WO1996016962A1 - Procede de production de derives de pyrazole - Google Patents
Procede de production de derives de pyrazole Download PDFInfo
- Publication number
- WO1996016962A1 WO1996016962A1 PCT/JP1995/002454 JP9502454W WO9616962A1 WO 1996016962 A1 WO1996016962 A1 WO 1996016962A1 JP 9502454 W JP9502454 W JP 9502454W WO 9616962 A1 WO9616962 A1 WO 9616962A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- formula
- compound
- general formula
- alkyl group
- compound represented
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 11
- 150000003217 pyrazoles Chemical class 0.000 title abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 33
- -1 halogenated sulfide compound Chemical class 0.000 claims description 161
- 150000001875 compounds Chemical class 0.000 claims description 81
- 238000004519 manufacturing process Methods 0.000 claims description 46
- 239000007800 oxidant agent Substances 0.000 claims description 22
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical class OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 19
- 150000002366 halogen compounds Chemical class 0.000 claims description 16
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 15
- RMVRSNDYEFQCLF-UHFFFAOYSA-N phenyl mercaptan Natural products SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 claims description 15
- 125000005843 halogen group Chemical group 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 230000002140 halogenating effect Effects 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 8
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 claims description 7
- 239000012346 acetyl chloride Substances 0.000 claims description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 6
- 239000003377 acid catalyst Substances 0.000 claims description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 2
- 150000003457 sulfones Chemical class 0.000 claims description 2
- 235000012745 brilliant blue FCF Nutrition 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 79
- 150000002367 halogens Chemical class 0.000 abstract description 9
- 229910052736 halogen Inorganic materials 0.000 abstract description 8
- 125000003118 aryl group Chemical group 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 57
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 45
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 33
- 239000000243 solution Substances 0.000 description 24
- 239000002904 solvent Substances 0.000 description 23
- 230000015572 biosynthetic process Effects 0.000 description 20
- 239000000543 intermediate Substances 0.000 description 20
- 238000003786 synthesis reaction Methods 0.000 description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 14
- 239000012044 organic layer Substances 0.000 description 14
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 12
- 239000002253 acid Substances 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 12
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 11
- IWUCXVSUMQZMFG-AFCXAGJDSA-N Ribavirin Chemical class N1=C(C(=O)N)N=CN1[C@H]1[C@H](O)[C@H](O)[C@@H](CO)O1 IWUCXVSUMQZMFG-AFCXAGJDSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 239000011541 reaction mixture Substances 0.000 description 10
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 238000010992 reflux Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 8
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 8
- 229910052794 bromium Inorganic materials 0.000 description 8
- 239000004009 herbicide Substances 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 description 8
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 8
- 238000003747 Grignard reaction Methods 0.000 description 7
- 230000002378 acidificating effect Effects 0.000 description 7
- 239000002585 base Substances 0.000 description 7
- 238000007796 conventional method Methods 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- 238000010898 silica gel chromatography Methods 0.000 description 7
- WZULMCXCRDVBQV-UHFFFAOYSA-N 4,4,5,8-tetramethyl-2,3-dihydrothiochromene Chemical compound S1CCC(C)(C)C2=C1C(C)=CC=C2C WZULMCXCRDVBQV-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000002363 herbicidal effect Effects 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 6
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 5
- 239000003456 ion exchange resin Substances 0.000 description 5
- 229920003303 ion-exchange polymer Polymers 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 150000003462 sulfoxides Chemical class 0.000 description 5
- 239000013076 target substance Substances 0.000 description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 4
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 3
- WPWNEKFMGCWNPR-UHFFFAOYSA-N 3,4-dihydro-2h-thiochromene Chemical group C1=CC=C2CCCSC2=C1 WPWNEKFMGCWNPR-UHFFFAOYSA-N 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- OEUGJRBXURGMFG-UHFFFAOYSA-N CC1=CC(=C(C2=C1S(=O)(=O)CCC2(C)C)C)C(=O)C Chemical compound CC1=CC(=C(C2=C1S(=O)(=O)CCC2(C)C)C)C(=O)C OEUGJRBXURGMFG-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 240000008042 Zea mays Species 0.000 description 3
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 3
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 235000005822 corn Nutrition 0.000 description 3
- 239000012024 dehydrating agents Substances 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 238000005658 halogenation reaction Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 3
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 3
- 229940100050 virazole Drugs 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- NHAUBUMQRJWWAT-UHFFFAOYSA-N 2,5-dimethylbenzenethiol Chemical compound CC1=CC=C(C)C(S)=C1 NHAUBUMQRJWWAT-UHFFFAOYSA-N 0.000 description 2
- QTUYDYRWHDPRIT-UHFFFAOYSA-N CC1=CC(=C(C2=C1SCCC2(C)C)C)C(=O)C Chemical compound CC1=CC(=C(C2=C1SCCC2(C)C)C)C(=O)C QTUYDYRWHDPRIT-UHFFFAOYSA-N 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 240000005979 Hordeum vulgare Species 0.000 description 2
- 235000007340 Hordeum vulgare Nutrition 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 231100000674 Phytotoxicity Toxicity 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- 241000209140 Triticum Species 0.000 description 2
- 235000021307 Triticum Nutrition 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- MXWJVTOOROXGIU-UHFFFAOYSA-N atrazine Chemical compound CCNC1=NC(Cl)=NC(NC(C)C)=N1 MXWJVTOOROXGIU-UHFFFAOYSA-N 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000026030 halogenation Effects 0.000 description 2
- 239000012433 hydrogen halide Substances 0.000 description 2
- 229910000039 hydrogen halide Inorganic materials 0.000 description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000003444 phase transfer catalyst Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- ASUAYTHWZCLXAN-UHFFFAOYSA-N prenol Chemical compound CC(C)=CCO ASUAYTHWZCLXAN-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 238000004809 thin layer chromatography Methods 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- IFLHMLZQXNYVMA-UHFFFAOYSA-N (1,1-dioxo-3,4-dihydrothiochromen-2-ylidene)methanone Chemical compound C1=CC=C2S(=O)(=O)C(=C=O)CCC2=C1 IFLHMLZQXNYVMA-UHFFFAOYSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 description 1
- WVQBLGZPHOPPFO-UHFFFAOYSA-N 2-chloro-N-(2-ethyl-6-methylphenyl)-N-(1-methoxypropan-2-yl)acetamide Chemical compound CCC1=CC=CC(C)=C1N(C(C)COC)C(=O)CCl WVQBLGZPHOPPFO-UHFFFAOYSA-N 0.000 description 1
- PCRJGAAYKMGCHL-UHFFFAOYSA-N 2-methyl-3,4-dihydro-2h-thiochromene Chemical compound C1=CC=C2SC(C)CCC2=C1 PCRJGAAYKMGCHL-UHFFFAOYSA-N 0.000 description 1
- JMMZCWZIJXAGKW-UHFFFAOYSA-N 2-methylpent-2-ene Chemical compound CCC=C(C)C JMMZCWZIJXAGKW-UHFFFAOYSA-N 0.000 description 1
- NSPPRYXGGYQMPY-UHFFFAOYSA-N 3-Methylbuten-2-ol-1 Natural products CC(C)C(O)=C NSPPRYXGGYQMPY-UHFFFAOYSA-N 0.000 description 1
- QVDTXNVYSHVCGW-UHFFFAOYSA-N 3-methylbut-1-en-1-ol Chemical compound CC(C)C=CO QVDTXNVYSHVCGW-UHFFFAOYSA-N 0.000 description 1
- XPFCZYUVICHKDS-UHFFFAOYSA-N 3-methylbutane-1,3-diol Chemical compound CC(C)(O)CCO XPFCZYUVICHKDS-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 241000282994 Cervidae Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- 241000209504 Poaceae Species 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 241001148683 Zostera marina Species 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000003931 anilides Chemical class 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229910052811 halogen oxide Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 150000007529 inorganic bases Chemical class 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
- 238000002955 isolation Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
- C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D335/06—Benzothiopyrans; Hydrogenated benzothiopyrans
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
Definitions
- the present invention relates to a method for producing a virazole derivative useful as a herbicide, an intermediate useful for producing the virazole derivative, and a method for producing the intermediate.
- Atrazine a triazine herbicide, and arachlor and metolachlor, which are acid anilide herbicides
- Atrazine has a low activity against grass weeds.
- Metrachlor on the other hand, has low activity against broadleaf weeds. Therefore, it is currently difficult to control grass and broadleaf weeds at once with a single agent.
- the above herbicides require a high dose, which is not preferable in terms of environmental problems.
- the present inventors have proposed a novel virazo having excellent selectivity that can control both grass and broadleaf weeds at a low dose without causing phytotoxicity to useful crops such as corn, wheat and barley.
- a novel derivative was found (International Publication No. W095 / 0404).
- R 1 represents a hydrogen atom or a ( ⁇ ⁇ 0 4 alkyl group;
- R 2 is - ( ⁇ alkyl group;
- X 1 is a hydrogen atom, a halogen atom or ( ⁇ ⁇ 4 alkyl group;
- X 2 and X 3 Each It is independently C, -C 4 alkyl group;
- X 4 is a hydrogen atom, the 7-position of Chiokuroman ring or 8-position by halogen atoms or substituted.
- ⁇ C 4 alkyl group; and n is 0, 1 or represents the integer 2.
- X 1 and X 4 are C, to C 4 alkyl groups, and the substitution position of X 4 is the 8-position of the chiochroman ring.
- the following reaction steps are disclosed as a method for producing compound (a).
- X 1 , X 3 and X 4 each independently represent a C! C alkyl group, and Ha 1 represents a halogen atom.
- the above production method involves halogenating the thiochroman compound of the general formula (I), then subjecting the thiochroman compound to a Grignard reaction to carboxylize the halogen, and then oxidizing the halogen, and includes a Grignard reaction.
- Grignard leather is expensive and not industrially advantageous.
- Sun and moon are all 13 ⁇ 4
- the object of the present invention is, in the broadest sense, to synthesize a pyrazole derivative useful as a herbicide and its intermediate with a carboxylic acid intermediate requiring a costly step such as the Grignard reaction as described above.
- An object of the present invention is to provide an industrially advantageous production method without the need for steps or many complicated steps.
- a first object of the present invention is to provide a novel method for producing a pyrazole derivative useful as a herbicide.
- a second object of the present invention is to provide a method for producing a nuclear halogen compound which is a production intermediate for producing a novel virazole derivative and is a novel compound.
- a third object of the present invention is to provide a process for producing the above-mentioned nuclear halogen compound, which is a production intermediate, and a novel compound, which is a novel compound.
- Another object of the present invention is to provide a novel method for producing an aromatic carboxylic acid derivative which is useful as an intermediate for producing a birazol derivative which is useful as a herbicide.
- a fifth object of the present invention is to provide a method for producing an acetylated sulfone compound, which is a production intermediate for producing an aromatic carboxylic acid derivative and is a novel compound.
- a sixth object of the present invention is to provide a method for producing an acetylated sulfide compound which is a production intermediate for producing the acetylated sulfone compound and is a novel compound. Disclosure of the invention
- the present inventors have conducted intensive studies to achieve the above object, and as a result, obtained from the following steps, an industrially advantageous biazole derivative which does not include a carboxylic acid synthesis step:
- an industrially advantageous biazole derivative which does not include a carboxylic acid synthesis step:
- a method for producing a novel intermediate used therefor and a simpler and industrially advantageous method for producing an aromatic carboxylic acid derivative containing no Grignard reaction, and a novel intermediate used therefor. It has been completed.
- the first object of the present invention is to provide a compound represented by the general formula ( ⁇ )
- X 1 , X 2 , X 3 and X 4 are represented by-(indicating a 4- alkyl group, X 5 being a halogen atom, and n being an integer of 0, 1 or 2).
- a nuclear halogen compound and a compound represented by the general formula (II) are represented by-(indicating a 4- alkyl group, X 5 being a halogen atom, and n being an integer of 0, 1 or 2).
- R 1 represents a hydrogen atom or a C, ⁇ . Alkyl group
- R 2 represents a bisazole compound represented by ( ⁇ ⁇ ( ⁇ an alkyl group.)
- a base and a metal catalyst Characterized by reacting with carbon monoxide in the presence of
- a second object of the present invention is to provide a compound of the general formula (IV)
- a second object of the present invention is to provide a compound of the general formula (IIIA-a)
- X 1 , X 2 , X 3 , X 4 and X 5 are as defined above, and m represents 1 or 2.
- a halogenated sulfoxide compound or a halogenated sulfone represented by the following formula: This can also be achieved by a method for producing a compound (corresponding to the compound of the general formula (IIIA) where n 1 or 2).
- a second object of the present invention is to provide a compound of the general formula (IV)
- halogenated thiochroman compound is first halogenated with a halogenating agent, and then oxidized.
- X 1 , X 2 , X 3 and X 4 are as defined above, X 5 represents a halogen atom, and m represents an integer of 1 or 2.
- a halogenated sulfoxide represented by the following formula: Compound or nuclear halogenated sulfone compound (in general formula (IIIA), n l or Is also achieved by the manufacturing method of
- a third object of the present invention is to provide a compound of the general formula (V)
- a third object of the present invention is to provide a compound represented by the general formula (VIII)
- a fourth object of the present invention is to provide a compound of the general formula (X)
- acetylated sulfone compound (X) wherein the compound is oxidized with an oxidizing agent, wherein the compound is represented by the general formula (IIIB):
- aromatic carboxylic acid derivative (IIIB) ⁇ ) aromatic carboxylic acid derivative
- a fifth object of the present invention is to provide a compound of the general formula (IX)
- acetylated sulfide compound (IX) each independently represent a C, ⁇ ( ⁇ alkyl group.
- Acetylated sulfide compound (IX) Oxidizing the compound represented by the general formula (X):
- a sixth object of the present invention is to provide a compound of the general formula (IV)
- thiochroman compound (IV) Is reacted with acetyl chloride or acetic anhydride in the presence of an acid catalyst to introduce an acetyl group at the 6-position of the thiochroman ring.
- FIG. 1 is a view showing a production process of a birazol derivative (I) of the present invention without passing through an aromatic carboxylic acid derivative.
- FIG. 2 is a view showing a production process of the aromatic carboxylic acid derivative (II IB) of the present invention without passing through the Grignard reaction.
- the method for producing the nuclear halogen compound represented by -b) and the thiochroman compound represented by the general formula (IV) will be sequentially described.
- the compound names in the reaction process diagram of FIG. 1 are abbreviated as follows.
- the thiophenol compound of the general formula (V) is a “thiophenol compound (V)”
- the thiochroman compound of the general formula (IV) is a “thiochroman compound (IV)”
- the “nuclear halogenated sulfide compound (IIIA-b)” and the nuclear halogenated sulfoxide compound of the general formula (IIIA-b) and the nuclear halogenated sulfone compound are collectively referred to as “nuclear halogenated sulfoxide / sulfone compound (IIIA-b).
- a nuclear halogen compound of the general formula (IIIA) is referred to as a "nuclear halogen compound (IIIA)", a virazole compound of the general formula (II) is referred to as a "virazole compound (II)", a general formula (VI) and a general formula (VII) Alcohol compounds (VI) and alcohol compounds (VII), and sulfide compounds of the general formula (VIII) as sulfide compounds VIII) ", and virazole derivatives of general formula (I) is referred to as” Birazo Ichiru derivative (I) ".
- the method for producing the virazole derivative (I) that achieves the first object of the present invention comprises a reaction scheme
- Examples of the metal catalyst used in this reaction include transition metals such as palladium, rhodium, ruthenium, and platinum, but palladium is preferable.
- the amount of the metal catalyst to be added is 0.1 to 1.0 times, preferably 0 to 0.5 times the weight of the nuclear halogen compound (0).
- the ligand used for the metal of the metal catalyst is not particularly limited, but an organophosphine compound such as triphenylphosphine or tri-n-butylphosphine is preferred.
- the addition amount of the ligand is 2.0 to: L 0.0 equivalent, preferably 2.0 to 4.0 equivalent, based on the metal of the metal catalyst.
- an organic base such as pyridine, triethylamine, N, N-dimethylaniline, or an inorganic base such as sodium carbonate, potassium carbonate, or sodium hydroxide can be used, and preferably triethylamine.
- the amount of the base to be added is 1.0 to 20.0 equivalents, preferably 1.0 to 10.0 equivalents to the nuclear halogen compound (IIIA).
- a phase transfer catalyst such as tetra-n-butylamine bromide together with these bases is effective from the viewpoint of improving the reactivity.
- This reaction is performed in a carbon monoxide atmosphere.
- the pressure of carbon monoxide is in the range of normal pressure to 200 kg / cm 2 , and is usually preferably about 50 to 150 kg / cm 2 .
- the reaction temperature is from room temperature to 200 ° (preferably from 50 to 180 ° C.
- the reaction time is from 30 minutes to 200 hours, usually completed in 1 to 100 hours.
- the reaction solvent interferes with the reaction.
- the amount of the virazole compound ( ⁇ ⁇ ⁇ ) used in the reaction is 1.0 to the amount of the nuclear halogen compound ( ⁇ ). To 10.0 equivalents, preferably 1.0 to 5.0 equivalents.
- the reaction solvent is distilled off according to a conventional method, and an organic solvent (insoluble in water, for example, ethyl acetate, toluene, methylene chloride, etc.) is added to the obtained residue, and an aqueous solution of alcohol (for example, Extract the target with an aqueous solution of sodium bicarbonate, aqueous solution of sodium carbonate). Adjust the pH to 1 by adding an acid (eg, hydrochloric acid) to the resulting aqueous layer Then, the precipitated solid is collected by filtration and dried to isolate the target crystal.
- halogenating agent used in this reaction examples include bromine, sulfuryl chloride, and chlorine, and bromine is preferable.
- the amount of the halogenating agent is 1 to 2 equivalents, preferably 1 to 1.1 equivalents, relative to the thiochroman compound (IV).
- the solvent used is not particularly limited as long as it does not hinder the reaction, and includes acetic acid, methylene chloride, chloroform, carbon tetrachloride and the like, and preferably methylene chloride.
- the reaction temperature is usually from 0 to 80 ° C, preferably from 20 to 30 ° C.
- the reaction time is usually 1 to 80 hours, preferably 1 to 3 hours.
- a reducing agent for example, an aqueous solution of sodium hydrogen sulfite
- a reaction solution for washing to remove the remaining excess halogenating agent according to a conventional method.
- the reaction solution is washed with an aqueous alkaline solution (eg, an aqueous solution of sodium bicarbonate, an aqueous solution of sodium carbonate, etc.) to remove the generated hydrogen halide.
- an aqueous alkaline solution eg, an aqueous solution of sodium bicarbonate, an aqueous solution of sodium carbonate, etc.
- the target substance can be isolated by purifying the obtained oily substance by means such as silica gel column chromatography and distillation.
- the oxidizing agent used in this reaction includes hydrogen peroxide, peracetic acid, sodium metaperiodate, and the like, and hydrogen peroxide is preferred.
- the solvent used is not particularly limited as long as it does not interfere with the reaction, and includes acetic acid, water, methanol and the like, with acetic acid being preferred.
- the reaction temperature is not particularly limited from room temperature to the reflux temperature of the solvent, but is preferably about 80 ° C.
- the reaction time is about 30 minutes to 24 hours, preferably about 1 to 3 hours.
- a reducing agent for example, an aqueous solution of sodium hydrogen sulfite
- a reducing agent for example, an aqueous solution of sodium hydrogen sulfite
- Steps B and C in Fig. 1 can be performed in succession in one pot instead of as separate steps, and the halogenated sulfoxide / sulfone compound (IIIA-b) can be directly obtained from the thiochroman compound (IV). It is.
- the method for obtaining the nuclear halogenated sulfoxide / sulfone compound (IIIA-b) in this one pot is represented by the reaction formula
- X 1 , XX 3 , X 4 , X 5 and m are as defined above.
- An oxidizing agent is added to the reaction system without isolation of the reaction product, the nuclear halogenated sulfide compound (IIIA-a), and the same oxidation reaction is performed continuously as in the above step. , and the indicated by step C 2 in FIG. 1.
- the solvent used in this reaction is not particularly limited as long as it does not hinder the reaction, but includes acetic acid, water and the like, and acetic acid is preferred.
- Examples of the halogenating agent and the oxidizing agent to be used include those exemplified in the above Steps B and.
- the reaction conditions are the same as in Steps B and B above for the nuclear halogenation and oxidation.
- a reducing agent for example, an aqueous solution of sodium bisulfite
- a reaction solution for example, an organic solvent
- an organic solvent insoluble in water, for example, ethyl acetate, toluene, methylene chloride, etc.
- an aqueous alkaline solution for example, aqueous sodium bicarbonate, sodium carbonate, etc.
- the desired product can be isolated by distilling off the organic solvent and purifying the obtained oily substance by means such as silica gel column chromatography.
- a method for producing a thiochroman compound (IV), which achieves the third object of the present invention, comprises a reaction formula
- Examples of the solvent used in this step include acetic anhydride, acetic acid, and formic acid, and formic acid is preferred.
- the amount of the alcohol compound (VI) or (VI I) is 1 to 5 equivalents, preferably 1 to 1.5 equivalents, relative to the thiophenol compound (V).
- the reaction temperature is not particularly limited from room temperature to the reflux temperature of the solvent, but is preferably the reflux temperature of the solvent.
- the reaction time is usually 30 minutes to 24 hours, but preferably about 7 hours.
- an organic solvent insoluble in water, for example, ethyl acetate, toluene, methylene chloride, etc.
- an organic solvent is added to the reaction solution to extract the desired product according to a conventional method. Wash the organic layer with an aqueous alkali solution (eg, aqueous sodium bicarbonate, aqueous sodium carbonate, etc.). After distilling off the organic solvent, the target substance can be isolated by purifying the obtained oily substance by means such as distillation and silica gel column chromatography.
- a method for producing a thiochroman compound (IV), which achieves the third object of the present invention, comprises a reaction formula
- step 1 this is indicated by step A-3.
- the sulfide compound (VIII) can be synthesized by the method described in International Publication WO95 / 04054.
- Examples of the acid used in this reaction include Lewis acids such as aluminum chloride, zinc chloride, and iron chloride; protonic acids such as methyl sulfonic acid; and acidic ion exchange resins. Acid ion exchange resins are preferred.
- the amount of the acid used is 0.1 to 3 equivalents, preferably 0.1 to 1.2 equivalents, relative to the sulfide compound (VIII).
- the solvent used is not particularly limited as long as it does not hinder the reaction, and includes toluene, benzene, nitrobenzene, dichloromethane, n-hexane and the like, and is preferably toluene.
- the reaction temperature is from 0 ° C to the reflux temperature of the solvent, preferably the reflux temperature of the solvent.
- the reaction time is usually 1 to 80 hours, preferably 3 to 12 hours.
- the target product can be isolated by filtering off the resin after completion of the reaction and distilling off the filtrate.
- an aqueous alkali solution for example, aqueous sodium bicarbonate, aqueous sodium carbonate, etc.
- aqueous sodium bicarbonate for example, aqueous sodium bicarbonate, aqueous sodium carbonate, etc.
- the desired product can be isolated by purification by means such as silica gel column chromatography.
- the first novel intermediate is a compound obtained as a result of the reaction in step A in FIG.
- X ′, X 2 , X 3 and X 4 in the formula each represent a c! C ⁇ alkyl group, preferably each a methyl group.
- X 1 , X 2 , X 3 and X 4 in the formula each represent a C! C ⁇ alkyl group, preferably each a methyl group.
- X 5 represents a halogen atom, and is preferably a bromine atom.
- n represents an integer of 0, 1 or 2, and is preferably 2.
- an aromatic carboxylic acid derivative ( ⁇ ), an acetylated sulfone compound (X), an acetylated sulfide compound ( IX) will be described sequentially.
- the method for producing the aromatic carboxylic acid derivative ( ⁇ ), which is the fourth object of the present invention comprises a reaction scheme
- X 1 , X 2 , X 3 and X 4 are as defined above.
- the acetyl group at the 6-position of the acetylated sulfone compound (X) is formed by using an oxidizing agent. It is converted to a carboxyl group to obtain an aromatic carboxylic acid derivative (II IB), which is shown by step G in FIG.
- oxidizing agent examples include permanganate, chromate, halogen, oxygen, sulfuric acid, and the like, and halogen is preferable.
- halogen chlorine and bromine are preferable as the halogen.
- a halogen is used as an oxidizing agent, it is used as a hypohalite together with a sodium hydroxide such as sodium hydroxide or potassium hydroxide or a carbonate such as sodium carbonate or potassium carbonate to form a hypohalogen. It is preferable to use 3 or more equivalents of the acid salt with respect to the acetylated sulfone compound (X).
- the amount of halogen used for this purpose is preferably 3 equivalents or more based on the acetylated sulfone compound (X), and the amount of the hydroxyl hydroxide or carbonate is preferably 9 equivalents or more based on the acetylated sulfone compound (X).
- hypohalite instead of generating hypohalite from halogen and alkali hydroxide or carbonate, hypohalite can be directly used as an oxidizing agent.
- sodium hypochlorite is preferred as the hypohalite.
- the amount of hypohalite used in this case is the same as described above.
- the solvent used is not particularly limited as long as it does not interfere with the reaction, but water, dioxane and the like are preferable.
- the reaction temperature is generally preferably from room temperature to the reflux temperature of the solvent.
- the reaction time is generally preferably about 3 to 24 hours.
- the target substance can be isolated by dehydrating the obtained organic layer with a dehydrating agent such as anhydrous sodium sulfate and distilling off the solvent.
- the isolated aromatic carboxylic acid derivative ( ⁇ ) is used for producing the virazole derivative (I).
- the method for producing the acetylated sulfone compound (X), which is the fifth object of the present invention, comprises a reaction scheme
- Examples of the oxidizing agent that can be used in this reaction include hydrogen peroxide, peracetic acid, sodium periodate and the like, and hydrogen peroxide is preferable.
- the amount of the oxidizing agent used is 2 equivalents or more based on the acetylated sulfide compound (IX).
- the solvent to be used is not particularly limited as long as it does not hinder the reaction, but includes acetic acid, water, methanol and the like, and is preferably acetic acid.
- the reaction temperature is generally not particularly limited from the room temperature to the reflux temperature of the solvent, but is preferably about 80 to 100 ° C.
- the reaction time is preferably about 30 minutes to 2 hours.
- the reaction mixture is cooled according to a conventional method, and sodium bisulfite or the like is added thereto to remove excess oxidizing agent, and the target substance (acetylated sulfone compound (X)) is dissolved in an organic solvent such as ethyl acetate. Extract.
- the desired product can be isolated by dehydrating the obtained organic layer with a dehydrating agent such as anhydrous sodium sulfate and then distilling off the solvent.
- the acetylated sulfone compound (X) thus obtained is a novel compound, It is useful as an intermediate for producing the aromatic carboxylic acid derivative (IIIB).
- the method for producing the acetylated sulfide compound (IX), which is the sixth object of the present invention, comprises:
- Lewis acids such as zinc chloride and iron chloride, or protonic acids such as hydrogen fluoride, sulfuric acid and phosphoric acid, preferably aluminum chloride.
- the amount of the acid catalyst used is based on the amount of the chiochroman compound (IV). Usually 1.0 to 3.0 equivalents, preferably 1.0 to 1.5 equivalents
- acetyl halide used in this reaction for example, acetyl chloride, acetyl chloride, acetyl chloride or acetyl chloride is used. And the like, chlorides Asechiru are preferred.
- the amount of acetyl halide or acetic anhydride used in this reaction is generally 1.0 to 3.0 equivalents, preferably 1.0 to 1.5 equivalents, relative to the thiochroman compound (IV).
- This reaction is carried out in a solvent.
- solvents include methylene chloride, nitromethane, acetonitrile, benzene and the like, and preferably, methylene chloride.
- the reaction temperature is usually 0-80. C, but 0. C to around room temperature is preferred.
- the reaction time is generally about 30 minutes to 8 hours, preferably about 30 minutes to 3 hours.
- the reaction mixture is poured into an aqueous acid solution such as hydrochloric acid to which ice has been added according to a conventional method. Separate the organic layer. The obtained organic layer is washed successively with a saturated aqueous sodium hydrogen carbonate solution, a saturated saline solution and the like, dehydrated with a dehydrating agent such as anhydrous sodium sulfate, and then the solvent is distilled off to isolate the desired product.
- aqueous acid solution such as hydrochloric acid to which ice has been added according to a conventional method.
- the acetylated sulfide compound (IX) thus obtained is a novel compound and is useful as an intermediate for producing the acetylated sulfone compound (X).
- Step A-1 except that 3-methyl-1,3-butanediol (alcohol compound (VII)) was used in place of 3-methyl-2-buten-1-ol used in (Step A-1) above.
- the same procedure as described above was carried out to obtain 0.91 g (yield 44%) of the title compound (Tiochroman compound (IV)).
- 6-Acetyl-4,4,5,8-tetramethylthiochroman-1,1-dioxide obtained in Example 8 above (Compound No. 6) 2.10 g (7.5 To 10 ml of a dioxane solution (mmol) was added 31 ml (22.5 mmol, 3.0 equivalents) of a 5% aqueous solution of sodium hypochlorite (oxidizing agent) at room temperature, followed by stirring for 3 hours. To the reaction mixture, 10 ml of a 10% aqueous sodium hydroxide solution was added, and the mixture was washed with methylene chloride.
- a novel virazole derivative capable of selectively controlling both grasses and broadleaf weeds at a low dose without causing phytotoxicity to useful crops such as corn, wheat, barley, etc.
- a method that can be industrially advantageously produced without requiring many steps is provided.
- an aromatic carboxylic acid derivative which is a useful intermediate for producing a birazol derivative useful as a herbicide, does not involve a costly Grignard reaction, and is simpler and more industrial.
- the present invention provides a method for producing an aromatic carboxylic acid derivative which is more advantageous.
- a virazole derivative can be produced at lower cost.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
Cette invention se rapporte à un procédé permettant de produire des dérivés de pyrazole selon la formule de réaction (A), où R1 représente H ou alkyle C¿1?-C4; R?2, X1, X2, X3 et X4¿ représentent chacun alkyle C¿1?-C4; X?5¿ représente halogène; et n est égal à 0, 1 ou 2; ainsi qu'à un procédé pour produire un dérivé carboxylique aromatique selon la formule de réaction (B) où X?1, X2, X3 et X4¿ représentent chacun séparément alkyle C¿1?-C4.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU39941/95A AU3994195A (en) | 1994-12-02 | 1995-12-01 | Process for producing pyrazole derivative |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6/299230 | 1994-12-02 | ||
JP6299230A JPH08157472A (ja) | 1994-12-02 | 1994-12-02 | ピラゾール誘導体の製造方法 |
JP6/322615 | 1994-12-26 | ||
JP6322615A JPH08176142A (ja) | 1994-12-26 | 1994-12-26 | 芳香族カルボン酸誘導体の製造法 |
Publications (1)
Publication Number | Publication Date |
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WO1996016962A1 true WO1996016962A1 (fr) | 1996-06-06 |
Family
ID=26561838
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP1995/002454 WO1996016962A1 (fr) | 1994-12-02 | 1995-12-01 | Procede de production de derives de pyrazole |
Country Status (3)
Country | Link |
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AR (1) | AR001772A1 (fr) |
AU (1) | AU3994195A (fr) |
WO (1) | WO1996016962A1 (fr) |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1993018031A1 (fr) * | 1992-03-03 | 1993-09-16 | Idemitsu Kosan Co., Ltd. | Derive de pyrazole |
JPH06340654A (ja) * | 1991-01-25 | 1994-12-13 | Nippon Kayaku Co Ltd | 新規ヒドラジン誘導体およびそれを有効成分とする殺虫組成物 |
WO1995004054A1 (fr) * | 1993-08-02 | 1995-02-09 | Idemitsu Kosan Co., Ltd. | Derive de pyrazole |
JPH0826914A (ja) * | 1994-07-15 | 1996-01-30 | Idemitsu Kosan Co Ltd | トリケトン誘導体 |
-
1995
- 1995-12-01 WO PCT/JP1995/002454 patent/WO1996016962A1/fr active Application Filing
- 1995-12-01 AR AR33448395A patent/AR001772A1/es unknown
- 1995-12-01 AU AU39941/95A patent/AU3994195A/en not_active Abandoned
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06340654A (ja) * | 1991-01-25 | 1994-12-13 | Nippon Kayaku Co Ltd | 新規ヒドラジン誘導体およびそれを有効成分とする殺虫組成物 |
WO1993018031A1 (fr) * | 1992-03-03 | 1993-09-16 | Idemitsu Kosan Co., Ltd. | Derive de pyrazole |
WO1995004054A1 (fr) * | 1993-08-02 | 1995-02-09 | Idemitsu Kosan Co., Ltd. | Derive de pyrazole |
JPH0826914A (ja) * | 1994-07-15 | 1996-01-30 | Idemitsu Kosan Co Ltd | トリケトン誘導体 |
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AU3994195A (en) | 1996-06-19 |
AR001772A1 (es) | 1997-12-10 |
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