CN101279950A - 2-嘧啶氧(硫)基苯甲酸基乙酰胺类化合物及其应用 - Google Patents
2-嘧啶氧(硫)基苯甲酸基乙酰胺类化合物及其应用 Download PDFInfo
- Publication number
- CN101279950A CN101279950A CNA2007100108571A CN200710010857A CN101279950A CN 101279950 A CN101279950 A CN 101279950A CN A2007100108571 A CNA2007100108571 A CN A2007100108571A CN 200710010857 A CN200710010857 A CN 200710010857A CN 101279950 A CN101279950 A CN 101279950A
- Authority
- CN
- China
- Prior art keywords
- alkyl
- compound
- phenyl
- halogen
- general formula
- 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
- -1 benzoxy acetamide compound Chemical class 0.000 title abstract description 3
- 150000001875 compounds Chemical class 0.000 claims abstract description 37
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 14
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 13
- 150000002367 halogens Chemical class 0.000 claims abstract description 13
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 10
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 7
- 238000009333 weeding Methods 0.000 claims abstract description 6
- 125000000714 pyrimidinyl group Chemical group 0.000 claims abstract description 3
- 241000196324 Embryophyta Species 0.000 claims description 14
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 230000002363 herbicidal effect Effects 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 239000005711 Benzoic acid Substances 0.000 claims description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 239000005864 Sulphur Chemical group 0.000 claims description 6
- XOCUXOWLYLLJLV-UHFFFAOYSA-N [O].[S] Chemical compound [O].[S] XOCUXOWLYLLJLV-UHFFFAOYSA-N 0.000 claims description 6
- 150000003869 acetamides Chemical class 0.000 claims description 6
- 235000010233 benzoic acid Nutrition 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000004480 active ingredient Substances 0.000 claims description 5
- 230000012010 growth Effects 0.000 claims description 5
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical group C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 4
- 150000003053 piperidines Chemical class 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 150000001721 carbon Chemical group 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 8
- 244000105624 Arachis hypogaea Species 0.000 abstract description 7
- 235000010777 Arachis hypogaea Nutrition 0.000 abstract description 7
- 240000008042 Zea mays Species 0.000 abstract description 6
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 abstract description 6
- 235000002017 Zea mays subsp mays Nutrition 0.000 abstract description 6
- 235000005822 corn Nutrition 0.000 abstract description 6
- 229920000742 Cotton Polymers 0.000 abstract description 5
- 244000068988 Glycine max Species 0.000 abstract description 5
- 235000010469 Glycine max Nutrition 0.000 abstract description 5
- 241000219146 Gossypium Species 0.000 abstract description 5
- 235000008692 Carum bulbocastanum Nutrition 0.000 abstract 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract 1
- 125000004432 carbon atom Chemical group C* 0.000 abstract 1
- 229910052757 nitrogen Chemical group 0.000 abstract 1
- 125000004430 oxygen atom Chemical group O* 0.000 abstract 1
- 229910052717 sulfur Inorganic materials 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 235000017060 Arachis glabrata Nutrition 0.000 description 6
- 235000018262 Arachis monticola Nutrition 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 235000020232 peanut Nutrition 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 5
- 235000015320 potassium carbonate Nutrition 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 230000002401 inhibitory effect Effects 0.000 description 4
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 244000025254 Cannabis sativa Species 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 3
- 229920000053 polysorbate 80 Polymers 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 235000017550 sodium carbonate Nutrition 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000008399 tap water Substances 0.000 description 3
- 235000020679 tap water Nutrition 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- 240000006995 Abutilon theophrasti Species 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical group ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- 244000058871 Echinochloa crus-galli Species 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 241000209140 Triticum Species 0.000 description 2
- 235000021307 Triticum Nutrition 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229930013930 alkaloid Natural products 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000012258 culturing Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 235000011167 hydrochloric acid Nutrition 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229940095102 methyl benzoate Drugs 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 235000014347 soups Nutrition 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- AOSZTAHDEDLTLQ-AZKQZHLXSA-N (1S,2S,4R,8S,9S,11S,12R,13S,19S)-6-[(3-chlorophenyl)methyl]-12,19-difluoro-11-hydroxy-8-(2-hydroxyacetyl)-9,13-dimethyl-6-azapentacyclo[10.8.0.02,9.04,8.013,18]icosa-14,17-dien-16-one Chemical compound C([C@@H]1C[C@H]2[C@H]3[C@]([C@]4(C=CC(=O)C=C4[C@@H](F)C3)C)(F)[C@@H](O)C[C@@]2([C@@]1(C1)C(=O)CO)C)N1CC1=CC=CC(Cl)=C1 AOSZTAHDEDLTLQ-AZKQZHLXSA-N 0.000 description 1
- GLGNXYJARSMNGJ-VKTIVEEGSA-N (1s,2s,3r,4r)-3-[[5-chloro-2-[(1-ethyl-6-methoxy-2-oxo-4,5-dihydro-3h-1-benzazepin-7-yl)amino]pyrimidin-4-yl]amino]bicyclo[2.2.1]hept-5-ene-2-carboxamide Chemical compound CCN1C(=O)CCCC2=C(OC)C(NC=3N=C(C(=CN=3)Cl)N[C@H]3[C@H]([C@@]4([H])C[C@@]3(C=C4)[H])C(N)=O)=CC=C21 GLGNXYJARSMNGJ-VKTIVEEGSA-N 0.000 description 1
- SZUVGFMDDVSKSI-WIFOCOSTSA-N (1s,2s,3s,5r)-1-(carboxymethyl)-3,5-bis[(4-phenoxyphenyl)methyl-propylcarbamoyl]cyclopentane-1,2-dicarboxylic acid Chemical compound O=C([C@@H]1[C@@H]([C@](CC(O)=O)([C@H](C(=O)N(CCC)CC=2C=CC(OC=3C=CC=CC=3)=CC=2)C1)C(O)=O)C(O)=O)N(CCC)CC(C=C1)=CC=C1OC1=CC=CC=C1 SZUVGFMDDVSKSI-WIFOCOSTSA-N 0.000 description 1
- GHYOCDFICYLMRF-UTIIJYGPSA-N (2S,3R)-N-[(2S)-3-(cyclopenten-1-yl)-1-[(2R)-2-methyloxiran-2-yl]-1-oxopropan-2-yl]-3-hydroxy-3-(4-methoxyphenyl)-2-[[(2S)-2-[(2-morpholin-4-ylacetyl)amino]propanoyl]amino]propanamide Chemical compound C1(=CCCC1)C[C@@H](C(=O)[C@@]1(OC1)C)NC([C@H]([C@@H](C1=CC=C(C=C1)OC)O)NC([C@H](C)NC(CN1CCOCC1)=O)=O)=O GHYOCDFICYLMRF-UTIIJYGPSA-N 0.000 description 1
- WWTBZEKOSBFBEM-SPWPXUSOSA-N (2s)-2-[[2-benzyl-3-[hydroxy-[(1r)-2-phenyl-1-(phenylmethoxycarbonylamino)ethyl]phosphoryl]propanoyl]amino]-3-(1h-indol-3-yl)propanoic acid Chemical compound N([C@@H](CC=1C2=CC=CC=C2NC=1)C(=O)O)C(=O)C(CP(O)(=O)[C@H](CC=1C=CC=CC=1)NC(=O)OCC=1C=CC=CC=1)CC1=CC=CC=C1 WWTBZEKOSBFBEM-SPWPXUSOSA-N 0.000 description 1
- QFLWZFQWSBQYPS-AWRAUJHKSA-N (3S)-3-[[(2S)-2-[[(2S)-2-[5-[(3aS,6aR)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoylamino]-3-methylbutanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-4-[1-bis(4-chlorophenoxy)phosphorylbutylamino]-4-oxobutanoic acid Chemical compound CCCC(NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@@H](NC(=O)CCCCC1SC[C@@H]2NC(=O)N[C@H]12)C(C)C)P(=O)(Oc1ccc(Cl)cc1)Oc1ccc(Cl)cc1 QFLWZFQWSBQYPS-AWRAUJHKSA-N 0.000 description 1
- IWZSHWBGHQBIML-ZGGLMWTQSA-N (3S,8S,10R,13S,14S,17S)-17-isoquinolin-7-yl-N,N,10,13-tetramethyl-2,3,4,7,8,9,11,12,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthren-3-amine Chemical compound CN(C)[C@H]1CC[C@]2(C)C3CC[C@@]4(C)[C@@H](CC[C@@H]4c4ccc5ccncc5c4)[C@@H]3CC=C2C1 IWZSHWBGHQBIML-ZGGLMWTQSA-N 0.000 description 1
- KQZLRWGGWXJPOS-NLFPWZOASA-N 1-[(1R)-1-(2,4-dichlorophenyl)ethyl]-6-[(4S,5R)-4-[(2S)-2-(hydroxymethyl)pyrrolidin-1-yl]-5-methylcyclohexen-1-yl]pyrazolo[3,4-b]pyrazine-3-carbonitrile Chemical compound ClC1=C(C=CC(=C1)Cl)[C@@H](C)N1N=C(C=2C1=NC(=CN=2)C1=CC[C@@H]([C@@H](C1)C)N1[C@@H](CCC1)CO)C#N KQZLRWGGWXJPOS-NLFPWZOASA-N 0.000 description 1
- ONBQEOIKXPHGMB-VBSBHUPXSA-N 1-[2-[(2s,3r,4s,5r)-3,4-dihydroxy-5-(hydroxymethyl)oxolan-2-yl]oxy-4,6-dihydroxyphenyl]-3-(4-hydroxyphenyl)propan-1-one Chemical compound O[C@@H]1[C@H](O)[C@@H](CO)O[C@H]1OC1=CC(O)=CC(O)=C1C(=O)CCC1=CC=C(O)C=C1 ONBQEOIKXPHGMB-VBSBHUPXSA-N 0.000 description 1
- UNILWMWFPHPYOR-KXEYIPSPSA-M 1-[6-[2-[3-[3-[3-[2-[2-[3-[[2-[2-[[(2r)-1-[[2-[[(2r)-1-[3-[2-[2-[3-[[2-(2-amino-2-oxoethoxy)acetyl]amino]propoxy]ethoxy]ethoxy]propylamino]-3-hydroxy-1-oxopropan-2-yl]amino]-2-oxoethyl]amino]-3-[(2r)-2,3-di(hexadecanoyloxy)propyl]sulfanyl-1-oxopropan-2-yl Chemical compound O=C1C(SCCC(=O)NCCCOCCOCCOCCCNC(=O)COCC(=O)N[C@@H](CSC[C@@H](COC(=O)CCCCCCCCCCCCCCC)OC(=O)CCCCCCCCCCCCCCC)C(=O)NCC(=O)N[C@H](CO)C(=O)NCCCOCCOCCOCCCNC(=O)COCC(N)=O)CC(=O)N1CCNC(=O)CCCCCN\1C2=CC=C(S([O-])(=O)=O)C=C2CC/1=C/C=C/C=C/C1=[N+](CC)C2=CC=C(S([O-])(=O)=O)C=C2C1 UNILWMWFPHPYOR-KXEYIPSPSA-M 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- YSUIQYOGTINQIN-UZFYAQMZSA-N 2-amino-9-[(1S,6R,8R,9S,10R,15R,17R,18R)-8-(6-aminopurin-9-yl)-9,18-difluoro-3,12-dihydroxy-3,12-bis(sulfanylidene)-2,4,7,11,13,16-hexaoxa-3lambda5,12lambda5-diphosphatricyclo[13.2.1.06,10]octadecan-17-yl]-1H-purin-6-one Chemical compound NC1=NC2=C(N=CN2[C@@H]2O[C@@H]3COP(S)(=O)O[C@@H]4[C@@H](COP(S)(=O)O[C@@H]2[C@@H]3F)O[C@H]([C@H]4F)N2C=NC3=C2N=CN=C3N)C(=O)N1 YSUIQYOGTINQIN-UZFYAQMZSA-N 0.000 description 1
- TVTJUIAKQFIXCE-HUKYDQBMSA-N 2-amino-9-[(2R,3S,4S,5R)-4-fluoro-3-hydroxy-5-(hydroxymethyl)oxolan-2-yl]-7-prop-2-ynyl-1H-purine-6,8-dione Chemical compound NC=1NC(C=2N(C(N(C=2N=1)[C@@H]1O[C@@H]([C@H]([C@H]1O)F)CO)=O)CC#C)=O TVTJUIAKQFIXCE-HUKYDQBMSA-N 0.000 description 1
- QBWKPGNFQQJGFY-QLFBSQMISA-N 3-[(1r)-1-[(2r,6s)-2,6-dimethylmorpholin-4-yl]ethyl]-n-[6-methyl-3-(1h-pyrazol-4-yl)imidazo[1,2-a]pyrazin-8-yl]-1,2-thiazol-5-amine Chemical compound N1([C@H](C)C2=NSC(NC=3C4=NC=C(N4C=C(C)N=3)C3=CNN=C3)=C2)C[C@H](C)O[C@H](C)C1 QBWKPGNFQQJGFY-QLFBSQMISA-N 0.000 description 1
- ITDVJJVNAASTRS-UHFFFAOYSA-N 4,6-dimethoxy-2-methylsulfonylpyrimidine Chemical compound COC1=CC(OC)=NC(S(C)(=O)=O)=N1 ITDVJJVNAASTRS-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229940126657 Compound 17 Drugs 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 240000001238 Gaultheria procumbens Species 0.000 description 1
- 235000007297 Gaultheria procumbens Nutrition 0.000 description 1
- 244000020551 Helianthus annuus Species 0.000 description 1
- 235000003222 Helianthus annuus Nutrition 0.000 description 1
- OPFJDXRVMFKJJO-ZHHKINOHSA-N N-{[3-(2-benzamido-4-methyl-1,3-thiazol-5-yl)-pyrazol-5-yl]carbonyl}-G-dR-G-dD-dD-dD-NH2 Chemical compound S1C(C=2NN=C(C=2)C(=O)NCC(=O)N[C@H](CCCN=C(N)N)C(=O)NCC(=O)N[C@H](CC(O)=O)C(=O)N[C@H](CC(O)=O)C(=O)N[C@H](CC(O)=O)C(N)=O)=C(C)N=C1NC(=O)C1=CC=CC=C1 OPFJDXRVMFKJJO-ZHHKINOHSA-N 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- LNUFLCYMSVYYNW-ZPJMAFJPSA-N [(2r,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6r)-6-[(2r,3r,4s,5r,6r)-6-[(2r,3r,4s,5r,6r)-6-[[(3s,5s,8r,9s,10s,13r,14s,17r)-10,13-dimethyl-17-[(2r)-6-methylheptan-2-yl]-2,3,4,5,6,7,8,9,11,12,14,15,16,17-tetradecahydro-1h-cyclopenta[a]phenanthren-3-yl]oxy]-4,5-disulfo Chemical compound O([C@@H]1[C@@H](COS(O)(=O)=O)O[C@@H]([C@@H]([C@H]1OS(O)(=O)=O)OS(O)(=O)=O)O[C@@H]1[C@@H](COS(O)(=O)=O)O[C@@H]([C@@H]([C@H]1OS(O)(=O)=O)OS(O)(=O)=O)O[C@@H]1[C@@H](COS(O)(=O)=O)O[C@H]([C@@H]([C@H]1OS(O)(=O)=O)OS(O)(=O)=O)O[C@@H]1C[C@@H]2CC[C@H]3[C@@H]4CC[C@@H]([C@]4(CC[C@@H]3[C@@]2(C)CC1)C)[C@H](C)CCCC(C)C)[C@H]1O[C@H](COS(O)(=O)=O)[C@@H](OS(O)(=O)=O)[C@H](OS(O)(=O)=O)[C@H]1OS(O)(=O)=O LNUFLCYMSVYYNW-ZPJMAFJPSA-N 0.000 description 1
- SRDRYTRKCQSMKY-UHFFFAOYSA-N acetamide;benzoic acid Chemical compound CC(N)=O.OC(=O)C1=CC=CC=C1 SRDRYTRKCQSMKY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- XRWSZZJLZRKHHD-WVWIJVSJSA-N asunaprevir Chemical compound O=C([C@@H]1C[C@H](CN1C(=O)[C@@H](NC(=O)OC(C)(C)C)C(C)(C)C)OC1=NC=C(C2=CC=C(Cl)C=C21)OC)N[C@]1(C(=O)NS(=O)(=O)C2CC2)C[C@H]1C=C XRWSZZJLZRKHHD-WVWIJVSJSA-N 0.000 description 1
- KGNDCEVUMONOKF-UGPLYTSKSA-N benzyl n-[(2r)-1-[(2s,4r)-2-[[(2s)-6-amino-1-(1,3-benzoxazol-2-yl)-1,1-dihydroxyhexan-2-yl]carbamoyl]-4-[(4-methylphenyl)methoxy]pyrrolidin-1-yl]-1-oxo-4-phenylbutan-2-yl]carbamate Chemical compound C1=CC(C)=CC=C1CO[C@H]1CN(C(=O)[C@@H](CCC=2C=CC=CC=2)NC(=O)OCC=2C=CC=CC=2)[C@H](C(=O)N[C@@H](CCCCN)C(O)(O)C=2OC3=CC=CC=C3N=2)C1 KGNDCEVUMONOKF-UGPLYTSKSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229940125773 compound 10 Drugs 0.000 description 1
- 229940125797 compound 12 Drugs 0.000 description 1
- 229940126543 compound 14 Drugs 0.000 description 1
- 229940125758 compound 15 Drugs 0.000 description 1
- 229940126142 compound 16 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940125810 compound 20 Drugs 0.000 description 1
- 229940126086 compound 21 Drugs 0.000 description 1
- 229940126208 compound 22 Drugs 0.000 description 1
- 229940125833 compound 23 Drugs 0.000 description 1
- 229940125961 compound 24 Drugs 0.000 description 1
- 229940125846 compound 25 Drugs 0.000 description 1
- 229940125851 compound 27 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 229940125877 compound 31 Drugs 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- JAXFJECJQZDFJS-XHEPKHHKSA-N gtpl8555 Chemical compound OC(=O)C[C@H](N)C(=O)N[C@@H](CCC(O)=O)C(=O)N[C@@H](C(C)C)C(=O)N[C@@H](C(C)C)C(=O)N1CCC[C@@H]1C(=O)N[C@H](B1O[C@@]2(C)[C@H]3C[C@H](C3(C)C)C[C@H]2O1)CCC1=CC=C(F)C=C1 JAXFJECJQZDFJS-XHEPKHHKSA-N 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 208000006278 hypochromic anemia Diseases 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- OSWPMRLSEDHDFF-UHFFFAOYSA-N methyl salicylate Chemical compound COC(=O)C1=CC=CC=C1O OSWPMRLSEDHDFF-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 239000005648 plant growth regulator Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 239000004563 wettable powder Substances 0.000 description 1
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
本发明公开了一种2－嘧啶氧(硫)基苯甲酸基乙酰胺类化合物，如通式(I)所示：其中：X选自氧或硫；R1选自H，卤素或4，6－二甲氧基嘧啶－2－基；R2选自H或C1－C6烷基；R3选自C1－C6烷基，苯基或取代的苯基，C1－C3烷基或C1－C3烷氧基取代的嘧啶基；R4选自H或C1－C6烷基；当R3，R4同时为烷基时，R3与R4可同所连接的氮原子一起形成5元或6元环，环上的1－2个碳原子可被氧、氮原子取代。化合物(I)具有除草活性，对大豆、棉花、花生、油菜、玉米等作物安全。
Description
技术领域
本发明属于除草剂领域，具体涉及一种2-嘧啶氧(硫)基苯甲酸基乙酰胺类化合物及其应用。
背景技术
由于杂草种群的演替、变迁以及对化学农药抗药性的产生和迅速发展，人们对生态环境保护意识的不断加强，对化学农药污染、农药对非靶标生物影响的认识以及在农药生态环境中归宿问题的重视不断提高。随着世界耕地面积的逐渐减少、人口的不断增长及对粮食需求量的增加，迫使人们迅速发展农业生产技术、改进完善耕作制度，并需要不断发明新型的和改进的除草化合物和组合物。
EP223406报道了某些2-嘧啶氧基苯甲酸酯类化合物具有除草活性，并对花生、向日葵安全。
在现有技术中均未涉及如本发明所示的2-嘧啶氧(硫)基苯甲酸基乙酰胺类化合物。
发明内容
本发明的目的是提供一种结构新颖、具有很好除草活性且对作物安全的2-嘧啶氧(硫)基苯甲酸基乙酰胺类化合物及其以该类化合物为活性组分的除草组合物，以满足农业生产迅速发展的需要。
本发明的技术方案如下：
本发明提供了一种结构新颖的2-嘧啶氧(硫)基苯甲酸基乙酰胺类化合物，如通式(I)所示：
其中：
X选自氧或硫；
R1选自H，卤素或4，6-二甲氧基嘧啶-2-基；
R2选自H或C1-C6烷基；
R3选自C1-C6烷基，苯基或被C1-C6烷基、C1-C6烷氧基、C1-C3烷氧羰基、硝基、卤素、苄基、苯氧基进一步取代的苯基，C1-C3烷基或C1-C3烷氧基取代的嘧啶基；
R4选自H或C1-C6烷基；
当R3、R4同时为烷基时，R3与R4可同所连接的氮原子一起形成5元或6元环，环上的1-2个碳原子可被氧或氮原子取代。
本发明较为优选的化合物为，通式(I)中：
X选自氧或硫；
R1选自H，卤素或4，6-二甲氧基嘧啶-2-基；
R2选自H或C1-C3烷基；
R3选自C1-C3烷基，苯基或被C1-C6烷基、C1-C3烷氧基、卤素进一步取代的苯基，4，6-二甲氧基嘧啶-2-基或4-甲氧基-6-甲基嘧啶-2-基；
R4选自H或C1-C3烷基；
或者R3与R4同所连接的氮原子一起形成哌啶、吗啉环。
本发明进一步优选的化合物为，通式(I)中：
X选自氧或硫；
R1选自H或卤素；
R2选自H；
R3选自C1-C3烷基，苯基或被C1-C6烷基、卤素进一步取代的苯基；
R4选自H或C1-C3烷基；
或者R3与R4同所连接的氮原子一起形成哌啶、吗啉环。
通式(I)中所指的烷基包括直链或支链烷基，例如甲基，异丙基等。烷氧基包括直链或支链烷氧基，例如甲氧基，异丙氧基等。卤原子包括氟，氯，溴，碘。
本发明的通式(I)化合物可由如下方法制备：
将化合物(II)(有市售，也可自制、制备方法参见Pestic.Sci.1996，47，115-124)与化合物(III)(制备方法参见J Org Chem 32：3229(1967))溶于适宜的溶剂中，在温度为-10℃到沸点之间反应0.5-48小时制得化合物(IV)。适宜的溶剂可选自例如甲苯、丙酮、DMF、THF或二氧六环等。加入碱类物质，如三乙胺、吡啶、氢氧化钠、氢氧化钾、碳酸钠、碳酸钾等对反应有利。
将化合物(IV)与适宜的碱加入到适宜的有机溶剂和水形成的混合溶剂中，在温度为-10℃到沸点之间反应0.5-48小时，反应液经盐酸或硫酸酸化，制得中间体酸即化合物(V)。适宜的有机溶剂选自氯仿、二氯甲烷、四氯化碳、正己烷、苯、甲苯、乙酸乙酯、甲醇、乙醇、THF或二氧六环等；适宜的碱选自氢氧化钠、氢氧化钾、碳酸钠或碳酸钾等。
化合物(V)与化合物(VI)(制备方法参见J Med Chem，46(3)，399-408，(2003))溶于适宜的溶剂例如甲苯、丙酮、DMF、THF或二氧六环等，在温度为-10℃到沸点之间反应0.5-48小时，制得化合物(I)。加入碱类物质如三乙胺、吡啶、氢氧化钠、氢氧化钾、碳酸钠、碳酸钾等对反应有利。
表1：部分如通式I所示的本发明化合物
表1中部分化合物的1H NMR(CDCl3，300MHz)δ(ppm)数据如下：
化合物1
2.856(m，3H，CH3)，3.790(s，6H，OCH3)，4.635(d，2H，J＝2.4Hz，CH2)，5.792(s，1H)，6.777(s，1H，NH)，7.394(m，2H，Ar-H)，7.659(m，1H，Ar-H)，8.063(q，1H，J＝1.8Hz，Ar-H).
化合物2
1.626(m，6H，CH2)，3.288(t，2H，J＝6Hz，CH2)，3.542(t，2H，J＝5.4Hz，CH2)，3.794(s，6H，OCH3)，4.796(s，2H，CH2)，5.740(s，1H)，7.326(m，2H，Ar-H)，7.592(m，1H，Ar-H)，8.158(q，1H，J＝1.8Hz，Ar-H).
化合物3
1.223(d，6H，J＝2.1Hz，CH3)，3.788(s，6H，OCH3)，4.085(m，1H，CH)，4.584(s，2H，CH2)，5.777(s，1H)，6.230(s，1H，NH)，7.282(m，1H，Ar-H)，7.365(m，1H，Ar-H)，7.629(m，1H，Ar-H)，8.032(q，1H，J＝1.3Hz，Ar-H).
化合物4
3.664(s，6H，OCH3)，4.780(s，2H，CH2)，5.704(s，1H)，7.358(m，4H，Ar-H)，7.659(m，1H，Ar-H)，8.084(q，1H，J＝1.8Hz，Ar-H)，8.293(d，1H，J＝8.7Hz，Ar-H)，8.626(s，1H，NH).
化合物5
3.595(s，6H，OCH3)，4.740(s，2H，CH2)，5.771(s，1H)，7.351(m，2H，Ar-H)，7.790(m，3H，Ar-H)，8.107(m，1H，Ar-H)，8.269(m，2H，Ar-H)，8.286(s，1H，NH).
化合物6
3.561(s，6H，OCH3)，4.762(s，2H，CH2)，5.731(s，1H)，7.161(m，1H，Ar-H)，7.404(m，4H，Ar-H)，7.765(m，3H，Ar-H)，8.099(q，1H，Ar-H)，8.700(s，1H，NH).
化合物7
2.259(s，6H，CH3)，3.590(s，6H，OCH3)，4.739(s，2H，CH2)，5.731(s，1H)，7.096(m，1H，Ar-H)，7.370(m，3H，Ar-H)，7.424(m，1H，Ar-H)，7.661(m，1H，Ar-H)，8.093(q，1H，J＝1.9Hz，Ar-H)，8.462(s，1H，NH).
化合物8
3.595(s，6H，OCH3)，4.773(s，2H，CH2)，5.750(s，1H)，7.129(m，1H，Ar-H)，7.274(m，1H，Ar-H)，7.432(m，2H，Ar-H)，7.708(m，2H，Ar-H)，7.882(m，1H，Ar-H)，8.094(q，1H，J＝2.0Hz，Ar-H)，8.809(s，1H，NH).
化合物9
3.563(s，6H，OCH3)，3.913(s，3H，CH3)，4.781(s，2H，CH2)，5.744(s，1H)，7.409(m，2H，Ar-H)，7.660(m，1H，Ar-H)，7.916(m，2H，Ar-H)，8.099(m，3H，Ar-H)，8.975(s，1H，NH).
化合物10
2.348(s，3H，CH3)，3.865(s，6H，OCH3)，3.911(s，3H，OCH3)，5.264(s，2H，CH2)，5.726(s，1H)，6.262(s，1H)，7.347(m，2H，Ar-H)，7.615(m，1H，Ar-H)，8.024(s，1H，NH)，8.149(q，1H，J＝1.8Hz，Ar-H).
化合物11
3.785(s，6H，OCH3)，3.914(s，6H，OCH3)，5.302(s，2H，CH2)，5.726(s，1H)，5.754(s，1H)，7.370(m，2H，Ar-H)，7.614(m，1H，Ar-H)，7.880(s，1H，NH)，8.152(q，1H，J＝1.6Hz，Ar-H).
化合物12
1.162(d，12H，J＝7.5Hz，CH3)，2.962(m，2H，CH)，3.542(s，6H，OCH3)，4.905(s，2H，CH2)，5.735(s，1H)，6.831(s，2H，Ar-H)，7.031(m，2H，Ar-H)，7.114(m，1H，Ar-H)，7.275(q，1H，J＝0.9Hz，Ar-H)，7.403(m，3H，Ar-H)，7.636(m，1H，Ar-H)，7.769(s，1H，NH)，8.130(q，1H，J＝1.5Hz，Ar-H).
化合物13
3.595(s，6H，OCH3)，4.759(s，2H，CH2)，5.745(s，1H)，7.382(m，4H，Ar-H)，7.673(m，1H，Ar-H)，7.767(m，2H，Ar-H)，8.096(q，1H，J＝1.8Hz，Ar-H).
化合物14
3.633(s，6H，OCH3)，4.776(s，2H，CH2)，5.763(s，1H)，7.391(m，3H，Ar-H)，7.684(m，2H，Ar-H)，8.070(m，2H，Ar-H)，8.885(s，1H，NH).
化合物15
3.676(s，6H，OCH3)，4.804(s，2H，CH2)，5.699(s，1H)，7.266(m，2H，Ar-H)，7.346(m，1H，Ar-H)，7.397(m，1H，Ar-H)，7.676(m，1H，Ar-H)，8.121(q，1H，J＝1.6Hz，Ar-H)，8.271(q，1H，J＝2.6Hz，Ar-H)，8.758(s，1H，NH).
化合物16
3.724(s，6H，OCH3)，4.518(d，2H，J＝6.3Hz，CH2)，4.707(s，2H，CH2)，5.727(s，1H)，6.940(s，1H，NH)，7.351(m，10H，Ar-H)，7.639(m，1H，Ar-H)，8.032(q，1H，J＝1.8Hz，Ar-H).
化合物17
2.322(s，3H，CH3)，3.576(s，6H，OCH3)，4.745(s，2H，CH2)，5.731(s，1H)，7.155(m，2H，Ar-H)，7.396(m，2H，Ar-H)，7.636(m，3H，Ar-H)，8.094(q，1H，J＝1.8Hz，Ar-H)，8.577(s，1H，NH).
化合物18
3.600(s，6H，OCH3)，4.781(s，2H，CH2)，5.696(s，1H)，7.107(m，3H，Ar-H)，7.368(m，2H，Ar-H)，7.641(q，1H，J＝1.8Hz，Ar-H)，8.073(q，1H，J＝1.6Hz，Ar-H)，8.237(m，1H，Ar-H)，8.526(s，1H，NH).
化合物19
1.270(s，9H，CH3)，3.716(s，6H，OCH3)，4.693(s，2H，CH2)，5.729(s，1H)，6.882(s，1H，NH)，7.243(m，3H，Ar-H)，7.375(m，3H，Ar-H)，7.593(q，1H，J＝2.0Hz，Ar-H)，8.007(q，1H，J＝1.5Hz，Ar-H).
化合物20
1.290(t，3H，CH3)，3.702(s，6H，OCH3)，4.062(q，2H，CH2)，4.757(s，2H，CH2)，5.715(s，1H)，6.850(dd，1H，J＝1.5Hz，Ar-H)，6.955(m，1H，Ar-H)，7.059(m，1H，Ar-H)，7.376(m，2H，Ar-H)，7.686(m，1H，Ar-H)，8.127(dd，1H，J＝1.8Hz，Ar-H)，8.362(dd，1H，J＝1.5Hz，Ar-H)，8.770(s，1H，NH).
化合物21
3.589(s，6H，OCH3)，3.824(s，3H，CH3)，4.751(s，2H，CH2)，5.734(s，1H)，6.702(m，1H，Ar-H)，7.239(m，2H，Ar-H)，7.373(m，2H，Ar-H)，7.512(d，1H，J＝1.5Hz，Ar-H)，7.671(m，1H，Ar-H)，8.093(m，1H，Ar-H)，8.672(s，1H，NH).
化合物22
3.620(s，6H，OCH3)，4.773(s，2H，CH2)，5.707(s，1H)，7.139(m，2H，Ar-H)，7.369(m，2H，Ar-H)，7.646(m，1H，Ar-H)，8.058(m，1H，Ar-H)，8.226(m，1H，Ar-H)，8.525(s，1H，NH).
化合物23
3.394(m，2H，CH2)，3.607(m，6H，CH2)，3.793(s，6H，OCH3)，4.791(s，2H，CH2)，5.745(s，1H)，7.249(m，1H，Ar-H)，7.336(m，1H，Ar-H)，7.613(m，1H，Ar-H)，8.115(m，1H，Ar-H).
化合物24
0.973(q，3H，CH3)，1.595(m，2H，CH2)，3.244(m，2H，CH2)，3.787(s，6H，OCH3)，4.629(s，2H，CH2)，5.784(s，1H)，6.614(s，1H，NH)，7.293(m，1H，Ar-H)，7.397(m，1H，Ar-H)，7.641(m，1H，Ar-H)，8.052(m，1H，Ar-H).
化合物25
1.150(m，6H，CH3)，3.358(m，4H，CH2)，3.795(s，6H，OCH3)，4.794(s，2H，CH2)，5.740(s，1H)，7.299(m，2H，Ar-H)，7.589(m，1H，Ar-H)，8.157(m，1H，Ar-H).
化合物26
2.952(s，6H，N(CH3)2)，3.793(s，6H，OCH3)，4.794(s，2H，CH2)，5.741(s，1H)，7.238(m，2H，Ar-H)，7.569(m，1H，Ar-H)，8.162(m，1H，Ar-H).
化合物27
1.164(t，J＝7.2Hz，3H，CH3)，3.301(m，2H，CH2)，3.727(s，6H，OCH3)，4.791(s，2H，CH2)，5.754(s，1H)，6.21(br，s，1H，NH)，7.545(m，2H，Ar-H)，7.672(q，J＝1.35Hz，1H，Ar-H).
化合物31
1.184(t，J＝7.2Hz，3H，CH3)，3.332(m，2H，CH2)，3.787(s，6H，OCH3)，4.6221(s，2H，CH2)，5.785(s，1H)，6.64(br，s，1H，NH)，7.30(m，2H，Ar-H)，7.632(t，1H，Ar-H)，8.053(d，1H，Ar-H).
本发明的通式(I)化合物具有除草活性。与现有技术中公开的化合物相比，本发明的化合物在较低剂量下苗前、苗后使用可有效控制单双子叶杂草，尤其对禾本科杂草具有较高的防除活性。因此本发明的技术方案包括通式(I)化合物用于控制杂草的用途。
本发明的通式(I)化合物在苗前使用，对大豆、棉花、花生等作物安全；在苗后使用，对玉米、花生、油菜等作物安全，尤其对禾本科作物玉米的安全性具有令人出乎意料的满意效果，同时保持了对禾本科杂草稗草的高防除活性。
本发明还包括以通式(I)化合物作为活性组分的除草组合物。该除草组合物中活性组分的重量百分含量为5-90％。该除草组合物中还包括农业上可接受的载体。
本发明的除草组合物可以多种制剂的形式施用。通常将本发明的化合物溶解或分散于载体中配制成制剂以便作为除草剂使用时更易于分散。例如：这些化学制剂可被制成可湿性粉剂或乳油。因此，在这些组合物中，至少加入一种液体或固体载体，并且通常需要加入适当的表面活性剂。
本发明另外的实施方案为防治杂草的方法，该方法包括将本发明的除草组合物施于所述杂草或所述杂草生长的场所或其生长介质的表面上。通常选择的较为适宜有效量为每公顷10克到5000克，优选有效量为每公顷20克到2500克。对于某些应用，可在本发明的除草组合物中加入一种或多种其它的除草剂，由此可产生附加的优点和效果。
本发明的化合物既可以单独使用也可以和其它已知的杀虫剂、杀菌剂、植物生长调节剂或肥料等一起混合使用。
应明确的是，在本发明的权利要求所限定的范围内，可进行各种变换和改动
具体实施方式
下列实施例和生测试验结果可用来进一步说明本发明，但不意味着限制本发明。
合成实例
化合物1的合成：
向250毫升的单口圆底烧瓶中加入4，6-二甲氧基-2-甲磺酰基嘧啶7克(0.036摩尔)，水杨酸甲酯6毫升(0.047摩尔)，碳酸钾6克(0.043摩尔)，N，N-二甲基甲酰胺100毫升。温度为110-130℃搅拌反应4小时后，冷却至室温，向反应液中加入乙酸乙酯200毫升和水180毫升，萃取。有机相依次用50毫升1％稀盐酸、50毫升饱和碳酸氢钠、3×50毫升饱和氯化钠水溶液洗涤，无水硫酸镁干燥，脱溶后得到的残余物经硅胶柱色谱(石油醚/乙酸乙酯＝5/1)纯化，得到2-(4，6-二甲氧基-2-嘧啶氧基)苯甲酸甲酯8.35克。
向150毫升的单口圆底烧瓶中依次加入2-(4，6-二甲氧基-2-嘧啶氧基)苯甲酸甲酯2.93克(0.01摩尔)，四氢呋喃50毫升，氢氧化钠0.4克(0.01摩尔)溶于50毫升水的溶液，常温搅拌反应8小时。反应完全后减压蒸出四氢呋喃。向残余物中加入200毫升乙酸乙酯，浓盐酸2毫升，萃取。有机相依次用50毫升水、3×50毫升饱和氯化钠水溶液洗涤，无水硫酸镁干燥，脱溶后得2-(4，6-二甲氧基-2-嘧啶氧基)苯甲酸2.05克。
向100毫升的三口圆底烧瓶中依次加入2-(4，6-二甲氧基-2-嘧啶氧基)苯甲酸1.0克(3.6毫摩尔)，N，N-二甲基甲酰胺30毫升，碳酸钾0.50克(3.6毫摩尔)，N-甲基氯乙酰胺0.39克(3.6毫摩尔)。温度为40-60℃下搅拌反应8小时后，向反应液中加入乙酸乙酯200毫升和水180毫升，萃取。用180毫升的饱和氯化钠水溶液洗涤有机相，再用无水硫酸镁干燥，脱溶后得到的残余物经硅胶柱色谱(石油醚/乙酸乙酯＝3/1)纯化，得到目的产物N-甲基-2-(4，6-二甲氧基-2-嘧啶氧基)苯甲酸乙酰胺0.70克。
表1中的其他化合物可通过以上类似的方法制得。
生测实例
原药用丙酮溶解后，按试验要求用1‰的吐温80静置自来水配制所需浓度的待测液。用履带式作物喷雾机(英国Engineer Research Ltd.设计生产)进行喷雾处理(喷雾压力1.95kg/cm2，喷液量50ml/m2，履带速度30cm/s，喷嘴为扇形喷嘴)。
苗前试验：将定量的杂草(苘麻、稗草、狗尾草)和作物(水稻、小麦、玉米、棉花、花生、大豆)种子分别播于截面积为100cm2的培养钵中，播后覆土1cm，供试化合物喷雾于土壤表面，处理后置于温室，然后浇水，以1‰的吐温80静置自来水处理作为对照。
苗后试验：将定量的杂草(苘麻、稗草、狗尾草)和作物(玉米、棉花、花生、油菜、大豆)种子分别播于截面积为100cm2的培养钵中，播后覆土1cm，在温室按常规方法培养。待杂草长至1.5叶期，水稻、小麦、玉米、棉花、花生、油菜和大豆2-3叶期，选取生长均匀一致的试材进行苗后茎叶喷雾处理，以1‰的吐温80静置自来水处理作为对照。试材处理后放在干燥通风处，待药液自然风干后，置于温室内按常规方法管理，处理后48小时内采用从底部灌水的方法，避免药液被冲刷。
处理后4周进行目测调查，抑制率为与对照相比的各种损伤程度，包括杀死、失绿、枯斑、扭曲、畸形、生长抑制或叶片灼烧等。部分测试结果见表2、3。
表2：部分通式(I)化合物的除草活性(苗前/苗后，抑制率％)
表3：部分通式(I)化合物对作物的安全性(苗前/苗后，抑制率％)
注*：表2、表3中，“-”表示未测。
Claims (6)
1. 一种2-嘧啶氧(硫)基苯甲酸基乙酰胺类化合物，如通式(I)所示：
其中：
X选自氧或硫；
R1选自H，卤素或4，6-二甲氧基嘧啶-2-基；
R2选自H或C1-C6烷基；
R3选自C1-C6烷基，苯基或被C1-C6烷基、C1-C6烷氧基、C1-C3烷氧羰基、硝基、卤素、苄基、苯氧基进一步取代的苯基，C1-C3烷基或C1-C3烷氧基取代的嘧啶基；
R4选自H或C1-C6烷基；
当R3、R4同时为烷基时，R3与R4可同所连接的氮原子一起形成5元或6元环，环上的1-2个碳原子可被氧或氮原子取代。
2. 按照权利要求1所述的化合物，其特征在于，通式(I)中：
X选自氧或硫；
R1选自H，卤素或4，6-二甲氧基嘧啶-2-基；
R2选自H或C1-C3烷基；
R3选自C1-C3烷基，苯基或被C1-C6烷基、C1-C3烷氧基、卤素进一步取代的苯基，4，6-二甲氧基嘧啶-2-基或4-甲氧基-6-甲基嘧啶-2-基；
R4选自H或C1-C3烷基；
或者R3与R4同所连接的氮原子一起形成哌啶、吗啉环。
3. 按照权利要求2所述的化合物，其特征在于，通式(I)中：
X选自氧或硫；
R1选自H或卤素；
R2选自H；
R3选自C1-C3烷基，苯基或被C1-C6烷基、卤素进一步取代的苯基；
R4选自H或C1-C3烷基；
或者R3与R4同所连接的氮原子一起形成哌啶、吗啉环。
4. 权利要求1所述的通式(I)化合物用于控制杂草的用途。
5. 一种除草组合物，含有如权利要求1所述的作为活性组分的通式(I)化合物和农业上可接受的载体，组合物中活性组分的重量百分含量为5-90％。
6. 一种控制杂草的方法，其特征在于：向杂草或杂草的生长介质或地点上施用除草有效剂量的如权利要求5所述的除草组合物。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100108571A CN101279950B (zh) | 2007-04-06 | 2007-04-06 | 2-嘧啶氧(硫)基苯甲酸基乙酰胺类化合物及其应用 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100108571A CN101279950B (zh) | 2007-04-06 | 2007-04-06 | 2-嘧啶氧(硫)基苯甲酸基乙酰胺类化合物及其应用 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101279950A true CN101279950A (zh) | 2008-10-08 |
| CN101279950B CN101279950B (zh) | 2010-08-11 |
Family
ID=40012643
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007100108571A Expired - Fee Related CN101279950B (zh) | 2007-04-06 | 2007-04-06 | 2-嘧啶氧(硫)基苯甲酸基乙酰胺类化合物及其应用 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101279950B (zh) |
Cited By (30)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014151255A1 (en) | 2013-03-15 | 2014-09-25 | Monsanto Technology Llc | Methods and compositions for weed control |
| US9121022B2 (en) | 2010-03-08 | 2015-09-01 | Monsanto Technology Llc | Method for controlling herbicide-resistant plants |
| US9416363B2 (en) | 2011-09-13 | 2016-08-16 | Monsanto Technology Llc | Methods and compositions for weed control |
| US9422558B2 (en) | 2011-09-13 | 2016-08-23 | Monsanto Technology Llc | Methods and compositions for weed control |
| US9422557B2 (en) | 2011-09-13 | 2016-08-23 | Monsanto Technology Llc | Methods and compositions for weed control |
| US9540642B2 (en) | 2013-11-04 | 2017-01-10 | The United States Of America, As Represented By The Secretary Of Agriculture | Compositions and methods for controlling arthropod parasite and pest infestations |
| US9777288B2 (en) | 2013-07-19 | 2017-10-03 | Monsanto Technology Llc | Compositions and methods for controlling leptinotarsa |
| US9850496B2 (en) | 2013-07-19 | 2017-12-26 | Monsanto Technology Llc | Compositions and methods for controlling Leptinotarsa |
| CN108024537A (zh) * | 2015-07-13 | 2018-05-11 | 纳幕尔杜邦公司 | 作为除草剂的芳氧基嘧啶基醚 |
| US10041068B2 (en) | 2013-01-01 | 2018-08-07 | A. B. Seeds Ltd. | Isolated dsRNA molecules and methods of using same for silencing target molecules of interest |
| EP3434779A1 (en) | 2011-09-13 | 2019-01-30 | Monsanto Technology LLC | Methods and compositions for weed control |
| US10240162B2 (en) | 2012-05-24 | 2019-03-26 | A.B. Seeds Ltd. | Compositions and methods for silencing gene expression |
| US10334848B2 (en) | 2014-01-15 | 2019-07-02 | Monsanto Technology Llc | Methods and compositions for weed control using EPSPS polynucleotides |
| US10378012B2 (en) | 2014-07-29 | 2019-08-13 | Monsanto Technology Llc | Compositions and methods for controlling insect pests |
| US10557138B2 (en) | 2013-12-10 | 2020-02-11 | Beeologics, Inc. | Compositions and methods for virus control in Varroa mite and bees |
| US10609930B2 (en) | 2013-03-13 | 2020-04-07 | Monsanto Technology Llc | Methods and compositions for weed control |
| US10612019B2 (en) | 2013-03-13 | 2020-04-07 | Monsanto Technology Llc | Methods and compositions for weed control |
| US10655136B2 (en) | 2015-06-03 | 2020-05-19 | Monsanto Technology Llc | Methods and compositions for introducing nucleic acids into plants |
| US10683505B2 (en) | 2013-01-01 | 2020-06-16 | Monsanto Technology Llc | Methods of introducing dsRNA to plant seeds for modulating gene expression |
| US10760086B2 (en) | 2011-09-13 | 2020-09-01 | Monsanto Technology Llc | Methods and compositions for weed control |
| US10801028B2 (en) | 2009-10-14 | 2020-10-13 | Beeologics Inc. | Compositions for controlling Varroa mites in bees |
| US10808249B2 (en) | 2011-09-13 | 2020-10-20 | Monsanto Technology Llc | Methods and compositions for weed control |
| US10806146B2 (en) | 2011-09-13 | 2020-10-20 | Monsanto Technology Llc | Methods and compositions for weed control |
| US10829828B2 (en) | 2011-09-13 | 2020-11-10 | Monsanto Technology Llc | Methods and compositions for weed control |
| US10883103B2 (en) | 2015-06-02 | 2021-01-05 | Monsanto Technology Llc | Compositions and methods for delivery of a polynucleotide into a plant |
| US10888579B2 (en) | 2007-11-07 | 2021-01-12 | Beeologics Inc. | Compositions for conferring tolerance to viral disease in social insects, and the use thereof |
| US10968449B2 (en) | 2015-01-22 | 2021-04-06 | Monsanto Technology Llc | Compositions and methods for controlling Leptinotarsa |
| US10988764B2 (en) | 2014-06-23 | 2021-04-27 | Monsanto Technology Llc | Compositions and methods for regulating gene expression via RNA interference |
| US11091770B2 (en) | 2014-04-01 | 2021-08-17 | Monsanto Technology Llc | Compositions and methods for controlling insect pests |
| US11807857B2 (en) | 2014-06-25 | 2023-11-07 | Monsanto Technology Llc | Methods and compositions for delivering nucleic acids to plant cells and regulating gene expression |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0651684B2 (ja) * | 1985-10-15 | 1994-07-06 | クミアイ化学工業株式会社 | ピリミジン誘導体および除草剤 |
| CN1028171C (zh) * | 1987-11-04 | 1995-04-12 | 古米埃化学工业株式会社 | 嘧啶衍生物及其盐的制备方法 |
| AU7324291A (en) * | 1990-02-20 | 1991-09-18 | Fmc Corporation | 6-aryl-2-substituted benzoic acid herbicides |
| CN1158925C (zh) * | 2002-04-24 | 2004-07-28 | 黑龙江大学化学化工学院 | 杂环类氧乙酰胺除草剂及其制备方法 |
| CN100384840C (zh) * | 2005-09-02 | 2008-04-30 | 中国科学院上海有机化学研究所 | 2-嘧啶氧基苯甲酸[2-(嘧啶氨基甲基)]苯酯类化合物、制备方法及其用途 |
-
2007
- 2007-04-06 CN CN2007100108571A patent/CN101279950B/zh not_active Expired - Fee Related
Cited By (44)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10888579B2 (en) | 2007-11-07 | 2021-01-12 | Beeologics Inc. | Compositions for conferring tolerance to viral disease in social insects, and the use thereof |
| US10801028B2 (en) | 2009-10-14 | 2020-10-13 | Beeologics Inc. | Compositions for controlling Varroa mites in bees |
| US11812738B2 (en) | 2010-03-08 | 2023-11-14 | Monsanto Technology Llc | Polynucleotide molecules for gene regulation in plants |
| US9121022B2 (en) | 2010-03-08 | 2015-09-01 | Monsanto Technology Llc | Method for controlling herbicide-resistant plants |
| US9988634B2 (en) | 2010-03-08 | 2018-06-05 | Monsanto Technology Llc | Polynucleotide molecules for gene regulation in plants |
| US10806146B2 (en) | 2011-09-13 | 2020-10-20 | Monsanto Technology Llc | Methods and compositions for weed control |
| EP3434780A1 (en) | 2011-09-13 | 2019-01-30 | Monsanto Technology LLC | Methods and compositions for weed control |
| US9422557B2 (en) | 2011-09-13 | 2016-08-23 | Monsanto Technology Llc | Methods and compositions for weed control |
| US10829828B2 (en) | 2011-09-13 | 2020-11-10 | Monsanto Technology Llc | Methods and compositions for weed control |
| EP3296402A2 (en) | 2011-09-13 | 2018-03-21 | Monsanto Technology LLC | Methods and compositions for weed control |
| US10760086B2 (en) | 2011-09-13 | 2020-09-01 | Monsanto Technology Llc | Methods and compositions for weed control |
| US9422558B2 (en) | 2011-09-13 | 2016-08-23 | Monsanto Technology Llc | Methods and compositions for weed control |
| US9416363B2 (en) | 2011-09-13 | 2016-08-16 | Monsanto Technology Llc | Methods and compositions for weed control |
| EP3382027A2 (en) | 2011-09-13 | 2018-10-03 | Monsanto Technology LLC | Methods and compositions for weed control |
| US10808249B2 (en) | 2011-09-13 | 2020-10-20 | Monsanto Technology Llc | Methods and compositions for weed control |
| EP3434779A1 (en) | 2011-09-13 | 2019-01-30 | Monsanto Technology LLC | Methods and compositions for weed control |
| US10240161B2 (en) | 2012-05-24 | 2019-03-26 | A.B. Seeds Ltd. | Compositions and methods for silencing gene expression |
| US10240162B2 (en) | 2012-05-24 | 2019-03-26 | A.B. Seeds Ltd. | Compositions and methods for silencing gene expression |
| US10934555B2 (en) | 2012-05-24 | 2021-03-02 | Monsanto Technology Llc | Compositions and methods for silencing gene expression |
| US10041068B2 (en) | 2013-01-01 | 2018-08-07 | A. B. Seeds Ltd. | Isolated dsRNA molecules and methods of using same for silencing target molecules of interest |
| US10683505B2 (en) | 2013-01-01 | 2020-06-16 | Monsanto Technology Llc | Methods of introducing dsRNA to plant seeds for modulating gene expression |
| US10609930B2 (en) | 2013-03-13 | 2020-04-07 | Monsanto Technology Llc | Methods and compositions for weed control |
| US10612019B2 (en) | 2013-03-13 | 2020-04-07 | Monsanto Technology Llc | Methods and compositions for weed control |
| US10568328B2 (en) | 2013-03-15 | 2020-02-25 | Monsanto Technology Llc | Methods and compositions for weed control |
| WO2014151255A1 (en) | 2013-03-15 | 2014-09-25 | Monsanto Technology Llc | Methods and compositions for weed control |
| US9850496B2 (en) | 2013-07-19 | 2017-12-26 | Monsanto Technology Llc | Compositions and methods for controlling Leptinotarsa |
| US11377667B2 (en) | 2013-07-19 | 2022-07-05 | Monsanto Technology Llc | Compositions and methods for controlling Leptinotarsa |
| US10597676B2 (en) | 2013-07-19 | 2020-03-24 | Monsanto Technology Llc | Compositions and methods for controlling Leptinotarsa |
| US9777288B2 (en) | 2013-07-19 | 2017-10-03 | Monsanto Technology Llc | Compositions and methods for controlling leptinotarsa |
| US9856495B2 (en) | 2013-07-19 | 2018-01-02 | Monsanto Technology Llc | Compositions and methods for controlling Leptinotarsa |
| US9540642B2 (en) | 2013-11-04 | 2017-01-10 | The United States Of America, As Represented By The Secretary Of Agriculture | Compositions and methods for controlling arthropod parasite and pest infestations |
| US10100306B2 (en) | 2013-11-04 | 2018-10-16 | Monsanto Technology Llc | Compositions and methods for controlling arthropod parasite and pest infestations |
| US10927374B2 (en) | 2013-11-04 | 2021-02-23 | Monsanto Technology Llc | Compositions and methods for controlling arthropod parasite and pest infestations |
| US10557138B2 (en) | 2013-12-10 | 2020-02-11 | Beeologics, Inc. | Compositions and methods for virus control in Varroa mite and bees |
| US10334848B2 (en) | 2014-01-15 | 2019-07-02 | Monsanto Technology Llc | Methods and compositions for weed control using EPSPS polynucleotides |
| US11091770B2 (en) | 2014-04-01 | 2021-08-17 | Monsanto Technology Llc | Compositions and methods for controlling insect pests |
| US10988764B2 (en) | 2014-06-23 | 2021-04-27 | Monsanto Technology Llc | Compositions and methods for regulating gene expression via RNA interference |
| US11807857B2 (en) | 2014-06-25 | 2023-11-07 | Monsanto Technology Llc | Methods and compositions for delivering nucleic acids to plant cells and regulating gene expression |
| US11124792B2 (en) | 2014-07-29 | 2021-09-21 | Monsanto Technology Llc | Compositions and methods for controlling insect pests |
| US10378012B2 (en) | 2014-07-29 | 2019-08-13 | Monsanto Technology Llc | Compositions and methods for controlling insect pests |
| US10968449B2 (en) | 2015-01-22 | 2021-04-06 | Monsanto Technology Llc | Compositions and methods for controlling Leptinotarsa |
| US10883103B2 (en) | 2015-06-02 | 2021-01-05 | Monsanto Technology Llc | Compositions and methods for delivery of a polynucleotide into a plant |
| US10655136B2 (en) | 2015-06-03 | 2020-05-19 | Monsanto Technology Llc | Methods and compositions for introducing nucleic acids into plants |
| CN108024537A (zh) * | 2015-07-13 | 2018-05-11 | 纳幕尔杜邦公司 | 作为除草剂的芳氧基嘧啶基醚 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101279950B (zh) | 2010-08-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101279950B (zh) | 2-嘧啶氧(硫)基苯甲酸基乙酰胺类化合物及其应用 | |
| CN101279951B (zh) | 2-嘧啶氧(硫)基苯甲酸基烯酸酯类化合物及其应用 | |
| CN102731381A (zh) | 6-（多取代芳基）-4-氨基吡啶甲酸酯及其作为除草剂的用途 | |
| CN102249996A (zh) | 2-(喹啉-8-基)羰基-环己烷-1,3-二酮类化合物 | |
| CN105418532A (zh) | 具有除草活性的n-取代烷基芳氧苯氧基丙酰胺类化合物及其制备与应用 | |
| CN101407491B (zh) | 异吲哚类化合物及其应用 | |
| CN103275029B (zh) | 一种水油兼溶的芳氧苯氧丙酸酯类衍生物制备及应用研究 | |
| CN101407490B (zh) | 3-苯甲酸基丙烯酸酯类化合物及其应用 | |
| CN100443475C (zh) | 一种2-取代烷基丙烯酸酯类化合物及其应用 | |
| CN101407462B (zh) | 二苯醚类化合物及其应用 | |
| CN1927811B (zh) | 一种4-苯甲酸基丁烯酸酯类化合物及其应用 | |
| CN101096338B (zh) | 一种苯甲酸酯类化合物及其应用 | |
| CN101747202B (zh) | 2-氯苯甲酸酯类化合物及其应用 | |
| CN100364955C (zh) | 一种2-(二取代)甲基丙烯酸酯类化合物及其应用 | |
| CN100427466C (zh) | 一种2-苯甲酸基丙烯酸酯类化合物及其应用 | |
| CN106831631B (zh) | 一种6-氯代苯并恶(噻)唑氧基苯氧丙酸酯类化合物及其应用 | |
| CN101407489B (zh) | 2-烷基丙烯酸酯类化合物及其应用 | |
| CN104649995B (zh) | 一种6‑氯代苯并恶唑氧基苯氧丙酸烯丙酯类化合物及其作为除草剂的应用 | |
| CN100519508C (zh) | 2-苯甲酰基-2-烷基甲酰基乙酸酯类化合物及其应用 | |
| CN100360509C (zh) | 用作除草剂的1-嘧啶酮基-4-氯-5-苯甲酸酯类化合物及其制备方法 | |
| CN109836393B (zh) | 一种环己烯羧酸铵盐类化合物及其应用 | |
| CN112939958B (zh) | 一种稠环酰基类化合物及其应用 | |
| CN101096342B (zh) | 3-苯甲酸基丙烯酸酯类化合物及其应用 | |
| CN109867624A (zh) | 一种3-氟-5-氯吡啶氧基苯氧丙酰胺类化合物及其应用 | |
| CN103833638B (zh) | 苯基吡唑基丙烯腈类化合物及其应用 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| ASS | Succession or assignment of patent right |
Owner name: SHENYANG RESEARCH INSTITUTE OF CHEMICAL INDUSTRY C Owner name: SINOCHEM CORPORATION Free format text: FORMER OWNER: SHENYANG RESEARCH INSTITUTE OF CHEMICAL INDUSTRY Effective date: 20100618 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 110021 NO.8, SHENLIAO EAST ROAD, TIEXI DISTRICT, SHENYANG CITY, LIAONING PROVINCE TO: 100031 NO.28, FUXINGMEN INNER STREET, XICHENG DISTRICT, BEIJING |
|
| TA01 | Transfer of patent application right |
Effective date of registration: 20100618 Address after: 100031 Beijing, Xicheng District, the door of the revitalization of the main street, No. 28 Applicant after: SINOCHEM Corp. Co-applicant after: SHENYANG RESEARCH INSTITUTE OF CHEMICAL INDUSTRY Co.,Ltd. Address before: 110021 Liaodong, Liaoning, Tiexi Shen road, No. 8, No. Applicant before: Shenyang Research Institute of Chemical Industry |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20160120 Address after: 110021 Liaodong Road, Tiexi District, Liaoning, No. 8-1, No. Patentee after: SHENYANG SINOCHEM AGROCHEMICALS R&D Co.,Ltd. Address before: 100031 Beijing, Xicheng District, the door of the revitalization of the main street, No. 28 Patentee before: SINOCHEM Corp. Patentee before: SHENYANG RESEARCH INSTITUTE OF CHEMICAL INDUSTRY Co.,Ltd. |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100811 |