JPH054977A - Benzoxazine derivative and herbicide containing the derivative as active component - Google Patents
Benzoxazine derivative and herbicide containing the derivative as active componentInfo
- Publication number
- JPH054977A JPH054977A JP18883591A JP18883591A JPH054977A JP H054977 A JPH054977 A JP H054977A JP 18883591 A JP18883591 A JP 18883591A JP 18883591 A JP18883591 A JP 18883591A JP H054977 A JPH054977 A JP H054977A
- Authority
- JP
- Japan
- Prior art keywords
- group
- halogen atom
- lower alkyl
- hydrogen atom
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 230000002363 herbicidal effect Effects 0.000 title claims abstract description 17
- 239000004009 herbicide Substances 0.000 title claims abstract description 13
- 150000005130 benzoxazines Chemical class 0.000 title claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 65
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 51
- 125000005843 halogen group Chemical group 0.000 claims abstract description 49
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 18
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 7
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 34
- 125000001424 substituent group Chemical group 0.000 claims description 31
- 125000003545 alkoxy group Chemical group 0.000 claims description 23
- 125000002252 acyl group Chemical group 0.000 claims description 21
- 125000001931 aliphatic group Chemical group 0.000 claims description 17
- 125000000304 alkynyl group Chemical group 0.000 claims description 17
- 125000003118 aryl group Chemical group 0.000 claims description 16
- 239000004480 active ingredient Substances 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 125000003302 alkenyloxy group Chemical group 0.000 claims description 6
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 6
- 125000003282 alkyl amino group Chemical group 0.000 claims description 6
- 125000005133 alkynyloxy group Chemical group 0.000 claims description 6
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 claims description 5
- 125000003107 substituted aryl group Chemical group 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 125000006165 cyclic alkyl group Chemical group 0.000 claims description 3
- 125000004423 acyloxy group Chemical group 0.000 claims description 2
- 125000005078 alkoxycarbonylalkyl group Chemical group 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 125000001072 heteroaryl group Chemical group 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- 125000002813 thiocarbonyl group Chemical group *C(*)=S 0.000 claims description 2
- -1 alkali metal salt Chemical class 0.000 abstract description 80
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 abstract description 5
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 3
- 125000004685 alkoxythiocarbonyl group Chemical group 0.000 abstract description 3
- 239000012442 inert solvent Substances 0.000 abstract description 3
- HVQAHNBSEFQMPZ-UHFFFAOYSA-N 2-phenoxypropanedioic acid Chemical class OC(=O)C(C(O)=O)OC1=CC=CC=C1 HVQAHNBSEFQMPZ-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract description 2
- 230000007062 hydrolysis Effects 0.000 abstract description 2
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 2
- 229910052736 halogen Inorganic materials 0.000 abstract 2
- VGUWZCUCNQXGBU-UHFFFAOYSA-N 3-[(4-methylpiperazin-1-yl)methyl]-5-nitro-1h-indole Chemical class C1CN(C)CCN1CC1=CNC2=CC=C([N+]([O-])=O)C=C12 VGUWZCUCNQXGBU-UHFFFAOYSA-N 0.000 abstract 1
- MBEDOUCBDWKNBJ-UHFFFAOYSA-N ethyl 7-[2-chloro-4-(trifluoromethyl)phenoxy]-3-oxo-4h-1,4-benzoxazine-2-carboxylate Chemical compound C=1C=C2NC(=O)C(C(=O)OCC)OC2=CC=1OC1=CC=C(C(F)(F)F)C=C1Cl MBEDOUCBDWKNBJ-UHFFFAOYSA-N 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 90
- 239000002904 solvent Substances 0.000 description 38
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 36
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 30
- 125000004432 carbon atom Chemical group C* 0.000 description 28
- 239000000203 mixture Substances 0.000 description 27
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- 239000000243 solution Substances 0.000 description 23
- 238000010898 silica gel chromatography Methods 0.000 description 18
- 238000003786 synthesis reaction Methods 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 17
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 13
- 235000019341 magnesium sulphate Nutrition 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 239000013078 crystal Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000012230 colorless oil Substances 0.000 description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 8
- 239000002689 soil Substances 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 7
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000012312 sodium hydride Substances 0.000 description 6
- 229910000104 sodium hydride Inorganic materials 0.000 description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 5
- KCBAMQOKOLXLOX-BSZYMOERSA-N CC1=C(SC=N1)C2=CC=C(C=C2)[C@H](C)NC(=O)[C@@H]3C[C@H](CN3C(=O)[C@H](C(C)(C)C)NC(=O)CCCCCCCCCCNCCCONC(=O)C4=C(C(=C(C=C4)F)F)NC5=C(C=C(C=C5)I)F)O Chemical compound CC1=C(SC=N1)C2=CC=C(C=C2)[C@H](C)NC(=O)[C@@H]3C[C@H](CN3C(=O)[C@H](C(C)(C)C)NC(=O)CCCCCCCCCCNCCCONC(=O)C4=C(C(=C(C=C4)F)F)NC5=C(C=C(C=C5)I)F)O KCBAMQOKOLXLOX-BSZYMOERSA-N 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 229940125833 compound 23 Drugs 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 125000001153 fluoro group Chemical group F* 0.000 description 5
- 229910052740 iodine Inorganic materials 0.000 description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 4
- QBWKPGNFQQJGFY-QLFBSQMISA-N 3-[(1r)-1-[(2r,6s)-2,6-dimethylmorpholin-4-yl]ethyl]-n-[6-methyl-3-(1h-pyrazol-4-yl)imidazo[1,2-a]pyrazin-8-yl]-1,2-thiazol-5-amine Chemical compound N1([C@H](C)C2=NSC(NC=3C4=NC=C(N4C=C(C)N=3)C3=CNN=C3)=C2)C[C@H](C)O[C@H](C)C1 QBWKPGNFQQJGFY-QLFBSQMISA-N 0.000 description 4
- DDPUVXPWPSEWIN-UHFFFAOYSA-N 7-[2-chloro-4-(trifluoromethyl)phenoxy]-2,4-dimethyl-3-oxo-1,4-benzoxazine-2-carboxylic acid Chemical compound C=1C=C2N(C)C(=O)C(C)(C(O)=O)OC2=CC=1OC1=CC=C(C(F)(F)F)C=C1Cl DDPUVXPWPSEWIN-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 125000001309 chloro group Chemical group Cl* 0.000 description 4
- 229940125846 compound 25 Drugs 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- 239000004563 wettable powder Substances 0.000 description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 3
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 description 3
- 125000000474 3-butynyl group Chemical group [H]C#CC([H])([H])C([H])([H])* 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 3
- 125000004063 butyryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229940125904 compound 1 Drugs 0.000 description 3
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 3
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 2
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 2
- SNDTUIDMFPGRFE-UHFFFAOYSA-N ClC1=C(OC2=CC3=C(N(C(C(O3)C(C(Cl)C)=O)=O)C)C=C2)C(=CC(=C1)C(F)(F)F)F Chemical compound ClC1=C(OC2=CC3=C(N(C(C(O3)C(C(Cl)C)=O)=O)C)C=C2)C(=CC(=C1)C(F)(F)F)F SNDTUIDMFPGRFE-UHFFFAOYSA-N 0.000 description 2
- ZJQZJQYQOWIYGR-UHFFFAOYSA-N ClC1=C(OC2=CC3=C(N(C(C(O3)C(C(O)C)=O)=O)C)C=C2)C(=CC(=C1)C(F)(F)F)F Chemical compound ClC1=C(OC2=CC3=C(N(C(C(O3)C(C(O)C)=O)=O)C)C=C2)C(=CC(=C1)C(F)(F)F)F ZJQZJQYQOWIYGR-UHFFFAOYSA-N 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
- 241000237858 Gastropoda Species 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- 240000005979 Hordeum vulgare Species 0.000 description 2
- 235000007340 Hordeum vulgare Nutrition 0.000 description 2
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 241000254158 Lampyridae Species 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229910000564 Raney nickel Inorganic materials 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 240000008042 Zea mays Species 0.000 description 2
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 2
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 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
- RBHJBMIOOPYDBQ-UHFFFAOYSA-N carbon dioxide;propan-2-one Chemical compound O=C=O.CC(C)=O RBHJBMIOOPYDBQ-UHFFFAOYSA-N 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 229940125898 compound 5 Drugs 0.000 description 2
- 235000005822 corn Nutrition 0.000 description 2
- FNJVDWXUKLTFFL-UHFFFAOYSA-N diethyl 2-bromopropanedioate Chemical compound CCOC(=O)C(Br)C(=O)OCC FNJVDWXUKLTFFL-UHFFFAOYSA-N 0.000 description 2
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- XWBDWHCCBGMXKG-UHFFFAOYSA-N ethanamine;hydron;chloride Chemical compound Cl.CCN XWBDWHCCBGMXKG-UHFFFAOYSA-N 0.000 description 2
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 2
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 2
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 2
- 230000035784 germination Effects 0.000 description 2
- 125000001188 haloalkyl group Chemical group 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 229940071870 hydroiodic acid Drugs 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 2
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 125000004344 phenylpropyl group Chemical group 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- 125000003774 valeryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- IUSARDYWEPUTPN-OZBXUNDUSA-N (2r)-n-[(2s,3r)-4-[[(4s)-6-(2,2-dimethylpropyl)spiro[3,4-dihydropyrano[2,3-b]pyridine-2,1'-cyclobutane]-4-yl]amino]-3-hydroxy-1-[3-(1,3-thiazol-2-yl)phenyl]butan-2-yl]-2-methoxypropanamide Chemical compound C([C@H](NC(=O)[C@@H](C)OC)[C@H](O)CN[C@@H]1C2=CC(CC(C)(C)C)=CN=C2OC2(CCC2)C1)C(C=1)=CC=CC=1C1=NC=CS1 IUSARDYWEPUTPN-OZBXUNDUSA-N 0.000 description 1
- YJLIKUSWRSEPSM-WGQQHEPDSA-N (2r,3r,4s,5r)-2-[6-amino-8-[(4-phenylphenyl)methylamino]purin-9-yl]-5-(hydroxymethyl)oxolane-3,4-diol Chemical compound C=1C=C(C=2C=CC=CC=2)C=CC=1CNC1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](CO)[C@@H](O)[C@H]1O YJLIKUSWRSEPSM-WGQQHEPDSA-N 0.000 description 1
- ITOFPJRDSCGOSA-KZLRUDJFSA-N (2s)-2-[[(4r)-4-[(3r,5r,8r,9s,10s,13r,14s,17r)-3-hydroxy-10,13-dimethyl-2,3,4,5,6,7,8,9,11,12,14,15,16,17-tetradecahydro-1h-cyclopenta[a]phenanthren-17-yl]pentanoyl]amino]-3-(1h-indol-3-yl)propanoic acid Chemical compound C([C@H]1CC2)[C@H](O)CC[C@]1(C)[C@@H](CC[C@]13C)[C@@H]2[C@@H]3CC[C@@H]1[C@H](C)CCC(=O)N[C@H](C(O)=O)CC1=CNC2=CC=CC=C12 ITOFPJRDSCGOSA-KZLRUDJFSA-N 0.000 description 1
- YQOLEILXOBUDMU-KRWDZBQOSA-N (4R)-5-[(6-bromo-3-methyl-2-pyrrolidin-1-ylquinoline-4-carbonyl)amino]-4-(2-chlorophenyl)pentanoic acid Chemical compound CC1=C(C2=C(C=CC(=C2)Br)N=C1N3CCCC3)C(=O)NC[C@H](CCC(=O)O)C4=CC=CC=C4Cl YQOLEILXOBUDMU-KRWDZBQOSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- QEBYEVQKHRUYPE-UHFFFAOYSA-N 2-(2-chlorophenyl)-5-[(1-methylpyrazol-3-yl)methyl]-4-[[methyl(pyridin-3-ylmethyl)amino]methyl]-1h-pyrazolo[4,3-c]pyridine-3,6-dione Chemical compound C1=CN(C)N=C1CN1C(=O)C=C2NN(C=3C(=CC=CC=3)Cl)C(=O)C2=C1CN(C)CC1=CC=CN=C1 QEBYEVQKHRUYPE-UHFFFAOYSA-N 0.000 description 1
- VVCMGAUPZIKYTH-VGHSCWAPSA-N 2-acetyloxybenzoic acid;[(2s,3r)-4-(dimethylamino)-3-methyl-1,2-diphenylbutan-2-yl] propanoate;1,3,7-trimethylpurine-2,6-dione Chemical group CC(=O)OC1=CC=CC=C1C(O)=O.CN1C(=O)N(C)C(=O)C2=C1N=CN2C.C([C@](OC(=O)CC)([C@H](C)CN(C)C)C=1C=CC=CC=1)C1=CC=CC=C1 VVCMGAUPZIKYTH-VGHSCWAPSA-N 0.000 description 1
- 125000004198 2-fluorophenyl group Chemical group [H]C1=C([H])C(F)=C(*)C([H])=C1[H] 0.000 description 1
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical class OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 1
- WFOVEDJTASPCIR-UHFFFAOYSA-N 3-[(4-methyl-5-pyridin-4-yl-1,2,4-triazol-3-yl)methylamino]-n-[[2-(trifluoromethyl)phenyl]methyl]benzamide Chemical compound N=1N=C(C=2C=CN=CC=2)N(C)C=1CNC(C=1)=CC=CC=1C(=O)NCC1=CC=CC=C1C(F)(F)F WFOVEDJTASPCIR-UHFFFAOYSA-N 0.000 description 1
- 125000006275 3-bromophenyl group Chemical group [H]C1=C([H])C(Br)=C([H])C(*)=C1[H] 0.000 description 1
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 1
- UCNYJKIKOWQRHM-UHFFFAOYSA-N 3-phenoxy-2h-1,2-benzoxazine Chemical class N1OC2=CC=CC=C2C=C1OC1=CC=CC=C1 UCNYJKIKOWQRHM-UHFFFAOYSA-N 0.000 description 1
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- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
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- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000005092 alkenyloxycarbonyl group Chemical group 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000004691 alkyl thio carbonyl group Chemical group 0.000 description 1
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- 230000009435 amidation Effects 0.000 description 1
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- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000005098 aryl alkoxy carbonyl group Chemical group 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000003857 carboxamides Chemical class 0.000 description 1
- 125000004181 carboxyalkyl group Chemical group 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
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- 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
- KPUNOVLMCQQCSK-UHFFFAOYSA-N diazomethane;ethoxyethane Chemical compound C=[N+]=[N-].CCOCC KPUNOVLMCQQCSK-UHFFFAOYSA-N 0.000 description 1
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- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
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- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 1
- FSOFRGKGDUMWBP-UHFFFAOYSA-N ethyl 1,2-benzoxazine-2-carboxylate Chemical compound C(=O)(OCC)N1OC2=C(C=C1)C=CC=C2 FSOFRGKGDUMWBP-UHFFFAOYSA-N 0.000 description 1
- GWNFQAKCJYEJEW-UHFFFAOYSA-N ethyl 3-[8-[[4-methyl-5-[(3-methyl-4-oxophthalazin-1-yl)methyl]-1,2,4-triazol-3-yl]sulfanyl]octanoylamino]benzoate Chemical compound CCOC(=O)C1=CC(NC(=O)CCCCCCCSC2=NN=C(CC3=NN(C)C(=O)C4=CC=CC=C34)N2C)=CC=C1 GWNFQAKCJYEJEW-UHFFFAOYSA-N 0.000 description 1
- RJCGNNHKSNIUAT-UHFFFAOYSA-N ethyl 3-aminopropanoate;hydron;chloride Chemical compound Cl.CCOC(=O)CCN RJCGNNHKSNIUAT-UHFFFAOYSA-N 0.000 description 1
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- XNXVOSBNFZWHBV-UHFFFAOYSA-N hydron;o-methylhydroxylamine;chloride Chemical compound Cl.CON XNXVOSBNFZWHBV-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
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- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 1
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- 238000000034 method Methods 0.000 description 1
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Landscapes
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Plural Heterocyclic Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、新規なベンズオキサジ
ン誘導体及びそれを有効成分として含有する除草剤に関
する。FIELD OF THE INVENTION The present invention relates to a novel benzoxazine derivative and a herbicide containing the derivative as an active ingredient.
【０００２】[0002]
【従来の技術】フェノキシベンズオキサジン誘導体につ
いては、J. Med. Chem., 17(10), 1125 等に開示されて
いるが、除草効果については全く記載がない。又、本発
明のベンズオキサジン誘導体は、置換基の種類、位置等
において前記文献化合物とは大きく異なり、いずれも新
規な化合物である。2. Description of the Related Art Phenoxybenzoxazine derivatives are disclosed in J. Med. Chem., 17 (10), 1125, etc., but the herbicidal effect is not described at all. Further, the benzoxazine derivative of the present invention is a novel compound, which is largely different from the above-mentioned literature compounds in the kind and position of the substituent.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、優れた除草
活性を有する新規なベンズオキサジン誘導体及びそれを
有効成分として含有する除草剤を提供することを目的と
する。SUMMARY OF THE INVENTION It is an object of the present invention to provide a novel benzoxazine derivative having excellent herbicidal activity and a herbicide containing the same as an active ingredient.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、ベンズオ
キサジン系化合物の除草効果について検討した結果、そ
のベンゼン環にフェノキシ基又はピリジルオキシ基が置
換された置換ベンズオキサジン誘導体は、優れた除草活
性を有することを見い出し本発明を完成したものであ
る。即ち、本発明に従えば式（Ｉ）：Means for Solving the Problems As a result of studies on the herbicidal effect of benzoxazine compounds, the present inventors have found that a substituted benzoxazine derivative having a phenoxy group or a pyridyloxy group substituted on its benzene ring is an excellent herbicidal agent. The present invention has been completed by finding out that it has activity. That is, according to the present invention, formula (I):
【０００５】[0005]
【化６】 [Chemical 6]
【０００６】〔式中、Ａは、Ｎ又は基ＣＹ（ここで、Ｙ
は水素原子又はハロゲン原子を示す）を表し、Ｘは、ハ
ロゲン原子を表し、Ｚは、酸素原子又は硫黄原子を表
し、Ｒ1 は、水素原子、置換されてもよい低級アルキル
基（ここで、置換基としてはハロゲン原子、低級アルコ
キシ基もしくはアリール基のいずれかである）、低級ア
ルケニル基、低級アルキニル基又は脂肪族アシル基を表
し、Ｒ2 は、水素原子又は低級アルキル基を表し、Ｒ3
は、エステル化またはアミド化されてもよいカルボキシ
ル基、置換されてもよい脂肪族アシル基（ここで、置換
基としてはハロゲン原子、ジアゾ基もしくはアシル化さ
れてもよい水酸基のいずれかである）、低級アルコキシ
チオカルボニル基、基Ｃ（＝ＮＲ4 ）Ｒ5 （ここで、Ｒ
4 は水酸基、低級アルコキシ基、低級アルケニルオキシ
基、低級アルキニルオキシ基、アミノ基、低級アルキル
アミノ基又はアルコキシカルボニルアルキルオキシ基を
示し、Ｒ5 は低級アルキル基を示す）、基Ｃ（ＯＲ6)2
Ｒ7 （ここで、Ｒ6 は低級アルキル基を示すか又は２個
のＲ6 でアルキレン基を形成する基を示し、Ｒ7 は低級
アルキル基を示す）又は基Ｃ（Ｒ8)2ＯＨ（ここで、Ｒ
8 は低級アルキル基を示す）を表す〕で表されるベンズ
オキサジン誘導体及びその塩、並びにそれを有効成分と
して含有する除草剤が提供される。[Wherein A is N or a group CY (where Y is
Represents a hydrogen atom or a halogen atom), X represents a halogen atom, Z represents an oxygen atom or a sulfur atom, R 1 represents a hydrogen atom or an optionally substituted lower alkyl group (wherein The substituent is a halogen atom, a lower alkoxy group or an aryl group), a lower alkenyl group, a lower alkynyl group or an aliphatic acyl group, R 2 represents a hydrogen atom or a lower alkyl group, and R 3
Is a carboxyl group which may be esterified or amidated, an aliphatic acyl group which may be substituted (wherein, the substituent is either a halogen atom, a diazo group or a hydroxyl group which may be acylated) , A lower alkoxythiocarbonyl group, a group C (= NR 4 ) R 5 (where R
4 represents a hydroxyl group, a lower alkoxy group, a lower alkenyloxy group, a lower alkynyloxy group, an amino group, a lower alkylamino group or an alkoxycarbonylalkyloxy group, and R 5 represents a lower alkyl group), a group C (OR 6 ). 2
R 7 (wherein R 6 represents a lower alkyl group or a group in which two R 6 form an alkylene group, and R 7 represents a lower alkyl group) or a group C (R 8 ) 2 OH ( Where R
And 8 represents a lower alkyl group] and a salt thereof, and a herbicide containing the same as an active ingredient.
【０００７】式（Ｉ）中、Ｘで示されるハロゲン原子並
びにＡで示される基ＣＹのＹで示されるハロゲン原子と
しては、フッ素原子、塩素原子、臭素原子又はヨウ素原
子が挙げられる。Ｒ1 及びＲ2 で示される低級アルキル
基としては、直鎖及び分岐鎖の炭素数１〜５のアルキル
基（例えばメチル、エチル、プロピル、ブチル、ペンチ
ル、イソプロピル、イソブチル、イソペンチル、 sec−
ブチル等）が挙げられる。Ｒ1 で示される低級アルキル
基の置換基としては、ハロゲン原子としてフッ素原子、
塩素原子、臭素原子又はヨウ素原子の１個又は２個以上
が挙げられ、低級アルコキシ基としては、炭素数１〜５
のアルコキシ基（例えばメトキシ、エトキシ、プロピオ
キシ、ブトキシ、ペンチルオキシ等）が挙げられ、アリ
ール基としては、炭素数６〜１０のアリール基、例えば
フェニル基又はナフチル基等が挙げられる。Ｒ1 で示さ
れる低級アルケニル基としては、炭素数２〜５のアルケ
ニル基（例えばビニル、２−プロペニル、３−ブテニ
ル、４−ペンテニル等）が挙げられる。Ｒ1 で示される
低級アルキニル基としては、炭素数２〜５のアルキニル
基（例えばエチニル、２−プロピニル、３−ブチニル、
４−ペンチニル等）が挙げられる。Ｒ1 で示される脂肪
族アシル基としては、炭素数１〜５のアシル基（例えば
ホルミル、アセチル、プロピオニル、ブチリル、バレリ
ル等）が挙げられる。In the formula (I), the halogen atom represented by X and the halogen atom represented by Y of the group CY represented by A include a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. The lower alkyl group represented by R 1 and R 2 is a linear or branched alkyl group having 1 to 5 carbon atoms (for example, methyl, ethyl, propyl, butyl, pentyl, isopropyl, isobutyl, isopentyl, sec-
Butyl). As the substituent of the lower alkyl group represented by R 1 , a halogen atom is a fluorine atom,
One or more of a chlorine atom, a bromine atom or an iodine atom can be mentioned, and the lower alkoxy group has 1 to 5 carbon atoms.
(For example, methoxy, ethoxy, propioxy, butoxy, pentyloxy, etc.), and the aryl group includes an aryl group having 6 to 10 carbon atoms, such as a phenyl group or a naphthyl group. Examples of the lower alkenyl group represented by R 1 include alkenyl groups having 2 to 5 carbon atoms (for example, vinyl, 2-propenyl, 3-butenyl, 4-pentenyl, etc.). The lower alkynyl group represented by R 1 is an alkynyl group having 2 to 5 carbon atoms (eg, ethynyl, 2-propynyl, 3-butynyl,
4-pentynyl and the like). Examples of the aliphatic acyl group represented by R 1 include an acyl group having 1 to 5 carbon atoms (eg formyl, acetyl, propionyl, butyryl, valeryl etc.).
【０００８】式（Ｉ）中、Ｒ3 で示されるカルボキシル
基としては、遊離の酸であってもよく、又はアルカリ金
属（例えば、ナトリウム、カリウム）もしくはアルカリ
土類金属（例えば、カルシウム、マグネシウム）の塩で
あってもよい。
Ｒ3 で示されるエステル化されたカルボキシル基として
は、炭素数２〜７の直鎖又は分岐鎖アルコキシカルボニ
ル基（ここで、直鎖又は分岐鎖アルコキシ基としては例
えば、メトキシ、エトキシ、ｎ−プロピオキシ、ｎ−ブ
トキシ、ｎ−ペンチルオキシ、ｔ−ブトキシ、イソプロ
ピオキシ等があげられる）、炭素数３〜６のアルケニル
オキシカルボニル基（ここで、アルケニル基としては例
えば、ビニル、アリル、イソプロペニル、イソプレニル
等があげられる）、炭素数３〜６のアルキニルオキシカ
ルボニル基（ここで、アルキニル基としては例えば、エ
チニル、２−プロピニル、３−ブチニル、４−ペンチニ
ル等があげられる）、置換されてもよいフェノキシカル
ボニル基（ここで、置換フェノキシ基としては例えば、
ｐ−クロロフェノキシ、ｍ−ブロモフェノキシ、ｏ−フ
ルオロフェノキシ等があげられる）、炭素数８〜１０の
アラルキルオキシカルボニル基（ここで、アラルキル基
としては例えば、ベンジル、フェネチル、フェニルプロ
ピル等があげられる）、炭素数２〜６のハロアルキルオ
キシカルボニル基（ここで、ハロアルキル基としては、
同一又は異なって塩素原子、臭素原子、ヨウ素原子又は
フッ素原子の１〜３個が置換したメチル、エチル、プロ
ピル、ブチル、ペンチル等で、例えば、クロロメチル、
ジフルオロメチル、トリフルオロメチル、２，２，２−
トリフルオロエチル、３，３，３−トリフルオロロプロ
ピル等があげられる）、炭素数３〜６のアルコキシアル
キルオキシカルボニル基（ここで、アルコキシアルキル
基としては例えば、メトキシメチル、メトキシエチル、
エトキシエチル等があげられる）、炭素数３〜６のアル
コキシカルボニルアルキルオキシカルボニル基（ここ
で、アルコキシカルボニルアルキル基としては例えば、
メトキシカルボニルメチル、エトキシカルボニルメチ
ル、エトキシカルボニルエチル等があげられる）、炭素
数３〜９のアミドカルボニルアルキルオキシカルボニル
基（ここで、アミドカルボニルアルキル基としては例え
ば、アミドカルボニルメチル、エチルアミドカルボニル
メチル、ジメチルアミドカルボニルメチル、ジエチルア
ミドカルボニルメチル、ジエチルアミドカルボニルエチ
ル等があげられる）又は炭素数２〜５のアルキルチオカ
ルボニル基（ここで、アルキルチオ基としては例えば、
メチルチオ、エチルチオ、プロピルチオ等があげられ
る）が挙げられる。In formula (I), the carboxyl group represented by R 3 may be a free acid, or an alkali metal (eg, sodium, potassium) or alkaline earth metal (eg, calcium, magnesium). It may be a salt of. The esterified carboxyl group represented by R 3 is a linear or branched alkoxycarbonyl group having 2 to 7 carbon atoms (wherein the linear or branched alkoxy group is, for example, methoxy, ethoxy, n-propoxy). , N-butoxy, n-pentyloxy, t-butoxy, isopropoxy and the like), and an alkenyloxycarbonyl group having 3 to 6 carbon atoms (wherein the alkenyl group is, for example, vinyl, allyl, isopropenyl, isoprenyl). Etc.), an alkynyloxycarbonyl group having a carbon number of 3 to 6 (wherein, as the alkynyl group, for example, ethynyl, 2-propynyl, 3-butynyl, 4-pentynyl, etc.) may be substituted. Phenoxycarbonyl group (wherein the substituted phenoxy group is, for example,
p-chlorophenoxy, m-bromophenoxy, o-fluorophenoxy and the like), and an aralkyloxycarbonyl group having 8 to 10 carbon atoms (here, examples of the aralkyl group include benzyl, phenethyl, phenylpropyl and the like. ), A haloalkyloxycarbonyl group having 2 to 6 carbon atoms (wherein the haloalkyl group is
Methyl, ethyl, propyl, butyl, pentyl and the like, which is the same or different and has 1 to 3 substituents of chlorine atom, bromine atom, iodine atom or fluorine atom, such as chloromethyl,
Difluoromethyl, trifluoromethyl, 2,2,2-
Trifluoroethyl, 3,3,3-trifluororopropyl, etc.), an alkoxyalkyloxycarbonyl group having 3 to 6 carbon atoms (wherein the alkoxyalkyl group is, for example, methoxymethyl, methoxyethyl,
Ethoxyethyl and the like), an alkoxycarbonylalkyloxycarbonyl group having 3 to 6 carbon atoms (wherein the alkoxycarbonylalkyl group is, for example,
Methoxycarbonylmethyl, ethoxycarbonylmethyl, ethoxycarbonylethyl, etc.), an amidocarbonylalkyloxycarbonyl group having a carbon number of 3 to 9 (wherein, as the amidocarbonylalkyl group, for example, amidocarbonylmethyl, ethylamidocarbonylmethyl, Dimethylamidocarbonylmethyl, diethylamidocarbonylmethyl, diethylamidocarbonylethyl, etc.) or an alkylthiocarbonyl group having 2 to 5 carbon atoms (wherein the alkylthio group is, for example,
And methylthio, ethylthio, propylthio and the like).
【０００９】Ｒ3 で示されるアミド化されたカルボキシ
ル基としては、アミドカルボニル基又は置換基が、同一
又は異なって、１個又は２個結合した１級アミドカルボ
ニル基又は２級アミドカルボニル基が挙げられ、置換基
としては、炭素数１〜１０の直鎖、分岐鎖又は環状のア
ルキル基（例えば、メチル、エチル、ｎ−プロピル、イ
ソプロピル、ｎ−ブチル、ｎ−ヘキシル、ｎ−オクチ
ル、シクロヘキシル等）、炭素数２〜６のアルケニル基
（例えば、ビニル、アリル、イソプロペニル、イソプレ
ニル等）、炭素数２〜６のアルキニル基（例えば、エチ
ニル、２−プロピニル、３−ブチニル、４−ペンチニル
等）、炭素数７〜１０のアラルキル基（例えば、ベンジ
ル、フェネチル、フェニルプロピル等）、置換されても
よいフェニル基（例えば、フェニル基、ｐ−クロロフェ
ニル、ｍ−ブロモフェニル、ｏ−フルオロフェニル等が
あげられる）、異項環基（例えば、ピリジル、ピラジ
ル、ピリミジル、フリル等）、炭素数１〜３のハロアル
キル基（同一又は異なって塩素原子、臭素原子、ヨウ素
原子又はフッ素原子の１〜３個が結合したメチル基、エ
チル基又はプロピル基で、例えば、クロロメチル、ジフ
ルオロメチル、トリフルオロメチル、２，２，２−トリ
フルオロエチル、３，３，３−トリフルオロロプロピル
等があげられる）、炭素数１〜３のアルコキシ基（例え
ば、メトキシ、エトキシ、プロピルオキシ等）、炭素数
２〜５のアルコキシアルキル基（例えば、メトキシメチ
ル、エトキシメチル、エトキシエチル等）、炭素数２〜
５のエステル化又はアミド化されたカルボキシ基（例え
ば、メトキシカルボニル、エトキシカルボニル、メチル
アミドカルボニル、エチルアミドカルボニル等があげら
れる）、炭素数２〜５のエステル化又はアミド化されも
よいカルボキシアルキル基（例えば、カルボキシメチ
ル、メトキシカルボニルメチル、エトキシカルボニルメ
チル、エトキシカルボニルエチル、１−エトキシカルボ
ニルエチル、エチルアミドカルボニルメチル、１−エチ
ルアミドカルボニルエチル等があげられる）、炭素数２
〜５の脂肪族アシル基（例えば、アセチル、プロピオニ
ル、ブチリル等）、メタンスルホニリル基、エチルアミ
ノチオカルボニル基、エトキシチオカルボニル基又はジ
メチルアミノ基が挙げられる。Examples of the amidated carboxyl group represented by R 3 include a primary amide carbonyl group or a secondary amide carbonyl group in which one or two amido carbonyl groups or substituents are the same or different and are bonded. As the substituent, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms (for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, n-hexyl, n-octyl, cyclohexyl, etc. ), A C2-C6 alkenyl group (for example, vinyl, allyl, isopropenyl, isoprenyl, etc.), a C2-C6 alkynyl group (for example, ethynyl, 2-propynyl, 3-butynyl, 4-pentynyl, etc.). , An aralkyl group having 7 to 10 carbon atoms (eg, benzyl, phenethyl, phenylpropyl, etc.), an optionally substituted phenyl group (eg, Examples thereof include a phenyl group, p-chlorophenyl, m-bromophenyl, o-fluorophenyl, etc.), a heterocyclic group (eg, pyridyl, pyrazyl, pyrimidyl, furyl, etc.), and a haloalkyl group having 1 to 3 carbon atoms ( The same or different, a methyl group, an ethyl group or a propyl group in which 1 to 3 chlorine, bromine, iodine or fluorine atoms are bonded, and examples thereof include chloromethyl, difluoromethyl, trifluoromethyl, 2,2,2 -Trifluoroethyl, 3,3,3-trifluororopropyl and the like), an alkoxy group having 1 to 3 carbon atoms (for example, methoxy, ethoxy, propyloxy and the like), an alkoxyalkyl group having 2 to 5 carbon atoms ( (Eg, methoxymethyl, ethoxymethyl, ethoxyethyl, etc.), having 2 to 2 carbon atoms
5 esterified or amidated carboxy group (for example, methoxycarbonyl, ethoxycarbonyl, methylamidocarbonyl, ethylamidocarbonyl, etc.), C2-5 optionally esterified or amidated carboxyalkyl group (For example, carboxymethyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, ethoxycarbonylethyl, 1-ethoxycarbonylethyl, ethylamidocarbonylmethyl, 1-ethylamidocarbonylethyl, etc.), carbon number 2
To 5 aliphatic acyl groups (eg, acetyl, propionyl, butyryl, etc.), methanesulfonylyl group, ethylaminothiocarbonyl group, ethoxythiocarbonyl group, or dimethylamino group.
【００１０】Ｒ3 で示される低級アルコキシチオカルボ
ニル基としては、例えばメトキシチオカルボニル基又は
エトキシチオカルボニル基が挙げられる。
Ｒ3 で示される置換されてもよい脂肪族アシル基として
は、炭素数２〜５のアシル基（例えば、ホルミル、アセ
チル、プロピオニル、ブチリル、バレリル等）で、置換
基としては水酸基、アセトキシ基、アセトキシアセチル
オキシ基、ジアゾ基又は１〜３個の同一又は異なったハ
ロゲン原子（例えば、塩素原子、臭素原子、フッ素原子
又はヨウ素原子）が挙げられる。Examples of the lower alkoxythiocarbonyl group represented by R 3 include a methoxythiocarbonyl group and an ethoxythiocarbonyl group. The optionally substituted aliphatic acyl group represented by R 3 is an acyl group having 2 to 5 carbon atoms (for example, formyl, acetyl, propionyl, butyryl, valeryl etc.), the substituent is a hydroxyl group, an acetoxy group, An acetoxyacetyloxy group, a diazo group or 1 to 3 same or different halogen atoms (for example, a chlorine atom, a bromine atom, a fluorine atom or an iodine atom) can be mentioned.
【００１１】Ｒ3 で示される基Ｃ（＝ＮＲ4 ）Ｒ5 にお
いて、Ｒ4 で表される低級アルコキシ基としては、炭素
数１〜５のアルコキシ基（例えば、メトキシ、エトキ
シ、ｎ−プロピオキシ、ｎ−ブトキシ、ｎ−ペンチルオ
キシ、ｔ−ブトキシ、イソプロピルオキシ等）が挙げら
れ、Ｒ4 で表される低級アルケニルオキシ基としては炭
素数１〜５のアルケニルオキシ基（例えば、ビニルオキ
シ、アリルオキシ、イソプロペニルオキシ、イソプレニ
ルオキシ等）が挙げられ、Ｒ4 で表される低級アルキニ
ルオキシ基としては炭素数１〜５のアルキニルオキシ基
（例えば、エチニルオキシ、２−プロピニルオキシ、３
−ブチニルオキシ、４−ペンチニルオキシ等）が挙げら
れ、Ｒ4 で表される低級アルキルアミノ基としては炭素
数１〜５のアルキルアミノ基（例えば、メチルアミノ、
エチルアミノ、ジメチルアミノ、ジエチルアミノ等）が
挙げられ、Ｒ4 で表されるアルコキシカルボニルアルキ
ルオキシ基としては例えば、メチル・エトキシカルブニ
ルメチルオキシ基が挙げられる。又、Ｒ5 で表される低
級アルキル基としては炭素数１〜５のアルキル基（例え
ば、メチル、エチル、ｎ−プロピル、イソプロピル、ｎ
−ブチル、ｎ−ヘキシル等）が挙げられる。[0011] In the group C (= NR 4) R 5 represented by R 3, examples of the lower alkoxy group represented by R 4, alkoxy groups having 1 to 5 carbon atoms (e.g., methoxy, ethoxy, n- propoxy, n-butoxy, n-pentyloxy, t-butoxy, isopropyloxy and the like), and the lower alkenyloxy group represented by R 4 is an alkenyloxy group having 1 to 5 carbon atoms (for example, vinyloxy, allyloxy, isooxy). Examples of the lower alkynyloxy group represented by R 4 include propenyloxy, isoprenyloxy, etc., and alkynyloxy groups having 1 to 5 carbon atoms (eg, ethynyloxy, 2-propynyloxy, 3
-Butynyloxy, 4-pentynyloxy and the like), and the lower alkylamino group represented by R 4 is an alkylamino group having 1 to 5 carbon atoms (for example, methylamino,
(Eg, ethylamino, dimethylamino, diethylamino, etc.), and the alkoxycarbonylalkyloxy group represented by R 4 includes, for example, a methylethoxycarbenylmethyloxy group. The lower alkyl group represented by R 5 is an alkyl group having 1 to 5 carbon atoms (eg, methyl, ethyl, n-propyl, isopropyl, n
-Butyl, n-hexyl and the like).
【００１２】Ｒ3 で示される基Ｃ（ＯＲ6)2 Ｒ7 におい
て、Ｒ6 及びＲ7 で表される低級アルキル基としては炭
素数１〜５のアルキル基（例えば、メチル、エチル、ｎ
−プロピル、イソプロピル、ｎ−ブチル、ｎ−ヘキシル
等）が挙げられ、Ｒ6 で示される２個のＲ6 でアルキレ
ン基を形成する基としては、エチレン基が挙げられる。
Ｒ3 で示される基Ｃ（Ｒ8)2 ＯＨにおいて、Ｒ8 で表さ
れる低級アルキル基としては炭素数１〜５のアルキル基
（例えば、メチル、エチル、ｎ−プロピル、イソプロピ
ル、ｎ−ブチル、ｎ−ヘキシル等）が挙げられる。In the group C (OR 6 ) 2 R 7 represented by R 3 , the lower alkyl group represented by R 6 and R 7 is an alkyl group having 1 to 5 carbon atoms (for example, methyl, ethyl, n
- propyl, isopropyl, n- butyl, n- hexyl and the like). Examples of the group to form two alkylene groups in R 6 represented by R 6, include an ethylene group. In the group C (R 8) 2 OH represented by R 3, the lower alkyl group represented by R 8 an alkyl group having 1 to 5 carbon atoms (e.g., methyl, ethyl, n- propyl, isopropyl, n- butyl , N-hexyl and the like).
【００１３】本発明に従った好ましい化合物は式（II
ａ）：Preferred compounds according to the invention are of formula (II
a):
【００１４】[0014]
【化７】 [Chemical 7]
【００１５】〔式中、Ａは、Ｎ又は基ＣＹ（ここで、Ｙ
は水素原子又はハロゲン原子を示す）を表し、Ｘは、ハ
ロゲン原子を表し、Ｒ1 は、水素原子、置換されてもよ
い低級アルキル基（ここで、置換基としてはハロゲン原
子、低級アルコキシ基、又はアリール基のいずれかであ
る）、低級アルケニル基、低級アルキニル基又は脂肪族
アシル基を表し、Ｒ2 は、水素原子又は低級アルキル基
を表し、Ｒ9 は、水素原子、置換されてもよい直鎖乃至
は分岐鎖低級アルキル基（ここで、置換基としてはハロ
ゲン原子、低級アルコキシ基、低級アシル基、低級アル
コキシカルボニル基もしくはアリール基のいずれかであ
る）、低級アルケニル基、低級アルキニル基又は置換さ
れてもよいアリール基（ここで、置換基としてはハロゲ
ン原子もしくは低級アルキル基のいずれかである）を表
す〕で表されるベンズオキサジン誘導体及びその塩であ
る。[In the formula, A is N or a group CY (where Y is
Represents a hydrogen atom or a halogen atom), X represents a halogen atom, R 1 represents a hydrogen atom, an optionally substituted lower alkyl group (wherein the substituent is a halogen atom, a lower alkoxy group, Or an aryl group), a lower alkenyl group, a lower alkynyl group or an aliphatic acyl group, R 2 represents a hydrogen atom or a lower alkyl group, and R 9 represents a hydrogen atom or may be substituted. A straight-chain or branched-chain lower alkyl group (wherein the substituent is a halogen atom, a lower alkoxy group, a lower acyl group, a lower alkoxycarbonyl group or an aryl group), a lower alkenyl group, a lower alkynyl group or A benzene represented by an optionally substituted aryl group (wherein the substituent is either a halogen atom or a lower alkyl group). Oxazine derivatives and salts thereof.
【００１６】本発明に従った他の好ましい化合物は、式
（IIｂ）：Other preferred compounds according to the invention are of formula (IIb):
【００１７】[0017]
【化８】 [Chemical 8]
【００１８】〔式中、Ａは、Ｎ又は基ＣＹ（ここで、Ｙ
は水素原子又はハロゲン原子を示す）を表し、Ｘは、ハ
ロゲン原子を表し、Ｒ1 は、水素原子、置換されてもよ
い低級アルキル基（ここで、置換基としてはハロゲン原
子、低級アルコキシ基もしくはアリール基のいずれかで
ある）、低級アルケニル基、低級アルキニル基又は脂肪
族アシル基を表し、Ｒ2 は、水素原子又は低級アルキル
基を表し、Ｒ10及びＲ11は、同一又は異なり水素原子、
置換されてもよい炭素数１〜１０の直鎖、分岐鎖乃至は
環状アルキル基（ここで、置換基としてはハロゲン原
子、低級アルコキシ基、低級アシル基、低級アルコキシ
カルボニル基もしくはアリール基のいずれかである）、
低級アルケニル基、低級アルキニル基、置換されてもよ
いアリール基（ここで、置換基としてはハロゲン原子も
しくは低級アルキル基のいずれかである）、又は置換さ
れてもよいヘテロアリール基（ここで、置換基としては
ハロゲン原子もしくは低級アルキル基のいずれかであ
る）を表す〕で表されるベンズオキサジン誘導体及びそ
の塩である。[Wherein A is N or a group CY (where Y is
Represents a hydrogen atom or a halogen atom), X represents a halogen atom, R 1 represents a hydrogen atom or an optionally substituted lower alkyl group (wherein the substituent is a halogen atom, a lower alkoxy group or An aryl group), a lower alkenyl group, a lower alkynyl group or an aliphatic acyl group, R 2 represents a hydrogen atom or a lower alkyl group, R 10 and R 11 represent the same or different hydrogen atom,
A linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may be substituted (wherein the substituent is any one of a halogen atom, a lower alkoxy group, a lower acyl group, a lower alkoxycarbonyl group or an aryl group). Is),
Lower alkenyl group, lower alkynyl group, optionally substituted aryl group (wherein the substituent is either a halogen atom or a lower alkyl group), or optionally substituted heteroaryl group (here, substituted The group is either a halogen atom or a lower alkyl group)].
【００１９】本発明に従った更に他の好ましい化合物
は、式（IIｃ）：Still other preferred compounds according to the invention are of formula (IIc):
【００２０】[0020]
【化９】 [Chemical 9]
【００２１】〔式中、Ａは、Ｎ又は基ＣＹ（ここで、Ｙ
は水素原子又はハロゲン原子を示す）を表し、Ｘは、ハ
ロゲン原子を表し、Ｒ1 は、水素原子、置換されてもよ
い低級アルキル基（ここで、置換基としてはハロゲン原
子、低級アルコキシ基もしくはアリール基のいずれかで
ある）、低級アルケニル基、低級アルキニル基又は脂肪
族アシル基を表し、Ｒ2 は、水素原子又は低級アルキル
基を表し、Ｒ12は、置換されてもよい低級アルキル基
（ここで、置換基としてはハロゲン原子、水酸基、ジア
ゾ基もしくは脂肪族アシルオキシ基のいずれかである）
を表す〕で表されるベンズオキサジン誘導体及びその塩
である。[Wherein A is N or a group CY (where Y is
Represents a hydrogen atom or a halogen atom), X represents a halogen atom, R 1 represents a hydrogen atom or an optionally substituted lower alkyl group (wherein the substituent is a halogen atom, a lower alkoxy group or An aryl group), a lower alkenyl group, a lower alkynyl group or an aliphatic acyl group, R 2 represents a hydrogen atom or a lower alkyl group, and R 12 represents an optionally substituted lower alkyl group ( Here, the substituent is either a halogen atom, a hydroxyl group, a diazo group or an aliphatic acyloxy group)
The benzoxazine derivative and a salt thereof represented by
【００２２】本発明に従った更に他の好ましい化合物
は、式（IIｄ）：Still other preferred compounds according to the invention are of formula (IId):
【００２３】[0023]
【化10】 [Chemical 10]
【００２４】〔式中、Ａは、Ｎ又は基ＣＹ（ここで、Ｙ
は水素原子又はハロゲン原子を示す）を表し、Ｘは、ハ
ロゲン原子を表し、Ｒ1 は、水素原子、置換されてもよ
い低級アルキル基（ここで、置換基としてはハロゲン原
子、低級アルコキシ基もしくはアリール基のいずれかで
ある）、低級アルケニル基、低級アルキニル基又は脂肪
族アシル基を表し、Ｒ2 は、水素原子又は低級アルキル
基を表し、Ｒ13は、低級アルキル基を表し、Ｒ14は、水
酸基、低級アルコキシ基、低級アルケニルオキシ基、低
級アルキニルオキシ基、低級アルキルアミノ基又はアル
コキシカルボニルアルキルオキシ基を表す〕で表される
ベンズオキサジン誘導体及びその塩である。[In the formula, A is N or a group CY (where Y is
Represents a hydrogen atom or a halogen atom), X represents a halogen atom, R 1 represents a hydrogen atom or an optionally substituted lower alkyl group (wherein the substituent is a halogen atom, a lower alkoxy group or An aryl group), a lower alkenyl group, a lower alkynyl group or an aliphatic acyl group, R 2 represents a hydrogen atom or a lower alkyl group, R 13 represents a lower alkyl group, and R 14 represents Represents a hydroxyl group, a lower alkoxy group, a lower alkenyloxy group, a lower alkynyloxy group, a lower alkylamino group or an alkoxycarbonylalkyloxy group], and a salt thereof.
【００２５】本発明の式（Ｉ）で表されるベンズオキサ
ジン誘導体は、式(III) で示される２−ニトロフェノー
ル誘導体から、下記反応式に従い製造することができ
る。The benzoxazine derivative represented by the formula (I) of the present invention can be produced from the 2-nitrophenol derivative represented by the formula (III) according to the following reaction formula.
【００２６】[0026]
【化11】 [Chemical 11]
【００２７】（反応式中、Ａ、Ｘ、Ｚ、Ｒ1 、Ｒ2 及び
Ｒ3 示される各基は、前記定義と同じである）
即ち、式(III) で表されるフェノキシ又はピリジルオキ
シニトロフェノール誘導体（ドイツ公開特許公報第２，
３１１，６３８号）のアルカリ金属塩、例えばナトリウ
ム塩とハロマロン酸ジエチル誘導体とを、不活性溶媒、
例えばジメチルフォルムアミド（ＤＭＦ）中で反応させ
ることにより、式（IV）で表されるフェノキシマロン酸
誘導体を得ることができる。(In the reaction formula, the groups represented by A, X, Z, R 1 , R 2 and R 3 are the same as defined above.) That is, the phenoxy or pyridyloxynitro represented by the formula (III) Phenol derivative (German published patent publication No. 2,
311,638) alkali metal salt, for example, sodium salt and diethyl halomalonate derivative, and an inert solvent,
For example, the phenoxymalonic acid derivative represented by the formula (IV) can be obtained by reacting in dimethylformamide (DMF).
【００２８】化合物（IV）は、ラネーニッケル触媒の存
在下に、不活性溶媒、例えばエタノール中で、通常の方
法により接触還元することにより、本発明の一部である
ベンズオキサジン誘導体（Ｉ′）を得ることができる。
化合物（Ｉ′）は、４位窒素原子への各種置換基の導入
（アルキル化又はアシル化）、３位カルボニル基のチオ
カルボニル基への変換及び２位エトキシカルボニル基の
各種誘導体への変換（加水分解、エステル化、アミド
化、グリニヤ反応、イミド化等）を、必要により適宜組
み合わせて反応することにより、本発明の式（Ｉ）で表
される化合物を得ることができる。本発明の化合物
（Ｉ）には、その置換基に基づく各種光学異性体が存在
するが、それらは全て本発明に含まれるものである。The compound (IV) is subjected to catalytic reduction in the presence of a Raney nickel catalyst in an inert solvent such as ethanol by a conventional method to give the benzoxazine derivative (I ') which is a part of the present invention. Obtainable.
The compound (I ′) is introduced by introducing various substituents into the 4-position nitrogen atom (alkylation or acylation), converting the 3-position carbonyl group into a thiocarbonyl group, and converting the 2-position ethoxycarbonyl group into various derivatives ( Hydrolysis, esterification, amidation, Grignard reaction, imidization, etc.) are optionally combined and reacted to obtain the compound represented by the formula (I) of the present invention. The compound (I) of the present invention has various optical isomers based on the substituents, all of which are included in the present invention.
【００２９】[0029]
【実施例】以下、実施例及び参考例をもって本発明をよ
り詳細に説明する。実施例１ ７−（２−クロロ−４−トリフルオロメチルフェノキ
シ）−３，４−ジヒドロ−３−オキソ−２Ｈ−１，４−
ベンズオキサジン−２−カルボン酸エチル（化合物１）
の合成
２−〔５−（２−クロロ−４−トリフルオロメチルフェ
ノキシ）−２−ニトロフェノキシ〕マロン酸ジエチル
（参考例化合物IV−１）（２．０ｇ）をエタノール（２
０ml）に溶解し、ラネーニッケルを触媒として加えて室
温、常圧で１０時間水素添加を行った。反応液をろ過
し、ろ液を減圧下に濃縮した。得られた残渣をシリカゲ
ルクロマトグラフィー（展開溶媒：ｎ−ヘキサン／酢酸
エチル＝３／１）を用いて精製すると、標記化合物（無
色結晶）０．９ｇを得た。EXAMPLES The present invention will be described in more detail below with reference to examples and reference examples. Example 1 7- (2-chloro-4-trifluoromethylphenoxy
Si) -3,4-dihydro-3-oxo-2H-1,4-
Ethyl benzoxazine-2-carboxylate (Compound 1)
Synthesis of 2- [5- (2-chloro-4-trifluoromethylphenoxy) -2-nitrophenoxy] malonate diethyl (Reference Example compound IV-1) (2.0 g) was added to ethanol (2
(0 ml), Raney nickel was added as a catalyst, and hydrogenation was carried out at room temperature and atmospheric pressure for 10 hours. The reaction solution was filtered, and the filtrate was concentrated under reduced pressure. The obtained residue was purified by silica gel chromatography (developing solvent: n-hexane / ethyl acetate = 3/1) to obtain 0.9 g of the title compound (colorless crystals).
【００３０】実施例１において、参考例化合物IV−１に
代え参考例化合物IV−２、参考例化合物IV−３、参考例
化合物IV−４、及び参考例化合物IV−５を用いて同様に
反応することにより、７−（２−クロロ−４−トリフル
オロメチルフェノキシ）−２−メチル−３，４−ジヒド
ロ−３−オキソ−２Ｈ−１，４−ベンズオキサジン−２
−カルボン酸エチル（化合物２）、７−（２，６−ジク
ロロ−４−トリフルオロメチルフェノキシ）−２−メチ
ル−３，４−ジヒドロ−３−オキソ−２Ｈ−１，４−ベ
ンズオキサジン−２−カルボン酸エチル（化合物３）、
７−（２−クロロ−６−フルオロ−４−トリフルオロメ
チルフェノキシ）−２−メチル−３，４−ジヒドロ−３
−オキソ−２Ｈ−１，４−ベンズオキサジン−２−カル
ボン酸エチル（化合物４）及び６−（３−クロロ−５−
トリフルオロメチルピリジン−２−イル）−３，４−ジ
ヒドロ−３−オキソ−２Ｈ−１，４−ベンズオキサジン
−２−カルボン酸エチル（化合物５）が得られた。In the same manner as in Example 1, using Reference Example Compound IV-2, Reference Example Compound IV-3, Reference Example Compound IV-4, and Reference Example Compound IV-5 instead of Reference Example Compound IV-1, the same reaction was conducted. To give 7- (2-chloro-4-trifluoromethylphenoxy) -2-methyl-3,4-dihydro-3-oxo-2H-1,4-benzoxazine-2.
-Ethyl carboxylate (compound 2), 7- (2,6-dichloro-4-trifluoromethylphenoxy) -2-methyl-3,4-dihydro-3-oxo-2H-1,4-benzoxazine-2 -Ethyl carboxylate (compound 3),
7- (2-chloro-6-fluoro-4-trifluoromethylphenoxy) -2-methyl-3,4-dihydro-3
-Oxo-2H-1,4-benzoxazine-2-carboxylate ethyl (Compound 4) and 6- (3-chloro-5-
Ethyl trifluoromethylpyridin-2-yl) -3,4-dihydro-3-oxo-2H-1,4-benzoxazine-2-carboxylate (Compound 5) was obtained.
【００３１】実施例２ ７−（２−クロロ−４−トリフルオロメチルフェノキ
シ）−４−メチル−３，４−ジヒドロ−３−オキソ−２
Ｈ−１，４−ベンズオキサジン−２−カルボン酸エチル
（化合物６）の合成
６０％水素化ナトリウム（１．０ｇ）をジメチルホルム
アミド（以下、ＤＭＦと略す）（５ml）に懸濁し、氷冷
下に７−（２−クロロ−４−トリフルオロメチルフェノ
キシ）−３，４−ジヒドロ−３−オキソ−２Ｈ−１，４
−ベンズオキサジン−２−カルボン酸エチル（化合物
１）（０．８ｇ）のＤＭＦ（５ml）溶液を滴下し、１０
分間攪拌した。ヨウ化メチル（０．４ｇ）を加え、更に
１０分間攪拌した。反応液に水（２０ml）を加え、酢酸
エチル（５０ml）で２度抽出した。抽出液を水、ついで
飽和食塩水で洗浄し、硫酸マグネシウムで乾燥した。溶
媒を減圧下に留去し、残渣をシリカゲルクロマトグラフ
ィー（展開溶媒：ｎ−ヘキサン／酢酸エチル＝３／１）
を用いて精製して、標記化合物（無色油状）０．４ｇを
得た。 Example 2 7- (2-chloro-4-trifluoromethylphenoxy)
Si) -4-Methyl-3,4-dihydro-3-oxo-2
Ethyl H-1,4-benzoxazine-2-carboxylate
Synthesis of (Compound 6) 60% Sodium hydride (1.0 g) was suspended in dimethylformamide (hereinafter abbreviated as DMF) (5 ml), and 7- (2-chloro-4-trifluoromethylphenoxy) was cooled with ice. ) -3,4-Dihydro-3-oxo-2H-1,4
-A solution of ethyl benzoxazine-2-carboxylate (Compound 1) (0.8g) in DMF (5ml) was added dropwise and 10
Stir for minutes. Methyl iodide (0.4 g) was added, and the mixture was further stirred for 10 minutes. Water (20 ml) was added to the reaction solution, and the mixture was extracted twice with ethyl acetate (50 ml). The extract was washed with water and then with saturated saline, and dried over magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was subjected to silica gel chromatography (developing solvent: n-hexane / ethyl acetate = 3/1).
The product was purified by to obtain 0.4 g of the title compound (colorless oily substance).
【００３２】実施例２において、水素化ナトリウムおよ
びヨウ化メチルの２倍量を用い、同様に反応することに
より、７−（２−クロロ−４−トリフルオロメチルフェ
ノキシ）−２，４−ジメチル−３，４−ジヒドロ−３−
オキソ−２Ｈ−１，４−ベンズオキサジン−２−カルボ
ン酸エチル（化合物７）が得られ、又、ヨウ化メチルに
代えて２倍量の臭化エチルを用いることにより７−（２
−クロロ−４−トリフルオロメチルフェノキシ）−２，
４−ジメチル−３，４−ジヒドロ−３−オキソ−２Ｈ−
１，４−ベンズオキサジン−２−カルボン酸エチル（化
合物８）が得られた。In Example 2, double amounts of sodium hydride and methyl iodide were used and reacted in the same manner to give 7- (2-chloro-4-trifluoromethylphenoxy) -2,4-dimethyl-. 3,4-dihydro-3-
Ethyl oxo-2H-1,4-benzoxazine-2-carboxylate (Compound 7) was obtained, and 7- (2 was obtained by substituting twice the amount of ethyl bromide for methyl iodide.
-Chloro-4-trifluoromethylphenoxy) -2,
4-dimethyl-3,4-dihydro-3-oxo-2H-
Ethyl 1,4-benzoxazine-2-carboxylate (Compound 8) was obtained.
【００３３】実施例３ ７−（２，６−ジクロロ−４−トリフルオロメチルフェ
ノキシ）−４−ジフルオロメチル−３，４−ジヒドロ−
３−オキソ−２Ｈ−１，４−ベンズオキサジン−２−カ
ルボン酸エチル（化合物２０）の合成
７−（２，６−ジクロロ−４−トリフルオロメチルフェ
ノキシ）−３，４−ジヒドロ−３−オキソ−２Ｈ−１，
４−ベンズオキサジン−２−カルボン酸エチル（化合物
５）（１．５ｇ）のＤＭＦ（５０ml）溶液に、６０％水
素化ナトリウム（０．２ｇ）を加え、１時間攪拌した。
ドライアイス−アセトン浴で冷却下クロロジフロロメタ
ンガスを１時間導入し、その後２昼夜攪拌した。水（５
０ml）を加え、酢酸エチル（５０ml）で２度抽出した。
抽出液を水、次いで飽和食塩水で洗浄し、硫酸マグネシ
ウムで乾燥した。溶媒を減圧下に留去し、残渣をシリカ
ゲルクロマトグラフィー（展開溶媒：ｎ−ヘキサン／酢
酸エチル＝９／１）を用いて精製して、標記化合物（無
色油状）０．６ｇを得た。 Example 3 7- (2,6-dichloro-4-trifluoromethylphene
Noxy) -4-difluoromethyl-3,4-dihydro-
3-oxo-2H-1,4-benzoxazine-2-ca
Synthesis of ethyl rubonate (Compound 20) 7- (2,6-dichloro-4-trifluoromethylphenoxy) -3,4-dihydro-3-oxo-2H-1,
To a solution of ethyl 4-benzoxazine-2-carboxylate (Compound 5) (1.5 g) in DMF (50 ml) was added 60% sodium hydride (0.2 g), and the mixture was stirred for 1 hour.
Chlorodifluoromethane gas was introduced for 1 hour while cooling in a dry ice-acetone bath, and then stirred for 2 days. Water (5
0 ml) was added, and the mixture was extracted twice with ethyl acetate (50 ml).
The extract was washed with water and then saturated saline, and dried over magnesium sulfate. The solvent was evaporated under reduced pressure, and the residue was purified by silica gel chromatography (developing solvent: n-hexane / ethyl acetate = 9/1) to obtain 0.6 g of the title compound (colorless oil).
【００３４】実施例４ ７−（２−クロロ−４−トリフルオロメチルフェノキ
シ）−３，４−ジヒドロ−３−チオ−２Ｈ−１，４−ベ
ンズオキサジン−２−カルボン酸エチル（化合物２１）
の合成
７−（２−クロロ−４−トリフルオロメチルフェノキ
シ）−３，４−ジヒドロ−３−オキソ−２Ｈ−１，４−
ベンズオキサジン−２−カルボン酸エチル（化合物１）
（０．４ｇ）をトルエン（５ml）に溶解し、２，４−ビ
ス（４−メトキシフェニル）−１，３−ジチア−２，４
−ジフォスフェタン−２，４−ジスルフィド（ローソン
試薬）（０．２ｇ）を加えて、２時間加熱還流した。溶
媒を減圧下に留去し、残渣をシリカゲルクロマトグラフ
ィー（展開溶媒：ｎ−ヘキサン／酢酸エチル＝５／１）
を用いて精製して、標記化合物（無色結晶）０．４ｇを
得た。 Example 4 7- (2-chloro-4-trifluoromethylphenoxy
Si) -3,4-dihydro-3-thio-2H-1,4-be
Ethnoxazin-2-carboxylate (Compound 21)
Synthesis of 7- (2-chloro-4-trifluoromethylphenoxy) -3,4-dihydro-3-oxo-2H-1,4-
Ethyl benzoxazine-2-carboxylate (Compound 1)
(0.4 g) was dissolved in toluene (5 ml) to give 2,4-bis (4-methoxyphenyl) -1,3-dithia-2,4.
-Diphosphetan-2,4-disulfide (Lawson's reagent) (0.2 g) was added, and the mixture was heated under reflux for 2 hours. The solvent was distilled off under reduced pressure, and the residue was subjected to silica gel chromatography (developing solvent: n-hexane / ethyl acetate = 5/1).
The product was purified by to obtain 0.4 g of the title compound (colorless crystals).
【００３５】実施例５ ７−（２−クロロ−４−トリフルオロメチルフェノキ
シ）−２，４−ジメチル−３，４−ジヒドロ−３−オキ
ソ−２Ｈ−１，４−ベンズオキサジン−２−カルボン酸
（化合物２３）の合成
７−（２−クロロ−４−トリフルオロメチルフェノキ
シ）−４−メチル−３，４−ジヒドロ−３−オキソ−２
Ｈ−１，４−ベンズオキサジン−２−カルボン酸エチル
（化合物６）（１．１ｇ）をメタノール（１０ml）に溶
解し、１Ｎ水酸化ナトリウム（３ml）を加えて室温で２
時間攪拌した。１Ｎ塩酸（５ml）を加え、溶媒を減圧下
に留去、残渣を酢酸エチル（２０ml）で２度抽出した。
抽出液を水、ついで飽和食塩水で洗浄し、硫酸マグネシ
ウムで乾燥した後、溶媒を減圧下に留去して、標記化合
物（無色油状）０．９ｇを得た。 Example 5 7- (2-chloro-4-trifluoromethylphenoxy)
Si) -2,4-dimethyl-3,4-dihydro-3-oxy
So-2H-1,4-benzoxazine-2-carboxylic acid
Synthesis of (Compound 23) 7- (2-chloro-4-trifluoromethylphenoxy) -4-methyl-3,4-dihydro-3-oxo-2
Ethyl H-1,4-benzoxazine-2-carboxylate (Compound 6) (1.1 g) was dissolved in methanol (10 ml), 1N sodium hydroxide (3 ml) was added and the mixture was stirred at room temperature for 2 hours.
Stir for hours. 1N hydrochloric acid (5 ml) was added, the solvent was evaporated under reduced pressure, and the residue was extracted twice with ethyl acetate (20 ml).
The extract was washed with water and then with saturated brine, dried over magnesium sulfate, and the solvent was evaporated under reduced pressure to give the title compound (colorless oil) 0.9 g.
【００３６】実施例６ ７−（２−クロロ−４−トリフルオロメチルフェノキ
シ）−２，４−ジメチル−３，４−ジヒドロ−３−オキ
ソ−２Ｈ−１，４−ベンズオキサジン−２−カルボン酸
メチル（化合物２９）の合成
７−（２−クロロ−４−トリフルオロメチルフェノキ
シ）−２，４−ジメチル−３，４−ジヒドロ−３−オキ
ソ−２Ｈ−１，４−ベンズオキサジン−２−カルボン酸
（化合物２３）（０．４ｇ）をベンゼン（１０ml）に溶
解し、塩化チオニル（２ml）を加えて３時間加熱還流し
た。溶媒を減圧下に留去し、メタノール（５ml）を加え
て室温で１時間攪拌した。溶媒を減圧下に留去、残渣を
シリカゲルクロマトグラフィー（展開溶媒：ｎ−ヘキサ
ン／酢酸エチル＝３／１）を用いて精製して、標記化合
物（無色結晶）０．２ｇを得た。 Example 6 7- (2-chloro-4-trifluoromethylphenoxy
Si) -2,4-dimethyl-3,4-dihydro-3-oxy
So-2H-1,4-benzoxazine-2-carboxylic acid
Synthesis of methyl (compound 29) 7- (2-chloro-4-trifluoromethylphenoxy) -2,4-dimethyl-3,4-dihydro-3-oxo-2H-1,4-benzoxazine-2-carboxylic The acid (compound 23) (0.4 g) was dissolved in benzene (10 ml), thionyl chloride (2 ml) was added, and the mixture was heated under reflux for 3 hours. The solvent was evaporated under reduced pressure, methanol (5 ml) was added, and the mixture was stirred at room temperature for 1 hr. The solvent was evaporated under reduced pressure, and the residue was purified by silica gel chromatography (developing solvent: n-hexane / ethyl acetate = 3/1) to obtain 0.2 g of the title compound (colorless crystals).
【００３７】実施例７ ７−（２−クロロ−４−トリフルオロメチルフェノキ
シ）−２，４−ジメチル−３，４−ジヒドロ−３−オキ
ソ−２Ｈ−１，４−ベンズオキサジン−２−カルボン酸
メトキシカルボニルメチルエステル（化合物４６）の合
成
７−（２−クロロ−４−トリフルオロメチルフェノキ
シ）−２，４−ジメチル−３，４−ジヒドロ−３−オキ
ソ−２Ｈ−１，４−ベンズオキサジン−２−カルボン酸
（化合物２３）（０．４ｇ）をＤＭＦ（０．２ml）に溶
解し、ジシクロヘキシルアミン（０．２ml）を加えて６
０℃で１５分間攪拌した。ブロモ酢酸メチル（０．２
ｇ）を加え、６０℃で更に３時間攪拌した。反応液に水
（２０ml）を加え、酢酸エチル（２０ml）で２度抽出し
た。抽出液を水、ついで飽和食塩水で洗浄し、硫酸マグ
ネシウムで乾燥した後、溶媒を減圧下に留去した。残渣
をシリカゲルクロマトグラフィー（展開溶媒：ｎ−ヘキ
サン／酢酸エチル＝３／１）を用いて精製して、標記化
合物（無色結晶）０．３ｇを得た。 Example 7 7- (2-chloro-4-trifluoromethylphenoxy
Si) -2,4-dimethyl-3,4-dihydro-3-oxy
So-2H-1,4-benzoxazine-2-carboxylic acid
Combination of methoxycarbonyl methyl ester (compound 46)
Formed 7- (2-chloro-4-trifluoromethylphenoxy) -2,4-dimethyl-3,4-dihydro-3-oxo-2H-1,4-benzoxazine-2-carboxylic acid (Compound 23) ( 0.4 g) was dissolved in DMF (0.2 ml) and dicyclohexylamine (0.2 ml) was added to the solution to give 6
The mixture was stirred at 0 ° C for 15 minutes. Methyl bromoacetate (0.2
g) was added and the mixture was stirred at 60 ° C. for another 3 hours. Water (20 ml) was added to the reaction solution, and the mixture was extracted twice with ethyl acetate (20 ml). The extract was washed with water and then with saturated brine, dried over magnesium sulfate, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel chromatography (developing solvent: n-hexane / ethyl acetate = 3/1) to obtain 0.3 g of the title compound (colorless crystals).
【００３８】実施例８ ７−（２−クロロ−６−フルオロ−４−トリフルオロメ
チルフェノキシ）−２，４−ジメチル−３，４−ジヒド
ロ−３−オキソ−２Ｈ−１，４−ベンズオキサジン−２
−カルボン酸（エチルアミドカルボニル）メチルエステ
ル（化合物４７）の合成
グリコール酸（０．３ｇ）及びトリエチルアミン（１．
０ml）のジクロロメタン（２０ml）溶液に、７−（２−
クロロ−６−フルオロ−４−トリフルオロメチルフェノ
キシ）−２，４−ジメチル−３，４−ジヒドロ−３−オ
キソ−２Ｈ−１，４−ベンズオキサジン−２−カルボン
酸（化合物２５）より実施例６と同様にして調整した酸
塩化物（１．５ｇ）を加え、室温で１時間攪拌した。反
応液を減圧下に濃縮、残渣を酢酸エチル（２０ml）で２
度抽出した。抽出液を水、ついで飽和食塩水で洗浄し、
硫酸マグネシウムで乾燥した後溶媒を減圧下に留去し
て、７−（２−クロロ−６−フルオロ−４−トリフルオ
ロメチルフェノキシ）−２，４−ジメチル−３，４−ジ
ヒドロ−３−オキソ−２Ｈ−１，４−ベンズオキサジン
−２−カルボン酸カルボキシメチルエスエルを得た。こ
の酸をベンゼン（２０ml）に溶解し、塩化チオニル
（０．９ｇ）を加えて３時間加熱還流した。溶媒を減圧
下に留去後、残渣をジクロロメタン（２０ml）に溶解
し、エチルアミン塩酸塩（０．６ｇ）及びトリエチルア
ミン（２ml）を加えて１時間攪拌した。反応液を減圧下
に濃縮、残渣を酢酸エチル（２０ml）で２度抽出した。
抽出液を水、ついで飽和食塩水で洗浄し、硫酸マグネシ
ウムで乾燥した後溶媒を減圧下に留去した。残渣をシリ
カゲルクロマトグラフィー（展開溶媒：ｎ−ヘキサン／
酢酸エチル＝３／１）を用いて精製して、標記化合物
（無色油状）０．５ｇを得た。 Example 8 7- (2-chloro-6-fluoro-4-trifluorome
Tilphenoxy) -2,4-dimethyl-3,4-dihydride
Ro-3-oxo-2H-1,4-benzoxazine-2
-Carboxylic acid (ethylamidocarbonyl) methyl ester
Synthesis of compound (compound 47) Glycolic acid (0.3 g) and triethylamine (1.
0-ml) in dichloromethane (20 ml), 7- (2-
Example from chloro-6-fluoro-4-trifluoromethylphenoxy) -2,4-dimethyl-3,4-dihydro-3-oxo-2H-1,4-benzoxazine-2-carboxylic acid (Compound 25) The acid chloride (1.5 g) prepared in the same manner as in 6 was added, and the mixture was stirred at room temperature for 1 hour. The reaction mixture was concentrated under reduced pressure, and the residue was diluted with ethyl acetate (20 ml) to give 2
Extracted once. The extract was washed with water and then with saturated saline,
After drying over magnesium sulfate, the solvent was evaporated under reduced pressure to give 7- (2-chloro-6-fluoro-4-trifluoromethylphenoxy) -2,4-dimethyl-3,4-dihydro-3-oxo. A carboxymethyl ester of -2H-1,4-benzoxazine-2-carboxylic acid was obtained. This acid was dissolved in benzene (20 ml), thionyl chloride (0.9 g) was added, and the mixture was heated under reflux for 3 hours. After evaporating the solvent under reduced pressure, the residue was dissolved in dichloromethane (20 ml), ethylamine hydrochloride (0.6 g) and triethylamine (2 ml) were added, and the mixture was stirred for 1 hr. The reaction mixture was concentrated under reduced pressure, and the residue was extracted twice with ethyl acetate (20 ml).
The extract was washed with water and then with saturated brine, dried over magnesium sulfate, and the solvent was evaporated under reduced pressure. The residue is subjected to silica gel chromatography (developing solvent: n-hexane /
Purification using ethyl acetate = 3/1) gave 0.5 g of the title compound (colorless oil).
【００３９】実施例９ ７−（２−クロロ−４−トリフルオロメチルフェノキ
シ）−２，４−ジメチル−３，４−ジヒドロ−３−オキ
ソ−２Ｈ−１，４−ベンズオキサジン−２−カルボキサ
ミド（化合物４８）の合成
７−（２−クロロ−４−トリフルオロメチルフェノキ
シ）−２，４−ジメチル−３，４−ジヒドロ−３−オキ
ソ−２Ｈ−１，４−ベンズオキサジン−２−カルボン酸
（化合物２３）より実施例６と同様にして調整した酸塩
化物（０．４ｇ）をテトラヒドロフラン（以下、ＴＨＦ
と略す）（５ml）に溶解し、アンモニアガスを吹き込み
ながら１時間攪拌した。溶媒を減圧下に留去、残渣をシ
リカゲルクロマトグラフィー（展開溶媒：ｎ−ヘキサン
／酢酸エチル＝１／１）を用いて精製して、標記化合物
（無色結晶）０．３ｇを得た。 Example 9 7- (2-chloro-4-trifluoromethylphenoxy
Si) -2,4-dimethyl-3,4-dihydro-3-oxy
So-2H-1,4-benzoxazine-2-carboxa
Synthesis of amide (compound 48) 7- (2-chloro-4-trifluoromethylphenoxy) -2,4-dimethyl-3,4-dihydro-3-oxo-2H-1,4-benzoxazine-2-carboxylic An acid chloride (0.4 g) prepared from an acid (compound 23) in the same manner as in Example 6 was converted into tetrahydrofuran (hereinafter, THF).
Abbreviated) (5 ml) and stirred for 1 hour while blowing in ammonia gas. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel chromatography (developing solvent: n-hexane / ethyl acetate = 1/1) to obtain 0.3 g of the title compound (colorless crystals).
【００４０】実施例１０ Ｎ−エチル−７−（２−クロロ−４−トリフルオロメチ
ルフェノキシ）−２，４−ジメチル−３，４−ジヒドロ
−３−オキソ−２Ｈ−１，４−ベンズオキサジン−２−
カルボキサミド（化合物４９）の合成
７−（２−クロロ−４−トリフルオロメチルフェノキ
シ）−２，４−ジメチル−３，４−ジヒドロ−３−オキ
ソ−２Ｈ−１，４−ベンズオキサジン−２−カルボン酸
（化合物２３）より実施例６と同様にして調整した酸塩
化物（０．４ｇ）をジオキサン（５ml）に溶解し、エチ
ルアミン塩酸塩（０．１ｇ）を加えて３時間加熱還流し
た。溶媒を減圧下に留去、残渣をシリカゲルクロマトグ
ラフィー（展開溶媒：ｎ−ヘキサン／酢酸エチル＝２／
１）を用いて精製して、標記化合物（無色結晶）０．３
ｇを得た。 Example 10 N-ethyl-7- (2-chloro-4-trifluoromethyi)
Ruphenoxy) -2,4-dimethyl-3,4-dihydro
-3-oxo-2H-1,4-benzoxazine-2-
Synthesis of carboxamide (Compound 49) 7- (2-chloro-4-trifluoromethylphenoxy) -2,4-dimethyl-3,4-dihydro-3-oxo-2H-1,4-benzoxazine-2-carboxylic The acid chloride (0.4 g) prepared from the acid (compound 23) in the same manner as in Example 6 was dissolved in dioxane (5 ml), ethylamine hydrochloride (0.1 g) was added, and the mixture was heated under reflux for 3 hr. The solvent was distilled off under reduced pressure, and the residue was subjected to silica gel chromatography (developing solvent: n-hexane / ethyl acetate = 2 /
1) and the title compound (colorless crystals) 0.3
g was obtained.
【００４１】実施例１１ Ｎ−メトキシメチル−７−（２−クロロ−６−フルオロ
−４−トリフルオロメチルフェノキシ）−２，４−ジメ
チル−３，４−ジヒドロ−３−オキソ−２Ｈ−１，４−
ベンズオキサジン−２−カルボキサミド（化合物７２）
の合成
７−（２−クロロ−６−フルオロ−４−トリフルオロメ
チルフェノキシ）−２，４−ジメチル−３，４−ジヒド
ロ−３−オキソ−２Ｈ−１，４−ベンズオキサジン−２
−カルボキサミド（化合物５５）（０．４ｇ）をトルエ
ン（５ml）に溶解し、クロロジメチルエーテル（０．１
ml）及び水素化ナトリウム（０．１ｇ）を加え、室温で
２時間攪拌した。反応液を氷水に注ぎ、酢酸エチル（２
０ml）で２度抽出した。抽出液を水、ついで飽和食塩水
で洗浄し、硫酸マグネシウムで乾燥した後溶媒を減圧下
に留去した。残渣をシリカゲルクロマトグラフィー（展
開溶媒：ｎ−ヘキサン／酢酸エチル＝２／１）を用いて
精製して、標記化合物（無色油状）０．３ｇを得た。 Example 11 N-methoxymethyl-7- (2-chloro-6-fluoro
-4-Trifluoromethylphenoxy) -2,4-dime
Cyl-3,4-dihydro-3-oxo-2H-1,4-
Benzoxazine-2-carboxamide (Compound 72)
Synthesis of 7- (2-chloro-6-fluoro-4-trifluoromethylphenoxy) -2,4-dimethyl-3,4-dihydro-3-oxo-2H-1,4-benzoxazine-2
-Carboxamide (Compound 55) (0.4g) was dissolved in toluene (5ml) and chlorodimethyl ether (0.1g) was added.
ml) and sodium hydride (0.1 g) were added, and the mixture was stirred at room temperature for 2 hours. The reaction solution was poured into ice water, and ethyl acetate (2
It was extracted twice with 0 ml). The extract was washed with water and then with saturated brine, dried over magnesium sulfate, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel chromatography (developing solvent: n-hexane / ethyl acetate = 2/1) to obtain 0.3 g of the title compound (colorless oil).
【００４２】実施例１２ Ｎ−（２−エコキシカルボニルエチル）─７−（２−ク
ロロ−６−フルオロ−４−トリフルオロメチルフェノキ
シ）−２，４−ジメチル−３，４−ジヒドロ−３−オキ
ソ−２Ｈ−１，４−ベンズオキサジン−２−カルボキサ
ミド（化合物７６）の合成
β−アラニンエチルエステル塩酸塩（０．２ｇ）を塩化
メチレン（５ml）に溶解し、トリエチルアミン（０．４
ml）と７−（２−クロロ−６−フルオロ−４−トリフル
オロメチルフェノキシ）−２，４−ジメチル−３，４−
ジヒドロ−３−オキソ−２Ｈ−１，４−ベンズオキサジ
ン−２−カルボン酸（化合物２５）より実施例６と同様
にして得た酸塩化物（０．５ｇ）の塩化メチレン（５m
l）溶液を加え、室温で２時間攪拌した。反応液を減圧
下に濃縮、残渣を酢酸エチル（２０ml）で２度抽出し
た。抽出液を１Ｎ−塩酸、水、飽和重曹水、飽和食塩水
で順次洗浄し、硫酸マグネシウムで乾燥した。溶媒を減
圧下に留去、残渣をシリカゲルクロマトグラフィー（展
開溶媒：ｎ−ヘキサン／酢酸エチル＝１／１）を用いて
精製して、標記化合物（無色油状）０．４ｇを得た。 Example 12 N- (2-Ecoxycarbonylethyl) -7- (2-ku)
Lolo-6-fluoro-4-trifluoromethylphenoxy
Si) -2,4-dimethyl-3,4-dihydro-3-oxy
So-2H-1,4-benzoxazine-2-carboxa
Synthesis of amide (compound 76) β-alanine ethyl ester hydrochloride (0.2 g) was dissolved in methylene chloride (5 ml) to give triethylamine (0.4 g).
ml) and 7- (2-chloro-6-fluoro-4-trifluoromethylphenoxy) -2,4-dimethyl-3,4-
The acid chloride (0.5 g) obtained from dihydro-3-oxo-2H-1,4-benzoxazine-2-carboxylic acid (Compound 25) in the same manner as in Example 6 was treated with methylene chloride (5 m
l) The solution was added and stirred at room temperature for 2 hours. The reaction mixture was concentrated under reduced pressure, and the residue was extracted twice with ethyl acetate (20 ml). The extract was washed successively with 1N-hydrochloric acid, water, saturated aqueous sodium hydrogen carbonate and saturated brine, and dried over magnesium sulfate. The solvent was evaporated under reduced pressure, and the residue was purified by silica gel chromatography (developing solvent: n-hexane / ethyl acetate = 1/1) to obtain 0.4 g of the title compound (colorless oil).
【００４３】実施例１３ ７−（２−クロロ−６−フルオロ−４−トリフルオロメ
チルフェノキシ）−２，４−ジメチル−２−プロピオニ
ル−３，４−ジヒドロ−３−オキソ−２Ｈ−１，４−ベ
ンズオキサジン（化合物８７）及び７−（２−クロロ−
６−フルオロ−４−トリフルオロメチルフェノキシ）−
２，４−ジメチル−２−〔３−（３−ヒドロキシペンチ
ル）〕−３，４−ジヒドロ−３−オキソ−２Ｈ−１，４
−ベンズオキサジン（化合物８８）の合成
７−（２−クロロ−６−フルオロ−４ −トリフルオロ
メチルフェノキシ）−２，４−ジメチル−３，４−ジヒ
ドロ−３−オキソ−２Ｈ−１，４−ベンズオキサジン−
２−カルボン酸（化合物２５）から実施例６と同様にし
て得た酸塩化物（０．８ｇ）をＴＨＦ（５ml）に溶解
し、窒素ガス雰囲気下ドライアイス−アセトン浴で冷却
し、１Ｍ−エチルマグネシウムブロミドＴＨＦ溶液
（１．９ml）を５分間で滴下した。室温で１夜攪拌後、
反応液に水を加え、酢酸エチル（２０ml）で２度抽出し
た。抽出液を水、次いで飽和食塩水で洗浄し、硫酸マグ
ネシウムで乾燥した。溶媒を減圧下に留去、残渣をシリ
カゲルクロマトグラフィー（展開溶媒：ｎ−ヘキサン／
酢酸エチル＝３／１）を用いて分離精製して、標記２化
合物（無色結晶）のそれぞれ０．３ｇ及び０．２ｇを得
た。 Example 13 7- (2-chloro-6-fluoro-4-trifluorome
Tilphenoxy) -2,4-dimethyl-2-propioni
Le-3,4-dihydro-3-oxo-2H-1,4-be
Indoxazine (Compound 87) and 7- (2-chloro-
6-fluoro-4-trifluoromethylphenoxy)-
2,4-dimethyl-2- [3- (3-hydroxy pliers
)]-3,4-Dihydro-3-oxo-2H-1,4
-Synthesis of benzoxazine (Compound 88) 7- (2-chloro-6-fluoro-4-trifluoromethylphenoxy) -2,4-dimethyl-3,4-dihydro-3-oxo-2H-1,4- Benzoxazine-
The acid chloride (0.8 g) obtained from 2-carboxylic acid (Compound 25) in the same manner as in Example 6 was dissolved in THF (5 ml), cooled in a dry ice-acetone bath under a nitrogen gas atmosphere, and 1M- Ethyl magnesium bromide THF solution (1.9 ml) was added dropwise over 5 minutes. After stirring overnight at room temperature,
Water was added to the reaction solution, and the mixture was extracted twice with ethyl acetate (20 ml). The extract was washed with water and then saturated saline, and dried over magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was subjected to silica gel chromatography (developing solvent: n-hexane /
Separation and purification using ethyl acetate = 3/1) gave 0.3 g and 0.2 g of the title 2 compound (colorless crystals), respectively.
【００４４】実施例１４ ７−（２−クロロ−６−フルオロ−４−トリフルオロメ
チルフェノキシ）−２，４−ジメチル−２−ジアゾアセ
チル−３，４−ジヒドロ−３−オキソ−２Ｈ−１，４−
ベンズオキサジン（化合物９１）の合成
常法により調整したジアゾメタンエーテル溶液（２５０
ml）に、７−（２−クロロ−６−フルオロ−４ −トリ
フルオロメチルフェノキシ）−２，４−ジメチル−３，
４−ジヒドロ−３−オキソ−２Ｈ−１，４−ベンズオキ
サジン−２−カルボン酸（化合物２５）より実施例６と
同様にして得た酸塩化物（３．０ｇ）のＴＨＦ（５ml）
溶液を氷冷下に加え、室温で１０分間攪拌した。反応液
を減圧下に濃縮、残渣をシリカゲルクロマトグラフィー
（展開溶媒：ｎ−ヘキサン／酢酸エチル＝３／１）を用
いて精製して、標記化合物（無色結晶）２．８ｇを得
た。 Example 14 7- (2-chloro-6-fluoro-4-trifluorome
Tylphenoxy) -2,4-dimethyl-2-diazoacetate
Cyl-3,4-dihydro-3-oxo-2H-1,4-
Synthesis of Benzoxazine (Compound 91) Diazomethane ether solution (250
ml), 7- (2-chloro-6-fluoro-4-trifluoromethylphenoxy) -2,4-dimethyl-3,
THF (5 ml) of acid chloride (3.0 g) obtained from 4-dihydro-3-oxo-2H-1,4-benzoxazine-2-carboxylic acid (Compound 25) in the same manner as in Example 6.
The solution was added under ice cooling and stirred at room temperature for 10 minutes. The reaction solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (developing solvent: n-hexane / ethyl acetate = 3/1) to obtain 2.8 g of the title compound (colorless crystals).
【００４５】実施例１５ ７−（２−クロロ−６−フルオロ−４−トリフルオロメ
チルフェノキシ）−２，４−ジメチル−２−アセチル−
３，４−ジヒドロ−３−オキソ−２Ｈ−１，４−ベンズ
オキサジン（化合物９３）の合成
氷冷下、実施例１４で得た７−（２−クロロ−６−フル
オロ−４−トリフルオロメチルフェノキシ）−２，４−
ジメチル−２−ジアゾアセチル−３，４−ジヒドロ−３
−オキソ−２Ｈ−１，４−ベンズオキサジン（化合物９
１）（１．８ｇ）のエーテル（１０ml）溶液に５５％ヨ
ウ化水素酸（１ml）を加え、３０分間攪拌した。反応液
を水で洗浄後硫酸マグネシウムで乾燥し、減圧下に濃縮
した。残渣をシリカゲルクロマトグラフィー（展開溶
媒：ｎ−ヘキサン／酢酸エチル＝２／１）を用いて精製
して、標記化合物（無色結晶）０．４ｇを得た。実施例
１５において、溶媒としてジクロロメタンを用い、ヨウ
化水素酸に代えトリフロロ酢酸又は濃塩酸を用いること
により、７−（２−クロロ−６−フルオロ−４−トリフ
ルオロメチルフェノキシ）−２，４−ジメチル−２−ヒ
ドロキシアセチル−３，４−ジヒドロ−３−オキソ−２
Ｈ−１，４−ベンズオキサジン（化合物９５）及び７−
（２−クロロ−６−フルオロ−４−トリフルオロメチル
フェノキシ）−２，４−ジメチル−２−クロロアセチル
−３，４−ジヒドロ−３−オキソ−２Ｈ−１，４−ベン
ズオキサジン（化合物９７）が得られた。 Example 15 7- (2-chloro-6-fluoro-4-trifluorome
Tilphenoxy) -2,4-dimethyl-2-acetyl-
3,4-dihydro-3-oxo-2H-1,4-benz
Synthesis of Oxazine (Compound 93) 7- (2-chloro-6-fluoro-4-trifluoromethylphenoxy) -2,4-obtained in Example 14 under ice cooling.
Dimethyl-2-diazoacetyl-3,4-dihydro-3
-Oxo-2H-1,4-benzoxazine (compound 9
1) To a solution of (1.8 g) in ether (10 ml) was added 55% hydroiodic acid (1 ml), and the mixture was stirred for 30 minutes. The reaction solution was washed with water, dried over magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel chromatography (developing solvent: n-hexane / ethyl acetate = 2/1) to obtain 0.4 g of the title compound (colorless crystals). In Example 15, by using dichloromethane as a solvent and using trifluoroacetic acid or concentrated hydrochloric acid in place of hydroiodic acid, 7- (2-chloro-6-fluoro-4-trifluoromethylphenoxy) -2,4- Dimethyl-2-hydroxyacetyl-3,4-dihydro-3-oxo-2
H-1,4-benzoxazine (Compound 95) and 7-
(2-Chloro-6-fluoro-4-trifluoromethylphenoxy) -2,4-dimethyl-2-chloroacetyl-3,4-dihydro-3-oxo-2H-1,4-benzoxazine (Compound 97) was gotten.
【００４６】実施例１６ ７−（２−クロロ−６−フルオロ−４−トリフルオロメ
チルフェノキシ）−２，４−ジメチル−２−〔１−（ヒ
ドロキシイミノ）エチル〕−３，４−ジヒドロ−３−オ
キソ−２Ｈ−１，４−ベンズオキサジン（化合物１０
１）の合成
実施例１５で得た７−（２−クロロ−６−フルオロ−４
−トリフルオロメチルフェノキシ）−２，４−ジメチル
−２−アセチル−３，４−ジヒドロ−３−オキソ−２Ｈ
−１，４−ベンズオキサジン（化合物９３）（０．３
ｇ）をエタノール（１０ml）に溶解し、ヒドキシルアミ
ン塩酸塩（０．１ｇ）及び１Ｎ−水酸化ナトリウム
（０．８ml）を加えて９０℃で２時間攪拌した。反応液
を減圧下に濃縮し、残渣をシリカゲルクロマトグラフィ
ー（展開溶媒：ｎ−ヘキサン／酢酸エチル＝２／１）を
用いて精製して、標記化合物（無色結晶）０．３ｇを得
た。 Example 16 7- (2-chloro-6-fluoro-4-trifluorome
Tilphenoxy) -2,4-dimethyl-2- [1- (hi
Droxyimino) ethyl] -3,4-dihydro-3-o
Xo-2H-1,4-benzoxazine (Compound 10
Synthesis of 1) 7- (2-chloro-6-fluoro-4 obtained in Example 15
-Trifluoromethylphenoxy) -2,4-dimethyl-2-acetyl-3,4-dihydro-3-oxo-2H
-1,4-Benzoxazine (Compound 93) (0.3
g) was dissolved in ethanol (10 ml), hydroxylamine hydrochloride (0.1 g) and 1N-sodium hydroxide (0.8 ml) were added, and the mixture was stirred at 90 ° C. for 2 hours. The reaction solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (developing solvent: n-hexane / ethyl acetate = 2/1) to obtain 0.3 g of the title compound (colorless crystals).
【００４７】実施例１７ ７−（２−クロロ−６−フルオロ−４−トリフルオロメ
チルフェノキシ）−２，４−ジメチル−２−〔１−（メ
トキシイミノ）エチル〕−３，４−ジヒドロ−３−オキ
ソ−２Ｈ−１，４−ベンズオキサジン（化合物１０２）
の合成
実施例１５で得た７−（２−クロロ−６−フルオロ−４
−トリフルオロメチルフェノキシ）−２，４−ジメチル
−２−アセチル−３，４−ジヒドロ−３−オキソ−２Ｈ
−１，４−ベンズオキサジン（化合物９３）（０．３
ｇ）をピリジン（４ml）に溶解し、Ｏ−メチルヒドロキ
シアミン塩酸塩（０．１ｇ）を加えて室温で４時間、更
に６０℃で１時間攪拌した。反応液を氷水に注ぎ、酢酸
エチル（２０ml）で２度抽出した。抽出液を１Ｎ−塩
酸、次いで飽和食塩水で洗浄し、硫酸マグネシウムで乾
燥した。溶媒を減圧下に留去、残渣をシリカゲルクロマ
トグラフィー（展開溶媒：ｎ−ヘキサン／酢酸エチル＝
４／１）を用いて精製して、標記化合物（無色油状）
０．３ｇを得た。 Example 17 7- (2-chloro-6-fluoro-4-trifluorome
Tilphenoxy) -2,4-dimethyl-2- [1- (me
Toxiimino) ethyl] -3,4-dihydro-3-oxy
So-2H-1,4-benzoxazine (Compound 102)
Synthesis of 7- (2-chloro-6-fluoro-4 obtained in Example 15
-Trifluoromethylphenoxy) -2,4-dimethyl-2-acetyl-3,4-dihydro-3-oxo-2H
-1,4-Benzoxazine (Compound 93) (0.3
g) was dissolved in pyridine (4 ml), O-methylhydroxyamine hydrochloride (0.1 g) was added, and the mixture was stirred at room temperature for 4 hours and further at 60 ° C. for 1 hour. The reaction solution was poured into ice water and extracted twice with ethyl acetate (20 ml). The extract was washed with 1N-hydrochloric acid and then with saturated saline, and dried over magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was subjected to silica gel chromatography (developing solvent: n-hexane / ethyl acetate =
4/1) to give the title compound (colorless oil)
0.3 g was obtained.
【００４８】実施例１８ ７−（２−クロロ−６−フルオロ−４−トリフルオロメ
チルフェノキシ）−２，４−ジメチル−２−〔１−（エ
トキシイミノ）エチル〕−３，４−ジヒドロ−３−オキ
ソ−２Ｈ−１，４−ベンズオキサジン（化合物１０４）
の合成
実施例１６で得た７−（２−クロロ−６−フルオロ−４
−トリフルオロメチルフェノキシ）−２，４−ジメチル
−２−〔１−（ヒドロキシイミノ）エチル〕−３，４−
ジヒドロ−３−オキソ−２Ｈ−１，４−ベンズオキサジ
ン（化合物１０１）（０．３ｇ）のＤＭＦ（１０ml）溶
液に、氷冷下に６０％水素化ナトリウム（０．０３ｇ）
を加え、２０分間攪拌後ブロモエタン（０．１ｇ）を滴
下した。２時間攪拌後１Ｎ塩酸を加え、酢酸エチル（２
０ml）で２度抽出した。抽出液を水、次いで飽和食塩水
で洗浄し、硫酸マグネシウムで乾燥した。溶媒を減圧下
に留去、残渣をシリカゲルクロマトグラフィー（展開溶
媒：ｎ−ヘキサン／酢酸エチル＝４／１）を用いて精製
して、標記化合物（無色油状）０．３ｇを得た。 Example 18 7- (2-chloro-6-fluoro-4-trifluorome
Tilphenoxy) -2,4-dimethyl-2- [1- (d
Toxiimino) ethyl] -3,4-dihydro-3-oxy
So-2H-1,4-benzoxazine (Compound 104)
Synthesis of 7- (2-chloro-6-fluoro-4 obtained in Example 16
-Trifluoromethylphenoxy) -2,4-dimethyl-2- [1- (hydroxyimino) ethyl] -3,4-
A solution of dihydro-3-oxo-2H-1,4-benzoxazine (Compound 101) (0.3 g) in DMF (10 ml) was added to 60% sodium hydride (0.03 g) under ice cooling.
Was added, and after stirring for 20 minutes, bromoethane (0.1 g) was added dropwise. After stirring for 2 hours, 1N hydrochloric acid was added, and ethyl acetate (2
It was extracted twice with 0 ml). The extract was washed with water and then saturated saline, and dried over magnesium sulfate. The solvent was evaporated under reduced pressure, and the residue was purified by silica gel chromatography (developing solvent: n-hexane / ethyl acetate = 4/1) to obtain 0.3 g of the title compound (colorless oil).
【００４９】上で得られた実施例化合物及び実施例１〜
１８に示したいずれかの方法に準じて製造することがで
きたその他の化合物について、その物性ともに第１表
（表中、＊は置換位置を示す）に記載した。Example compounds obtained above and Examples 1-
The physical properties of the other compounds that could be produced according to any of the methods shown in 18 are described in Table 1 (* indicates the substitution position in the table).
【００５０】[0050]
【表１】 [Table 1]
【００５１】[0051]
【表２】 [Table 2]
【００５２】[0052]
【表３】 [Table 3]
【００５３】参考例１ ２−〔５−（２−クロロ−４−トリフルオロメチルフェ
ノキシ）−２−ニトロフェノキシ〕マロン酸ジエチル
（IV−１）の合成
６０％水素化ナトリウム（０．４ｇ）をＤＭＦ（５ml）
中に懸濁し、氷冷下に５−（２−クロロ−４−トリフル
オロメチルフェノキシ）−２−ニトロフェノノール
（３．３ｇ）のＤＭＦ（５ml）溶液を滴下し、１０分間
攪拌した。この溶液中にブロモマロン酸ジエチル（２．
１ml）を加え、７０℃で３０分間攪拌した。反応液に水
（１０ml）を加え、酢酸エチル（２０ml）で２度抽出し
た。抽出液を水、ついで飽和食塩水で洗浄し、硫酸マグ
ネシウムで乾燥した。溶媒を減圧下に留去し、残渣をシ
リカゲルクロマトグラフィー（展開溶媒：ｎ−ヘキサン
／酢酸エチル＝５／１）を用いて精製して、標記化合物
（無色油状）３．０ｇを得た。また、原料のフェノール
誘導体０．７ｇが回収された。 Reference Example 1 2- [5- (2-chloro-4-trifluoromethylphene)
(Noxy) -2-nitrophenoxy] malonate diethyl
Synthesis of (IV-1) 60% sodium hydride (0.4g) in DMF (5ml)
A solution of 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitrophenonol (3.3 g) in DMF (5 ml) was added dropwise under ice-cooling, and the mixture was stirred for 10 minutes. Diethyl bromomalonate (2.
1 ml) was added and the mixture was stirred at 70 ° C. for 30 minutes. Water (10 ml) was added to the reaction solution, and the mixture was extracted twice with ethyl acetate (20 ml). The extract was washed with water and then with saturated saline, and dried over magnesium sulfate. The solvent was evaporated under reduced pressure, and the residue was purified by silica gel chromatography (developing solvent: n-hexane / ethyl acetate = 5/1) to obtain 3.0 g of the title compound (colorless oil). In addition, 0.7 g of the raw material phenol derivative was recovered.
【００５４】ＮＭＲ（δppm, CDCl3）：1.29(6H, t, J=
8Hz)，4.30(4H, q, J=8Hz)，5.16(1H, s), 6.56 〜6.68
(2H, m), 7.20(1H, d, J=9Hz), 7.59(1H, dd, J=9&2H
z), 7.77(1H, d, J=2Hz), 7.97(1H, d, J=10Hz)NMR (δ ppm, CDCl 3 ): 1.29 (6H, t, J =
8Hz), 4.30 (4H, q, J = 8Hz), 5.16 (1H, s), 6.56 ~ 6.68
(2H, m), 7.20 (1H, d, J = 9Hz), 7.59 (1H, dd, J = 9 & 2H
z), 7.77 (1H, d, J = 2Hz), 7.97 (1H, d, J = 10Hz)
【００５５】参考例１において、５−（２−クロロ−４
−トリフルオロメチルフェノキシ）−２−ニトロフェノ
ールに代え４−（３−クロロ−５−トリフルオロメチル
ピリジン−２−イル）−２−ニトロフェノールを用いて
同様に反応することにより、２−〔４−（３−クロロ−
５−トリフルオロメチルピリジン−２−イル）−２−ニ
トロフェノキシ〕マロン酸ジエチル（IV−５）が得られ
た。同様に、ブロモマロン酸ジエチルに代えブロモメチ
ルマロン酸ジエチルを用い、５−（２−クロロ−４−ト
リフルオロメチルフェノキシ）−２−ニトロフェノー
ル、５−（２，６−ジクロロ−４−トリフルオロメチル
フェノキシ）−２−ニトロフェノール又は５−（２−ク
ロロ−６−フルオロ−４−トリフルオロメチルフェノキ
シ）−２−ニトロフェノールと反応することにより２−
〔５−（２−クロロ−４−トリフルオロメチルフェノキ
シ）−２−ニトロフェノキシ〕−２−メチルマロン酸ジ
エチル（IV−２）、２−〔５−（２，６−ジクロロ−４
−トリフルオロメチルフェノキシ）−２−ニトロフェノ
キシ〕−２−メチルマロン酸ジエチル（IV−３）及び２
−〔５−（２−クロロ−６−フルオロ−４−トリフルオ
ロメチルフェノキシ）−２−ニトロフェノキシ〕−２−
メチルマロン酸ジエチル（IV−４）が得られた。これら
の化合物の物性を第２表（表中、＊は置換位置を示す）
に示す。In Reference Example 1, 5- (2-chloro-4)
-[4-fluoromethylphenoxy) -2-nitrophenol was replaced with 4- (3-chloro-5-trifluoromethylpyridin-2-yl) -2-nitrophenol to carry out a similar reaction to give 2- [4 -(3-chloro-
Diethyl 5-IV-trifluoromethylpyridin-2-yl) -2-nitrophenoxy] malonate (IV-5) was obtained. Similarly, using diethyl bromomethylmalonate instead of diethyl bromomalonate, 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitrophenol, 5- (2,6-dichloro-4-trifluoromethyl) 2- by reacting with phenoxy) -2-nitrophenol or 5- (2-chloro-6-fluoro-4-trifluoromethylphenoxy) -2-nitrophenol
[5- (2-chloro-4-trifluoromethylphenoxy) -2-nitrophenoxy] -2-methylmalonate diethyl (IV-2), 2- [5- (2,6-dichloro-4)
-Trifluoromethylphenoxy) -2-nitrophenoxy] -2-methylmalonate diethyl (IV-3) and 2
-[5- (2-Chloro-6-fluoro-4-trifluoromethylphenoxy) -2-nitrophenoxy] -2-
Diethyl methylmalonate (IV-4) was obtained. The physical properties of these compounds are shown in Table 2 (in the table, * indicates a substitution position).
Shown in.
【００５６】[0056]
【表４】 [Table 4]
【００５７】試験例１（土壌処理）
土壌を充填した６cm×１５cm×１０cmシードリングケー
スにメヒシバ、イヌビユ、スベリヒユ、イヌタデ及びカ
ヤツリグサの各種子を播種した。播種翌日に、２０％水
和剤とした試験化合物を、有効成分で１０ａ当り４００
ｇ又は５０ｇとなるよう１０ａ当り２００リットルの水
で希釈し、土壌表面に散布した。薬剤処理後２週間目に
殺草程度（５：完全枯死〜０：無作用）を肉眼で観察評
価して、第３表の結果を得た。 Test Example 1 (Soil Treatment ) Various seeds of crabgrass, Amaranthus persicae, Acacia nilotica, Spodoptera litura and Cyperus communis were sown in a 6 cm × 15 cm × 10 cm seedling case filled with soil. On the day after seeding, the test compound as a 20% wettable powder was added as an active ingredient in an amount of 400 per 10a.
It was diluted with 200 liters of water per 10a so as to be g or 50 g, and sprayed on the soil surface. Two weeks after the chemical treatment, the herbicidal degree (5: complete death to 0: no action) was visually observed and evaluated, and the results shown in Table 3 were obtained.
【００５８】[0058]
【表５】 [Table 5]
【００５９】試験例２（茎葉処理）
土壌を充填した６cm×１５cm×１０cmシードリングケー
スにメヒシバ、イヌビユ、スベリヒユ、イヌタデ及びカ
ヤツリグサの各種子を播種した。温室内で１０日間育成
後、２０％水和剤とした試験化合物を、有効成分で１０
ａ当り４００ｇ又は５０ｇとなるよう１０ａ当り２００
リットルの水で希釈し、茎葉表面に散布した。薬剤処理
後２週間目に殺草程度（５：完全枯死〜０：無作用）を
肉眼で観察評価して、第４表の結果を得た。 Test Example 2 (Stems and Leaves Treatment ) Various seeds of crabgrass, Aedes persicae, purslane, Acacia catechu and Cyperaceae were sown in a 6 cm × 15 cm × 10 cm seedling case filled with soil. After growing in a greenhouse for 10 days, a test compound containing 20% wettable powder was used as an active ingredient at 10%.
200 per 10a so that 400g or 50g per a
It was diluted with 1 liter of water and sprayed on the surface of foliage. Two weeks after the chemical treatment, the degree of herbicidal activity (5: complete death to 0: no action) was visually observed and evaluated, and the results shown in Table 4 were obtained.
【００６０】[0060]
【表６】 [Table 6]
【００６１】試験例３（土壌処理）
土壌を充填し、湛水した６cm×１６cm×１１cm塩ビパッ
クにタイヌビエ、コナギ、タマガヤツリ、ヒメミソハギ
及びホタルイの各種子を播種した。播種翌日に、試験化
合物のアセトン溶液（場合によりエタノール又は水溶
液）を、有効成分で１０ａ当り４００ｇ又は２５ｇとな
るよう１パック当り６０mlの水で希釈し、湛水滴下処理
した。薬剤処理後４週間目に殺草程度（５：完全枯死〜
０：無作用）を肉眼で観察評価して、第５表の結果を得
た。 Test Example 3 (Soil Treatment ) Soil-filled and flooded 6 cm × 16 cm × 11 cm PVC packs were inoculated with various seeds of rice barley, eel, corn snail, scutellaria and firefly. On the day after seeding, an acetone solution of the test compound (optionally ethanol or an aqueous solution) was diluted with 60 ml of water per pack so that the active ingredient was 400 g or 25 g per 10 a, and the water was added dropwise. 4 weeks after the chemical treatment, the degree of herbicide (5: complete withering ~
0: no effect) was visually observed and evaluated, and the results shown in Table 5 were obtained.
【００６２】[0062]
【表７】 [Table 7]
【００６３】試験例４（茎葉処理）
土壌を充填し、湛水した６cm×１６cm×１１cm塩ビパッ
クにタイヌビエ、コナギ、タマガヤツリ、ヒメミソハギ
及びホタルイの各種子を播種した。温室内で約２週間育
成後、試験化合物のアセトン溶液（場合によりエタノー
ル又は水溶液）を、有効成分で１０ａ当り４００ｇ又は
２５ｇとなるよう１パック当り６０mlの水で希釈し、茎
葉表面に散布した。薬剤処理後３週間目に殺草程度
（５：完全枯死〜０：無作用）を肉眼で観察評価して、
第６表の結果を得た。 Test Example 4 (Stem and Leaf Treatment ) Soil-filled and submerged 6 cm × 16 cm × 11 cm PVC packs were inoculated with various seeds of rice barley, eel, corn snail, lanceolate and firefly. After growing in a greenhouse for about 2 weeks, an acetone solution of the test compound (in some cases, ethanol or an aqueous solution) was diluted with 60 ml of water per pack so that the active ingredient was 400 g or 25 g per 10 a and sprayed on the surface of the foliage. Three weeks after the drug treatment, the degree of herbicide (5: complete death to 0: no action) was visually observed and evaluated,
The results shown in Table 6 were obtained.
【００６４】[0064]
【表８】 [Table 8]
【００６５】試験例１〜４から明らかなように、本発明
化合物は発芽前及び発芽後の各種雑草に対して優れた除
草活性を示し、除草剤として有用な化合物である。式
（Ｉ）で表される本発明化合物は、その除草作用から、
単独又は合剤で、各種製剤として、発芽前又は発芽後に
使用することができる。本発明の化合物を除草剤として
施用するにあたっては、一般には通常の担体、例えば、
クレー又は珪草土等の固体担体、あるいは水、アルコー
ル類、芳香族炭化水素類、エーテル類、ケトン類又はエ
ステル類等の液体担体と混用して適用することができ、
また必要・所望により乳化剤、分散剤、懸濁剤、展着
剤、安定剤等を添加し、他種除草剤、殺虫剤、殺菌剤、
植物成長調整剤等と混合して使用することができ、かか
る各種製剤を製造するに際しては有効成分含量を、例え
ば１〜９０重量％の範囲で含ませるのが好ましい。本発
明の除草剤は、発芽前の土壌処理剤又は発芽後の茎葉処
理剤として使用することができ、その施用量は広範囲に
わたり変えることができるが、一般には１０アール当た
り０．１〜４００ｇの範囲で使用するのが好ましい。As is clear from Test Examples 1 to 4, the compounds of the present invention exhibit excellent herbicidal activity against various weeds before and after germination and are useful as herbicides. The compound of the present invention represented by the formula (I) has the following herbicidal action:
They can be used alone or in combination as various preparations before or after germination. In applying the compound of the present invention as a herbicide, generally a conventional carrier, for example,
It can be applied by mixing with a solid carrier such as clay or diatomaceous earth, or a liquid carrier such as water, alcohols, aromatic hydrocarbons, ethers, ketones or esters,
If necessary or desired, an emulsifier, a dispersant, a suspending agent, a spreading agent, a stabilizer, etc. are added, and other herbicides, insecticides, bactericides,
It can be used as a mixture with a plant growth regulator or the like, and when producing such various preparations, it is preferable that the content of the active ingredient is contained in the range of, for example, 1 to 90% by weight. The herbicide of the present invention can be used as a pre-emergence soil treatment agent or a post-emergence foliar treatment agent, and its application amount can be widely varied, but generally 0.1 to 400 g per 10 are. It is preferably used in the range.
【００６６】製剤例１（乳剤）
常法により、化合物３７を１５重量部、キシレンを６５
重量部、及びポリオキシエチレンアルキルアリルエーテ
ルを２０重量部を混合して均一な溶液とし、有効成分１
５％を含有する乳剤を得た。 Formulation Example 1 (emulsion ) 15 parts by weight of compound 37 and 65 parts of xylene were prepared by a conventional method.
By mixing 20 parts by weight of polyoxyethylene alkylallyl ether and 20 parts by weight of polyoxyethylene alkyl allyl ether into a uniform solution, the active ingredient 1
An emulsion containing 5% was obtained.
【００６７】製剤例２（水和剤）
常法により、化合物５６を４０重量部、ジークライトを
５５重量部、アルキルベンゼンスルホン酸ソーダを２重
量部、及びポリオキシエチレンアルキルアリルエーテル
を３重量部を均一に粉砕混合し、有効成分４０％を含有
する水和剤を得た。 Formulation Example 2 (wettable powder) 40 parts by weight of compound 56, 55 parts by weight of dichlite, 2 parts by weight of sodium alkylbenzene sulfonate, and 3 parts by weight of polyoxyethylene alkyl allyl ether were prepared by a conventional method. The ingredients were uniformly pulverized and mixed to obtain a wettable powder containing 40% of the active ingredient.
【００６８】製剤例３（粉剤）
常法により、化合物８２を５重量部、，ペントナイトを
２０重量部、クレー７３重量部、及びドデシルベンゼン
スルホン酸ソーダを２重量部を均一に混合し、水約２０
重量部を加えて混練機で練り合わせた。これを造粒機を
通して造粒し、乾燥後、製粒して有効成分５％を含有す
る粒剤を得た。 Formulation Example 3 (powder ) By a conventional method, 5 parts by weight of compound 82, 20 parts by weight of pentonite, 73 parts by weight of clay, and 2 parts by weight of sodium dodecylbenzene sulfonate were uniformly mixed and mixed with water. About 20
Parts by weight were added and kneaded with a kneader. This was granulated through a granulator, dried and granulated to obtain a granule containing 5% of the active ingredient.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 佐合 隆一 神奈川県伊勢原市下糟屋1787−１ (72)発明者 井貝 敬太郎 神奈川県平塚市田村6348 全農協同住宅 104号 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Ryuichi Saai 1787-1 Shimotsukeya, Isehara City, Kanagawa Prefecture (72) Inventor Keitaro Igai 6348 Tamura, Hiratsuka, Kanagawa Prefecture Agricultural cooperative housing No. 104
Claims (6)
はハロゲン原子を示す）を表し、Ｘは、ハロゲン原子を
表し、Ｚは、酸素原子又は硫黄原子を表し、Ｒ1 は、水
素原子、置換されてもよい低級アルキル基（ここで、置
換基としてはハロゲン原子、低級アルコキシ基もしくは
アリール基のいずれかである）、低級アルケニル基、低
級アルキニル基又は脂肪族アシル基を表し、Ｒ2 は、水
素原子又は低級アルキル基を表し、Ｒ3 は、エステル化
またはアミド化されてもよいカルボキシル基、置換され
てもよい脂肪族アシル基（ここで、置換基としてはハロ
ゲン原子、ジアゾ基もしくはアシル化されてもよい水酸
基のいずれかである）、低級アルコキシチオカルボニル
基、基Ｃ（＝ＮＲ4 ）Ｒ5 （ここで、Ｒ4 は水酸基、低
級アルコキシ基、低級アルケニルオキシ基、低級アルキ
ニルオキシ基、アミノ基、低級アルキルアミノ基又はア
ルコキシカルボニルアルキルオキシ基を示し、Ｒ5 は低
級アルキル基を示す）、基Ｃ（ＯＲ6)2 Ｒ7 （ここで、
Ｒ6 は低級アルキル基を示すか又は２個のＲ6 でアルキ
レン基を形成する基を示し、Ｒ7 は低級アルキル基を示
す）又は基Ｃ（Ｒ8)2 ＯＨ（ここで、Ｒ8 は低級アルキ
ル基を示す）を表す〕で表されるベンズオキサジン誘導
体及びその塩。1. Formula (I): [In the formula, A represents N or a group CY (wherein Y represents a hydrogen atom or a halogen atom), X represents a halogen atom, Z represents an oxygen atom or a sulfur atom, and R 1 represents Represents a hydrogen atom, an optionally substituted lower alkyl group (wherein the substituent is a halogen atom, a lower alkoxy group or an aryl group), a lower alkenyl group, a lower alkynyl group or an aliphatic acyl group. , R 2 represents a hydrogen atom or a lower alkyl group, R 3 represents a carboxyl group which may be esterified or amidated, an aliphatic acyl group which may be substituted (wherein the substituent is a halogen atom, diazo group or acylated be either good hydroxyl group), lower alkoxycarbonyl thiocarbonyl group, group C (= NR 4) R 5 ( wherein, R 4 is a hydroxyl group, a lower alkoxy group, lower Alkenyloxy group, a lower alkynyloxy group, an amino group, a lower alkyl amino group or alkoxycarbonylalkyl group, R 5 represents a lower alkyl group), group C (OR 6) 2 R 7 ( wherein,
R 6 represents a lower alkyl group or a group in which two R 6 form an alkylene group, R 7 represents a lower alkyl group) or a group C (R 8 ) 2 OH (wherein R 8 represents Represents a lower alkyl group] and a salt thereof.
はハロゲン原子を示す）を表し、Ｘは、ハロゲン原子を
表し、Ｒ1 は、水素原子、置換されてもよい低級アルキ
ル基（ここで、置換基としてはハロゲン原子、低級アル
コキシ基、又はアリール基のいずれかである）、低級ア
ルケニル基、低級アルキニル基又は脂肪族アシル基を表
し、Ｒ2 は、水素原子又は低級アルキル基を表し、Ｒ9
は、水素原子、置換されてもよい直鎖乃至は分岐鎖低級
アルキル基（ここで、置換基としてはハロゲン原子、低
級アルコキシ基、低級アシル基、低級アルコキシカルボ
ニル基もしくはアリール基のいずれかである）、低級ア
ルケニル基、低級アルキニル基又は置換されてもよいア
リール基（ここで、置換基としてはハロゲン原子もしく
は低級アルキル基のいずれかである）を表す〕で表され
るベンズオキサジン誘導体及びその塩。2. Formula (IIa): embedded image [In the formula, A represents N or a group CY (wherein Y represents a hydrogen atom or a halogen atom), X represents a halogen atom, R 1 represents a hydrogen atom or an optionally substituted lower alkyl. A group (wherein the substituent is a halogen atom, a lower alkoxy group or an aryl group), a lower alkenyl group, a lower alkynyl group or an aliphatic acyl group, and R 2 is a hydrogen atom or a lower alkyl group. Represents a group, R 9
Is a hydrogen atom, a linear or branched lower alkyl group which may be substituted (wherein the substituent is any of a halogen atom, a lower alkoxy group, a lower acyl group, a lower alkoxycarbonyl group or an aryl group). ), A lower alkenyl group, a lower alkynyl group or an optionally substituted aryl group (wherein the substituent is either a halogen atom or a lower alkyl group)] and a salt thereof. .
はハロゲン原子を示す）を表し、Ｘは、ハロゲン原子を
表し、Ｒ1 は、水素原子、置換されてもよい低級アルキ
ル基（ここで、置換基としてはハロゲン原子、低級アル
コキシ基もしくはアリール基のいずれかである）、低級
アルケニル基、低級アルキニル基又は脂肪族アシル基を
表し、Ｒ2 は、水素原子又は低級アルキル基を表し、Ｒ
10及びＲ11は、同一又は異なり水素原子、置換されても
よい炭素数１〜１０の直鎖、分岐鎖乃至は環状アルキル
基（ここで、置換基としてはハロゲン原子、低級アルコ
キシ基、低級アシル基、低級アルコキシカルボニル基も
しくはアリール基のいずれかである）、低級アルケニル
基、低級アルキニル基、置換されてもよいアリール基
（ここで、置換基としてはハロゲン原子もしくは低級ア
ルキル基のいずれかである）、又は置換されてもよいヘ
テロアリール基（ここで、置換基としてはハロゲン原子
もしくは低級アルキル基のいずれかである）を表す〕で
表されるベンズオキサジン誘導体及びその塩。3. Formula (IIb): embedded image [In the formula, A represents N or a group CY (wherein Y represents a hydrogen atom or a halogen atom), X represents a halogen atom, R 1 represents a hydrogen atom or an optionally substituted lower alkyl. A group (wherein the substituent is a halogen atom, a lower alkoxy group or an aryl group), a lower alkenyl group, a lower alkynyl group or an aliphatic acyl group, and R 2 is a hydrogen atom or a lower alkyl group. Represents R
10 and R 11 are the same or different and each is a hydrogen atom, an optionally substituted linear, branched or cyclic alkyl group (wherein the substituent is a halogen atom, a lower alkoxy group, a lower acyl group). Group, a lower alkoxycarbonyl group or an aryl group), a lower alkenyl group, a lower alkynyl group, an optionally substituted aryl group (wherein the substituent is either a halogen atom or a lower alkyl group) ) Or a heteroaryl group which may be substituted (wherein the substituent is either a halogen atom or a lower alkyl group)], and a salt thereof.
はハロゲン原子を示す）を表し、Ｘは、ハロゲン原子を
表し、Ｒ1 は、水素原子、置換されてもよい低級アルキ
ル基（ここで、置換基としてはハロゲン原子、低級アル
コキシ基もしくはアリール基のいずれかである）、低級
アルケニル基、低級アルキニル基又は脂肪族アシル基を
表し、Ｒ2 は、水素原子又は低級アルキル基を表し、Ｒ
12は、置換されてもよい低級アルキル基（ここで、置換
基としてはハロゲン原子、水酸基、ジアゾ基もしくは脂
肪族アシルオキシ基のいずれかである）を表す〕で表さ
れるベンズオキサジン誘導体及びその塩。4. Formula (IIc): [In the formula, A represents N or a group CY (wherein Y represents a hydrogen atom or a halogen atom), X represents a halogen atom, R 1 represents a hydrogen atom or an optionally substituted lower alkyl. A group (wherein the substituent is a halogen atom, a lower alkoxy group or an aryl group), a lower alkenyl group, a lower alkynyl group or an aliphatic acyl group, and R 2 is a hydrogen atom or a lower alkyl group. Represents R
12 represents an optionally substituted lower alkyl group (wherein, the substituent is a halogen atom, a hydroxyl group, a diazo group or an aliphatic acyloxy group)] and a benzoxazine derivative and a salt thereof. .
はハロゲン原子を示す）を表し、Ｘは、ハロゲン原子を
表し、Ｒ1 は、水素原子、置換されてもよい低級アルキ
ル基（ここで、置換基としてはハロゲン原子、低級アル
コキシ基もしくはアリール基のいずれかである）、低級
アルケニル基、低級アルキニル基又は脂肪族アシル基を
表し、Ｒ2 は、水素原子又は低級アルキル基を表し、Ｒ
13は、低級アルキル基を表し、Ｒ14は、水酸基、低級ア
ルコキシ基、低級アルケニルオキシ基、低級アルキニル
オキシ基、低級アルキルアミノ基又はアルコキシカルボ
ニルアルキルオキシ基を表す〕で表されるベンズオキサ
ジン誘導体及びその塩。5. Formula (IId): [In the formula, A represents N or a group CY (wherein Y represents a hydrogen atom or a halogen atom), X represents a halogen atom, R 1 represents a hydrogen atom or an optionally substituted lower alkyl. A group (wherein the substituent is a halogen atom, a lower alkoxy group or an aryl group), a lower alkenyl group, a lower alkynyl group or an aliphatic acyl group, and R 2 is a hydrogen atom or a lower alkyl group. Represents R
13 represents a lower alkyl group, R 14 represents a hydroxyl group, a lower alkoxy group, a lower alkenyloxy group, a lower alkynyloxy group, a lower alkylamino group or an alkoxycarbonylalkyloxy group], and a benzoxazine derivative represented by Its salt.
含有する除草剤。6. A herbicide containing the compound according to claim 1 as an active ingredient.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03188835A JP3119681B2 (en) | 1990-10-04 | 1991-07-29 | Benzoxazine derivatives and herbicides containing the same as active ingredients |
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2-265072 | 1990-10-04 | ||
| JP26507190 | 1990-10-04 | ||
| JP26507290 | 1990-10-04 | ||
| JP2-265071 | 1990-10-04 | ||
| JP03188835A JP3119681B2 (en) | 1990-10-04 | 1991-07-29 | Benzoxazine derivatives and herbicides containing the same as active ingredients |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH054977A true JPH054977A (en) | 1993-01-14 |
| JP3119681B2 JP3119681B2 (en) | 2000-12-25 |
Family
ID=27326102
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03188835A Expired - Fee Related JP3119681B2 (en) | 1990-10-04 | 1991-07-29 | Benzoxazine derivatives and herbicides containing the same as active ingredients |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3119681B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023112856A1 (en) * | 2021-12-15 | 2023-06-22 | クミアイ化学工業株式会社 | Fused heterocyclic derivative and herbicide containing same as active ingredient |
-
1991
- 1991-07-29 JP JP03188835A patent/JP3119681B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023112856A1 (en) * | 2021-12-15 | 2023-06-22 | クミアイ化学工業株式会社 | Fused heterocyclic derivative and herbicide containing same as active ingredient |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3119681B2 (en) | 2000-12-25 |
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