CN87107276A - 具有除草活性的取代苯并呋喃和苯并吡喃 - Google Patents
具有除草活性的取代苯并呋喃和苯并吡喃 Download PDFInfo
- Publication number
- CN87107276A CN87107276A CN87107276.9A CN87107276A CN87107276A CN 87107276 A CN87107276 A CN 87107276A CN 87107276 A CN87107276 A CN 87107276A CN 87107276 A CN87107276 A CN 87107276A
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- Prior art keywords
- alkyl
- compound
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- Prior art date
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- 230000002363 herbicidal effect Effects 0.000 title abstract description 3
- 150000001907 coumarones Chemical class 0.000 title abstract 3
- 150000001562 benzopyrans Chemical class 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims description 108
- 239000000203 mixture Substances 0.000 claims description 67
- 229910052799 carbon Inorganic materials 0.000 claims description 54
- -1 amido formyl radical Chemical compound 0.000 claims description 52
- 238000000034 method Methods 0.000 claims description 47
- 125000000217 alkyl group Chemical group 0.000 claims description 45
- 125000004432 carbon atom Chemical group C* 0.000 claims description 42
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 39
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 29
- 239000001257 hydrogen Substances 0.000 claims description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims description 27
- 238000002360 preparation method Methods 0.000 claims description 27
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 21
- 125000003342 alkenyl group Chemical group 0.000 claims description 19
- 239000002585 base Substances 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 150000003839 salts Chemical class 0.000 claims description 17
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 14
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 125000004429 atom Chemical group 0.000 claims description 11
- 230000000694 effects Effects 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- 125000000304 alkynyl group Chemical group 0.000 claims description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims description 8
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- 239000005864 Sulphur Substances 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 5
- 238000006462 rearrangement reaction Methods 0.000 claims description 5
- 150000008065 acid anhydrides Chemical class 0.000 claims description 4
- 125000002723 alicyclic group Chemical group 0.000 claims description 4
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 4
- 125000005078 alkoxycarbonylalkyl group Chemical group 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 claims description 4
- 125000003884 phenylalkyl group Chemical group 0.000 claims description 4
- 125000006325 2-propenyl amino group Chemical group [H]C([H])=C([H])C([H])([H])N([H])* 0.000 claims description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 3
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 claims description 3
- 125000004390 alkyl sulfonyl group Chemical group 0.000 claims description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- 238000006735 epoxidation reaction Methods 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- GJAWHXHKYYXBSV-UHFFFAOYSA-N quinolinic acid Chemical compound OC(=O)C1=CC=CN=C1C(O)=O GJAWHXHKYYXBSV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 125000006350 alkyl thio alkyl group Chemical group 0.000 claims description 2
- 125000004414 alkyl thio group Chemical group 0.000 claims description 2
- 125000001118 alkylidene group Chemical group 0.000 claims description 2
- 125000001316 cycloalkyl alkyl group Chemical group 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 125000003170 phenylsulfonyl group Chemical group C1(=CC=CC=C1)S(=O)(=O)* 0.000 claims description 2
- FCSKOFQQCWLGMV-UHFFFAOYSA-N 5-{5-[2-chloro-4-(4,5-dihydro-1,3-oxazol-2-yl)phenoxy]pentyl}-3-methylisoxazole Chemical compound O1N=C(C)C=C1CCCCCOC1=CC=C(C=2OCCN=2)C=C1Cl FCSKOFQQCWLGMV-UHFFFAOYSA-N 0.000 claims 1
- 230000002378 acidificating effect Effects 0.000 claims 1
- 125000005038 alkynylalkyl group Chemical group 0.000 claims 1
- 150000008064 anhydrides Chemical class 0.000 claims 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims 1
- 230000008676 import Effects 0.000 claims 1
- 230000008635 plant growth Effects 0.000 claims 1
- 125000000623 heterocyclic group Chemical group 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 93
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 72
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 47
- 239000007787 solid Substances 0.000 description 38
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 35
- 239000000460 chlorine Substances 0.000 description 34
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 33
- 235000019439 ethyl acetate Nutrition 0.000 description 31
- 239000002904 solvent Substances 0.000 description 30
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 28
- 239000000243 solution Substances 0.000 description 25
- 241000196324 Embryophyta Species 0.000 description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 23
- 239000000047 product Substances 0.000 description 23
- 150000001721 carbon Chemical group 0.000 description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 239000003795 chemical substances by application Substances 0.000 description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 20
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 19
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 18
- 239000007788 liquid Substances 0.000 description 18
- 238000003756 stirring Methods 0.000 description 18
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 17
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 17
- 238000005406 washing Methods 0.000 description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 15
- 229910002027 silica gel Inorganic materials 0.000 description 15
- 239000000741 silica gel Substances 0.000 description 15
- 229960001866 silicon dioxide Drugs 0.000 description 15
- 239000003921 oil Substances 0.000 description 14
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 14
- 239000013078 crystal Substances 0.000 description 13
- 239000002243 precursor Substances 0.000 description 13
- 238000010992 reflux Methods 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 238000000605 extraction Methods 0.000 description 12
- 239000012442 inert solvent Substances 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 11
- 238000003818 flash chromatography Methods 0.000 description 11
- 150000002431 hydrogen Chemical class 0.000 description 11
- 239000002689 soil Substances 0.000 description 11
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 10
- 239000013543 active substance Substances 0.000 description 10
- 150000002148 esters Chemical class 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 9
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 9
- 230000008859 change Effects 0.000 description 9
- 238000000354 decomposition reaction Methods 0.000 description 9
- 238000012545 processing Methods 0.000 description 8
- 238000001953 recrystallisation Methods 0.000 description 8
- 239000003643 water by type Substances 0.000 description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 239000000543 intermediate Substances 0.000 description 7
- 150000002576 ketones Chemical class 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 7
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000006193 diazotization reaction Methods 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 238000003810 ethyl acetate extraction Methods 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 description 6
- 235000011152 sodium sulphate Nutrition 0.000 description 6
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 5
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 5
- 101150065749 Churc1 gene Proteins 0.000 description 5
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- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 5
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 5
- 159000000000 sodium salts Chemical class 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- ULDKKRDHLKJHEP-UHFFFAOYSA-N 2-(2,7-dimethyl-2,3-dihydro-1-benzofuran-4-yl)-4,5,6,7-tetrahydroisoindole-1,3-dione Chemical compound O1C(C)CC2=C1C(C)=CC=C2N(C1=O)C(=O)C2=C1CCCC2 ULDKKRDHLKJHEP-UHFFFAOYSA-N 0.000 description 4
- OIKFOTBXANCNFK-UHFFFAOYSA-N 2-(7-chloro-2-methyl-2,3-dihydro-1-benzofuran-4-yl)-4,5,6,7-tetrahydroisoindole-1,3-dione Chemical compound O1C(C)CC2=C1C(Cl)=CC=C2N(C1=O)C(=O)C2=C1CCCC2 OIKFOTBXANCNFK-UHFFFAOYSA-N 0.000 description 4
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- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 4
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- WQJONRMBVKFKOB-UHFFFAOYSA-N cyanatosulfanyl cyanate Chemical compound N#COSOC#N WQJONRMBVKFKOB-UHFFFAOYSA-N 0.000 description 4
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- 238000007363 ring formation reaction Methods 0.000 description 4
- 239000012312 sodium hydride Substances 0.000 description 4
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- 239000004563 wettable powder Substances 0.000 description 4
- KMOUUZVZFBCRAM-UHFFFAOYSA-N 1,2,3,6-tetrahydrophthalic anhydride Chemical compound C1C=CCC2C(=O)OC(=O)C21 KMOUUZVZFBCRAM-UHFFFAOYSA-N 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- QXCAHNPZTJSIQA-UHFFFAOYSA-N 2-(2-methyl-2,3-dihydro-1-benzofuran-4-yl)-4,5,6,7-tetrahydroisoindole-1,3-dione Chemical compound O1C(C)CC2=C1C=CC=C2N(C1=O)C(=O)C2=C1CCCC2 QXCAHNPZTJSIQA-UHFFFAOYSA-N 0.000 description 3
- ZQGFPKBMKOJBBZ-UHFFFAOYSA-N 2-(2-methyl-2,3-dihydro-1-benzofuran-6-yl)-4,5,6,7-tetrahydroisoindole-1,3-dione Chemical compound C1=C2OC(C)CC2=CC=C1N(C1=O)C(=O)C2=C1CCCC2 ZQGFPKBMKOJBBZ-UHFFFAOYSA-N 0.000 description 3
- IUAXMMIRYTVHJX-UHFFFAOYSA-N 2-(7-chloro-2-methyl-2,3-dihydro-1-benzofuran-4-yl)isoindole-1,3-dione Chemical compound O=C1C2=CC=CC=C2C(=O)N1C1=CC=C(Cl)C2=C1CC(C)O2 IUAXMMIRYTVHJX-UHFFFAOYSA-N 0.000 description 3
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- 244000017020 Ipomoea batatas Species 0.000 description 3
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- 125000004494 ethyl ester group Chemical group 0.000 description 3
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- AFVFQIVMOAPDHO-UHFFFAOYSA-M methanesulfonate group Chemical class CS(=O)(=O)[O-] AFVFQIVMOAPDHO-UHFFFAOYSA-M 0.000 description 3
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 3
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- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 1
- MKRTXPORKIRPDG-UHFFFAOYSA-N diphenylphosphoryl azide Chemical compound C=1C=CC=CC=1P(=O)(N=[N+]=[N-])C1=CC=CC=C1 MKRTXPORKIRPDG-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000010413 gardening Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 208000021302 gastroesophageal reflux disease Diseases 0.000 description 1
- 230000002070 germicidal effect Effects 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N glycolonitrile Natural products N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 125000003453 indazolyl group Chemical group N1N=C(C2=C1C=CC=C2)* 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- CTAPFRYPJLPFDF-UHFFFAOYSA-N isoxazole Chemical compound C=1C=NOC=1 CTAPFRYPJLPFDF-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical group O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- CFHGBZLNZZVTAY-UHFFFAOYSA-N lawesson's reagent Chemical compound C1=CC(OC)=CC=C1P1(=S)SP(=S)(C=2C=CC(OC)=CC=2)S1 CFHGBZLNZZVTAY-UHFFFAOYSA-N 0.000 description 1
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 1
- 229940059904 light mineral oil Drugs 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000008268 mayonnaise Substances 0.000 description 1
- 235000010746 mayonnaise Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- QARBMVPHQWIHKH-UHFFFAOYSA-N methanesulfonyl chloride Chemical compound CS(Cl)(=O)=O QARBMVPHQWIHKH-UHFFFAOYSA-N 0.000 description 1
- 125000006431 methyl cyclopropyl group Chemical group 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000012184 mineral wax Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 235000019691 monocalcium phosphate Nutrition 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- KPTCZURLWZSRKB-UHFFFAOYSA-N o-prop-2-enylhydroxylamine Chemical compound NOCC=C KPTCZURLWZSRKB-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 208000014380 ornithine aminotransferase deficiency Diseases 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- CFHIDWOYWUOIHU-UHFFFAOYSA-N oxomethyl Chemical compound O=[CH] CFHIDWOYWUOIHU-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229940059574 pentaerithrityl Drugs 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 230000000361 pesticidal effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 229940107700 pyruvic acid Drugs 0.000 description 1
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000007226 seed germination Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000010572 single replacement reaction Methods 0.000 description 1
- 150000003385 sodium Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 229940001516 sodium nitrate Drugs 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000009331 sowing Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical class BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- 125000005306 thianaphthenyl group Chemical group 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- PVFOMCVHYWHZJE-UHFFFAOYSA-N trichloroacetyl chloride Chemical compound ClC(=O)C(Cl)(Cl)Cl PVFOMCVHYWHZJE-UHFFFAOYSA-N 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/44—Iso-indoles; Hydrogenated iso-indoles
- C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
-
- 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
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
- A01N43/12—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings condensed with a carbocyclic ring
-
- 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
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
- A01N43/16—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with oxygen as the ring hetero atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/04—Ortho-condensed systems
Landscapes
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Environmental Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Plant Pathology (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Plural Heterocyclic Compounds (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
具有杀草活性的N-(杂环基)-取代苯并呋喃和苯并呋喃,通式为I所示:
式中各符号的意义在专利说明书中都有解释。
Description
本发明涉及某些含氮杂环取代的苯并呋喃和苯并吡喃的制备方法,包括这些化合物的除草组合物和它们作为除草剂的用法。本发明也还包括在制备苯并呋喃和苯并吡喃中得到的新的中间体。
本发明所涉及的化合物为式(Ⅰ)所示:
式中,
R和R1分别代表一个氢或一个囟原子;氰基;1-4个碳原子的烷基或烷氧基;三囟代甲基;羟甲基;最多为4个碳原子的烷基,链烯基或烷酰氧甲基;或-OCFnHn,n为1、2或3。
R4为一个氢原子或一个1-4个碳原子的烷基
R5为一个氢原子或一个1-4个碳原子的烷基;
R6为氢或一个羟基;R5,R6可以是一个氧代(=O)氧原子或=NO(R8)基团;或当R5为氢时,R6为-CN,-C(O)Cl,-C(O)R8,-C(O)O(R8)或-C(O)N(R8)(R8);
R7为-CN,-CH(R9)CN,-CH(R2)(R3),-C(O)Cl,-CO(R8),-C(O)O(R8),-CH(R9)-O(R10),C(O)N(R8)(R8)或-C(R9)=NO(R8)式中R2和R3分别代表一个氢原子,1-4个碳原子的烷基或囟代烷基;或7-10个碳原子的苯烷基;
R8为一个氢原子;最多为4个碳原子的烷基,囟代烷基,链烯基,囟代链烯基或链炔基;苯基或7-10个碳原子的苯基烷基;最多为10个碳原子的杂环芳基或杂环芳烷基;最多为6个碳原子的烷氧烷基或烷氧羰基烷基;
R9为一个氢原子或1-4个碳原子的烷基;
R10为一个氢原子;最多为4个碳原子的烷基,囟代烷基,链烯基,囟代链烯基或链炔基;7-10个碳原子的苯烷基;最多为10个碳原子的杂环芳基烷基;或羰基部分连接有上述各基团的羰氧基。最多为6个碳原子的烷氧烷基或烷氧羰基烷基;1-4个碳原子的烷基磺酰基;环上可被1个到几个囟素原子和/或1-4个碳原子的烷基取代了的苯磺酰基;氨基甲酰基或最多为6个碳原子的烷基氨基甲酰基或二烷基氨基甲酰基;
式中:
X和Y为O或S;
Z为C或N;
W为S或SO;
m为0、1或2;
R11为一个囟原子,或1-4个碳原子的烷基,囟代烷基或烷氧基;
R12和R13每一个都分别代表一个氢原子或1-4个碳原子的烷基;或R12和R13由碳原子连结在一起形成的被1-3个甲基所取代的六元脂环。
R14为一个氢原子或囟素原子;或烷基;或1-4个碳原子的烷基-S(O)a-基,这儿a为0、1或2;
R15为一个氢原子或囟素原子;1-4个碳原子的烷基,烷硫基或烷基磺酰基;
R16为1-4个碳原子的烷基;或R15,R16构成-(CH2)b-,b为3或4,并可被1-3个甲基所取代。
R17为一个氢原子或最多为6个碳原子的烷基,链烯基,囟代烷基或烷氧基烷基;或3-6个碳原子的环烷基;4-8个碳原子的环烷基烷基,它们均可被1-3个具有1-4个碳原子的烷基所取代;
R18为1-6个碳原子的烷基、囟代烷基、氰基烷基、烷氧基烷基、链烯基、链炔基或是烷基-S(O)a-烷基,这里a为0、1或2;
R19为一氢原子;或如R18中所规定了的一个基团,或R18,R19为R16中所规定的亚烷基,-(CH2)b-或是-(CH2)c-u-(CH2)d-,这里c,d分别为0、1、2或3或c加d为2或3,u为氧,-S(O)a-或-NR烷基,这里a为0、1或2,当u为-S(O)a-时,c不是0。
R20为1-6个碳原子的烷基,囟代烷基、烷氧基烷基、烷硫基烷基、氰基烷基、囟代烷氧基烷基、链烯基和囟代链烯基;
R21为一氢原子,或1-4个碳原子的烷基、囟代烷基、氰基烷基、链烯基、链炔基、烷氧基烷基、氨基或烷氧基羰基;
R22为R20中所规定了的一个基团,或是一个羰基或烷氧基羰基;
或J是二苯甲基氨基、苯甲酰基氨基、乙酰基氨基、苄基氨基、烯丙基氨基、三氯乙酰基氨基、氨基或异氰酸基;
和与碱金属碱、氨和胺生成的盐。
在这些化合物中,脂基可以是直链的也可以是叉链的,囟素是指溴、氯和氟,合适的胺盐是单取代,二取代和三取代烷基和烷氧基的胺,每个烷基部分包括1-20个碳原子;杂环芳基和杂环芳基烷基部分,下述杂环芳基均适合:呋喃基、吡咯基、噻嗯基、吡啶基、噻唑基、异唑基、吡唑基、咪唑基、(1,2,3)或(1,2,4)***基、苯并呋喃基、吲哚基、吲唑基、硫茚基、哒嗪基、嘧啶基、吡嗪基、啉基、喹唑啉基或喹喔啉基。
式ⅠA的化合物特别有意义。尤其是R1为囟原子,如氯原子;J是J-1和J-2,m为0;R3和R4以碳原子连接在一起形成一个六元脂环的化合物。
当J是J-1或J-2,X和Y都是氧原子,R7是-CH(R2)(R3),R6为氢原子的化合物Ⅰ可以从下述通式(Ⅱ)J-1和J-2相应的酚通过环化反应来制备。
和
环化反应可通过三个一般方法中的某个或某几个方法来制备:
(a)加热法:酚前体物(Ⅱ),于各种溶剂如:二甲苯中,在150-159℃下加热。
(b)酸催化法:酸前体物(Ⅱ)在含有催化量的对甲苯磺酸(PTSA)的惰性溶剂如二甲苯的溶液中回流反应。
(c)自由基法:在过氧化物存在下,用溴化氢处理酚前体物(Ⅱ)。
这些方法L.I.Smith在Chemical Reriews(化学评论)中已有叙述(P.287,1940)。
也可以通过在二氯甲烷那样的惰性溶剂中,于0-80℃下,处理酚(Ⅱ)和适当化学计算过量的环氧化试剂-如过氧乙酸,间-氯-过氧苯甲酸或类似的试剂来制备J为J-1或J-2的化合物Ⅰ。生成过氧化物Ⅲ:
和
反应最好是回流酚,环氧化试剂和溶剂混合物,直到反应完成,然后用亚硫酸钠水溶液处理反应液,一直到淀粉碘化钾试剂上没有反应。
环氧化物可以在室温下自发环化,它可通过下述方法来环化:(a)在如1,2-二氯乙烷这样的惰性溶剂中酸(PTSA)催化和(或)质子催化,(b)在如四氢呋喃(THF)或N,N-二甲基甲酰胺(DMF)那样的惰性溶剂中,于大约0-100℃下,如氢化钠或三级胺这样的碱催化产物为式(Ⅳ):
酚前体物(Ⅱ)可由下式(Ⅴ)的合适的J-1或J-2化合物通过Claisen(克莱逊)重排反应来制备。
当R1为氢时,产物一般是ⅡA和ⅡB两个异构体的混合物;当R1不为氢时,仅能得到ⅡA异构体。重排反应可在适当高温,例如温度范围在150-250℃左右加热烯丙氧基苯基前体物Ⅴ来实现。前体物Ⅴ可以采用纯样,也可以溶在合适的惰性溶剂中。若采用路易斯酸催化,(如三氯化硼),在惰性溶剂(如二氯甲烷)中进行重排反应,反应温度可变为0℃到室温。在某些例子中至少也要注意到前体物加热到上述温度范围的上限时(如大约200℃以上),除发生重排反应外,还要发生环合作用。
一般来说,通过环化反应所得到的是苯并呋喃和苯并吡喃的混合物,两者的相对比例则要根据R和R部分的特点和合成所采用的是a,b,c或环氧化方法,以及用酸还是用碱处理来决定。
烯丙氧基苯基前体物Ⅴ则可由相应的J-1或J-2化合物(Ⅵ)和适当的烯丙基囟化物(Ⅶ)制备得到。(最好选用溴化物)反应在碳酸钾存在
下,在惰性溶剂中了回流囟化物溶液。
前体物酚(Ⅵ)可由方便的方法来制备,如在醋酸中加热适合的邻苯二甲酸,3,4,5,6-四氢邻苯二甲酸、喹啉酸或马来酸的酸酐与适当苯胺(式Ⅷ)的混合物得到。
制备这种前体物酚Ⅵ的方法是已知的,尤其在美国专利4,452,981,欧洲专利61,741(申请号)和联合王国专利2046754(申请号)以及在这些专利中所列的参考文献中均有叙述。
烯丙氧基苯基前体物还可以用另外的方法制备:在醋酸中加热相应的酸酐,如:邻苯二甲酸,3,4,5,6-四氢邻苯二甲酸,喹啉酸或马来酸的酸酐,与如式(Ⅸ)所示的适合的烯丙氧基苯胺的混合物得到。
这些苯胺可从相应的烯丙氧基硝基苯来制备(在如乙酸乙酯的溶剂中,用氯化亚锡处理硝基苯),而烯丙氧基硝基苯则可以用适当的烯丙基囟代物(式Ⅶ)处理相应的硝基酚来得到。
当R7是所限定的基团时,化合物ⅠA和ⅠB可用方便的方法和试剂处理适合的化合物Ⅰ来制备,这在以后的实例中将予以说明。这样,各种化合物ⅠA和ⅠB则可从下列前体物制备得到,这里R7为-CH(R9)-O(R10)和R10为氢:
R7是-CH(R9)-O(R10),R10不是氢的化合物可这样制备:
(1)用适合的囟代物(R10-囟素)或硫酸二烷基酯((R10)2SO4)处理适当的化合物Ⅰ的碱金属(最好是钠)衍生物(式中R是-CH(R9)OH),产物为醚;
(2)用羧酸酐或酰囟处理醇-CH(R9)-OH,产物为酯;
(3)用烷基或苯基磺酰氯处理醇,产物为磺酸酯;
或(4)用氰酸、烷基氰酸酯或氨基甲酰氯处理醇,产物为氨基甲酸酯。
R7为-C(R9)=NO(R8)的化合物也可以用方便的方法来制备:用草酰氯、二甲亚砜和三乙胺的混合物来氧化相应的适当的化合物ⅠA和ⅠB,这儿R7是-CH(R9)OH,生成醛或酮,R7为-C(O)-R9,然后再用羟胺处理,生成肟(-C(R9)=NOR8)。
R7是-C(O)-O(R8),-C(O)N(R8)(R8),-C(O)Cl或-CN的化合物可这样方便地制备:Jone′s试剂或重铬酸吡啶盐处理醇,-CH(R9)-O(R10),R9和R10都是氢,得到相应的羧酸,R7是-C(O)OH,它可以处理为盐,也可以用二氯亚砜处理酸,得到酰氯(R7为-C(O)Cl)后,再用适合的醇(R8-OH)或胺H-N(R8)(R8)处理,分别可得到R8的酯和酰胺-C(O)N(R8)(R8)。酰氯和氨反应则产生没有取代的酰胺,它可以用方便的方法脱水生成腈(R7=-CN)。
R7为-CH(R9)CN的化合物可这样制备:用甲磺酰氯处理合适的化合物ⅠA和ⅠB,这里R7为-CH(R9)OH,生成甲磺酸酯,然后再用***处理甲磺酸酯即可得到。
R7为-CH(R2)(R3),R3为囟素的化合物可以这样制备:用四囟化碳在三苯基膦存在下处理合适的化合物Ⅰ,R为-CH(R2)OH。
式ⅠC和ⅠD的化合物(式中R6是所规定了的基团之一)可以这样制备:如上述R7部分中所叙述的那样,可用方便的方法和试剂处理适合的化合物Ⅰ,这里R5为氢,R6为羟基。这样,当R5为氢,R6是-OH时,化合物ⅠC或ⅠD可被氧化为酮,可再转变为肟,或转变为甲磺酸酯,后者是制备腈、羧酸、酰氯、酯或酰胺的前体物。
用Jone′s试剂处理R5为氢,R6为羟基的化合物ⅠC和ⅠD可以转变为R5,R6为氧代(=O)的氧原子的化合物。
化合物Ⅰ可用下述一般方法制备之:
J=J-1,J-2(Z=碳或R12和R13连结成环):除了已叙述过的方法,这些化合物可以这样制备:用一个合适的苯胺处理合适的邻苯二甲酸,四氢邻苯二甲酸或马来酸酸酐;可以在120-220℃下熔融这两个试剂,也可以在溶剂中回流这些试剂混合物,试剂可以是乙酸、甲苯或二甲苯。在二甲苯或甲苯中的反应,可用如三乙胺或DBU*那样的胺催化。X和Y中有一个是硫或二个都是硫的产物可以这样制备:在如苯、甲苯、二甲苯或氯仿那样的惰性溶剂中,在室温到回流温度下,用五硫化二磷或Lawesson′s试剂[2,4-双-(4-甲氧基苯基)-1-,3-二硫代-2,4-二膦烷-2,4-二硫化物]处理(也就是硫化X、Y都是氧的产物。在Z为氮的情况下,则用合适的苯胺两步处理喹啉酸酸酐:(a)在室温到回流温度下,在如二氯甲烷或四氢呋喃那样的惰性溶剂中搅拌这些反应物,得到中间体酰胺/酸,然后,(b)用乙酸酐,在80℃到回流温度下,将中间体脱水。也可改用两个反应物在室温下搅拌反应,生成中间体,然后再用0.1到0.5当量的三乙胺作为催化剂反应,接着共沸蒸馏得到产物。参考文献:美国之专利4,406,690;4,439,229联合王国专利2,150,929。
J=J-3其制备方法如同前述的制备Z=氮原子的J-1和J-2化合物的方法,只是酰胺/酸中间体的脱水反应是用DCC(1,3-二环己基碳二亚胺)或类似的脱水缩合剂。参考文献:美国专利4,472,190
J=J-4,Z为氮,X为氧,Y为氧或硫:用异(硫)氰酸酯(它可以用方便的方法从合适的苯胺来制备)处理1-(乙氧基羰基)六氢哒嗪( ),所得到的中间产物再用氢化钠处理。也可以采用异(硫)氰酸酯处理合适的N-(烷氧基羰基)肼,所得到的中间产物用碱环化反应得到一个尿唑,再用1,4-二溴丁烷,使尿唑二钠盐烷基化得到所需要的产物。参考文献:欧洲专利104484,德国公开专利3504051;Z=碳,X=O或S,Y=O的J-4化合物:用异(硫)氰酸酯(它可以从合适的苯胺来制备)处理哌啶酸乙酯,可在如THF(四氢呋喃)那样惰性溶剂中进行,得到的(硫)脲中间体再和氯化氢的乙醇溶液在回流下反应。参考文献:美国专利4,560,752。如J=J-1中所叙述的硫化反应,得到X和Y都是硫的化合物。
J=J-5:这些化合物的制备方法相同于前述的J=J-4,Z=氮的方法,只是(硫)脲中间体可以用盐酸水溶液也可以用甲醇钠的甲醇溶液来处理。参考文献:欧洲专利70,389。
J=J-6:用一个合适的苯胺重氮化,并在三乙胺存在下与哌啶酸偶合。参考文献:美国专利4,599,104;4,002,636;3,939,194。
J=J-7:用一个合适的苯胺重氮化,产物用氯化亚锡还原得到肼,肼再在脱水条件下用2-(烷氧基羰基)环己酮处理得到六氢吲哚-3-酮,该产物可以氯化,可选择再在脱囟化氢试剂存在下得到J-7化合物,这里R14是氢。参考文献:欧洲专利152,890。制备R14不是氢的这类化合物的方法见欧洲专利138,527。这些专利也还涉及制备R15和R16为不相同的那些J-7化合物。
J=J-8:用一个合适的苯胺,转变为肼,再用6-(羟亚胺基)-1-吗啉基环己烷处理,所得产物再在吡啶中用硫化亚铜氧化。参考文献:欧洲专利142769。
J=J-9:用一个合适的苯胺,转变为肼,再用酰囟处理,生成酰肼,然后可选择在三乙胺存在下,用氯甲酸三氯甲酯或光气处理得到。
J=J-10:用一个合适的苯胺,转变为肼,再和一个α-酮酸缩合生成腙,这个腙再在三乙胺存在下用二苯基磷酰基叠氮化物处理得到J-10化合物,这里X=O,R18=氢,用五硫化二磷进行硫化反应,可将X变为硫。这类化合物可用方便的方法进行烷基化反应得到R18为烷基的化合物。参考文献:美国专利4,213,773;4315767;WIPO*(国际专利)WO 85/01637。
J=J-11:用三甲基硅基叠氮化物(R20为氢)处理一个异(硫)氰酸酯(这个酯可从合适的苯胺来制备)然后再用方便的方法烷基化得到。参考文献:国家专利85/01939。
J=J-12:将一个合适的苯胺重氮化并用丙二酰二氨基甲酸乙酯处理,所得到的产物环化,方法是先用氢氧化钾的醇溶液在THF中处理,然后用盐酸水溶液,得到三吖嗪二酮羧酸;并可在巯基乙酸和二甲苯存在下脱羧得到J-12,这里R21为氢,还可以进一步转变为R21不是氢而是所规定了的基团。还可以选择的一个方法是用亚硝酸钠和氯化锡()在盐酸中处理合适的取代苯胺得到相应的肼,这个肼在硫酸和THF中,和丙酮反应生成腙,腙再在乙酸水溶液中用***处理得到***烷二酮,再用R22COCO2H和硫酸在二氧六环中处理,即可得到J-12,这里R21为氢。参考文献:国际专利WO 86/00072,该专利还述及了其它合适的方法。
J=J-13:用一个合适的苯胺在溶剂为回流的乙酸中和四氢高酞酸(2-羧基环己烯-1-乙酸)反应来制备。R.Grewe和A.Mondon《Chemische Berychte 81卷,P.276-286(1948),283页)。
J=J-14:在三乙胺的存在下,用肌氨酸甲酯盐酸处理一个异氰酸酯,(该酯可从一个合适的苯胺来制备),然后再用含水氯化氢醇溶液处理所得到的脲。参考文献:美国专利4.560,752。
一个合适的苯胺或异氰酸酯反应物既可从化合物(Ⅰ),也可以从J不是所限定了的基团的化合物(Ⅰ)采用本文所叙述的方法制备。在这种情况下,较合适的J部分利于是二苯甲基氨基,苯甲酰基氨基或乙酰基氨基,苄基氨基,烯丙基氨基和三氯乙酰基氨基。正如在实例中所说明的那样,苯胺或异氰酸酯可采用方便的方法从J-化合物来制备。
很清楚,下列各类化合物都是新的,也是本发明所涉及的内容。
(1)化合物Ⅰ,包括J是从J-1到J-14中的一个,J是上述文章中所述及的一个和J是氨基(-NH)或异氰酸基(-NCO);
(2)化合物Ⅱ
(3)化合物Ⅲ
(4)化合物Ⅳ
(5)化合物Ⅴ
(6)化合物Ⅵ
(7)化合物Ⅸ
化合物Ⅰ的典型个别化合物的制备方法,分离和试验在下面实例部分都要述及。化合物ⅠA的实例化合物(R4是氢)为简便和明了起见,也为了避免有时重复使用较长的化学命名,则用ⅠA和其中使用的其它符号来表明。
化合物 R R1R5R7
A H Cl 甲基 甲基
B F Cl 甲基 甲基
C F 甲基 H 甲基
D H Br H 甲基
E F Cl H 乙基
F F Cl H 异丙基
G Cl Cl 甲基 甲基
下述化合物都是化合物ⅠA的实例,式中R4和R5都是氢和R7是-CH2-O-R10。
化合物 R R1R10
H H Cl (苯甲酰基)
I H Cl (异丙基)
J H Cl (叔丁基羰基-)
K H Cl (甲基环丙基
羰基-)
L H Cl (甲氨基) CH3-NH-
M H Cl (对氯苯磺酰基)
N F Cl (乙基)
O F Cl (叔丁基)
P F Cl (甲基环丙基羰
基)
Q F Cl (N-甲基氨基
甲酰基)
R H Br (甲磺酰基)
S H Br (叔丁基)
化合物 R R1R10
T H Br (甲基环丙基羰
基)
U H 甲基 (异丙基)
V F 甲基 (甲基)
W Cl Cl (乙酰基)
X Cl Cl (异丙基)
Y H Cl (N,N-二甲基
氨基甲酰基)
Z H Cl (N-甲基-N-
甲氧基氨基甲酰
基)
AA H Cl (4-氯苯甲酰基)
下列化合物是化合物ⅠA的实例,式中R5为氢,R7为-CH=N-O-R8。
化合物 R R1R8
AB H Cl (CH3)2CH- (异丙基)
AC H Cl CH2COOCH2CH3(乙氧基羰基甲
基)
AD H Cl CHCH3COOCH2CH3(1-乙氧基羰基
-1-乙基)
AE H Cl CH2=CH-CH2- (烯丙基)
AG F Cl (CH3)2CH- (异丙基)
AH H Br (CH3)2CH- (异丙基)
AI H 甲基 (CH3)2CH- (异丙基)
AJ F 甲基 (CH3)2CH- (异丙基)
AK Cl Cl (CH3)2CH- (异丙基)
AL F Cl CH2CO)O-CH2CH3(乙氧基羰基甲
基)
下列化合物是化合物ⅠA的实例,式中R5为氢和R7是-C(O)OR8。
化合物 R R1R8
AM H Cl CH2=CH-CH2- (烯丙基)
AO H Cl CH=CCH2- (炔丙基)
AP H Cl -CHCH3COOC2H5(1-乙氧羰基
-1-乙基)
AQ F Cl CH2=CHCH2- (烯丙基)
AR F 甲基 CH2=CHCH2- (烯丙基)
AS Cl Cl CH2=CHCH2- (烯丙基)
AT H 甲基 CH2=CHCH2- (烯丙基)
AU F Cl CH≡CCH2- (炔丙基)
AV F 甲基 -CHCH3COOC2H5(1-乙氧羰基
-1-乙基)
AW F 甲基 CH≡CCH2- (炔丙基)
在所有情况下,J=J-1,m=0,Z=C和J=J-2,R12+R13=-(CH2)4-的那些化合物都是特别可以选用的。
已发现化合物Ⅰ对某些植物的生长是不利的,它们多数是杂草,因此可以用来控制不需要植物的生长。也已发现化合物Ⅰ对某些作物具有选择性,亦即它们在一定剂量下,可以杀死杂草而对作物无明显伤害。因此在牙前或栽种前混用(在种子发芽前,施到土壤中),化合物Ⅰ是有效的,而在芽后施用(对生长中的植物叶面喷洒),大部分效果更好。
因此,本发明包括消灭不需要植物的一种方法,方法中也包括施用有效用量的化合物Ⅰ的到该地点。在种植作物时需要消灭杂草的情况下,当然要选用低剂量来防治杂草,这样化合物对作物所可能产生的毒害作用变得最小。
使用时,通常将化合物Ⅰ与一种合适的惰性载体或表面活性剂,(或两者都有)加工成制剂使用最为有效。因此,本发明也包括适用于消灭不需要植物的各种组合物,如含有一种惰性载体或表面活性剂(或两者都有)和至少含有一种化合物Ⅰ作为活性成分的组合物。
在这儿所述的“载体”是指惰性固体或液体物质,它们可以是无机的,或有机的,可以是合成的或天然的。为利于在植物、种子、土壤或其它要被处理目标上的应用,或贮藏运输和/或管理,而将这些载体与活性化合物混合或加工通常在加工杀虫剂、除草剂或杀菌剂中所使用的物质均是合适的,亦即园艺上可接受的载体均适用。
合适的固体载体包括天然和合成的粘土和硅酸盐,例如天然硅石,如硅藻土;硅酸镁,如滑石;硅酸铝镁,如活性的土和蛭石;硅酸铝,为高岭土、蒙脱土和云母片;碳酸钙;硫酸钙;合成水和氧化硅和合成硅酸钙或硅酸铝;元素,如碳和硫;天然和合成树脂,如苯并呋喃树脂,聚氯乙烯和苯乙烯的聚合物和共聚物;沥青;蜡,如峰蜡,石蜡和氯化了的矿物蜡;固体肥料,如过磷酸钙;和天然的多孔物质颗粒,如颗粒状的玉米芯。
适用的液体载体的例子有水;醇类,如异丙醇、乙二醇;酮类,如丙酮、甲乙酮、甲基异丁基酮和环己酮;醚类,如乙二醇单-***;芳烃类如苯、甲苯、和二甲苯;石油馏分,如煤油和轻矿物油;囟代烃,如四氯化碳、全氯乙烯和三氯甲烷。液化了的通常是气态的化合物,也可适用。不同液体的混合物常常是适用的。
表面活性剂可以是乳化剂或分散剂或湿润剂;它们可以是非离子型或离子型。在加工除草剂或杀虫剂中通常使用的任何表面活性剂都可使用。适用的表面活性剂的例子有聚丙烯酸和木质磺酸钠盐和钙盐;最少含有12个碳原子的脂肪酸、或脂肪胺,或酰胺和环氧乙烷和(或)环氧丙烷的缩合产物;甘油、山梨糖醇酐、蔗糖或季戊四醇的脂肪酸酯;这些醇和环氧乙烷或环氧丙烷的缩合产物;脂肪醇或烷基酚的缩合产物,如对-辛基酚或对-辛基甲酚和环氧乙烷和/或环氧丙烷的缩合产物;这些缩合产物的硫酸酯或磺酸酯,分子中最少含有10个碳原子的硫酸酯或磺酸酯的碱金属或碱土金属盐,特别是钠盐,例如月桂基硫酸钠盐,仲烷基硫酸、钠盐、磺化凯斯特罗油*的钠盐和烷基芳基磺酸钠,如十二烷基苯磺酸钠;以及环氧乙烷的聚合物和环氧乙烷与环氧丙烷的共聚物。
本发明的组合物可以制成可湿性粉剂、粉剂、颗粒剂、溶液、乳油、乳剂、悬浮剂和气雾剂。可湿性粉剂一般包含25-75%(重量比)的活性化合物,加上固体载体,以及通常还有3-10%(重量比)的分散剂,2-15%表面活性剂,必要时,加0-10%(重量比)的稳定剂和/或其它添加剂如渗透剂或粘着剂。粉剂一般加工成与可湿性粉剂相似组成的粉剂母粉,只是没有分散剂或表面活性剂,并且在田间进一步用固体载体稀释成含有0.5-10%(重量比)活性成分的组合物。颗粒剂通常加Ⅰ成颗粒大小为10-100目(英制)(1.676-0.152毫米),使用附聚法或浸渍法进行生产。一般颗粒剂包括活性成分为0.5-25%(重量比),0-1%(重量比)的添加剂,如稳定剂、缓释剂和粘结剂。乳油通常除了溶剂而外(必要时,还要有共溶剂)含有活性成分10-50%(重量/体积),乳化剂2-20%(重量/体积)和适合的添加剂0-20%(重量.体积),如稳定剂、渗透剂和腐蚀抑制剂。悬浮剂是要加工成稳定的,不沉积的可流动的产品,通常包括10-75%(重量比)活性化合物,0.5-5%(重量比)分散剂,1-5%表面活性剂,0.1-10%(重量比)的悬浮剂,如消泡剂、腐蚀抑制剂、稳定剂、渗透剂和粘结剂,作为载体的水或有机液体,活性化合物在它们中间明显不溶;某些有机固体或无机盐可以渗在载体中有助于抑制沉淀,或作为水的抗冻剂。
在最近的实际使用中,特别有意义的是水分散颗粒剂,它是一种干而硬的无尘颗粒剂,且在运输管理中是抗磨损的,因此不易形成粉末,当和水接触时,颗粒随即碎裂,形成活性物质颗粒的稳定悬浮剂。这些剂型含有90%或90%以上高达95%(重量比)的精细粉碎过的活性物质,3-7%(重量比)作用是湿润、分散、悬浮和粘着的表面活性剂混合物,和最多达3%,(重量比)作为再悬浮剂的精细粉碎过的载体。
水分散体系和乳剂,例如,按本发明用水稀释可湿性粉剂或乳油后得到的制剂,也在本发明所保护的范围之内。所述的乳剂可以是油包水,也可以是水包油,具有粘稠的,似蛋黄酱的稠度。
很显然,从本发明前面所述及的组合物中,作为活性成分的化合物Ⅰ在制剂中的含量(重量比),少至0.5%,多达95%。
本发明的组合物中也还可以包括其它成分,例如具有农药活性,特别是具有杀虫、杀螨、杀草或杀菌作用的其它化合物,以满足予订的用途。
防治不需要植物以保护土地或领域是由于施用了化合物Ⅰ的效果,一般是将前面所提到的各种组合物中的一个制剂施到存在不需要植物种子的土壤中,或喷洒在不需要植物的叶子上。当然活性物质的施用量要能充分发挥所需要的作用。
用于防治不需要植物的本发明化合物的施用量系根据植物的条件,所需要活性的等级,所使用的制剂、施药方式、气候、季节和其它变化而定。然而,要推荐一个准确用量是不可能的,但一般来说,施用到要保护地方的化合物Ⅰ的量每公顷0.02-10公斤,即是满意的。
下述实例中叙述了典型个别化合物Ⅰ的制备、分离和物理性质。在所有例子中,每个产物和所有涉及到的中间体的鉴定均由化学和光谱分析所确定。
实例1
N-(2,3-二氢-2-甲基-6-苯并呋喃基)-3,4,5,6-四氢酞酰亚胺(1)
得25.0克3,4,5,6-四氢邻苯二甲酸酐(THPA),17.9克3-氨基苯酚和350毫升冰乙酸的混合物回流1小时,然后冷却,并慢慢地倒入1400毫升冰水中。得到的混合物过滤。收集固体并用冷水洗涤后干燥(真空烘箱内),得到N-(3-羟基苯基)-3,4,5,6-四氢酞酰亚胺(1A),为黄色结晶,熔点196~197.5℃。
先将3.0克粉状碳酸钾,然后将2.6克烯丙基溴搅拌下加入含有5.0克1A的25毫升丙酮悬浮液中。混合物回流1小时,然后在室温下搅拌过夜,蒸去溶剂,残渣中加入水,用10%氢氧化钠水溶液调节混合液的PH为11,再用乙酸乙酯萃取,萃取液用盐水洗涤,并用硫酸钠干燥,蒸去溶剂,残渣在硅胶上进行快速层析,洗脱液为1∶9(体积比)乙酸乙酯∶己烷,得到N-(3-烯丙氧基苯基)-3,4,5,6-四氢酞酰亚胺(1B),为黄色结晶,熔点:88~90℃。
1克1B在油浴上加热至200~210℃,5小时后产物在硅胶上进行快速层析,洗脱液用1∶4(体积比)乙酸乙酯∶己烷。可以分离到两个产物,N-(4-烯丙基-3-羟基-苯基)-3,4,5,6-四氢酞酰亚胺(1C),为黄色结晶,熔点:147~148℃和N-(2-烯丙基-3-羟基-苯基)-3,4,5,6-四氢酞酰亚胺(1D)为白色固体,熔点72~75℃。
0.20克1C,100毫克对甲苯磺酸(PTSA)和10毫升二甲苯的混合物回流24小时,然后冷却,倒入饱和碳酸氢钠水溶液中。用乙酸乙酯萃取所得到的混合物,萃取液依次用碳酸氢钠溶液、水、盐水洗涤,用硫酸钠干燥,过滤。蒸去溶剂,残渣用Chromatotron板进行色谱分离,开始用3∶17乙酸乙酯∶己烷混合液洗脱,逐渐增加乙酸乙酯的比例,洗脱后得到1,为黄色结晶,熔点:114~118℃。
实例2
N-(2,3-二氢-2-甲基-4-苯并呋喃基)-3,4,5,6-四氢酞酰亚胺(2)
制备的2是一个黄色油状物,按实例1中从1C制备1的方法处理0.48克1D制备2。
实例3
N-(7-氯-2,3-二氢-2-甲基-4-苯并呋喃基)3,4,5,6-四氢酞酰亚胺(3)
7.4克2-氯-5-硝基酚,5.4克烯丙基溴,5.9克无水碳酸钾和50毫升干燥过的N,N-二甲基甲酰胺(DMF)的混合物室温下搅拌一周。然后将混合物倒入水中,得到的混合物用乙酸乙酯萃取两次,用***萃取两次。合并萃取液并用水洗涤,然后用盐水洗涤,无水硫酸钠干燥,过滤后除去溶剂。残渣在己烷中重结晶,得到1-(烯丙氧基)-2-氯-5-硝基-苯(3A),为桔黄色针状结晶,熔点:58~59.5℃。
将1.0克3A和5.3克二水合氯化亚锡的50毫升无水乙醇悬浮液加热1小时,混合物倒入100克冰中,然后,在搅拌下加入足够的10%氢氧化钠水溶液,使混合液的PH为10。然后先用乙酸乙酯再用***萃取,合并萃取液先用水洗后用盐水洗,用硫酸钠干燥后脱去溶剂,得到3-(烯丙氧基)-4-氯-苯胺(3B),为一褐色油状物。
4.4克THPA,5.3克3B和60毫升冰乙酸的混合物回流1小时,然后倒入300毫升冰水中。得到的混合物放置10分钟后过滤。收集固体并用冷水洗涤,减压下干燥,并在乙酸乙酯/己烷中重结晶,得到N-(3-(烯丙氧基)-4-氯苯基)-3,4,5,6-四氢酞酰亚胺(3C),为黄色结晶,熔点:118.5~200℃。
7.2克3C于210℃下加热1.5小时,产品冷却后在硅胶上快速层析,用1∶5(体积比)乙酸乙酯∶己烷洗脱,得到黄色粘稠油状物,放置固化后,得到N-(2-烯丙基-4-氯-3-羟基苯基)-3,4,5,6-四氢酞酰亚胺(3D),熔点:80~82.5℃。
3可以从3D制备,方法按实例1中从1C制备1的方法,3为一黄色结晶,熔点:134~137℃。
实例4
N-(7-氯-2,3-二氢-2-(羟基甲基)-4-苯并呋喃)-3,4,5,6-四氢酞酰亚胺(4)
室温下将0.37克间-氯过氧苯甲酸(MCPBA)与5毫升二氯甲烷的溶液滴加到0.5克3D的10毫升二氯甲烷溶液中,然后回流过夜,冷却,用几毫升饱和亚硫酸钠水溶液搅拌,直到淀粉/碘试纸上没有反应为止。分出有机相,用饱和碳酸氢钠水溶液洗涤,硫酸钠干燥和蒸去溶剂。残渣通过硅胶进行快速层析,用2∶3(体积比)乙酸乙酯∶己烷混合液洗脱,得到4为一黄色结晶,熔点:196~197.5℃。
实例5
N-(2,3-二氢-2,7-二甲基-4-苯并呋喃基)-3,4,5,6-四氢酞酰亚胺(5)
按上述实例3中从2-氯-5-硝基酚和烯丙基溴制备3D的方法,从2-甲基-5-硝基酚和烯丙基溴可制备N-(2-烯丙基-3-羟基-4-甲基苯基)-3,4,5,6-四氢酞酰亚胺(5A),为一黄色结晶,熔点:141~143℃。
按上述实例1中从1C制备1的方法,从5A可制备5,为一黄色结晶,熔点:158~160℃。
实例6
N-(2,3-二氢-2(羟甲基)-7-甲基-4-苯并呋喃基)-3,4,5,6-四氢酞酰亚胺(6)
按上述实例4中从3D制备4的方法,从5A可制备6,为一黄色结晶,熔点:177~179℃。
实例7
N-(2)-(烯丙氧基亚胺基)甲基)-7-氯-2,3-二氢-4-苯并呋喃基)-3,4,5,6-四氢酞酰亚胺(7)
在-60℃,氩气保护下将40微升草酰氯溶于4毫升二氯甲烷的溶液中,搅拌下加入65微升二甲亚砜,混合物搅拌10分钟后,加入0.1克4的4毫升二氯甲烷溶液,并再搅拌30分钟。加入0.28毫升三乙胺,并使反应混合液热至室温。再加4毫升干燥吡啶和40毫克烯丙氧基胺盐酸盐,混合物在室温下搅拌1.5小时,用甲苯蒸馏除去溶剂。所得残渣溶于乙酸乙酯中,溶液过滤,滤液在Chromatotron板上进行色谱分离,开始用1∶9(体积比)乙酸乙酯∶己烷,然后逐渐增加乙酸乙酯比例进行洗脱,可得到7,为一黄色油状物。
实例8
回流4和对甲苯磺酸的二甲苯溶液可制备4的对甲苯磺酸酯,即8,为一黄色固体,熔点:188~190℃。
实例9
N-(2-乙酰氧甲基)-7-氯-2,3-二氢-4-苯并呋喃基)-3,4,5,6-四氢酞酰亚胺(9)
在4-(二甲胺基)吡啶(DMAP)和吡啶存在下,4-和乙酸酐反应可制备4的乙酸酯,即9,为一黄色玻璃物。
实例10
N-(2-羧基-7-氯-2,3-二氢-4-苯并呋喃基)-3,4,5,6-四氢酞酰亚胺(10)
用Jone′s试剂处理醇的方法,将醇,4转变为酸,10,得到一米色固体,熔点:215~217℃。
实例11
N-(2-溴甲基)-7-氯-2,3-二氢-4-苯并呋喃基)-3,4,5,6-四氢酞酰亚胺(11)
1.67克4溶于少量二氯甲烷中,加入2.07克四溴化碳,然后溶液在氮气中,5℃及搅拌下,在10分钟内分批加入2.0克三苯基膦。混合物再在冰浴上搅拌十分钟,然后在室温下搅拌4小时。蒸去溶剂,残渣用9∶1(体积比)***∶己烷混合液研磨,弃去上层清液,蒸去溶剂,残渣在硅胶上进行快速层析,用1∶4(体积比)乙酸乙酯∶己烷洗脱,得到11,为一白色结晶,熔点:134~136℃。
实例12
N-(2-叔-丁氧羰基)-2,3-二氢-7-氯-4-苯并呋喃基)-3,4,5,6-四氢酞酰亚胺(12)
0.33克4溶于少量二氯甲烷中,加入1.5克叔丁醇,1.0毫升乙酸酐和0.75克吡啶重铬酸盐,混合物在室温下搅拌1小时。将混合物通过硅胶柱,然后用二氯甲烷淋洗,蒸去溶剂,残渣在硅胶上进行色谱分离,用1∶4(体积比)乙酸乙酯∶己烷洗脱,得到12,为一黄色玻璃物。
实例13
在DMAP和吡啶存在下用乙酸酐处理6,可得到6的乙酸酯,即13,为一黄色固体,熔点:130~132℃。
实例14和15
在PTSA的存在下,分别用甲醇或乙醇处理10,可得到10的甲酯14,为一黄色固体,熔点121~123℃;10的乙酯15,为一黄色固体,熔点71~76℃。
实例16和17
分别用氨气或异丙胺处理10,可得到10的铵盐,16,为一白色粉末,熔点:197~198℃(分解);10的异丙胺盐,为一褐色固体,熔点:211~213℃(分解)。
实例18
用碳酸氢钠水溶液在乙醇中处理10可得到10的钠盐,为一黄色粉末,熔点:280~284℃(分解)。
实例19
用Jone′s试剂处理醇的方法,醇6可转变为酸19,为一褐色固体,熔点229~231℃(分解)。
实例20
N-(7-氯-2,3-二氢-5-氟-2-甲基-4-苯并呋喃基)-3,4,5,6-四氢酞酰亚胺(20)
按美国专利4,452,981的叙述的方法,可从2-氯-4-氟苯酚和烯丙基溴制备3-(烯丙氧基)-4-氯-6-氟苯胺(20A),为一褐色油状物。
9.0克20A,6.8克THPA和100毫升冰乙酸加热回流4小时,冷却至室温,倒入450毫升水中并用***萃取。萃取液用水洗涤,硫酸钠干燥后过滤,滤液蒸去溶剂,残渣在硅胶上进行快速层析,用15∶85(体积比)乙酸乙酯∶己烷洗脱,得到N-(3-(烯丙氧基)-4-氯-6-氟苯基)-3,4,5,6-四氢酞酰亚胺(20B)为一桔黄色油状物。
9.8克20B在油浴上加热至200℃1小时,得到的粗产物冷却至室温,并在硅胶上进行快速层析,用5∶95(体积比)丙酮和甲苯为洗脱剂,得到N-(2-烯丙基-4-氯-6-氟-3-羟基苯基)-3,4,5,6-四氢酞酰亚胺(20C),为一褐色固体,熔点109~111℃。
80毫升二甲苯和0.5克一水合PTSA的混合物共沸脱水30分钟。所得到的溶液冷至室温。加入1.70克20C,混合物加热回流18小时,然后在室温下放置过夜。先用饱和碳酸氢钠水溶液洗涤反应物,再用水和盐水洗涤,干燥(Na2SO4),过滤,蒸去溶剂。残渣在硅胶上进行快速层析,用1∶4(体积比)乙酸乙酯∶己烷洗脱,得到20,为一灰白色结晶,熔点:169~171℃。
实例21
N-(7-氯-2,3-二氢-5-氟-2-(羟甲基)-4-苯并呋喃基)-3,4,5,6-四氢酞酰亚胺(21)
将溶有0.67克20C和475毫克80%MCPBA的15毫升1,2-二氯乙烷在油浴上,70℃下加热2.5小时,加入几毫升PTSA。混合物冷至室温,先用饱和亚硫酸钠水溶液,后用饱和碳酸氢钠水溶液洗涤,硫酸钠干燥,过滤和蒸去溶剂,残渣在硅胶上进行快速层析,用40∶60(体积比)乙酸乙酯∶己烷洗脱,得到21,为一白色结晶,熔点:193~195℃。
实例22
N-(2-乙酰氧基甲基)-7-氯-2,3-二氢-5-氟-4-苯并呋喃基)-3,4,5,6-四氢酞酰亚胺(22)
在DMAP和吡啶存在下,用乙酸酐处理21,即可得到21的乙酸酯,即22,为一灰白色结晶,熔点:129~131℃。
实例23
N-(2-羧基-7-氯-2,3-二氢-5-氟-4-苯并呋喃基)-3,4,5,6-四氢酞酰亚胺(23)
用Jone′s试剂处理21即可得到23,为一白色粉末,熔点:209~211℃(分解)。
实例24
N-(7-氯-2,3-二氢-5-氟-2-(甲氧基羰基)-4-苯并呋喃基)-3,4,5,6-四氢酞酰亚胺(24)。
在PTSA存在下,用甲醇处理23,即可得到24,为一黄色半固体。
实例25
N-(7-氯-2,3-二氢-2-(1-乙氧基羰基)乙氧基羰基)-5-氟-4-苯并呋喃基)-3,4,5,6-四氢酞酰亚胺(25)。
将0.300克23,120微升3-溴丙酸乙酯,0.136克碳酸钾、0.136克碘化钾和8毫升乙腈加热回流3小时,产物分成水层和醚层,分出醚层,并先用水洗涤后用盐水洗涤,硫酸镁干燥,过滤,滤液蒸去溶剂,残渣在硅胶上进行快速层析,用1∶3(体积比)乙酸乙酯∶己烷混合液洗脱,得到黄色半固体,为25。
实例26
N-(7-氯-2,3-二氢-2-(羟基甲基)-4-苯并呋喃基)酞酰亚胺(26)
按前述的从3D制备4的方法,从3B和邻苯二甲酸酐三步合成26,为一白色固体,熔点:181~183℃。
实例27
N-(2-羧基-7-氯-2,3-二氢-4-苯并呋喃基)-酞酰亚胺(27)
用Jone′s试剂处理26,可得到27,为一米色结晶,熔点:236~239℃(分解)。
实例28~31
按前述实例中所叙述的方法,可制备下列化合物Ⅰ:
28,为27的乙酯,黄色固体,熔点:134~136℃
29,为27的甲酯,黄色固体,熔点:136~138℃
30,为27的钠盐,黄色固体,熔点:未定,300℃以上分解
31,为27的铵盐,黄色粉末,熔点:220~223℃(分解)
实例32
N-(7-氯-2,3-二氢-2-甲基-4-苯并呋喃基)酞酰亚胺(32)
按所叙述的从3B制备3的方法,从3B和邻苯二甲酸酐可以制备32,为一米色固体,熔点197~198℃。
实例33
2-(7-氯-2,3-二氢-2-甲基-4-苯并呋喃基)-2,3,4,5-四氢-3,5-二氧代-1,2,4-三嗪-6-腈(33)
在氮气保护下,室温时将1.5克肼加入30克32和120克二甲亚砜的混合物中,搅拌16小时后,加入到600毫升水中。混合物用***萃取,萃取液先用水后用盐水洗涤,干燥后蒸去溶剂,得到4-氨基-7-氯-2,3-二氢-2-甲基苯并呋喃(33A)为一固体,熔点70℃。
9.18克33A,10毫升12N(摩尔当量)盐酸和10毫升水在蒸汽浴上加热1小时,再加10毫升水并在室温下搅拌过夜,然后加30毫升水,并冷至0℃,搅拌下滴加含有3.45克硝酸钠的10毫升水溶液(滴加时间15分钟),然后再在0℃下搅拌1小时。所得到的混合物慢慢地加到搅拌着的含有7.8克N-氰基乙酰基氨基甲酸酯,25毫升吡啶和900毫升水的混合物中(温度为0℃),所得到的混合物在0℃下再搅拌1.5小时,过滤,收集固体。并用水洗涤,在减压下干燥,并在丙酮/石油醚中重结晶,得到N-((7-氯-2,3-二氢-2-甲基-4-苯并呋喃基肼叉)氰乙酰基)氨基甲酸乙酯(33B),为一固体,熔点:175~177℃(分解)。
12.5克33B和600毫升二甲苯混合物在装有4A分子筛的索氏提取器里搅拌回流过夜,收集所生成的醇。混合物冷却至室温,过滤,固体产物在减压下干燥便得到33,为一褐色固体,熔点:244~245℃。
实例34
2-(7-氯-2,3-二氢-2-甲基-4-苯并呋喃基)-2,3,4,5-四氢-3,5-二氧代1,2,4-三嗪-6-羧酸(34)。
9.0克33,150毫升二氧六环和100毫升6N盐酸搅拌下回流过夜。加入12N盐酸20毫升,混合物再搅拌回流2小时,脱去溶剂。残渣溶在乙酸乙酯中,溶液先用水后用盐水洗涤,硫酸镁干燥,蒸去溶剂。残渣在乙酸乙酯/石油醚中重结晶得到34,为一琥珀色固体,熔点:235~236℃(分解)。
实例35
2-(7-氯-2,3-二氢-2-甲基-4-苯并呋喃基)-1,2,4-三嗪-3,5-(2H,4H)-二酮(35)
8.0克34和80毫升导热姆*在200~250℃加热2小时,冷至室温,用石油醚稀释并过滤,收集固体,并在减压下干燥,在乙酸乙酯/石油醚中重结晶,得到35,为一褐色固体,熔点:184~186℃。
实例36
2-(7-氯-2,3-二氢-2-甲基-4-苯并呋喃基)-4-甲基-1,2,4-三嗪-3,5(2H,4H)-二酮(36)
在氮气保护下,0℃下,十五分钟内将2.8克35搅拌下加入到含有0.5克用己烷洗过的氢化钠,1.6克碘甲烷和30毫升干DMF的混合物中。当释放气体结束(30分钟),在室温下继续搅拌1.5小时,倒入冰水中,并过滤,将收集到的固体溶于乙酸乙酯中,得到的溶液先用水后用盐水洗涤,硫酸镁干燥后脱去溶剂。残渣在乙酸乙酯/己烷中重结晶得到36,为一褐色固体,熔点:131~132℃。
实例37和38
2-(7-氯-2,3-二氢-2-甲基-4-苯并呋喃基)-4-(二氟甲基)-5-甲基-2H-1,2,4-***-3(4H)酮(37);
2-(7-氯-2,3-二氢-2-甲基-4-苯并呋喃基)-1-(二氟甲基)-5-甲基-1H-1,2,4-***-3(2H)酮(38);
5.5克33A按实例33所提供的方法进行重氮化,将这重氮化产物冷至-25℃。将含有19.7克氯化亚锡(二价锡)二水合物的25毫升12N盐酸溶液在20分钟内搅拌下滴加到上述重氮化产物中,在-25℃下再搅拌4小时,然后将含有2.82克重新蒸馏过的丙酮酸的20毫升水溶液在-25℃搅拌下滴加到上述混合物中,然后搅拌下慢慢地升温至室温,搅拌一周。然后过滤反应混合物,固体物质用水洗,并溶于饱和碳酸氢钠水溶液。再用乙酸乙酯萃取此溶液,水相用12N盐酸酸化,并用乙酸乙酯萃取、后面的萃取液先用水后用盐水洗涤,硫酸镁干燥,脱去溶剂。残渣在乙酸乙酯/己烷中重结晶得到2-((7-氯-2,3-二氢-2-甲基-4-苯并呋喃基)肼叉)丙酸(37A),为各种异构体的混合物,熔点:155~157℃。
5.1克三乙胺在搅拌下加入到5.0克37A和100毫升甲苯混合物中,然后加入1.9克二苯基磷酰叠氮,在两小时内,将反应混合物加热至回流温度,回流后将所得到的混合物倒入100毫升10%冰冷的氢氧化钾水溶液(重量/体积)中。产生两相液体层,分离之,水层用12N盐酸酸化后用乙酸乙酯萃取,萃取液先用水,后用盐水洗涤,硫酸镁干燥后脱去溶剂,残渣在乙酸乙酯/己烷中重结晶得到2-(7-氯-2,3-二氢-2-甲基-4-苯并呋喃基)-5-甲基-2H-1,2,4-***-3(4H)-酮(37B),是一无色固体,熔点:208~209℃。
0℃下,0.6克用己烷洗过的氢化钠和30毫升THF的混合物用氟里昂22(二氟氯甲烷)饱和,然后加入1.33克37B和10毫升THF的混合物,混合物在室温下搅拌6小时,在此期间二氟氯甲烷鼓泡通入;然后,在室温下再搅拌一星期后再滴加15毫升水,蒸去溶剂,残渣溶于乙酸乙酯中,溶液先用水,再用盐水洗涤,硫酸镁干燥后脱去溶剂。残渣在硅胶上进行色谱分离,用1∶3(体积比)己烷∶二氯甲烷洗脱得到两个馏分,为两个异构体产物:37,为一无色固体,熔点122.5~123.5℃;和38,为一奶油色固体,熔点:78~79℃。
实例39
2-(7-氯-2,3-二氢-2-甲基-4-苯并呋喃基)六氢-1H-咪唑并〔3,4-a〕吡啶-1,3(2H)-二酮(39)
6.07克三乙胺加入到9.18克33A,11.87克氯甲酸三氯甲酯和250毫升二氧六环混合物中,并回流6小时。混合物过滤,滤液脱去溶剂,得到7-氯-4-异氰酸基-2-甲基苯并呋喃(39A),为一褐色液体。
在氮气保护下,室温下将2.36克哌啶酸乙酯和20毫升干THF所成溶液加入到2.10克39A和60毫升干THF的混合物中,加入的速度为保持反应物的温度在25~32℃,然后混合物于室温下搅拌过夜,用250毫升己烷稀释后过滤,收集到的固体被鉴定为1((7-氯-2,3-二氢-2-甲基-4-苯并呋喃基)-氨基)羰基)-2哌啶羧酸乙酯(39B),熔点:169~171℃。
将2.0克39B,25毫升乙醇和25毫升2N盐酸混合物搅拌并回流2小时,然后蒸去溶剂,残渣和50毫升水混合,所得到的混合物用二氯甲烷萃取。萃取液用硫酸镁干燥后蒸去溶剂。残余物通过一短层硅胶过滤纯化,用1∶1(体积比)乙酸乙酯∶己烷洗脱,得到39,为一固体,溶点:145~148℃。
实例40
3-(7-氯-2,3-二氢-2-甲基-4-苯并呋喃基)-1-甲基咪唑烷-2,4-二酮(40)
在氮气保护下,于25~30℃,五分钟内将2.30克肌氨酸乙酯盐酸盐加到2.10克39A,1.52克三乙胺和60毫升二氯甲烷的混合物中,混合物在室温下搅拌24小时,然后用100毫升二氯甲烷稀释,先用水后用盐水洗涤,硫酸镁干燥后脱去溶剂。残渣溶于70毫升1∶1(体积比)乙醇∶2N盐酸混合溶剂中。溶液回流4小时,所得到的混合物室温下搅拌过夜,脱去挥发物,用水稀释后用二氯甲烷萃取,萃取液硫酸镁干燥后脱去溶剂。残渣的纯化可通过56~60目硅胶进行快速层析用1∶2(体积比)己烷∶乙酸乙酯为洗脱剂,得到40,为一玻璃状粘稠固体。
实例41
杀草活性
在下面的实例中,被试验的植物品种计有:
缩写
稗 Barnyardgrass-Echinochloa crus-galli BYGR
旱雀麦 Downy brome-Bromus tectorum DOBR
狗尾草 Yellow foxtail-Setaria glauca YEFT
决明 Sicklepod-Cassia obtusifolia SIPO
野茼麻 Velvetleaf-Abutilon theophrasti VELE
独行菜 Garden cress-Lepidium sativum GACR
石茅高粱 Johnsongrass-Sorghum halepense JOGR
甘薯属 Morninglory-Ipomoea sp. MOGL
田旋花 Field bindweed-Convolvulus arvensis FIBW
茄属 Nightshade-Solanum sp. NISH
鼠尾看麦娘 Blackgrass-Alopecurus myosuroides BLGR
稷 Yellow millet-Panicum miliceum YEMI
马唐 Large crabgrass-Dinitaria sanguinalis LACG
反枝苋 Redroot pigweed-Amaranthus retroflexus RRPW
大果田菁 Hemp sesbania-Sesbania exaltata HESE
刺黄花稔 Prickly sida-Sida spinosa PRSI
试验方法
化合物Ⅰ的芽前(土壤处理)杀草活性测定:在试管中插种旱雀麦、石茅高粱、狗尾草、稗稷、鼠尾看麦娘、大果田菁、野茼麻、甘薯属杂草、刺黄花稔、决明和独行莱的种子,试管的大小为25×200毫升。方法是先在试管内装入3/4没有处理过的土壤,然后在上面装上2.5cm3用0.1毫克试验化合物处理过的土壤,这样所用的剂量为每公顷1.12公斤试验化合物(1.0磅/英亩)将上述杂草种子播种在处理过的土壤上,再用大约1.5cm3没有处理过的土壤复盖上。播种过的土壤置于控制温度,湿度和光线的地方,10天后按0到9测定每个试管内发芽和生长的情况。数字分级处理所有的数字等级具有下述意义:
数字等级 意义
9 没有生命组织
8 植物严重受损害和不能存活
7 植物严重受损、但还能存活
6 中等受害,但不能完全恢复
5 中等受害,(可能没有被作物所吸收)
3-4 可观察到受损害
1-2 植物轻微受害,可能是化学作用也可能是生理变异
0 没有观察到作用
化合物Ⅰ的芽后(叶面喷洒)杀草活性测定:
喷雾在9天龄的马唐,9天龄的藜*,6天龄的石茅高粱,9天龄的野茼麻,8天龄的狗尾草,9天龄的决明,5天龄的甘薯属杂草,5天龄稗,6天龄稷,9天龄茄属杂草,9天龄的刺黄花稔和7天龄田旋花上进行。用含有试验化合物0.5毫克的2.4毫升液体制剂喷酒。(剂量为每公顷1.12公斤试验化合物)喷洒过的植物置于控制温度,湿度和光线的地方,7~8天后,当试验化合物的作用明显可见时,按上述的数字等级测定结果。
芽前和芽后杀草活性试验的结果都列在表Ⅰ和表Ⅱ之中。
文件名称 页 行 补正前 补正后
说明书 1 倒1 Hn H3-n
6 12 异唑基 异噁唑基
6 14 啉基 噌啉基
10 倒1 要根据R和R 要根据R2和R3
11 6 在惰性溶剂中了回 在惰性溶剂中回流
流
12 倒3 (式中R是 (式中R7是
13 例7 R为-CH(R2)OH R7为-CH(R2)OH
16 13 国家专利85/ 国际专利85/01939
01939
16 18 和氯化锡() 和氯化锡(Ⅱ)
17 1 肌氨酸甲酯盐酸 肌氨酸甲酯盐酸盐
17 6 J部分利于是 J部分可以是
17 11 J是氨基(-NH) (-NH2)
23 6 牙前或栽种前 芽前或栽种前
权利 1 7 Hn H3-n
要求书 4 3 E Z
4 4 W是S或SO W是S或SO2
Claims (12)
1、具有通式Ⅰ的任一化合物
式中
R和R1分别为一个氢或囟原子;氰基;具有1-4个碳原子的烷基或烷氧基;三囟代甲基;羟甲基;最多为4个碳原子的烷基、链烯基或烷酰氧甲基;或-OCFn H n,n为1、2或3。
每个R4都独立地为一氢原子或具有1-4个碳原子的烷基;
R5代表一氢原子或具有1-4个碳原子的烷基;
R6为一氢原子或一羟基;R5和R6可以同是氧代的氧原子或为一个=NO(R8)部分;或R5为氢原子时,R6为-CN,-C(O)Cl,-C(O)R8,-C(O)O(R8)或-C(O)N(R8)(R8);
R7代表一个-CN,-CH(R9)CN,-CH(R2)(R3),-C(O)Cl,-CO(R8),-C(O)O(R8),-CH(R9)-O(R10),C(O)N(R8)(R8)或-C(R9)=NO(R8),这里每个R2和R3都分别代表一氢原子;1-4个碳原子的烷基或囟代烷基;苯基;或具有7-10个碳原子的苯基烷基;
R8代表一氢原子;最多为4个碳原子的烷基,囟代烷基,链烯基,囟代链烯基或链炔基;苯基或具有7-10个碳原子的苯基烷基;杂环芳基或最多为10个碳原子的杂环芳烷基;最多为6个碳原子的烷氧烷基或烷氧羰基烷基;
R9代表一氢原子或具有1-4个碳原子的烷基;
R10代表一氢原子;或具有最多4个碳原子的烷基,囟代烷基,链烯基或链炔基;具有7-10个碳原子的苯基烷基;最多为10个碳原子的杂环芳烷基;或连接在羰氧基的羰基上的前述基团(注:即 中的R);最多为6个碳原子的烷氧烷基或烷氧羰基烷基;具有1-4个碳原子的烷基磺酰基;环上可被1个或多个囟原子和/或具有1-4个碳原子的烷基取代的苯磺酰基;氨基甲酰基;或最多为6个碳原子的一烷基或二烷基氨基甲酰基;
和J是下述部分之中的一个:
式中:
X和Y每个是O或S;
E是C或N;
W是S或SO;
m是0、1或2;
R11是一囟原子或一个具有1-4个碳原子的烷基,囟代烷基或烷氧基;
R12和R13都分别是一氢原子或1-4个碳原子的烷基,或R12和R13用碳原子连结在一起形成一个六元脂环,该脂环可被1-3个甲基所取代;
R14是一氢或囟原子;或具有1-4个碳原子的烷基或烷基-S(O)a-基,a为0、1或2;
R15是一个-氢或囟原子;或1-4个碳原子的烷基,烷硫基或烷磺酰基;
R16是一个具有1-4个碳原子的烷基;
或R15,R16联在一起形式-(CH2)b-,b为3或4,同时可以被1-3个甲基所取代。
R17是一个氢原子或一个最多为6个碳原子的烷基,链烯基,囟代烷基或烷氧基烷基,或具有3-6个碳原子的环烷基,具有4-8个碳原子的环烷基烷基,或上述两种被1-3个具有1-4个碳原子的烷基取代了的基团;
R18是1-6个碳原子的烷基,囟代烷基、氰烷基、烷氧烷基、链烯基、链炔基或烷基-S(O)a-,烷基,a为0、1或2;
R19是一个氢原子;R18中所规定了的一个基团,或R18,R19共同为亚烷基-(CH2)b-,相同于R16中所规定的基团,或-(CH2)c-O-(CH2)d-,c和d可以是0、1、2或3和c和d都为2或都为3,O是氧、
-S(O)a-,或NR烷基-,a为0、1或2,u为-S(O)a-时,c不是0。
R20是一个1-6个碳原子的烷基,囟代烷基、烷氧基烷基,烷硫基烷基,氰烷基,囟代烷氧烷基,链烯基和囟代链烯基;
R21是一个氢原子,或1-4个碳原子的烷基、囟代烷基、氰烷基、链烯基、链炔基、烷氧基烷基、氨基或烷氧基羰基;
R22是一个由R20中所规定了的一个基团,或羧基或烷氧基羰基;
或J是二苯甲基氨基,苯甲酰基氨基,乙酰基氨基,苄基氨基,烯丙基氨基,三氯乙酰基氨基、氨基或异氰酸基;
和其酸性部分和碱金属碱、氨和胺生成的盐。
2、按权项要求1所规定的通式为ⅠA的任一化合物,J为J-1或J-2。
3、按权项要求2所规定的任一化合物当J为J-1时m是0;当J为J-2时,R12+R13为-(CH2)4-。
4、按权项要求1、2或3所规定的任一化合物,R1是氢原子。
6、按权项要求5的方法所制备的化合物Ⅰ。
9、按权项要求8中所规定的化合物Ⅴ,Ⅵ或Ⅷ中的任一化合物。
10、按权项要求1至4或6中任一项的任一化合物与至少一种载体所组成的具有杀草活性的组合物。
11、用按权项要求1至4或6中任一项所规定的化合物或按权项要求10中所规定的组合物在所防治的地方,防治不需要植物生长的方法。
12、将按权项要求1至4或6中任一项所规定的化合物或按权项要求10中所规定的组合物作为除草剂的用法。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US94336586A | 1986-12-10 | 1986-12-10 | |
US943,365 | 1986-12-10 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN87107276A true CN87107276A (zh) | 1988-10-19 |
CN1021824C CN1021824C (zh) | 1993-08-18 |
Family
ID=25479528
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN87107276A Expired - Fee Related CN1021824C (zh) | 1986-12-10 | 1987-12-07 | 含取代苯并呋喃的除草活性组合物 |
Country Status (12)
Country | Link |
---|---|
EP (1) | EP0271170A3 (zh) |
JP (1) | JPS63156787A (zh) |
CN (1) | CN1021824C (zh) |
AR (1) | AR243522A1 (zh) |
AU (1) | AU8215287A (zh) |
BR (1) | BR8706588A (zh) |
DD (1) | DD270532A5 (zh) |
DK (1) | DK641587A (zh) |
IE (1) | IE873313L (zh) |
IL (1) | IL84727A0 (zh) |
MA (1) | MA21126A1 (zh) |
ZA (1) | ZA879171B (zh) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005037789A1 (fr) * | 2003-10-21 | 2005-04-28 | Zhengquan Wang | Herbicides a base de phtalimide |
CN102971302A (zh) * | 2010-06-29 | 2013-03-13 | 组合化学工业株式会社 | 6-酰基-1,2,4-三嗪-3,5-二酮衍生物及除草剂 |
CN105693672A (zh) * | 2016-04-14 | 2016-06-22 | 青岛科技大学 | 一种多取代2-亚胺-2h-苯并吡喃衍生物的制备方法 |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3924052A1 (de) * | 1989-07-21 | 1991-01-24 | Bayer Ag | N- (indol-6-yl)-heterocyclen |
DE69124613T2 (de) * | 1990-09-13 | 1997-09-04 | E.I. Du Pont De Nemours & Co., Wilmington, Del. | Verwendung von herbiziden substituierten bicyclischen triazolen für perennierende plantagen |
WO1992013453A1 (en) * | 1991-02-01 | 1992-08-20 | E.I. Du Pont De Nemours And Company | Herbicides for citrus, sugarcane, oil palm and the like |
US5480856A (en) * | 1991-02-01 | 1996-01-02 | E. I. Du Pont De Nemours And Company | 1,2,4-triazolo[1,2-a]pyridazine-1,3(2H)-dione herbicides for citrus, sugarcane, oil palm and the like |
US5476834A (en) * | 1993-03-17 | 1995-12-19 | Sumitomo Chemical Company, Limited | Dihydrobenzofuran derivatives, their production and use |
BR9507902A (pt) * | 1994-05-27 | 2004-10-19 | Du Pont | Método para controle de ervas daninhas em culturas de plantação |
CA2156652A1 (en) | 1994-08-31 | 1996-03-01 | Minoru Takano | Epoxyphenol derivatives and herbicides containing them as active ingredients |
US6130187A (en) * | 1996-02-09 | 2000-10-10 | Kumiai Chemical Industry Co., Ltd. | Benzofuran-7-yl uracil derivatives and herbicides |
ES2159386T3 (es) * | 1996-03-19 | 2001-10-01 | Syngenta Participations Ag | Compuestos de accion herbicida substituidos con (dihidro)benzofuranilo. |
AU6018799A (en) | 1998-09-09 | 2000-03-27 | Ishihara Sangyo Kaisha Ltd. | Fused-benzene derivatives useful as herbicides |
US20040157738A1 (en) * | 2003-02-12 | 2004-08-12 | Ishihara Sangyo Kaisha, Ltd. | Novel oxygen containing fused cyclic derivatives and herbicidal, desiccant and defoliate compositions containing them |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA1076114A (en) * | 1975-02-10 | 1980-04-22 | Mitsubishi Chemical Industries Limited | 1,5-alkylene-3-aryl hydantoin derivatives |
DK156573C (da) * | 1981-06-16 | 1990-01-29 | Sumitomo Chemical Co | 2-(2-fluor-4-halogen-5-substitueret-phenyl)-hydantoinderivater, et herbicidt praeparat indeholdende disse, en fremgangsmaade til bekaempelse af ukrudt under anvendelse af disse samt anvendelse af disse som herbicid |
US4439229A (en) * | 1981-06-29 | 1984-03-27 | Rohm And Haas Company | Substituted phthalimides herbicides |
JPS58194870A (ja) * | 1982-05-07 | 1983-11-12 | Sumitomo Chem Co Ltd | オキサジアゾリノン誘導体、その製造法およびそれを有効成分として含有する殺虫、殺ダニ剤 |
-
1987
- 1987-12-07 MA MA21367A patent/MA21126A1/fr unknown
- 1987-12-07 BR BR8706588A patent/BR8706588A/pt not_active Application Discontinuation
- 1987-12-07 JP JP62307797A patent/JPS63156787A/ja active Pending
- 1987-12-07 IL IL84727A patent/IL84727A0/xx unknown
- 1987-12-07 AR AR87309518A patent/AR243522A1/es active
- 1987-12-07 DD DD87310042A patent/DD270532A5/de not_active IP Right Cessation
- 1987-12-07 DK DK641587A patent/DK641587A/da not_active Application Discontinuation
- 1987-12-07 IE IE873313A patent/IE873313L/xx unknown
- 1987-12-07 CN CN87107276A patent/CN1021824C/zh not_active Expired - Fee Related
- 1987-12-07 AU AU82152/87A patent/AU8215287A/en not_active Abandoned
- 1987-12-07 ZA ZA879171A patent/ZA879171B/xx unknown
- 1987-12-08 EP EP87202464A patent/EP0271170A3/en not_active Withdrawn
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005037789A1 (fr) * | 2003-10-21 | 2005-04-28 | Zhengquan Wang | Herbicides a base de phtalimide |
CN102971302A (zh) * | 2010-06-29 | 2013-03-13 | 组合化学工业株式会社 | 6-酰基-1,2,4-三嗪-3,5-二酮衍生物及除草剂 |
US8969554B2 (en) | 2010-06-29 | 2015-03-03 | Kumiai Chemical Industry Co., Ltd. | 6-acyl-1,2,4-triazine-3,5-dione derivative and herbicides |
CN102971302B (zh) * | 2010-06-29 | 2015-11-25 | Fmc公司 | 6-酰基-1,2,4-三嗪-3,5-二酮衍生物及除草剂 |
US9573909B2 (en) | 2010-06-29 | 2017-02-21 | Fmc Corporation | 6-acyl-1,2,4-triazine-3,5-dione derivative and herbicides |
US10081608B2 (en) | 2010-06-29 | 2018-09-25 | Fmc Corporation | 6-acyl-1,2,4-triazine-3,5-dione derivative and herbicides |
CN105693672A (zh) * | 2016-04-14 | 2016-06-22 | 青岛科技大学 | 一种多取代2-亚胺-2h-苯并吡喃衍生物的制备方法 |
Also Published As
Publication number | Publication date |
---|---|
BR8706588A (pt) | 1988-07-26 |
DK641587A (da) | 1988-06-11 |
EP0271170A2 (en) | 1988-06-15 |
JPS63156787A (ja) | 1988-06-29 |
EP0271170A3 (en) | 1989-12-13 |
IE873313L (en) | 1988-06-10 |
DD270532A5 (de) | 1989-08-02 |
AR243522A1 (es) | 1993-08-31 |
CN1021824C (zh) | 1993-08-18 |
MA21126A1 (fr) | 1988-07-01 |
AU8215287A (en) | 1988-06-16 |
IL84727A0 (en) | 1988-05-31 |
DK641587D0 (da) | 1987-12-07 |
ZA879171B (en) | 1988-08-31 |
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