CN1160046A - 具有除草活性的芳基噻二唑酮类 - Google Patents
具有除草活性的芳基噻二唑酮类 Download PDFInfo
- Publication number
- CN1160046A CN1160046A CN96123923A CN96123923A CN1160046A CN 1160046 A CN1160046 A CN 1160046A CN 96123923 A CN96123923 A CN 96123923A CN 96123923 A CN96123923 A CN 96123923A CN 1160046 A CN1160046 A CN 1160046A
- Authority
- CN
- China
- Prior art keywords
- straight
- branched
- ketone
- thiadiazoles
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 230000002363 herbicidal effect Effects 0.000 title abstract description 7
- 241000196324 Embryophyta Species 0.000 claims abstract description 22
- 239000002585 base Substances 0.000 claims description 79
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 79
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 33
- 239000001301 oxygen Substances 0.000 claims description 33
- 229910052760 oxygen Inorganic materials 0.000 claims description 33
- -1 aryl thiadiazoles ketone Chemical class 0.000 claims description 31
- 125000003545 alkoxy group Chemical group 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 22
- 229910052801 chlorine Inorganic materials 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 21
- 238000007363 ring formation reaction Methods 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 19
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical class CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 18
- 125000004414 alkyl thio group Chemical group 0.000 claims description 17
- 125000003342 alkenyl group Chemical group 0.000 claims description 16
- 230000000694 effects Effects 0.000 claims description 15
- 239000000460 chlorine Substances 0.000 claims description 14
- 125000001188 haloalkyl group Chemical group 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 14
- 238000009333 weeding Methods 0.000 claims description 14
- 239000003153 chemical reaction reagent Substances 0.000 claims description 13
- 229910052731 fluorine Inorganic materials 0.000 claims description 12
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 10
- 125000005843 halogen group Chemical group 0.000 claims description 10
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 9
- 239000011737 fluorine Substances 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 8
- 239000013543 active substance Substances 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 8
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052794 bromium Inorganic materials 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 125000000304 alkynyl group Chemical group 0.000 claims description 7
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 7
- 150000007530 organic bases Chemical class 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 125000001316 cycloalkyl alkyl group Chemical group 0.000 claims description 6
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 6
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 6
- PVFOMCVHYWHZJE-UHFFFAOYSA-N trichloroacetyl chloride Chemical compound ClC(=O)C(Cl)(Cl)Cl PVFOMCVHYWHZJE-UHFFFAOYSA-N 0.000 claims description 6
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims description 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 claims description 4
- 125000004644 alkyl sulfinyl group Chemical group 0.000 claims description 4
- 125000004390 alkyl sulfonyl group Chemical group 0.000 claims description 4
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 claims description 4
- 150000007529 inorganic bases Chemical class 0.000 claims description 4
- 125000000449 nitro group Chemical class [O-][N+](*)=O 0.000 claims description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 3
- 125000003302 alkenyloxy group Chemical group 0.000 claims description 3
- 125000005108 alkenylthio group Chemical group 0.000 claims description 3
- 125000005133 alkynyloxy group Chemical group 0.000 claims description 3
- 125000001246 bromo group Chemical group Br* 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 125000001153 fluoro group Chemical group F* 0.000 claims description 3
- 125000000232 haloalkynyl group Chemical group 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 239000011630 iodine Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- 235000010755 mineral Nutrition 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 2
- 125000005134 alkynylsulfinyl group Chemical group 0.000 claims description 2
- HSDAJNMJOMSNEV-UHFFFAOYSA-N benzyl chloroformate Chemical compound ClC(=O)OCC1=CC=CC=C1 HSDAJNMJOMSNEV-UHFFFAOYSA-N 0.000 claims description 2
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 claims description 2
- 239000003085 diluting agent Substances 0.000 claims description 2
- HCUYBXPSSCRKRF-UHFFFAOYSA-N diphosgene Chemical compound ClC(=O)OC(Cl)(Cl)Cl HCUYBXPSSCRKRF-UHFFFAOYSA-N 0.000 claims description 2
- AHWALFGBDFAJAI-UHFFFAOYSA-N phenyl carbonochloridate Chemical compound ClC(=O)OC1=CC=CC=C1 AHWALFGBDFAJAI-UHFFFAOYSA-N 0.000 claims description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 2
- 235000015320 potassium carbonate Nutrition 0.000 claims description 2
- 239000012312 sodium hydride Substances 0.000 claims description 2
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 2
- 238000007039 two-step reaction Methods 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 4
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims 1
- 239000004480 active ingredient Substances 0.000 claims 1
- 239000004009 herbicide Substances 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 34
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 21
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 11
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 244000237956 Amaranthus retroflexus Species 0.000 description 5
- 235000013479 Amaranthus retroflexus Nutrition 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- 235000010469 Glycine max Nutrition 0.000 description 5
- 244000068988 Glycine max Species 0.000 description 5
- 240000007594 Oryza sativa Species 0.000 description 5
- 235000007164 Oryza sativa Nutrition 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 235000021307 Triticum Nutrition 0.000 description 5
- 241000209140 Triticum Species 0.000 description 5
- 240000008042 Zea mays Species 0.000 description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 4
- 229920001213 Polysorbate 20 Polymers 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 125000000623 heterocyclic group Chemical group 0.000 description 4
- 230000036571 hydration Effects 0.000 description 4
- 238000006703 hydration reaction Methods 0.000 description 4
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 4
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 241000217446 Calystegia sepium Species 0.000 description 3
- 240000006122 Chenopodium album Species 0.000 description 3
- 235000009344 Chenopodium album Nutrition 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 244000234609 Portulaca oleracea Species 0.000 description 3
- 235000001855 Portulaca oleracea Nutrition 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 235000002594 Solanum nigrum Nutrition 0.000 description 3
- 240000002307 Solanum ptychanthum Species 0.000 description 3
- 235000007244 Zea mays Nutrition 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229940125904 compound 1 Drugs 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
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- 239000002689 soil Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- ASGMFNBUXDJWJJ-JLCFBVMHSA-N (1R,3R)-3-[[3-bromo-1-[4-(5-methyl-1,3,4-thiadiazol-2-yl)phenyl]pyrazolo[3,4-d]pyrimidin-6-yl]amino]-N,1-dimethylcyclopentane-1-carboxamide Chemical compound BrC1=NN(C2=NC(=NC=C21)N[C@H]1C[C@@](CC1)(C(=O)NC)C)C1=CC=C(C=C1)C=1SC(=NN=1)C ASGMFNBUXDJWJJ-JLCFBVMHSA-N 0.000 description 2
- UAOUIVVJBYDFKD-XKCDOFEDSA-N (1R,9R,10S,11R,12R,15S,18S,21R)-10,11,21-trihydroxy-8,8-dimethyl-14-methylidene-4-(prop-2-enylamino)-20-oxa-5-thia-3-azahexacyclo[9.7.2.112,15.01,9.02,6.012,18]henicosa-2(6),3-dien-13-one Chemical compound C([C@@H]1[C@@H](O)[C@@]23C(C1=C)=O)C[C@H]2[C@]12C(N=C(NCC=C)S4)=C4CC(C)(C)[C@H]1[C@H](O)[C@]3(O)OC2 UAOUIVVJBYDFKD-XKCDOFEDSA-N 0.000 description 2
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- C07D285/125—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles with oxygen, sulfur or nitrogen atoms, directly attached to ring carbon atoms, the nitrogen atoms not forming part of a nitro radical
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/82—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 three ring hetero atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
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- Pest Control & Pesticides (AREA)
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- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
具能通式(I)的芳基噻二唑酮：通式(I)的芳基噻二唑酮具有很高的除草活性，并可用作除草剂在农作物栽培中控制杂草。
Description
本发明涉及新的芳基噻二唑酮类。
更具体地，本发明涉及具有高除草活性的芳基噻二唑酮类，制备它们的方法和它们作为除草剂用于控制农作物中的杂草。
具有除草活性的噻二唑酮类已描述于美国专利3.801.589，3.746.719和3.776.919中。但这些产品由于它们通常对绝大多数重要的农作物栽培有毒，因而不是很有选择性。
本申请人已经发现新的芳基噻二唑酮类，在对多种杂草有高除草活性的同时，对一种或多种最有益的农作物栽培具有低植物毒性，因此可用作选择性的除草剂。
因此本发明涉及通式(I)的芳基噻二唑酮类：
其中：-R代表C1-C6直链或支链烷基或卤代烷基；C3-C6环烷基或卤代环烷基；C4-C7环烷基烷基或卤代环烷基烷基；C2-C6直链或支链链烯基或卤代链烯基；-X代表氢原子；氟原子；氯原子；溴原子；甲基；-Y代表氢原子，卤原子如氯、氟、溴或碘；C1-C4直链或支链烷基或卤代烷基；C1-C4直链或支链烷氧基或卤代烷氧基；C1-C4直链或支链烷硫基或卤代烷硫基；C1-C4直链或支链烷基磺酰基；C1-C4直链或支链烷基亚磺酰基；氰基；硝基；-R1代表C1-C8直链或支链烷基；C1-C8直链或支链烷氧基；C1-C8直链或支链烷硫基；C3-C6环烷氧基；C3-C6环烷硫基；C4-C8环烷基烷基；C4-C8环烷基烷氧基；C4-C8环烷基烷硫基；C2-C8直链或支链链烯基；C2-C8直链或支链链烯氧基；C2-C8直链或支链链烯硫基；C2-C8直链或支链炔基；C3-C8直链或支链炔氧基；C3-C8直链或支链炔硫基；C3-C8直链或支链炔基亚磺酰基；C3-C8直链或支链炔基磺酰基；OH；SH；所述基团又可任选地被一个或多个选自下列的基团取代：卤原子如氯、氟、溴或碘，C1-C4直链或支链烷基或卤代烷基；C1-C4直链或支链烷氧基或卤代烷氧基；C1-C4直链或支链烷硫基或卤代烷硫基；-或，Y和R1相连代表O-CH2-CO-NR4基团，其中R4代表氢原子，C1-C8直链或支链烷基或卤代烷基；C4-C8环烷基烷基或卤代环烷基烷基；C2-C8直链或支链链烯基或卤代链烯基；C3-C8直链或支链炔基或卤代炔基；C5-C8直链或支链烷氧基炔基或卤代烷氧基炔基。
通式(I)的芳基噻二唑酮具有高除草活性。
优选的有除草活性的通式(I)的芳基噻二唑酮是如下化合物，其中：-R1代表C3-C5炔氧基；C3-C5炔硫基；C3-C5链烯氧基；C3-C5链烯硫基，它们可任选地被卤原子取代。
具有有利的除草活性的通式(I)芳基噻二唑酮的具体实例是：-5-叔丁基-3-[2，4-二氯-5-(丙-2-炔氧基)苯基]-1，3，4-噻二唑-2(3H)-酮(化合物1)；-5-叔丁基-3-[5-(丁-3-炔-2-基氧基)-2，4-二氯苯基]-1，3，4-噻二唑-2(3 H)-酮(化合物2)；-5-叔丁基-3-[4-氯-2-氟-5-(丙-2-炔氧基)苯基]-1，3，4-噻二唑-2(3H)-酮(化合物3)；-5-叔丁基-3-[5-(丁-3-炔-2-基氧基)-4-氯-2-氟苯基]-1，3，4-噻二唑-2(3H)-酮；-5-叔丁基-3-[2-氯-4-氟-5-(丙-2-炔氧基)苯基]-1，3，4-噻二唑-2(3H)-酮(化合物4)；-5-叔丁基-3-[5-(丁-3-炔-2-基氧基)-2-氯-4-氟苯基]-1，3，4-噻二唑-2(3H)-酮；-3-[4-溴-2-氯-5-(丙-2-炔氧基)苯基]-5-叔丁基-1，3，4-噻二唑-2(3 H)-酮(化合物5)；-3-[4-溴-5-(丁-3-炔-2-基氧基)-2-氯苯基]-5-叔丁基-1，3，4-噻二唑-2(3H)-酮；-3-[4-溴-2-氟-5-(丙-2-炔氧基)苯基]-5-叔丁基-1，3，4-噻二唑-2(3H)-酮(化合物6)；-3-[4-溴-5-(丁-3-炔-2-基氧基)-2-氟苯基)-5-叔丁基-1，3，4-噻二唑-2(3H)-酮；-5-环丙基-3-[2，4-二氯-5-(丙-2-炔氧基)苯基]-1，3，4-噻二唑-2(3H)-酮(化合物7)；-3-[5-(丁-3-炔-2-基氧基)-2，4-二氯苯基]-5-环丙基-1，3，4-噻二唑-2(3H)-酮(化合物8)；-5-环丙基-3-[4-氯-2-氟-5-(丙-2-炔氧基)苯基]-1，3，4-噻二唑-2(3H)-酮(化合物9)；-3-[5-(丁-3-炔-2-基氧基)-4-氯-2-氟苯基]-5-环丙基-1，3，4-噻二唑-2(3H)-酮；-5-环丙基-3-[2-氯-4-氟-(5-丙-2-炔氧基)苯基]-1，3，4-噻二唑-2(3H)-酮(化合物10)；-3-[5-丁-3-炔-2-基氧基)-2-氯-4-氟苯基)-5-环丙基-1，3，4-噻二唑-2(3H)-酮；-3-[4-溴-2-氯-5-(丙-2-炔氧基)苯基]-5-环丙基-1，3，4-噻二唑-2(3H)-酮(化合物11)；-3-[4-溴-5-(丁-3-炔-2-基氧基)-2-氯苯基]-5-环丙基-1，3，4-噻二唑-2(3H)-酮；-3-[4-溴-2-氟-5-(丙-2-炔氧基)苯基]-5-环丙基-1，3，4-噻二唑-2(3H)-酮；-3-[4-溴-5-(丁-3-炔-2-基氧基)-2-氟苯基]-5-环丙基-1，3，4-噻二唑-2(3H)-酮；-3-[2，4-二氯-5-(丙-2-炔氧基)苯基]-5-乙基-1，3，4-噻二唑-2(3 H)-酮(化合物12)；-3-[5-(丁-3-炔-2-基氧基)-2，4-二氯苯基]-5-乙基-1，3，4-噻二唑-2(3 H)-酮(化合物13)；-3-[4-氯-2-氟-5-(丙-2-炔氧基)苯基]-5-乙基-1，3，4-噻二唑-2(3H)-酮(化合物14)；-3-[5-(丁-3-炔-2-基氧基)-4-氯-2-氟苯基]-5-乙基-1，3，4-噻二唑-2(3H)-酮；-3-[2，4-二氯-5-(丙-2-炔氧基)苯基]-5-异丙基-1，3，4-噻二唑-2(3H)-酮(化合物15)；-3-[5-(丁-3-炔-2-基氧基)-2，4-二氯苯基]-5-异丙基-1，3，4-噻二唑-2(3H)-酮(化合16)；-3-[4-氯-2-氟-5-(丙-2-炔氧基)苯基]-5-异丙基-1，3，4-噻二唑-2(3 H)-酮(化合物17)；-3-[5-(丁-3-炔-2-基氧基)-4-氯-2-氟苯基]-5-异丙基-1，3，4-噻二唑-2(3 H)-酮(化合物18)；-3-[2，4-二氯-5-(丙-2-炔氧基)苯基]-5-(1-甲基环丙基)-1，3，4-噻二唑-2(3H)-酮(化合物19)；-3-[4-氯-2-氟-5-(丙-2-炔氧基)苯基]-5-(1-甲基环丙基)-1，3，4-噻二唑-2(3H)-酮(化合物20)；-5-仲丁基-3-[2，4-二氯-5-(丙-2-炔氧基)苯基]-1，3，4-噻二唑-2(3H)-酮(化合物21)；-5-仲丁基-3-[2-氯-4-氟-5-(丙-2-炔氧基)苯基]-1，3，4-噻二唑-2(3H)-酮(化合物22)；-3-[2，4-二氯-5-(丙-2-炔氧基)苯基]-5-(2-甲基丁-2-基)-1，3，4-噻二唑-2(3H)-酮(化合物23)；-3-[2-氯-4-氟-5-(丙-2-炔氧基)苯基]-5-(2-甲基丁-2-基)-1，3，4-噻二唑-2(3H)-酮(化合物24)；-3-[2，4-二氯-5-(丙-2-炔氧基)苯基]-5-(1-甲基乙烯基)-1，3，4-噻二唑-2(3H)-酮(化合物25)；-3-[4-氯-2-氟-5-(丙-2-炔氧基)苯基]-5-(1-甲基乙烯基)-1，3，4-噻二唑-2(3H)-酮(化合物26)；-5-叔丁基-3-[2，4-二氯-5-(丙-2-炔硫基)苯基]-1，3，4-噻二唑-2(3H)-酮(化合物27)；-5-叔丁基-3-[5-(丁-3-炔-2-基硫基)-2，4-二氯苯基]-1，3，4-噻二唑-2(3H)-酮(化合物28)；-5-叔丁基-3-[4-氯-2-氟-5-(丙-2-炔硫基)苯基]-1，3，4-噻二唑-2(3H)-酮(化合物29)；-5-叔丁基-3-[5-(丁-3-炔-2-基硫基)-4-氯-2-氟苯基]-1，3，4-噻二唑-2(3H)-酮(化合物30)；-5-环丙基-3-[2，4-二氯-5-(丙-2-炔硫基)苯基]-1，3，4-噻二唑-2(3H)-酮；-3-[5-(丁-3-炔-2-基硫基)-2，4-二氯苯基]-5-环丙基-1，3，4-噻二唑-2(3H)-酮；-5-环丙基-3-[4-氯-2-氟-5-(丙-2-炔硫基)苯基]-1，3，4-噻二唑-2-(3H)-酮；-3-[5-(丁-3-炔-2-基硫基)-4-氯-2-氟苯基]-5-环丙基-1，3，4-噻二唑-2(3H)-酮；-5-叔丁基-3-[4-氯-2-甲基-5-(丙-2-炔氧基)苯基]-1，3，4-噻二唑-2(3H)-酮(化合物31)；-5-环丙基-3-[4-氯-2-甲基-5-(丙-2-炔氧基)苯基]-1，3，4-噻二唑-2(3H)-酮(化合物32)；-5-叔丁基-3-[5-(丁-2-炔氧基)-2，4-二氯苯基]-1，3，4-噻二唑-2(3H)-酮(化合物33)；-5-叔丁基-3-[5-(丁-2-炔氧基)-4-氯-2-氟苯基]-1，3，4-噻二唑-2(3H)-酮(化合物34)；-3-[5-(丁-2-炔氧基)-2，4-二氯苯基]-5-环丙基-1，3，4-噻二唑-2(3H)-酮(化合物35)；-3-[5-(丁-2-炔氧基)-4-氯-2-氟苯基]-5-环丙基-1，3，4-噻二唑-2(3H)-酮(化合物36)；-5-叔丁基-3-[5-(3-氯丙-2-炔氧基)-2，4-二氯苯基]-1，3，4-噻二唑-2(3H)-酮(化合物37)；-5-环丙基-3-[5-(3-氯丙-2-炔氧基)-2，4-二氯苯基]-1，3，4-噻二唑-2(3H)-酮(化合物38)；-5-叔丁基-3-[2，4-二氯-5-(丙-2-烯氧基)苯基]-1，3，4-噻二唑-2(3H)-酮(化合物39)；-5-叔丁基-3-[4-氯-2-氟-5-(丙-2-烯氧基)苯基]-1，3，4-噻二唑-2(3H)-酮(化合物40)；-5-环丙基-3-[2，4-二氯-5-(丙-2-烯氧基)苯基]-1，3，4-噻二唑-2(3H)-酮；-5-环丙基-3-[4-氯-2-氟-5-(丙-2-烯氧基)苯基]-1，3，4-噻二唑-2(3H)-酮；-5-叔丁基-3-[2，4-二氯-5-(3，3-二氯丙-2-烯氧基)苯基]-1，3，4-噻二唑-2(3H)-酮(化合物41)；-5-叔丁基-3-[4-氯-5-(3，3-二氯丙-2-烯氧基)-2-氟苯基]-1，3，4-噻二唑-2(3H)-酮(化合物42)；-5-环丙基-3-[2，4-二氯-5-(3，3-二氯丙-2-烯氧基)苯基]-1，3，4-噻二唑-2(3H)-酮；-5-环丙基-3-[4-氯-5-(3，3-二氯丙-2-烯氧基)-2-氟苯基]-1，3，4-噻二唑-2(3H)-酮；-5-叔丁基-3-[7-氯-3，4-二氢-4-(丙-2-炔基)-2H-1，4-苯并噁嗪-3-酮基)-1，3，4-噻二唑-2(3H)-酮(化合物43)；-5-叔丁基-3-[7-氟-3，4-二氢-4-(丙-2-炔基)-2H-1，4-苯并噁嗪-3-酮基]-1，3，4-噻二唑-2(3H)-酮(化合物44)；-5-叔丁基-3-[2-氯-5-(丙-2-炔氧基)苯基]-1，3，4-噻二唑-2(3H)-酮(化合物45)；-5-叔丁基-3-[4-氯-5-(丙-2-炔氧基)苯基]-1，3，4-噻二唑-2(3H)-酮(化合物46)；-3-[2-溴-4-氯-5-(丙-2-炔氧基)苯基]-5-叔丁基-1，3，4-噻二唑-2(3H)-酮(化合物47)；-5-叔丁基-3-[2-氯-4-氰基-5-(丙-2-炔氧基)苯基]-1，3，4-噻二唑-2(3H)-酮(化合物49)；-5-叔丁基-3-[2-氯-5-(丙-2-炔氧基)-4-三氟甲基苯基]-1，3，4-噻二唑-2(3H)-酮(化合物50)。
本发明进一步的目的是提供通式(I)化合物的制备方法。
通式(I)化合物可以通过下列方法制得，该方法包括使通式(II)的硫代酰肼：其中R，X，Y和R1与上述定义相同，与通式(III)的环化试剂反应：其中：-L代表氯原子；C1-C4直链或支链烷氧基；苯氧基；-L’代表氯原子；C1-C4直链或支链烷氧基；苯氧基；或当L代表氯原子时，L’代表三氯甲氧基或苄氧基。
上述环化反应可依据所用环化试剂类型经一步反应或两步反应而完成。
为达到此目的所用的环化剂是光气，氯甲酸三氯甲酯(双光气)，或氯甲酸烷基酯例如，氯甲酸甲酯或氯甲酸乙酯，氯甲酸苄酯，氯甲酸苯酯等。
当所用环化试剂是光气或氯甲酸三氯甲酯时，上述环化反应可一步完成。为此，可将通式(II)的硫代酰肼溶解或悬浮在适当的惰性有机溶剂中，再用环化试剂处理，环化试剂也可任选地溶解在适当的惰性有机溶剂中，反应温度为20℃至混合物本身的沸点的温度范围内，可任选地在无机或有机碱的存在下进行反应。
用于此目的惰性有机溶剂是氯代烃(如二氯甲烷，氯仿，1，2-二氯乙烷等)；芳香烃(例如苯，甲苯，二甲苯等)；氯代芳烃(例如氯苯等)；醚(例如乙醚，四氢呋喃，二噁烷等)；酯(例如乙酸乙酯等)。
用于此目的的碱是无机碱例如碳酸氢钠，氢氧化钠，碳酸钠，氢化钠，氢氧化钾，碳酸钾，或有机碱如，三乙胺，吡啶，4-二甲氨基吡啶等。
当所用环化试剂是氯甲酸烷基酯、苄酯或苯酯时，环化反应通常要经过两步完成。为此，将通式(II)的硫代酰肼溶解或悬浮于惰性有机溶剂(选自上述所列溶剂)中，再用氯甲酸酯在无机或有机碱(选自上述所列碱)存在下，在0℃至混合物自身的沸点温度下处理，得到通式(IV)的中间体：
其中R，X，Y和R1与上述定义相同和L’代表C1-C4直链或支链烷氧基，苯氧基或苄氧基，随后加热至120℃和200℃之间的温度进行环化反应，反应可任选地在高沸点有机溶剂如二甲苯，或邻-二氯苯、和碱例如4-二甲氨基吡啶的存在下进行，类似于“杂环化学期刊(Journal of Heterocyclic Chemistry)”(1986)，Vol.23，417-419页所述的反应。
通式(II)的硫代酰肼可以按照已知方法如“Beilstein”15，Vol.II，92页和94页及Vol.III，156页；“化学杂志(Acta Chemica Scandinavica)”，Vol.6(1952)，957页和Vol.15(1961)，1097页；“杂环化学期刊(Journal of Heterocyclic Chemistry)”，Vol.17(1980)，191页和Vol.23(1986)，417页；“氟化学期刊(Journal of Fluorine Chemistry)”，Vol.12(1978)，1-21页；“化学快报(Chemistry Express)”，Vol.6(1991)，411页上所述的方法制备。例如，绝大多数通式(II)的硫代酰肼可以从相应的酰肼开始通过五硫化二磷或Lawesson试剂的硫化反应方便地制得。酰肼又可以通过被适当取代的芳基肼与酰氯反应而被方便地制得。
通式(I)的化合物(其中R1代表通过氧原子与芳基相连的醚基)也可以通过通式(V)的5-羟基芳基噻二唑酮：
其中R，X和Y定义同上，与通式(VI)的化合物的醚化反应制得：
Z-R’1 (VI)其中：-Z代表卤原子，优选氯或溴、或R’SO2O基，其中R’代表C1-C4直链或支链烷基或卤代烷基或代表可任选地被C1-C3直链或支链烷基，硝基，卤原子如氯、氟或溴取代的苯基；-R1’代表C1-C8直链或支链烷基，C3-C6环烷基，C4-C8环烷基烷基，C2-C8直链或支链链烯基，C3-C8直链或支链炔基，所有基团又可任选地被卤原子，C1-C4直链或支链烷基或卤代烷基，C1-C4直链或支链烷氧基或卤代烷氧基，C1-C4直链或支链烷硫基或卤代烷硫基所取代。
醚化反应在惰性有机溶剂存在下和有机或无机碱存在下，在-10℃至所用溶剂沸点温度，优选0℃至100℃下进行较为有利。
用于此目的的惰性有机溶剂是例如苯、甲苯，二甲苯，丙酮，甲乙酮，甲丙酮，乙酸乙酯，二甲氧基乙烷，二异丙醚，四氢呋喃，二噁烷，乙腈，N，N-二甲基甲酰胺，N，N-二甲基乙酰胺，N-甲基吡咯烷酮，二甲亚砜。
用于此目的无机碱是例如氢氧化钠、钾、钙和碳酸钠、钾、钙。
用于此目的有机碱是例如三乙胺、吡啶，4-二甲氨基吡啶，二氮杂双环辛烷(DABCO)，二氮杂双环十一碳烯(DBU)。
式(V)的5-羟基芳基噻二唑酮类可以使式(I)的芳基噻二唑酮(其中R1代表C1-C4烷氧基如异丙氧基)用氯化铝处理制得。
本发明通式(I)的化合物显示高除草活性，使得它们适于在农业领域中使有用栽培物抵御杂草。
特别地，通式(I)化合物可有效地控制出苗前和出苗后大量单子叶和双子叶杂草。同时，这些化合物是相容的，或在出苗前或出苗后使用时对有用的农作物无毒害作用。
可用本发明通式(I)化合物有效控制的杂草实例是：龙葵，稗，稻稗(Echinocloa oryzicola)，野燕麦，番薯属，苘麻，春蓼，旋花属(Convolvulus sepium)，反枝苋，藜，猪殃殃，虞美人，看麦娘(Alopercurus myosuroides)，莎草属，秋稷，狗尾草，Heteranthera spp.，马齿苋，马唐，荠菜，鸭舌草，节节菜，萤蔺，矮慈菇等。
在农业应用的剂量下，上述化合物对重要的农作物不显示毒性作用，这些农作物是：水稻(Oryza sativa)，小麦属(Triticum spp.)，玉蜀黍(Zea mais)，大豆(Glycine max)等。
本发明的进一步目的涉及用通式(I)化合物控制栽培区域杂草的方法。
为达到所需效果所用的化合物的量可根据不同因素而改变，如所用化合物，要保护的作物，要除的杂草，(杂草)蔓延的程度，气候条件，土壤特性，使用方法等。
化合物的剂量在每公倾1g至1000g之间通常足以控制杂草。
对于农业中的实际应用，通常使用含1种或多种通式(I)化合物为活性物质的具有除草活性的组合物较为有利。
可能使用的组合物形式为干粉剂，可湿性粉剂，可乳化的浓缩物，微乳化剂，膏剂，颗粒剂，溶液，悬浮液等，组合物类型的选择取决于具体的用途。
组合物可根据已知方法制备，例如通过将活性物质稀释或溶解在溶剂和/或固体稀释剂中，可能的活在表面活性剂存在下制得组合物。
作为固体惰性稀释剂，或载体，可以使用高岭土，氧化铝，硅石，滑石，皂土，白垩，石英，白云石，硅镁土，蒙脱石，硅藻土，纤维素，淀粉等。
作为液体惰性稀释剂，除了显而易见的水之外，可以使用有机溶剂例如芳香烃(混合二甲苯，烷基苯的混合物)，脂族烃(己烷，环己烷等)，卤代芳烃(氯苯等)，醇(甲醇，丙醇，丁醇，辛醇等)，酯(乙酸异丁酯等)，酮(丙酮，环己酮，苯乙酮，异佛尔酮，乙基戊酮等)或植物或矿物油或其混合物等。
作为表面活性剂使用的润湿和乳化剂可以是非离子型表面活性剂(聚乙氧基化的烷基苯酚，聚乙氧基化的脂肪醇等)，阴离子型表面活性剂(烷基苯磺酸盐，烷基磺酸盐等)，阳离子型表面活性剂(烷基季铵盐等)。
也可以加入分散剂(例如木质素及其盐，纤维素衍生物，藻酸盐等)，稳定剂(例如抗氧化剂，紫外线吸收剂等)。
为了增加上述组合物的作用范围，也可以加入其它活性成分，例如，其它除草剂，杀真菌剂，杀虫剂或杀螨剂，肥料。
上述组合物中活性物质的浓度根据活性化合物，所要达到的应用，环境条件和所用制剂类型在很宽的范围变化。
活性物质的浓度通常介于1％到90％之间，优选5％到50％。
下列实施例用于说明本发明但并不限制其范围。实施例1N’-[2，4-二氯-5-(丙-2-炔氧基)苯基]-N-硫代新戊酰基肼的制备
将五硫化二磷(P4S10：0.720g，1.6mmol)加入N’-[2，4-二氯-5-(丙-2-炔氧基)苯基]-N-新戊酰基肼(2g；6.4mmol)的二噁烷(40ml)溶液中，并将混合物加热到60℃保持3小时。然后将混合物倒入水中再用乙醚萃取。有机相再用水洗涤，用硫酸钠干燥并浓缩。将剩余物(2.8g)溶解在1∶1的乙醚/己烷中，用硅胶过滤、浓缩并用己烷重结晶。得到1.7g熔点为126-128℃的产物。实施例25-叔丁基-3-[2，4-二氯-5-(丙-2-炔氧基)苯基]-1，3，4-噻二唑-2(3H)-酮(化合物1)的制备
将三滴吡啶和0.5g(2.5mmol)氯甲酸三氯甲酯在氮气气氛下加入1.65g(5mmol)N’-[2，4-二氯-5-(丙-2-炔氧基)苯基]-N-硫代新戊酰肼(由实施例1制得)的25ml二噁烷溶液中。将反应混合物在室温下搅拌3小时。
将混合物倒入水(250ml)中并用乙醚萃取(3×100ml)。将有机相用饱和氯化钠溶液洗至中性，用硫酸钠干燥并用旋转蒸发器浓缩。将粗产物用硅胶色谱以正己烷/乙酸乙酯9∶1洗脱进行纯化。
得到1.4g固体产物为化合物1，熔点为92℃。实施例3
按实施例2类似地操作，从相应的硫代酰肼开始并用氯甲酸三氯甲酯或光气为环化试剂制备下列化合物：-5-叔丁基-3-[5-(丁-3-炔-2-基氧基)-2，4-二氯苯基]-1，3，4-噻二唑-2(3H)-酮(m.p.100-102℃；化合物2)；-5-叔丁基-3-[4-氯-2-氟-5-(丙-2-炔氧基)苯基]-1，3，4-噻二唑-2(3H)-酮(m.p.73-75℃；化合物3)；-5-叔丁基-3-[2-氯-4-氟-5-(丙-2-炔氧基)苯基]-1，3，4-噻二唑-2(3H)-酮(化合物4)；-3-[4-溴-2-氯-5-(丙-2-炔氧基)苯基]-5-叔丁基-1，3，4-噻二唑-2(3H)-酮(化合物5)；-3-[4-溴-2-氟-5-(丙-2-炔氧基)苯基]-5-叔丁基-1，3，4-噻二唑-2(3H)-酮(化合物6)；-5-环丙基-3-[2，4-二氯-5-(丙-2-炔氧基)苯基]-1，3，4-噻二唑-2(3H)-酮(m.p.99-101℃；化合物7)；-3-[5-(丁-3-炔-2-基氧基)-2，4-二氯苯基]-5-环丙基-1，3，4-噻二唑-2(3H)-酮(m.p.109-110℃；化合物8)；-5-环丙基-3-[4-氯-2-氟-5-(丙-2-炔氧基)苯基]-1，3，4-噻二唑-2(3H)-酮(化合物9)；-5-环丙基-3-[2-氯-4-氟-5-(丙-2-炔氧基)苯基]-1，3，4-噻二唑-2(3H)-酮(化合物10)；-3-[4-溴-2-氯-5-(丙-2-炔氧基)苯基]-5-环丙基-1，3，4-噻二唑-2(3H)-酮(化合物11)；-3-[2，4-二氯-5-(丙-2-炔氧基)苯基]-5-乙基-1，3，4-噻二唑-2(3H)-酮(m.p.98-100℃，化合物12)；-3-[5-(丁-3-炔-2-基氧基)-2，4-二氯苯基]-5-乙基-1，3，4-噻二唑-2(3H)酮(m.p.69-71℃；化合物13)；-3-[4-氯-2-氟-5-(丙-2-炔氧基)苯基]-5-乙基-1，3，4-噻二唑-2(3H)-酮(m.p.92-94℃；化合物14)；-3-[2，4-二氯-5-(丙-2-炔氧基)苯基]-5-异丙基-1，3，4-噻二唑-2(3H)-酮(m.p.55-57℃；化合物15)；-3-[5-(丁-3-炔-2-基氧基)-2，4-二氯苯基]-5-异丙基-1，3，4-噻二唑-2(3H)-酮(m.p.72-74℃；化合16)；-3-[4-氯-2-氟-5-(丙-2-炔氧基)苯基]-5-异丙基-1，3，4-噻二唑-2(3H)-酮(化合物17)；-3-[5-(丁-3-炔-2-基氧基)-4-氯-2-氟苯基]-5-异丙基-1，3，4-噻二唑-2(3H)-酮(化合物18)；-3-[2，4-二氯-5-(丙-2-炔氧基)苯基]-5-(1-甲基环丙基)-1，3，4-噻二唑-2(3H)-酮(化合物19)；-3-[4-氯-2-氟-5-(丙-2-炔氧基)苯基]-5-(1-甲基环丙基)-1，3，4-噻二唑-2(3H)-酮(化合物20)；-5-仲丁基-3-[2，4-二氯-5-(丙-2-炔氧基)苯基]-1，3，4-噻二唑-2(3H)-酮(化合物21)；-5-仲丁基-3-[2-氯-4-氟-5-(丙-2-炔氧基)苯基]-1，3，4-噻二唑-2(3H)-酮(化合物22)；-3-[2，4-二氯-5-(丙-2-炔氧基)苯基]-5-(2-甲基丁-2-基)-1，3，4-噻二唑-2(3H)-酮(化合物23)；-3-[2-氯-4-氟-5-(丙-2-炔氧基)苯基]-5-(2-甲基丁-2-基)-1，3，4-噻二唑-2(3H)-酮(化合物24)；-3-[2，4-二氯-5-(丙-2-炔氧基)苯基]-5-(1-甲基乙烯基)-1，3，4-噻二唑-2(3H)-酮(化合物25)；-3-[4-氯-2-氟-5-(丙-2-炔氧基)苯基]-5-(1-甲基乙烯基)-1，3，4-噻二唑-2(3H)-酮(化合物26)；-5-叔丁基-3-[2，4-二氯-5-(丙-2-炔硫基)苯基]-1，3，4-噻二唑-2(3H)-酮(化合物27)；-5-叔丁基-3-[5-(丁-3-炔-2-基硫基)-2，4-二氯苯基]-1，3，4-噻二唑-2(3H)-酮(化合物28)；-5-叔丁基-3-[4-氯-2-氟-5-(丙-2-炔硫基)苯基]-1，3，4-噻二唑-2(3H)-酮(化合物29)；-5-叔丁基-3-[5-(丁-3-炔-2-基硫基)-4-氯-2-氟苯基]-1，3，4-噻二唑-2(3H)-酮(化合物30)；-5-叔丁基-3-[4-氯-2-甲基-5-(丙-2-炔氧基)苯基]-1，3，4-噻二唑-2(3H)-酮(化合物31)；-5-环丙基-3-[4-氯-2-甲基-5-(丙-2-炔氧基)苯基]-1，3，4-噻二唑-2(3H)-酮(化合物32)；-5-叔丁基-3-[5-(丁-2-炔氧基)-2，4-二氯苯基]-1，3，4-噻二唑-2(3H)-酮(化合物33)；-5-叔丁基-3-[5-(丁-2-炔氧基)-4-氯-2-氟苯基]-1，3，4-噻二唑-2(3H)-酮(化合物34)；-3-[5-(丁-2-炔氧基)-2，4-二氧苯基]-5-环丙基-1，3，4-噻二唑-2(3H)-酮(化合物35)；-3-[5-(丁-2-炔氧基)-4-氯-2-氟苯基]-5-环丙基-1，3，4-噻二唑-2(3H)-酮(化合物36)；-5-叔丁基-3-[5-(3-氯丙-2-炔氧基)-2，4-二氯苯]-1，3，4-噻二唑-2(3H)-酮(化合物37)；-5-环丙基-3-[5-(3-氯丙-2-炔氧基)-2，4-二氯苯基]-1，3，4-噻二唑-2(3H)-酮(化合物38)；-5-叔丁基-3-[2，4-二氯-5-(丙-2烯氧基)苯基-1，3，4-噻二唑-2(3H)-酮(化合物39)；-5-叔丁基-3-[4-氯-2-氟-5-(丙-2-烯氧基)苯基]-1，3，4-噻二唑-2(3H)-酮(化合物40)；-5-叔丁基-3-[2，4-二氯-5-(3，3-二氯丙-2-烯氧基)苯基]-1，3，4-噻二唑-2(3H)-酮(化合物41)；-5-叔丁基-3-[4-氯-5-(3，3-二氯丙-2-烯氧基)-2-氟苯基]-1，3，4-噻二唑-2(3H)-酮(化合物42)；-5-叔丁基-3-[7-氯-3，4-二氢-4-(丙-2-炔基)-2H-1，4-苯并噁嗪-3-酮基)-1，3，4-噻二唑-2(3H)-酮(化合物43)；-5-叔丁基-3-[7-氟-3，4-二氢-4-(丙-2-炔基)-2H-1，4-苯并噁嗪-3-酮基]-1，3，4-噻二唑-2(3H)-酮(化合物44)；-5-叔丁基-3-[2-氯-5-(丙-2-炔氧基)苯基]-1，3，4-噻二唑-2(3H)-酮(化合物45)；-5-叔丁基-3-[4-氯-5-(丙-2-炔氧基)苯基]-1，3，4-噻二唑-2(3H)-酮(化合物46)；-3-[2-溴-4-氯-5-(丙-2-炔氧基)苯基]-5-叔丁基-1，3，4-噻二唑-2(3H)-酮(化合物47)；-5-叔丁基-3-[2，4-二氯-5-异丙氧苯基)-1，3，4-噻二唑-2(3H)-酮(化合物48)；-5-叔丁基-3-[2-氯-4-氰基-5-(丙-2-炔氧基)苯基]-1，3，4-噻二唑-2(3H)-酮(化合物49)；-5-叔丁基-3-[2-氯-5-(丙-2-炔氧基)-4-三氟甲基苯基]-1，3，4-噻二唑-2(3H)-酮(化合物50)。实施例45-叔丁基-3-(2，4-二氯-5-羟基苯基)-1，3，4-噻二唑-2(3H)-酮(化合物51)的制备
将11.7g5-叔丁基-3-(2，4-二氯-5-异丙氧苯基)-1，3，4-噻二唑-2(3H)-酮(化合物48；32.4mmol)和250ml二氯甲烷在氮气中装入500ml烧瓶中。将AlCl3(12.9g；96.7mmol)分批加入该溶液中并将混合物在室温搅拌2小时。将混合物小心倒入100g其中已加入100ml饱和氯化钠溶液的冰中。然后加入200ml乙醚，将两相分离后，有机相用饱和氯化钠溶液洗涤，硫酸钠干燥并用旋转蒸发器浓缩。得到10g所需产物，m.p.130-132℃。实施例5出苗后除草活性的测定
化合物1，2，7和15的除草活性可以通过出苗后处理中对单子叶和双子叶杂草的活性而评价，所用对照物是美国专利3.746.719中实施例2中的化合物5-氨基-3-苯基-1，3，4-噻二唑-2(3H)-酮(RC)[其中称为4-苯基-2-氨基-1，3，4-噻二唑酮-(5)]。
每种产品的评价试验按照下列操作方法进行。
将下列杂草播种于含有沙土的瓶中(直径大于10cm，高10cm)(每一品种种10瓶)：-双子叶植物：苘麻(AT)，反枝苋(AR)，藜(CA)，旋花属(CS)，圆叶牵牛(IP)，春蓼(PP)，马齿苋(PO)，龙葵(SN)-单子叶植物：看麦娘(AM)，马唐(DS)，秋稷(PD)，狗尾草(SV)
在每个瓶中加入适量的水以促使种子发芽良好。
将播种每种杂草的瓶分成两组，每组5瓶。
将第一组瓶在播种15天后，即当杂草10-15cm高(取决于杂草种)时，用含所需浓度的试验化合物、丙酮(10％体积)、Tween 20(0.5％)的水合丙酮(hydroacetonic)分散液处理。
第二组仅用含丙酮(10％体积)和Tween 20(0.5％)的水合丙酮溶液处理，作为对比(对照组)。
每个瓶每两天均匀地浇水使其保持下列环境条件：-温度：240℃；-相对温度：60％；-光周期：16小时；-光照强度：10000luX。
在处理15天后，除草活性可根据下列值的大小来评价，该值是指被处理植物损伤数与未处理(对照)植物的损伤数之比的百分数：-0＝0％-9％损伤-1＝10％-29％损伤-2＝30％-49％损伤-3＝50％-69％损伤-4＝70％-89％损伤-5＝90％损伤-被处理植物死亡。
结果示于下列表1中。
表1150g/HA剂量的出苗后除草活性化合物种类 1 2 7 15 RCAT 5 5 5 5 0AR 5 5 5 5 0CA 5 5 5 5 1CS 5 5 5 5 0IP 5 5 5 5 1PP 5 2 5 5 0PO 5 5 5 5 0SN 5 5 5 5 1AM 5 NT NT NT 0DS 5 NT NT NT 0PD 5 NT NT NT 0SV 5 NT NT NT 0NT＝未试验实施例6出苗前除草活性的测定
将化合物1，7，8，9，14，15和17出苗前施药对单子叶和双子叶杂草，及对一些重要作物的除草活性进行评价，此时用作对照的是5-氨基-3-苯基-1，3，4-噻二唑-2(3H)-酮(RC)，即美国专利3.746.719中实施例2化合物。
每一个产物的评价试验按下列操作方法进行。
将下列杂草和作物播种于含沙土的瓶中(直径大于10cm，高10cm)(每个品种种10瓶)：-双子叶植物：反枝苋(AR)，藜(CA)，荠菜(CB)，虞美人(PR)，马齿苋(PO)，龙葵(SN)-单子叶植物：马唐(DS)，稗(EC)，秋稷(PD)-作物：水稻(Oryza sativa)，玉蜀黍(Zea mays)，大豆(Glycine max)，小麦属(Triticum spp.)
将每种杂草或农作物的瓶分成两组，每组5瓶。
播种24小时后，将第一组瓶用轻微的淋水浸润，浇水1小时后，用含所需浓度试验化合物、丙酮(10体积)和Tween 20(0.5％)的水合丙酮分散液处理。
第二组仅用含丙酮(10％体积)和Tween 20(0.5％)的水合丙酮溶液处理，用作对比(对照组)。
所有瓶子处理完后每两天均匀地浇水使环境保持在如下条件下：-温度：240℃；-相对湿度：60％；-光周期：16小时；-光照强度：10000lux。
在处理28天后除草活性可根据下列值的大小来评价，该值是指被处理植物的损伤数与未处理(对照组)植物的损伤数之比的百分数：-0＝0％-9％损伤-1＝10％-29％损伤-2＝30％-49％损伤-3＝50％-69％损伤-4＝70％-89％损伤-5＝90％损伤-被处理植物死亡。
所得结果示于下列表2中。
表2150G/HA剂量的出苗前除草活性化合物种类 1 7 8 9 14 15 17 RCAR 5 5 5 5 5 5 5 0CA 5 5 5 5 5 5 5 0CB 5 5 5 5 5 5 5 0PR 5 5 5 5 5 5 5 0PO 5 5 5 3 5 5 1 0SN 5 4 5 5 5 5 5 0DS 5 5 5 5 5 5 5 0EC 5 5 4 5 5 5 5 0PD 5 5 5 5 5 5 5 0水稻 0 0 NT 0 1 0 0 0玉蜀黍 0 1 NT 0 0 NT 0 0大豆 0 1 NT 0 0 NT 0 0小麦属 0 0 NT 0 0 NT 1 0NT＝未试验
Claims (24)
1.通式(I)的芳基噻二唑酮类：其中：-R代表C1-C6直链或支链烷基或卤代烷基；C3-C6环烷基或卤代环烷基；C4-C7环烷基烷基或卤代环烷基烷基；C2-C6直链或支链链烯基或卤代链烯基；-X代表氢原子；氟原子；氯原子；溴原子；甲基；-Y代表氢原子，卤原子如氯、氟、溴或碘；C1-C4直链或支链烷基或卤代烷基；C1-C4直链或支链烷氧基或卤代烷氧基；C1-C4直链或支链烷硫基或卤代烷硫基；C1-C4直链或支链烷基磺酰基；C1-C4直链或支链烷基亚磺酰基；氰基；硝基；-R1代表C1-C8直链或支链烷基；C1-C8直链或支链烷氧基；C1-C8直链或支链烷硫基；C3-C6环烷氧基；C3-C6环烷硫基；C4-C8环烷基烷基；C4-C8环烷基烷氧基；C4-C8环烷基烷硫基；C2-C8直链或支链链烯基；C2-C8直链或支链链烯氧基；C2-C8直链或支链链烯硫基；C2-C8直链或支链炔基；C3-C8直链或支链炔氧基；C3-C8直链或支链炔硫基；C3-C8直链或支链炔基亚磺酰基；C3-C8直链或支链炔基磺酰基；OH；SH；所述基团又可任选地被1个或多个选自下列的基团取代：卤原子如氯、氟、溴或碘，C1-C4直链或支链烷基或卤代烷基；C1-C4直链或支链烷氧基或卤代烷氧基；C1-C4直链或支链烷硫基或卤代烷硫基；-或，Y和R1相连代表O-CH2-CO-NR4基团，其中R4代表氢原子，C1-C8直链或支链烷基或卤代烷基；C4-C8环烷基烷基或卤代环烷基烷基；C2-C8直链或支链链烯基或卤代链烯基；C3-C8直链或支链炔基或卤代炔基；C5-C8直链或支链烷氧基炔基或卤代烷氧基炔基。
2.含有通式(I)的芳基噻二唑酮的除草剂：
其中：-R代表C1-C6直链或支链烷基或卤代烷基；C3-C6环烷基或卤代环烷基；C4-C7环烷基烷基或卤代环烷基烷基；C2-C6直链或支链链烯基或卤代链烯基；-X代表氢原子；氟原子；氯原子；溴原子；甲基；-Y代表氢原子，卤原子如氯、氟、溴或碘；C1-C4直链或支链烷基或卤代烷基；C1-C4直链或支链烷氧基或卤代烷氧基；C1-C4直链或支链烷硫基或卤代烷硫基；C1-C4直链或支链烷基磺酰基；C1-C4直链或支链烷基亚磺酰基；氰基；硝基；-R1代表C1-C8直链或支链烷基；C1-C8直链或支链烷氧基；C1-C8直链或支链烷硫基；C3-C6环烷氧基；C3-C6环烷硫基；C4-C8环烷基烷基；C4-C8环烷基烷氧基；C4-C8环烷基烷硫基；C2-C8直链或支链链烯基；C2-C8直链或支链链烯氧基；C2-C8直链或支链链烯硫基；C2-C8直链或支链炔基；C3-C8直链或支链炔氧基；C3-C8直链或支链炔硫基；C3-C8直链或支链烷基亚磺酰基；C3-C8直链或支链烷基磺酰基；OH；SH；所述基团又可任选地被一个或多个选自下列的基团取代：卤原子如氯、氟、溴或碘，C1-C4直链或支链烷基或卤代烷基；C1-C4直链或支链烷氧基或卤代烷氧基；C1-C4直链或支链烷硫基或卤代烷硫基；-或，Y和R1相连代表O-CH2-CO-NR4基团，其中R4代表氢原子，C1-C8直链或支链烷基或卤代烷基；C4-C8环烷基烷基或卤代环烷基烷基；C2-C8直链或支链链烯基或卤代链烯基；C3-C8直链或支链炔基或卤代炔基；C5-C8直链或支链烷氧基炔基或卤代烷氧基炔基。
3.根据权利要求2的除草剂，含有5-叔丁基-3-(2，4-二氯-5-丙-2-炔氧基)苯基-1，3，4-噻二唑-2(3H)-酮。
4.根据权利要求2的除草剂，含有5-叔丁基-3-[5-(丁-3-炔-2-基氧基)-2，4-二氯苯基]-1，3，4-噻二唑-2-(3H)-酮。
5.根据权利要求2的除草剂，含有5-环丙基-3-[2，4-二氯-5-(丙-2-炔氧基)苯基]-1，3，4-噻二唑-2-(3H)-酮。
6.根据权利要求2的除草剂，含有3-[5-(丁-3-炔-2-基氧基)-2，4-二氯苯基]-5-环丙基-1，3，4-噻二唑-2(3H)-酮。
7.根据权利要求2的除草剂，含有5-环丙基-3-[4-氯-2-氟-5-(丙-2-炔氧基)苯基]-1，3，4-噻二唑-2(3H)-酮。
8.根据权利要求2的除草剂，含有3-[4-氯-2-氟-5-(丙-2-炔氧基)苯基]-5-乙基-1，3，4-噻二唑-2(3H)-酮。
9.根据权利要求2的除草剂，含有3-[2，4-二氯-5-(丙-2-炔氧基)苯基]-5-异丙基-1，3，4-噻二唑-2(3H)-酮。
10.根据权利要求2的除草剂，含有3-[4-氯-2-氟-5-(丙-2-炔氧基)苯基]-5-异丙基-1，3，4-噻二唑-2(3H)-酮。
11.一种制备前述任一权利要求的芳基噻二唑酮的方法，包括使通式(II)的硫代酰肼：
其中R，X，Y和R1与上述定义相同，与通式(III)的环化试剂反应：
其中：-L代表氯原子；C1-C4直链或支链烷氧基；苯氧基；-L’代表氯原子；C1-C4直链或支链烷氧基；苯氧基；或，当L代表氯原子时，L’代表三氯甲氧基或苄氧基。
12.根据权利要求11的方法，其中通式(III)的环化试剂选自光气，氯甲酸三氯甲酯(双光气)，氯甲酸烷基酯，氯甲酸苄酯，氯甲酸苯酯。
13.根据权利要求11或12的方法，其中通式(III)的环化试剂是光气或氯甲酸三氯甲酯且环化反应是一步完成的。
14.根据权利要求13的方法，其中溶解在或悬浮在适当惰性有机溶剂中的通式(II)的硫代酰肼用环化试剂在20℃至混合物自身的沸点之间的温度下，任选地在无机或有机碱的存在下处理，环化试剂也可任选地溶于合适的惰性有机溶剂中。
15.根据权利要求14的方法，其中惰性有机溶剂选自氯代烃，芳烃，氯代芳烃，醚，酯。
16.根据权利要求14的方法，其中无机碱是碳酸氢钠，氢氧化钠，碳酸钠，氢化钠，氢氧化钾，碳酸钾。
17.根据权利要求14的方法，其中有机碱选自三乙胺，吡啶，4-二甲氨基吡啶。
18.根据权利要求11的方法，其中通式(III)的环化试剂是氯甲酸烷基酯，苄酯或苯酯且环化反应是经两步反应完成的。
19.根据权利要求18的方法，其中将通式(II)的硫代酰肼溶解或悬浮于权利要求15的惰性有机溶剂中，再在权利要求16或17的无机或有机碱存在下，在0℃至混合物本身的沸点的温度下用氯甲酸酯处理，得到通式(IV)的中间体：其中R，X，Y和R1与前面定义相同，L’代表C1-C4直链或支链烷氧基，苯氧基或苄氧基，随后加热至120℃和200℃之间的温度，任选地在高沸点有机溶剂和碱存在下进行环化反应。
20.根据权利要求19的方法，其中高沸点有机溶剂选自二甲苯和邻二氯苯。
21.根据权利要求19的方法，其中碱是4-二甲氨基吡啶。
22.具有除草活性的组合物，含有一种或多种根据权利要求2至21中任一项的芳基噻二唑酮类，单独或者在固体载体，液体稀释剂，表面活性剂或其它活性组分存在下。
23.根据权利要求22的具有除草活性的组合物，其中活性物质的浓度为1％至90％。
24.一种在耕种区控制杂草的方法，包括将权利要求22和23的组合物用于该区域中。
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT002705A/1995 | 1995-12-21 | ||
| IT95MI002705A IT1277681B1 (it) | 1995-12-21 | 1995-12-21 | Ariltiadiazoloni ad attivita' erbicida |
| IT002705A/95 | 1995-12-21 |
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| Publication Number | Publication Date |
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| CN1160046A true CN1160046A (zh) | 1997-09-24 |
| CN1059439C CN1059439C (zh) | 2000-12-13 |
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| Country | Link |
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| US (1) | US5821197A (zh) |
| EP (1) | EP0780385B1 (zh) |
| JP (1) | JPH09221483A (zh) |
| KR (1) | KR970042534A (zh) |
| CN (1) | CN1059439C (zh) |
| BR (1) | BR9606090A (zh) |
| DE (1) | DE69608222T2 (zh) |
| ES (1) | ES2145964T3 (zh) |
| IT (1) | IT1277681B1 (zh) |
| MY (1) | MY113549A (zh) |
| PT (1) | PT780385E (zh) |
| SG (1) | SG43453A1 (zh) |
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| KR970061878A (ko) * | 1996-02-23 | 1997-09-12 | 성재갑 | 신규한 아릴티아졸 유도체, 그의 제조방법 및 그를 유효성분으로 하는 제초제 조성물 |
| EP1020448B1 (en) * | 1996-03-21 | 2005-02-16 | Isagro Ricerca S.r.l. | Arylheterocycles with herbicidal activity |
| IT1292088B1 (it) * | 1997-06-05 | 1999-01-25 | Isagro Ricerca Srl | Composizioni erbicide |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US3801589A (en) | 1968-04-19 | 1974-04-02 | Bayer Ag | 1,3,4-thiadiazol-5-one-yl-ureas |
| BE757940A (fr) | 1969-10-25 | 1971-04-23 | Bayer Ag | Procede de preparation de 2-amino-1,3,4-thiadiazolones -(5) substitueesen position 4 et produits obtenus |
| DE2003145A1 (de) | 1970-01-24 | 1971-08-12 | Bayer Ag | 2-Acylamino-1,3,4-thiadiazol-(thi)one-(5),Verfahren zu ihrer Herstellung und ihre Verwendung als Herbizide |
| FR2141442B1 (zh) * | 1971-06-02 | 1973-06-29 | Rhone Poulenc Sa | |
| CH583213A5 (zh) * | 1973-05-21 | 1976-12-31 | Ciba Geigy Ag | |
| US4602454A (en) * | 1978-05-15 | 1986-07-29 | Monsanto Company | 2,4-disubstituted-5-thiazole-carboxylic acids and derivatives |
| US4298375A (en) * | 1979-10-01 | 1981-11-03 | Monsanto Company | 2-Substituted-5-phenyl-4-thiazolecarboxylic acids and their derivatives as safening agents |
| US4943312A (en) * | 1983-04-04 | 1990-07-24 | E. I. Du Pont De Nemours And Company | Herbicidal thiazole derivatives |
| DE3633840A1 (de) * | 1986-10-04 | 1988-04-14 | Hoechst Ag | Phenylpyrazolcarbonsaeurederivate, ihre herstellung und verwendung als pflanzenwachstumsregulatoren und safener |
| DK570987A (da) * | 1986-12-01 | 1988-06-02 | Hoffmann La Roche | Oxadiazol-, thiadiazol- og triazolforbindelser |
| JPS63150267A (ja) * | 1986-12-16 | 1988-06-22 | Showa Roodeia Kagaku Kk | オキサジアゾロン誘導体及び除草剤 |
| GB8826035D0 (en) * | 1988-11-07 | 1988-12-14 | Ici Plc | Herbicidal compositions |
| IT1251488B (it) * | 1991-09-17 | 1995-05-15 | Mini Ricerca Scient Tecnolog | Ossa(tia)diazol- e triazol-oni(tioni) ad attivita' acaricida ed insetticida |
| EP0762955A4 (en) * | 1994-05-31 | 1998-01-07 | Us Health | Anti-fouling coating |
-
1995
- 1995-12-21 IT IT95MI002705A patent/IT1277681B1/it active IP Right Grant
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1996
- 1996-12-17 ES ES96120218T patent/ES2145964T3/es not_active Expired - Lifetime
- 1996-12-17 EP EP96120218A patent/EP0780385B1/en not_active Expired - Lifetime
- 1996-12-17 DE DE69608222T patent/DE69608222T2/de not_active Expired - Fee Related
- 1996-12-17 PT PT96120218T patent/PT780385E/pt unknown
- 1996-12-19 BR BR9606090A patent/BR9606090A/pt not_active IP Right Cessation
- 1996-12-19 SG SG1996011851A patent/SG43453A1/en unknown
- 1996-12-19 MY MYPI96005363A patent/MY113549A/en unknown
- 1996-12-20 CN CN96123923A patent/CN1059439C/zh not_active Expired - Fee Related
- 1996-12-21 KR KR1019960069909A patent/KR970042534A/ko not_active Application Discontinuation
- 1996-12-24 JP JP8344183A patent/JPH09221483A/ja active Pending
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Also Published As
| Publication number | Publication date |
|---|---|
| ITMI952705A0 (zh) | 1995-12-21 |
| BR9606090A (pt) | 1998-09-01 |
| ITMI952705A1 (it) | 1997-06-21 |
| EP0780385B1 (en) | 2000-05-10 |
| IT1277681B1 (it) | 1997-11-11 |
| ES2145964T3 (es) | 2000-07-16 |
| US5821197A (en) | 1998-10-13 |
| CN1059439C (zh) | 2000-12-13 |
| DE69608222T2 (de) | 2001-02-08 |
| KR970042534A (ko) | 1997-07-24 |
| EP0780385A1 (en) | 1997-06-25 |
| DE69608222D1 (de) | 2000-06-15 |
| JPH09221483A (ja) | 1997-08-26 |
| PT780385E (pt) | 2000-08-31 |
| MY113549A (en) | 2002-03-30 |
| SG43453A1 (en) | 1997-10-17 |
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