JP2506063B2 - Substituted pyridine compound - Google Patents
Substituted pyridine compoundInfo
- Publication number
- JP2506063B2 JP2506063B2 JP29594694A JP29594694A JP2506063B2 JP 2506063 B2 JP2506063 B2 JP 2506063B2 JP 29594694 A JP29594694 A JP 29594694A JP 29594694 A JP29594694 A JP 29594694A JP 2506063 B2 JP2506063 B2 JP 2506063B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- reaction
- methylene chloride
- compound
- added
- 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
Links
- -1 pyridine compound Chemical class 0.000 title claims description 33
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 title claims description 13
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 title claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 46
- 125000000217 alkyl group Chemical group 0.000 claims description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 14
- 125000005843 halogen group Chemical group 0.000 claims description 10
- 125000004438 haloalkoxy group Chemical group 0.000 claims description 9
- 125000001188 haloalkyl group Chemical group 0.000 claims description 9
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- 125000004994 halo alkoxy alkyl group Chemical group 0.000 claims description 8
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 125000004995 haloalkylthio group Chemical group 0.000 claims description 5
- 125000000623 heterocyclic group Chemical group 0.000 claims description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 125000004414 alkyl thio group Chemical group 0.000 claims description 4
- 125000000304 alkynyl group Chemical group 0.000 claims description 4
- 125000004993 haloalkoxycarbonyl group Chemical group 0.000 claims description 4
- 125000005347 halocycloalkyl group Chemical group 0.000 claims description 4
- 125000005059 halophenyl group Chemical group 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 213
- 238000006243 chemical reaction Methods 0.000 description 66
- 238000003786 synthesis reaction Methods 0.000 description 44
- 230000015572 biosynthetic process Effects 0.000 description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 42
- 239000000203 mixture Substances 0.000 description 40
- 239000000543 intermediate Substances 0.000 description 25
- 239000000243 solution Substances 0.000 description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 23
- 238000002844 melting Methods 0.000 description 23
- 230000008018 melting Effects 0.000 description 22
- 238000000034 method Methods 0.000 description 22
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 22
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 21
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 21
- 238000010898 silica gel chromatography Methods 0.000 description 20
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 17
- 239000000126 substance Substances 0.000 description 16
- 239000007795 chemical reaction product Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 239000004009 herbicide Substances 0.000 description 12
- 238000010992 reflux Methods 0.000 description 11
- 241000196324 Embryophyta Species 0.000 description 10
- 230000002363 herbicidal effect Effects 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 8
- 239000004480 active ingredient Substances 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 238000009472 formulation Methods 0.000 description 7
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 6
- 240000008042 Zea mays Species 0.000 description 6
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 6
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 235000005822 corn Nutrition 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- DWJMBQYORXLGAE-UHFFFAOYSA-N pyridine-2-sulfonamide Chemical class NS(=O)(=O)C1=CC=CC=N1 DWJMBQYORXLGAE-UHFFFAOYSA-N 0.000 description 6
- 239000004563 wettable powder Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000005457 ice water Substances 0.000 description 5
- 239000002689 soil Substances 0.000 description 5
- 238000003892 spreading Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 230000009036 growth inhibition Effects 0.000 description 4
- FJEVKYZLIRAAKE-UHFFFAOYSA-N n,n-dimethylpyridine-3-carboxamide Chemical compound CN(C)C(=O)C1=CC=CN=C1 FJEVKYZLIRAAKE-UHFFFAOYSA-N 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- MPQHBWNDIOJYNP-UHFFFAOYSA-N 2,6-dimethylpyridine-3-carboxamide Chemical compound CC1=CC=C(C(N)=O)C(C)=N1 MPQHBWNDIOJYNP-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 125000000520 N-substituted aminocarbonyl group Chemical group [*]NC(=O)* 0.000 description 3
- 244000064622 Physalis edulis Species 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- WYFKZPLSYVJLRB-UHFFFAOYSA-N n,n-dimethyl-2-sulfamoylpyridine-3-carboxamide Chemical compound CN(C)C(=O)C1=CC=CN=C1S(N)(=O)=O WYFKZPLSYVJLRB-UHFFFAOYSA-N 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- AJPKQSSFYHPYMH-UHFFFAOYSA-N 2,6-dichloropyridine-3-carboxylic acid Chemical compound OC(=O)C1=CC=C(Cl)N=C1Cl AJPKQSSFYHPYMH-UHFFFAOYSA-N 0.000 description 2
- HTGJPRDRGIIRRL-UHFFFAOYSA-N 2-(tert-butylsulfamoyl)-5-chloro-n,n-dimethylpyridine-3-carboxamide Chemical compound CN(C)C(=O)C1=CC(Cl)=CN=C1S(=O)(=O)NC(C)(C)C HTGJPRDRGIIRRL-UHFFFAOYSA-N 0.000 description 2
- VYPQLHHBFVLLBS-UHFFFAOYSA-N 2-benzylsulfanyl-5-chloro-n,n-dimethylpyridine-3-carboxamide Chemical compound CN(C)C(=O)C1=CC(Cl)=CN=C1SCC1=CC=CC=C1 VYPQLHHBFVLLBS-UHFFFAOYSA-N 0.000 description 2
- PDLRIXBMOCLBPT-UHFFFAOYSA-N 2-benzylsulfanyl-n,n-dimethyl-6-oxo-1h-pyridine-3-carboxamide Chemical compound C1=CC(=O)NC(SCC=2C=CC=CC=2)=C1C(=O)N(C)C PDLRIXBMOCLBPT-UHFFFAOYSA-N 0.000 description 2
- CAUFLQMTRGNOBS-UHFFFAOYSA-N 2-benzylsulfanyl-n,n-dimethyl-6-phenylmethoxypyridine-3-carboxamide Chemical compound N1=C(SCC=2C=CC=CC=2)C(C(=O)N(C)C)=CC=C1OCC1=CC=CC=C1 CAUFLQMTRGNOBS-UHFFFAOYSA-N 0.000 description 2
- WYKHFQKONWMWQM-UHFFFAOYSA-N 2-sulfanylidene-1h-pyridine-3-carboxylic acid Chemical compound OC(=O)C1=CC=CN=C1S WYKHFQKONWMWQM-UHFFFAOYSA-N 0.000 description 2
- DOLQYFPDPKPQSS-UHFFFAOYSA-N 3,4-dimethylaniline Chemical group CC1=CC=C(N)C=C1C DOLQYFPDPKPQSS-UHFFFAOYSA-N 0.000 description 2
- OBMKLHWIDJBLRB-UHFFFAOYSA-N 5-chloro-n,n-dimethyl-2-sulfamoylpyridine-3-carboxamide Chemical compound CN(C)C(=O)C1=CC(Cl)=CN=C1S(N)(=O)=O OBMKLHWIDJBLRB-UHFFFAOYSA-N 0.000 description 2
- VWKZESPVAZDFST-UHFFFAOYSA-N 6-bromo-n,n-dimethyl-2-sulfamoylpyridine-3-carboxamide Chemical compound CN(C)C(=O)C1=CC=C(Br)N=C1S(N)(=O)=O VWKZESPVAZDFST-UHFFFAOYSA-N 0.000 description 2
- QXCYCYPGRYOFIE-UHFFFAOYSA-N 6-fluoro-n,n-dimethyl-2-sulfamoylpyridine-3-carboxamide Chemical compound CN(C)C(=O)C1=CC=C(F)N=C1S(N)(=O)=O QXCYCYPGRYOFIE-UHFFFAOYSA-N 0.000 description 2
- STXRMEVZAPNOJH-UHFFFAOYSA-N 6-methoxy-n,n-dimethyl-2-sulfamoylpyridine-3-carboxamide Chemical compound COC1=CC=C(C(=O)N(C)C)C(S(N)(=O)=O)=N1 STXRMEVZAPNOJH-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 241000234646 Cyperaceae Species 0.000 description 2
- 235000001602 Digitaria X umfolozi Nutrition 0.000 description 2
- 235000017898 Digitaria ciliaris Nutrition 0.000 description 2
- 235000005476 Digitaria cruciata Nutrition 0.000 description 2
- 235000006830 Digitaria didactyla Nutrition 0.000 description 2
- 235000005804 Digitaria eriantha ssp. eriantha Nutrition 0.000 description 2
- 235000010823 Digitaria sanguinalis Nutrition 0.000 description 2
- 244000025670 Eleusine indica Species 0.000 description 2
- 235000014716 Eleusine indica Nutrition 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 2
- DFPAKSUCGFBDDF-UHFFFAOYSA-N Nicotinamide Chemical compound NC(=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-UHFFFAOYSA-N 0.000 description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 240000006394 Sorghum bicolor Species 0.000 description 2
- 235000011684 Sorghum saccharatum Nutrition 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- MXWJVTOOROXGIU-UHFFFAOYSA-N atrazine Chemical compound CCNC1=NC(Cl)=NC(NC(C)C)=N1 MXWJVTOOROXGIU-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- UENWRTRMUIOCKN-UHFFFAOYSA-N benzyl thiol Chemical compound SCC1=CC=CC=C1 UENWRTRMUIOCKN-UHFFFAOYSA-N 0.000 description 2
- 125000006309 butyl amino group Chemical group 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- CSJLBAMHHLJAAS-UHFFFAOYSA-N diethylaminosulfur trifluoride Chemical compound CCN(CC)S(F)(F)F CSJLBAMHHLJAAS-UHFFFAOYSA-N 0.000 description 2
- XHFGWHUWQXTGAT-UHFFFAOYSA-N dimethylamine hydrochloride Natural products CNC(C)C XHFGWHUWQXTGAT-UHFFFAOYSA-N 0.000 description 2
- IQDGSYLLQPDQDV-UHFFFAOYSA-N dimethylazanium;chloride Chemical compound Cl.CNC IQDGSYLLQPDQDV-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000006198 methoxylation reaction Methods 0.000 description 2
- HVNUMYCORWOCEF-UHFFFAOYSA-N n-ethyl-n-methyl-2-sulfamoylpyridine-3-carboxamide Chemical compound CCN(C)C(=O)C1=CC=CN=C1S(N)(=O)=O HVNUMYCORWOCEF-UHFFFAOYSA-N 0.000 description 2
- BMHNLPXILGWEKG-UHFFFAOYSA-N n-methyl-2-sulfamoylpyridine-3-carboxamide Chemical compound CNC(=O)C1=CC=CN=C1S(N)(=O)=O BMHNLPXILGWEKG-UHFFFAOYSA-N 0.000 description 2
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229940124530 sulfonamide Drugs 0.000 description 2
- 238000005694 sulfonylation reaction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 1
- 239000005631 2,4-Dichlorophenoxyacetic acid Substances 0.000 description 1
- HXKWSTRRCHTUEC-UHFFFAOYSA-N 2,4-Dichlorophenoxyaceticacid Chemical compound OC(=O)C(Cl)OC1=CC=C(Cl)C=C1 HXKWSTRRCHTUEC-UHFFFAOYSA-N 0.000 description 1
- JIBKMAZCRPWLEP-UHFFFAOYSA-N 2,5-dichloro-n,n-dimethylpyridine-3-carboxamide Chemical compound CN(C)C(=O)C1=CC(Cl)=CN=C1Cl JIBKMAZCRPWLEP-UHFFFAOYSA-N 0.000 description 1
- SXQSMLIMBNMUNB-UHFFFAOYSA-N 2,5-dichloropyridine-3-carboxylic acid Chemical compound OC(=O)C1=CC(Cl)=CN=C1Cl SXQSMLIMBNMUNB-UHFFFAOYSA-N 0.000 description 1
- GQGNVBMAXYTSAH-UHFFFAOYSA-N 2,6-dichloro-n,n-dimethylpyridine-3-carboxamide Chemical compound CN(C)C(=O)C1=CC=C(Cl)N=C1Cl GQGNVBMAXYTSAH-UHFFFAOYSA-N 0.000 description 1
- HXYUIZQJWGDLQI-UHFFFAOYSA-N 2-(tert-butylsulfamoyl)-6-chloro-n,n-dimethylpyridine-3-carboxamide Chemical compound CN(C)C(=O)C1=CC=C(Cl)N=C1S(=O)(=O)NC(C)(C)C HXYUIZQJWGDLQI-UHFFFAOYSA-N 0.000 description 1
- XNZALHDFEICXBM-UHFFFAOYSA-N 2-(tert-butylsulfamoyl)-n,n-dimethylpyridine-3-carboxamide Chemical compound CN(C)C(=O)C1=CC=CN=C1S(=O)(=O)NC(C)(C)C XNZALHDFEICXBM-UHFFFAOYSA-N 0.000 description 1
- QVZHGILPVSPOSZ-UHFFFAOYSA-N 2-(tert-butylsulfamoyl)pyridine-3-carboxylic acid Chemical compound CC(C)(C)NS(=O)(=O)C1=NC=CC=C1C(O)=O QVZHGILPVSPOSZ-UHFFFAOYSA-N 0.000 description 1
- RVVNVPPMDJWKBJ-UHFFFAOYSA-N 2-benzylsulfanyl-6-chloro-n,n-dimethylpyridine-3-carboxamide Chemical compound CN(C)C(=O)C1=CC=C(Cl)N=C1SCC1=CC=CC=C1 RVVNVPPMDJWKBJ-UHFFFAOYSA-N 0.000 description 1
- MPGOCEUHZWEFJX-UHFFFAOYSA-N 2-benzylsulfanyl-n,n-dimethylpyridine-3-carboxamide Chemical compound CN(C)C(=O)C1=CC=CN=C1SCC1=CC=CC=C1 MPGOCEUHZWEFJX-UHFFFAOYSA-N 0.000 description 1
- YEGHRZGEUMDQBO-UHFFFAOYSA-N 2-chloro-6-ethoxy-n,n-dimethylpyridine-3-carboxamide Chemical compound CCOC1=CC=C(C(=O)N(C)C)C(Cl)=N1 YEGHRZGEUMDQBO-UHFFFAOYSA-N 0.000 description 1
- DAJFJXPMGNAONI-UHFFFAOYSA-N 2-chloro-n,n-dimethyl-6-phenylmethoxypyridine-3-carboxamide Chemical compound N1=C(Cl)C(C(=O)N(C)C)=CC=C1OCC1=CC=CC=C1 DAJFJXPMGNAONI-UHFFFAOYSA-N 0.000 description 1
- OKOCIHPHSMRJDK-UHFFFAOYSA-N 2-chloro-n-ethyl-n-methylpyridine-3-carboxamide Chemical compound CCN(C)C(=O)C1=CC=CN=C1Cl OKOCIHPHSMRJDK-UHFFFAOYSA-N 0.000 description 1
- AVRKRDJKETWGRR-UHFFFAOYSA-N 2-chloro-n-methylpyridine-3-carboxamide Chemical compound CNC(=O)C1=CC=CN=C1Cl AVRKRDJKETWGRR-UHFFFAOYSA-N 0.000 description 1
- IBRSSZOHCGUTHI-UHFFFAOYSA-N 2-chloropyridine-3-carboxylic acid Chemical compound OC(=O)C1=CC=CN=C1Cl IBRSSZOHCGUTHI-UHFFFAOYSA-N 0.000 description 1
- 125000004189 3,4-dichlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(Cl)C([H])=C1* 0.000 description 1
- PENVYHXKYYCYML-UHFFFAOYSA-N 4-methoxypyrimidine Chemical compound COC1=CC=NC=N1 PENVYHXKYYCYML-UHFFFAOYSA-N 0.000 description 1
- JNRHHJGOFNAMHP-UHFFFAOYSA-N 5-chloro-2-[(4,6-dimethoxypyrimidin-2-yl)carbamoylsulfamoyl]-n,n-dimethylpyridine-3-carboxamide Chemical compound COC1=CC(OC)=NC(NC(=O)NS(=O)(=O)C=2C(=CC(Cl)=CN=2)C(=O)N(C)C)=N1 JNRHHJGOFNAMHP-UHFFFAOYSA-N 0.000 description 1
- XITGGJGQUYXRIE-UHFFFAOYSA-N 6-(difluoromethyl)-n,n-dimethyl-2-sulfamoylpyridine-3-carboxamide Chemical class CN(C)C(=O)C1=CC=C(C(F)F)N=C1S(N)(=O)=O XITGGJGQUYXRIE-UHFFFAOYSA-N 0.000 description 1
- KPROXEPAIVTJAI-UHFFFAOYSA-N 6-chloro-n,n-dimethyl-2-sulfamoylpyridine-3-carboxamide Chemical compound CN(C)C(=O)C1=CC=C(Cl)N=C1S(N)(=O)=O KPROXEPAIVTJAI-UHFFFAOYSA-N 0.000 description 1
- IGJIMWAYAASGJG-UHFFFAOYSA-N 6-ethoxy-n,n-dimethyl-2-sulfamoylpyridine-3-carboxamide Chemical compound CCOC1=CC=C(C(=O)N(C)C)C(S(N)(=O)=O)=N1 IGJIMWAYAASGJG-UHFFFAOYSA-N 0.000 description 1
- XRIHTJYXIHOBDQ-UHFFFAOYSA-N 6-methyl-2-oxo-1h-pyridine-3-carboxylic acid Chemical compound CC1=CC=C(C(O)=O)C(=O)N1 XRIHTJYXIHOBDQ-UHFFFAOYSA-N 0.000 description 1
- IJXDURUAYOKSIS-UHFFFAOYSA-N 6-methylpyridine-3-carboxamide Chemical compound CC1=CC=C(C(N)=O)C=N1 IJXDURUAYOKSIS-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 235000007320 Avena fatua Nutrition 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical group C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- BMTAFVWTTFSTOG-UHFFFAOYSA-N Butylate Chemical compound CCSC(=O)N(CC(C)C)CC(C)C BMTAFVWTTFSTOG-UHFFFAOYSA-N 0.000 description 1
- MAMILCDGUBDOIW-UHFFFAOYSA-N CCCCNS(=O)(=O)OC(=O)C1=CN=CC=C1 Chemical compound CCCCNS(=O)(=O)OC(=O)C1=CN=CC=C1 MAMILCDGUBDOIW-UHFFFAOYSA-N 0.000 description 1
- KYJUCPHVTKFJGQ-UHFFFAOYSA-N CN(C)C(=O)C1=C(N=CC=C1)C(F)F Chemical compound CN(C)C(=O)C1=C(N=CC=C1)C(F)F KYJUCPHVTKFJGQ-UHFFFAOYSA-N 0.000 description 1
- QWGDNKSCSKSBCN-UHFFFAOYSA-N CN(C)C(N1C(C(NC2=NC(OC)=CC(Cl)=N2)=O)=CC=NC1S(N)(=O)=O)=O Chemical compound CN(C)C(N1C(C(NC2=NC(OC)=CC(Cl)=N2)=O)=CC=NC1S(N)(=O)=O)=O QWGDNKSCSKSBCN-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 244000277285 Cassia obtusifolia Species 0.000 description 1
- 235000006719 Cassia obtusifolia Nutrition 0.000 description 1
- 241000282994 Cervidae Species 0.000 description 1
- HSSBORCLYSCBJR-UHFFFAOYSA-N Chloramben Chemical compound NC1=CC(Cl)=CC(C(O)=O)=C1Cl HSSBORCLYSCBJR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- GUVLYNGULCJVDO-UHFFFAOYSA-N EPTC Chemical compound CCCN(CCC)C(=O)SCC GUVLYNGULCJVDO-UHFFFAOYSA-N 0.000 description 1
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 1
- 240000001549 Ipomoea eriocarpa Species 0.000 description 1
- 235000005146 Ipomoea eriocarpa Nutrition 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 241000254158 Lampyridae Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical group C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 1
- ZYVXHFWBYUDDBM-UHFFFAOYSA-N N-methylnicotinamide Chemical compound CNC(=O)C1=CC=CN=C1 ZYVXHFWBYUDDBM-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 241000009328 Perro Species 0.000 description 1
- 241000205407 Polygonum Species 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical group C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 1
- 241000269435 Rana <genus> Species 0.000 description 1
- 241000681978 Rhododendron japonicum Species 0.000 description 1
- OKUGPJPKMAEJOE-UHFFFAOYSA-N S-propyl dipropylcarbamothioate Chemical compound CCCSC(=O)N(CCC)CCC OKUGPJPKMAEJOE-UHFFFAOYSA-N 0.000 description 1
- 241001125046 Sardina pilchardus Species 0.000 description 1
- 241000555745 Sciuridae Species 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 229920000142 Sodium polycarboxylate Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 241001504592 Trachurus trachurus Species 0.000 description 1
- WHKUVVPPKQRRBV-UHFFFAOYSA-N Trasan Chemical compound CC1=CC(Cl)=CC=C1OCC(O)=O WHKUVVPPKQRRBV-UHFFFAOYSA-N 0.000 description 1
- 241000005601 Trisetum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 244000098338 Triticum aestivum Species 0.000 description 1
- 241000001727 Tropicoporus linteus Species 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- XCSGPAVHZFQHGE-UHFFFAOYSA-N alachlor Chemical compound CCC1=CC=CC(CC)=C1N(COC)C(=O)CCl XCSGPAVHZFQHGE-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 125000004849 alkoxymethyl group Chemical group 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000000480 butynyl group Chemical group [*]C#CC([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- IWEDIXLBFLAXBO-UHFFFAOYSA-N dicamba Chemical compound COC1=C(Cl)C=CC(Cl)=C1C(O)=O IWEDIXLBFLAXBO-UHFFFAOYSA-N 0.000 description 1
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 description 1
- 239000013583 drug formulation Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000007046 ethoxylation reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- PZTGZTFXZUGYKS-UHFFFAOYSA-N formyl pyridine-3-carboxylate Chemical class O=COC(=O)C1=CC=CN=C1 PZTGZTFXZUGYKS-UHFFFAOYSA-N 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 229940097275 indigo Drugs 0.000 description 1
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- ARFMOJCNMOVFSI-UHFFFAOYSA-N methyl 2-(tert-butylsulfamoyl)-6-(dibromomethyl)pyridine-3-carboxylate Chemical compound COC(=O)C1=CC=C(C(Br)Br)N=C1S(=O)(=O)NC(C)(C)C ARFMOJCNMOVFSI-UHFFFAOYSA-N 0.000 description 1
- CDCIALMFTSFSSW-UHFFFAOYSA-N methyl 2-(tert-butylsulfamoyl)-6-(difluoromethyl)pyridine-3-carboxylate Chemical compound COC(=O)C1=CC=C(C(F)F)N=C1S(=O)(=O)NC(C)(C)C CDCIALMFTSFSSW-UHFFFAOYSA-N 0.000 description 1
- XPJADFAAWMHEDS-UHFFFAOYSA-N methyl 2-(tert-butylsulfamoyl)-6-methylpyridine-3-carboxylate Chemical compound COC(=O)C1=CC=C(C)N=C1S(=O)(=O)NC(C)(C)C XPJADFAAWMHEDS-UHFFFAOYSA-N 0.000 description 1
- UJSNWSDDKBTZNI-UHFFFAOYSA-N methyl 2-(tert-butylsulfamoyl)pyridine-3-carboxylate Chemical compound COC(=O)C1=CC=CN=C1S(=O)(=O)NC(C)(C)C UJSNWSDDKBTZNI-UHFFFAOYSA-N 0.000 description 1
- BQQXUGGTSVMBLL-UHFFFAOYSA-N methyl 2-sulfanylidene-1h-pyridine-3-carboxylate Chemical compound COC(=O)C1=CC=CNC1=S BQQXUGGTSVMBLL-UHFFFAOYSA-N 0.000 description 1
- NQMRYBIKMRVZLB-UHFFFAOYSA-N methylamine hydrochloride Chemical compound [Cl-].[NH3+]C NQMRYBIKMRVZLB-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- OWNRCTRVXIEWMH-UHFFFAOYSA-N n,n,6-trimethyl-2-sulfamoylpyridine-3-carboxamide Chemical compound CN(C)C(=O)C1=CC=C(C)N=C1S(N)(=O)=O OWNRCTRVXIEWMH-UHFFFAOYSA-N 0.000 description 1
- UIAVVZBCWDBVDI-UHFFFAOYSA-N n,n,6-trimethylpyridine-2-carboxamide Chemical compound CN(C)C(=O)C1=CC=CC(C)=N1 UIAVVZBCWDBVDI-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000017066 negative regulation of growth Effects 0.000 description 1
- 235000005152 nicotinamide Nutrition 0.000 description 1
- 239000011570 nicotinamide Substances 0.000 description 1
- 229960003966 nicotinamide Drugs 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- MESPVSMSORHLAX-UHFFFAOYSA-N phenyl n-(4,6-dimethoxypyrimidin-2-yl)carbamate Chemical compound COC1=CC(OC)=NC(NC(=O)OC=2C=CC=CC=2)=N1 MESPVSMSORHLAX-UHFFFAOYSA-N 0.000 description 1
- NHNQLTZFUJPTCB-UHFFFAOYSA-N phenyl n-[3-(dimethylcarbamoyl)pyridin-2-yl]sulfonylcarbamate Chemical compound CN(C)C(=O)C1=CC=CN=C1S(=O)(=O)NC(=O)OC1=CC=CC=C1 NHNQLTZFUJPTCB-UHFFFAOYSA-N 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- ILVXOBCQQYKLDS-UHFFFAOYSA-N pyridine N-oxide Chemical class [O-][N+]1=CC=CC=C1 ILVXOBCQQYKLDS-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 235000019512 sardine Nutrition 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- ODCWYMIRDDJXKW-UHFFFAOYSA-N simazine Chemical compound CCNC1=NC(Cl)=NC(NCC)=N1 ODCWYMIRDDJXKW-UHFFFAOYSA-N 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 description 1
- XHFLOLLMZOTPSM-UHFFFAOYSA-M sodium;hydrogen carbonate;hydrate Chemical compound [OH-].[Na+].OC(O)=O XHFLOLLMZOTPSM-UHFFFAOYSA-M 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 125000000565 sulfonamide group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Pyridine Compounds (AREA)
- Plural Heterocyclic Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、新規な置換ピリジンス
ルホンアミド系化合物及びその塩、それらを有効成分と
して含有する除草剤、それらの化合物の製造方法並びに
それらの化合物を製造するための中間体としての置換ピ
リジン系化合物に関する。FIELD OF THE INVENTION The present invention relates to novel substituted pyridinesulfonamide compounds and salts thereof, herbicides containing them as active ingredients, a process for producing these compounds, and intermediates for producing these compounds. As a substituted pyridine compound.
【０００２】[0002]
【先行技術及び本発明に至った経緯】本発明の置換ピリ
ジンスルホンアミド系化合物は、該ピリジン環にＮ−置
換アミノカルボニル基を有することを特徴とする。前記
置換ピリジンスルホンアミド系化合物は特開昭５９−３
９８７８号公報、特開昭５９−５９６７１号公報、特開
昭５９−９８０６６号公報において広く一般式で示され
ていることにより、概念的には知られている。しかしな
がら本発明化合物は前記明細書中には何ら具体的に開示
されていない。また、或る置換ピリジンスルホンアミド
系化合物は米国特許第４，４３５，２０６号明細書に記
載されているが、該明細書にはピリジン環にＮ−置換ア
ミノカルボニル基を有するピリジンスルホンアミド系化
合物は記載されていない。一方、スルホンアミド系化合
物を有効成分とする除草剤は従来多くの類縁体が開発さ
れているが、トウモロコシに対して安全性が高く、しか
も高い除草効果を有するものは未だ開発されていない。
本発明者等は、スルホンアミド系化合物についてその化
学構造と植物に対する生理活性とを詳細に検討し、特に
トウモロコシ畑用除草剤を見出すべく検討を重ねた結
果、ピリジンスルホンアミド系化合物において、ピリジ
ン環にＮ−置換アミノカルボニル基を有し、かつ他の特
定の置換基を有してもよく、さらにスルホンアミド部分
の窒素原子に置換ピリミジン−２−イル−アミノカルボ
ニル基を結合させた化合物がトウモロコシ畑用除草剤と
して有用であるとの知見を得て、本発明を完成した。Prior Art and Background of the Invention The substituted pyridinesulfonamide compound of the present invention is characterized by having an N-substituted aminocarbonyl group in the pyridine ring. The substituted pyridinesulfonamide compounds are disclosed in JP-A-59-3
It is conceptually known because it is widely represented by the general formulas in JP-A-9878, JP-A-59-59671, and JP-A-59-98066. However, the compound of the present invention is not specifically disclosed in the above specification. Further, some substituted pyridinesulfonamide compounds are described in U.S. Pat. No. 4,435,206, which describes a pyridinesulfonamide compound having an N-substituted aminocarbonyl group in the pyridine ring. Is not listed. On the other hand, many herbicides having a sulfonamide compound as an active ingredient have been developed in the past, but a herbicide having high safety against corn and having a high herbicidal effect has not yet been developed.
The present inventors have studied the chemical structure of a sulfonamide compound and its physiological activity against plants in detail, and as a result of repeated studies to find a herbicide for corn fields, as a result, in the pyridinesulfonamide compound, a pyridine ring Has a N-substituted aminocarbonyl group and may have other specific substituents, and a compound having a substituted pyrimidin-2-yl-aminocarbonyl group bonded to the nitrogen atom of the sulfonamide moiety is corn. The present invention has been completed based on the finding that it is useful as a herbicide for fields.
【０００３】[0003]
【発明の開示】本発明は、一般式（Ｉ）：DISCLOSURE OF THE INVENTION The present invention has the general formula (I):
【０００４】[0004]
【化３】 Embedded image
【０００５】〔Ｒ1 及びＲ2 は水素原子、アルキル基、
ハロアルキル基、アルケニル基、アルキニル基、アルコ
キシ基、ハロアルコキシ基、アルコキシアルキル基、ハ
ロアルコキシアルキル基、シクロアルキル基、ハロシク
ロアルキル基、アルコキシカルボニル基、ハロアルコキ
シカルボニル基、フェニル基又はハロフェニル基であ
り、Ｒ1 及びＲ2 の一方が水素原子の場合他方は水素原
子以外のものであり、Ｒ1及びＲ2 が隣接している窒素
原子と共に複素環を形成してもよく、Ｙはハロゲン原
子、アルキル基、ハロアルキル基、アルコキシ基、ハロ
アルコキシ基、アルキルチオ基、ハロアルキルチオ基、
アルコキシアルキル基、ハロアルコキシアルキル基又は[R 1 and R 2 are a hydrogen atom, an alkyl group,
A haloalkyl group, an alkenyl group, an alkynyl group, an alkoxy group, a haloalkoxy group, an alkoxyalkyl group, a haloalkoxyalkyl group, a cycloalkyl group, a halocycloalkyl group, an alkoxycarbonyl group, a haloalkoxycarbonyl group, a phenyl group or a halophenyl group. , One of R 1 and R 2 is a hydrogen atom and the other is other than a hydrogen atom, and R 1 and R 2 may form a heterocycle with the adjacent nitrogen atom, Y is a halogen atom, Alkyl group, haloalkyl group, alkoxy group, haloalkoxy group, alkylthio group, haloalkylthio group,
An alkoxyalkyl group, a haloalkoxyalkyl group or
【０００６】[0006]
【化４】 Embedded image
【０００７】（Ｒ3 及びＲ4 は水素原子又はアルキル基
である）であり、ｎは０又は１或いは２の整数であり、
Ｘ1 及びＸ2 はメチル基、メトキシ基又はエトキシ基で
ある〕である｝で表わされる置換ピリジンスルホンアミ
ド系化合物及びその塩、それらを含有する除草剤、それ
らの化合物の製造方法並びにそれらの化合物を製造する
ための中間体としての置換ピリジン系化合物である。(R 3 and R 4 are a hydrogen atom or an alkyl group), n is 0 or an integer of 1 or 2,
X 1 and X 2 are a methyl group, a methoxy group or an ethoxy group] and a salt thereof, a herbicide containing the same, a method for producing the compound and the compound thereof. It is a substituted pyridine compound as an intermediate for producing.
【０００８】前記一般式（Ｉ）中、Ｒ1 、Ｒ2 、Ｒ3 、
Ｒ4 及びＹに含まれるアルキル基或いはアルキル部分と
しては、炭素数１〜６のもの、例えば、メチル基、エチ
ル基、プロピル基、ブチル基などが挙げられ、Ｒ1 及び
Ｒ2 に含まれるアルケニル基としては、炭素数２〜６の
もの、例えば、プロペニル基、ブテニル基などが挙げら
れ、アルキニル基としては、炭素数２〜６のもの、例え
ば、プロピニル基、ブチニル基などが挙げられ、シクロ
アルキル基としては炭素数３〜６のもの、例えばシクロ
プロピル基、シクロブチル基、シクロペンチル基、シク
ロヘキシル基などが挙げられ、Ｒ1 、Ｒ2 及びＹに関す
るハロゲン原子としては、弗素原子、塩素原子、臭素原
子、沃素原子が挙げられる。また、Ｒ1 とＲ2 は窒素原
子と共に複素環を形成してもよいが、その複素環として
は例えばモルフォリン環、エチレンイミン環、ピロリジ
ン環、ピペリジン環などが挙げられる。In the general formula (I), R 1 , R 2 , R 3 ,
The alkyl group or alkyl moiety contained in R 4 and Y includes those having 1 to 6 carbon atoms, for example, methyl group, ethyl group, propyl group, butyl group and the like, and alkenyl contained in R 1 and R 2. Examples of the group include those having 2 to 6 carbon atoms, such as a propenyl group and butenyl group, and examples of the alkynyl group include those having 2 to 6 carbon atoms, such as a propynyl group and a butynyl group. Examples of the alkyl group include those having 3 to 6 carbon atoms, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and the halogen atom for R 1 , R 2 and Y includes a fluorine atom, a chlorine atom and a bromine atom. Atoms and iodine atoms are mentioned. R 1 and R 2 may form a heterocycle with a nitrogen atom, and examples of the heterocycle include a morpholine ring, an ethyleneimine ring, a pyrrolidine ring, and a piperidine ring.
【０００９】本発明の置換ピリジンスルホンアミド系化
合物の塩は前記一般式（Ｉ）の化合物と塩基性の塩形成
物質との塩であり、具体的には例えばナトリウム、カリ
ウムなどのアルカリ金属塩、マグネシウム、カルシウム
などのアルカリ土類金属塩或いはモノメチルアミン、ジ
メチルアミン、トリエチルアミンなどのアミン塩などが
挙げられ、またそれらは、通常の方法で製造することが
できる。前記一般式（Ｉ）に於いてＲ1 及びＲ2 に含ま
れるハロアルキル基、ハロアルコキシ基、ハロアルコキ
シアルキル基、ハロアルコキシカルボニル基、ハロシク
ロアルキル基又はハロフェニル基、並びにＹに含まれる
ハロアルキル基、ハロアルコキシ基、ハロアルキルチオ
基又はハロアルコキシアルキル基はいずれもそれらが１
ケ又は２ケ以上のハロゲン原子により置換されたものを
表わす。前記一般式（Ｉ）で表わされる置換ピリジンス
ルホンアミド系化合物中、下記一般式で表わされる化合
物及びその塩が望ましい。The salt of the substituted pyridinesulfonamide compound of the present invention is a salt of the compound of the general formula (I) and a basic salt-forming substance, specifically, an alkali metal salt such as sodium or potassium, Examples thereof include alkaline earth metal salts such as magnesium and calcium, amine salts such as monomethylamine, dimethylamine and triethylamine, and these can be produced by a usual method. A haloalkyl group contained in R 1 and R 2 in the general formula (I), a haloalkoxy group, a haloalkoxyalkyl group, a haloalkoxycarbonyl group, a halocycloalkyl group or a halophenyl group, and a haloalkyl group contained in Y, Each of haloalkoxy group, haloalkylthio group and haloalkoxyalkyl group has 1
And those substituted with two or more halogen atoms. Among the substituted pyridinesulfonamide compounds represented by the general formula (I), the compounds represented by the following general formula and salts thereof are preferable.
【００１０】[0010]
【化５】 Embedded image
【００１１】更に望ましい態様を下記する。 （１）Ｒ1 は水素原子又はアルキル基、好ましくは水素
原子又はメチル基であり、Ｒ2 はアルキル基好ましくは
メチル基である。 （２）Ｙはハロゲン原子、アルキル基、ハロアルキル
基、アルコキシ基又はアルコキシアルキル基であり、好
ましくは塩素原子、臭素原子、メチル基又はジフルオロ
メチル基であってしかもそれらがピリジン核の６位に位
置し、ｎは０又は１である。Further desirable embodiments will be described below. (1) R 1 is a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group, and R 2 is an alkyl group, preferably a methyl group. (2) Y is a halogen atom, an alkyl group, a haloalkyl group, an alkoxy group or an alkoxyalkyl group, preferably a chlorine atom, a bromine atom, a methyl group or a difluoromethyl group, and they are located at the 6-position of the pyridine nucleus. However, n is 0 or 1.
【００１２】（３）Ｘ1 及びＸ2 はメトキシ基である。 （４）具体的には下記化合物が望ましいものとして挙げ
られる。Ｎ−〔（４，６−ジメトキシピリミジン−２−
イル）アミノカルボニル〕−３−メチルアミノカルボニ
ル（又はジメチルアミノカルボニル）−２−ピリジンス
ルホンアミド或いは６−クロロ（又はブロモ、ジフルオ
ロメチル或いはメチル）−Ｎ−〔（４，６−ジメトキシ
ピリミジン−２−イル）アミノカルボニル〕−３−ジメ
チルアミノカルボニル−２−ピリジンスルホンアミド。(3) X 1 and X 2 are methoxy groups. (4) Specifically, the following compounds are mentioned as desirable compounds. N-[(4,6-dimethoxypyrimidine-2-
Aryl) aminocarbonyl] -3-methylaminocarbonyl (or dimethylaminocarbonyl) -2-pyridinesulfonamide or 6-chloro (or bromo, difluoromethyl or methyl) -N-[(4,6-dimethoxypyrimidine-2- Il) aminocarbonyl] -3-dimethylaminocarbonyl-2-pyridinesulfonamide.
【００１３】前記一般式（Ｉ）で表わされる本発明の置
換ピリジンスルホンアミド系化合物及びそれらの塩は、
例えば次のような方法によって製造することができる。 一般式（II）： Ｒ−ＳＯ2 Ｚ1 …（II） 〔式中、Ｒは前述の通りであり、Ｚ1 は−ＮＨ2 基、−
ＮＣＯ基、−ＮＨＣＯＣｌ基又は−ＮＨＣＯＯＲ5 基
（Ｒ5 はアルキル基又はアリール基である）である〕で
表わされるピリジン系化合物と、一般式（III)：The substituted pyridinesulfonamide compounds of the present invention represented by the above general formula (I) and salts thereof are
For example, it can be manufactured by the following method. Formula (II): R-SO 2 Z 1 ... (II) wherein, R is as defined above, Z 1 is -NH 2 group, -
A pyridine compound represented by an NCO group, an -NHCOCl group or an -NHCOOR 5 group (R 5 is an alkyl group or an aryl group), and a general formula (III):
【化６】 〔式中、Ｘ3 及びＸ4 はハロゲン原子、メチル基、メト
キシ基、又はエトキシ基であり、Ｚ2 は−ＮＨ2 基、−
ＮＣＯ基、−ＮＨＣＯＣｌ基又は−ＮＨＣＯＯＲ5 基
（Ｒ5 は前述の通りである）であり、Ｚ1 が−ＮＨ2 基
の場合Ｚ2 は−ＮＣＯ基、−ＮＨＣＯＣｌ基又は−ＮＨ
ＣＯＯＲ5 基であり、Ｚ2 が−ＮＨ2 基の場合Ｚ1 は−
ＮＣＯ基、−ＮＨＣＯＣｌ基又は−ＮＨＣＯＯＲ5 基で
ある）で表わされるピリミジン系化合物とを反応させ、
次いでＸ3 及び／又はＸ4 がハロゲン原子の場合メトキ
シ化或いはエトキシ化を行ない、さらに所望により塩形
成処理を行なう。具体的には、次の〔Ａ〕〜〔Ｇ〕法に
よって製造することができる。[Chemical 6] [In the formula, X 3 and X 4 represent a halogen atom, a methyl group, a methoxy group, or an ethoxy group, and Z 2 represents a —NH 2 group,
NCO group, an -NHCOCl group or -NHCOOR 5 group (R 5 are as defined above), when Z 1 is -NH 2 group Z 2 is -NCO group, -NHCOCl group or -NH
It is a COOR 5 group, and when Z 2 is a —NH 2 group, Z 1 is
NCO group, —NHCOCl group or —NHCOOR 5 group) and a pyrimidine compound represented by
Next, when X 3 and / or X 4 is a halogen atom, methoxylation or ethoxylation is carried out, and if desired, salt formation treatment is carried out. Specifically, it can be manufactured by the following methods [A] to [G].
【００１４】[0014]
【化７】 [Chemical 7]
【００１５】更に、別法として次のものが挙げられる。 前記〔Ａ〕〜〔Ｈ〕の反応式において、Ｈａｌ．はハロ
ゲン原子であり、Ｒ、Ｒ5 、Ｘ1 、Ｘ2 及びＸ3 は前述
の通りである。前記一般式（II−５）で表わされる化合
物は、前記〔Ａ〕〜〔Ｆ〕法に準じて製造でき、また前
記一般式（II−６）で表わされる化合物は前記（II−
２）〜（II−４）で表わされる化合物とアンモニアとを
反応させることにより容易に得られる。前記一般式(III
−１）及び（II−２）中のＲ5 で表わされるアリール基
としては、塩素原子或いはメチル基で置換されてもよい
フェニル基又はナフチル基などが挙げられる。上記反応
〔Ａ〕及び〔Ｄ〕の反応においては、必要に応じて反応
を促進させるために、１，８−ジアザビシクロ〔５・４
・０〕−７−ウンデセンを添加してもよく、また
〔Ｂ〕、〔Ｃ〕、〔Ｅ〕及び〔Ｆ〕においては、必要に
応じて１，４−ジアザビシクロ〔２・２・２〕オクタン
を添加してもよい。さらに〔Ｂ〕、〔Ｃ〕、〔Ｅ〕及び
〔Ｆ〕の反応においては、必要に応じてトリエチルアミ
ン、ピリジンなどの塩基を添加してもよい。また上記反
応〔Ａ〕〜〔Ｈ〕は、必要に応じて溶媒の存在下で行わ
れる。溶媒としては、ベンゼン、トルエン、キシレン、
クロロベンゼンなどの芳香族炭化水素類：クロロホル
ム、四塩化炭素、塩化メチレン、ジクロロエタン、トリ
クロロエタン、ヘキサン、シクロヘキサンなどの環状又
は非環状脂肪族炭化水素類：ジエチルエーテル、ジオキ
サン、テトラヒドロフランなどのエーテル類：アセトニ
トリル、プロピオニトリル、アクリロニトリルなどのニ
トリル類：ジメチルスルホキシド、スルホランなどの非
プロトン性極性溶媒などが挙げられる。 （１）前記反応式中の出発原料である一般式（II−１）
中のピリジン系化合物（II−１′）は、下記第１〜２フ
ローに示した工程により製造することが示される。Further, as another method, the following can be mentioned. In the reaction formulas [A] to [H], Hal. Is a halogen atom, and R, R 5 , X 1 , X 2 and X 3 are as described above. The compound represented by the general formula (II-5) can be produced according to the above methods [A] to [F], and the compound represented by the general formula (II-6) is the compound represented by the above (II-
It can be easily obtained by reacting the compounds represented by 2) to (II-4) with ammonia. The general formula (III
Examples of the aryl group represented by R 5 in -1) and (II-2) include a phenyl group or a naphthyl group which may be substituted with a chlorine atom or a methyl group. In the reactions [A] and [D], 1,8-diazabicyclo [5.4] may be added in order to accelerate the reaction if necessary.
.0] -7-undecene may be added, and in [B], [C], [E] and [F], 1,4-diazabicyclo [2.2.2] octane may be added if necessary. May be added. Further, in the reaction of [B], [C], [E] and [F], a base such as triethylamine or pyridine may be added if necessary. The above reactions [A] to [H] are carried out in the presence of a solvent, if necessary. Solvents include benzene, toluene, xylene,
Aromatic hydrocarbons such as chlorobenzene: Chloroform, carbon tetrachloride, methylene chloride, dichloroethane, trichloroethane, hexane, cyclohexane and other cyclic or acyclic aliphatic hydrocarbons: diethyl ether, dioxane, ethers such as tetrahydrofuran: acetonitrile, Nitriles such as propionitrile and acrylonitrile: aprotic polar solvents such as dimethyl sulfoxide and sulfolane. (1) General formula (II-1) which is a starting material in the above reaction formula
It is shown that the pyridine compound (II-1 ′) therein is produced by the steps shown in the following first and second flows.
【００１６】[0016]
【化８】 Embedded image
【００１７】[0017]
【化９】 [Chemical 9]
【００１８】（注）ＥＧはエチレングリコール、ＭｅＯ
Ｈはメタノール、ＥｔＯＨはエタノール、ＤＭＦはジメ
チルホルムアミド、ＤＭＳＯはジメチルスルホキシド、
Ｂｚはベンジル基、−Ｂｕ（ｔ）はターシャリーブチル
基、ＡｃＯＨは酢酸、をそれぞれ表わす。また１）及び
２）の各物質は１）の物質の作用後、２）の物質を作用
させることを表わす。 （２）一般式（II−１′）において、Ｙが弗素原子で置
換されたアルキル基のものの場合は、下記第３フローに
示した工程によっても製造することが示される。(Note) EG is ethylene glycol, MeO
H is methanol, EtOH is ethanol, DMF is dimethylformamide, DMSO is dimethylsulfoxide,
Bz represents a benzyl group, -Bu (t) represents a tertiary butyl group, and AcOH represents acetic acid. Further, each of the substances 1) and 2) means that the substance of 2) is caused to act after the action of the substance of 1). (2) In the general formula (II-1 ′), when Y is an alkyl group substituted with a fluorine atom, it can be produced by the process shown in the third flow below.
【００１９】[0019]
【化１０】 [Chemical 10]
【００２０】（３）一般式（II−１′）において、Ｙが
アルコキシ基、ハロアルコキシ基、アルキルチオ基又は
ハロアルキルチオ基の場合は、下記第４フローに示した
工程によっても製造することが示される。(3) In the general formula (II-1 '), when Y is an alkoxy group, a haloalkoxy group, an alkylthio group or a haloalkylthio group, it can be produced by the process shown in the following fourth flow. Be done.
【００２１】[0021]
【化１１】 [Chemical 11]
【００２２】（４）一般式（II−１′）において、Ｙが
アルコキシメチル基又はハロアルコキシメチル基のもの
の場合は、第５フローに示した工程によっても製造する
ことが示される。(4) In the general formula (II-1 '), when Y is an alkoxymethyl group or a haloalkoxymethyl group, it can be produced by the process shown in the fifth flow.
【００２３】[0023]
【化１２】 [Chemical 12]
【００２４】（５）一般式（II−１′）において、Ｙが(5) In the general formula (II-1 '), Y is
【００２５】[0025]
【化１３】 [Chemical 13]
【００２６】基のものの場合は、第６フローに示した工
程によっても製造することが示される。In the case of the base one, it is shown that it is also manufactured by the process shown in the sixth flow.
【００２７】[0027]
【化１４】 Embedded image
【００２８】（６）一般式（II−１′）において、Ｙが
ハロゲン原子である場合、第７フローに示した工程によ
っても製造することが示される。(6) In the general formula (II-1 '), when Y is a halogen atom, it can be produced by the process shown in the seventh flow.
【００２９】[0029]
【化１５】 Embedded image
【００３０】（７）一般式（II−１′）において、３−
ピリジンスルホンアミド系化合物は、第８フローに示し
た工程によっても製造することが示される。(7) In the general formula (II-1 '), 3-
It is shown that the pyridinesulfonamide compound is also produced by the process shown in the eighth flow.
【００３１】[0031]
【化１６】 Embedded image
【００３２】（８）一般式（II−１）において、ピリジ
ン−Ｎ−オキシド系化合物（II−１″）は、第９フロー
に示した工程によっても製造することが示される。(8) It is shown that in the general formula (II-1), the pyridine-N-oxide type compound (II-1 ″) is also produced by the process shown in the ninth flow.
【００３３】[0033]
【化１７】 [Chemical 17]
【００３４】（９）前記一般式（II−２）〜（II−４）
で表わされる化合物は、一般式（II−１）で表わされる
化合物から製造することが示される。(9) The above general formulas (II-2) to (II-4)
The compound represented by is shown to be produced from the compound represented by the general formula (II-1).
【００３５】[0035]
【化１８】 Embedded image
【００３６】前記一般式（II−１′）中、一般式（IV）
で示される化合物すなわち一般式（IV）：In the general formula (II-1 '), the general formula (IV)
A compound represented by the general formula (IV):
【００３７】[0037]
【化１９】 （式中、Ｒ1 及びＲ2 は水素原子、アルキル基、ハロア
ルキル基、アルケニル基、アルキニル基、アルコキシ
基、ハロアルコキシ基、アルコキシアルキル基、ハロア
ルコキシアルキル基、シクロアルキル基、ハロシクロア
ルキル基、アルコキシカルボニル基、ハロアルコキシカ
ルボニル基、フェニル基又はハロフェニル基であり、Ｒ
1 及びＲ2 の一方が水素原子の場合他方は水素原子以外
のものであり、Ｒ1 及びＲ2 が隣接している窒素原子と
共に複素環を形成してもよく、Ｙはハロゲン原子、アル
キル基、ハロアルキル基、アルコキシ基、ハロアルコキ
シ基、アルキルチオ基、ハロアルキルチオ基、アルコキ
シアルキル基、ハロアルコキシアルキル基又は[Chemical 19] (In the formula, R 1 and R 2 are a hydrogen atom, an alkyl group, a haloalkyl group, an alkenyl group, an alkynyl group, an alkoxy group, a haloalkoxy group, an alkoxyalkyl group, a haloalkoxyalkyl group, a cycloalkyl group, a halocycloalkyl group, An alkoxycarbonyl group, a haloalkoxycarbonyl group, a phenyl group or a halophenyl group, R
When one of R 1 and R 2 is a hydrogen atom, the other is other than a hydrogen atom, and R 1 and R 2 may form a heterocycle with the adjacent nitrogen atom, and Y is a halogen atom or an alkyl group. , Haloalkyl group, alkoxy group, haloalkoxy group, alkylthio group, haloalkylthio group, alkoxyalkyl group, haloalkoxyalkyl group or
【００３８】[0038]
【化２０】 Embedded image
【００３９】（Ｒ3 及びＲ4 は水素原子又はアルキル基
である）であり、ｎは０又は１或いは２の整数であり、
Ｚ1 は−ＮＨ2 基、−ＮＣＯ基、−ＮＨＣＯＣｌ基又は
−ＮＨＣＯＯＲ5 基（Ｒ5 はアルキル基又はアリール基
である）である。但しＲ1 及びＲ2 が共にメチル基であ
り、ｎが０であり、かつＺ1 が−ＮＨ2 基又は−ＮＨＣ
ＯＯＲ5 基であり、Ｒ5 がアルキル基又はアリール基で
ある化合物を除く）で表わされる置換ピリジン系化合物
は新規である。(R 3 and R 4 are a hydrogen atom or an alkyl group), n is 0 or an integer of 1 or 2,
Z 1 is a —NH 2 group, a —NCO group, a —NHCOCl group or a —NHCOOR 5 group (R 5 is an alkyl group or an aryl group). However, R 1 and R 2 are both methyl groups, n is 0, and Z 1 is an —NH 2 group or —NHC.
Substituted pyridine-based compounds represented by OOR 5 groups, excluding compounds in which R 5 is an alkyl group or an aryl group) are novel.
【００４０】なお、原料化合物の製造法における各反応
の反応温度、反応時間、必要に応じて使用される溶媒、
アルカリ性物質などの反応条件は、通常同様の反応にお
ける反応条件から適宜選択できる。本発明化合物の具体
的な中間体の合成例を下記する。The reaction temperature and reaction time of each reaction in the method for producing the raw material compound, the solvent used as necessary,
The reaction conditions for the alkaline substance and the like can be appropriately selected from the reaction conditions for the same reactions. The synthesis examples of specific intermediates of the compound of the present invention are shown below.
【００４１】中間体合成例１ ２−アミノスルホニル−５−クロロ−Ｎ，Ｎ−ジメチル
ニコチンアミドの合成 〔Ｉ〕 ２，５−ジクロロニコチン酸６．５ｇを２４．
７ｍｌの塩化チオニル中に投入し還流下で２時間反応さ
せた。反応後、過剰の塩化チオニルを留去し、３９ｍｌ
の塩化メチレンを加えた。さらにその中へジメチルアミ
ンの塩酸塩２．７７ｇを投入し、次いでトリエチルアミ
ン８．６０ｇを約１時間で滴下した後、室温で約１時間
反応させた。反応終了後、反応物を水中に投入し、塩化
メチレン抽出を行ない、塩化メチレン層を無水硫酸ナト
リウムで乾燥した後、塩化メチレンを減圧留去した。得
られた残渣をシリカゲルカラムクロマトグラフィーで精
製し、融点１２０〜１２２℃の２，５−ジクロロ−Ｎ，
Ｎ−ジメチルニコチンアミド５．５ｇを得た。Intermediate Synthesis Example 1 Synthesis of 2-aminosulfonyl-5-chloro-N, N-dimethylnicotinamide [I] 6.5 g of 2,5-dichloronicotinic acid was added to 24.
The mixture was put into 7 ml of thionyl chloride and reacted for 2 hours under reflux. After the reaction, excess thionyl chloride was distilled off to give 39 ml.
Methylene chloride was added. Further, 2.77 g of dimethylamine hydrochloride was added thereto, and then 8.60 g of triethylamine was added dropwise over about 1 hour, followed by reaction at room temperature for about 1 hour. After the reaction was completed, the reaction product was put into water, methylene chloride extraction was performed, the methylene chloride layer was dried over anhydrous sodium sulfate, and then methylene chloride was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography to give 2,5-dichloro-N, having a melting point of 120 to 122 ° C.
5.5 g of N-dimethylnicotinamide was obtained.
【００４２】〔II〕 無水炭酸カリウム１．８９ｇのジ
メチルスルホキシド２８ｍｌの懸濁液に８０℃で前記工
程〔Ｉ〕で得られた２，５−ジクロロ−Ｎ，Ｎ−ジメチ
ルニコチンアミド３．０ｇ、ベンジルメルカプタン１．
７０ｇ及びジメチルスルホキシド５ｍｌの混合物を約１
時間で滴下し、次いで１３０〜１４０℃で３０分間反応
させた。反応終了後、反応物を水中に投入し塩化メチレ
ン抽出を行った。塩化メチレン層を無水硫酸ナトリウム
で乾燥した後、塩化メチレンを減圧留去し、得られた残
渣をシリカゲルカラムクロマトグラフィーで精製しオイ
ル状の２−ベンジルチオ−５−クロロ−Ｎ，Ｎ−ジメチ
ルニコチンアミド２．１８ｇを得た。[II] 3.0 g of 2,5-dichloro-N, N-dimethylnicotinamide obtained in the above step [I] was added to a suspension of 1.89 g of anhydrous potassium carbonate in 28 ml of dimethyl sulfoxide at 80 ° C. Benzyl mercaptan 1.
About 1 part of a mixture of 70 g and 5 ml of dimethyl sulfoxide.
The mixture was added dropwise over a period of time and then reacted at 130 to 140 ° C. for 30 minutes. After completion of the reaction, the reaction product was put into water and extracted with methylene chloride. The methylene chloride layer was dried over anhydrous sodium sulfate, methylene chloride was distilled off under reduced pressure, and the obtained residue was purified by silica gel column chromatography to give oily 2-benzylthio-5-chloro-N, N-dimethylnicotinamide. 2.18 g was obtained.
【００４３】〔III 〕 前記工程〔II〕で得られた２−
ベンジルチオ−５−クロロ−Ｎ，Ｎ−ジメチルニコチン
アミド２．３６ｇの２０ｍｌ ５０％酢酸溶液中に０〜
５℃で塩素ガスを導入した。過剰の塩素が出始めた段階
で反応を終了した。反応終了後、反応物を氷１５０ｇと
塩化メチレン２００ｍｌ中に投入し塩化メチレン層を分
液し、さらに３００ｍｌの氷水で洗浄し塩化メチレン層
を０℃に冷却した。続いてこの中へｔｅｒｔ−ブチルア
ミンを滴下し室温にもどるまで撹拌し、反応液が弱アル
カリ性であることを確認し、反応を終了した。反応終了
後、反応物を水中に投入し塩化メチレン抽出し、無水硫
酸ナトリウムで乾燥の後、塩化メチレンを留去した。得
られた残渣をシリカゲルカラムクロマトグラフィーで精
製し、融点１４３〜１４５℃の２−ｔｅｒｔ−ブチルア
ミノスルホニル−５−クロロ−Ｎ，Ｎ−ジメチルニコチ
ンアミド１．２１ｇを得た。[III] 2-obtained in the above step [II]
Benzylthio-5-chloro-N, N-dimethylnicotinamide 0-36 in 20 ml 50% acetic acid solution of 2.36 g.
Chlorine gas was introduced at 5 ° C. The reaction was terminated when excess chlorine started to be generated. After completion of the reaction, the reaction product was poured into 150 g of ice and 200 ml of methylene chloride, the methylene chloride layer was separated, and further washed with 300 ml of ice water, and the methylene chloride layer was cooled to 0 ° C. Subsequently, tert-butylamine was added dropwise thereto and stirred until the temperature returned to room temperature, and it was confirmed that the reaction solution was weakly alkaline, and the reaction was completed. After completion of the reaction, the reaction product was put into water, extracted with methylene chloride, dried over anhydrous sodium sulfate, and then methylene chloride was distilled off. The obtained residue was purified by silica gel column chromatography to obtain 1.21 g of 2-tert-butylaminosulfonyl-5-chloro-N, N-dimethylnicotinamide having a melting point of 143-145 ° C.
【００４４】〔IV〕 トリフルオロ酢酸１０ｍｌ中に前
記工程〔III 〕で得られた２−ｔｅｒｔ−ブチルアミノ
スルホニル−５−クロロ−Ｎ，Ｎ−ジメチルニコチンア
ミド１．０ｇを加え還流下で約１時間反応させた。反応
終了後、反応物よりトリフルオロ酢酸を減圧留去した
後、得られた残渣物をシリカゲルカラムクロマトグラフ
ィーにより精製して融点１５５〜１５７℃の２−アミノ
スルホニル−５−クロロ−Ｎ，Ｎ−ジメチルニコチンア
ミド０．７１ｇを得た。[IV] 1.0 g of 2-tert-butylaminosulfonyl-5-chloro-N, N-dimethylnicotinamide obtained in the above step [III] was added to 10 ml of trifluoroacetic acid, and the mixture was refluxed to about 1 Reacted for hours. After completion of the reaction, trifluoroacetic acid was distilled off from the reaction product under reduced pressure, and the obtained residue was purified by silica gel column chromatography to give 2-aminosulfonyl-5-chloro-N, N- having a melting point of 155 to 157 ° C. 0.71 g of dimethylnicotinamide was obtained.
【００４５】中間体合成例２ ２−アミノスルホニル−６−クロロ−Ｎ，Ｎ−ジメチル
ニコチンアミドの合成 〔Ｉ〕 ２，６−ジクロロニコチン酸２３ｇを１００ｍ
ｌの塩化チオニル中に投入し還流下で１時間半反応させ
た。反応後、過剰の塩化チオニルを留去し、３００ｍｌ
の塩化メチレンを加えた。さらにその中へジメチルアミ
ンの塩酸塩１１．７ｇを投入し、次いでトリエチルアミ
ン１５．８ｇを約１時間で滴下した後、室温で約１時間
反応させた。反応終了後、反応物を水５００ｍｌ中に投
入し、塩化メチレン抽出を行ない、塩化メチレン層を無
水硫酸ナトリウムで乾燥した後塩化メチレンを減圧留去
した。得られた残渣をシリカゲルカラムクロマトグラフ
ィーで精製し、融点６２．５〜６５℃の２，６−ジクロ
ロ−Ｎ，Ｎ−ジメチルニコチンアミド１９ｇを得た。Intermediate Synthesis Example 2 Synthesis of 2-aminosulfonyl-6-chloro-N, N-dimethylnicotinamide [I] 23 g of 2,6-dichloronicotinic acid was added to 100 m.
It was put into 1 thionyl chloride and reacted for 1 and a half hours under reflux. After the reaction, excess thionyl chloride was distilled off, and 300 ml was added.
Methylene chloride was added. Further, 11.7 g of dimethylamine hydrochloride was added thereto, and then 15.8 g of triethylamine was added dropwise in about 1 hour, and then the reaction was carried out at room temperature for about 1 hour. After completion of the reaction, the reaction product was poured into 500 ml of water, methylene chloride extraction was performed, the methylene chloride layer was dried over anhydrous sodium sulfate, and then methylene chloride was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography to obtain 19 g of 2,6-dichloro-N, N-dimethylnicotinamide having a melting point of 62.5 to 65 ° C.
【００４６】〔II〕 無水炭酸カリウム６．６ｇのジメ
チルスルホキシド５０ｍｌの懸濁液に１３０〜１４０℃
で前記工程〔Ｉ〕で得られた２，６−ジクロロ−Ｎ，Ｎ
−ジメチルニコチンアミド７．０ｇ、ベンジルアルコー
ル３．８ｇ及びジメチルスルホキシド２０ｍｌの混合物
を約１時間で滴下し、次いで１５０℃で約２時間反応さ
せた。反応終了後、反応物を水中に投入し塩化メチレン
抽出を行った。塩化メチレン層は無水硫酸ナトリウムで
乾燥した後、塩化メチレンを減圧留去し、得られた残渣
をシリカゲルカラムクロマトグラフィーで精製しオイル
状の６−ベンジルオキシ−２−クロロ−Ｎ，Ｎ−ジメチ
ルニコチンアミド６．０ｇを得た。[II] 130-140 ° C. in a suspension of 6.6 g of anhydrous potassium carbonate in 50 ml of dimethyl sulfoxide.
2,6-dichloro-N, N obtained in the above step [I]
A mixture of 7.0 g of dimethyl nicotinamide, 3.8 g of benzyl alcohol and 20 ml of dimethyl sulfoxide was added dropwise in about 1 hour and then reacted at 150 ° C. for about 2 hours. After completion of the reaction, the reaction product was put into water and extracted with methylene chloride. The methylene chloride layer was dried over anhydrous sodium sulfate, methylene chloride was distilled off under reduced pressure, and the resulting residue was purified by silica gel column chromatography to give oily 6-benzyloxy-2-chloro-N, N-dimethylnicotine. 6.0 g of amide was obtained.
【００４７】〔III 〕 無水炭酸カリウム２．２ｇのジ
メチルスルホキシド３０ｍｌの懸濁液中に１５０℃で前
記工程〔II〕で得られた６−ベンジルオキシ−２−クロ
ロ−Ｎ，Ｎ−ジメチルニコチンアミド２．９ｇ、ベンジ
ルメルカプタン１．５ｇ及びジメチルスルホキシド２０
ｍｌの混合物を約３０分で滴下し、次いで１５０℃で約
１．５時間反応させた。反応終了後、反応物を水中に投
入し塩化メチレン抽出を行ない、塩化メチレン層を無水
硫酸ナトリウムで乾燥した後塩化メチレンを減圧留去
し、得られた残渣物をシリカゲルカラムクロマトグラフ
ィーで精製しオイル状の６−ベンジルオキシ−２−ベン
ジルチオ−Ｎ，Ｎ−ジメチルニコチンアミド０．９８ｇ
を得た。[III] 6-benzyloxy-2-chloro-N, N-dimethylnicotinamide obtained in the above step [II] at 150 ° C. in a suspension of 2.2 g of anhydrous potassium carbonate in 30 ml of dimethyl sulfoxide. 2.9 g, benzyl mercaptan 1.5 g and dimethyl sulfoxide 20
The mixture of ml was added dropwise in about 30 minutes, and then the mixture was reacted at 150 ° C. for about 1.5 hours. After the reaction was completed, the reaction product was put into water and extracted with methylene chloride. The methylene chloride layer was dried over anhydrous sodium sulfate, and the methylene chloride was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography to obtain an oil. 6-benzyloxy-2-benzylthio-N, N-dimethylnicotinamide 0.98 g
I got
【００４８】〔IV〕 濃塩酸６ｃｃ中に前記工程〔III
〕で得られた６−ベンジルオキシ−２−ベンジルチオ
−Ｎ，Ｎ−ジメチルニコチンアミド０．６９ｇを投入
し、室温で撹拌下約１５時間反応させた。反応終了後、
反応物を水中に投入し、塩化メチレンで目的物を抽出し
た。塩化メチレン層は無水硫酸ナトリウムで乾燥した
後、塩化メチレンを減圧留去した。得られた残渣物をシ
リカゲルクロマトグラフィーで精製し、融点５２〜６０
℃の２−ベンジルチオ−Ｎ，Ｎ−ジメチル−６−ヒドロ
キシニコチンアミド０．４１ｇを得た。[IV] The above-mentioned step [III] was carried out in 6 cc of concentrated hydrochloric acid.
] 6-Benzyloxy-2-benzylthio-N, N-dimethylnicotinamide (0.69 g) obtained above was added, and the mixture was reacted at room temperature for about 15 hours with stirring. After the reaction,
The reaction product was put into water and the desired product was extracted with methylene chloride. The methylene chloride layer was dried over anhydrous sodium sulfate, and then methylene chloride was distilled off under reduced pressure. The residue obtained is purified by silica gel chromatography, melting point 52-60.
0.41 g of 2-benzylthio-N, N-dimethyl-6-hydroxynicotinamide at 0 ° C was obtained.
【００４９】〔Ｖ〕 ５ｃｃの塩化チオニル中に前記工
程〔IV〕で得られた２−ベンジルチオ−Ｎ，Ｎ−ジメチ
ル−６−ヒドロキシニコチンアミド１．０ｇ及びジメチ
ルホルムアミド０．３ｍｌを加え還流下で約１時間反応
させた。反応終了後、反応物を氷中に投入し、塩化メチ
レンで目的物を抽出した。塩化メチレン層を水洗いした
後、無水硫酸ナトリウムで乾燥し、塩化メチレンを減圧
留去した後、得られた残渣物をシリカゲルクロマトグラ
フィーで精製し、オイル状の２−ベンジルチオ−６−ク
ロロ−Ｎ，Ｎ−ジメチルニコチンアミド０．４５ｇを得
た。[V] 1.0 g of 2-benzylthio-N, N-dimethyl-6-hydroxynicotinamide obtained in the above step [IV] and 0.3 ml of dimethylformamide were added to 5 cc of thionyl chloride, and the mixture was refluxed. The reaction was performed for about 1 hour. After completion of the reaction, the reaction product was put into ice and the target product was extracted with methylene chloride. The methylene chloride layer was washed with water, dried over anhydrous sodium sulfate, and the methylene chloride was distilled off under reduced pressure. The obtained residue was purified by silica gel chromatography to give oily 2-benzylthio-6-chloro-N, 0.45 g of N-dimethylnicotinamide was obtained.
【００５０】〔VI〕 このものを用い、前記中間体合成
例１の工程〔III 〕及び〔IV〕と同様の方法で融点１７
１〜１７３℃の２−アミノスルホニル−６−クロロ−
Ｎ，Ｎ−ジメチルニコチンアミドを得た。[VI] Using this, a melting point of 17 was obtained in the same manner as in the steps [III] and [IV] of the above-mentioned Intermediate Synthesis Example 1.
2-aminosulfonyl-6-chloro- at 1 to 173 ° C
N, N-dimethylnicotinamide was obtained.
【００５１】中間体合成例３ ２−アミノスルホニル−Ｎ，Ｎ−ジメチル−６−エトキ
シニコチンアミドの合成 〔Ｉ〕 無水エタノール５０ｍｌ中に金属ナトリウム
０．２３１ｇを投入し、ナトリウムエトキサイドのエタ
ノール溶液を調製した。この中へ前記中間体合成例１の
工程〔Ｉ〕と同様の方法で得られた２，６−ジクロロ−
Ｎ，Ｎ−ジメチルニコチンアミド２．０ｇを投入し、約
１時間還流下で反応させた。反応液を水中に投入し、塩
化メチレン抽出を行なった。塩化メチレン層は無水硫酸
ナトリウムで乾燥した後、塩化メチレンを減圧留去し
た。シリカゲルカラムクロマトグラフィーで精製して、
油状の２−クロロ−Ｎ，Ｎ−ジメチル−６−エトキシニ
コチンアミド１．９５ｇを得た。 〔II〕 このものを用い、前記中間体合成例１の工程
〔II〕、〔III 〕及び〔IV〕と同様の方法で融点１５
０．５〜１５１．５℃の２−アミノスルホニル−Ｎ，Ｎ
−ジメチル−６−エトキシニコチンアミドを得た。Intermediate Synthesis Example 3 Synthesis of 2-aminosulfonyl-N, N-dimethyl-6-ethoxynicotinamide [I] 0.231 g of metallic sodium was added to 50 ml of anhydrous ethanol to prepare an ethanol solution of sodium ethoxide. Prepared. 2,6-dichloro-obtained in the same manner as in Step [I] of Intermediate Synthesis Example 1
2.0 g of N, N-dimethylnicotinamide was added, and the mixture was reacted under reflux for about 1 hour. The reaction solution was put into water and extracted with methylene chloride. The methylene chloride layer was dried over anhydrous sodium sulfate, and then methylene chloride was distilled off under reduced pressure. Purify by silica gel column chromatography,
1.95 g of oily 2-chloro-N, N-dimethyl-6-ethoxynicotinamide was obtained. [II] Using this, a melting point of 15 was obtained in the same manner as in the steps [II], [III] and [IV] of the above-mentioned Intermediate Synthesis Example 1.
2-aminosulfonyl-N, N at 0.5 to 151.5 ° C
-Dimethyl-6-ethoxynicotinamide was obtained.
【００５２】中間体合成例４ ２−アミノスルホニル−Ｎ，Ｎ−ジメチル−６−フルオ
ロニコチンアミドの合成 〔Ｉ〕 ２−ｔｅｒｔ−ブチルアミノスルホニル−６−
クロロ−Ｎ，Ｎ−ジメチルニコチンアミド０．３０２ｇ
及びスプレードライフッ化カリウム０．１１６ｇのジメ
チルスルホキシドスラリー溶液１０ｍｌを１５０℃で撹
拌下約３時間反応させた。反応終了後、反応液を１００
ｍｌの水中に投入し塩化メチレンで抽出した。抽出物は
水洗をくり返した後、無水硫酸ナトリウムで乾燥した
後、塩化メチレンを減圧留去し、シリカゲルクロマトグ
ラフィーで精製して２−ｔｅｒｔ−ブチルアミノスルホ
ニル−Ｎ，Ｎ−ジメチル−６−フルオロニコチンアミド
０．２０４ｇを得た。 〔II〕 このものを用い、前記中間体合成例１の工程
〔IV〕と同様の方法で融点１６４〜１６５℃の２−アミ
ノスルホニル−Ｎ，Ｎ−ジメチル−６−フルオロニコチ
ンアミドを得た。Intermediate Synthesis Example 4 Synthesis of 2-aminosulfonyl-N, N-dimethyl-6-fluoronicotinamide [I] 2-tert-butylaminosulfonyl-6-
Chloro-N, N-dimethylnicotinamide 0.302 g
Then, 10 ml of a dimethylsulfoxide slurry solution containing 0.116 g of spray-dried potassium fluoride was reacted at 150 ° C. for about 3 hours with stirring. After the reaction is complete, add 100
It was put into ml of water and extracted with methylene chloride. The extract was washed with water repeatedly, dried over anhydrous sodium sulfate, methylene chloride was distilled off under reduced pressure, and the residue was purified by silica gel chromatography to give 2-tert-butylaminosulfonyl-N, N-dimethyl-6-fluoronicotine. 0.204 g of amide was obtained. [II] Using this compound, 2-aminosulfonyl-N, N-dimethyl-6-fluoronicotinamide having a melting point of 164 to 165 ° C was obtained in the same manner as in Step [IV] of Intermediate Synthesis Example 1 above.
【００５３】中間体合成例５ ２−アミノスルホニル−Ｎ−メチルニコチンアミドの合
成 〔Ｉ〕 乾燥したメタノール２５０ｍｌに室温で塩酸ガ
スを飽和させた後、２５０ｍｌのメタノール及び２−メ
ルカプトニコチン酸３０ｇを加え、室温で終夜反応させ
た。反応後、アンモニアガスで反応液を弱アルカリ性と
した後、メタノールを減圧留去した。続いて生じた結晶
を水洗後、濾取し、減圧乾燥して融点１３６〜１４０℃
のメチル ２−メルカプトニコチネート２４ｇを得た。Intermediate Synthesis Example 5 Synthesis of 2-aminosulfonyl-N-methylnicotinamide [I] 250 ml of dried methanol was saturated with hydrochloric acid gas at room temperature, and then 250 ml of methanol and 30 g of 2-mercaptonicotinic acid were added. , Reacted overnight at room temperature. After the reaction, the reaction solution was made weakly alkaline with ammonia gas, and then methanol was distilled off under reduced pressure. Subsequently, the crystals formed are washed with water, collected by filtration, dried under reduced pressure, and have a melting point of 136 to 140 ° C.
24 g of methyl 2-mercaptonicotinate was obtained.
【００５４】〔II〕 前記工程〔Ｉ〕で得たメチル ２
−メルカプトニコチネート１０ｇを、５０ｍｌの酢酸を
５０ｍｌの水で希釈した溶液に加えた後、０℃以下で塩
素ガスを反応系内に導入し、過剰の塩素が出始めた段階
で反応を終了した。反応後、生じた溶液を氷１５０ｇと
塩化メチレン５００ｍｌの混合物中に投入し、塩化メチ
レン層を分液した。さらに５００ｍｌの氷水で洗浄し、
塩化メチレン層を０℃に冷却した。続いてこの中へ、ｔ
ｅｒｔ−ブチルアミン１２．９ｇを滴下し、室温にもど
るまで撹拌した。撹拌後、この反応液を５００ｍｌの水
中に投入し、塩化メチレン抽出し、無水硫酸ナトリウム
で乾燥の後、塩化メチレンを留去し、粗結晶１３ｇを得
た。このものを塩化メチレン、ノルマルヘキサンで再結
晶し、融点１６９〜１７１℃のメチル ２−ｔｅｒｔ−
ブチルアミノスルホニルニコチネートを得た。[II] Methyl 2 obtained in the above step [I]
-After adding 10 g of mercaptonicotinate to a solution prepared by diluting 50 ml of acetic acid with 50 ml of water, chlorine gas was introduced into the reaction system at 0 ° C or lower, and the reaction was terminated when excess chlorine started to be generated. . After the reaction, the resulting solution was poured into a mixture of 150 g of ice and 500 ml of methylene chloride to separate the methylene chloride layer. Wash with an additional 500 ml of ice water,
The methylene chloride layer was cooled to 0 ° C. Then into this, t
12.9 g of ert-butylamine was added dropwise, and the mixture was stirred until it returned to room temperature. After stirring, the reaction solution was poured into 500 ml of water, extracted with methylene chloride, dried over anhydrous sodium sulfate, and then methylene chloride was distilled off to obtain 13 g of crude crystals. This product was recrystallized from methylene chloride and normal hexane to give methyl 2-tert- having a melting point of 169 to 171 ° C.
Butylaminosulfonyl nicotinate was obtained.
【００５５】〔III 〕 無水メタノール２０ｍｌに大過
剰のメチルアミンを吸収させた後、室温で前記工程〔I
I〕で得たメチル ２−ｔｅｒｔ−ブチルアミノスルホ
ニルニコチネート１．０ｇを加え、１５時間撹拌し反応
を終了した。反応後、反応物を水中に投入し塩化メチレ
ンで抽出し、抽出液を無水硫酸ナトリウムで乾燥し、塩
化メチレンを減圧で留去して、融点１８９〜１９２℃の
２−ｔｅｒｔ−ブチルアミノスルホニル−Ｎ−メチルニ
コチンアミド０．７３ｇを得た。 〔IV〕 このものを用い、前記中間体合成例１の工程
〔IV〕と同様の方法で融点２０７〜２０９．５℃の２−
アミノスルホニル−Ｎ−メチルニコチンアミドを得た。[III] After absorbing a large excess of methylamine in 20 ml of anhydrous methanol, the above-mentioned step [I
1.0 g of methyl 2-tert-butylaminosulfonylnicotinate obtained in [I] was added, and the reaction was completed by stirring for 15 hours. After the reaction, the reaction product was poured into water and extracted with methylene chloride, the extract was dried over anhydrous sodium sulfate, and methylene chloride was distilled off under reduced pressure to give 2-tert-butylaminosulfonyl-melting point 189 to 192 ° C. 0.73 g of N-methylnicotinamide was obtained. [IV] Using this compound, the melting point of 207 to 209.5 ° C of 2-
Aminosulfonyl-N-methylnicotinamide was obtained.
【００５６】中間体合成例６ ２−アミノスルホニル−Ｎ，Ｎ−ジメチルニコチンアミ
ドの合成 〔Ａ法〕 〔Ｉ〕 ジメチルアミン１．３ｍｌを１０ｍｌの無水ベ
ンゼンに溶解した溶液に窒素雰囲気下１０℃以下で１９
％トリメチルアルミニウムのノルマルヘキサン溶液１０
ｍｌを加えた。室温になるまで反応させた後、メチル
２−ｔｅｒｔ−ブチルアミノスルホニルニコチネートを
ベンゼン４０ｍｌ、塩化メチレン２０ｍｌに溶解した溶
液を滴下した。続いて還流下で約９時間撹拌し反応を終
了した。反応終了後、反応液を希塩酸中に投入し、塩化
メチレンで抽出し、抽出物を無水硫酸ナトリウムで乾燥
した後、減圧下で塩化メチレンを留去し、シリカゲルカ
ラムクロマトグラフィーで精製して２−ｔｅｒｔ−ブチ
ルアミノスルホニル−Ｎ，Ｎ−ジメチルニコチンアミド
１．０ｇを得た。Intermediate Synthesis Example 6 Synthesis of 2-aminosulfonyl-N, N-dimethylnicotinamide [Method A] [I] Dimethylamine (1.3 ml) dissolved in 10 ml of anhydrous benzene was dissolved in a solution of benzene under nitrogen atmosphere at 10 ° C. or lower. At 19
% Trimethylaluminum solution in normal hexane 10
ml was added. After reacting to room temperature, methyl
A solution of 2-tert-butylaminosulfonylnicotinate in 40 ml of benzene and 20 ml of methylene chloride was added dropwise. Then, the mixture was stirred under reflux for about 9 hours to complete the reaction. After completion of the reaction, the reaction solution was poured into dilute hydrochloric acid, extracted with methylene chloride, the extract was dried over anhydrous sodium sulfate, methylene chloride was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography. 1.0 g of tert-butylaminosulfonyl-N, N-dimethylnicotinamide was obtained.
【００５７】〔II〕 このものを用い、前記中間体合成
例１の工程〔IV〕と同様の方法で融点２０９〜２１１℃
の２−アミノスルホニルＮ，Ｎ−ジメチルニコチンアミ
ドを得た。 〔Ｂ法〕２−ベンジルチオ−Ｎ，Ｎ−ジメチルニコチン
アミド２．７ｇの５０ｍｌ ５０％酢酸溶液中に０〜５
℃で塩素ガスを過剰の塩素が出るまで導入した。反応終
了後、反応混合物を２００ｍｌの氷水中に投入し、６０
ｍｌの塩化メチレンで抽出した。次いで塩化メチレン層
を１００ｍｌの氷水で洗浄し、０℃に冷却してアルカリ
性になるまでアンモニアガスを導入した。塩化メチレン
を留去した後、残渣に水１５ｍｌを加え撹拌した。生じ
た結晶を濾取し、少量の水で洗浄した後、減圧乾燥して
融点２０９〜２１１℃を有する２−アミノスルホニル−
Ｎ，Ｎ−ジメチルニコチンアミド１．２７ｇを得た。[II] Using this compound, the melting point of 209 to 211 ° C. was measured in the same manner as in the step [IV] of Intermediate Synthesis Example 1 above.
2-aminosulfonyl N, N-dimethylnicotinamide was obtained. [Method B] 2-benzylthio-N, N-dimethylnicotinamide (2.7 g) in a 50% 50% acetic acid solution was added with 0-5.
Chlorine gas was introduced at ° C until excess chlorine was released. After the reaction was completed, the reaction mixture was poured into 200 ml of ice water,
Extracted with ml methylene chloride. Next, the methylene chloride layer was washed with 100 ml of ice water, cooled to 0 ° C., and ammonia gas was introduced until it became alkaline. After distilling off methylene chloride, 15 ml of water was added to the residue and the mixture was stirred. The resulting crystals were collected by filtration, washed with a small amount of water, and dried under reduced pressure to give 2-aminosulfonyl- having a melting point of 209 to 211 ° C.
1.27 g of N, N-dimethylnicotinamide was obtained.
【００５８】中間体合成例７ ２−アミノスルホニル−Ｎ−エチル−Ｎ−メチルニコチ
ンアミドの合成 〔Ｉ〕 ２−クロロニコチン酸３０ｇ及び塩化チオニル
の混合物を還流下で４時間反応させた。反応液より、過
剰の塩化チオニルを減圧で留去した後、塩化メチレン５
００ｍｌを加え室温でメチルアミンガスを反応液が弱ア
ルカリ性になるまで導入した。生じたメチルアミンの塩
酸塩を濾別し、濾液を濃縮した。生じた結晶をノルマル
ヘキサンと塩化メチレンより再結晶して、融点１０６〜
１０７℃の２−クロロ−Ｎ−メチルニコチンアミド２７
ｇを得た。Intermediate Synthesis Example 7 Synthesis of 2-aminosulfonyl-N-ethyl-N-methylnicotinamide [I] A mixture of 30 g of 2-chloronicotinic acid and thionyl chloride was reacted under reflux for 4 hours. After distilling off excess thionyl chloride from the reaction solution under reduced pressure, methylene chloride
00 ml was added and methylamine gas was introduced at room temperature until the reaction solution became weakly alkaline. The generated methylamine hydrochloride was filtered off and the filtrate was concentrated. The resulting crystals are recrystallized from normal hexane and methylene chloride to give a melting point of 106-
2-chloro-N-methylnicotinamide 27 at 107 ° C
g was obtained.
【００５９】〔II〕 ジメチルホルムアミド５０ｍｌ中
に懸濁させた６０％ナトリウムハイドロライド１．１７
ｇ中に前記工程〔Ｉ〕で得られた２−クロロ−Ｎ−メチ
ルニコチンアミド５ｇのジメチルホルムアミド１０ｍｌ
溶液を０〜５℃で滴下した。０〜５℃で約３０分間反応
させた後、３．５ｇのエチルブロマイドを０℃で滴下し
た。室温で約２．５時間反応させた後、水中に投入し、
塩化メチレンで抽出した。抽出物は水洗を行なった後、
無水硫酸ナトリウムで乾燥し、塩化メチレンを減圧で留
去した。シリカゲルカラムクロマトグラフィーで精製を
行ない、オイル状の２−クロロ−Ｎ−エチル−Ｎ−メチ
ルニコチンアミド５．７ｇを得た。 〔III 〕 このものを用い、前記中間体合成例１の工程
〔II〕〜〔IV〕と同様の方法で融点２０２〜２０３℃の
２−アミノスルホニル−Ｎ−エチル−Ｎ−メチルニコチ
ンアミドを得た。[II] 60% sodium hydroxide 1.17 suspended in 50 ml of dimethylformamide
5 g of 2-chloro-N-methylnicotinamide obtained in the above step [I] in 10 g of dimethylformamide
The solution was added dropwise at 0-5 ° C. After reacting at 0 to 5 ° C for about 30 minutes, 3.5 g of ethyl bromide was added dropwise at 0 ° C. After reacting at room temperature for about 2.5 hours, put into water,
It was extracted with methylene chloride. After washing the extract with water,
After drying over anhydrous sodium sulfate, methylene chloride was distilled off under reduced pressure. Purification was performed by silica gel column chromatography to obtain 5.7 g of oily 2-chloro-N-ethyl-N-methylnicotinamide. [III] Using this, 2-aminosulfonyl-N-ethyl-N-methylnicotinamide having a melting point of 202 to 203 ° C. was obtained in the same manner as in Steps [II] to [IV] of Intermediate Synthesis Example 1 above. It was
【００６０】中間体合成例８ ２−アミノスルホニル−Ｎ，Ｎ−ジメチル−６−メチル
ニコチンアミドの合成 〔Ｉ〕 ２−ヒドロキシ−６−メチルニコチン酸１．３
５ｇ及び塩化チオニル１５ｍｌの混合物にジメチルホル
ムアミドを一滴加え、還流下で約２時間反応させた後、
過剰の塩化チオニルを減圧留去し、残渣に塩化メチレン
５０ｍｌを加えた。このものを３０％ジメチルアミン水
溶液３０ｍｌ及び塩化メチレン５０ｍｌの混合物中に滴
下し、室温で１５分間反応させた。Intermediate Synthesis Example 8 Synthesis of 2-aminosulfonyl-N, N-dimethyl-6-methylnicotinamide [I] 2-hydroxy-6-methylnicotinic acid 1.3
A drop of dimethylformamide was added to a mixture of 5 g and thionyl chloride 15 ml, and the mixture was reacted under reflux for about 2 hours.
Excess thionyl chloride was distilled off under reduced pressure, and 50 ml of methylene chloride was added to the residue. This was added dropwise to a mixture of 30 ml of 30% dimethylamine aqueous solution and 50 ml of methylene chloride, and the mixture was reacted at room temperature for 15 minutes.
【００６１】反応終了後、反応混合物を水中投入し、塩
化メチレン抽出した。塩化メチレン層は水洗した後、無
水硫酸ナトリウムで乾燥し、減圧で塩化メチレンを留去
し、シリカゲルカラムクロマトグラフィーにより精製
し、融点６６〜６７．５℃の２−クロロ−３−Ｎ，Ｎ−
ジメチルアミノカルボニル−６−メチルピリジン１．５
７ｇ（ｍ．ｐ．６６〜６７．５℃）を得た。 〔II〕 このものを用い、前記中間体合成例１の工程
〔II〕〜〔IV〕と同様の方法で融点１８８．５〜１９
０．５℃の２−アミノスルホニル−Ｎ，Ｎ−ジメチル−
６−メチルニコチンアミドを得た。After completion of the reaction, the reaction mixture was put into water and extracted with methylene chloride. The methylene chloride layer was washed with water, dried over anhydrous sodium sulfate, methylene chloride was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography to give 2-chloro-3-N, N- having a melting point of 66 to 67.5 ° C.
Dimethylaminocarbonyl-6-methylpyridine 1.5
7 g (mp 66-67.5 ° C.) was obtained. [II] Using this compound, the melting point of 188.5 to 19 was obtained in the same manner as in Steps [II] to [IV] of Intermediate Synthesis Example 1 above.
2-aminosulfonyl-N, N-dimethyl-at 0.5 ° C
6-Methylnicotinamide was obtained.
【００６２】中間体合成例９ ２−アミノスルホニル−Ｎ，Ｎ−ジメチル−６−メトキ
シニコチンアミドの合成 〔Ｉ〕 ２，６−ジクロロニコチン酸３３ｇ及び塩化チ
オニル１００ｍｌを混合し、還流下で約３時間反応を行
なった。反応終了後、過剰の塩化チオニルを減圧留去し
た後、塩化メチレン５００ｍｌをこの中へ投入した。室
温から４０℃でこの混合物中に無水メタノールを滴下し
た。滴下終了後、約１時間還流下で反応させた。反応終
了後、反応液を５００ｍｌの水中に投入し、塩化メチレ
ンで分液し、水洗した後、無水硫酸ナトリウムで乾燥
し、減圧で塩化メチレンを留去した。次いでシリカゲル
カラムクロマトグラフィーで精製して、融点４５．５〜
４８．０℃のメチル ２，６−ジクロロニコチネート２
７ｇを得た。Intermediate Synthesis Example 9 Synthesis of 2-aminosulfonyl-N, N-dimethyl-6-methoxynicotinamide [I] 33 g of 2,6-dichloronicotinic acid and 100 ml of thionyl chloride were mixed and refluxed to about 3 A time reaction was performed. After completion of the reaction, excess thionyl chloride was distilled off under reduced pressure, and then 500 ml of methylene chloride was added thereto. Anhydrous methanol was added dropwise to this mixture at room temperature to 40 ° C. After the dropping was completed, the reaction was carried out under reflux for about 1 hour. After completion of the reaction, the reaction solution was poured into 500 ml of water, separated with methylene chloride, washed with water, dried over anhydrous sodium sulfate, and methylene chloride was distilled off under reduced pressure. Then purified by silica gel column chromatography, melting point 45.5-
Methyl 2,6-dichloronicotinate 2 at 48.0 ° C
7 g were obtained.
【００６３】〔II〕 このものを用い、６位のメトキシ
化反応、２位のベンジルチオ化反応、アミド化反応、２
位のターシャリーブチルアミノスルホニル化反応次いで
脱ターシャリーブチル化反応を行ない（それぞれ前記中
間体合成例３の工程〔Ｉ〕、同合成例１の工程〔II〕、
同合成例６の〔Ａ法〕工程〔Ｉ〕、同合成例１の工程
〔III 〕及び〔IV〕と同様の方法）２−アミノスルホニ
ル−Ｎ，Ｎ−ジメチル−６−メトキシニコチンアミドを
得た。[II] Using this, methoxylation reaction at 6-position, benzylthiolation reaction at 2-position, amidation reaction, 2
Position tertiary butylamino sulfonylation reaction and then detertiary butyl amino sulfonylation reaction (step [I] of Intermediate Synthesis Example 3 and step [II] of Synthesis Example 1, respectively)
Method similar to [Method A] Step [I] of Synthesis Example 6 and Steps [III] and [IV] of Synthesis Example 1) to obtain 2-aminosulfonyl-N, N-dimethyl-6-methoxynicotinamide. It was
【００６４】中間体合成例１０ ２−アミノスルホニル−６−ジフルオロメチル−Ｎ，Ｎ
−ジメチルニコチンアミドの合成 〔Ｉ〕 前記中間体合成例５の工程〔Ｉ〕及び〔II〕と
同様な方法で得たメチル２−ｔｅｒｔ−ブチルアミノス
ルホニル−６−メチルニコチネート１１．５ｇ、四塩化
炭素１８６ｍｌ、Ｎ−ブロモスクシンイミド１４．８４
ｇ及び過酸化ベンゾイル０．６８ｇの混合物を３時間加
熱還流した。反応終了後、反応混合物を濾過し、濾液を
減圧濃縮しシリカゲルカラムクロマトグラフィーにて精
製してメチル ２−ｔｅｒｔ−ブチルアミノスルホニル
−６−ジブロモメチルニコチネート４．５ｇを得た。Intermediate Synthesis Example 10 2-Aminosulfonyl-6-difluoromethyl-N, N
-Synthesis of dimethylnicotinamide [I] 11.5 g of methyl 2-tert-butylaminosulfonyl-6-methylnicotinate obtained in the same manner as in Steps [I] and [II] of Intermediate Synthesis Example 5 above, Carbon chloride 186 ml, N-bromosuccinimide 14.84
g and 0.68 g of benzoyl peroxide were heated to reflux for 3 hours. After completion of the reaction, the reaction mixture was filtered, the filtrate was concentrated under reduced pressure and purified by silica gel column chromatography to obtain 4.5 g of methyl 2-tert-butylaminosulfonyl-6-dibromomethylnicotinate.
【００６５】〔II〕 このものの４．４ｇ、エタノール
３５ｍｌ、及び水２９ｍｌの混合物に硝酸銀３．７ｇを
加え３時間加熱還流した。反応終了後、反応混合物を水
中に投入し、塩化メチレンで抽出し、水洗後、無水硫酸
ナトリウムで乾燥し溶媒を留去した。残渣をシリカゲル
カラムクロマトグラフィーにて精製してメチル ２−ｔ
ｅｒｔ−ブチルアミノスルホニル−６−ホルミルニコチ
ネート２．９２ｇを得た。[II] To a mixture of 4.4 g of this product, 35 ml of ethanol, and 29 ml of water was added 3.7 g of silver nitrate, and the mixture was heated under reflux for 3 hours. After completion of the reaction, the reaction mixture was put into water, extracted with methylene chloride, washed with water, dried over anhydrous sodium sulfate, and the solvent was distilled off. The residue is purified by silica gel column chromatography to produce methyl 2-t.
2.92 g of ert-butylaminosulfonyl-6-formylnicotinate was obtained.
【００６６】〔III 〕 このホルミルニコチネート０．
４８ｇの塩化メチレン１９ｍｌ溶液に氷冷下ジエチルア
ミノ三ふっ化イオウ０．６２ｇの塩化メチレン５ｍｌ溶
液を加え室温で１時間撹拌した。反応終了後、反応混合
物を水中投入し、塩化メチレンで抽出して水洗を行な
い、無水硫酸ナトリウムで乾燥後溶媒を留去した。残渣
をシリカゲルカラムクロマトグラフィーにて精製し、メ
チル ２−ｔｅｒｔ−ブチルアミノスルホニル−６−ジ
フルオロメチルニコチネート０．２５ｇを得た。[III] This formyl nicotinate 0.
A solution of 0.62 g of diethylaminosulfur trifluoride in 5 ml of methylene chloride was added to a solution of 48 g of methylene chloride in 19 ml of a solution under ice-cooling, and the mixture was stirred at room temperature for 1 hour. After completion of the reaction, the reaction mixture was put into water, extracted with methylene chloride, washed with water, dried over anhydrous sodium sulfate, and the solvent was distilled off. The residue was purified by silica gel column chromatography to obtain 0.25 g of methyl 2-tert-butylaminosulfonyl-6-difluoromethylnicotinate.
【００６７】〔IV〕 このものの０．５０ｇと、ジメチ
ルアミンを飽和させた無水メタノール１０ｍｌとの混合
物を室温で１晩放置した。反応終了後、反応物より溶媒
を留去し、残渣をシリカゲルカラムクロマトグラフィー
で精製し２−ｔｅｒｔ−ブチルアミノスルホニル−６−
ジフルオロメチル−Ｎ，Ｎ−ジメチルニコチンアミド
０．１５ｇを得た。 〔Ｖ〕 このものを用い、前記中間体合成例１の工程
〔IV〕と同様の方法で、２−アミノスルホニル−６−ジ
フルオロメチル−Ｎ，Ｎ−ジメチルニコチンアミドを得
た。[IV] A mixture of 0.50 g of this product and 10 ml of anhydrous methanol saturated with dimethylamine was left overnight at room temperature. After completion of the reaction, the solvent was distilled off from the reaction product, and the residue was purified by silica gel column chromatography to give 2-tert-butylaminosulfonyl-6-
0.15 g of difluoromethyl-N, N-dimethylnicotinamide was obtained. [V] Using this compound, 2-aminosulfonyl-6-difluoromethyl-N, N-dimethylnicotinamide was obtained in the same manner as in Step [IV] of Intermediate Synthesis Example 1 above.
【００６８】中間体合成例１１ ２−アミノスルホニル−６−ブロモ−Ｎ，Ｎ−ジメチル
ニコチンアミドの合成 〔Ｉ〕 ２−ベンジルチオ−６−クロロ−Ｎ，Ｎ−ジメ
チルニコチンアミド１．２ｇに酢酸５ｍｌを加え、１０
℃まで昇温し臭化水素ガスを３０分間導入し、更に３０
分間反応を行った。反応終了後、反応混合物を冷却した
後、氷水中に投入し、塩化メチレンで抽出し重ソウ水で
洗浄し、更に水洗を行った。ついで無水硫酸ナトリウム
で乾燥し、塩化メチレンを留去後、シリカゲルカラムク
ロマトグラフィーで精製して融点１０５〜１０６℃の２
−ベンジルチオ−６−ブロモ−Ｎ，Ｎ−ジメチルニコチ
ンアミド１．０ｇを得た。 〔II〕 このものを用い、前記中間体合成例１の工程
〔III 〕及び〔IV〕と同様の方法で融点１５４〜１５６
℃の２−アミノスルホニル−６−ブロモ−Ｎ，Ｎ−ジメ
チルニコチンアミドを得た。前記一般式（II−１′）で
表わされる化合物につき、その代表例を第１表に掲載す
る。Intermediate Synthesis Example 11 Synthesis of 2-aminosulfonyl-6-bromo-N, N-dimethylnicotinamide [I] 1.2 g of 2-benzylthio-6-chloro-N, N-dimethylnicotinamide and 5 ml of acetic acid Add 10
The temperature is raised to ℃ and hydrogen bromide gas is introduced for 30 minutes,
Reaction was carried out for a minute. After the completion of the reaction, the reaction mixture was cooled, then poured into ice water, extracted with methylene chloride, washed with sodium bicarbonate water, and further washed with water. Then, it is dried over anhydrous sodium sulfate, and after distilling off methylene chloride, the product is purified by silica gel column chromatography to obtain 2 having a melting point of 105 to 106 ° C.
1.0 g of -benzylthio-6-bromo-N, N-dimethylnicotinamide was obtained. [II] Using this compound, melting points 154 to 156 were carried out in the same manner as in Steps [III] and [IV] of Intermediate Synthesis Example 1 above.
C. 2-Aminosulfonyl-6-bromo-N, N-dimethylnicotinamide was obtained. Typical examples of the compounds represented by the general formula (II-1 ′) are shown in Table 1.
【００６９】[0069]
【表１】 [Table 1]
【００７０】[0070]
【表２】 [Table 2]
【００７１】[0071]
【表３】 [Table 3]
【００７２】次に本発明化合物の具体的合成例を記載す
る。 合成例Ｎｏ．１ ５−クロロ−Ｎ−〔（４，６−ジメトキシピリミジン−
２−イル）アミノカルボニル〕−３−ジメチルアミノカ
ルボニル−２−ピリジンスルホンアミド（化合物Ｎｏ．
９）の合成 ２−アミノスルホニル−５−クロロ−Ｎ，Ｎ−ジメチル
ニコチンアミド０．３０ｇ及び２−フェノキシカルボニ
ルアミノ−４，６−ジメトキシピリミジン０．３５ｇを
無水アセトニトリル１０ｍｌに加えた懸濁液に１，８−
ジアザビシクロ〔５・４・０〕−７−ウンデセン０．１
９ｇを加え室温で４５分間反応させた。反応終了後、反
応物を水中に投入し、不溶物を濾別した後、濃塩酸で弱
酸性として塩化メチレンで抽出した。次いで無水硫酸ナ
トリウムで乾燥後、溶媒を留去し、融点１５２〜１５５
℃の目的物０．２６ｇを得た。 合成例 Ｎｏ．２〜Ｎｏ．１３ 前記合成例１と同様の方法を行ない、第２表の結果を得
た。Next, specific synthesis examples of the compound of the present invention will be described. Synthesis example No. 1 5-Chloro-N-[(4,6-dimethoxypyrimidine-
2-yl) aminocarbonyl] -3-dimethylaminocarbonyl-2-pyridinesulfonamide (Compound No.
Synthesis of 9) 2-aminosulfonyl-5-chloro-N, N-dimethylnicotinamide 0.30 g and 2-phenoxycarbonylamino-4,6-dimethoxypyrimidine 0.35 g were added to a suspension prepared by adding anhydrous acetonitrile 10 ml. 1,8-
Diazabicyclo [5,4,0] -7-undecene 0.1
9 g was added and reacted at room temperature for 45 minutes. After completion of the reaction, the reaction product was poured into water, the insoluble material was filtered off, the mixture was made weakly acidic with concentrated hydrochloric acid and extracted with methylene chloride. Then, after drying over anhydrous sodium sulfate, the solvent is distilled off to give a melting point of 152-155.
As a result, 0.26 g of the desired product (° C.) was obtained. Synthesis Example No. 2 to No. 13 The same method as in Synthesis Example 1 was performed, and the results in Table 2 were obtained.
【００７３】[0073]
【表４】 [Table 4]
【００７４】[0074]
【表５】 [Table 5]
【００７５】合成例Ｎｏ．１４ Ｎ−〔（４，６−ジメトキシピリミジン−２−イル）ア
ミノカルボニル〕−３−ジメチルアミノカルボニル−２
−ピリジンスルホンアミドの合成 方法１：２０％ホスゲンの酢酸エチル溶液６．３ｇに１
５℃で２−アミノ−４，６−ジメトキシピリミジン２５
０ｍｇ、トリエチルアミン０．６５ｇ及び酢酸エチル
２．５ｇの混合溶液を滴下し、１５℃に保ちながら１時
間反応を行った。次いで、９０℃の油浴上で加温し、過
剰のホスゲン及び酢酸エチルを留去した後、２−アミノ
スルホニル−Ｎ，Ｎ−ジメチルニコチンアミド３００ｍ
ｇを１０ｍｌのアセトニトリルに溶解した溶液を加え、
更に０．２ｇのトリエチルアミンを滴下し、室温で１時
間反応した。反応終了後、生成物を水中に投入し、塩酸
で酸性化し、析出した結晶を濾取し、水洗及び乾燥を行
ない０．４６ｇの目的物を得た。Synthesis Example No. 14 N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -3-dimethylaminocarbonyl-2
-Synthesis of pyridinesulfonamide Method 1: 1 to 6.3 g of a 20% solution of phosgene in ethyl acetate
2-amino-4,6-dimethoxypyrimidine 25 at 5 ° C
A mixed solution of 0 mg, triethylamine 0.65 g and ethyl acetate 2.5 g was added dropwise, and the reaction was carried out for 1 hour while maintaining the temperature at 15 ° C. Then, the mixture was heated on an oil bath at 90 ° C., excess phosgene and ethyl acetate were distilled off, and then 2-aminosulfonyl-N, N-dimethylnicotinamide 300 m
a solution of g in 10 ml of acetonitrile was added,
Further, 0.2 g of triethylamine was added dropwise and the reaction was carried out at room temperature for 1 hour. After completion of the reaction, the product was put into water, acidified with hydrochloric acid, and the precipitated crystals were collected by filtration, washed with water and dried to obtain 0.46 g of the desired product.
【００７６】方法２： 〔Ｉ〕６０％水素化ナトリウムの５ｍｌジメチルホルム
アミドスラリー中に−５℃で２−アミノスルホニル−
Ｎ，Ｎ−ジメチルニコチンアミド２．１３ｇを加え約１
時間反応させた。この中へ−５℃でジフェニルカーボネ
ート２．１４ｇのジメチルホルムアミド１０ｍｌ溶液を
滴下した。約３０分で室温にもどし反応を完了した。反
応液を水中に投入し、塩化メチレン洗浄を行なった後、
水層を塩酸酸性とし、塩化メチレン抽出を行なった。塩
化メチレン層を無水硫酸ナトリウムで乾燥した後、減圧
下塩化メチレンを留去した。生じた結晶を酢酸エチル、
ヘキサンより再結晶し、融点１８９〜１９４℃のＮ，Ｎ
−ジメチル−２−フェノキシカルボニルアミノスルホニ
ルニコチンアミド０．９１ｇを得た。Method 2: [I] 2-Aminosulfonyl-in a 5 ml dimethylformamide slurry of 60% sodium hydride at -5 ° C.
2.13 g of N, N-dimethylnicotinamide was added to about 1
Allowed to react for hours. A solution of 2.14 g of diphenyl carbonate in 10 ml of dimethylformamide was added dropwise thereto at -5 ° C. In about 30 minutes, the temperature was returned to room temperature to complete the reaction. After pouring the reaction solution into water and washing with methylene chloride,
The aqueous layer was acidified with hydrochloric acid and extracted with methylene chloride. The methylene chloride layer was dried over anhydrous sodium sulfate, and methylene chloride was distilled off under reduced pressure. The resulting crystals are ethyl acetate,
Recrystallized from hexane to give N, N having a melting point of 189-194 ° C.
-0.91 g of dimethyl-2-phenoxycarbonylaminosulfonyl nicotinamide was obtained.
【００７７】〔II〕 前記工程〔Ｉ〕で得たＮ，Ｎ−ジ
メチル−２−フェノキシカルボニルアミノスルホニルニ
コチンアミド０．２８ｇ及び２−アミノ−４−クロロ−
６−メトキシピリミジン０．１４ｇを無水ジオキサン８
ｍｌ中に加え、還流下で約４０分間反応させた。反応終
了後、反応混合物を２００ｍｌの水中に投入し、生じた
結晶を濾取し融点１５７〜１５８．５℃のＮ−〔（４−
クロロ−６−メトキシピリミジン−２−イル）アミノカ
ルボニル〕−３−ジメチルアミノカルボニル−２−ピリ
ミジンスルホンアミドを０．２１ｇ得た。 〔III 〕 無水メタノール７ｍｌ中に金属ナトリウム１
８．３ｍｇを加えたのち前記工程〔Ｉ〕で得たＮ−
〔（４−クロロ−６−メトキシピリミジン−２−イル）
アミノカルボニル〕−３−ジメチルアミノカルボニル−
２−ピリミジンスルホンアミド０．１１ｇを加え１２時
間加熱還流させた。反応終了後、反応混合物を水中に投
入し塩酸で酸性化し、生じた結晶を濾取し水洗及び乾燥
を行ない、目的物７０ｍｇを得た。前記一般式（Ｉ）で
表わされる本発明化合物及びその塩の代表例を第３表に
掲載する。[II] 0.28 g of N, N-dimethyl-2-phenoxycarbonylaminosulfonylnicotinamide obtained in the above step [I] and 2-amino-4-chloro-
0.14 g of 6-methoxypyrimidine was added to anhydrous dioxane 8
The mixture was added to the mixture and the mixture was reacted under reflux for about 40 minutes. After completion of the reaction, the reaction mixture was poured into 200 ml of water, and the crystals formed were collected by filtration and N-[(4-
0.21 g of chloro-6-methoxypyrimidin-2-yl) aminocarbonyl] -3-dimethylaminocarbonyl-2-pyrimidinesulfonamide was obtained. [III] Metallic sodium 1 in 7 ml of anhydrous methanol
After adding 8.3 mg, the N-obtained in the above step [I]
[(4-chloro-6-methoxypyrimidin-2-yl)
Aminocarbonyl] -3-dimethylaminocarbonyl-
2-Pyrimidinesulfonamide (0.11 g) was added, and the mixture was heated under reflux for 12 hours. After completion of the reaction, the reaction mixture was put into water and acidified with hydrochloric acid, and the generated crystals were collected by filtration, washed with water and dried to obtain 70 mg of the desired product. Representative examples of the compound of the present invention represented by the above general formula (I) and salts thereof are listed in Table 3.
【００７８】[0078]
【表６】 [Table 6]
【００７９】[0079]
【表７】 [Table 7]
【００８０】[0080]
【表８】 [Table 8]
【００８１】[0081]
【表９】 [Table 9]
【００８２】本発明化合物は、コゴメガヤツリ、ホタル
イ、ハマスゲなどのカヤツリグサ科雑草、イヌビエ、メ
ヒシバ、エノコログサ、オヒシバ、カラスムギ、セイバ
ンモロコシ、シバムギなどのイネ科雑草、イチビ、マル
バアサガオ、シロザ、アメリカキンゴジカ、スベリヒ
ユ、アオビユ、エビスグサ、イヌホオズキ、タデ、ハコ
ベ、オナモミ、タネツケバナなどの広葉雑草など、広い
範囲の雑草を防除することができるので、その適用範囲
は畑地は勿論畑地以外に果樹園、桑畑などの農耕地、山
林、農道、グランド、工場敷地、芝地などの非農耕地と
多岐にわたることができ、また、適用方法も土壌処理、
茎葉処理を適宜選択できる。The compound of the present invention is a Cyperaceae weeds such as Kogomegayatsu, Firefly, Rana edulis, Cyperaceae weeds, Indigo, Mexisia, Echinocloga, Ohishiba, Oat grass, Seibanmokoshi, Shibamugi, etc. It is possible to control a wide range of weeds, such as broad-leaved, yellow-tailed, black-tailed squirrel, Ebisugusa, dog physalis, Polygonum japonicus, broad-leaved weeds such as Onami, Rhododendron japonicum. It can be used in a wide variety of non-agricultural areas such as land, forests, farm roads, grounds, factory sites, turf, and the application method is soil treatment,
Stem and leaf treatment can be appropriately selected.
【００８３】特に、本発明化合物は、後記試験例にみる
通り、トウモロコシに害を与えずに有害雑草を防除する
ことができることから、非常に有用である。本発明除草
剤を施用する場合、通常は担体、必要に応じて希釈剤、
溶剤、乳化剤、展着剤、界面活性剤などの各種補助剤と
混合して、粒剤、水和剤、乳剤、液剤などに製剤して使
用する。有効成分化合物と農薬用補助剤との適当な配合
重量比は、一般に１：９９〜９０：１０、望ましくは
５：９５〜６０：４０である。有効成分化合物の使用適
量は気象条件、土壌条件、薬剤の製剤形態、対象雑草の
種類、施用時期などの相違により一概に規定できない
が、一般に１アール当りの施用有効成分量としては０．
１ｇ〜１００ｇ、望ましくは０．２ｇ〜５０ｇ、更に望
ましくは０．５ｇ〜１０ｇである。In particular, the compound of the present invention is very useful because it can control harmful weeds without damaging corn, as will be seen in the test examples below. When applying the herbicide of the present invention, usually a carrier, if necessary a diluent,
It is mixed with various auxiliary agents such as a solvent, an emulsifier, a spreading agent, and a surfactant, and is used as a granule, a wettable powder, an emulsion, a liquid agent or the like. A suitable compounding weight ratio of the active ingredient compound to the agricultural chemical auxiliary is generally 1:99 to 90:10, preferably 5:95 to 60:40. The appropriate amount of the active ingredient compound to be used cannot be unconditionally specified due to differences in weather conditions, soil conditions, drug formulation, target weed types, application time, etc. However, generally, the effective application amount per ares is 0.
It is 1 g to 100 g, preferably 0.2 g to 50 g, and more preferably 0.5 g to 10 g.
【００８４】本発明除草剤は、他の農薬、肥料、土壌、
薬害軽減剤などと混用或いは併用することができ、この
場合に一層優れた効果・作用性を示すことがある。他の
除草剤と混用或いは併用する場合、その混合相手除草剤
の有効成分としては、例えば次のようなものが挙げられ
る。その場合相乗効果が得られることもある。 ・３，６−ジクロロ−２−メトキシ安息香酸 ・２，５−ジクロロ−３−アミノ安息香酸 ・２，４−ジクロロフェノキシ酢酸 ・４−クロロ−２−メチルフェノキシ酢酸 ・２−クロロ−４，６−ビス（エチルアミノ）−１，
３，５−トリアジンThe herbicides of the present invention include other pesticides, fertilizers, soil,
It can be mixed or used in combination with a phytotoxicity-reducing agent and the like, and in this case, more excellent effect and action may be exhibited. When mixed or used in combination with other herbicides, examples of the active ingredient of the mixed partner herbicide include the following. In that case, a synergistic effect may be obtained.・ 3,6-Dichloro-2-methoxybenzoic acid ・ 2,5-dichloro-3-aminobenzoic acid ・ 2,4-dichlorophenoxyacetic acid ・ 4-chloro-2-methylphenoxyacetic acid ・ 2-chloro-4,6 -Bis (ethylamino) -1,
3,5-triazine
【００８５】・２−クロロ−４−エチルアミノ−６−イ
ソプロピルアミノ−１，３，５−トリアジン ・２−（４−クロロ−６−エチルアミノ−１，３，５−
トリアジン−２−イルアミノ）−２−メチルプロピオニ
トリル ・２−エチルアミノ−４−イソプロピルアミノ−６−メ
チルチオ−１，３，５−トリアジン ・２−クロロ−２′，６′−ジエチル−Ｎ−（メトキシ
メチル）アセトアニリド ・２−クロロ−６′−エチル−Ｎ−（２−メトキシ−１
−メチルエチル）アセト−ｏ−トルイジド2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine 2- (4-chloro-6-ethylamino-1,3,5-
Triazin-2-ylamino) -2-methylpropionitrile-2-ethylamino-4-isopropylamino-6-methylthio-1,3,5-triazine-2-chloro-2 ', 6'-diethyl-N- (Methoxymethyl) acetanilide.2-chloro-6'-ethyl-N- (2-methoxy-1)
-Methylethyl) aceto-o-toluidide
【００８６】・２−クロロ−Ｎ−イソプロピルアセトア
ニリド ・２−クロロ−Ｎ，Ｎ−ジ−２−プロペニルアセトアミ
ド ・Ｓ−エチル ジプロピルチオカーバメート ・Ｓ−エチル ジイソブチルチオカーバメート ・Ｓ−プロピル ジプロピルチオカーバメート ・Ｎ−（１−エチルプロピル）−２，６−ジニトロ−
３，４−キシリジン ・α，α，α−トリフルオロ−２，６−ジニトロ−Ｎ，
Ｎ−ジプロピル−ｐ−トルイジン2-chloro-N-isopropylacetanilide 2-chloro-N, N-di-2-propenylacetamide S-ethyl dipropyl thiocarbamate S-ethyl diisobutyl thiocarbamate S-propyl dipropyl thiocarbamate -N- (1-ethylpropyl) -2,6-dinitro-
3,4-xylidine-α, α, α-trifluoro-2,6-dinitro-N,
N-dipropyl-p-toluidine
【００８７】・２−（３，５−ジクロロフェニル）−２
−（２，２，２−トリクロロエチル）オキシラン ・３−イソプロピル−（１Ｈ）−ベンゾ−２，１，３−
チアジアジン−４−オン−２，２−ジオキシド ・３−（３，４−ジクロロフェニル）−１−メトキシ−
１−メチルウレア ・３，５−ジブロモ−４−ヒドロキシベンゾニトリル ・２−クロロ−４−トリフルオロメチルフェニル−３−
エトキシ−４−ニトロフェニルエーテル2- (3,5-dichlorophenyl) -2
-(2,2,2-Trichloroethyl) oxirane-3-isopropyl- (1H) -benzo-2,1,3-
Thiadiazin-4-one-2,2-dioxide-3- (3,4-dichlorophenyl) -1-methoxy-
1-methylurea3,5-dibromo-4-hydroxybenzonitrile2-chloro-4-trifluoromethylphenyl-3-
Ethoxy-4-nitrophenyl ether
【００８８】具体的には例えば本発明化合物中、Ｎ−
〔４，６−ジメトキシピリミジン−２−イル）アミノカ
ルボニル〕−３−メチルアミノカルボニル（又はジメチ
ルアミノカルボニル）−２−ピリジンスルホンアミド或
いは６−クロロ（又はブロモ、ジフルオロメチル或いは
メチル）−Ｎ−〔（４，６−ジメトキシピリミジン−２
−イル）アミノカルボニル〕−３−ジメチルアミノカル
ボニル−２−ピリジンスルホンアミドと上記混合相手除
草剤中、２−クロロ−４−エチルアミノ−６−イソプロ
ピルアミノ−１，３，５−トリアジン、２−（４−クロ
ロ−６−エチルアミノ−１，３，５−トリアジン−２−
イルアミノ）−２−メチルプロピオニトリル、２−クロ
ロ−２′，６′−ジエチル−Ｎ−（メトキシメチル）ア
セトアニリド、２−クロロ−６′−エチル−Ｎ−（２−
メトキシ−１−メチルエチル）アセト−ｏ−トルイジド
又はＮ−（１−エチルプロピル）−２，６−ジニトロ−
３，４−キシリジンとを混用した場合、トウモロコシに
薬害を与えずに、雑草をほぼ完全に防除することができ
る。Specifically, for example, in the compound of the present invention, N-
[4,6-Dimethoxypyrimidin-2-yl) aminocarbonyl] -3-methylaminocarbonyl (or dimethylaminocarbonyl) -2-pyridinesulfonamide or 6-chloro (or bromo, difluoromethyl or methyl) -N- [ (4,6-dimethoxypyrimidine-2
-Yl) aminocarbonyl] -3-dimethylaminocarbonyl-2-pyridinesulfonamide and the above mixed partner herbicide, 2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine, 2- (4-chloro-6-ethylamino-1,3,5-triazine-2-
Ilamino) -2-methylpropionitrile, 2-chloro-2 ', 6'-diethyl-N- (methoxymethyl) acetanilide, 2-chloro-6'-ethyl-N- (2-
Methoxy-1-methylethyl) aceto-o-toluidide or N- (1-ethylpropyl) -2,6-dinitro-
When 3,4-xylidine is mixed, weeds can be controlled almost completely without damaging corn.
【００８９】試験例１ １／１，５００アールポットに畑作土壌をつめ、各種植
物の種を播種した。その後、植物が一定の葉令（トウモ
ロコシ２．２〜３．５葉期、小麦２．０〜３．５葉期、
オナモミ２．０〜３．５葉期、アサガオ０．５〜１．２
葉期、タデ０．５〜１．２葉期、アメリカキンゴジカ
０．１〜１．５葉期、オアビユ０．１〜１．５葉期、ヒ
エ２．０〜２．５葉期）に達したとき、本発明除草剤の
水和剤を所定量となるように秤量し、アール当り５リッ
トルの水に希釈した。更にその水溶液に農業用展着剤を
０．２％となるように加えて、小型スプレーで茎葉処理
した。処理後、２２〜３７日目に各種植物の生育状態を
肉眼で観察調査を行い、１０段階（１：無処理区と同様
〜１０：完全に抑制）で生育抑制程度を評価し、第４表
の結果を得た。Test Example 1 Upland soil was filled in 1 / 1,500 are pots and seeds of various plants were sown. After that, the plant has a certain leaf age (corn 2.2 to 3.5 leaf stage, wheat 2.0 to 3.5 leaf stage,
Onamomi 2.0-3.5 leaf stage, morning glory 0.5-1.2
Leaf stage, Japanese horse mackerel 0.5 to 1.2 leaf stage, American stag deer 0.1 to 1.5 leaf stage, Oayuyu 0.1 to 1.5 leaf stage, Hie 2.0 to 2.5 leaf stage) When reached, the wettable powder of the herbicide of the present invention was weighed to a predetermined amount and diluted with 5 liters of water per are. Further, an agricultural spreading agent was added to the aqueous solution so as to be 0.2%, and the leaves were treated with a small spray. After the treatment, on the 22nd to the 37th day, the growth state of each plant was visually inspected and evaluated, and the degree of growth inhibition was evaluated in 10 stages (1: similar to the untreated plot; 10: complete inhibition). Got the result.
【００９０】[0090]
【表１０】 [Table 10]
【００９１】[0091]
【表１１】 [Table 11]
【００９２】[0092]
【表１２】 [Table 12]
【００９３】[0093]
【表１３】 [Table 13]
【００９４】[0094]
【表１４】 [Table 14]
【００９５】試験例２ １／１０，０００アールポットに畑土壌を詰め、それぞ
れ別々のポットにメヒシバ、イヌホオズキを播種した。
その後、メヒシバが２葉期、イヌホオズキ０．５葉期に
生育した時、供試化合物の有効成分が所定量となるよう
に秤量し、これらをアール当り５リットルの水に希釈し
た。更にこの水溶液に農業用展着剤を０．２％となるよ
うに加えて、小型スプレーで茎葉散布した。処理後２３
日目に各雑草の生育状態を肉眼観察し、試験例１と同様
の方法で生育抑制程度を評価して、第５表の結果を得
た。Test Example 2 1 / 10,000 ares pots were filled with upland soil, and the individual crabgrass and the physalis stamen were sown in separate pots.
After that, when the crabgrass grew at the 2-leaf stage and the physalis phosphatidus at the 0.5 leaf stage, the active ingredients of the test compound were weighed so as to reach a predetermined amount, and these were diluted with 5 liters of water per are. Further, an agricultural spreading agent was added to this aqueous solution so as to be 0.2%, and the leaves were sprayed with a small spray. After processing 23
On the day, the growth condition of each weed was visually observed and the degree of growth inhibition was evaluated in the same manner as in Test Example 1 to obtain the results shown in Table 5.
【００９６】[0096]
【表１５】 [Table 15]
【００９７】試験例３ 長さ約１５ｃｍのセイバンモロコシ地下茎を１／３，０
００アールポットに２本植え込み、温室内で生育させ
た。葉令が４〜５葉期に達した時、供試化合物の有効成
分が所定量になるように秤量し、これらをアール当り５
リットルの水に希釈した。更にこの水溶液に農業用展着
剤を０．２％となるように加えて、小型スプレーで茎葉
散布した。処理後３５日目に、セイバンモロコシの生育
抑制程度を肉眼観察し、試験例１と同様の方法で生育抑
制程度を評価して、第６表の結果を得た。Test Example 3 1 / 3,0 of a sardine sorghum rhizome having a length of about 15 cm
Two of them were planted in 00 are pots and grown in a greenhouse. When the leaf age reaches the 4 to 5 leaf stage, the active ingredient of the test compound is weighed so as to reach a predetermined amount, and these are 5 per R.
Diluted in 1 liter of water. Further, an agricultural spreading agent was added to this aqueous solution so as to be 0.2%, and the leaves were sprayed with a small spray. On the 35th day after the treatment, the degree of growth inhibition of sorghum was visually observed, and the degree of growth inhibition was evaluated in the same manner as in Test Example 1, and the results in Table 6 were obtained.
【００９８】[0098]
【表１６】 [Table 16]
【００９９】試験例４ ハマスゲ塊茎を１／１０，０００アールポットに４粒植
え込み、温室内で生育させた。葉令が３〜４期に達した
時、本発明化合物の有効成分が所定量となるように秤量
し、これらをアール当り５リットルの水に希釈した。更
にこの水溶液に農業用展着剤を０．２％となるように加
えて、小型スプレーで茎葉散布した。処理後５１日目に
ハマスゲの生育抑制程度を肉眼観察し、試験例１と同様
の方法で生育抑制程度を評価して、第７表の結果を得
た。Test Example 4 Four tuberous tubers were planted in 1 / 10,000 are pots and grown in a greenhouse. When the leaf age reached the 3rd to 4th stage, the active ingredient of the compound of the present invention was weighed so as to have a predetermined amount, and these were diluted with 5 liters of water per are. Further, an agricultural spreading agent was added to this aqueous solution so as to be 0.2%, and the leaves were sprayed with a small spray. On the 51st day after the treatment, the degree of inhibition of the growth of Phellinus linteus was visually observed, and the degree of the inhibition of growth was evaluated by the same method as in Test Example 1, and the results in Table 7 were obtained.
【０１００】[0100]
【表１７】 [Table 17]
【０１０１】次に、本発明除草性組成物の製剤例を記載
する。 製剤例１ （１）ニューライト（商品名：日本耐火原料（株）製） ９７重量部 （２）ディクスゾールＷ−９２ (商品名：第一工業製薬（株）製） ２重量部 （３）化合物Ｎｏ．１５ １重量部 以上の各成分を混合、粉砕して粉剤が得られる。 製剤例２ （１）水溶性デンプン ５５重量部 （２）リグニンスルホン酸ソーダ ５重量部 （３）化合物Ｎｏ．５９ ４０重量部 以上の各成分を混合して水溶剤が得られる。Next, formulation examples of the herbicidal composition of the present invention will be described. Formulation Example 1 (1) New Light (trade name: manufactured by Nippon Fire Refractory Raw Materials Co., Ltd.) 97 parts by weight (2) Dixsol W-92 (trade name: manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) 2 parts by weight (3) Compound No. 15 1 part by weight The above components are mixed and pulverized to obtain a powder. Formulation Example 2 (1) Water-soluble starch 55 parts by weight (2) Sodium lignin sulfonate 5 parts by weight (3) Compound No. 59 40 parts by weight The above components are mixed to obtain a water solvent.
【０１０２】製剤例３ （１）カオリン ７８重量部 （２）ラベリンＳ（商品名：第一工業製薬（株）製） ２重量部 （３）ソルポール５０３９ (商品名：東邦化学工業（株）製） ５重量部 （４）カープレックス（商品名：塩野義製薬（株）製） １５重量部 以上（１）〜（４）の成分の混合物と本発明化合物とを
９：１の重量割合で混合して水和剤が得られる。 製剤例４ （１）珪藻土 ６３重量部 （２）ディクスゾールＷ−６６ (商品名：第一工業製薬（株）製） ５重量部 （３）ディクスゾールＷ−０９Ｂ (商品名：同上） ２重量部 （４）化合物Ｎｏ．２９ ３０重量部 以上の各成分を混合して水和剤が得られる。Formulation Example 3 (1) Kaolin 78 parts by weight (2) Laberin S (trade name: manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) 2 parts by weight (3) Solpol 5039 (trade name: manufactured by Toho Chemical Industry Co., Ltd.) ) 5 parts by weight (4) Carplex (trade name: manufactured by Shionogi & Co., Ltd.) 15 parts by weight The mixture of the components (1) to (4) and the compound of the present invention are mixed at a weight ratio of 9: 1. A wettable powder is obtained. Formulation Example 4 (1) Diatomaceous earth 63 parts by weight (2) Dixsol W-66 (trade name: manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) 5 parts by weight (3) Dixsol W-09B (trade name: same as above) 2 parts by weight Part (4) Compound No. 29 30 parts by weight The above components are mixed to obtain a wettable powder.
【０１０３】製剤例５ （１）ハイフィラーＮｏ．１０ (商品名：松村産業（株）製） ３３重量部 （２）ソルポール５０５０ (商品名：東邦化学（株）製） ３重量部 （３）ソルポール５０７３ (商品名：同上） ４重量部 （４）化合物Ｎｏ．３４ ６０重量部 以上の各成分を混合して、水和剤が得られる。 製剤例６ （１）フェニルスルホン酸ナトリウム ４重量部 （２）ポリカルボン酸ナトリウム ３重量部 （３）アルキルアリールスルホン酸ナトリウム １重量部 （４）カオリン １２重量部 （５）化合物Ｎｏ．２５ ８０重量部 以上の各成分に水を加え混練し、乾燥後破壊して水和剤
が得られる。Formulation Example 5 (1) High Filler No. 10 (Product name: manufactured by Matsumura Sangyo Co., Ltd.) 33 parts by weight (2) Solpol 5050 (Product name: manufactured by Toho Chemical Co., Ltd.) 3 parts by weight (3) Solpol 5073 (Product name: same as above) 4 parts by weight (4 ) Compound No. 34 60 parts by weight The above components are mixed to obtain a wettable powder. Formulation Example 6 (1) Sodium phenyl sulfonate 4 parts by weight (2) Sodium polycarboxylate 3 parts by weight (3) Sodium alkylaryl sulfonate 1 part by weight (4) Kaolin 12 parts by weight (5) Compound No. 25 80 parts by weight Water is added to each of the above components, and the mixture is kneaded, dried and then broken to obtain a wettable powder.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ａ０１Ｎ 47/36 １０１ Ａ０１Ｎ 47/36 １０１Ｅ Ｃ０７Ｄ 401/12 ２３９ Ｃ０７Ｄ 401/12 ２３９ (Ｃ０７Ｄ 401/12 (Ｃ０７Ｄ 401/12 213:81 213:81 239:52） 239:52） (Ｃ０７Ｄ 401/12 (Ｃ０７Ｄ 401/12 213:00 213:00 251:00） 251:00） (72)発明者 本多 千元 滋賀県草津市西渋川二丁目３番１号 石 原産業株式会社 中央研究所内 (72)発明者 村井 重夫 滋賀県草津市西渋川二丁目３番１号 石 原産業株式会社 中央研究所内─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Office reference number FI Technical display location A01N 47/36 101 A01N 47/36 101E C07D 401/12 239 C07D 401/12 239 (C07D 401/12) (C07D 401/12 213: 81 213: 81 239: 52) 239: 52) (C07D 401/12 (C07D 401/12 213: 00 213: 00 251: 00) 251: 00) (72) Inventor Honda Chiyuan Kusatsu City, Shiga Prefecture 2-3-1, Nishi-Shibukawa Ishihara Sangyo Co., Ltd. Central Research Institute (72) Inventor Shigeo Murai Nishi-Shibukawa 2-3-1, Ishihara Industry Co., Ltd. Central Research Institute
Claims (1)
ルキル基、アルケニル基、アルキニル基、アルコキシ
基、ハロアルコキシ基、アルコキシアルキル基、ハロア
ルコキシアルキル基、シクロアルキル基、ハロシクロア
ルキル基、アルコキシカルボニル基、ハロアルコキシカ
ルボニル基、フェニル基又はハロフェニル基であり、Ｒ
1 及びＲ2 の一方が水素原子の場合他方は水素原子以外
のものであり、Ｒ1 及びＲ2 が隣接している窒素原子と
共に複素環を形成してもよく、Ｙはハロゲン原子、アル
キル基、ハロアルキル基、アルコキシ基、ハロアルコキ
シ基、アルキルチオ基、ハロアルキルチオ基、アルコキ
シアルキル基、ハロアルコキシアルキル基又は 【化２】 （Ｒ3 及びＲ4 は水素原子又はアルキル基である）であ
り、ｎは０又は１或いは２の整数であり、Ｚ1 は−ＮＨ
2 基、−ＮＣＯ基、−ＮＨＣＯＣｌ基又は−ＮＨＣＯＯ
Ｒ5 基（Ｒ5 はアルキル基又はアリール基である）であ
る。但しＲ1 及びＲ2 が共にメチル基であり、ｎが０で
あり、かつＺ1 が−ＮＨ2 基又は−ＮＨＣＯＯＲ5 基で
あり、Ｒ5 がアルキル基又はアリール基である化合物を
除く）で表わされる置換ピリジン系化合物。1. A compound represented by the general formula (IV): (In the formula, R 1 and R 2 are a hydrogen atom, an alkyl group, a haloalkyl group, an alkenyl group, an alkynyl group, an alkoxy group, a haloalkoxy group, an alkoxyalkyl group, a haloalkoxyalkyl group, a cycloalkyl group, a halocycloalkyl group, An alkoxycarbonyl group, a haloalkoxycarbonyl group, a phenyl group or a halophenyl group, R
When one of R 1 and R 2 is a hydrogen atom, the other is other than a hydrogen atom, and R 1 and R 2 may form a heterocycle with the adjacent nitrogen atom, and Y is a halogen atom or an alkyl group. , Haloalkyl group, alkoxy group, haloalkoxy group, alkylthio group, haloalkylthio group, alkoxyalkyl group, haloalkoxyalkyl group or (R 3 and R 4 are a hydrogen atom or an alkyl group), n is 0 or an integer of 1 or 2, and Z 1 is —NH.
2 groups, -NCO group, -NHCOCl group or -NHCOO
R 5 group (R 5 is an alkyl group or an aryl group). Provided that R 1 and R 2 are both methyl groups, n is 0, Z 1 is an —NH 2 group or an —NHCOOR 5 group, and R 5 is an alkyl group or an aryl group. A substituted pyridine compound represented.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29594694A JP2506063B2 (en) | 1986-01-30 | 1994-11-07 | Substituted pyridine compound |
Applications Claiming Priority (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1900686 | 1986-01-30 | ||
| JP61019863 | 1986-01-31 | ||
| JP8684786 | 1986-04-15 | ||
| JP61-19863 | 1986-07-29 | ||
| JP61-19006 | 1986-07-29 | ||
| JP61-86847 | 1986-07-29 | ||
| JP17848986 | 1986-07-29 | ||
| JP61-178489 | 1986-07-29 | ||
| JP29594694A JP2506063B2 (en) | 1986-01-30 | 1994-11-07 | Substituted pyridine compound |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62017323A Division JP2567235B2 (en) | 1986-01-30 | 1987-01-29 | Substituted pyridine sulfonamide compounds, herbicides containing them and method for producing them |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07267928A JPH07267928A (en) | 1995-10-17 |
| JP2506063B2 true JP2506063B2 (en) | 1996-06-12 |
Family
ID=27520100
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29594694A Expired - Lifetime JP2506063B2 (en) | 1986-01-30 | 1994-11-07 | Substituted pyridine compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2506063B2 (en) |
-
1994
- 1994-11-07 JP JP29594694A patent/JP2506063B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07267928A (en) | 1995-10-17 |
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