-基)-4-氟苯甲酸的合成：
4-氯-3-(4-氯-2-氟-5-甲基苯基)-1-甲基-5-三氟甲基-1H-吡唑12g、冰乙酸120ml、浓硫酸12ml，搅拌下，分批加入三氧化铬约10g，HPLC控制反应终点。原料转化完全后，将反应液倒入水中，过滤，水洗，干燥，得白色固体10.3g，收率78.6％。
实施例10
N，N-二乙基-2-氯-5-(4-氯-1-甲基-5-三氟甲基-1H-吡唑-3-基)-4-氟苯甲酰胺(化合物15)的合成：
2-氯-5-(4-氯-1-甲基-5-三氟甲基-1H-吡唑-3-基)-4-氟苯甲酸2g、甲苯10ml、N，N-二甲基甲酰胺3滴、氯化亚砜1ml，升温至回流反应2h，蒸出甲苯和未反应完的氯化亚砜，得油状液体。向上述所得酰氯中加入甲苯20ml，乙二胺1g，回流反应1.5h。降温，反应液先后用1mol/L盐酸10ml，1mol/L氢氧化钠溶液10ml，10ml水洗，干燥，蒸出甲苯，加少量乙醇重结晶，得白色固体1.5g，收率69.7％。
化合物16-24、44-48可按类似方法合成。
实施例11
O-甲基-2-氯-5-(4-氯-1-甲基-5-三氟甲基-1H-吡唑-3-基)-4-氟苯甲醛肟(化合物9)的合成：
2-氯-5-(4-氯-1-甲基-5-三氟甲基-1H-吡唑-3-基)-4-氟苯甲醛肟2g、无水碳酸钾2g、丙酮15ml、硫酸二甲酯1ml，室温下反应2h。将反应液倒入水中，过滤，水洗，干燥，得白色固体2g，收率96.6％。
化合物10、12、13可按类似方法合成。
实施例12
2-氯-3-(4-氯-2-氟-5-羟基苯基)-1-甲基-5-三氟甲基-1H-吡唑的合成：
2-氯-3-(4-氯-2-氟-5-甲氧基苯基)-1-甲基-5-三氟甲基-1H-吡唑12g，硫酸100ml，升温至100℃反应1.5h。反应液降至室温，倒入冰水中，过滤，水洗，干燥，得白色固体10.5g，收率91.6％。
实施例13
2-氯-5-(1-甲基-5-三氟甲基-1H-吡唑-3-基)-4-氟苯氧基乙酸甲酯(化合物1)的合成：
3-(4-氯-2-氟-5-羟基苯基)-1-甲基-5-三氟甲基1-H-吡唑2g，丙酮20ml，无水碳酸钾2g、氯乙酸甲酯1.5ml，升温至回流反应2h。将反应液倒入水中，过滤，水洗，干燥，得白色固体2g，收率80.4％。
化合物2-8、26-39可按类似方法合成。
实施例14
3-(4-氯-2-氟-5-甲氧基苯基)-5-三氟甲基-4-异噁唑的合成：
1-(4-氯-2-氟-5-甲氧基苯基)-4，4，4-三氟-1，3-丁二酮10g，乙酸100ml，盐酸羟氨5g，升温至回流反应30min。降温，将反应物倒入水中，过滤，水洗，干燥，得白色固体10.4g，收率约100％.
实施例15
3-(4-氯-2-氟-5-甲氧基苯基)-5-三氟甲基异噁唑的合成：
3-(4-氯-2-氟-5-甲氧基苯基)-5-三氟甲基-4-异噁唑10.4g，硫酸90ml，升温至100℃反应2.5h。反应液降于室温，倒入冰水中，过滤，水洗，干燥，得灰白色固体9g，收率约100％。
实施例16
2-氯1-(4-氯-2-氟-5-甲基苯基)-4，4，4-三氟-1，3-丁二酮的合成：
1-(4-氯-2-氟-5-甲基苯基)-4，4，4-三氟-1，3-丁二酮18g，二氯乙烷180ml，氯化硫酰6ml，室温反应24h。加入1mol/L氢氧化钠溶液50ml，搅拌1h，分液，二氯乙烷层用水洗两遍，干燥，蒸出溶剂，得白色固体20.2g，收率约100％。
除草活性测试
试验材料：
禾本科杂草稗草(Echinochloa crusgalli)、狗尾草(Setaria viridis)和阔叶杂草苘麻(Abutilon theophrasti)、苋菜(Acalypha australis)；所成的化合物配制成22g/L乳油，然后加水配制成0.3g/L乳液；25％氟磺胺草醚水剂(大连瑞泽农药股份有限公司)。
茎叶处理：
4种杂草种子于30℃恒温箱中浸种6h，虑出催芽24h。选取胚根长度一致的种子，将其播于口径0.4m的纸盆中(每盆10株)，置于温室中培养，至稗草长至3叶期、狗尾2叶1心期、二中阔叶杂草2-2.5片真叶期时进行芽后处理。采用压力喷雾器喷施药液，药剂(原药)用量150g/hm2，不施药为空白对照。15天后测量杂草地上部分鲜重，计算鲜重抑制率。
土壤处理：
播种后第二天施药，药剂(原药)用量150g/hm2，不施药为空白对照。施药20天后测量杂草地上部分鲜重，计算鲜重抑制率。
Claims (1)
1. 一类由取代苯基异噁唑构成的除草剂，其特征在于该类除草剂为取代苯基异噁唑构成的化合物，苯环上1-位连接的是异噁唑环，苯环2，4-位碳原子上的氢原子分别被氟原子、氯原子取代，5-位上连接不同的取代基，异噁唑环上的5位为三氟甲基取代，4位为氢或氯原子，除草剂的分子结构通式为：
其中：
R1＝H时，R2＝-OCH2COOCH3，-OCH2COOC2H5，-OCH2CON(C2H5)2，-OCH2C(CH3)＝CH2，-OCOOC2H5，-OCH3，-CH(OCOCH3)2，-CHO；
R1＝Cl时，R2＝-CH(OCOCH3)2，-CHO，-COOCH3，-COOC2H5，-COOCH(CH3)2，-CON(C2H5)2，-CONHC6H5。
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| CN101279972B (zh) * | 2008-05-12 | 2011-02-02 | 大连理工大学 | 苯并噁唑类除草剂及其制备方法 |
| CN109896973B (zh) * | 2019-02-22 | 2021-12-24 | 中国热带农业科学院热带生物技术研究所 | 一种肉桂酰胺衍生物及其用途 |
| CN111004173A (zh) * | 2019-12-31 | 2020-04-14 | 北京康蒂尼药业有限公司 | 一种羟尼酮的制备方法 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1073432A (zh) * | 1990-02-21 | 1993-06-23 | 日本农药株式会社 | 3-(取代苯基)吡唑衍生物及其盐的制备方法 |
| US5281571A (en) * | 1990-10-18 | 1994-01-25 | Monsanto Company | Herbicidal benzoxazinone- and benzothiazinone-substituted pyrazoles |
| US6197973B1 (en) * | 1996-08-01 | 2001-03-06 | Basf Aktiengesellschaft | Substituted 3-phenylpyrazoles |
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| DE19634701A1 (de) * | 1996-08-28 | 1998-03-05 | Bayer Ag | Herbizide Mittel auf Basis von 4-Brom-l-methyl-5-trifluormethyl-3-(2-fluor-4-chlor-5-isopropoxycarbonsylphenyl)pyrazol |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1073432A (zh) * | 1990-02-21 | 1993-06-23 | 日本农药株式会社 | 3-(取代苯基)吡唑衍生物及其盐的制备方法 |
| US5281571A (en) * | 1990-10-18 | 1994-01-25 | Monsanto Company | Herbicidal benzoxazinone- and benzothiazinone-substituted pyrazoles |
| US6197973B1 (en) * | 1996-08-01 | 2001-03-06 | Basf Aktiengesellschaft | Substituted 3-phenylpyrazoles |
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| Title |
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| 具有生物活性的异噁唑衍生物的研究动态. 贺红武等.农药，第39卷第8期. 2000 |
| 具有生物活性的异噁唑衍生物的研究动态. 贺红武等.农药，第39卷第8期. 2000 * |
| 取代异噁唑衍生物的合成. 李美强等.化学试剂，第23卷第5期. 2001 |
| 取代异噁唑衍生物的合成. 李美强等.化学试剂，第23卷第5期. 2001 * |
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| CN1233631C (zh) | 2005-12-28 |
| CN1939127A (zh) | 2007-04-04 |
| AU2003242087A1 (en) | 2004-04-19 |
| CN1402979A (zh) | 2003-03-19 |
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