JP2008231040A - アミド化合物およびその製造方法 - Google Patents
アミド化合物およびその製造方法 Download PDFInfo
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- JP2008231040A JP2008231040A JP2007073965A JP2007073965A JP2008231040A JP 2008231040 A JP2008231040 A JP 2008231040A JP 2007073965 A JP2007073965 A JP 2007073965A JP 2007073965 A JP2007073965 A JP 2007073965A JP 2008231040 A JP2008231040 A JP 2008231040A
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- -1 Amide compound Chemical class 0.000 title claims abstract description 105
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000002506 iron compounds Chemical class 0.000 claims abstract description 10
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims abstract description 9
- 150000002978 peroxides Chemical class 0.000 claims abstract description 8
- 125000005843 halogen group Chemical group 0.000 claims abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 21
- 150000003462 sulfoxides Chemical class 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical class NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 claims description 5
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 125000005004 perfluoroethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- KSNKQSPJFRQSEI-UHFFFAOYSA-N 3,3,3-trifluoropropanoic acid Chemical compound OC(=O)CC(F)(F)F KSNKQSPJFRQSEI-UHFFFAOYSA-N 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000003905 agrochemical Substances 0.000 abstract description 4
- 239000008204 material by function Substances 0.000 abstract description 4
- 239000003814 drug Substances 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 40
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 36
- 238000006243 chemical reaction Methods 0.000 description 27
- 239000000243 solution Substances 0.000 description 23
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 22
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 18
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 15
- 229910052786 argon Inorganic materials 0.000 description 11
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 9
- 238000001953 recrystallisation Methods 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 238000005481 NMR spectroscopy Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- VPAYJEUHKVESSD-UHFFFAOYSA-N trifluoroiodomethane Chemical compound FC(F)(F)I VPAYJEUHKVESSD-UHFFFAOYSA-N 0.000 description 8
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000000605 extraction Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 6
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 5
- RFHRKNHEYSQLBU-UHFFFAOYSA-N 1-(3,3,3-trifluoro-1-hydroxypropyl)pyrrolidin-2-one Chemical compound FC(F)(F)CC(O)N1CCCC1=O RFHRKNHEYSQLBU-UHFFFAOYSA-N 0.000 description 4
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical class [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- WCODQJVSBRIGGH-UHFFFAOYSA-N 1-(3,3,3-trifluoro-1-hydroxypropyl)azepan-2-one Chemical compound FC(F)(F)CC(O)N1CCCCCC1=O WCODQJVSBRIGGH-UHFFFAOYSA-N 0.000 description 3
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 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 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 235000011054 acetic acid Nutrition 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- MQLVWQSVRZVNIP-UHFFFAOYSA-L ferrous ammonium sulfate hexahydrate Chemical compound [NH4+].[NH4+].O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O MQLVWQSVRZVNIP-UHFFFAOYSA-L 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- SHFJWMWCIHQNCP-UHFFFAOYSA-M hydron;tetrabutylazanium;sulfate Chemical compound OS([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC SHFJWMWCIHQNCP-UHFFFAOYSA-M 0.000 description 2
- PNLUGRYDUHRLOF-UHFFFAOYSA-N n-ethenyl-n-methylacetamide Chemical compound C=CN(C)C(C)=O PNLUGRYDUHRLOF-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 2
- 125000005003 perfluorobutyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 2
- 125000005005 perfluorohexyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 2
- 125000005009 perfluoropropyl group Chemical group FC(C(C(F)(F)F)(F)F)(F)* 0.000 description 2
- 238000004262 preparative liquid chromatography Methods 0.000 description 2
- 238000012746 preparative thin layer chromatography Methods 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- AQLJVWUFPCUVLO-UHFFFAOYSA-N urea hydrogen peroxide Chemical compound OO.NC(N)=O AQLJVWUFPCUVLO-UHFFFAOYSA-N 0.000 description 2
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 1
- JXTGICXCHWMCPM-UHFFFAOYSA-N (methylsulfinyl)benzene Chemical compound CS(=O)C1=CC=CC=C1 JXTGICXCHWMCPM-UHFFFAOYSA-N 0.000 description 1
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- IPRROFRGPQGDOX-UHFFFAOYSA-K 1,2,3,4,5-pentamethylcyclopenta-1,3-diene;trichlorotitanium Chemical group Cl[Ti](Cl)Cl.CC=1C(C)=C(C)[C-](C)C=1C IPRROFRGPQGDOX-UHFFFAOYSA-K 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- PQVGOQLFKZJVOB-UHFFFAOYSA-N 1-(3,3,3-trifluoro-1-methylsulfonylpropyl)azepan-2-one Chemical compound FC(F)(F)CC(S(=O)(=O)C)N1CCCCCC1=O PQVGOQLFKZJVOB-UHFFFAOYSA-N 0.000 description 1
- DZGBRAGOJGBDFL-UHFFFAOYSA-N 1-(3,3,3-trifluoro-1-methylsulfonylpropyl)pyrrolidin-2-one Chemical compound FC(F)(F)CC(S(=O)(=O)C)N1CCCC1=O DZGBRAGOJGBDFL-UHFFFAOYSA-N 0.000 description 1
- AVCMONGOKLNSJG-HWKANZROSA-N 1-[(E)-3,3,3-trifluoroprop-1-enyl]pyrrolidin-2-one Chemical compound FC(F)(F)\C=C\N1CCCC1=O AVCMONGOKLNSJG-HWKANZROSA-N 0.000 description 1
- LOWMYOWHQMKBTM-UHFFFAOYSA-N 1-butylsulfinylbutane Chemical compound CCCCS(=O)CCCC LOWMYOWHQMKBTM-UHFFFAOYSA-N 0.000 description 1
- FEVALTJSQBFLEU-UHFFFAOYSA-N 1-methyl-4-methylsulfinylbenzene Chemical compound CC1=CC=C(S(C)=O)C=C1 FEVALTJSQBFLEU-UHFFFAOYSA-N 0.000 description 1
- BQCCJWMQESHLIT-UHFFFAOYSA-N 1-propylsulfinylpropane Chemical compound CCCS(=O)CCC BQCCJWMQESHLIT-UHFFFAOYSA-N 0.000 description 1
- PARCUCWFQOWGFX-UHFFFAOYSA-N 2-butan-2-ylsulfinylbutane Chemical compound CCC(C)S(=O)C(C)CC PARCUCWFQOWGFX-UHFFFAOYSA-N 0.000 description 1
- WFJXYIUAMJAURQ-UHFFFAOYSA-N 2-propan-2-ylsulfinylpropane Chemical compound CC(C)S(=O)C(C)C WFJXYIUAMJAURQ-UHFFFAOYSA-N 0.000 description 1
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 1
- JJHHIJFTHRNPIK-UHFFFAOYSA-N Diphenyl sulfoxide Chemical compound C=1C=CC=CC=1S(=O)C1=CC=CC=C1 JJHHIJFTHRNPIK-UHFFFAOYSA-N 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- 229910021579 Iron(II) iodide Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 description 1
- WZGNVVUXVXNNOX-UHFFFAOYSA-N [Fe+] Chemical class [Fe+] WZGNVVUXVXNNOX-UHFFFAOYSA-N 0.000 description 1
- 150000008043 acidic salts Chemical class 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 125000004186 cyclopropylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C1([H])[H] 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- CCAFPWNGIUBUSD-UHFFFAOYSA-N diethyl sulfoxide Chemical compound CCS(=O)CC CCAFPWNGIUBUSD-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- GUVUOGQBMYCBQP-UHFFFAOYSA-N dmpu Chemical compound CN1CCCN(C)C1=O GUVUOGQBMYCBQP-UHFFFAOYSA-N 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229910000043 hydrogen iodide Inorganic materials 0.000 description 1
- PFUBERZHXYBBDK-UHFFFAOYSA-M hydrogen sulfate;tetraphenylphosphanium Chemical compound OS([O-])(=O)=O.C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 PFUBERZHXYBBDK-UHFFFAOYSA-M 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- CREVBWLEPKAZBH-UHFFFAOYSA-M hydron;tetraethylazanium;sulfate Chemical compound OS([O-])(=O)=O.CC[N+](CC)(CC)CC CREVBWLEPKAZBH-UHFFFAOYSA-M 0.000 description 1
- DWTYPCUOWWOADE-UHFFFAOYSA-M hydron;tetramethylazanium;sulfate Chemical compound C[N+](C)(C)C.OS([O-])(=O)=O DWTYPCUOWWOADE-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 description 1
- LNOZJRCUHSPCDZ-UHFFFAOYSA-L iron(ii) acetate Chemical compound [Fe+2].CC([O-])=O.CC([O-])=O LNOZJRCUHSPCDZ-UHFFFAOYSA-L 0.000 description 1
- BQZGVMWPHXIKEQ-UHFFFAOYSA-L iron(ii) iodide Chemical compound [Fe+2].[I-].[I-] BQZGVMWPHXIKEQ-UHFFFAOYSA-L 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
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- IHPHPGLJYCDONF-UHFFFAOYSA-N n-propylacetamide Chemical compound CCCNC(C)=O IHPHPGLJYCDONF-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000005008 perfluoropentyl group Chemical group FC(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)* 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Landscapes
- Other In-Based Heterocyclic Compounds (AREA)
- Pyrrole Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Chemische Berichte,101巻,923ページ,1968年.
N−ビニルアミド化合物(2)と鉄化合物のモル比は、1:0.01から1:10が望ましく、収率が良い点で1:0.1から1:1がさらに望ましい。
反応を密閉系で行う場合、大気圧(0.1MPa)から1.0MPaの範囲から適宜選ばれた圧力で行うことができるが、大気圧でも反応は充分に進行する。また、反応の際の雰囲気は、アルゴン、窒素等の不活性ガスでも良いが、空気中でも充分に進行する。
本反応系では、一般式(5)の化合物が併産される場合がある。一般式(2)の化合物で、R1とR2が一体となって炭素数3から10のポリメチレン基である場合、触媒としてフェロセンを用いると一般式(5)の化合物は併産されない傾向にある。また、R1およびR2が炭素数1から4のアルキル基の場合は、いずれの鉄化合物を用いても一般式(5)の化合物が併産される。
また一般式(5)の化合物は、前記のスルホキシド類(3)、過酸化物、鉄化合物および場合によっては酸の存在下に化合物(1)を処理することにより、製造することもできる。
その際に用いる脱水用試薬として、塩化チオニル、五酸化二リン、ヨウ素、三フッ化ホウ素−ジエチルエーテル、無水フタル酸等を例示することができる。
1H−NMR(重クロロホルム):δ2.06(m,2H),2.39(m,2H),2.59(m,2H),3.42(m,1H),3.54(m,1H),5.01(d,J=4.6Hz,1H),5.82(dt,J=6.3,4.6Hz,1H).
13C−NMR(重クロロホルム):δ17.8,31.5,37.5(q,JCF=27.8Hz),41.3,69.7(q,JCF=3.8Hz),124.9(q,JCF=275.0Hz),175.7.
19F−NMR(重クロロホルム):δ−64.4.
MS(m/z):197[M]+
(実施例2)
N−(3,3,3−トリフルオロ−1−メチルスルホニル)プロピルピロリドン
1H−NMR(重クロロホルム):δ2.14(m,2H),2.49(m,2H),2.82(brs,1H),2.91(s,3H),3.05(m,1H),3.52(m,1H),3.89(m,1H),5.52(brs,1H).
13C−NMR(重クロロホルム):δ18.5,26.8(q,JCF=31.8Hz),38.8,43.0,64.9,124.9(q,JCF=275.8Hz),175.9.
19F−NMR(重クロロホルム):δ−65.4.
MS(m/z):180[M−SO2Me]+
(実施例3)
二口フラスコ容器内にフェロセン2.8g(15mmol)を量り取り、容器内をアルゴンで置換した。ここにN−ビニルピロリドン5.25mL、ジメチルスルホキシド200mL、ヨウ化トリフルオロメチルの3.0mol/Lジメチルスルホキシド溶液50mLおよび30%過酸化水素水10mLを加えた。40から50℃で20分間撹拌した後、反応溶液を室温まで冷却した。酢酸エチルで抽出後、濃縮し、メタノール/ヘキサンで再結晶してN−(3,3,3−トリフルオロ−1−ヒドロキシプロピル)ピロリドンを白色結晶として得た(5.60g、収率57%)。
(実施例4)
1H−NMR(重クロロホルム):δ1.70(m,6H),2.50(m,4H),3.38(m,2H),5.07(d,J=6.2Hz,1H),5.97(dt,J=6.2,6.3Hz,1H).
13C−NMR(重クロロホルム):δ23.0,29.0,29.8,37.5,38.3(q,JCF=27.5Hz),43.4,73.3,125.1(q,JCF=276.8Hz),177.0.
19F−NMR(重クロロホルム):δ−64.1.
MS(m/z):208[M−OH]+
(実施例5)
N−(3,3,3−トリフルオロ−1−メチルスルホニル)プロピル−ε−カプロラクタム
1H−NMR(重クロロホルム):δ1.69−1.88(m,6H),2.58−2.72(m,3H),2.90(s,3H),3.01−3.12(m,1H),3.50−3.65(m,2H),6.21(dd,J=1.7,11.5Hz,1H).
13C−NMR(重クロロホルム):δ22.8,27.4(q,JCF=30.6Hz),28.3,29.4,36.8,38.5,44.3,65.5(q,JCF=2.3Hz),125.0(q,JCF=277.6Hz),176.9.
19F−NMR(重クロロホルム):δ−64.3.
MS(m/z):208[M−SO2Me]+
(実施例6)
二口フラスコ容器内にフェロセン1.4g(7.4mmol)を量り取り、容器内をアルゴンで置換した。ここにN−ビニル−ε−カプロラクタム3.48g(25mmol)、ジメチルスルホキシド100mL、ヨウ化トリフルオロメチルの3.0mol/Lジメチルスルホキシド溶液40mLおよび30%過酸化水素水9.0mLを加えた。40から50℃で20分間撹拌した後、反応溶液を室温まで冷却した。酢酸エチルで抽出後、濃縮し、メタノール/ヘキサンで再結晶してN−(3,3,3−トリフルオロ−1−ヒドロキシプロピル)−ε−カプロラクタムを白色結晶として得た(3.20g、収率57%)。
(実施例7)
N−メチル−N−(3,3,3−トリフルオロ−1−ヒドロキシプロピル)アセトアミド
1H−NMR(重クロロホルム):δ2.09(s,3H),2.59(m,2H),2.98(s,3H),4.50(d,J=7.5Hz,1H),5.80(m,1H).
13C−NMR(重クロロホルム):δ21.9,29.0,37.5(q,JCF=27.7Hz),71.7(q,JCF=3.3Hz),125.0(q,JCF=276.6Hz),171.9.
19F−NMR(重クロロホルム):δ−64.4.
MS(m/z):185[M]+
N−メチル−N−(3,3,3−トリフルオロ−1−メチルスルホニルプロピル)アセトアミド
1H−NMR(重クロロホルム):δ2.23(s,3H),2.28(m,2H),2.88(s,3H),3.15(s,3H),6.21(m,1H).
13C−NMR(重クロロホルム):δ21.8,26.9(q,JCF=30.8Hz),31.0,38.8,65.0(q,JCF=2.3Hz),124.9(q,JCF=277.4Hz),172.2.
19F−NMR(重クロロホルム):δ−64.7.
MS(m/z):168[M−SO2Me]+
(実施例8)
二口フラスコ容器内にフェロセン0.056g(0.3mmol)を量り取り、容器内をアルゴンで置換した。ここにN−メチル−N−ビニルアセトアミド0.105mL、ジメチルスルホキシド4.0mL、ヨウ化トリフルオロメチルの3.0mol/Lジメチルスルホキシド溶液1.0mLおよび30%過酸化水素水0.2mLを加えた。40から50℃で20分間撹拌した後、反応溶液を室温まで冷却した。反応液の19F−NMRにより、N−メチル−N−(3,3,3−トリフルオロ−1−ヒドロキシプロピル)アセトアミドの生成率が34%、N−メチル−N−(3,3,3−トリフルオロ−1−メチルスルホニルプロピル)アセトアミドの生成率が30%であることを確認した。
(参考例1)
1H−NMR(重クロロホルム):δ2.19(tt,J=7.3,8.0,2H),2.55(t,J=8.0Hz,2H),3.54(t,J=7.3Hz,2H),5.01(dq,J=14.4Hz,JHF=6.3Hz,1H),7.63(dq,J=14.4Hz,JHF=1.8Hz,1H).
13C−NMR(重クロロホルム):δ17.4,30.8,44.8,98.4(q,JCF=34.8Hz),124.3(q,JCF=265.6Hz),131.1(q,JCF=7.4Hz),174.1.
19F−NMR(重クロロホルム):δ−60.7.
MS(m/z):179[M]+
Claims (5)
- 一般式(2)
- 一般式(2)
- Xがヨウ素原子または臭素原子である請求項2に記載の製造方法。
- Rfがトリフルオロメチル基またはパーフルオロエチル基である請求項2または3のいずれかに記載の製造方法。
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CN110655451A (zh) * | 2019-09-19 | 2020-01-07 | 中山大学 | 一种烯烃与三氟溴甲烷反应制备羟基和三氟甲基取代化合物的方法 |
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CN110655451A (zh) * | 2019-09-19 | 2020-01-07 | 中山大学 | 一种烯烃与三氟溴甲烷反应制备羟基和三氟甲基取代化合物的方法 |
CN110655451B (zh) * | 2019-09-19 | 2020-10-27 | 中山大学 | 一种烯烃与三氟溴甲烷反应制备羟基和三氟甲基取代化合物的方法 |
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