JP2009073770A - 含フッ素ビニルスルフィド誘導体並びに含フッ素ピラゾール誘導体の製造方法 - Google Patents
含フッ素ビニルスルフィド誘導体並びに含フッ素ピラゾール誘導体の製造方法 Download PDFInfo
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- JP2009073770A JP2009073770A JP2007244677A JP2007244677A JP2009073770A JP 2009073770 A JP2009073770 A JP 2009073770A JP 2007244677 A JP2007244677 A JP 2007244677A JP 2007244677 A JP2007244677 A JP 2007244677A JP 2009073770 A JP2009073770 A JP 2009073770A
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- Prior art keywords
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- trifluoromethyl
- vinyl sulfide
- atom
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- 150000008127 vinyl sulfides Chemical class 0.000 title claims abstract description 21
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title abstract description 10
- 239000011737 fluorine Substances 0.000 title abstract description 10
- 150000003217 pyrazoles Chemical class 0.000 title description 4
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 18
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 16
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 13
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 13
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 11
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims abstract description 9
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims abstract description 9
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims abstract description 9
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims abstract description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 104
- -1 aromatic thiol Chemical class 0.000 claims description 34
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- QKBKGNDTLQFSEU-UHFFFAOYSA-N 2-bromo-3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)C(Br)=C QKBKGNDTLQFSEU-UHFFFAOYSA-N 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 125000001153 fluoro group Chemical group F* 0.000 claims description 4
- 150000002429 hydrazines Chemical class 0.000 claims description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 125000004176 4-fluorobenzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1F)C([H])([H])* 0.000 claims description 2
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 claims description 2
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 2
- 125000001318 4-trifluoromethylbenzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C([H])([H])*)C(F)(F)F 0.000 claims description 2
- 125000004199 4-trifluoromethylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C(F)(F)F 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 125000006165 cyclic alkyl group Chemical group 0.000 claims description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 2
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 claims description 2
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- PIILXFBHQILWPS-UHFFFAOYSA-N tributyltin Chemical group CCCC[Sn](CCCC)CCCC PIILXFBHQILWPS-UHFFFAOYSA-N 0.000 claims description 2
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 claims description 2
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000000782 4-ethoxyphenylcarbonyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1OC([H])([H])C([H])([H])[H])C(*)=O 0.000 claims 1
- 239000003905 agrochemical Substances 0.000 abstract description 4
- 229940079593 drug Drugs 0.000 abstract description 3
- 239000003814 drug Substances 0.000 abstract description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 43
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 24
- UIYCHXAGWOYNNA-UHFFFAOYSA-N vinyl sulfide Chemical compound C=CSC=C UIYCHXAGWOYNNA-UHFFFAOYSA-N 0.000 description 24
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 16
- 238000005160 1H NMR spectroscopy Methods 0.000 description 15
- 238000002360 preparation method Methods 0.000 description 15
- 238000005481 NMR spectroscopy Methods 0.000 description 14
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 13
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 8
- 238000000921 elemental analysis Methods 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 239000011780 sodium chloride Substances 0.000 description 8
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 0 Cc(cc1)ccc1SC(C(c1ccc(*)cc1)=O)=CC(F)(F)F Chemical compound Cc(cc1)ccc1SC(C(c1ccc(*)cc1)=O)=CC(F)(F)F 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- RNVDLDAMMFSMIG-UHFFFAOYSA-N 1-ethenylsulfanyl-4-methylbenzene Chemical compound CC1=CC=C(SC=C)C=C1 RNVDLDAMMFSMIG-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- NQEFIPVOJGJVRG-UHFFFAOYSA-N 3-(4-methylphenyl)-5-(trifluoromethyl)-1h-pyrazole Chemical compound C1=CC(C)=CC=C1C1=NNC(C(F)(F)F)=C1 NQEFIPVOJGJVRG-UHFFFAOYSA-N 0.000 description 3
- WLHCBQAPPJAULW-UHFFFAOYSA-N 4-methylbenzenethiol Chemical compound CC1=CC=C(S)C=C1 WLHCBQAPPJAULW-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- BDAJBOIAMYRWFR-UHFFFAOYSA-N 1-methyl-2-(2-methylphenyl)sulfanylbenzene Chemical compound CC1=CC=CC=C1SC1=CC=CC=C1C BDAJBOIAMYRWFR-UHFFFAOYSA-N 0.000 description 2
- LXUNZSDDXMPKLP-UHFFFAOYSA-N 2-Methylbenzenethiol Chemical compound CC1=CC=CC=C1S LXUNZSDDXMPKLP-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- WHRIKZCFRVTHJH-UHFFFAOYSA-N ethylhydrazine Chemical compound CCNN WHRIKZCFRVTHJH-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- WHMDPDGBKYUEMW-UHFFFAOYSA-N pyridine-2-thiol Chemical compound SC1=CC=CC=N1 WHMDPDGBKYUEMW-UHFFFAOYSA-N 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- HIJAZWASVSEKNA-UHFFFAOYSA-N trifluoromethylsulfanylethene Chemical compound FC(F)(F)SC=C HIJAZWASVSEKNA-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- PYKGJRLOHQGKFI-UHFFFAOYSA-N (4-propan-2-ylphenyl) hydrogen carbonate Chemical compound CC(C)C1=CC=C(OC(O)=O)C=C1 PYKGJRLOHQGKFI-UHFFFAOYSA-N 0.000 description 1
- FHTDDANQIMVWKZ-UHFFFAOYSA-N 1h-pyridine-4-thione Chemical compound SC1=CC=NC=C1 FHTDDANQIMVWKZ-UHFFFAOYSA-N 0.000 description 1
- ABROBCBIIWHVNS-UHFFFAOYSA-N 2-Ethylbenzenethiol Chemical compound CCC1=CC=CC=C1S ABROBCBIIWHVNS-UHFFFAOYSA-N 0.000 description 1
- UNNGUFMVYQJGTD-UHFFFAOYSA-N 2-Ethylbutanal Chemical group CCC(CC)C=O UNNGUFMVYQJGTD-UHFFFAOYSA-N 0.000 description 1
- DSCJETUEDFKYGN-UHFFFAOYSA-N 2-Methoxybenzenethiol Chemical compound COC1=CC=CC=C1S DSCJETUEDFKYGN-UHFFFAOYSA-N 0.000 description 1
- WJFIVNWCJZUQMI-UHFFFAOYSA-N 2-bromo-1,1,1-trifluoropropane Chemical compound CC(Br)C(F)(F)F WJFIVNWCJZUQMI-UHFFFAOYSA-N 0.000 description 1
- WBSONQUHDWJABP-UHFFFAOYSA-N 2-ethoxybenzenethiol Chemical compound CCOC1=CC=CC=C1S WBSONQUHDWJABP-UHFFFAOYSA-N 0.000 description 1
- RTGLJCSUKOLTEM-UHFFFAOYSA-N 2-ethylhexyl carbonochloridate Chemical group CCCCC(CC)COC(Cl)=O RTGLJCSUKOLTEM-UHFFFAOYSA-N 0.000 description 1
- RTJMJGJLVSKSEB-UHFFFAOYSA-N 3-ethoxybenzenethiol Chemical compound CCOC1=CC=CC(S)=C1 RTJMJGJLVSKSEB-UHFFFAOYSA-N 0.000 description 1
- WULNDUPZYLKLBH-UHFFFAOYSA-N 3-ethylbenzenethiol Chemical compound CCC1=CC=CC(S)=C1 WULNDUPZYLKLBH-UHFFFAOYSA-N 0.000 description 1
- QMVAZEHZOPDGHA-UHFFFAOYSA-N 3-methoxybenzenethiol Chemical compound COC1=CC=CC(S)=C1 QMVAZEHZOPDGHA-UHFFFAOYSA-N 0.000 description 1
- WRXOZRLZDJAYDR-UHFFFAOYSA-N 3-methylbenzenethiol Chemical compound CC1=CC=CC(S)=C1 WRXOZRLZDJAYDR-UHFFFAOYSA-N 0.000 description 1
- OXWOIUVGAWIZQQ-UHFFFAOYSA-N 4-ethoxybenzenethiol Chemical compound CCOC1=CC=C(S)C=C1 OXWOIUVGAWIZQQ-UHFFFAOYSA-N 0.000 description 1
- WWQQPHUHTAZWDH-UHFFFAOYSA-N 4-ethylbenzenethiol Chemical compound CCC1=CC=C(S)C=C1 WWQQPHUHTAZWDH-UHFFFAOYSA-N 0.000 description 1
- ZRSNZINYAWTAHE-PTQBSOBMSA-N 4-methoxybenzaldehyde Chemical group COC1=CC=C([13CH]=O)C=C1 ZRSNZINYAWTAHE-PTQBSOBMSA-N 0.000 description 1
- NIFAOMSJMGEFTQ-UHFFFAOYSA-N 4-methoxybenzenethiol Chemical compound COC1=CC=C(S)C=C1 NIFAOMSJMGEFTQ-UHFFFAOYSA-N 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- NQUVCRCCRXRJCK-UHFFFAOYSA-N 4-methylbenzoyl chloride Chemical group CC1=CC=C(C(Cl)=O)C=C1 NQUVCRCCRXRJCK-UHFFFAOYSA-N 0.000 description 1
- ZRSNZINYAWTAHE-UHFFFAOYSA-N Anisaldehyde Natural products COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- GCTFWCDSFPMHHS-UHFFFAOYSA-M Tributyltin chloride Chemical group CCCC[Sn](Cl)(CCCC)CCCC GCTFWCDSFPMHHS-UHFFFAOYSA-M 0.000 description 1
- OKJPEAGHQZHRQV-UHFFFAOYSA-N Triiodomethane Natural products IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- ATKJLMWDXASAJA-UHFFFAOYSA-N benzenesulfonylsulfanylbenzene Chemical group C=1C=CC=CC=1S(=O)(=O)SC1=CC=CC=C1 ATKJLMWDXASAJA-UHFFFAOYSA-N 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 239000012039 electrophile Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- MSMGXWFHBSCQFB-UHFFFAOYSA-N ethyl cyanoformate Chemical group CCOC(=O)C#N MSMGXWFHBSCQFB-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000002035 hexane extract Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- INQOMBQAUSQDDS-BJUDXGSMSA-N iodomethane Chemical group I[11CH3] INQOMBQAUSQDDS-BJUDXGSMSA-N 0.000 description 1
- VZNYXGQMDSRJAL-UHFFFAOYSA-N iodomethyl(trimethyl)silane Chemical group C[Si](C)(C)CI VZNYXGQMDSRJAL-UHFFFAOYSA-N 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 1
- JJXWKXZOHOUFCX-UHFFFAOYSA-N methylhydrazine;hydrate Chemical compound O.CNN JJXWKXZOHOUFCX-UHFFFAOYSA-N 0.000 description 1
- HDZGCSFEDULWCS-UHFFFAOYSA-N monomethylhydrazine Chemical compound CNN HDZGCSFEDULWCS-UHFFFAOYSA-N 0.000 description 1
- 125000006606 n-butoxy group Chemical group 0.000 description 1
- CMWTZPSULFXXJA-VIFPVBQESA-N naproxen Chemical group C1=C([C@H](C)C(O)=O)C=CC2=CC(OC)=CC=C21 CMWTZPSULFXXJA-VIFPVBQESA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical group O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- FFWJHVGUAKWTKW-UHFFFAOYSA-N pyridine-3-thiol Chemical compound SC1=CC=CN=C1 FFWJHVGUAKWTKW-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- FKHIFSZMMVMEQY-UHFFFAOYSA-N talc Chemical compound [Mg+2].[O-][Si]([O-])=O FKHIFSZMMVMEQY-UHFFFAOYSA-N 0.000 description 1
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- Pyridine Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
で表される(E)−アリール β−(トリフルオロメチル)ビニルスルフィド誘導体。
で表される芳香族チオールを反応させることを特徴とする項1に記載の一般式(1)で表される(E)アリール β−(トリフルオロメチル)ビニルスルフィド誘導体の製造方法。
で表される(E)−アリール β−(トリフルオロメチル)−α−置換ビニルスルフィド誘導体。
で表される誘導体と、下記一般式(5)
で表されるヒドラジン誘導体を反応させることを特徴とする下記一般式(6)
で表される3−p−置換−5−(トリフルオロメチル)−1H−ピラゾール誘導体の製造方法を提供するものである。
(実施例)
以下実施例により本発明を具体的に説明するが、本発明はこれらの実施例のみに限定されるものではない。
融点:Yanako製MP−S3。
1H−NMR、13C−NMR、19F−NMR:JEOL製AL−300。
IR:Perkin Elmer製SPECTRUM 2000 FT−IR。
GC−MS:JEOL製JMS−AWII15。
Rf=0.68(ヘキサン)。
1H−NMR(CDCl3,300MHz)δ2.38(3H,s)、5.32(1H,dq、J=15.2,6.4Hz)、7.11(1H,dq,J=15.2,2.0Hz)、7.20−7.40(4H,m)。
13C−NMR(CDCl3,75.5MHz)δ21.18(1C,s)、112.61(1C,q,J=34.3Hz)、123.00(1C,q,J=269.1Hz)、126.28(1C,s)、130.57(2C,s)、133.55(2C,s)、138.97(1C,q,J=6.9Hz)、139.74(1C,s)。
19F−NMR(CDCl3,282MHz)δ−63.41(3F,dd,J=6.6,2.7Hz)。
IR(NaCl)1619、1300、1279、1119、938、832cm−1。
GC−MS(EI,m/Z,70eV)218(84,M+)、217(18)、134(80)、123(37)、91(100)、77(51)、69(47)、65(79)。
元素分析 計算値C;55.03、H;4.16
測定値C;55.12、H;4.16。
実施例1で用いた4−メチルベンゼンチオールを2−メルカトピリジンに替えた以外実施例1と同じ操作を行い目的物の(E)−(2−ピリジル) β−(トリフルオロメチル)ビニルスルフィドを得た(収率59%)。
1H−NMR(CDCl3,300MHz)δ5.95(1H,dq,J=16.0,6.2Hz)、7.14(1H,ddd,J=7.3,5.0,1.1Hz)、7.24(1H,dt,J=7.9,1.1Hz)、7.60(1H,ddd,J=7.9,7.5,2.0Hz)、8.08(1H,dq,J=16.0,2.0Hz)、8.52(1H,ddd,J=5.0,1.8,0.9Hz)。
Rf=0.76(ヘキサン)。
1H−NMR(CDCl3,300MHz)δ0.38(9H,s)、2.43(3H,s)、5.25(1H,q,J=9.0Hz)、7.25−7.37(4H,m)。
13C−NMR(CDCl3,75.5MHz)δ−0.46(3C,s)、21.31(1C,s)、117.71(1C,q,J=35.5Hz)、123.62(1C,q,J=333.8Hz)、126.29(1C,s)、130.78(2C,s)、135.68(2C,s)、140.11(1C,s)、155.88(1C,q,J=5.6)。
19F−NMR(CDCl3,282MHz)δ−56.87(3F,d,J=10.0Hz)。
IR(NaCl)1585、1276、1134、1109、847、817cm−1。
GC−MS(EI,m/Z,70eV)290(0.46,M+)、114(48)、107(46)、91(20)、77(55)、73(100)、65(17)。
元素分析 計算値C;53.76、H;5.90
測定値C;53.87、H;5.78。
Rf=0.71(ヘキサン)。
1H−NMR(CDCl3,300MHz)δ2.13(3H,dq,J=1.1,2.2Hz)、2.39(3H,s)、4.93(1H,qq,J=8.3,1.1Hz)、7.21−7.39(4H,m)。
19F−NMR(CDCl3,282MHz)δ−57.18(3F,d,J=6.4Hz)
IR(NaCl)1638、1493、1265、1173、1109、939、846cm−1。
GC−MS(EI,m/Z,70eV)232(8,M+)、148(14)、91(50)、77(22)、65(15)、59(100)。
Rf=0.65(ヘキサン/酢酸エチル=3:1,vol/vol)。
1H−NMR(CDCl3,300MHz)δ0.16(9H,s)、2.09(2H,dd,J=6.1,4.2Hz)、2.39(3H,s)、4.69(1H,q,J=8.4Hz)、7.21〜7.36(4H,m)。
19F−NMR(CDCl3,282MHz)δ−56.35(3F,d,J=8.8Hz)。
GC−MS(EI,m/Z,70eV)304(0.58,M+)、107(17)、91(22)、77(48)、73(100)。
元素分析 計算値C;55.23、H;6.29
測定値C;55.53、H;6.31。
Rf=0.75(ヘキサン)。
1H−NMR(CDCl3,300MHz)δ0.92(9H,t,J=7.9Hz)、1.09−1.21(6H,m)、1.30−1.42(6H,m),1.51−1.62(6H,m)、2.38(3H,s)、5.37(1H,q,J=7.9Hz),7.24−7.32(4H,m)。
13C−NMR(CDCl3,75.5MHz)δ11.64(3C,s)、13.62(3C,s)、31.31(1C,s)、27.15(3C,s)、28.74(3C,s)、116.27(1C,q,J=33.6Hz)、127.16(1C,s)、127.95(1C,q,J=303.9Hz)、130.59(2C,s)、135.20(2C,s),139.78(1C,s)、156.47(1C,q,J=7.5Hz)。
19F−NMR(CDCl3,282MHz)δ−59.27(3F,d,J=6.1Hz)。
IR(NaCl)2953、2923、1578、1271、1128、1106、960、811cm−1。
GC−MS(EI,m/Z,70eV)450(4.3,M+−57)、449(1.8)、179(75)、178(100)、135(2.1)、123(10)、119(16)、107(41)、91(72)、65(8)。
元素分析 計算値C;52.09、H;6.95
測定値C;51.82、H;6.99。
1H−NMR(CDCl3,300MHz)δ2.37(3H,s)、5.38(1H,q,J=7.9Hz)、7.15−7.25(4H,m)、7.34−7.50(5H.m)。
19F−NMR(CDCl3,282MHz)δ−56.80(3F,d,J=8.7Hz)。
IR(NaCl)1586、1296、1138、841cm−1。
GC−MS(EI,m/Z,70eV)326(2.2,M+)、134(50)、124(54)、91(67)、77(100)、65(69)。
元素分析 計算値C;58.88、H;4.01
測定値C;58.99、H;4.06。
融点:126.9−128.3℃。
Rf=0.51(ヘキサン/酢酸エチル=3:1,vol/vol)。
1H−NMR(CDCl3,300MHz)δ1.58(1H,s)、2.39(3H,s)、5.23(1H,q,J=7.7Hz)、7.24−7.36(4H,m)、7.42−7.46(5H,m)。
13C−NMR(CDCl3,75.5MHz)δ21.29(1C,s)、112.22(1C,q,J=36.1Hz)、121.95(1C,q,J=270.9Hz)、120.47(2C,s)、123.58(1C,s)、125.35(1C,s)、129.05(2C,s)、130.94(2C,s)、135.23(2C,s)、136.59(1C,s)、141.12(1C,s)、148.68(1C,q,J=5.6Hz)、160.98(1C,s)。
19F−NMR(CDCl3,282MHz)δ−58.76(3F,d,J=8.0Hz)。
IR(KBr)3301、1663、1536、1143、1106、756cm−1。
GC−MS(EI,m/Z,70eV)337(M+,6)、217(5)、123(49)、91(74)、77(81)、65(100)。
元素分析 計算値C;60.52、H;4.18、N;4.15
測定値C;60.43、H;4.16、N;4.16。
1H−NMR(CDCl3,300MHz)δ2.39(3H,s)、5.81(1H,q,J=7.2Hz)、7.24−7.43(4H,m)。
19F−NMR(CDCl3,282MHz)δ−59.17(3F,d,J=6.9Hz)。
GC−MS(EI,m/Z,70eV)344(0.38,M+)、217(26)、147(31)、123(33)、91(68)、77(20)、65(100)。
1H−NMR(CDCl3,300MHz)δ0.93(6H,dd,J=13.9,7.3Hz)、1.24−1.80(6H,m)、2.40(3H,s)、4.75(1H,d,J=8.6Hz)、4.84(1H,q,J=8.8Hz)、7.24−7.40(4H,m)。
19F−NMR(CDCl3,282MHz)δ−55.10(3F,d,J=9.2Hz)
GC−MS(EI,m/Z,70eV)318(0.78,M+)、124(100)、91(59)、77(21)、65(15)。
Rf=0.57(ヘキサン/酢酸エチル=3:1,vol/vol)。
1H−NMR(CDCl3,300MHz)δ1.55(1H,s)、2.38(3H,s)、2.41(1H,d,J=5.3Hz)、3.90(3H,s)、4.93(1H,q,J=8.8Hz)、6.90−7.03(4H,m)、7.21−7.60(4H,m)。
13C−NMR(CDCl3,75.5MHz)δ21.17(1C,s)、55.13(1C,s)、70.72(1C,s)、110.30(1C,q,J=34.9Hz)、113.75(2C,s)、123.07(1C,q,J=271.5Hz)、125.40(1C,s)、127.42(2C,s)、130.75(2C,s)、131.98(1C,s)、135.67(2C,s)、140.26(1C,s)、159.39(1C,s)、159.80(1C,q,J=5.6Hz)。
19F−NMR(CDCl3,282MHz)δ−55.42(3F,d,J=8.4Hz)。
IR(NaCl)3443、1713、1513、1265、1149、1109、856、812cm−1。
GC−MS(EI,m/Z,70eV)354(0.01,M+)、217(9)、137(100)、123(12)、109(45)、94(35)、77(44)、65(20)。
1H−NMR(CDCl3,300MHz)δ2.38(3H,s)、2.43(3H,s)、5.28(1H,q,J=7.9Hz)、7.14−7.30(4H,m)、7.40(2H,d,J=8.3Hz)、7.84(2H,d,J=8.1Hz)。
19F−NMR(CDCl3,282MHz)δ−58.74(3F,d,J=8.8Hz)。
GC−MS(EI,m/Z,70eV)336(0.8,M+)、119(100)、91(39)、65(15)。
Rf=0.54(ヘキサン/酢酸エチル=10:1,vol/vol)。
1H−NMR(CDCl3,300MHz)δ1.25(3H,t,J=7.2Hz)、2.39(3H,S)、4.20(2H,q,J=7.2Hz)、5.23(1H,q,J=7.9Hz)、7.23−7.44(4H,m)。
19F−NMR(CDCl3,282MHz)δ−59.57(3F,d,J=8.1Hz)。
IR(NaCl)1741、1629、1334、1275、1140、984、811cm−1。
GC−MS(EI,m/Z,70eV)290(7.1,M+)、217(3.0)、149(94)、123(53)、108(18)、91(87)、77(29)、65(100)。
元素分析 計算値C;53.78、H;4.51
測定値C;53.83、H;4.40。
Rf=0.61(ヘキサン/酢酸エチル=10:1,vol/vol)。
1H−NMR(CDCl3,300MHz)δ0.85−0.96(6H,m)、1.27−1.36(8H,m)、1.55(2H,s)、2.39(3H,s)、3.90−4.10(2H,m)、5.26(1H,q,J=7.9Hz)、7.22−7.43(4H,m)。
19F−NMR(CDCl3,282MHz)δ−59.70(3F,d,J=8.0Hz)。
IR(NaCl)2961、2931、1741、1335、1276、1141、855、811cm−1。
GC−MS(EI,m/Z,70eV)374(0.66,M+)、373(4,M+−1)、217(2.5)、149(22)、123(20)、91(24)、77(6.8)、71(54)、65(21)、57(100)。
元素分析 計算値C;60.94、H;6.73
測定値C;61.18、H;6.67。
乾燥、アルゴン置換した25mlの二口フラスコに(E)−β−(トリフルオロメチル)−α−(4−メチルフェニルカルボニル)ビニル p−トリルスルフィド(23.1mg、0.0687mmol)と無水エタノール(2ml)を加えた。次いでこの溶液にマイクロシリンジを用いてヒドラジン1水和物(8.6μl、0.1374mmol)を加え、80℃で15時間反応を行った。反応終了後、室温に冷却、濃縮しエタノールを除去し、残渣に水と酢酸エチルを加え有機層を分離した。残った水層に酢酸エチルを加え再び抽出し、先ほどの有機層と合わせた後、この溶液を硫酸ナトリウムで乾燥後濃縮した。残渣をシリカゲルのカラム(ヘキサン/酢酸エチル=4/1,vol/vol)で精製し、目的物の5−(トリフルオロメチル)−3−p−トリル−1H−ピラゾール(13.6mg、収率87.7%)を得た。
Claims (5)
- 下記一般式(3)
で表される(E)アリール β−(トリフルオロメチル)−α−置換ビニルスルフィド誘導体。 - 塩基存在下、請求項1に記載の一般式(1)で表されるβ−(トリフルオロメチル)ビニルスルフィド誘導体と親電子試剤を反応させることを特徴とする請求項3に記載の一般式(3)で表される(E)アリール β−(トリフルオロメチル)−α−置換ビニルスルフィド誘導体の製造方法。
- 請求項3に記載の一般式(3)で表される(E)アリール β−(トリフルオロメチル)−α−置換ビニルスルフィド誘導体の内、下記式(4)
で表される誘導体と、下記一般式(5)
で表されるヒドラジン誘導体を反応させることを特徴とする下記一般式(6)
で表される3−p−置換−5−(トリフルオロメチル)−1H−ピラゾール誘導体の製造方法。
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Non-Patent Citations (8)
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JPN6012060473; HASZELDINE,R.N. et al.: 'Polyfluorocarbanion chemistry. IV. Reactions of 2H- and 1H-pentafluoropropene with nucleophiles' Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (20), 1975, 2015-19 * |
JPN6012060475; GAZIEVA,N.I. et al.: 'Interaction of fluorine-containing acetylenes with mercaptans' Zhurnal Organicheskoi Khimii 7(9), 1971, 1815-16 * |
JPN6012060476; HU,C.M. et al.: 'Diels-Alder reaction of 1-phenylsulfonyl-3,3,3-trifluoropropyne with 1,3-dienes' Journal of Fluorine Chemistry 66(3), 1994, 215-17 * |
JPN6012060477; CHAMBERS,R.D. et al.: 'Cycloadditions and nucleophilic attack on Z-2H-heptafluorobut-2-ene' Tetrahedron 54(19), 1998, 4949-4964 * |
JPN6012060478; BONACORSO,H.G. et al.: 'Haloacetylated enol ethers. 10. Condensation of beta-alkoxyvinyl trifluoromethyl ketones with thiosemi' Journal of Fluorine Chemistry 92(1), 1998, 23-26 * |
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