CN1171875C - 尿嘧啶取代的苯基氨磺酰羧酰胺 - Google Patents
尿嘧啶取代的苯基氨磺酰羧酰胺 Download PDFInfo
- Publication number
- CN1171875C CN1171875C CNB018018963A CN01801896A CN1171875C CN 1171875 C CN1171875 C CN 1171875C CN B018018963 A CNB018018963 A CN B018018963A CN 01801896 A CN01801896 A CN 01801896A CN 1171875 C CN1171875 C CN 1171875C
- Authority
- CN
- China
- Prior art keywords
- methyl
- chloro
- phenyl
- compound
- trifluoromethyl
- 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.)
- Expired - Lifetime
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- ZTVLRVZYZTUUFA-UHFFFAOYSA-N N-phenyl-1-sulfamoylformamide Chemical class NS(=O)(=O)C(=O)NC1=CC=CC=C1 ZTVLRVZYZTUUFA-UHFFFAOYSA-N 0.000 title claims abstract description 17
- ISAKRJDGNUQOIC-UHFFFAOYSA-N Uracil Chemical group O=C1C=CNC(=O)N1 ISAKRJDGNUQOIC-UHFFFAOYSA-N 0.000 title abstract 4
- 229940035893 uracil Drugs 0.000 title abstract 2
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 55
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 41
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000001301 oxygen Substances 0.000 claims abstract description 36
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 36
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 24
- 150000002367 halogens Chemical class 0.000 claims abstract description 23
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 20
- 150000003839 salts Chemical class 0.000 claims abstract description 20
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 16
- 125000006374 C2-C10 alkenyl group Chemical group 0.000 claims abstract description 3
- -1 Sulfuryl amine Chemical class 0.000 claims description 194
- 150000001875 compounds Chemical class 0.000 claims description 138
- 239000000203 mixture Substances 0.000 claims description 87
- 238000000034 method Methods 0.000 claims description 58
- 239000001257 hydrogen Substances 0.000 claims description 53
- 239000007787 solid Substances 0.000 claims description 35
- 229940124530 sulfonamide Drugs 0.000 claims description 33
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 30
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 27
- 150000002431 hydrogen Chemical class 0.000 claims description 24
- 239000003795 chemical substances by application Substances 0.000 claims description 22
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 21
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 20
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 20
- 125000000171 (C1-C6) haloalkyl group Chemical group 0.000 claims description 19
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 19
- 125000003545 alkoxy group Chemical group 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 15
- 230000000694 effects Effects 0.000 claims description 14
- 239000005864 Sulphur Substances 0.000 claims description 13
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 13
- 230000002363 herbicidal effect Effects 0.000 claims description 13
- 238000009333 weeding Methods 0.000 claims description 10
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 8
- IOHPVZBSOKLVMN-UHFFFAOYSA-N 2-(2-phenylethyl)benzoic acid Chemical compound OC(=O)C1=CC=CC=C1CCC1=CC=CC=C1 IOHPVZBSOKLVMN-UHFFFAOYSA-N 0.000 claims description 7
- 230000000802 nitrating effect Effects 0.000 claims description 7
- 229920000742 Cotton Polymers 0.000 claims description 6
- 239000013543 active substance Substances 0.000 claims description 6
- 150000001263 acyl chlorides Chemical class 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N perisophthalic acid Natural products OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- 150000004678 hydrides Chemical class 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- 230000029936 alkylation Effects 0.000 claims description 2
- 238000005804 alkylation reaction Methods 0.000 claims description 2
- 150000001538 azepines Chemical class 0.000 claims description 2
- 125000002541 furyl group Chemical group 0.000 claims description 2
- 230000007062 hydrolysis Effects 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
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- VNDHYTGVCGVETQ-UHFFFAOYSA-N 4-fluorobenzamide Chemical compound NC(=O)C1=CC=C(F)C=C1 VNDHYTGVCGVETQ-UHFFFAOYSA-N 0.000 claims 8
- HNQIVZYLYMDVSB-UHFFFAOYSA-N methanesulfonimidic acid Chemical compound CS(N)(=O)=O HNQIVZYLYMDVSB-UHFFFAOYSA-N 0.000 claims 3
- 239000007822 coupling agent Substances 0.000 claims 2
- 125000004890 (C1-C6) alkylamino group Chemical group 0.000 claims 1
- IQYAGTXYYCZVNS-UHFFFAOYSA-N 2-chloro-n-(diethylsulfamoyl)-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]benzamide Chemical compound C1=C(Cl)C(C(=O)NS(=O)(=O)N(CC)CC)=CC(N2C(N(C)C(=CC2=O)C(F)(F)F)=O)=C1F IQYAGTXYYCZVNS-UHFFFAOYSA-N 0.000 claims 1
- GDIBNLIPFOYJON-UHFFFAOYSA-N 2-chloro-n-(dimethylsulfamoyl)-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]benzamide Chemical compound C1=C(Cl)C(C(=O)NS(=O)(=O)N(C)C)=CC(N2C(N(C)C(=CC2=O)C(F)(F)F)=O)=C1F GDIBNLIPFOYJON-UHFFFAOYSA-N 0.000 claims 1
- 125000001624 naphthyl group Chemical group 0.000 claims 1
- 125000004076 pyridyl group Chemical group 0.000 claims 1
- 125000001544 thienyl group Chemical group 0.000 claims 1
- 125000004765 (C1-C4) haloalkyl group Chemical group 0.000 abstract description 6
- 239000004009 herbicide Substances 0.000 abstract description 6
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 abstract 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 abstract 1
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 abstract 1
- 125000003341 7 membered heterocyclic group Chemical group 0.000 abstract 1
- 230000035613 defoliation Effects 0.000 abstract 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract 1
- 229910052717 sulfur Inorganic materials 0.000 abstract 1
- 239000011593 sulfur Substances 0.000 abstract 1
- 239000002585 base Substances 0.000 description 169
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 61
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 50
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 48
- 241000196324 Embryophyta Species 0.000 description 41
- 239000000460 chlorine Substances 0.000 description 40
- 238000002360 preparation method Methods 0.000 description 36
- 239000000243 solution Substances 0.000 description 31
- 230000002829 reductive effect Effects 0.000 description 29
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 27
- 229910052801 chlorine Inorganic materials 0.000 description 27
- 239000002253 acid Substances 0.000 description 25
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 23
- 238000012360 testing method Methods 0.000 description 23
- 229940073608 benzyl chloride Drugs 0.000 description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 18
- 235000019439 ethyl acetate Nutrition 0.000 description 16
- 239000012044 organic layer Substances 0.000 description 16
- 238000005481 NMR spectroscopy Methods 0.000 description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 13
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 13
- 229910052731 fluorine Inorganic materials 0.000 description 13
- 239000011737 fluorine Substances 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 12
- 229910052794 bromium Inorganic materials 0.000 description 12
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 12
- 239000003921 oil Substances 0.000 description 12
- 235000019198 oils Nutrition 0.000 description 12
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 description 11
- 239000004480 active ingredient Substances 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 125000000217 alkyl group Chemical group 0.000 description 9
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 9
- 235000011167 hydrochloric acid Nutrition 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 9
- VZAWCLCJGSBATP-UHFFFAOYSA-N 1-cycloundecyl-1,2-diazacycloundecane Chemical compound C1CCCCCCCCCC1N1NCCCCCCCCC1 VZAWCLCJGSBATP-UHFFFAOYSA-N 0.000 description 8
- 125000004217 4-methoxybenzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1OC([H])([H])[H])C([H])([H])* 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 125000003342 alkenyl group Chemical group 0.000 description 8
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- 238000004949 mass spectrometry Methods 0.000 description 8
- 238000012545 processing Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- UEMGWPRHOOEKTA-UHFFFAOYSA-N 1,3-difluorobenzene Chemical compound FC1=CC=CC(F)=C1 UEMGWPRHOOEKTA-UHFFFAOYSA-N 0.000 description 7
- 125000006497 3-methoxybenzyl group Chemical group [H]C1=C([H])C(=C([H])C(OC([H])([H])[H])=C1[H])C([H])([H])* 0.000 description 7
- 125000003349 3-pyridyl group Chemical group N1=C([H])C([*])=C([H])C([H])=C1[H] 0.000 description 7
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 7
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 7
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 7
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 7
- 240000007594 Oryza sativa Species 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- ZUSWDTWYONAOPH-UHFFFAOYSA-N [2-(trifluoromethyl)phenyl]hydrazine;hydrochloride Chemical group [Cl-].[NH3+]NC1=CC=CC=C1C(F)(F)F ZUSWDTWYONAOPH-UHFFFAOYSA-N 0.000 description 7
- 125000004429 atom Chemical group 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- 238000003810 ethyl acetate extraction Methods 0.000 description 7
- 238000000605 extraction Methods 0.000 description 7
- 125000005843 halogen group Chemical group 0.000 description 7
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- 238000010898 silica gel chromatography Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- ZPQOPVIELGIULI-UHFFFAOYSA-N 1,3-dichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1 ZPQOPVIELGIULI-UHFFFAOYSA-N 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- 125000004198 2-fluorophenyl group Chemical group [H]C1=C([H])C(F)=C(*)C([H])=C1[H] 0.000 description 6
- 125000002927 2-methoxybenzyl group Chemical group [H]C1=C([H])C([H])=C(C(OC([H])([H])[H])=C1[H])C([H])([H])* 0.000 description 6
- 125000004204 2-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C(OC([H])([H])[H])C([H])=C1[H] 0.000 description 6
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 description 6
- 125000004180 3-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(F)=C1[H] 0.000 description 6
- 125000004207 3-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(OC([H])([H])[H])=C1[H] 0.000 description 6
- 125000000339 4-pyridyl group Chemical group N1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 235000007164 Oryza sativa Nutrition 0.000 description 6
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 6
- 244000061456 Solanum tuberosum Species 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 6
- 239000004359 castor oil Substances 0.000 description 6
- 238000001311 chemical methods and process Methods 0.000 description 6
- 239000012141 concentrate Substances 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- 235000009566 rice Nutrition 0.000 description 6
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- 241000219146 Gossypium Species 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 235000002595 Solanum tuberosum Nutrition 0.000 description 5
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical group O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 5
- 229960001777 castor oil Drugs 0.000 description 5
- 235000019438 castor oil Nutrition 0.000 description 5
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 5
- 125000004786 difluoromethoxy group Chemical group [H]C(F)(F)O* 0.000 description 5
- 235000013399 edible fruits Nutrition 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 5
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 5
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- NEAQRZUHTPSBBM-UHFFFAOYSA-N 2-hydroxy-3,3-dimethyl-7-nitro-4h-isoquinolin-1-one Chemical compound C1=C([N+]([O-])=O)C=C2C(=O)N(O)C(C)(C)CC2=C1 NEAQRZUHTPSBBM-UHFFFAOYSA-N 0.000 description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 4
- 244000068988 Glycine max Species 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 230000006837 decompression Effects 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 150000002191 fatty alcohols Chemical class 0.000 description 4
- 125000000623 heterocyclic group Chemical group 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- SYZKAFCPWNFONG-UHFFFAOYSA-N 2-chloro-4-fluoro-5-nitrobenzoic acid Chemical compound OC(=O)C1=CC([N+]([O-])=O)=C(F)C=C1Cl SYZKAFCPWNFONG-UHFFFAOYSA-N 0.000 description 3
- ZRNSSRODJSSVEJ-UHFFFAOYSA-N 2-methylpentacosane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCC(C)C ZRNSSRODJSSVEJ-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- 235000010469 Glycine max Nutrition 0.000 description 3
- 244000110797 Polygonum persicaria Species 0.000 description 3
- 235000004442 Polygonum persicaria Nutrition 0.000 description 3
- 244000098338 Triticum aestivum Species 0.000 description 3
- 240000008042 Zea mays Species 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 125000001188 haloalkyl group Chemical group 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
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- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- PTMHPRAIXMAOOB-UHFFFAOYSA-N phosphoramidic acid Chemical compound NP(O)(O)=O PTMHPRAIXMAOOB-UHFFFAOYSA-N 0.000 description 1
- 229940061584 phosphoramidic acid Drugs 0.000 description 1
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910003446 platinum oxide Inorganic materials 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 239000011814 protection agent Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 229940107700 pyruvic acid Drugs 0.000 description 1
- LOAUVZALPPNFOQ-UHFFFAOYSA-N quinaldic acid Chemical compound C1=CC=CC2=NC(C(=O)O)=CC=C21 LOAUVZALPPNFOQ-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 235000013526 red clover Nutrition 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 210000000582 semen Anatomy 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 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 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 229920005552 sodium lignosulfonate Polymers 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000009331 sowing Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- SEEPANYCNGTZFQ-UHFFFAOYSA-N sulfadiazine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=NC=CC=N1 SEEPANYCNGTZFQ-UHFFFAOYSA-N 0.000 description 1
- QAHVHSLSRLSVGS-UHFFFAOYSA-N sulfamoyl chloride Chemical compound NS(Cl)(=O)=O QAHVHSLSRLSVGS-UHFFFAOYSA-N 0.000 description 1
- 230000019635 sulfation Effects 0.000 description 1
- 238000005670 sulfation reaction Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- YROXIXLRRCOBKF-UHFFFAOYSA-N sulfonylurea Chemical class OC(=N)N=S(=O)=O YROXIXLRRCOBKF-UHFFFAOYSA-N 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 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
- 235000013616 tea Nutrition 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- 125000005031 thiocyano group Chemical group S(C#N)* 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 229940087291 tridecyl alcohol Drugs 0.000 description 1
- 229910052722 tritium Inorganic materials 0.000 description 1
- 235000018322 upland cotton Nutrition 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 235000020234 walnut Nutrition 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000004562 water dispersible granule Substances 0.000 description 1
- 239000004563 wettable powder Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
- C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
- C07D239/52—Two oxygen atoms
- C07D239/54—Two oxygen atoms as doubly bound oxygen atoms or as unsubstituted hydroxy radicals
-
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- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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- A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
- A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- 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
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
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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
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
-
- 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
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/58—1,2-Diazines; Hydrogenated 1,2-diazines
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
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- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/647—Triazoles; Hydrogenated triazoles
- A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/707—1,2,3- or 1,2,4-triazines; Hydrogenated 1,2,3- or 1,2,4-triazines
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
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- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/61—Halogen atoms or nitro radicals
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- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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- C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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Abstract
公开了新型尿嘧啶取代的苯基氨磺酰羧酰胺(I)及其盐,其中A=氧或硫;X1=H,卤素,C1-C4烷基;X2=H,CN,CS-NH2,卤素,C1-C4烷基,C1-C4卤代烷基;X3=H,CN,C1-C6烷基,C1-C6烷氧基烷基,C3-C7环烷基,C3-C6链烯基,C3-C6炔基,任选取代的苄基;R1,R2=H,卤素,任选取代的羟基,C1-C10烷基,C2-C10链烯基,C3-C10炔基,C3-C7环烷基,苯基,苄基或C5-C7环烯基,或R1+R2与它们所连接的原子一起形成3-7元杂环;Q选自如说明书中所定义的Q1-Q40。还公开了其作为除草剂以及用于植物的干燥/脱叶的用途。
Description
杂草通过降低作物产量和降低作物质量而使全球遭受巨大的经济损失。在世界范围内,农艺作物必须与数百种杂草进行抗争。尽管目前存在可商购的除草剂,但杂草对作物的损害仍在发生。因此,仍然需要进行研究以开发更有效和/或更具选择性的除草剂。
在WO98/06706中公开了某些对-三氟甲基苯基尿嘧啶的使用、其生产方法及其作为除草剂的用途。此外,WO96/08151公开了除草的芳基尿嘧啶和芳基硫尿嘧啶,其中芳基环为任选取代的苯基。但这两篇文献均未提及氨磺酰羧酰胺取代基。
因此,本发明的目的是提供新型的3-苯基尿嘧啶,其高度有效地控制不希望有的植物品种。该目的还延伸到提供用作干燥剂/脱叶剂的新型化合物。
本发明的还一目的是提供一种控制不希望有的植物品种的方法以及用于该方法的组合物。
本发明的优点是用于控制不希望有的植物品种的方法可以在作物存在下使用。
本发明的再一目的是提供一种制备除草的苯基氨磺酰基羧酰胺的方法以及可用于该方法的中间体化合物。
本发明的这些和其它目的以及优点在阅读完下面的详细描述之后将变得更加清楚。
我们已经发现该目的按照本发明由式I的新型尿嘧啶取代的苯基氨磺酰羧酰胺达到:
其中各变量具有下列含义:
A为氧或硫;
X1为氢,卤素或C1-C4烷基;
X2为氢,氰基,CS-NH2,卤素,C1-C4烷基或C1-C4卤代烷基;
X3为氢,氰基,C1-C6烷基,C1-C6烷氧基烷基,C3-C7环烷基,C3-C6链烯基,C3-C6炔基或任选取代的苄基;
R1和R2各自独立地为氢,卤素,OR48,C1-C10烷基,C2-C10链烯基,C3-C10炔基,C3-C7环烷基,苯基,苄基或C5-C7环烯基,而后七个基团各自可被1-6个卤原子、1-3个C1-C6烷氧基、1或2个C1-C8卤代烷氧基、1或2个氰基、1或2个C3-C7环烷基、1或2个C(O)R49基团、1或2个CO-OR50基团、1或2个CO-SR51基团、1或2个CO-NR52R53基团、1-3个OR54基团、1-3个SR54基团、一个任选取代的4-10元单环或稠合双环杂环、1或2个任选取代的苯基或1或2个任选取代的苄基的任意组合所取代,
或R1和R2与它们所连接的原子一起形成3-7元杂环;
Q选自
其中
A1-A17各自独立地为氧或硫;
R3,R4,R7,R8,R11,R12,R18,R19,R27,R29,R32,R33,R38,R39,R44,R45,R46和R47各自独立地为氢,氰基,氨基,C1-C6烷基,C1-C6卤代烷基,C1-C6卤代烷氧基,C3-C7环烷基,C2-C6链烯基,C2-C6卤代链烯基,C3-C6炔基,苄基,OR55,C1-C3氰基烷基,或
R3和R4,R7和R8,R11和R12,R18和R19或R46和R47可以与它们所连接的原子一起代表任选被氧、硫或氮间隔且任选被一个或多个卤素或C1-C4烷基取代的4-7元环;
R5,R6,R9,R10,R15,R16,R20,R21,R30,R31,R35,R36,R41,R42和R43各自独立地为氢,C1-C6烷基,C1-C6卤代烷基,C3-C7环烷基,C2-C6链烯基,C2-C6卤代链烯基,C3-C6炔基,OR56,S(O)nR57,O-SO2-R57,NR58R59或
R5和R6,R9和R10,R15和R16,R20和R21或R30和R31可以与它们所连接的原子一起代表任选被一个或多个卤素或C1-C4烷基取代的4-7元环;
R13,R14,R22,R23,R25和R26各自独立地为氢,卤素或C1-C6烷基;R17,R28,R34,R37或R40各自独立地为氢,卤素,C1-C6烷基,C1-C6卤代烷基,C3-C7环烷基,C2-C6链烯基,C2-C6卤代链烯基,C3-C6炔基,OR60或SR61;
R24为氢,C1-C4烷基,C1-C4卤代烷基,C2-C4链烯基,C3-C4炔基,C1-C4卤代烷氧基或氨基;
R48,R49,R50,R51,R52,R53,R54,R55,R56,R57,R58,R59,R60和R61各自独立地为氢,C1-C6烷基,C1-C6卤代烷基,C3-C7环烷基,C2-C6链烯基,C3-C6炔基,任选取代的苯基或任选取代的苄基;
n为0,1或2;
及化合物I的农业上有用的盐。
此外,本发明涉及
—化合物I作为除草剂和/或用于植物的干燥/脱叶的用途;
—包含化合物I作为活性物质的除草组合物和用于植物的干燥/脱叶的组合物;
—制备化合物I以及使用化合物I的除草组合物和/或使植物干燥/脱叶的组合物的方法;
—使用化合物I控制不希望有的植物和使植物干燥/脱叶的方法;和
—式II的新型中间体:
其中Q,X1和X2如上所定义,
条件是Q必须不为Q21。
式I和II的优选化合物可以参见从属权利要求和后面的说明。
取决于取代方式,式I化合物可以含有一个或多个手性中心,此时它们以对映体或非对映体混合物的形式存在。本发明提供纯净的对映体或非对映体及其混合物。
农业上有用的盐特别是那些阳离子的盐以及其阳离子和阴离子分别不会不利地影响化合物I的除草活性的那些酸的酸加成盐。因此,合适的阳离子尤其是碱金属离子,优选钠离子和钾离子,碱土金属离子,优选钙离子、镁离子和钡离子,以及过渡金属离子,优选锰离子、铜离子、锌离子和铁离子,以及铵离子,其可以携带1-4个C1-C4烷基取代基,和/或一个苯基或苄基取代基,优选二异丙基铵、四甲基铵、四丁基铵、三甲基苄基铵,以及还有鏻离子,锍离子,优选三(C1-C4烷基)锍和氧化锍离子,优选三(C1-C4烷基)氧化锍。
有用的酸加成盐的阴离子主要是氯离子、溴离子、氟离子、硫酸氢根离子、硫酸根离子、磷酸二氢根离子、磷酸氢根离子、磷酸根离子、硝酸根离子、碳酸氢根离子、碳酸根离子、六氟硅酸根离子、六氟磷酸根离子、苯甲酸根离子和C1-C4链烷酸的阴离子,优选甲酸根离子、乙酸根离子、丙酸根离子和丁酸根离子。
对取代基X3和R1-R61提及的或作为苯基或杂环上的基团的有机部分是各基团成员的单独列举的集合术语,正如卤素的含义一样。所有碳链,即所有烷基、卤代烷基、链烯基、炔基和苯基烷基部分可以是直链的或支化的。
说明书和权利要求书中所用的术语卤代烷基、卤代烷氧基和卤代链烯基是指分别被一个或多个卤原子取代的烷基、烷氧基或链烯基。卤原子可以相同或不同。
卤代取代基优选具有1-5个连于其上的相同或不同的卤原子。
在上式I中,4-10元单环或稠合双环杂环包括但不限于苯并咪唑、咪唑、咪唑啉-2-硫酮、吲哚、靛红酸酐、吗啉、哌嗪、哌啶、嘌呤、吡唑、吡咯、吡咯烷和1,2,4-三唑环,其中各环任选被一个或多个独立地选自卤素、氰基、硝基、氨基、羟基、C1-C4烷基、C1-C4卤代烷基、C1-C4烷氧基、C1-C4卤代烷基或C1-C4卤代烷基磺酰基的基团取代。
当术语苯基或苄基是任选取代的时,任选存在的取代基可以是那些常用于开发农药化合物和/或改性该类化合物以影响其结构/活性、持久性、渗透或其他性能的基团中的一个或多个。这类取代基的具体例子例如包括卤原子、硝基、氰基、氰硫基、氰酰基、羟基、烷基、卤代烷基、烷氧基、卤代烷氧基、氨基、烷基氨基、二烷基氨基、甲酰基、烷氧基羰基、羧基、链烷酰基、烷硫基、烷基亚磺酰基、烷基磺酰基、氨基甲酰基、烷基酰氨基、苯基、苯氧基、苄基、苄氧基、杂环基,尤其是呋喃基,以及环烷基,尤其是环丙基。典型的是可以存在0-3个取代基。当任何前述取代基代表或含有烷基取代基时,其可以是线性或支化的且可以含有至多12,优选至多6,尤其是至多4个碳原子。
在上式I中,3-7元杂环包括但不限于咪唑和邻苯二甲酰亚胺环,其中各环任选被1-3个卤原子、1-3个C1-C4烷基、1-3个C1-C4卤代烷基、1-3个C1-C4烷氧基或1-3个C1-C4卤代烷氧基的任意组合所取代。
尿嘧啶取代的苯基氨磺酰羧酰胺I具有意想不到的除草活性水平和惊人的作物选择性。
单个含义的例子是:
—卤素:氟、氯、溴或碘,优选氟或氯;
—C1-C4烷基:CH3,C2H5,CH2-C2H5,CH(CH3)2,n-C4H9,CH(CH3)-C2H5,CH2-CH(CH3)2或C(CH3)3;
—C1-C6烷基和C1-C6烷氧基-C1-C6烷基的烷基部分:甲基、乙基、正丙基、1-甲基乙基、正丁基、1-甲基丙基、2-甲基丙基、1,1-二甲基乙基、正戊基、1-甲基丁基、2-甲基丁基、3-甲基丁基、2,2-二甲基丙基、1-乙基丙基、正己基、1,1-二甲基丙基、1,2-二甲基丙基、1-甲基戊基、2-甲基戊基、3-甲基戊基、4-甲基戊基、1,1-二甲基丁基、1,2-二甲基丁基、1,3-二甲基丁基、2,2-二甲基丁基、2,3-二甲基丁基、3,3-二甲基丁基、1-乙基丁基、2-乙基丁基、1,1,2-三甲基丙基、1,2,2-三甲基丙基、1-乙基-1-甲基丙基或1-乙基-2-甲基丙基,优选C1-C4烷基,特别是甲基或乙基;
—C1-C3氰基烷基:CH2CN、1-氰基乙基、2-氰基乙基、1-氰基丙-1-基、2-氰基丙-1-基、3-氰基丙-1-基或1-(CH2CN)乙-1-基;
—C1-C6卤代烷基:部分或全部被氟、氯、溴和/或碘取代的上述C1-C6烷基,如CH2F、CHF2、CF3、CH2Cl、CH(Cl)2、C(Cl)3、一氯一氟甲基、二氯一氟甲基、一氯二氟甲基、1-氟乙基、2-氟乙基、2,2-二氟乙基、2,2,2-三氟乙基、2-氯-2-氟乙基、2-氯-2,2-二氟乙基、2,2-二氯-2-氟乙基、2,2,2-三氯乙基、C2F5、3-氟丙基、3-氯丙基,氟甲基或1,2-二氯乙基;
—C2-C6链烯基:乙烯基、丙-1-烯-1-基、丙-2-烯-1-基、1-甲基乙烯基、正丁烯-1-基、正丁烯-2-基、正丁烯-3-基、1-甲基丙-1-烯-1-基、2-甲基丙-1-烯-1-基、1-甲基丙-2-烯-1-基、2-甲基丙-2-烯-1-基、正戊烯-1-基、正戊烯-2-基、正戊烯-3-基、正戊烯-4-基、1-甲基丁-1-烯-1-基、2-甲基丁-1-烯-1-基、3-甲基丁-1-烯-1-基、1-甲基丁-2-烯-1-基、2-甲基丁-2-烯-1-基、3-甲基丁-2-烯-1-基、1-甲基丁-3-烯-1-基、2-甲基丁-3-烯-1-基、3-甲基丁-3-烯-1-基、1,1-二甲基丙-2-烯-1-基、1,2-二甲基丙-1-烯-1-基、1,2-二甲基丙-2-烯-1-基、1-乙基丙-1-烯-2-基、1-乙基丙-2-烯-1-基、正己-1-烯-1-基、正己-2-烯-1-基、正己-3-烯-1-基、正己-4-烯-1-基、正己-5-烯-1-基、1-甲基戊-1-烯-1-基、2-甲基戊-1-烯-1-基、3-甲基戊-1-烯-1-基、4-甲基戊-1-烯-1-基、1-甲基戊-2-烯-1-基、2-甲基戊-2-烯-1-基、3-甲基戊-2-烯-1-基、4-甲基戊-2-烯-1-基、1-甲基戊-3-烯-1-基、2-甲基戊-3-烯-1-基、3-甲基戊-3-烯-1-基、4-甲基戊-3-烯-1-基、1-甲基戊-4-烯-1-基、2-甲基戊-4-烯-1-基、3-甲基戊-4-烯-1-基、4-甲基戊-4-烯-1-基、1,1-二甲基丁-2-烯-1-基、1,1-二甲基丁-3-烯-1-基、1,2-二甲基丁-1-烯-1-基、1,2-二甲基丁-2-烯-1-基、1,2-二甲基丁-3-烯-1-基、1,3-二甲基丁-1-烯-1-基、1,3-二甲基丁-2-烯-1-基、1,3-二甲基丁-3-烯-1-基、2,2-二甲基丁-3-烯-1-基、2,3-二甲基丁-1-烯-1-基、2,3-二甲基丁-2-烯-1-基、2,3-二甲基丁-3-烯-1-基、3,3-二甲基丁-1-烯-1-基、3,3-二甲基丁-2-烯-1-基、1-乙基丁-1-烯-1-基、1-乙基丁-2-烯-1-基、1-乙基丁-3-烯-1-基、2-乙基丁-1-烯-1-基、2-乙基丁-2-烯-1-基、2-乙基丁-3-烯-1-基、1,1,2-三甲基丙-2-烯-1-基、1-乙基-1-甲基丙-2-烯-1-基、1-乙基-2-甲基丙-1-烯-1-基或1-乙基-2-甲基丙-2-烯-1-基,优选C3-或C4-链烯基;
—C2-C6卤代链烯基:部分或全部被氟、氯、溴和/或碘取代的上述C2-C6链烯基,即例如2-氯烯丙基、3-氯烯丙基、2,3-二氯烯丙基、3,3-二氯烯丙基、2,3,4-三氯烯丙基、2,3-二氯丁-2-烯基、2-溴烯丙基、3-溴烯丙基、2,3-二溴烯丙基、3,3-二溴烯丙基、2,3,3-三溴烯丙基或2,3-二溴丁-2-烯基;
—C3-C6炔基:丙-1-炔-1-基、丙-2-炔-3-基、正丁-1-炔-1-基、正丁-1-炔-4-基、正丁-2-炔-1-基、正戊-1-炔-1-基、正戊-1-炔-3-基、正戊-1-炔-4-基、正戊-1-炔-5-基、正戊-2-炔-1-基、正戊-2-炔-4-基、正戊-2-炔-5-基、3-甲基丁-1-炔-1-基、3-甲基丁-1-炔-3-基、3-甲基丁-1-炔-4-基、正己-1-炔-1-基、正己-1-炔-3-基、正己-1-炔-4-基、正己-1-炔-5-基、正己-1-炔-6-基、正己-2-炔-1-基、正己-2-炔-4-基、正己-2-炔-5-基、正己-2-炔-6-基、正己-3-炔-1-基、正己-3-炔-2-基、3-甲基戊-1-炔-1-基、3-甲基戊-1-炔-3-基、3-甲基戊-1-炔-4-基、3-甲基戊-1-炔-5-基、4-甲基戊-1-炔-1-基、4-甲基戊-2-炔-4-基或4-甲基戊-2-炔-5-基,优选C3-或C4-炔基,尤其是丙-2-炔-3-基;
—苯基-C1-C6烷基:例如苄基、1-苯基乙-1-基、2-苯基乙-1-基、1-苯基丙-1-基、2-苯基丙-1-基、3-苯基丙-1-基、1-苯基丙-2-基、2-苯基丙-2-基、1-苯基丁-1-基、2-苯基丁-1-基、3-苯基丁-1-基、4-苯基丁-1-基、1-苯基丁-2-基、2-苯基丁-2-基、1-苯基丁-3-基、2-苯基丁-3-基、1-苯基-2-甲基丙-3-基、2-苯基-2-甲基丙-3-基、3-苯基-2-甲基丙-3-基或2-苄基丙-2-基,优选苯基-C1-C4烷基,特别是2-苯基乙-1-基;
—C1-C6烷氧基和C1-C6烷氧基-C1-C6烷基的烷氧基部分:甲氧基、乙氧基、正丙氧基、1-甲基乙氧基、正丁氧基、1-甲基丙氧基、2-甲基丙氧基、1,1-二甲基乙氧基、正戊氧基、1-甲基丁氧基、2-甲基丁氧基、3-甲基丁氧基、1,1-二甲基丙氧基、1,2-二甲基丙氧基、2,2-二甲基丙氧基、1-乙基丙氧基、正己氧基、1-甲基戊氧基、2-甲基戊氧基、3-甲基戊氧基、4-甲基戊氧基、1,1-二甲基丁氧基、1,2-二甲基丁氧基、1,3-二甲基丁氧基、2,2-二甲基丁氧基、2,3-二甲基丁氧基、3,3-二甲基丁氧基、1-乙基丁氧基、2-乙基丁氧基、1,1,2-三甲基丙氧基、1,2,2-三甲基丙氧基、1-乙基-1-甲基丙氧基或1-乙基-2-甲基丙氧基,优选C1-C4烷氧基,尤其是OCH3、OC2H5或OCH(CH3)2;
—C3-C7环烷基:环丙基、环丁基、环戊基、环己基和环庚基;
—C5-C7环烯基:环戊-1-烯基、环戊-2-烯基、环戊-3-烯基、环己-1-烯基、环己-2-烯基、环己-3-烯基、环庚-1-烯基、环庚-2-烯基、环庚-3-烯基、环庚-4-烯基、环辛-1-烯基、环辛-2-烯基、环辛-3-烯基和环辛-4-烯基。
3-7元杂环是具有1-3个选自如下的杂原子的饱和、部分或全部不饱和或芳族杂环:
—1-3个氮,
—1或2个氧,和
—1或2个硫原子。
为了将化合物I用作除草剂和/或具有干燥/脱叶作用的化合物,变量优选具有下列含义,确切地说在每种情况下是单独或组合的:
X1为氢或卤素,特别是氢或氯;
X2为氰基或卤素,特别是氰基或氯;
X3为氢;
Q为Q5、Q7、Q21、Q22、Q27、Q32、Q38、Q39或Q40;
A1为氧;
A3、A4各自独立地为氧;
A8,A9各自独立地为氧;
A10,A11各自独立地为氧;
A12为硫;
A13为氧;
A15为硫;
R1为C1-C4烷基;
R2为C1-C6烷基、C2-C6链烯基或C2-C6炔基;
R7为氨基、C1-C6烷基、C1-C6卤代烷基、C1-C6烷氧基或C1-C6卤代烷氧基;
R8为C1-C6烷基、C1-C6卤代烷基、C3-C7环烷基、C2-C6链烯基或C1-C6卤代烷氧基;
R7和R8可以与它们所连接的原子一起代表任选被氧、硫或氮间隔的4-7元环;
R9,R10各自独立地为氢、C1-C6烷基、C1-C6烷氧基或与它们所连接的原子一起代表5或6元环;
R29为氢、氨基或C1-C6烷基;
R30为C1-C6卤代烷基、C1-C6卤代烷氧基或C1-C6烷基磺酰基;以及
R31为氢、氨基、C1-C6烷基、C3-C7环烷基或C2-C6链烯基,或
R30和R31与它们所连接的原子一起代表5或6元环;
R32为氢、氨基、C1-C6烷基、C1-C6卤代烷基或C2-C6链烯基;
R33为氢、氨基、C1-C6烷基、C1-C6卤代烷基或C2-C6链烯基;
R34为氢或C1-C6烷基;
R35为C1-C6卤代烷基、C1-C6卤代烷氧基或C1-C6烷基磺酰基;
R36为氢、氨基、C1-C6烷基、C3-C7环烷基或C2-C6链烯基;
R37为氢、氰基、卤素、C1-C6烷基或C1-C6烷氧基;
R38为氰基、C1-C6烷基、C1-C6卤代烷基、C1-C6卤代烷氧基或C1-C6烷基磺酰基;
R39为氰基、C1-C6烷基、C1-C6卤代烷基、C1-C6卤代烷氧基或C1-C6烷基磺酰基;
R40为卤素;
R41为氢、氨基或C1-C6烷基;
R42为C1-C6卤代烷基、C1-C6卤代烷氧基、C1-C6烷基磺酰基或C1-C6烷基磺酰氧基;
R43为氢、氨基或C1-C6烷基;
R44为氢、氨基或C1-C6烷基;
R45为氢、氨基或C1-C6烷基;
R46,R47各自独立地为C1-C6卤代烷基或与它们所连接的氮原子一起代表任选被一个氧或硫环成员间隔的5或6元环。
非常优选的是式Ia的化合物(□I,其中X1=氟;X2=氯;Q=Q21;X3=氢;A,A8,A9=氧;R29=甲基;R30=三氟甲基;R31=氢)
尤其是表1的化合物:
表1
编号 | R1 | R2 |
Ia.1 | H | CH3 |
Ia.2 | H | C2H5 |
Ia.3 | H | CH2CH2-Cl |
Ia.4 | H | CH2CH2-CN |
Ia.5 | H | CH2-CO-OCH3 |
Ia.6 | H | CH2-CO-OC2H5 |
Ia.7 | H | CH(CH3)-CO-OCH3 |
Ia.8 | H | CH2CH2-OCH3 |
Ia.9 | H | CH2-C2H5 |
Ia.10 | H | CH2CH2-C2H5 |
Ia.11 | H | CH(CH3)2 |
Ia.12 | H | CH(CH3)-C2H5 |
Ia.13 | H | CH2-CH(CH3)2 |
Ia.14 | H | C(CH3)3 |
Ia.15 | H | CH(CH3)-CH2-C2H5 |
Ia.16 | H | CH2-CH(CH3)-C2H5 |
Ia.17 | H | CH2CH2-CH(CH3)2 |
Ia.18 | H | CH2-CH=CH2 |
Ia.19 | H | CH(CH3)=CH2 |
Ia.20 | H | CH2=CH-CH3 |
Ia.21 | H | CH2-C□CH |
Ia.22 | H | CH(CH3)-C□CH |
编号 | R1 | R2 |
Ia.23 | H | 环丙基 |
Ia.24 | H | CH2-环丙基 |
Ia.25 | H | 环戊基 |
Ia.26 | H | CH2-环戊基 |
Ia.27 | H | CH2-(1,3-二氧戊环基) |
Ia.28 | H | CH2-(2-呋喃基) |
Ia.29 | H | CH2-(3-呋喃基) |
Ia.30 | H | CH2-(2-噻吩基) |
Ia.31 | H | CH2-(3-噻吩基) |
Ia.32 | H | 苯基 |
Ia.33 | H | 2-氯苯基 |
Ia.34 | H | 3-氯苯基 |
Ia.35 | H | 4-氯苯基 |
Ia.36 | H | 2-氟苯基 |
Ia.37 | H | 3-氟苯基 |
Ia.38 | H | 4-氟苯基 |
Ia.39 | H | 2-甲基苯基 |
Ia.40 | H | 3-甲基苯基 |
Ia.41 | H | 4-甲基苯基 |
Ia.42 | H | 2-甲氧苯基 |
Ia.43 | H | 3-甲氧苯基 |
Ia.44 | H | 4-甲氧苯基 |
Ia.45 | H | 2-(甲氧羰基)苯基 |
Ia.46 | H | 3-(甲氧羰基)苯基 |
Ia.47 | H | 4-(甲氧羰基)苯基 |
Ia.48 | H | 2-硝基苯基 |
Ia.49 | H | 3-硝基苯基 |
Ia.50 | H | 4-硝基苯基 |
Ia.51 | H | 2-(二甲氨基)苯基 |
Ia.52 | H | 3-(二甲氨基)苯基 |
Ia.53 | H | 4-(二甲氨基)苯基 |
Ia.54 | H | 2-(三氟甲基)苯基 |
Ia.55 | H | 3-(三氟甲基)苯基 |
Ia.56 | H | 4-(三氟甲基)苯基 |
Ia.57 | H | 3-(苯氧基)苯基 |
Ia.58 | H | 4-(苯氧基)苯基 |
Ia.59 | H | 2,4-二氟苯基 |
Ia.60 | H | 2,4-二氯苯基 |
Ia.61 | H | 3,4-二氟苯基 |
编号 | R1 | R2 |
Ia.62 | H | 3,4-二氯苯基 |
Ia.63 | H | 3,5-二氟苯基 |
Ia.64 | H | 3,5-二氯苯基 |
Ia.65 | H | 2-吡啶基 |
Ia.66 | H | 3-吡啶基 |
Ia.67 | H | 4-吡啶基 |
Ia.68 | H | α-萘基 |
Ia.69 | H | 苄基 |
Ia.70 | H | 2-氯苄基 |
Ia.71 | H | 3-氯苄基 |
Ia.72 | H | 4-氯苄基 |
Ia.73 | H | 2-甲氧苄基 |
Ia.74 | H | 3-甲氧苄基 |
Ia.75 | H | 4-甲氧苄基 |
Ia.76 | CH3 | CH3 |
Ia.77 | CH3 | C2H5 |
Ia.78 | CH3 | CH2CH2-Cl |
Ia.79 | CH3 | CH2CH2-CN |
Ia.80 | CH3 | CH2-CO-OCH3 |
Ia.81 | CH3 | CH2-CO-OC2H5 |
Ia.82 | CH3 | CH(CH3)-CO-OCH3 |
Ia.83 | CH3 | CH2CH2-OCH3 |
Ia.84 | CH3 | CH2-C2H5 |
Ia.85 | CH3 | CH2CH2-C2H5 |
Ia.86 | CH3 | CH(CH3)2 |
Ia.87 | CH3 | CH(CH3)-C2H5 |
Ia.88 | CH3 | CH2-CH(CH3)2 |
Ia.89 | CH3 | C(CH3)3 |
Ia.90 | CH3 | CH(CH3)-CH2-C2H5 |
Ia.91 | CH3 | CH2-CH(CH3)-C2H5 |
Ia.92 | CH3 | CH2CH2-CH(CH3)2 |
Ia.93 | CH3 | CH2-CH=CH2 |
Ia.94 | CH3 | CH(CH3)=CH2 |
Ia.95 | CH3 | CH2=CH-CH3 |
Ia.96 | CH3 | CH2-C□CH |
Ia.97 | CH3 | CH(CH3)-C□CH |
Ia.98 | CH3 | 环丙基 |
Ia.99 | CH3 | CH2-环丙基 |
Ia.100 | CH3 | 环戊基 |
编号 | R1 | R2 |
Ia.101 | CH3 | CH2-环戊基 |
Ia.102 | CH3 | CH2-(1,3-二氧戊环基) |
Ia.103 | CH3 | CH2-(2-呋喃基) |
Ia.104 | CH3 | CH2-(3-呋喃基) |
Ia.105 | CH3 | CH2-(2-噻吩基) |
Ia.106 | CH3 | CH2-(3-噻吩基) |
Ia.107 | CH3 | 苯基 |
Ia.108 | CH3 | 2-氯苯基 |
Ia.109 | CH3 | 3-氯苯基 |
Ia.110 | CH3 | 4-氯苯基 |
Ia.111 | CH3 | 2-氟苯基 |
Ia.112 | CH3 | 3-氟苯基 |
Ia.113 | CH3 | 4-氟苯基 |
Ia.114 | CH3 | 2-甲基苯基 |
Ia.115 | CH3 | 3-甲基苯基 |
Ia.116 | CH3 | 4-甲基苯基 |
Ia.117 | CH3 | 2-甲氧苯基 |
Ia.118 | CH3 | 3-甲氧苯基 |
Ia.119 | CH3 | 4-甲氧苯基 |
Ia.120 | CH3 | 2-(甲氧羰基)苯基 |
Ia.121 | CH3 | 3-(甲氧羰基)苯基 |
Ia.122 | CH3 | 4-(甲氧羰基)苯基 |
Ia.123 | CH3 | 2-硝基苯基 |
Ia.124 | CH3 | 3-硝基苯基 |
Ia.125 | CH3 | 4-硝基苯基 |
Ia.126 | CH3 | 2-(二甲氨基)苯基 |
Ia.127 | CH3 | 3-(二甲氨基)苯基 |
Ia.128 | CH3 | 4-(二甲氨基)苯基 |
Ia.129 | CH3 | 2-(三氟甲基)苯基 |
Ia.130 | CH3 | 3-(三氟甲基)苯基 |
Ia.131 | CH3 | 4-(三氟甲基)苯基 |
Ia.132 | CH3 | 3-(苯氧基)苯基 |
Ia.133 | CH3 | 4-(苯氧基)苯基 |
Ia.134 | CH3 | 2,4-二氟苯基 |
Ia.135 | CH3 | 2,4-二氯苯基 |
Ia.136 | CH3 | 3,4-二氟苯基 |
Ia.137 | CH3 | 3,4-二氯苯基 |
Ia.138 | CH3 | 3,5-二氟苯基 |
Ia.139 | CH3 | 3,5-二氯苯基 |
编号 | R1 | R2 |
Ia.140 | CH3 | 2-吡啶基 |
Ia.141 | CH3 | 3-吡啶基 |
Ia.142 | CH3 | 4-吡啶基 |
Ia.143 | CH3 | α-萘基 |
Ia.144 | CH3 | 苄基 |
Ia.145 | CH3 | 2-氯苄基 |
Ia.146 | CH3 | 3-氯苄基 |
Ia.147 | CH3 | 4-氯苄基 |
Ia.148 | CH3 | 2-甲氧苄基 |
Ia.149 | CH3 | 3-甲氧苄基 |
Ia.150 | CH3 | 4-甲氧苄基 |
Ia.151 | C2H5 | C2H5 |
Ia.152 | C2H5 | CH2CH2-Cl |
Ia.153 | C2H5 | CH2CH2-CN |
Ia.154 | C2H5 | CH2-CO-OCH3 |
Ia.155 | C2H5 | CH2-CO-OC2H5 |
Ia.156 | C2H5 | CH(CH3)-CO-OCH3 |
Ia.157 | C2H5 | CH2CH2-OCH3 |
Ia.158 | C2H5 | CH2-C2H5 |
Ia.159 | C2H5 | CH2CH2-C2H5 |
Ia.160 | C2H5 | CH(CH3)2 |
Ia.161 | C2H5 | CH(CH3)-C2H5 |
Ia.162 | C2H5 | CH2-CH(CH3)2 |
Ia.163 | C2H5 | C(CH3)3 |
Ia.164 | C2H5 | CH(CH3)-CH2-C2H5 |
Ia.165 | C2H5 | CH2-CH(CH3)-C2H5 |
Ia.166 | C2H5 | CH2CH2-CH(CH3)2 |
Ia.167 | C2H5 | CH2-CH=CH2 |
Ia.168 | C2H5 | CH(CH3)=CH2 |
Ia.169 | C2H5 | CH2=CH-CH3 |
Ia.170 | C2H5 | CH2-C□CH |
Ia.171 | C2H5 | CH(CH3)-C□CH |
Ia.172 | C2H5 | 环丙基 |
Ia.173 | C2H5 | CH2-环丙基 |
Ia.174 | C2H5 | 环戊基 |
Ia.175 | C2H5 | CH2-环戊基 |
Ia.176 | C2H5 | CH2-(1,3-二氧戊环基) |
Ia.177 | C2H5 | CH2-(2-呋喃基) |
Ia.178 | C2H5 | CH2-(3-呋喃基) |
编号 | R1 | R2 |
Ia.179 | C2H5 | CH2-(2-噻吩基) |
Ia.180 | C2H5 | CH2-(3-噻吩基) |
Ia.181 | C2H5 | 苯基 |
Ia.182 | C2H5 | 2-氯苯基 |
Ia.183 | C2H5 | 3-氯苯基 |
Ia.184 | C2H5 | 4-氯苯基 |
Ia.185 | C2H5 | 2-氟苯基 |
Ia.186 | C2H5 | 3-氟苯基 |
Ia.187 | C2H5 | 4-甲苯基 |
Ia.188 | C2H5 | 2-甲基苯基 |
Ia.189 | C2H5 | 3-甲基苯基 |
Ia.190 | C2H5 | 4-甲基苯基 |
Ia.191 | C2H5 | 2-甲氧苯基 |
Ia.192 | C2H5 | 3-甲氧苯基 |
Ia.193 | C2H5 | 4-甲氧苯基 |
Ia.194 | C2H5 | 2-(甲氧羰基)苯基 |
Ia.195 | C2H5 | 3-(甲氧羰基)苯基 |
Ia.196 | C2H5 | 4-(甲氧羰基)苯基 |
Ia.197 | C2H5 | 2-硝基苯基 |
Ia.198 | C2H5 | 3-硝基苯基 |
Ia.199 | C2H5 | 4-硝基苯基 |
Ia.200 | C2H5 | 2-(二甲氨基)苯基 |
Ia.201 | C2H5 | 3-(二甲氨基)苯基 |
Ia.202 | C2H5 | 4-(二甲氨基)苯基 |
Ia.203 | C2H5 | 2-(三氟甲基)苯基 |
Ia.204 | C2H5 | 3-(三氟甲基)苯基 |
Ia.205 | C2H5 | 4-(三氟甲基)苯基 |
Ia.206 | C2H5 | 3-(苯氧基)苯基 |
Ia.207 | C2H5 | 4-(苯氧基)苯基 |
Ia.208 | C2H5 | 2,4-二氟苯基 |
Ia.209 | C2H5 | 2,4-二氯苯基 |
Ia.210 | C2H5 | 3,4-二氟苯基 |
Ia.211 | C2H5 | 3,4-二氯苯基 |
Ia.212 | C2H5 | 3,5-二氟苯基 |
Ia.213 | C2H5 | 3,5-二氯苯基 |
Ia.214 | C2H5 | 2-吡啶基 |
Ia.215 | C2H5 | 3-吡啶基 |
Ia.216 | C2H5 | 4-吡啶基 |
Ia.217 | C2H5 | α-萘基 |
编号 | R1 | R2 |
Ia.218 | C2H5 | 苄基 |
Ia.219 | C2H5 | 2-氯苄基 |
Ia.220 | C2H5 | 3-氯苄基 |
Ia.221 | C2H5 | 4-氯苄基 |
Ia.222 | C2H5 | 2-甲氧苄基 |
Ia.223 | C2H5 | 3-甲氧苄基 |
Ia.224 | C2H5 | 4-甲氧苄基 |
Ia.225 | CH2-C2H5 | C2H5 |
Ia.226 | CH2-C2H5 | CH2CH2-Cl |
Ia.227 | CH2-C2H5 | CH2CH2-CN |
Ia.228 | CH2-C2H5 | CH2-CO-OCH3 |
Ia.229 | CH2-C2H5 | CH2-CO-OC2H5 |
Ia.230 | CH2-C2H5 | CH(CH3)-CO-OCH3 |
Ia.231 | CH2-C2H5 | CH2CH2-OCH3 |
Ia.232 | CH2-C2H5 | CH2-C2H5 |
Ia.233 | CH2-C2H5 | CH2CH2-C2H5 |
Ia.234 | CH2-C2H5 | CH(CH3)2 |
Ia.235 | CH2-C2H5 | CH(CH3)-C2H5 |
Ia.236 | CH2-C2H5 | CH2-CH(CH3)2 |
Ia.237 | CH2-C2H5 | C(CH3)3 |
Ia.238 | CH2-C2H5 | CH(CH3)-CH2-C2H5 |
Ia.239 | CH2-C2H5 | CH2-CH(CH3)-C2H5 |
Ia.240 | CH2-C2H5 | CH2CH2-CH(CH3)2 |
Ia.241 | CH2-C2H5 | CH2-CH=CH2 |
Ia.242 | CH2-C2H5 | CH(CH3)=CH2 |
Ia.243 | CH2-C2H5 | CH2=CH-CH3 |
Ia.244 | CH2-C2H5 | CH2-C□CH |
Ia.245 | CH2-C2H5 | CH(CH3)-C□CH |
Ia.246 | CH2-C2H5 | 环丙基 |
Ia.247 | CH2-C2H5 | CH2-环丙基 |
Ia.248 | CH2-C2H5 | 环戊基 |
Ia.249 | CH2-C2H5 | CH2-环戊基 |
Ia.250 | CH2-C2H5 | CH2-(1,3-二氧戊环基) |
Ia.251 | CH2-C2H5 | CH2-(2-呋喃基) |
Ia.252 | CH2-C2H5 | CH2-(3-呋喃基) |
Ia.253 | CH2-C2H5 | CH2-(2-噻吩基) |
Ia.254 | CH2-C2H5 | CH2-(3-噻吩基) |
Ia.255 | CH2-C2H5 | 苯基 |
Ia.256 | CH2-C2H5 | 2-氯苯基 |
编号 | R1 | R2 |
Ia.257 | CH2-C2H5 | 3-氯苯基 |
Ia.258 | CH2-C2H5 | 4-氯苯基 |
Ia.259 | CH2-C2H5 | 2-氟苯基 |
Ia.260 | CH2-C2H5 | 3-氟苯基 |
Ia.261 | CH2-C2H5 | 4-氟苯基 |
Ia.262 | CH2-C2H5 | 2-甲基苯基 |
Ia.263 | CH2-C2H5 | 3-甲基苯基 |
Ia.264 | CH2-C2H5 | 4-甲基苯基 |
Ia.265 | CH2-C2H5 | 2-甲氧苯基 |
Ia.266 | CH2-C2H5 | 3-甲氧苯基 |
Ia.267 | CH2-C2H5 | 4-甲氧苯基 |
Ia.268 | CH2-C2H5 | 2-(甲氧羰基)苯基 |
Ia.269 | CH2-C2H5 | 3-(甲氧羰基)苯基 |
Ia.270 | CH2-C2H5 | 4-(甲氧羰基)苯基 |
Ia.271 | CH2-C2H5 | 2-硝基苯基 |
Ia.272 | CH2-C2H5 | 3-硝基苯基 |
Ia.273 | CH2-C2H5 | 4-硝基苯基 |
Ia.274 | CH2-C2H5 | 2-(二甲氨基)苯基 |
Ia.275 | CH2-C2H5 | 3-(二甲氨基)苯基 |
Ia.276 | CH2-C2H5 | 4-(二甲氨基)苯基 |
Ia.277 | CH2-C2H5 | 2-(三氟甲基)苯基 |
Ia.278 | CH2-C2H5 | 3-(三氟甲基)苯基 |
Ia.279 | CH2-C2H5 | 4-(三氟甲基)苯基 |
Ia.280 | CH2-C2H5 | 3-(苯氧基)苯基 |
Ia.281 | CH2-C2H5 | 4-(苯氧基)苯基 |
Ia.282 | CH2-C2H5 | 2,4-二氟苯基 |
Ia.283 | CH2-C2H5 | 2,4-二氯苯基 |
Ia.284 | CH2-C2H5 | 3,4-二氟苯基 |
Ia.285 | CH2-C2H5 | 3,4-二氯苯基 |
Ia.286 | CH2-C2H5 | 3,5-二氟苯基 |
Ia.287 | CH2-C2H5 | 3,5-二氯苯基 |
Ia.288 | CH2-C2H5 | 2-吡啶基 |
Ia.289 | CH2-C2H5 | 3-吡啶基 |
Ia.290 | CH2-C2H5 | 4-吡啶基 |
Ia.291 | CH2-C2H5 | α-萘基 |
Ia.292 | CH2-C2H5 | 苄基 |
Ia.293 | CH2-C2H5 | 2-氯苄基 |
Ia.294 | CH2-C2H5 | 3-氯苄基 |
Ia.295 | CH2-C2H5 | 4-氯苄基 |
编号 | R1 | R2 |
Ia.296 | CH2-C2H5 | 2-甲氧苄基 |
Ia.297 | CH2-C2H5 | 3-甲氧苄基 |
Ia.298 | CH2-C2H5 | 4-甲氧苄基 |
Ia.299 | CH2-CH2-C2H5 | CH2CH2-Cl |
Ia.300 | CH2-CH2-C2H5 | CH2CH2-CN |
Ia.301 | CH2-CH2-C2H5 | CH2-CO-OCH3 |
Ia.302 | CH2-CH2-C2H5 | CH2-CO-OC2H5 |
Ia.303 | CH2-CH2-C2H5 | CH(CH3)-CO-OCH3 |
Ia.304 | CH2-CH2-C2H5 | CH2CH2-OCH3 |
Ia.305 | CH2-CH2-C2H5 | CH2CH2-C2H5 |
Ia.306 | CH2-CH2-C2H5 | CH(CH3)2 |
Ia.307 | CH2-CH2-C2H5 | CH(CH3)-C2H5 |
Ia.308 | CH2-CH2-C2H5 | CH2-CH(CH3)2 |
Ia.309 | CH2-CH2-C2H5 | C(CH3)3 |
Ia.310 | CH2-CH2-C2H5 | CH(CH3)-CH2-C2H5 |
Ia.311 | CH2-CH2-C2H5 | CH2-CH(CH3)-C2H5 |
Ia.312 | CH2-CH2-C2H5 | CH2CH2-CH(CH3)2 |
Ia.313 | CH2-CH2-C2H5 | CH2-CH=CH2 |
Ia.314 | CH2-CH2-C2H5 | CH(CH3)=CH2 |
Ia.315 | CH2-CH2-C2H5 | CH2=CH-CH3 |
Ia.316 | CH2-CH2-C2H5 | CH2-C□CH |
Ia.317 | CH2-CH2-C2H5 | CH(CH3)-C□CH |
Ia.318 | CH2-CH2-C2H5 | 环丙基 |
Ia.319 | CH2-CH2-C2H5 | CH2-环丙基 |
Ia.320 | CH2-CH2-C2H5 | 环戊基 |
Ia.321 | CH2-CH2-C2H5 | CH2-环戊基 |
Ia.322 | CH2-CH2-C2H5 | CH2-(1,3-二氧戊环基) |
Ia.323 | CH2-CH2-C2H5 | CH2-(2-呋喃基) |
Ia.324 | CH2-CH2-C2H5 | CH2-(3-呋喃基) |
Ia.325 | CH2-CH2-C2H5 | CH2-(2-噻吩基) |
Ia.326 | CH2-CH2-C2H5 | CH2-(3-噻吩基) |
Ia.327 | CH2-CH2-C2H5 | 苯基 |
Ia.328 | CH2-CH2-C2H5 | 2-氯苯基 |
Ia.329 | CH2-CH2-C2H5 | 3-氯苯基 |
Ia.330 | CH2-CH2-C2H5 | 4-氯苯基 |
Ia.331 | CH2-CH2-C2H5 | 2-氟苯基 |
Ia.332 | CH2-CH2-C2H5 | 3-氟苯基 |
Ia.333 | CH2-CH2-C2H5 | 4-氟苯基 |
Ia.334 | CH2-CH2-C2H5 | 2-甲基苯基 |
编号 | R1 | R2 |
Ia.335 | CH2-CH2-C2H5 | 3-甲基苯基 |
Ia.336 | CH2-CH2-C2H5 | 4-甲基苯基 |
Ia.337 | CH2-CH2-C2H5 | 2-甲氧苯基 |
Ia.338 | CH2-CH2-C2H5 | 3-甲氧苯基 |
Ia.339 | CH2-CH2-C2H5 | 4-甲氧苯基 |
Ia.340 | CH2-CH2-C2H5 | 2-(甲氧羰基)苯基 |
Ia.341 | CH2-CH2-C2H5 | 3-(甲氧羰基)苯基 |
Ia.342 | CH2-CH2-C2H5 | 4-(甲氧羰基)苯基 |
Ia.343 | CH2-CH2-C2H5 | 2-硝基苯基 |
Ia.344 | CH2-CH2-C2H5 | 3-硝基苯基 |
Ia.345 | CH2-CH2-C2H5 | 4-硝基苯基 |
Ia.346 | CH2-CH2-C2H5 | 2-(二甲氨基)苯基 |
Ia.347 | CH2-CH2-C2H5 | 3-(二甲氨基)苯基 |
Ia.348 | CH2-CH2-C2H5 | 4-(二甲氨基)苯基 |
Ia.349 | CH2-CH2-C2H5 | 2-(三氟甲基)苯基 |
Ia.350 | CH2-CH2-C2H5 | 3-(三氟甲基)苯基 |
Ia.351 | CH2-CH2-C2H5 | 4-(三氟甲基)苯基 |
Ia.352 | CH2-CH2-C2H5 | 3-(苯氧基)苯基 |
Ia.353 | CH2-CH2-C2H5 | 4-(苯氧基)苯基 |
Ia.354 | CH2-CH2-C2H5 | 2,4-二氟苯基 |
Ia.355 | CH2-CH2-C2H5 | 2,4-二氯苯基 |
Ia.356 | CH2-CH2-C2H5 | 3,4-二氟苯基 |
Ia.357 | CH2-CH2-C2H5 | 3,4-二氯苯基 |
Ia.358 | CH2-CH2-C2H5 | 3,5-二氟苯基 |
Ia.359 | CH2-CH2-C2H5 | 3,5-二氯苯基 |
Ia.360 | CH2-CH2-C2H5 | 2-吡啶基 |
Ia.361 | CH2-CH2-C2H5 | 3-吡啶基 |
Ia.362 | CH2-CH2-C2H5 | 4-吡啶基 |
Ia.363 | CH2-CH2-C2H5 | α-萘基 |
Ia.364 | CH2-CH2-C2H5 | 苄基 |
Ia.365 | CH2-CH2-C2H5 | 2-氯苄基 |
Ia.366 | CH2-CH2-C2H5 | 3-氯苄基 |
Ia.367 | CH2-CH2-C2H5 | 4-氯苄基 |
Ia.368 | CH2-CH2-C2H5 | 2-甲氧苄基 |
Ia.369 | CH2-CH2-C2H5 | 3-甲氧苄基 |
Ia.370 | CH2-CH2-C2H5 | 4-甲氧苄基 |
Ia.371 | CH(CH3)2 | CH2CH2-Cl |
Ia.372 | CH(CH3)2 | CH2CH2-CN |
Ia.373 | CH(CH3)2 | CH2-CO-OCH3 |
编号 | R1 | R2 |
Ia.374 | CH(CH3)2 | CH2-CO-OC2H5 |
Ia.375 | CH(CH3)2 | CH(CH3)-CO-OCH3 |
Ia.376 | CH(CH3)2 | CH2CH2-OCH3 |
Ia.377 | CH(CH3)2 | CH(CH3)2 |
Ia.378 | CH(CH3)2 | CH(CH3)-C2H5 |
Ia.379 | CH(CH3)2 | CH2-CH(CH3)2 |
Ia.380 | CH(CH3)2 | C(CH3)3 |
Ia.381 | CH(CH3)2 | CH(CH3)-CH2-C2H5 |
Ia.382 | CH(CH3)2 | CH2-CH(CH3)-C2H5 |
Ia.383 | CH(CH3)2 | CH2CH2-CH(CH3)2 |
Ia.384 | CH(CH3)2 | CH2-CH=CH2 |
Ia.385 | CH(CH3)2 | CH(CH3)=CH2 |
Ia.386 | CH(CH3)2 | CH2=CH-CH3 |
Ia.387 | CH(CH3)2 | CH2-C□CH |
Ia.388 | CH(CH3)2 | CH(CH3)-C□CH |
Ia.389 | CH(CH3)2 | 环丙基 |
Ia.390 | CH(CH3)2 | CH2-环丙基 |
Ia.391 | CH(CH3)2 | 环戊基 |
Ia.392 | CH(CH3)2 | CH2-环戊基 |
Ia.393 | CH(CH3)2 | CH2-(1,3-二氧戊环基) |
Ia.394 | CH(CH3)2 | CH2-(2-呋喃基) |
Ia.395 | CH(CH3)2 | CH2-(3-呋喃基) |
Ia.396 | CH(CH3)2 | CH2-(2-噻吩基) |
Ia.397 | CH(CH3)2 | CH2-(3-噻吩基) |
Ia.398 | CH(CH3)2 | 苯基 |
Ia.399 | CH(CH3)2 | 2-氯苯基 |
Ia.400 | CH(CH3)2 | 3-氯苯基 |
Ia.401 | CH(CH3)2 | 4-氯苯基 |
Ia.402 | CH(CH3)2 | 2-氟苯基 |
Ia.403 | CH(CH3)2 | 3-氟苯基 |
Ia.404 | CH(CH3)2 | 4-氟苯基 |
Ia.405 | CH(CH3)2 | 2-甲基苯基 |
Ia.406 | CH(CH3)2 | 3-甲基苯基 |
Ia.407 | CH(CH3)2 | 4-甲基苯基 |
Ia.408 | CH(CH3)2 | 2-甲氧苯基 |
Ia.409 | CH(CH3)2 | 3-甲氧苯基 |
Ia.410 | CH(CH3)2 | 4-甲氧苯基 |
Ia.411 | CH(CH3)2 | 2-(甲氧羰基)苯基 |
Ia.412 | CH(CH3)2 | 3-(甲氧羰基)苯基 |
编号 | R1 | R2 |
Ia.413 | CH(CH3)2 | 4-(甲氧羰基)苯基 |
Ia.414 | CH(CH3)2 | 2-硝基苯基 |
Ia.415 | CH(CH3)2 | 3-硝基苯基 |
Ia.416 | CH(CH3)2 | 4-硝基苯基 |
Ia.417 | CH(CH3)2 | 2-(二甲氨基)苯基 |
Ia.418 | CH(CH3)2 | 3-(二甲氨基)苯基 |
Ia.419 | CH(CH3)2 | 4-(二甲氨基)苯基 |
Ia.420 | CH(CH3)2 | 2-(三氟甲基)苯基 |
Ia.421 | CH(CH3)2 | 3-(三氟甲基)苯基 |
Ia.422 | CH(CH3)2 | 4-(三氟甲基)苯基 |
Ia.423 | CH(CH3)2 | 3-(苯氧基)苯基 |
Ia.424 | CH(CH3)2 | 4-(苯氧基)苯基 |
Ia.425 | CH(CH3)2 | 2,4-二氟苯基 |
Ia.426 | CH(CH3)2 | 2,4-二氯苯基 |
Ia.427 | CH(CH3)2 | 3,4-二氟苯基 |
Ia.428 | CH(CH3)2 | 3,4-二氯苯基 |
Ia.429 | CH(CH3)2 | 3,5-二氟苯基 |
Ia.430 | CH(CH3)2 | 3,5-二氯苯基 |
Ia.431 | CH(CH3)2 | 2-吡啶基 |
Ia.432 | CH(CH3)2 | 3-吡啶基 |
Ia.433 | CH(CH3)2 | 4-吡啶基 |
Ia.434 | CH(CH3)2 | α-萘基 |
Ia.435 | CH(CH3)2 | 苄基 |
Ia.436 | CH(CH3)2 | 2-氯苄基 |
Ia.437 | CH(CH3)2 | 3-氯苄基 |
Ia.438 | CH(CH3)2 | 4-氯苄基 |
Ia.439 | CH(CH3)2 | 2-甲氧苄基 |
Ia.440 | CH(CH3)2 | 3-甲氧苄基 |
Ia.441 | CH(CH3)2 | 4-甲氧苄基 |
Ia.442 | -(CH2)4- | |
Ia.443 | -CH2-CH=CH-CH2- |
其他非常优选的化合物I是式Ib-Iz、I_、Iλ、Iπ、Iψ和Iζ的那些,尤其是
—化合物Ib.1-Ib.443,其与对应化合物Ia.1-Ia.443的不同仅在于R29为氨基:
—化合物Ic.1-Ic.443,其与对应化合物Ia.1-Ia.443的不同仅在于X1为氢:
—化合物Id.1-Id.443,其与对应化合物Ia.1-Ia.443的不同仅在于X1为氢且R29为氨基:
—化合物Ie.1-Ie.443,其与对应化合物Ia.1-Ia.443的不同仅在于Q为Q5,A1为氧,R7为二氟甲基且R8为甲基:
—化合物If.1-If.443,其与对应化合物Ia.1-Ia.443的不同仅在于X1为氯,Q为Q5,A1为氧,R7为二氟甲基,R8为甲基:
—化合物Ig.1-Ig.443,其与对应化合物Ia.1-Ia.443的不同仅在于Q为Q5,A1为氧,R7+R8为四亚甲基:
—化合物Ih.1-Ih.443,其与对应化合物Ia.1-Ia.443的不同仅在于X1为氯,Q为Q5,A1为氧,R7+R8为四甲基:
—化合物Ij.1-Ij.443,其与对应化合物Ia.1-Ia.443的不同仅在于Q为Q22,A10和A11为氧,A12为硫,R32,R33为甲基:
—化合物Ik.1-Ik.443,其与对应化合物Ia.1-Ia.443的不同仅在于Q为Q22,A10、A11和A12为氧,R32和R33为甲基:
—化合物Im.1-Im.443,其与对应化合物Ia.1-Ia.443的不同仅在于Q为Q27,A13为氧,R34和R36为氢,R35为三氟甲基:
—化合物In.1-In.443,其与对应化合物Ia.1-Ia.443的不同仅在于Q为Q27,A13为氧,R34为氢,R35为三氟甲基,R36为甲基:
—化合物Io.1-Io.443,其与对应化合物Ia.1-Ia.443的不同仅在于Q为Q27,A13为氧,R34为氢,R35为SO2-CH3,R36为氨基:
—化合物Ip.1-Ip.443,其与对应化合物Ia.1-Ia.443的不同仅在于Q为Q32,R37为氯,R38为二氟甲氧基,R39为甲基:
—化合物Iq.1-Iq.443,其与对应化合物Ia.1-Ia.443的不同仅在于Q为Q32,R37为溴,R38为二氟甲氧基,R39为甲基:
—化合物Ir.1-Ir.443,其与对应化合物Ia.1-Ia.443的不同仅在于X1为氯,Q为Q32,R37为溴,R38为二氟甲氧基,R39为甲基:
—化合物Is.1-Is.443,其与对应化合物Ia.1-Ia.443的不同仅在于Q为Q32,R37为氯,R38为三氟甲基,R39为甲基:
—化合物It.1-It.443,其与对应化合物Ia.1-Ia.443的不同仅在于Q为Q32,R37为溴,R38为三氟甲基,R39为甲基:
—化合物Iu.1-Iu.443,其与对应化合物Ia.1-Ia.443的不同仅在于X1为氯,Q为Q32,R37为溴,R38为三氟甲基,R39为甲基:
—化合物Iv.1-Iv.443,其与对应化合物Ia.1-Ia.443的不同仅在于Q为Q32,R37为氯,R38为SO2-CH3,R39为甲基:
—化合物Iw.1-Iw.443,其与对应化合物Ia.1-Ia.443的不同仅在于Q为Q32,R37为溴,R38为SO2-CH3,R39为甲基:
—化合物Ix.1-Ix.443,其与对应化合物Ia.1-Ia.443的不同仅在于X1为氯,Q为Q32,R37为溴,R38为SO2-CH3,R39为甲基:
—化合物Iy.1-Iy.443,其与对应化合物Ia.1-Ia.443的不同仅在于Q为Q38,R40为氯,R41,R43为氢,R42为三氟甲基:
—化合物Iz.1-Iz.443,其与对应化合物Ia.1-Ia.443的不同仅在于Q为Q39,A1为氧,A15为硫,R44和R45为甲基:
—化合物I_.1-I_.443,其与对应化合物Ia.1-Ia.443的不同仅在于Q为Q40,A16和A17为氧,R46+R47形成-CH2CH2-O-CH2-链:
—化合物Iλ.1-Iλ.443,其与对应化合物Ia.1-Ia.443的不同仅在于Q为Q40,A16为硫,A17为氧,R46+R47形成-CH2CH2-O-CH2-链:
—化合物Iπ.1-Iπ.443,其与对应化合物Ia.1-Ia.443的不同仅在于Q为Q40,A16和A17为硫,R46+R47形成-CH2CH2-O-CH2-链:
—化合物Iψ.1-Iψ.443,其与对应化合物Ia.1-Ia.443的不同仅在于Q为Q40,A16为氧,A17为硫,R46+R47形成-CH2CH2-O-CH2-链:
—化合物Iζ.1-Iζ.443,其与对应化合物Ia.1-Ia.443的不同仅在于Q为Q7,A3和A4为氧,R9+R10形成四亚甲基链:
本发明的尿嘧啶取代的苯基氨磺酰羧酰胺I可以通过各种本领域熟练技术人员可得和熟知的途径得到,优选通过下述方法之一得到。
A)苯甲酸衍生物II与磺酰胺III任选在偶联试剂如N,N-羰基二咪唑(CDI)存在下或在将II转化为相应的酰氯之后的反应:
将N,N’-羰基二咪唑(CDI)加入式II的羧酸衍生物在惰性溶剂如四氢呋喃中的溶液中。在回流下将所得混合物搅拌足够长的时间以使反应进行完全,然后冷却到室温。加入任选取代的磺酰胺III,然后加入二氮杂双环十一烷(DBU)并搅拌混合物直到反应完全。进行标准的处理和分离方法得到纯净形式的产物。
苯甲酸衍生物II-及相应的羧酸酯,其可以简单方式皂化得到游离酸II-在文献中已知或可以类似于文献中的已知方法制备。
将酯皂化成苯甲酸衍生物II的方法对本领域熟练技术人员来说是众所周知的;因此其细节是不必要的。作为举例,参考Kocienski的“保护基团”,Thieme Verlag1994,和Greene,Wuts,《有机合成中的保护基团》,Wiley1999,以及Houben-Weyl,《有机化学方法》(Methodender organishen Chemie),第E5卷,第I部分(1985),pp.223及以下各页。
除了活化到咪唑啉酮外,其他方法也是合适的。
各种方法均适合于活化该酸。可以通过用SOCl2、POCl3、PCl5、COCl2或(COCl)2处理将它们例如转化为酰氯。另外,咪唑烷可以通过与N,N-羰基二咪唑反应而制备。所用方法对本领域熟练技术人员来说是已知的,例如从Houben Weyl,《有机化学方法》,第E5卷(1985),第1部分,pp.587及以下各页和第E5卷(1985),第II部分,pp.934及以下各页。
用于制备其中Q不为Q21的苯甲酸衍生物II的方法包括US5,872,253;US5,484,763以及1999年8月4日提交的共同未决专利申请序列号09/368,340中所述的那些方法,这些文献引入本文供参考。
合成其中Q=Q21的化合物I,如2-氯-5-[3,6-二氢-3-甲基-2,6-二氧代-4-(三氟甲基)-1(2H)-嘧啶基]-4-氟苯甲酸(CAS No.120890-57-5)所需的前体例如描述于EP-A 195 346、WO89/02891、WO98/08151以及其中所列举的文献中,或可以按其中所公开的方式生产。
对于其中Q=Q5,A1=氧,R7=二氟甲基,R8=甲基,X1=氟或氯且X2=氯的酯II,可以参考US5,035,740和GB-A 22 53 625;对于其中Q=Q5且其中R7和R8与它们所连接的原子一起形成6元环的II,如2-氯-4-氟-5-(5,6,7,8-四氢-3-氧代-1,2,4-三唑并[4,3-a]吡啶-2(3H)-基)苯甲酸甲酯(CAS No.104799-37-3),可以参考JP-A61/069,776。这类化合物还在WO94/22860中提及。
其中Q为Q22,A10和A11=氧,A12=氧或硫,R32和R33=氨基或烷基,X1=氟且X2=氯的苯甲酸衍生物II从EP-A 584,655和WO00/50409中已知,例如2-氯-5-(3,5-二甲基-2,6-二氧代-4-硫代-1,3,5-三嗪烷(triazinan)-1-基)-4-氟苯甲酸(CAS No.289882-59-3)和2-氯-5-(3,5-二甲基-2,4,6-三氧代-1,3,5-三嗪烷-1-基)-4-氟苯甲酸甲酯(CASNo.154883-47-3)。
其中Q为Q27的苯甲酸衍生物II及其酯从WO97/07104、WO96/39392、WO99/14201和WO99/52878中已知,例如2-氯-4-氟-5-(5-三氟甲基-3-达嗪酮-2-基)苯甲酸(R34=氢,R35=三氟甲基,R36=氢,X1=氟且X2=氯)和2-氯-4-氟-5-(4-三氟甲基-5-三氟甲基-3-达嗪酮-2-基)苯甲酸(CAS No.259141-58-7;R34=氢,R35=三氟甲基,R36=甲基,X1=氟,X2=氯)。
其中Q为Q32的苯甲酸衍生物II从EP-A 361,114、WO92/06962、WO96/02515、US6,096,689和WO98/38169中已知,例如4-氯-3-[4-氯-2-氟-5-羧基苯基]-5-二氟甲氧基-1-甲基-1H-吡唑(CASNo.129631-53-4;Q=Q32,R37=氯,R38=二氟甲氧基,R39=甲基,X1=氟,X2=氯),4-氯-3-[4-氯-2-氟-5-羧基苯基]-5-三氟甲基-1-甲基-1H-吡唑(CASNo.142622-56-8;Q=Q32,R37=氯,R38=二氟甲氧基,R39=甲基,X1=氟,X2=氯),或可类似于其中所述的方法制备。
其中Q为Q38的苯甲酸衍生物II从WO95/02580、US5,783,522和WO98/07700已知,例如2-氯-5-[3-氯-5-(三氟甲基)-2-吡啶基]-4-氟苯甲酸(CAS No.188782-31-2),或可类似于其中所述的方法制备。
其中Q为Q39的苯甲酸衍生物II从WO99/59983和DE-A19 835 943已知,或可类似于其中所述的方法制备。
其中Q为Q40的苯甲酸衍生物II从WO94/10173和WO00/01700已知,或可类似于其中所述的方法制备。
其中Q为Q5的苯甲酸衍生物II可以根据US5,035,740按如下制备:
肼IV是已知的,例如见WO97/07104(X1=氟),或者可按已知方法制得。
式III的磺酰胺可按本身已知的方法制得,例如类似于Hamprecht等,Angew.Chemie 93,151(1981)和Houben-Weyl,《有机化学方法》,第E11卷(1985),PP.1019及以下各页中所述的方法。
例如,其中X3为氢的式III的磺酰胺可通过S-氯代磺酰胺与胺HNR1R2的反应制得:
III(X5=H)
其中X3不为氢的式III的磺酰胺可通过如下方法制备:将磺酰氯与胺HNR1R2反应,得到氨磺酰氯化合物Cl-SO2-NR1R2,然后将所述氨磺酰氯化合物与胺X3-NH2反应:
B)用Q置换卤化物:
Hal=卤素,优选氟、氯或溴。
利用该途径,将式IV的苯胺转化成重氮盐,再用碘和碘化钾处理得到式V的碘代化合物。在铜(I)催化剂存在下将式V化合物与未取代QH部分如式Q21H的尿嘧啶反应,即可得到式Ia的终产物。按此方式,其中Q=Q21的本发明化合物I可类似于T.Maruyama,K.Fujiwara和M.Fukuhara在J.Chem.Soc.,Pekin Trans.1995(7),pp.733-734中所述的方法制得,其中Hal=碘,且该反应是在加入Cu(I)源的情况下进行。
但是,如果适当地选择取代基Hal、X1和X2,则无过渡金属的方法也是适用的。这方面的文献例如可见WO96/39392,其中记载了适用于制备Q=Q27的化合物I的方法。
通过Sandmeyer反应,可由相应的苯胺制备卤代芳基前体V(也见反应式方案V)。这些方法是本领域技术人员熟知的,因此这里仅列出文献Houben-Weyl,《有机化学方法》(第5/4卷,第4版,1960,pp.438及以下各页)。
C)将苯胺中间体VI与式VII的恶嗪酮化合物反应,产生式I化合物,其中A为氧,X3为氢,Q为Q21,A8和A9为氧,且R29为氢,且任选接着进行烷基化和水解反应:
I(A=O;X3=H;Q=Q21;A8,A9
=O;R29□H;R30=CF3;R31=H)
R29-Hal代表C1-C6烷基,C1-C6卤代烷基,C3-C7环烷基,C2-C6链烯基,C2-C6卤代链烯基或C3-C6炔基卤化物。
已知制备噁嗪酮化合物VII的方法包括WO99/14216中所述的方法。
可按常规方法制备式VI的苯胺衍生物,如将适当取代的苯甲酸IX转化为相应的氨磺酰羧酰胺X(见上述方法A),然后进行硝化和还原:
适宜的硝化试剂是例如各种浓度的硝酸包括浓硝酸和发烟硝酸,硫酸和硝酸的混合物,硝酸乙酰酯和硝酸烷基酯。
该反应可在无溶剂的情况下在过量的硝化试剂中进行,或者在惰性溶剂或稀释剂中进行,适宜的惰性溶剂或稀释剂例如是水,无机酸,有机酸,卤代烃如二氯甲烷,酐如乙酸酐,以及它们的混合物。
便利地,可使用约等摩尔量的氨磺酰羧酰胺X和硝化试剂。为了提高X的产率,优选使用基于X的摩尔量过量至多约10倍的硝化试剂。当反应在无溶剂的硝化试剂中进行时,硝化试剂甚至过量更多。
反应温度一般为-100℃至200℃,优选-30℃至50℃。
然后可将硝化的化合物XI还原为苯胺衍生物VI。
还原反应通常是在酸性条件下通过硝基化合物与过渡金属如铁、锌或锡反应进行,或者利用复合氢化物如氢化铝锂和硼氢化钠进行,该还原反应可直接进行或者在溶剂或稀释剂中进行。
根据所选定的还原剂,适宜的溶剂的例子是水,醇如甲醇、乙醇和异丙醇,或者醚如乙醚、甲基叔丁基醚、二噁烷、四氢呋喃和乙二醇二甲醚。
如果用金属还原,则优选在无溶剂的情况下在无机酸尤其是浓盐酸或稀盐酸,或液体有机酸如乙酸和丙酸中进行。但是,也可用如前面提到的惰性溶剂稀释该酸。利用复合氢化物进行的还原反应优选在溶剂如醚或醇中进行。
硝化化合物XI和还原剂通常以约等摩尔的量使用。但是,为了优化反应,有利的是使其中一种成分的摩尔量过量至多约10倍。
酸的量并非关键。因此,为了尽可能完全还原起始反应物,可使用至少等 量的酸。通常,相对硝化的化合物XI过量使用该酸。
反应温度一般为-30℃至200℃,优选0-80℃。
为进行处理,通常用水稀释反应混合物,并且通过过滤、结晶或用溶剂萃取分离产物,该溶剂基本不与水混溶,如乙酸乙酯、乙醚或二氯甲烷。如果必要,然后可按常规方式纯化产物VI。
化合物XI的硝基也可用氢气催化氢化。适宜的催化剂的例子有阮内镍,碳载钯,氧化钯,铂和氧化铂。催化剂的用量通常为待还原化合物XI的0.05-50摩尔%。
可用溶剂分配或使用惰性溶剂或稀释剂,例如乙酸,乙酸与水的混合物,乙酸乙酯,乙醇或甲苯。分离掉催化剂后,可按常规方式处理反应溶液以得到产物VI。氢化反应可在大气或超计大气氢气压力下进行。
文献中给出了其它方法和反应条件(例如,见Houben-Weyl,《有机化学方法》,“氮化合物I”,第1部分(1971),第X/1卷,pp.463及以下各页)。
利用苯胺衍生物VI,不仅可以生产出其中Q=Q21的本发明化合物I,而且也可生产出其中Q=Q7、Q22或Q40的化合物I。有关其中Q=Q22的化合物I的制备可参见WO00/50409和EP-A584 655中所述的方法,而其中Q=Q40的化合物I的制备可参见WO94/10173和WO00/01700中所述的方法。
但是,也可按常规方法(例如见WO 97/07104和Houben-Weyl,《有机化学方法》,第E1卷,“氮化合物”)将苯胺衍生物VI转化成相应的肼,再由该肼制备其中Q=Q5或Q27的化合物I。
制备本发明化合物I的其它方法可见B_ger,WakabayashiPeroxidizing Herbicides,Springer Verlag 1999。
D)将苯甲酸衍生物VIII与亲电子胺化试剂在碱存在下反应,得到相应的N-氨基尿嘧啶苯甲酸酯,水解该酯得到苯甲酸II(Q=Q21;A8和A9=O;R29=NH2),并利用前述方法将该苯甲酸II转化为化合物I(A=O;Q=Q21;A8和A9=O;R29=NH2):
亲电子胺化试剂的具体例子有2,4-二硝基苯基羟胺和O-_磺酰羟胺。
DE-A19 652 431给出了适宜的反应条件实例。
以上所述所有方法有利地可在大气压力下或在所述反应混合物的固有压力下完成。
一般地,可利用本身已知的方法处理反应混合物,例如除去溶剂、将残余物在水和适宜有机溶剂的混合物间分配及处理有机相,从而得到产物。
本发明尿嘧啶取代的苯基氨磺酰羧酰胺I可以异构体混合物的形式制得,并根据需要可利用常规方法如结晶或在旋光活性吸附物上的层析分离成纯的异构体。也可由合适的旋光活性起始物制备出纯的旋光异构体。
按照本身已知的方法,通过与相应阳离子的碱反应,可将具有C-H酸性取代基的化合物I转化成其碱金属盐。
金属离子不是碱金属离子的化合物I的盐通常是通过相应碱金属盐在水溶液中的复分解制得。
按常规方式,可由钠盐制备出其它金属盐,如锰、铜、锌、铁、钙、镁、钡盐,并且也可借助氨、鏻、锍或氧化锍的氢氧化物制备铵和鏻盐。
化合物I及其农业上有用的盐,无论是异构体混合物形式还是纯异构体形式,均可作为除草剂使用。含有化合物I的除草组合物能够很好地控制非作物区中的植物,尤其是在高施用率的情况下更是如此。在诸如小麦、水稻、玉米、大豆和棉花的作物中,它们能够有效控制阔叶杂草和禾木科杂草,而不会对农作物造成显著影响。这一效果尤其在低施用率的情况下观察到。
根据施用方法的不同,化合物I或含有它们的组合物还可在许多其它农作物中使用,以消除不希望有的植物。适宜作物的例子如下:
洋葱、凤梨、落花生、石刁柏、甜菜altissima系,甜菜rapa系,欧洲油菜napus变种,欧洲油菜napobrassica变种,芜青silvestris变种,茶,红花,美国山核桃,柠檬,甜橙,小果咖啡(中果咖啡,大果咖啡),黄瓜,狗牙根,Daucus carota,油棕,野草莓,大豆,陆地棉,(树棉,草棉,棉属vitifolium种),向日葵,Hevea brasiliensis,大麦,啤酒花,甘薯,核桃,兵豆,亚麻,番茄,苹果属,Manihot esculenta,紫苜蓿,芭蕉属,烟草(黄花烟草),油橄榄,稻,金甲豆,菜豆,紫果挪威云杉,松属,豌豆,欧洲甜樱桃,桃,西洋梨,茶藨子属sylvestre种,蓖麻,甘蔗,黑麦,马铃薯,两色蜀黍(蜀黍),可可树,红车轴草,普通小麦,硬粒小麦,蚕豆,葡萄,玉蜀黍。
此外,化合物I也可用在由于育种(包括遗传工程方法)而导致对除草剂作用的完全或部分耐受的作物上。
另外,取代的羟肟酸衍生物I也适用于植物的干燥和/或脱叶。
作为干燥剂,它们尤其适用于使农作物如马铃薯、油菜、向日葵和大豆的地面上部分脱水。从而使得这些重要农作物可采用完全机械化的方法收获。
对于柑橘、橄榄或仁果、核果和坚果等植物种或品种,加速收获具有经济价值,这可通过在一段时间内集中、开裂或降低对树木的附着来实现。同样的机制,即促进植物的果实或叶与根之间开裂组织的形成,对于有用植物,尤其如棉花的易控脱叶同样是必需的。
而且,单个棉花植株成熟期的缩短导致了收获后纤维质量的提高。
化合物I或含有它们的组合物可以下列形式使用:可直接喷洒的水溶液,粉剂,悬浮剂,高浓缩的水性、油性或其它悬浮剂或分散剂,乳剂,油分散剂,膏剂,粉尘剂,铺展剂或颗粒剂,可采用的施用方式包括喷洒、喷雾、撒粉、铺展或浇灌。应用方法取决于所需目的。但是,在任何情况下,它们都应当保证本发明活性成分尽可能细地分散。
适宜的惰性添加剂是:中至高沸点的矿物油馏分如煤油和柴油,以及煤焦油和植物或动物来源的油,脂族、环状和芳香烃如链烷烃、四氢化萘、烷基化萘及其衍生物、烷基化苯及其衍生物,醇如甲醇、乙醇、丙醇、丁醇和环己醇,酮如环己酮,强极性溶剂如胺(例如N-甲基吡咯烷酮)或水。
含水使用形式可通过向乳油、悬浮剂、膏剂、可湿性粉剂或水可分散的颗粒剂中加水制得。为了制备乳液、膏剂或油分散剂,可利用湿润剂、增稠剂、分散剂或乳化剂均化取代的羟肟酸衍生物本身或溶于油或溶剂中的取代的羟肟酸衍生物。但是,也可制成由活性成分、湿润剂、增稠剂、分散剂或乳化剂及合适的话,溶剂或油组成的浓缩物,且这些浓缩物适合于用水稀释。
适宜的表面活性剂是芳族磺酸如木素-、苯酚-、萘-和二丁基萘磺酸、脂肪酸、烷基-和烷芳基磺酸、烷基硫酸、月桂基醚硫酸和脂肪醇硫酸的碱金属、碱土金属和铵盐;硫酸化十六-、十七-和十八烷醇的盐;脂肪醇乙二醇醚的盐;磺化萘及其衍生物与甲醛的缩合物;萘或萘磺酸与苯酚和甲醛的缩合物;聚氧乙烯辛基苯基醚;乙氧基化异辛基、辛基或壬基酚;烷基苯基和三丁基苯基聚乙二醇醚;烷芳基聚醚醇;异十三烷醇;脂肪醇/环氧乙烷缩合物;乙氧基化蓖麻油;聚氧乙烯烷基醚或聚氧丙烯烷基醚;月桂醇聚乙二醇醚乙酸酯;山梨醇酯;木素-亚硫酸盐废液或甲基纤维素。
通过将活性物质与固体载体一起混合或研磨可制备出粉剂、铺展材料和粉尘剂。
通过将活性成分与固体载体粘合可制备出颗粒剂,如包衣颗粒、浸渍颗粒或均匀颗粒。固体载体是矿物土,如硅石、硅胶、硅酸盐、滑石、高岭土、石灰石、石灰、白垩、胶块粘土、黄土、粘土、白云石、硅藻土、硫酸钙、硫酸镁、氧化镁,粉化合成材料,肥料如硫酸铵、磷酸铵、硝酸铵或尿素,以及植物来源产物,如谷粉、树皮粉、木粉和坚果壳粉,纤维素粉或其它固体载体。
待用产品中活性组分I的浓度的变化幅度很大。一般来说,配制组合物约含0.001-98%(重量),优选0.01-95%(重量)的至少一种活性组分。通常按90%-100%,优选95%-100%的纯度(根据NMR谱)使用活性组分。
下面的制剂实施例说明了这类制剂的制备。
I.将20重量份尿嘧啶取代的苯基氨磺酰羧酰胺I溶于一混合物中,该混合物由80重量份烷基化苯、10重量份8-10摩尔环氧乙烷和1摩尔油酸N-单乙醇酰胺的加合物、5重量份十二烷基苯磺酸钙和5重量份40摩尔环氧乙烷与1摩尔蓖麻油的加合物组成。将该溶液倒入100,000重量份的水中并在其中充分分散,得到一水性分散液,其中含0.02%(重量)活性组分。
II.将20重量份尿嘧啶取代的苯基氨磺酰羧酰胺I溶于一混合物中,该混合物由40重量份环己酮、30重量份异丁醇、20重量份7摩尔环氧乙烷与1摩尔异辛基酚的加合物以及10重量份40摩尔环氧乙烷与1摩尔蓖麻油的加合物组成。将该溶液倒入100,000重量份的水中并使其在其中充分分散,得到一水性分散液,其中含有0.02%(重量)活性组分。
III.将20重量份的尿嘧啶取代的苯基氨磺酰羧酰胺I溶于一混合物中,该混合物由25重量份环己酮、65重量份沸点为210-280℃之间的矿物油馏分和10重量份40摩尔环氧乙烷与1摩尔蓖麻油的加合物组成。将该溶液倒入100,000重量份的水中并在其中充分分散,得到水性分散液,其中含0.02%(重量)活性组分。
IV.20重量份的尿嘧啶取代的苯基氨磺酰羧酰胺I与3重量份的二异丁基萘-α-磺酸钠、17重量份得自亚硫酸盐废液的木素磺酸钠和60重量份粉状硅胶充分混合,将混合物在锤磨机中粉化后在20,000重量份水中充分分散,得到喷洒混合物,其中含0.1%(重量)活性成分。
V.将3重量份的尿嘧啶取代的苯基氨磺酰羧酰胺I与97重量份细碎高岭土混合,所得粉剂含3%(重量)活性组分。
VI.将20重量份的尿嘧啶取代的苯基氨磺酰羧酰胺I与2重量份十二烷基苯磺酸钠、8重量份脂肪醇聚乙二醇醚、2重量份苯酚/尿素/甲醛缩合物的钠盐和68重量份石蜡矿物油充分混合,得到稳定的油性分散液。
VII.1重量份的尿嘧啶取代的苯基氨磺酰羧酰胺I溶于由70重量份环己酮、20重量份乙氧基化异辛基酚和10重量份乙氧基化蓖麻油组成的混合物中,得到稳定的乳油。
VIII.1重量份的尿嘧啶取代的苯基氨磺酰羧酰胺I溶于由80重量份环己酮和20重量份Wettol_EM31(基于乙氧基化蓖麻油的非离子乳化剂;BASF AG组成的混合物中,产生稳定的乳油。
活性组分I或含有它们的除草组合物可在出苗前或出苗后施用。如果某些农作物对活性组分的耐受性较差,则可使用借助喷洒装置使除草组合物被喷洒的施用技术,以此方式使活性组分与敏感农作物的叶子尽可能少地接触,但却能够到达生长于农作物之下的不希望有的作物的叶面或裸露的土壤上(后定向(post-directed),最后耕作(lay-by))。
根据控制手段的意欲目的、季节、目标植物以及生长期,活性组分的施用率为0.001-3.0,优选0.01-1kg/ha活性物质(a.s.)。
为了拓宽作用谱并产生协同效应,可将取代的羟肟酸衍生物I与大量其它代表性除草或生长调节活性组分混合并共同施用。混合物中的适宜组分例如是:1,2,4-噻二唑,1,3,4-噻二唑,酰胺,氨基磷酸及其衍生物,氨基三唑,N-酰替苯胺,(杂)芳氧基链烷酸及其衍生物,苯甲酸及其衍生物,苯并噻二嗪酮,2-芳酰基-1,3-环己二酮,杂芳基芳基酮,苄基异噁唑烷酮,间-CF3-苯基衍生物,氨基甲酸酯,喹啉羧酸及其衍生物,氯代乙酰苯胺,环己烷-1,3-二酮衍生物,二嗪,二氯丙酸及其衍生物,二氢苯并呋喃,二氢呋喃-3-酮,二硝基苯胺,二硝基苯酚,二苯醚,联吡啶,卤代羧酸及其衍生物,尿素,3-苯基尿嘧啶,咪唑,咪唑啉酮,N-苯基-3,4,5,6-四氢苯邻二甲酰亚胺,噁二唑,环氧乙烷类,酚,芳氧基-或杂芳氧基苯氧基丙酸酯,苯基乙酸及其衍生物,苯基丙酸及其衍生物,吡唑,苯基吡唑,哒嗪,吡啶羧酸及其衍生物,嘧啶醚,磺酰胺,磺酰脲,三嗪,三嗪酮,三唑啉酮,三唑羧酰胺及尿嘧啶。
而且,化合物I可单独或与其它除草剂混合后,以与其它作物保护剂如农药或植物病原真菌或细菌控制剂混合的形式施用。另外,它们与无机盐溶液的混溶性也很有价值,可用于治疗营养和微量元素缺乏。也可加入非植物毒性的油和油浓缩物。
制备实施例
为了有助于更进一步理解本发明,提供下面的实施例来更具体地说明本发明。术语NMR代表核磁共振;HPLC代表高效液相色谱;TLC代表薄层色谱;GLC代表气液色谱;IR代表红外光谱。
实施例1
2-氯-4-氟-5-硝基苯甲酸的制备
将O℃的2-氯-4-氟苯甲酸(24.4克,0.142摩尔)的150毫升浓硫酸溶液用90%硝酸(13.2毫升,20摩尔%,0.284摩尔)在10℃滴加处理10分钟,在0-10℃搅拌2.5小时,然后将其倾于1升冰上。过滤白色固体,滤饼经空气干燥和乙酸乙酯/庚烷重结晶,得到标题化合物,为灰白色针状物。产率:18.0克(58.1%);NMR光谱分析鉴定了该化合物。
实施例2
2-氯-4-氟-5-硝基苯甲酸的制备
在回流温度下加热2-氯-4-氟-5-硝基苯甲酸(18.0克;0.0824摩尔)的75毫升乙酸溶液。分数份加入铁粉(18.4克,0.328摩尔),将所得悬浮液冷却至室温,用水和乙酸乙酯稀释。过滤该混合物,收集滤液。有机层用盐水洗涤,在无水硫酸镁上干燥,减压浓缩,得到标题化合物,为褐色固体。产率:9.00克(58.1%);熔点:153-155℃;NMR和质谱分析鉴定了该化合物。
实施例3
3-(5-羧基-4-氯-2-氟苯基)-1,2,3,4-二氢-6-三氟甲基嘧啶-2,4-二酮的制备
将2-氯-4-氟-5-氨基苯甲酸(8.30克;0.04308摩尔),2-二甲氨基-4-(三氟甲基)-6H-1,3-噁嗪-6-酮(9.57克;0.0460摩尔)和乙酸的混合物在回流温度下搅拌3小时,用冰水稀释,然后用乙酸乙酯萃取两次。合并的有机层用盐水洗,在无水硫酸镁上干燥,减压浓缩后得到标题化合物,为褐色固体。产率:14.0克(92.1%);NMR和质谱分析鉴定了该化合物。
实施例4
3-(5-羧基甲氧基-4-氯-2-氟苯基)-1,2,3,4-二氢-1-甲基-6-三氟甲基嘧啶-2,4-二酮的制备
3-(5-羧基-4-氯-2-氟苯基)-1,2,3,4-二氢-6-三氟甲基嘧啶-2,4-二酮(13.3克;0.0377摩尔),碳酸钾(13.0克;0.0943摩尔),甲基碘(5.87毫升;0.0943摩尔)和二甲基甲酰胺(150毫升)的混合物在室温下搅拌过夜,然后用水(500毫升)稀释。所得混合物用乙酸乙酯萃取三次。将合并的有机层用水,氢氧化钠水溶液(1N)和盐水洗三次,在无水硫酸镁上干燥,减压浓缩后得到米色固体。残余物经乙醇-水(250毫升)重结晶后,得到标题化合物,为白色针状物。产率:11.5克(80.4%);熔点:172-173℃;NMR和质谱分析鉴定了该化合物。
实施例5
3-(5-甲酯基-4-氯-2-氟苯基)-1,2,3,4-二氢-6-三氟甲基嘧啶-2,4-二酮的制备
将羰基二咪唑(2.97克,18.4毫摩尔)加到3-(5-羧基-4-氯-2-氟苯基)-1,2,3,4-二氢-6-三氟甲基嘧啶-2,4-二酮(4.61克;13.1毫摩尔)的四氢呋喃溶液中,将该混合物加热至回流温度,搅拌2分钟并冷却到室温。加入甲醇(2.70毫升,66.6毫摩尔),混合物在室温下搅拌过夜。然后在减压下浓缩该混合物,将所得残余物溶解于二氯甲烷。该有机混合物用盐酸洗两次(10%水溶液和5%水溶液),然后水洗。减压下浓缩有机层,得到褐色固体,将其悬浮于二氯甲烷,然后过滤。滤饼用二氯甲烷洗三次,过滤后干燥,得到标题化合物,为白色固体。产率:4.27克(89.0%);NMR光谱分析鉴定了该化合物。
实施例6
3-(5-甲酯基-4-氯-2-氟苯基)-1,2,3,4-二氢-1-氨基-6-三氟甲基嘧啶-2,4-二酮的制备
向3-(5-甲酯基-4-氯-2-氟苯基)-1,2,3,4-二氢-6-三氟甲基嘧啶-2,4-二酮(4.24克;11.6毫摩尔)和无水四氢呋喃的悬浮液中加碳酸钾(1.60克;11.6毫摩尔),然后加O-_磺酰羟胺(3.04克;14.1毫摩尔;J.G.Krause,“合成”,1972,140)。所得混合物在室温下搅拌过夜,然后用水稀释。用乙酸乙酯萃取混合物四次。合并的萃取液在无水硫酸镁上干燥,减压浓缩,得到标题化合物,为泡沫体,NMR光谱分析鉴定了该化合物,产率4.63克(>100%)。
实施例7
3-(5-羧基-4-氯-2-氟苯基)-1,2,3,4-二氢-1-氨基-6-三氟甲基嘧啶-2,4-二酮的制备
向3-(5-甲酯基-4-氯-2-氟苯基)-1,2,3,4-二氢-1-氨基-6-三氟甲基嘧啶-2,4-二酮(1.53克;4.01毫摩尔)的无水二氯甲烷溶液中加入三溴化硼(1M二氯甲烷溶液,16.0毫升,16.0毫摩尔)。该混合物在室温下搅拌过夜,然后用水稀释。分出水层,室温下静置过夜,过滤并干燥后,得到标题化合物,为白色固体,经NMR和质谱分析测定,产率:0.61克(41.5%)。
在减压下浓缩初始有机层,得到玻璃状固体,用水研制后得到附加量的标题化合物,为褐色固体,NMR和质谱分析鉴定了该化合物;产率:0.310克(21.1%);熔点:150℃(分解)。
实施例8
3-(5-羧基-4-氯-2-氟苯基)-1,2,3,4-二氢-1-甲基-6-三氟甲基嘧啶-2,4-二酮的制备
将三溴化硼(84.0毫升,0.0840摩尔,1M二氯甲烷溶液)滴加到3-(5-甲酯基-4-氯-2-氟苯基)-1,2,3,4-二氢-1-甲基-6-三氟甲基嘧啶-2,4-二酮(10.7克;0.0281摩尔)和二氯甲烷(150毫升)的混合物中。该混合物在室温下搅拌过夜,用冰水稀释。收集有机层,水层用乙酸乙酸萃取两次。将萃取液与有机层合并,用盐水洗,在无水硫酸镁上干燥,减压浓缩后得到标题化合物,为白色固体,NMR和质谱分析鉴定了该化合物:产率:10.2克(100%);熔点:240℃-241℃。
实施例9
S-氯磺酰胺的制备
将甲酸(10.8毫升,0.287摩尔)用时2小时滴加到异氰酸氯磺酰酯(25.0毫升,0.287摩尔)中,温度维持在低于20℃。该悬浮液在20℃搅拌2小时,然后用无水甲苯(100毫升)稀释。在环境温度下搅拌该混合物过夜,然后过滤,减压下浓缩滤液,得到标题化合物,为灰白色固体,IR光谱分析鉴定了该化合物。产率:32.1克(97.3%)。
实施例10
N-甲基磺酰胺的制备
将S-氯磺酰胺(3.00克,0.0260摩尔)的四氢呋喃(10毫升)溶液在10℃滴加到甲胺(40毫升,2M四氢呋喃溶液)中。所得混合物在0℃搅拌1小时,室温下搅拌3天。过滤该悬浮液,减压浓缩滤液,得到黄色固体。通过硅胶色谱(9∶1二氯甲烷-甲醇)得到标题化合物,为灰白色固体,NMR和质谱分析鉴定了该化合物。产率:1.36克(47.4%);
实施例11-15
N-取代的磺酰胺的制备
采用与实施例10基本上相同的步骤,通过取代适当的胺原料,制备下述化合物:
实施例 | R1 | R2 | mp.[℃] |
11 | H | CH2-C(CH3)3 | - |
12 | CH3 | CH2-CH=CH2 | 36-38 |
13 | CH3 | 苄基 | 91-94 |
14 | CH(CH3)2 | CH(CH3)2 | - |
15 | H | H | - |
实施例16
氨磺酸O-2,4,5-三氯苯酯的制备
在40-55℃用异氰酸氯磺酰酯(67.4毫升,0.476摩尔)滴加处理2,4,5-三氯苯酚(96.0克,0.486摩尔)的甲苯(95毫升)溶液。该混合物在回流温度搅拌3小时,冷却至40℃,用水猝灭至无气体释放。过滤该悬浮液,滤饼经空气干燥后得到标题化合物,为白色固体,NMR和IR光谱分析鉴定了该化合物。产率:118.5克(90.0%)。
实施例17
N-甲基-N-异丙基磺酰胺的制备
将三乙胺(2.50毫升,0.0181摩尔)加到甲基炔丙胺(1.55毫升,0.0181摩尔)的乙腈溶液中。向所得混合物中加入氨磺酸O-2,4,5-三氯苯酯(5.00克,0.0181摩尔)。室温下搅拌该混合物1小时,用二氯甲烷通过硅胶过滤,减压浓缩滤液,得到白色固体。该残余物通过硅胶色谱(0.5%甲醇-二氯甲烷),得到标题化合物,NMR光谱分析鉴定了该化合物。产率:1.84克(68.7%)。
实施例18-52
N-取代的磺酰胺的制备
采用与实施例17基本上相同的步骤,通过取代适当的胺原料,制备下述的磺酰胺:
实施例 | R1 | R2 | mp.[℃]/1H-NMR[ppm] |
18 | CH3 | CH3 | - |
19 | CH3 | 3-氯苄基 | - |
20 | CH3 | CH2-C2H5 | - |
21 | C2H5 | C2H5 | 39-41 |
22 | H | CH(CH3)-C2H5 | - |
23 | CH3 | C2H5 | 32-34 |
24 | H | C(CH3)3 | 49-53 |
25 | H | CH2-C2H5 | 32-35 |
26 | CH3 | 3-甲氧苄基 | - |
实施例 | R1 | R2 | mp.[℃]/1H-NMR[ppm] |
27 | CH3 | CH2-CH(CH3)2 | 103-104 |
28 | H | CH(CH3)2 | - |
29 | CH3 | CH(CH3)2 | 63-65 |
30 | H | C2H5 | - |
31 | C2H5 | CH2-C2H5 | - |
32 | H | CH2-CH2-CH (CH3)2 | - |
33 | CH3 | CH2-CH2-苯基 | - |
34 | CH3 | 苯基 | 84-86 |
35 | H | CH2-C≡CH | - |
36 | H | CH2-(2-呋喃基) | 62-64 |
37 | CH3 | CH(CH3)-C2H5 | - |
38 | H | CH2-(2-噻吩基) | 93-96 |
39 | H | 环戊基 | 55 |
40 | H | 4-甲氧苄基 | - |
41 | CH3 | CH2-CH2-C2H5 | - |
42 | CH3 | CH2-CH2-CN | - |
43 | CH3 | CH2-(1,3-二氧戊环基) | - |
44 | H | 4-氯苄基 | - |
45 | CH3 | C(CH3)3 | 54-57 |
46 | -CH2-CH=CH-CH2- | - | |
47 | H | 环丙基 | 58-60 |
48 | -CH2-CH2-CH2-CH2- | 84-86 | |
49 | CH3 | 环丙基 | - |
50 | C2H5 | CH(CH3)2 | - |
51 | H | CH2-CH(CH3)2 | - |
52 | H | CH2-CH2-C2H5 | - |
53 | CH3 | CH2-CO-OC2H5 | 5.1(br.,s,2H),4.25(q,2H),4.1(s,2H),3.0(s,3H),1.3(t,3H) |
实施例54
3-(5-(N,N-二甲基)氨磺酰羧酰氨基-4-氯-2-氟苯基)-1,2,3,4-二氢-6-三氟甲基嘧啶-2,4-二酮的制备
向3-(5-羧基-4-氯-2-氟苯基)-1,2,3,4-二氢-1-甲基-6-(三氟甲基)嘧啶-2,4-二酮(1.5克,4.09毫摩尔)的四氢呋喃溶液中加入N,N’-羰基二咪唑(1.00克,6.14毫摩尔)。所得混合物在回流温度下搅拌1小时,然后冷却至室温。加入二甲基磺酰胺(0.760克,6.14毫摩尔),10分钟后再加入二氮杂双环十一烷(0.930毫升,6.14摩尔)。所得混合物室温下搅拌过夜,然后减压浓缩。所得残余物在乙酸乙酯和盐酸(2N)间分配,保留有机层,水相用乙酸乙酯萃取三次。萃取液与保留的有机层合并,用10%碳酸氢钠洗涤,在无水硫酸镁上干燥,减压浓缩后得到第1份残余物。将水相酸化并用乙酸乙酯萃取。干燥有机层并减压浓缩,得到第2份残余物,将残余物合并。用乙酸乙酯洗涤,得到标题化合物,为白色固体,NMR和质谱分析鉴定了该化合物。产率:0.81克(42.0%);熔点:213-214℃。
实施例55-93
3-[5-(N-取代的)氨磺酰羧酰氨基-4-氯苯基)-1,2,3,4-二氢-6-(三氟甲基)嘧啶-2,4-二酮的制备
采用了实施例54所述基本相同的步骤,通过取代适当的磺酰胺原料,得到下述化合物:
实施例号 | X1 | R1 | R2 | R29 | mp.[℃] |
55 | F | CH3 | 3-氯苄基 | CH3 | 78-79 |
56 | F | H | CH3 | CH3 | 232-233 |
57 | F | CH3 | CH2-C≡CH | CH3 | 195-196 |
58 | F | H | H | CH3 | 141-142 |
59 | F | CH3 | 烯丙基 | CH3 | 189 |
60 | F | CH(CH3)2 | CH(CH3)2 | CH3 | 81-82 |
61 | F | CH3 | 苄基 | CH3 | 90-91 |
62 | F | C2H5 | CH2-C2H5 | CH3 | 74-76 |
63 | F | H | CH2-C2H5 | CH3 | 206-207 |
64 | F | H | CH(CH3)-C2H5 | CH3 | 221 |
65 | F | H | C(CH3)3 | CH3 | 115 |
66 | F | CH3 | C2H5 | CH3 | 215-216 |
67 | F | CH3 | CH2-C2H5 | CH3 | 72 |
68 | F | C2H5 | C2H5 | CH3 | 210-211 |
69 | F | CH3 | CH(CH3)-C2H5 | CH3 | 74 |
70 | F | CH3 | 3-甲氧苄基 | CH3 | 79 |
71 | F | H | CH2-C≡CH | CH3 | 195-196 |
72 | F | H | CH2-CH2-CH(CH3)2 | CH3 | 222-223 |
73 | F | CH3 | 苯基 | CH3 | 104-105 |
74 | F | CH3 | CH2-CH2-苯基 | CH3 | 90-91 |
75 | F | CH3 | 苯基 | NH2 | 120-142 |
76 | F | CH3 | CH(CH3)2 | NH2 | 117-120 |
77 | F | H | CH2-(2-噻吩基) | CH3 | 127-128 |
78 | F | H | 环戊基 | CH3 | 232-233 |
79 | F | H | CH(CH3)2 | CH3 | 221 |
80 | F | H | C2H5 | CH3 | 211 |
81 | F | H | CH2-(2-呋喃基) | CH3 | 178-180 |
82 | F | H | 4-甲氧苄基 | CH3 | 186-188 |
83 | F | CH3 | CH2-CH2-C2H5 | CH3 | 156-157 |
84 | F | CH3 | CH2-CH2-CN | CH3 | 99-103 |
85 | F | CH3 | CH2-(1,3-二氧戊环基) | CH3 | 93-96 |
实施例号 | X1 | R1 | R2 | R29 | mp.[℃] |
86 | F | H | 4-氯苄基 | CH3 | 95-99 |
87 | F | CH3 | C(CH3)3 | CH3 | 126 |
88 | F | -CH2-CH=CH-CH2- | CH3 | 231 | |
89 | F | H | 环丙基 | CH3 | 208 |
90 | F | -CH2-CH2-CH2-CH2- | CH3 | 230 | |
91 | F | CH3 | 环丙基 | CH3 | 156 |
92 | F | C2H5 | CH(CH3)2 | CH3 | 146 |
93 | F | H | CH2-CH(CH3)2 | CH3 | 202 |
94 | F | H | CH2-CH2-C2H5 | CH3 | 227 |
95 | H | CH3 | 苯基 | CH3 | 108-110 |
96 | F | CH3 | 4-(甲氧羰基)苯基 | CH3 | 102 |
97 | F | C2H5 | 苯基 | CH3 | 214-215 |
98 | F | CH3 | 3-吡啶基 | CH3 | 208 |
99 | F | CH3 | 3,4-二氯苯基 | CH3 | 118 |
100 | F | CH3 | 3-氯苯基 | CH3 | 183-184 |
101 | F | CH3 | CH(CH3)2 | CH3 | 93-95 |
102 | F | CH3 | CH3 | NH2 | 252 |
103 | H | CH3 | CH2-C≡CH | CH3 | 228.2-229.0 |
104 | F | CH3 | 4-甲氧苯基 | CH3 | 136-138 |
105 | F | CH3 | 4-氯苯基 | CH3 | 110-111 |
106 | F | CH3 | 4-硝基苯基 | CH3 | 111-112 |
107 | F | CH3 | 4-甲基苯基 | CH3 | 102 |
108 | H | H | H | CH3 | 143.5-145.8 |
109 | H | CH3 | CH2-C2H5 | CH3 | 187.0-189.5 |
110 | H | CH3 | C2H5 | CH3 | 245.5-246.0 |
111 | H | CH3 | CH2-CH(CH3)2 | CH3 | 164.1-164.7 |
112 | H | C2H5 | C2H5 | CH3 | 244.4-245.4 |
113 | H | CH3 | CH2-CH2-C2H5 | CH3 | 167.9-172.0 |
114 | H | CH3 | CH3 | CH3 | 228.8-231.5 |
115 | F | CH3 | 2-甲基苯基 | CH3 | 125-127 |
116 | F | CH3 | 3-甲基苯基 | CH3 | 187-189 |
117 | F | CH3 | α-萘基 | CH3 | 131-133 |
118 | F | CH3 | 2,4-二氟苯基 | CH3 | 118-119 |
119 | F | CH3 | 2-氯苯基 | CH3 | 133 |
120 | F | CH3 | 2-(三氟甲基)苯基 | CH3 | 98-106 |
121 | H | CH3 | 4-(苯氧基)苯基 | CH3 | 95 |
122 | F | CH3 | 4-(三氟甲基)苯基 | CH3 | 133 |
123 | F | CH3 | 4-(二甲氨基)苯基 | CH3 | 87 |
实施例135
N’-{2-氯-4-氟-5-[4-(二氟甲基)-4,5-二氢-3-甲基-5-氧代-1H-1,2,4-三唑-1-基]-苯甲酰基}-N-异丙基-N-甲基磺酰胺的制备
步骤1:
2-(2-氟-4-氯-5-甲酯基苯基腙基(hydrazonyl))丙酸
将丙酮酸(3.92克,44.5毫摩尔)与水(4毫升)的溶液加入到肼x1(8.00克,36.6毫摩尔)、乙醇(240毫升)和盐酸(10%浓度,37毫升)的混合物中,将该混合物在45-60℃搅拌35分钟,冷却到30℃并过滤。在减压下将滤液浓缩到原体积的约50%,并缓慢加入到水(700毫升)中。将得到的悬浮液搅拌20分钟并过滤。得到9.60克标题化合物(产率90.9%),为黄色固体。
步骤2:
2-氯-4-氟-5-[4,5-二氢-3-甲基-5-氧代-1H-1,2,4-三唑-1基]-苯甲酸甲酯
将由步骤1得到的腙(9.00克,31.0毫摩尔)和三乙胺(4.35毫升,31.0毫摩尔)的混合物加热到50℃并用叠氮化物12(7.98克,29.0毫摩尔)和甲苯(10毫升)的混合物处理。将所得到的混合物在50℃下搅拌100分钟,冷却到室温并在减压下浓缩。将残余物分配在水和乙酸乙酯之间。将有机层干燥并在减压下浓缩,得到6.35克(产率71.8%)标题化合物,为灰白色固体。该产物不经进一步处理而直接用于下一步骤。
步骤3:
2-氯-4-氟-5-[4-(二氟甲基)-4,5-二氢-3-甲基-5-氧代-1H-1,2,4-三唑-1-基]-苯甲酸甲酯
将过量的一氯二氟甲烷(97克)在30分钟内鼓泡通入到步骤2得到的三唑啉酮(7.04克,24.6毫摩尔)、四丁基溴化铵(9.67克,30.0毫摩尔)、碳酸钾(16.6克,122毫摩尔)和二甲基甲酰胺(200毫升)的混合物中,并使温度<36℃。将混合物冷却并过滤。在减压下浓缩滤液,并在水和二氯甲烷之间分配残余物。用水洗涤有机层,干燥并在减压下浓缩,得到9.00克深色油。将该油用硅胶层析(洗脱剂:乙酸乙酯/己烷),得到1.48克标题化合物,产率17.9%。
步骤4
2-氯-4-氟-5-[4-(二氟甲基)-4,5-二氢-3-甲基-5-氧代-1H-1,2,4-三唑-1-基]-苯甲酸(IIba)
将含有酯II(其中Q=Q5,R7=CHF2,A4=O,R8=CH3,X1=F,X2=Cl)(0.950克,2.83毫摩尔)、乙酸(10毫升)和盐酸(6N,5.0毫升)的混合物于64-100℃搅拌24小时,冷却到室温并在减压下浓缩。在水和二氯甲烷之间分配残余物。用水洗涤有机层两次,干燥并在减压下浓缩,得到0.42克标题化合物(产率46%),为淡黄色固体(熔点132-135℃)。
步骤5
N’-[[2-氯-4-氟-5-[4-(二氟甲基)-4,5-二氢-3-甲基-5-氧代-1H-1,2,4-三唑-1-基]-苯甲酰基]]-N-异丙基-N-甲基磺酰胺
将含有酸II(0.370克,1.15毫摩尔)、磺酰胺(0.210克,1.38毫摩尔)、羰基二咪唑(0.244克,1.50毫摩尔)、DBU(0.228克,1.50毫摩尔)和四氢呋喃的混合物在室温下搅拌4天。将得到的混合物再用磺酰胺(0.150克,0.986毫摩尔)和DBU(0.150克,0.986毫摩尔)处理。将混合物回流两个小时,冷却并在减压下浓缩。将残余物用水溶解并用盐酸(1N)酸化。用二氯甲烷萃取该混合物四次。用水洗涤萃取液,干燥并在减压下浓缩,将得到的黄色油用硅胶层析(洗脱剂:乙酸乙酯/己烷),得到0.160克标题化合物(产率30.5%),为灰白色固体,熔点为118-122℃。
实施例136
N’-{2-氯-4-氟-5-(5,6,7,8-四氢-3-氧代-1,2,4-三唑并[4,3-a]吡啶-2(3H)-基)-苯甲酰基}-N,N-二烷基磺酰胺的制备
步骤1:
2-氯-4-氟-5-(5,6,7,8-四氢-3-氧代-1,2,4-三唑并[4,3-a]吡啶-2(3H)-基)-苯甲酸
将三溴化硼(19.4毫升,19.4毫摩尔,1N二氯甲烷溶液)滴加到化合物I(其中A=O,X1=F,X2=Cl,Q=Q5,A4=O且R7+R8=-(CH2)4-(1.90克,5.54毫摩尔)和二氯甲烷(20毫升)的混合物中。将得到的混合物于室温下搅拌过夜。滴加水(40毫升)并于室温下搅拌混合物3小时。分离有机层,并使其在减压下浓缩,得到1.34克标题化合物(产率:77.4%),为淡黄色固体,熔点为91-94℃。
步骤2:
N’-{2-氯-4-氟-5-(5,6,7,8-四氢-3-氧代-1,2,4-三唑并[4,3-a]吡啶-2(3H)-基)-苯甲酰基}-N-异丙基-N-甲基磺酰胺
将羰基二咪唑(0.500克,3.08毫摩尔)加入到步骤1的化合物(0.640克,2.05毫摩尔)的无水二氯甲烷(15毫升)溶液中。将得到的混合物于室温下搅拌30分钟,升至回流温度并立即冷却到室温。加入磺酰胺(0.370克,2.46毫摩尔)和DBU(0.470克,3.08毫摩尔),并将得到的混合物于室温下搅拌过夜。将该混合物用乙酸乙酯(10毫升)和3%浓度的盐酸(15毫升)稀释,并搅拌10分钟。减压除去二氯甲烷后,得到水相残余物,并用乙酸乙酯萃取该水相残余物。将合并的有机层用水和盐水洗涤,用无水硫酸镁干燥。经减压浓缩和在二氯甲烷中重结晶,得到一种固体。将该固体溶解于二氯甲烷,并用甲醇/二氯甲烷经碱性氧化铝柱过滤,得到0.360克标题化合物(产率:39.4%),为白色固体,熔点为250-251℃。
实施例137
用与实施例136中所介绍的方法相同的方法和磺酰胺H2N-SO2-N(CH3)-苯基,分离出了下面的化合物,为白色固体,熔点为200-201℃。
实施例138
N’-[2-氯-5-(3,5-二甲基-2,6-二氧代-4-硫代-1,3,5-三嗪烷-1-基)-4-氟苯甲酰基]-N-异丙基-N-甲基磺酰胺的制备
于60℃,用0.283克(1.74毫摩尔)N,N-羰基二咪唑处理溶于5毫升四氢呋喃中的0.502克(1.45毫摩尔)酸III(其中X1=F,X2=Cl,Q=Q22,R32和R33=CH3,A15和A16=O且A17=S)的溶液。在将此溶液冷却到室温后,向其中加入0.287克(1.89毫摩尔)N,N-甲基二异丙基磺酰胺和0.276克(1.82毫摩尔)DBU于10毫升四氢呋喃中的溶液,并搅拌该混合物过夜。在减压除去挥发性物质后,粗产物用乙酸乙酯和环己烷经硅胶层析,得到0.180克所需的产物。1H-NMR(270MHz;CDCl3):δ[ppm]=1.25(d,6H),2.95(s,3H,SO2-NCH3),3.8(s,6H,NCH3),4.3(m,1H),7.4(d,1H,Ar-H),7.8(d,1H,Ar-H),8.9(bs,1H,NH)。
实施例139
N’-[2-氯-4-氟-5-(5-三氟甲基哒酮(pyridazon)-3-酮-2-基)-苯甲酰基]-N-异丙基-N-甲基亚磺酰胺的制备
步骤1:
2-氟-4-氯-5-(5-三氟甲基哒嗪-3-酮-2-基)-苯甲酸
将哒嗪酮酯II(其中X1=F,X2=Cl,Q=Q27,R34=H,R35=CF3,R36=H)(3克,8.56毫摩尔)溶于无水二氯甲烷(100毫升)中。将三溴化硼溶液(30毫升,1M二氯甲烷溶液,30毫摩尔)加入到该溶液中,并将该混合物在室温下搅拌17小时。向其中加入水(50毫升)并剧烈搅拌混合物3小时。用旋转蒸发器除去二氯甲烷,并将悬浮的固体过滤、用水洗涤、干燥,得到2.76克产物,为淡黄色固体。产率:95%。
用上文相同的方法,酯II(其中X1=F,X2=Cl,Q=Q27,R34=H,R35=CF3,R36=CH3)被转化为相应的酸III,产率为97%。
步骤2:
N’-{2-氯-4-氟-5-(5-三氟甲基哒酮-3-酮-2-基)-苯甲酰基}-N-异丙基-N-甲基亚磺酰胺
将羧酸III(其中X1=F,X2=Cl,Q=Q27,R34=H,R35=CF3,R36=CH3)(0.71克,2.10毫摩尔)溶于无水四氢呋喃(15毫升)中,并一次加入CDI(0.51克,3.15毫摩尔)。将混合物在室温下搅拌30分钟。将该混合物回流5分钟,然后冷却到室温。加入磺酰胺(0.32克,2.10毫摩尔),然后加入DBU(0.48克,3.15毫摩尔)。在室温下搅拌混合物17小时。向反应中加入5%浓度的盐酸(15毫升)和乙酸乙酯(10毫升),并剧烈搅拌混合物10分钟。用乙酸乙酯萃取混合物(3×15毫升),并将合并的萃取液用水洗涤,用硫酸镁干燥,并用旋转蒸发器浓缩,得到棕色半固体。将粗产物用碱性氧化铝柱层析纯化(洗脱液:二氯甲烷,1%,2%甲醇/二氯甲烷,然后1%乙酸/二氯甲烷),得到终产物Ida.xxx(0.45克),为灰白色固体,产率45%,熔点:82℃。
下列化合物是用同样的方法和合适的酸和磺酰胺制备的:
(A=O;X1=F;X2=Cl;X3=H;Q=Q27;A13=O;R34=H;R35=CF3)
实施例号 | R1 | R2 | R36 | mp.[℃] |
140 | CH3 | 苯基 | H | 182 |
141 | CH3 | 苯基 | CH3 | 74-75 |
142 | CH3 | CH(CH3)2 | CH3 | 181-182 |
143 | CH3 | CH3 | CH3 | 205-206 |
144 | CH3 | CH3 | H | 184-186 |
实施例145
4-氯-3-[4-氯-2-氟-5-(N-甲基-N-异丙基)-氨磺酰羧酰胺基苯基]-5-二氟甲氧基-1-甲基-1H-吡唑的制备
用N,N’-羰基二咪唑(1.13克,6.98毫摩尔)处理3-[5-羧基-4-氯-2-氟苯基]-4-氯-5-二氟甲氧基-1-甲基-1H-吡唑(2.00克,5.63毫摩尔)的四氢呋喃溶液,并将该溶液在回流条件下搅拌1小时,冷却到室温,用N-甲基-N-异丙基磺酰胺(1.10克,7.23毫摩尔)处理,搅拌10分钟,用二氮杂双环十一碳烯(1.06克,6.97毫摩尔)处理,于室温搅拌过夜并在减压下浓缩。用硅胶层析(环己烷/乙酸乙酯=4∶1),得到0.90克粗产物。再用环己烷/乙酸乙酯(4∶1)结晶得到0.45克(16.4%)的标题化合物(用NMR分析)。1H-NMR(CDCl3):δ[ppm]=8.8(s,1H,NH),8.0(d,1H),7.3(d,1H),6.7(t,1H),4.3(hpt,1H),3.8(s,3H),3.0(s,3H),1.2(d,6H)。
步骤1:2-氯-5-[3-氯-5-(三氟甲基)-2-吡啶基]-4-氟-苯甲酸
将溶于25毫升冰醋酸和125毫升浓盐酸中的5.3克(13.4毫摩尔)异丙基酯II(其中A=O,X1=F,X2=Cl,X3=H,Q=Q38,R40=Cl,R41和R43=H且R42=CF3)于70℃搅拌6小时并于室温搅拌过夜。然后,将反应混合物滴入冰水中,滤出沉淀物并用水洗,得到4.1克白色固体。1H-NMR[(CD3)2SO]:δ[ppm]=9.1(s,1H),8.7(s,1H),8.1(d,1H),7.8(d,1H)。(注:OH质子与水的质子的交换导致在3.3ppm处出现宽单峰(singulett))。
步骤2:
N’-[[2-氯-5-[3-氯-5-(三氟甲基)-2-吡啶基]-4-氟苯甲酰基]]-N-异丙基-N-甲基磺酰胺
将步骤1的1.0克(2.8毫摩尔)游离酸溶于10毫升四氢呋喃,向其中加入0.57克(3.5毫摩尔)羰基二咪唑,并将混合物于60℃加热1小时,冷却到室温。然后,向其中加入由0.55克(3.6毫摩尔)磺酰胺和0.54克(3.5毫摩尔)1,8-二氮杂双环[5,4,0]十一碳-7-烯于10毫升四氢呋喃中的溶液组成的混合物,并在室温下继续搅拌过夜。除去溶剂,将粗产物用甲基叔丁基醚和乙酸乙酯经柱色谱层析。将含产物的级分溶于甲基叔丁基醚,用10%浓度的盐酸洗涤三次,用水洗涤两次,用硫酸钠干燥。除去溶剂后,得到0.48克油状的标题化合物。1H-NMR[(CD3)2SO]:δ[ppm]=9.1(s,1H),8.7(s,1H),7.8-7.7(m,2H),4.1(m,1H),2.7(s,3H),1.1(m,6H)。(注:OH质子与水的质子的交换导致在3.3ppm处出现宽单峰)。
实施例146
8-(5’-N-异丙基-N-甲基氨磺酰羧酰胺基-4’-氯-2’-氟苯基)-4-氧代-7,9-二氧代-1,2,8-三氮杂(4.3.0)壬烷
将5.4克(45.5毫摩尔)亚硫酰氯加入到12.0克(36.4毫摩尔)酸III(其中X1=F,X2=Cl,Q=Q40,A20和A21=O,R46+R47=-(CH2)3-O-)和2滴吡啶于200毫升1,2-二氯乙烷中的混合物中。在83℃下4小时后,在减压下除去挥发性物质,并不经进一步纯化而直接使用得到的粗制酰氯(12.6克):
将溶于50毫升四氢呋喃中的0.44克(2.87毫摩尔)N-异丙基-N-甲基氨基磺酰胺加入到0.07克氢化钠(97%纯度)于50毫升四氢呋喃中的悬浮液中。置于室温下30分钟后,向其中加入1.0克(2.87毫摩尔)粗制酰氯,并在室温下搅拌反应混合物过夜,然后再在50℃搅拌2小时。减压除去溶剂,加入1N盐酸和二氯甲烷,分离有机层。经硅胶层析得到0.35克标题化合物,熔点为115-120℃。
除草活性的使用实施例
实施例147
试验化合物的出苗后除草活性评估
本发明化合物的除草活性按下述试验方法评估。
让植物秧苗在栽培架(jiffy flat)上生长约两周。将试验化合物分散于含有1.0%SUN-IT_II(甲基化种子油)的80/20丙酮/水混合物中,其量为在试验中用在40psi下工作的喷嘴在规定的时间内将其施用于植物上时足以产生相当于每公顷约0.016-0.032千克活性化合物的效果。喷施后,将植物置于温室的架子上,并按常规温室程序管理。大约在处理后二到三周,检查秧苗植物并根据下文所述的评价标准(0-9)进行评价。若某一化合物被测试了一次以上,则取平均值。下表I给出了测试结果。若某一化合物被测试了一次以上,则取平均值。
除草剂评分 | |
评分 | 与未处理对照相比较的%控制 |
9 | 100 |
8 | 91-99 |
7 | 80-90 |
6 | 65-79 |
5 | 45-64 |
4 | 30-44 |
3 | 16-29 |
2 | 6-15 |
1 | 1-5 |
0 | 0 |
该评分基于对植物挺立(stand)、活力(vigor)、畸形、尺寸、萎黄病(chlorosis)和总体植物外观的肉眼观察(与对照相比较)。
在这些评估中所用的植物品种以词头缩写、通用名和学名报道。
使用的植物品种 | ||
词头缩写 | 通用名 | 学名 |
ABUTH | 苘麻 | Abutilon theophrasti,Medic. |
AMBEL | 豚草 | Ambrosia artemiisifolia,L. |
CHEAL | 藜 | Chenopodium album,L.Common |
IPOHE | 土瓜(Morningglory,Ivyleaf) | Ipomoea hederacea,(L)Jacq. |
XANST | 欧洲苍耳 | Xanthium strumariam |
ALOMY | 看麦娘 | Alopecurus myosuroides |
DIGSA | 马唐 | Digitaria sanguinalis,(L)Scop |
ECHCG | 稗 | Echinochloa crusgalli,(L.)Beau |
SETVI | 狗尾草 | Setaria viridis,(L.)Beau |
GLXMA | 大豆 | Glycine max,(L.)Merr. |
TRZAW | 冬小麦 | Tritium Aestivum,L.(Winter) |
ZEAMX | 玉蜀黍 | Zea mays L. |
表A
出苗后除草效果评估
实施例 | 用量[kg/ha] | ABUTH | AMBEL | CHEAL | IPOHE | XANST | ALMOY | DIGSA | ECHCG | SETVI | GLXMA | TRZAW | ZEAMX |
53 | 0.032 | 9.0 | 9.0 | 8.4 | 9.0 | 9.0 | 3.0 | 6.6 | 8.8 | 7.5 | 8.4 | 6.2 | 7.6 |
0.016 | 9.0 | 8.9 | 8.1 | 8.8 | 9.0 | 2.3 | 5.3 | 8.1 | 6.4 | 8.1 | 5.6 | 7.2 | |
54 | 0.032 | 9.0 | 9.0 | 9.0 | 9.0 | 9.0 | 2.0 | 6.0 | 8.0 | 7.0 | 8.5 | 6.0 | 7.5 |
0.016 | 9.0 | 9.0 | 9.0 | 9.0 | 9.0 | 2.0 | 5.0 | 6.0 | 7.0 | 8.0 | 5.5 | 6.5 | |
55 | 0.032 | 9.0 | 9.0 | 7.0 | 9.0 | 8.0 | 2.0 | 6.0 | 7.0 | 8.0 | 8.0 | 6.0 | 8.0 |
0.016 | 9.0 | 8.0 | 7.0 | 8.0 | 9.0 | 2.0 | 5.0 | 7.0 | 7.0 | 8.0 | 6.0 | 8.0 | |
56 | 0.032 | 9.0 | 9.0 | 7.0 | 9.0 | 9.0 | 2.0 | 5.0 | 7.0 | 7.0 | 8.5 | 5.0 | 8.0 |
0.016 | 9.0 | 8.0 | 7.0 | 9.0 | 9.0 | 2.0 | 3.0 | 7.0 | 6.0 | 8.5 | 4.0 | 7.5 | |
57 | 0.032 | 5.0 | 2.0 | 2.0 | 4.0 | 3.0 | 1.0 | 2.0 | 2.0 | 3.0 | 6.5 | 2.5 | 5.0 |
0.016 | 2.0 | 1.0 | 1.0 | 6.0 | 2.0 | 0.0 | 1.0 | 1.0 | 1.0 | 6.0 | 2.0 | 2.0 | |
58 | 0.032 | 9.0 | 9.0 | 9.0 | 9.0 | 9.0 | 3.0 | 6.0 | 7.0 | 8.0 | 8.5 | 5.0 | 8.0 |
0.016 | 9.0 | 9.0 | 8.0 | 9.0 | 9.0 | 3.0 | 5.0 | 6.0 | 8.0 | 8.5 | 4.5 | 8.0 | |
59 | 0.032 | 9.0 | 9.0 | 8.0 | 9.0 | 9.0 | 4.0 | 5.0 | 7.0 | 8.0 | 8.5 | 4.5 | 8.0 |
0.016 | 9.0 | 7.0 | 7.0 | 9.0 | 9.0 | 3.0 | 4.0 | 6.0 | 7.0 | 8.0 | 4.0 | 8.0 |
续表A
实施例 | 用量[kg/ha] | ABUTH | AMBEL | CHEAL | IPOHE | XANST | ALMOY | DIGSA | ECHCG | SETVI | GLXMA | TRZAW | ZEAMX |
60 | 0.032 | 9.0 | 9.0 | 9.0 | 9.0 | 9.0 | 3.0 | 7.0 | 7.0 | 9.0 | 8.5 | 6.0 | 8.0 |
0.016 | 9.0 | 9.0 | 8.0 | 9.0 | 9.0 | 3.0 | 6.0 | 8.0 | 8.0 | 8.5 | 6.0 | 8.0 | |
61 | 0.032 | 9.0 | 9.0 | 8.0 | 9.0 | 9.0 | 1.0 | 6.0 | 8.0 | 9.0 | 8.5 | 6.5 | 7.5 |
0.016 | 9.0 | 9.0 | 9.0 | 8.0 | 9.0 | 1.0 | 7.0 | 7.0 | 7.0 | 8.5 | 6.0 | 7.5 | |
62 | 0.032 | 9.0 | 9.0 | 8.0 | 9.0 | 9.0 | 2.0 | 5.0 | 7.0 | 6.0 | 8.0 | 6.5 | 6.5 |
0.016 | 9.0 | 9.0 | 7.0 | 9.0 | 9.0 | 2.0 | 5.0 | 6.0 | 6.0 | 8.0 | 5.5 | 6.5 | |
63 | 0.032 | 9.0 | 9.0 | 9.0 | 9.0 | 9.0 | 2.0 | 4.0 | 6.0 | 9.0 | 8.0 | 7.0 | 8.0 |
0.016 | 9.0 | 9.0 | 7.0 | 9.0 | 9.0 | 2.0 | 4.0 | 4.0 | 7.0 | 8.0 | 6.0 | 7.0 | |
64 | 0.032 | 9.0 | 9.0 | 9.0 | 9.0 | 9.0 | 5.0 | 5.0 | 9.0 | 9.0 | 8.0 | 7.0 | 8.0 |
0.016 | 9.0 | 9.0 | 9.0 | 9.0 | 9.0 | 3.0 | 5.0 | 9.0 | 8.0 | 7.5 | 6.0 | 7.5 | |
65 | 0.032 | 9.0 | 9.0 | 9.0 | 9.0 | 9.0 | 3.0 | 8.0 | 9.0 | 8.0 | 8.5 | 6.5 | 8.0 |
0.016 | 9.0 | 9.0 | 8.0 | 9.0 | 9.0 | 2.0 | 6.0 | 8.0 | 8.0 | 8.0 | 5.5 | 7.5 | |
66 | 0.032 | 9.0 | 9.0 | 9.0 | 9.0 | 9.0 | 2.0 | 6.0 | 8.0 | 9.0 | 9.0 | 6.5 | 7.5 |
0.016 | 9.0 | 9.0 | 8.0 | 9.0 | 9.0 | 1.0 | 5.0 | 8.0 | 8.0 | 8.0 | 5.0 | 7.0 | |
67 | 0.032 | 9.0 | 9.0 | 9.0 | 9.0 | 9.0 | 3.0 | 6.0 | 8.0 | 8.0 | 8.5 | 7.0 | 7.5 |
0.016 | 9.0 | 9.0 | 9.0 | 9.0 | 9.0 | 2.0 | 6.0 | 8.0 | 8.0 | 8.0 | 6.5 | 7.5 |
续表A
实施例 | 用量[kg/ha] | ABUTH | AMBEL | CHEAL | IPOHE | XANST | ALMOY | DIGSA | ECHCG | SETVI | GLXMA | TRZAW | ZEAMX |
68 | 0.032 | 9.0 | 9.0 | 8.0 | 9.0 | 9.0 | 1.0 | 6.0 | 8.0 | 9.0 | 8.5 | 5.5 | 7.5 |
0.016 | 9.0 | 9.0 | 8.0 | 9.0 | 9.0 | 1.0 | 6.0 | 8.0 | 7.0 | 8.5 | 5.0 | 7.0 | |
69 | 0.032 | 9.0 | 9.0 | 8.0 | 9.0 | 9.0 | 2.0 | 6.0 | 7.0 | 6.0 | 8.0 | 6.5 | 7.5 |
0.016 | 9.0 | 9.0 | 8.0 | 9.0 | 9.0 | 1.0 | 4.0 | 5.0 | 5.0 | 8.0 | 5.0 | 7.0 | |
70 | 0.032 | 9.0 | 7.0 | 7.0 | 9.0 | - | 1.0 | 3.0 | 8.0 | 5.0 | 7.5 | 5.0 | 7.0 |
0.016 | 9.0 | 5.0 | 6.0 | 9.0 | - | 1.0 | 2.0 | 4.0 | 4.0 | 6.5 | 4.5 | 7.0 | |
71 | 0.032 | 9.0 | 9.0 | 5.0 | 9.0 | - | 1.0 | 3.0 | 3.0 | 5.0 | 8.0 | 4.5 | 6.5 |
0.016 | 9.0 | 6.0 | 5.0 | 8.0 | - | 1.0 | 2.0 | 2.0 | 4.0 | 8.0 | 4.5 | 6.5 | |
72 | 0.032 | 9.0 | 9.0 | 8.0 | 9.0 | - | 2.0 | 4.0 | 8.0 | 6.0 | 8.5 | 6.5 | 7.0 |
0.016 | 9.0 | 9.0 | 8.0 | 9.0 | - | 1.0 | 4.0 | 6.0 | 5.0 | 8.5 | 5.5 | 7.0 | |
73 | 0.032 | 9.0 | 9.0 | 9.0 | 9.0 | - | 3.0 | 6.0 | 7.0 | 5.0 | 8.5 | 6.5 | 7.5 |
0.016 | 9.0 | 9.0 | 8.0 | 9.0 | - | 2.0 | 4.0 | 4.0 | 4.0 | 8.5 | 5.5 | 7.0 | |
76 | 0.032 | 9.0 | 8.0 | 6.0 | 9.0 | 9.0 | 1.0 | 4.0 | 6.0 | 6.0 | 7.5 | 6.0 | 6.5 |
0.016 | 9.0 | 8.0 | 6.0 | 9.0 | 9.0 | 1.0 | 3.0 | 5.0 | 5.0 | 7.5 | 5.0 | 5.5 | |
77 | 0.032 | 9.0 | 8.0 | 7.0 | 9.0 | 9.0 | 1.0 | 4.0 | 6.0 | 6.0 | 7.5 | 5.0 | 6.5 |
0.016 | 9.0 | 8.0 | 6.0 | 9.0 | 9.0 | 1.0 | 4.0 | 4.0 | 5.0 | 7.5 | 4.5 | 6.0 |
续表A
实施例 | 用量[kg/ha] | ABUTH | AMBEL | CHEAL | IPOHE | XANST | ALMOY | DIGSA | ECHCG | SETVI | GLXMA | TRZAW | ZEAMX |
78 | 0.032 | 9.0 | 9.0 | 9.0 | 9.0 | 9.0 | 2.0 | 6.0 | 9.0 | 9.0 | 8.0 | 6.5 | 7.0 |
0.016 | 9.0 | 9.0 | 7.0 | 9.0 | 9.0 | 2.0 | 5.0 | 8.0 | 8.0 | 7.0 | 5.5 | 6.5 | |
80 | 0.032 | 9.0 | 8.0 | 4.0 | 9.0 | 9.0 | 1.0 | 4.0 | 6.0 | 6.0 | 8.0 | 4.0 | 4.0 |
0.016 | 7.0 | 7.0 | 3.0 | 9.0 | 8.0 | 0.0 | 3.0 | 4.0 | 5.0 | 8.0 | 3.0 | 1.5 | |
82 | 0.032 | 9.0 | 9.0 | 9.0 | 9.0 | 9.0 | 2.0 | 3.0 | 8.0 | 7.0 | 8.5 | 6.0 | 6.5 |
0.016 | 9.0 | 9.0 | 9.0 | 9.0 | 9.0 | 1.0 | 3.0 | 7.0 | 6.0 | 8.0 | 5.5 | 6.5 | |
83 | 0.032 | 9.0 | 8.0 | 5.0 | 9.0 | 9.0 | 1.0 | 4.0 | 8.0 | 8.0 | 7.5 | 5.5 | 6.0 |
0.016 | 9.0 | 6.0 | 5.0 | 8.0 | 9.0 | 0.0 | 3.0 | 8.0 | 7.0 | 7.0 | 4.5 | 5.5 | |
84 | 0.032 | 9.0 | 9.0 | 9.0 | 9.0 | 9.0 | 2.0 | 6.0 | 9.0 | 8.0 | 8.5 | 5.5 | 8.0 |
0.016 | 9.0 | 8.0 | 7.0 | 9.0 | 9.0 | 1.0 | 5.0 | 8.0 | 7.0 | 7.0 | 5.0 | 7.0 |
实施例148:试验化合物的出苗前除草效果评估
本发明化合物的除草活性通过下列试验评估,其中将各种单子叶和双子叶植物的种子单独与罐装土壤混合并在单独的品脱(pint)杯中种植在约1英寸土壤的顶部。种植后,将杯用选定的丙酮水溶液喷雾,该溶液含有足以提供约0.125-0.250kg/ha试验化合物/杯的试验化合物。然后将已处理的杯放置在温室架上,浇水并按常规温室程序管理。在处理开始2-4周后,终止试验并根据实施例94所提供的评分体系检查和评估各杯。若某一化合物被测试了一次以上,则取平均值。所得结果示于表B中。
表B
出苗前除草效果评估
实施例 | 用量[kg/ha] | ABUTH | AMBEL | CHEAL | IPOHE | XANST | ALMOY | DIGSA | ECHCG | SETVI | GLXMA | TRZAW | ZEAMX |
53 | 0.25 | 9.0 | 9.0 | 9.0 | 9.0 | 9.0 | 2.7 | 8.8 | 8.4 | 7.3 | 8.8 | 2.0 | 4.3 |
0.125 | 9.0 | 8.9 | 9.0 | 9.0 | 9.0 | 1.3 | 8.1 | 7.5 | 5.7 | 8.1 | 1.3 | 2.3 | |
54 | 0.25 | 9.0 | 8.0 | 9.0 | 1.0 | 3.0 | 0.0 | 6.0 | 3.0 | 3.0 | 0.0 | 0.0 | 0.0 |
0.125 | 9.0 | 7.0 | 9.0 | 0.0 | 1.0 | 0.0 | 4.0 | 3.0 | 2.0 | 0.0 | 0.0 | 0.0 | |
55 | 0.25 | 9.0 | 9.0 | 9.0 | 9.0 | 7.0 | 0.0 | 8.0 | 9.0 | 8.0 | 8.0 | 2.0 | 1.0 |
0.125 | 9.0 | 8.0 | 8.0 | 8.0 | 6.0 | 0.0 | 8.0 | 5.0 | 6.0 | 8.0 | 1.0 | 0.0 | |
56 | 0.25 | 9.0 | 9.0 | 9.0 | 9.0 | 9.0 | 0.0 | 7.0 | 7.0 | 8.0 | 9.0 | 0.0 | 2.0 |
0.125 | 9.0 | 9.0 | 9.0 | 8.0 | 8.0 | 0.0 | 7.0 | 3.0 | 4.0 | 2.0 | 0.0 | 0.0 | |
57 | 0.25 | 2.0 | 2.0 | 8.0 | 3.0 | 0.0 | 0.0 | 3.0 | 2.0 | 1.0 | 1.0 | 0.0 | 0.0 |
0.125 | 2.0 | 2.0 | 6.0 | 0.0 | 0.0 | 0.0 | 1.0 | 1.0 | 0.0 | 0.0 | 0.0 | 0.0 | |
58 | 0.25 | 9.0 | 9.0 | 9.0 | 9.0 | 8.0 | 0.0 | 3.0 | 6.0 | 6.0 | 9.0 | 3.0 | 1.0 |
0.125 | 9.0 | 9.0 | 9.0 | 9.0 | 5.0 | 0.0 | 0.0 | 4.0 | 2.0 | 9.0 | 0.0 | 0.0 | |
59 | 0.25 | 9.0 | 9.0 | 9.0 | 9.0 | 9.0 | 4.0 | 7.0 | 3.0 | 9.0 | 8.0 | 0.0 | 2.0 |
0.125 | 9.0 | 9.0 | 9.0 | 9.0 | 0.0 | 0.0 | 3.0 | 0.0 | 4.0 | 2.0 | 0.0 | 0.0 |
续表B
实施例 | 用量[kg/ha] | ABUTH | AMBEL | CHEAL | IPOHE | XANST | ALMOY | DIGSA | ECHCG | SETVI | GLXMA | TRZAW | ZEAMX |
60 | 0.25 | 9.0 | 9.0 | 9.0 | 6.0 | 4.0 | 0.0 | 6.0 | 4.0 | 9.0 | 6.0 | 0.0 | 0.0 |
0.125 | 9.0 | 9.0 | 9.0 | 7.0 | 0.0 | 0.0 | 6.0 | 0.0 | 5.0 | 0.0 | 0.0 | 0.0 | |
61 | 0.25 | 9.0 | 9.0 | 9.0 | 9.0 | 9.0 | 0.0 | 9.0 | 7.0 | 6.0 | 9.0 | 3.0 | 2.0 |
0.125 | 9.0 | 9.0 | 9.0 | 9.0 | 9.0 | 0.0 | 6.0 | 4.0 | 3.0 | 9.0 | 2.0 | 2.0 | |
62 | 0.25 | 9.0 | 9.0 | 9.0 | 9.0 | 9.0 | 0.0 | 7.0 | 6.0 | 7.0 | 9.0 | 5.0 | 1.0 |
0.125 | 9.0 | 9.0 | 9.0 | 9.0 | 9.0 | 0.0 | 5.0 | 3.0 | 3.0 | 5.0 | 3.0 | 1.0 | |
63 | 0.25 | 9.0 | 9.0 | 9.0 | 9.0 | - | 0.0 | 8.0 | 9.0 | 8.0 | 5.0 | 0.0 | 0.0 |
0.125 | 9.0 | 9.0 | 9.0 | 9.0 | - | 0.0 | 3.0 | 4.0 | 4.0 | 1.0 | 0.0 | 0.0 | |
64 | 0.25 | 9.0 | 9.0 | 9.0 | 9.0 | - | 4.0 | 9.0 | 7.0 | 9.0 | - | 3.0 | 2.0 |
0.125 | 9.0 | 9.0 | 9.0 | 9.0 | - | 0.0 | 8.0 | 3.0 | 8.0 | - | 0.0 | 0.0 | |
65 | 0.25 | 9.0 | 9.0 | 9.0 | 9.0 | - | 0.0 | 9.0 | 9.0 | 6.0 | - | 1.0 | 1.0 |
0.125 | 9.0 | 9.0 | 9.0 | 9.0 | - | 0.0 | 7.0 | 8.0 | 3.0 | - | 1.0 | 0.0 | |
66 | 0.25 | 9.0 | 9.0 | 9.0 | 9.0 | - | 2.0 | 8.0 | 8.0 | 6.0 | - | 1.0 | 2.0 |
0.125 | 9.0 | 9.0 | 9.0 | 9.0 | - | 0.0 | 4.0 | 4.0 | 4.0 | 0.0 | 1.0 | 1.0 | |
67 | 0.25 | 9.0 | 7.0 | 9.0 | 9.0 | - | 0.0 | 8.0 | 9.0 | 8.0 | - | 1.0 | 1.0 |
0.125 | 9.0 | 9.0 | 9.0 | 9.0 | - | 0.0 | 7.0 | 8.0 | 8.0 | - | 0.0 | 0.0 |
续表B
实施例 | 用量[kg/ha] | ABUTH | AMBEL | CHEAL | IPOHE | XANST | ALMOY | DIGSA | ECHCG | SETVI | GLXMA | TRZAW | ZEAMX |
68 | 0.25 | 9.0 | 9.0 | 8.0 | 9.0 | 9.0 | 0.0 | 4.0 | 4.0 | 8.0 | 8.0 | 0.0 | 2.0 |
0.125 | 9.0 | 9.0 | 8.0 | 9.0 | 9.0 | 0.0 | 3.0 | 3.0 | 4.0 | 7.0 | 0.0 | 1.0 | |
69 | 0.25 | 9.0 | 9.0 | 9.0 | 9.0 | 4.0 | 0.0 | 3.0 | 3.0 | 1.0 | 3.0 | 0.0 | 3.0 |
0.125 | 9.0 | 8.0 | 9.0 | 9.0 | 3.0 | 0.0 | 3.0 | 2.0 | 0.0 | 0.0 | 0.0 | 2.0 | |
70 | 0.25 | 9.0 | 9.0 | 9.0 | 9.0 | 9.0 | 0.0 | 5.0 | 7.0 | 5.0 | 3.0 | 1.0 | 0.0 |
0.125 | 9.0 | 9.0 | 8.0 | 9.0 | 8.0 | 0.0 | 2.0 | 2.0 | 3.0 | 1.0 | 0.0 | 0.0 | |
71 | 0.25 | 9.0 | 8.0 | 7.0 | 9.0 | 7.0 | 0.0 | 3.0 | 3.0 | 2.0 | 2.0 | 0.0 | 1.0 |
0.125 | 9.0 | 8.0 | 9.0 | 9.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | |
72 | 0.25 | 9.0 | 9.0 | 9.0 | 9.0 | 9.0 | 2.0 | 7.0 | 6.0 | 8.0 | 9.0 | 1.0 | 0.0 |
0.125 | 9.0 | 9.0 | 9.0 | 9.0 | 7.0 | 1.0 | 2.0 | 7.0 | 4.0 | 8.0 | 0.0 | 0.0 | |
73 | 0.25 | 9.0 | 9.0 | 9.0 | 9.0 | 9.0 | 0.0 | 3.0 | 3.0 | 5.0 | 0.0 | 0.0 | 0.0 |
0.125 | 9.0 | 9.0 | 9.0 | 9.0 | 3.0 | 0.0 | 3.0 | 0.0 | 2.0 | 0.0 | 0.0 | 0.0 | |
76 | 0.25 | 9.0 | 9.0 | 9.0 | 9.0 | 5.0 | 2.0 | 3.0 | 2.0 | 2.0 | 3.0 | 1.0 | 1.0 |
0.125 | 9.0 | 8.0 | 8.0 | 5.0 | 3.0 | 0.0 | 2.0 | 1.0 | 1.0 | 1.0 | 0.0 | 1.0 | |
77 | 0.25 | 9.0 | 9.0 | 9.0 | 9.0 | 8.0 | 0.0 | 4.0 | 3.0 | 2.0 | - | 0.0 | 1.0 |
0.125 | 9.0 | 9.0 | 9.0 | 7.0 | 3.0 | 0.0 | 2.0 | 2.0 | 2.0 | 1.0 | 0.0 | 0.0 |
续表B
实施例 | 用量[kg/ha] | ABUTH | AMBEL | CHEAL | IPOHE | XANST | ALMOY | DIGSA | ECHCG | SETVI | GLXMA | TRZAW | ZEAMX |
78 | 0.25 | 9.0 | 9.0 | 9.0 | 9.0 | 9.0 | 2.0 | 8.0 | 7.0 | 7.0 | 5.0 | 1.0 | 1.0 |
0.125 | 9.0 | 9.0 | 9.0 | 9.0 | 9.0 | 1.0 | 4.0 | 4.0 | 5.0 | 3.0 | 1.0 | 0.0 | |
80 | 0.25 | 5.0 | 3.0 | 8.0 | 0.0 | 1.0 | 0.0 | 1.0 | 3.0 | 0.0 | 0.0 | 0.0 | 0.0 |
0.125 | 1.0 | 1.0 | 5.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | |
82 | 0.25 | 9.0 | 9.0 | 9.0 | 9.0 | 9.0 | 0.0 | 4.0 | 4.0 | 7.0 | 9.0 | 1.0 | 2.0 |
0.125 | 9.0 | 9.0 | 9.0 | 9.0 | 9.0 | 0.0 | 4.0 | 3.0 | 3.0 | 9.0 | 0.0 | 0.0 | |
83 | 0.25 | 9.0 | 8.0 | 9.0 | 8.0 | 5.0 | 0.0 | 9.0 | 5.0 | 6.0 | 4.0 | 0.0 | 2.0 |
0.125 | 8.0 | 8.0 | 9.0 | 7.0 | 4.0 | 0.0 | 1.0 | 4.0 | 3.0 | 1.0 | 0.0 | 0.0 | |
84 | 0.25 | 9.0 | 9.0 | 9.0 | 9.0 | 9.0 | 1.0 | 8.0 | 6.0 | 7.0 | 7.0 | 2.0 | 1.0 |
0.125 | 9.0 | 9.0 | 9.0 | 9.0 | 9.0 | 0.0 | 7.0 | 5.0 | 7.0 | 2.0 | 0.0 | 0.0 |
实施例149
由下列温室试验评价尿嘧啶取代的苯基氨磺酰羧酰胺Ij.86、Ip.86和Iy.86的除草作用:
所用的培养容器为塑料花盆,其含有约3.0%腐殖土的壤质沙作为基质。将试验植物的种子以各品种单独播种。
对于出苗后处理,使试验植物生长到3-15厘米的植株高度,这取决于植物习性,然后仅用已经在水中悬浮或乳化的活性成分处理。为此,将试验植物或者在相同的容器中直接播种并生长,或者将它们首先作为秧苗单独生长,然后在处理前几天移植到试验容器中。出苗后处理的施用率为15.6或7.8g/ha活性成分。
取决于具体的品种,将植物分别保持在10-25℃和20-35℃。试验期跨越2-4周。在此期间,看护植物并评价它们对单个处理的响应。
使用0-100的评分进行评价。100表示植物没有出苗,或至少地面上部分完全损坏,而0表示没有损伤或正常的生长过程。
用于温室试验的植物属于下列品种:
学名 | 通用名 |
Amaranthus retroflexus(AMARE) | 反枝苋 |
Pharbitis purpurea(PHBPU) | 圆叶牵牛 |
Polygonum persicaria(POLPE) | 蓼(redshank;ladysthumb) |
在15.6或7.8g/ha a.i.的施用率下,化合物Ij.86、Ip.86和Iy.86对上述不希望有的植物显示出非常良好的除草作用。
化合物I的干燥/脱叶活性
实施例150:温室试验
所用试验植物为4片叶(无子叶)的棉花幼苗,其已经在温室条件(相对大气湿度50-70%;昼/夜温度27/20℃)下生长。
用活性成分的含水制剂(基于喷雾混合物加入0.15重量%脂肪醇烷氧基化物Plurafac_LF7001))对棉花幼苗进行叶面处理直到滴流点。施用的水量为1000l/ha(转化)。13天后,测定落叶数目和脱叶程度(%)。
在未处理对照植物中并未发现落叶。
1)低泡沫、非离子表面活性剂(BASF AG)
实施例151:稻田试验(field trials)
使用化合物Ia.86在几个不同的地方进行预收割干燥活性的稻田评价。
在各试验中以无规化全方块试验设计(randomized complete blockexperimental design)重复处理三次。使用各区域的良好农艺实践种植土豆。在计划收获土豆之前几个星期进行处理。
将试验化合物配制成120g a.i./L的乳油(EC)配方。用水稀释配方,加入喷雾助剂,并将处理溶液以187-600l/ha的总喷雾体积施用于土豆的叶面上。除非另有说明,处理还含有15v/v的甲基化种子油助剂(Hasten或SUN-IT II)。在分开施用的情况下,第二次施用在首次施用一周后进行。
在处理后的各个间隔中基于视觉干燥评分%单独评价茎和叶的干燥。在各试验中,试验化合物与合适的商业标准在各标准对该区域的正常施用率下对比。
所示结果表明上述化合物对土豆植株的叶和茎的干燥特别有效。
Claims (11)
1.式I的新型尿嘧啶取代的苯基氨磺酰羧酰胺:
其中各变量具有下列含义:
A为氧;
X1为氢或卤素;
X2为卤素;
X3为氢;
R1和R2各自独立地为氢,
C1-C10烷基,其可被1个选自氰基、C1-C6烷氧羰基、1,3-二氧戊环基、苯基、噻吩基和呋喃基的取代基取代,
C2-C10链烯基,
C3-C10炔基,
C3-C7环烷基,
苯基,其可被1个或2个选自卤素、C1-C6烷氧基、C1-C6烷氧羰基、苯氧基、苯基、硝基、C1-C6烷基、C1-C6卤代烷基、C1-C6烷基氨基和二(C1-C6烷基)氨基的取代基取代,
苄基,其可被卤素或C1-C6烷氧基取代,
吡啶基,
萘基,或
Q选自
其中
A1、A8、A9、A10、A11、A13、A16、A17各自为氧;
A12为硫;
R7为C1-C6烷基或C1-C6卤代烷基;
R8为C1-C6烷基;或
R7和R8一起形成-(CH2)4-;
R29为氢、C1-C6烷基或氨基;
R30为C1-C6卤代烷基;
R31为氢;
R32、R33为C1-C6烷基;
R34为氢;
R35为C1-C6卤代烷基;
R36为氢或C1-C6烷基;
R37为卤素;
R38为C1-C6卤代烷氧基;
R39为C1-C6烷基;
R40为卤素;
R41为氢;
R42为C1-C6卤代烷基;
R43为氢;以及
R46和R47一起形成基团-(CH2)3-O-;
及化合物I的农业上有用的盐。
2.如权利要求1所定义的化合物,其选自如下化合物:
2-氯-5-[3,6-二氢-3-甲基-2,6-二氧代-4-(三氟甲基)-1(2H)-嘧啶基]-N-(二甲基氨磺酰)-4-氟苯甲酰胺,
2-氯-5-[3,6-二氢-3-甲基-2,6-二氧代-4-(三氟甲基)-1(2H)-嘧啶基]-N-[(乙基)丙基氨磺酰]-4-氟苯甲酰胺,
2-氯-5-[3,6-二氢-3-甲基-2,6-二氧代-4-(三氟甲基)-1(2H)-嘧啶基]-N-(仲丁基氨磺酰)-4-氟苯甲酰胺,
2-氯-5-[3,6-二氢-3-甲基-2,6-二氧代-4-(三氟甲基)-1(2H)-嘧啶基]-N-(叔丁基氨磺酰)-4-氟苯甲酰胺,
2-氯-5-[3,6-二氢-3-甲基-2,6-二氧代-4-(三氟甲基)-1(2H)-嘧啶基]-N-[(乙基)甲基氨磺酰]-4-氟苯甲酰胺,
2-氯-5-[3,6-二氢-3-甲基-2,6-二氧代-4-(三氟甲基)-1(2H)-嘧啶基]-N-[(甲基)丙基氨磺酰]-4-氟苯甲酰胺,
2-氯-5-[3,6-二氢-3-甲基-2,6-二氧代-4-(三氟甲基)-1(2H)-嘧啶基]-N-(二乙基氨磺酰)-4-氟苯甲酰胺,
2-氯-5-[3,6-二氢-3-氨基-2,6-二氧代-4-(三氟甲基)-1(2H)-嘧啶基]-N-[(甲基)异丙基氨磺酰]-4-氟苯甲酰胺,
2-氯-5-[3,6-二氢-3-甲基-2,6-二氧代-4-(三氟甲基)-1(2H)-嘧啶基]-N-[(仲丁基)甲基氨磺酰]-4-氟苯甲酰胺,
2-氯-5-[3,6-二氢-3-甲基-2,6-二氧代-4-(三氟甲基)-1(2H)-嘧啶基]-N-[(甲基)苯基氨磺酰]-4-氟苯甲酰胺,
2-氯-5-[3,6-二氢-3-甲基-2,6-二氧代-4-(三氟甲基)-1(2H)-嘧啶基]-N-[(甲基)异丙基氨磺酰]-4-氟苯甲酰胺,
2-氯-5-[3,6-二氢-3-甲基-2,6-二氧代-4-(三氟甲基)-1(2H)-嘧啶基]-N-[(正丁基)甲基氨磺酰]-4-氟苯甲酰胺,
N’-[[2-氯-4-氟-5-[4-(二氟甲基)-4,5-二氢-3-甲基-5-氧代-1H-1,2,4-三唑-1-基]-苯甲酰基]]-N-异丙基-N-甲基磺酰胺,
N’-{2-氯-4-氟-5-(5,6,7,8-四氢-3-氧代-1,2,4-三唑并[4,3-a]吡啶-2(3H)-基)-苯甲酰基}-N-异丙基-N-甲基亚磺酰胺,
N’-[2-氯-5-(3,5-二甲基-2,6-二氧代-4-硫代-1,3,5-三嗪烷-1-基)-4-氟苯甲酰基]-N-异丙基-N-甲基磺酰胺,
N’-[2-氯-4-氟-5-(5-三氟甲基达酮-3-酮-2-基)-苯甲酰基]-N-异丙基-N-甲基亚磺酰胺,
4-氯-3-[4-氯-2-氟-5-(N-甲基-N-异丙基)氨磺酰羧酰胺基苯基]-5-二氟甲氧基-1-甲基-1H-吡唑,
N’-[[2-氯-5-[3-氯-5-(三氟甲基)-2-吡啶基]-4-氟苯甲酰基]]-N-异丙基-N-甲基磺酰胺,和
8-(5’-N-异丙基-N-甲基氨磺酰羧酰胺基-4’-氯-2’-氟苯基)-4-氧代-7,9-二氧代-1,2,8-三氮杂(4.3.0)壬烷。
3.一种除草组合物,包含除草有效量的至少一种权利要求1所定义的式I化合物或其农业上有用的盐和至少一种惰性液体和/或固体载体以及非必要的至少一种表面活性剂。
4.一种用于植物干燥和/或脱叶的组合物,包含至少一种权利要求1所定义的式I化合物或其农业上有用的盐和至少一种惰性液体和/或固体载体以及非必要的至少一种表面活性剂,该化合物的含量应使其能用作干燥剂和/或脱叶剂。
5.一种控制不希望有的植物的方法,包括将除草活性量的至少一种权利要求1所定义的式I化合物或其农业上有用的盐作用于植物、其环境或种子上。
6.一种使植物干燥/脱叶的方法,包括将至少一种权利要求1所定义的式I化合物或其农业上有用的盐以使其用作脱叶剂和/或干燥剂的量作用于植物上。
7.如权利要求6所要求的方法,其中处理棉花。
8.一种制备权利要求1所定义的式I化合物的方法,该方法包括使式II的苯甲酸衍生物
其中Q、X1和X2如权利要求1所定义,
非必要地在偶联剂的存在下,
或式II的相应酰氯,
与式III的磺酰胺反应:
其中X3、R1和R2如权利要求1所定义。
11.如权利要求10所定义的方法,其中式X化合物
其中X1,X2,X3,R1和R2如权利要求1所定义,
通过使苯甲酸IX
非必要地在偶联剂存在下,
或式IX的对应酰氯,
与式III的磺酰胺反应而制备
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