JPWO2013125688A1 - 9−アザノルアダマンタンn−オキシル化合物及びその製造方法、並びに9−アザノルアダマンタンn−オキシル化合物を用いた有機分子酸化触媒及びアルコール類の酸化方法 - Google Patents
9−アザノルアダマンタンn−オキシル化合物及びその製造方法、並びに9−アザノルアダマンタンn−オキシル化合物を用いた有機分子酸化触媒及びアルコール類の酸化方法 Download PDFInfo
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- JPWO2013125688A1 JPWO2013125688A1 JP2014500954A JP2014500954A JPWO2013125688A1 JP WO2013125688 A1 JPWO2013125688 A1 JP WO2013125688A1 JP 2014500954 A JP2014500954 A JP 2014500954A JP 2014500954 A JP2014500954 A JP 2014500954A JP WO2013125688 A1 JPWO2013125688 A1 JP WO2013125688A1
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- Japan
- Prior art keywords
- group
- optionally substituted
- alkyl
- azanoradamantane
- cycloalkyl
- Prior art date
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- Granted
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- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 73
- 230000003647 oxidation Effects 0.000 title claims abstract description 48
- 239000003054 catalyst Substances 0.000 title claims abstract description 35
- 230000001590 oxidative effect Effects 0.000 title claims abstract description 23
- 150000001298 alcohols Chemical class 0.000 title claims abstract description 11
- 150000001875 compounds Chemical class 0.000 title claims description 66
- 238000000034 method Methods 0.000 title claims description 40
- LNMXAQDYIPHBOF-UHFFFAOYSA-N C1C(C2)C3CC2NC1C3 Chemical compound C1C(C2)C3CC2NC1C3 LNMXAQDYIPHBOF-UHFFFAOYSA-N 0.000 title claims description 26
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- -1 pharmaceuticals Chemical class 0.000 claims abstract description 85
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 59
- 150000003138 primary alcohols Chemical class 0.000 claims abstract description 41
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 5
- 125000006652 (C3-C12) cycloalkyl group Chemical group 0.000 claims description 27
- 125000003277 amino group Chemical group 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000007800 oxidant agent Substances 0.000 claims description 20
- 125000001424 substituent group Chemical group 0.000 claims description 19
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 claims description 18
- 125000003118 aryl group Chemical group 0.000 claims description 14
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 14
- 125000000262 haloalkenyl group Chemical group 0.000 claims description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 9
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 claims description 9
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 claims description 9
- 125000003545 alkoxy group Chemical group 0.000 claims description 9
- 125000000232 haloalkynyl group Chemical group 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 150000003333 secondary alcohols Chemical class 0.000 claims description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 8
- 125000005843 halogen group Chemical group 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- VAIFYHGFLAPCON-UHFFFAOYSA-N 1,3-Diacetylpropane Chemical compound CC(=O)CCCC(C)=O VAIFYHGFLAPCON-UHFFFAOYSA-N 0.000 claims description 7
- 125000004448 alkyl carbonyl group Chemical group 0.000 claims description 7
- 125000005129 aryl carbonyl group Chemical group 0.000 claims description 7
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 7
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 claims description 7
- 125000000171 (C1-C6) haloalkyl group Chemical group 0.000 claims description 6
- 125000002252 acyl group Chemical group 0.000 claims description 6
- 125000005136 alkenylsulfinyl group Chemical group 0.000 claims description 6
- 125000004647 alkyl sulfenyl group Chemical group 0.000 claims description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 6
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 claims description 6
- 125000005708 carbonyloxy group Chemical group [*:2]OC([*:1])=O 0.000 claims description 6
- 125000006254 cycloalkyl carbonyl group Chemical group 0.000 claims description 6
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 claims description 6
- 125000005740 oxycarbonyl group Chemical group [*:1]OC([*:2])=O 0.000 claims description 6
- 125000004149 thio group Chemical group *S* 0.000 claims description 6
- 125000002813 thiocarbonyl group Chemical group *C(*)=S 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- BKIMMITUMNQMOS-UHFFFAOYSA-N normal nonane Natural products CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 5
- 125000000565 sulfonamide group Chemical group 0.000 claims description 5
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 4
- OXTNCQMOKLOUAM-UHFFFAOYSA-N 3-Oxoglutaric acid Chemical compound OC(=O)CC(=O)CC(O)=O OXTNCQMOKLOUAM-UHFFFAOYSA-N 0.000 claims description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 4
- 235000019270 ammonium chloride Nutrition 0.000 claims description 4
- 125000001584 benzyloxycarbonyl group Chemical group C(=O)(OCC1=CC=CC=C1)* 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
- YVOFTMXWTWHRBH-UHFFFAOYSA-N pentanedioyl dichloride Chemical compound ClC(=O)CCCC(Cl)=O YVOFTMXWTWHRBH-UHFFFAOYSA-N 0.000 claims description 4
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 4
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 4
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims description 3
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims description 3
- 125000004454 (C1-C6) alkoxycarbonyl group Chemical group 0.000 claims description 3
- 125000004738 (C1-C6) alkyl sulfinyl group Chemical group 0.000 claims description 3
- 125000004890 (C1-C6) alkylamino group Chemical group 0.000 claims description 3
- 125000004916 (C1-C6) alkylcarbonyl group Chemical group 0.000 claims description 3
- 125000004739 (C1-C6) alkylsulfonyl group Chemical group 0.000 claims description 3
- 125000006619 (C1-C6) dialkylamino group Chemical group 0.000 claims description 3
- 125000004737 (C1-C6) haloalkoxy group Chemical group 0.000 claims description 3
- 125000004749 (C1-C6) haloalkylsulfinyl group Chemical group 0.000 claims description 3
- 125000004741 (C1-C6) haloalkylsulfonyl group Chemical group 0.000 claims description 3
- 125000003320 C2-C6 alkenyloxy group Chemical group 0.000 claims description 3
- 125000003601 C2-C6 alkynyl group Chemical group 0.000 claims description 3
- 125000005137 alkenylsulfonyl group Chemical group 0.000 claims description 3
- 125000003282 alkyl amino group Chemical group 0.000 claims description 3
- 125000005196 alkyl carbonyloxy group Chemical group 0.000 claims description 3
- 125000005133 alkynyloxy group Chemical group 0.000 claims description 3
- 125000005134 alkynylsulfinyl group Chemical group 0.000 claims description 3
- 125000005100 aryl amino carbonyl group Chemical group 0.000 claims description 3
- 125000001769 aryl amino group Chemical group 0.000 claims description 3
- 125000004658 aryl carbonyl amino group Chemical group 0.000 claims description 3
- 125000005199 aryl carbonyloxy group Chemical group 0.000 claims description 3
- 125000005161 aryl oxy carbonyl group Chemical group 0.000 claims description 3
- 125000005110 aryl thio group Chemical group 0.000 claims description 3
- 125000004104 aryloxy group Chemical group 0.000 claims description 3
- 125000000440 benzylamino group Chemical group [H]N(*)C([H])([H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 3
- 125000000638 benzylaminocarbonyl group Chemical group C(C1=CC=CC=C1)NC(=O)* 0.000 claims description 3
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 150000007973 cyanuric acids Chemical class 0.000 claims description 3
- 125000000392 cycloalkenyl group Chemical group 0.000 claims description 3
- 125000004986 diarylamino group Chemical group 0.000 claims description 3
- 150000004820 halides Chemical class 0.000 claims description 3
- 125000005291 haloalkenyloxy group Chemical group 0.000 claims description 3
- 125000004692 haloalkylcarbonyl group Chemical group 0.000 claims description 3
- 125000005347 halocycloalkyl group Chemical group 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical group 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 230000011987 methylation Effects 0.000 claims description 3
- 238000007069 methylation reaction Methods 0.000 claims description 3
- 150000004965 peroxy acids Chemical group 0.000 claims description 3
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 3
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical group C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 claims description 2
- 230000002140 halogenating effect Effects 0.000 claims description 2
- 150000007857 hydrazones Chemical class 0.000 claims description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 abstract description 36
- YSNGTNPJJSRPHQ-UHFFFAOYSA-N C1C(C2)C3CC2(C)N([O])C1(C)C3 Chemical compound C1C(C2)C3CC2(C)N([O])C1(C)C3 YSNGTNPJJSRPHQ-UHFFFAOYSA-N 0.000 abstract description 33
- 238000003786 synthesis reaction Methods 0.000 abstract description 15
- 230000015572 biosynthetic process Effects 0.000 abstract description 13
- IBNXYCCLPCGKDM-UHFFFAOYSA-N 1-me-azado Chemical compound C1C(C2)CC3CC2N([O])C1(C)C3 IBNXYCCLPCGKDM-UHFFFAOYSA-N 0.000 abstract description 10
- BCJCJALHNXSXKE-UHFFFAOYSA-N azado Chemical compound C1C(C2)CC3CC1N([O])C2C3 BCJCJALHNXSXKE-UHFFFAOYSA-N 0.000 abstract description 10
- 239000000758 substrate Substances 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000003905 agrochemical Substances 0.000 abstract description 3
- 239000003814 drug Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract description 3
- 238000004904 shortening Methods 0.000 abstract description 3
- 239000002537 cosmetic Substances 0.000 abstract description 2
- 150000002894 organic compounds Chemical class 0.000 abstract description 2
- 239000011368 organic material Substances 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 229920005862 polyol Polymers 0.000 abstract 1
- 150000003077 polyols Chemical class 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 42
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 35
- 239000000243 solution Substances 0.000 description 24
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 23
- 238000005160 1H NMR spectroscopy Methods 0.000 description 23
- 238000006243 chemical reaction Methods 0.000 description 22
- 239000000203 mixture Substances 0.000 description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 14
- 229920006395 saturated elastomer Polymers 0.000 description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 11
- 238000010898 silica gel chromatography Methods 0.000 description 11
- 230000035484 reaction time Effects 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- UQYVIPDHWFDNMT-UHFFFAOYSA-N 2,2-dimethyl-5-phenylpentane-1,3-diol Chemical compound OCC(C)(C)C(O)CCC1=CC=CC=C1 UQYVIPDHWFDNMT-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 9
- 239000012044 organic layer Substances 0.000 description 9
- UFDULEKOJAEIRI-UHFFFAOYSA-N (2-acetyloxy-3-iodophenyl) acetate Chemical compound CC(=O)OC1=CC=CC(I)=C1OC(C)=O UFDULEKOJAEIRI-UHFFFAOYSA-N 0.000 description 8
- 239000005708 Sodium hypochlorite Substances 0.000 description 8
- YLFIGGHWWPSIEG-UHFFFAOYSA-N aminoxyl Chemical compound [O]N YLFIGGHWWPSIEG-UHFFFAOYSA-N 0.000 description 8
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 8
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 8
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 8
- YJLUBHOZZTYQIP-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=N2 YJLUBHOZZTYQIP-UHFFFAOYSA-N 0.000 description 7
- MNJNAIZKGZUROM-UHFFFAOYSA-N CC12CCCC(C)(CC(=O)C1)N2 Chemical compound CC12CCCC(C)(CC(=O)C1)N2 MNJNAIZKGZUROM-UHFFFAOYSA-N 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 7
- 235000019341 magnesium sulphate Nutrition 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- NKLCNNUWBJBICK-UHFFFAOYSA-N dess–martin periodinane Chemical compound C1=CC=C2I(OC(=O)C)(OC(C)=O)(OC(C)=O)OC(=O)C2=C1 NKLCNNUWBJBICK-UHFFFAOYSA-N 0.000 description 6
- 125000000623 heterocyclic group Chemical group 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 125000006239 protecting group Chemical group 0.000 description 6
- 230000009257 reactivity Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- SXAMGRAIZSSWIH-UHFFFAOYSA-N 2-[3-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,2,4-oxadiazol-5-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NOC(=N1)CC(=O)N1CC2=C(CC1)NN=N2 SXAMGRAIZSSWIH-UHFFFAOYSA-N 0.000 description 5
- IPKSOGRIMJTYKC-UHFFFAOYSA-N 3-hydroxy-2,2-dimethyl-5-phenylpentanal Chemical compound CC(C)(C=O)C(O)CCc1ccccc1 IPKSOGRIMJTYKC-UHFFFAOYSA-N 0.000 description 5
- NIBIYOITBUQSJO-UHFFFAOYSA-N CC(C)(C)OC(=O)N1C2(C)CCCC1(C)CC(=O)C2 Chemical compound CC(C)(C)OC(=O)N1C2(C)CCCC1(C)CC(=O)C2 NIBIYOITBUQSJO-UHFFFAOYSA-N 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 5
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 5
- 235000011054 acetic acid Nutrition 0.000 description 5
- 150000001340 alkali metals Chemical class 0.000 description 5
- 150000002009 diols Chemical class 0.000 description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- QPGWDTADWJBIOE-UHFFFAOYSA-N Cc1ccc(cc1)S(=O)(=O)NN=C1CC2(C)CCCC(C)(C1)N2C(=O)OC(C)(C)C Chemical compound Cc1ccc(cc1)S(=O)(=O)NN=C1CC2(C)CCCC(C)(C1)N2C(=O)OC(C)(C)C QPGWDTADWJBIOE-UHFFFAOYSA-N 0.000 description 4
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 4
- JYDNKGUBLIKNAM-UHFFFAOYSA-N Oxyallobutulin Natural products C1CC(=O)C(C)(C)C2CCC3(C)C4(C)CCC5(CO)CCC(C(=C)C)C5C4CCC3C21C JYDNKGUBLIKNAM-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- FVWJYYTZTCVBKE-ROUWMTJPSA-N betulin Chemical compound C1C[C@H](O)C(C)(C)[C@@H]2CC[C@@]3(C)[C@]4(C)CC[C@@]5(CO)CC[C@@H](C(=C)C)[C@@H]5[C@H]4CC[C@@H]3[C@]21C FVWJYYTZTCVBKE-ROUWMTJPSA-N 0.000 description 4
- MVIRREHRVZLANQ-UHFFFAOYSA-N betulin Natural products CC(=O)OC1CCC2(C)C(CCC3(C)C2CC=C4C5C(CCC5(CO)CCC34C)C(=C)C)C1(C)C MVIRREHRVZLANQ-UHFFFAOYSA-N 0.000 description 4
- 150000004702 methyl esters Chemical group 0.000 description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 235000010288 sodium nitrite Nutrition 0.000 description 4
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 4
- AOHYQGVMTDLXSL-YMQHIKHWSA-N (2r,3r,4s,5r,6r)-2-(hydroxymethyl)-6-methoxy-4,5-bis(phenylmethoxy)oxan-3-ol Chemical compound O([C@H]1[C@H](O)[C@@H](CO)O[C@H]([C@@H]1OCC=1C=CC=CC=1)OC)CC1=CC=CC=C1 AOHYQGVMTDLXSL-YMQHIKHWSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical group 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 125000006165 cyclic alkyl group Chemical group 0.000 description 3
- 125000005594 diketone group Chemical group 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 125000002950 monocyclic group Chemical group 0.000 description 3
- ODUCDPQEXGNKDN-UHFFFAOYSA-N nitroxyl Chemical class O=N ODUCDPQEXGNKDN-UHFFFAOYSA-N 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 235000019345 sodium thiosulphate Nutrition 0.000 description 3
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- 125000004054 acenaphthylenyl group Chemical group C1(=CC2=CC=CC3=CC=CC1=C23)* 0.000 description 1
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- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
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- 239000007853 buffer solution Substances 0.000 description 1
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- 239000010949 copper Substances 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
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- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010511 deprotection reaction Methods 0.000 description 1
- KPUNOVLMCQQCSK-UHFFFAOYSA-N diazomethane;ethoxyethane Chemical compound C=[N+]=[N-].CCOCC KPUNOVLMCQQCSK-UHFFFAOYSA-N 0.000 description 1
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- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
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- 238000001035 drying Methods 0.000 description 1
- ZCRZCMUDOWDGOB-UHFFFAOYSA-N ethanesulfonimidic acid Chemical group CCS(N)(=O)=O ZCRZCMUDOWDGOB-UHFFFAOYSA-N 0.000 description 1
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- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
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- 238000001704 evaporation Methods 0.000 description 1
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- 239000000706 filtrate Substances 0.000 description 1
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- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 125000003838 furazanyl group Chemical group 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
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- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 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
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
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- USZLCYNVCCDPLQ-UHFFFAOYSA-N hydron;n-methoxymethanamine;chloride Chemical compound Cl.CNOC USZLCYNVCCDPLQ-UHFFFAOYSA-N 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
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- 238000011835 investigation Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 1
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- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
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- HNQIVZYLYMDVSB-UHFFFAOYSA-N methanesulfonimidic acid Chemical group CS(N)(=O)=O HNQIVZYLYMDVSB-UHFFFAOYSA-N 0.000 description 1
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- CBAMORLIFHEPLB-UHFFFAOYSA-N methyl 3-hydroxy-2,2-dimethyl-5-phenylpentanoate Chemical compound COC(=O)C(C)(C)C(O)CCC1=CC=CC=C1 CBAMORLIFHEPLB-UHFFFAOYSA-N 0.000 description 1
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- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
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- 125000004593 naphthyridinyl group Chemical group N1=C(C=CC2=CC=CN=C12)* 0.000 description 1
- SVYVNSVHGRUROS-UHFFFAOYSA-N nitro(phenyl)methanesulfonamide Chemical group NS(=O)(=O)C([N+]([O-])=O)C1=CC=CC=C1 SVYVNSVHGRUROS-UHFFFAOYSA-N 0.000 description 1
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 1
- KHLCTMQBMINUNT-UHFFFAOYSA-N octadecane-1,12-diol Chemical compound CCCCCCC(O)CCCCCCCCCCCO KHLCTMQBMINUNT-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 125000001644 phenoxazinyl group Chemical group C1(=CC=CC=2OC3=CC=CC=C3NC12)* 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
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- 229910052698 phosphorus Inorganic materials 0.000 description 1
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- SATVIFGJTRRDQU-UHFFFAOYSA-N potassium hypochlorite Chemical compound [K+].Cl[O-] SATVIFGJTRRDQU-UHFFFAOYSA-N 0.000 description 1
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- 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
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- CRWJEUDFKNYSBX-UHFFFAOYSA-N sodium;hypobromite Chemical compound [Na+].Br[O-] CRWJEUDFKNYSBX-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 125000005420 sulfonamido group Chemical group S(=O)(=O)(N*)* 0.000 description 1
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- 229950009390 symclosene Drugs 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- IOGXOCVLYRDXLW-UHFFFAOYSA-N tert-butyl nitrite Chemical compound CC(C)(C)ON=O IOGXOCVLYRDXLW-UHFFFAOYSA-N 0.000 description 1
- 239000012414 tert-butyl nitrite Substances 0.000 description 1
- 125000001981 tert-butyldimethylsilyl group Chemical group [H]C([H])([H])[Si]([H])(C([H])([H])[H])[*]C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005931 tert-butyloxycarbonyl group Chemical group [H]C([H])([H])C(OC(*)=O)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003509 tertiary alcohols Chemical class 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- 125000003831 tetrazolyl group Chemical group 0.000 description 1
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- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
- ZKWDCFPLNQTHSH-UHFFFAOYSA-N tribromoisocyanuric acid Chemical compound BrN1C(=O)N(Br)C(=O)N(Br)C1=O ZKWDCFPLNQTHSH-UHFFFAOYSA-N 0.000 description 1
- KAKQVSNHTBLJCH-UHFFFAOYSA-N trifluoromethanesulfonimidic acid Chemical group NS(=O)(=O)C(F)(F)F KAKQVSNHTBLJCH-UHFFFAOYSA-N 0.000 description 1
- 125000000025 triisopropylsilyl group Chemical group C(C)(C)[Si](C(C)C)(C(C)C)* 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0271—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds also containing elements or functional groups covered by B01J31/0201 - B01J31/0231
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/006—Catalysts comprising hydrides, coordination complexes or organic compounds comprising organic radicals, e.g. TEMPO
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
Description
(上式中、R1及びR2は水素原子又はアルキル基を示す。ただし、R1及びR2の一方が水素の場合、もう一方はアルキル基である)
で表される9−アザノルアダマンタンN−オキシル化合物。
(2)上記(1)に記載の9−アザノルアダマンタンN−オキシル化合物を含有することを特徴とする有機分子酸化触媒。
(3)第1級アルコール選択性を有することを特徴とする上記(2)に記載の触媒。
(4)式(2):
(上式中、R1及びR2は上記と同義である。)
で表されるアザノルアダマンタン化合物を酸化する工程を少なくとも経由することを特徴とする上記式(1)で表される9−アザノルアダマンタンN−オキシル化合物の製造方法。
(5)式(3):
(上式中、R1及びR2は、上記と同義である。R3は、水素原子、ハロゲン原子、ニトロ基、シアノ基、ヒドロキシ基、メルカプト基、アミノ基、ホルミル基、カルボキシル基、スルホ基、直鎖または分岐鎖であるC1-12アルキル基、C3-12シクロアルキル基、(C1-12アルキル)オキシ基、(C3-12シクロアルキル)オキシ基、(C1-12アルキル)チオ基、(C3-12シクロアルキル)チオ基、(C1-12アルキル)アミノ基、(C3-12シクロアルキル)アミノ基、ジ(C1-6アルキル)アミノ基、ジ(C3-6シクロアルキル)アミノ基、C1-12アルキルカルボニル基、C3-12シクロアルキルカルボニル基、(C1-12アルキル)オキシカルボニル基、(C3-12シクロアルキル)オキシカルボニル基、(C1-12アルキル)チオカルボニル基、(C3-12シクロアルキル)チオカルボニル基、(C1-12アルキル)アミノカルボニル基、(C3-12シクロアルキル)アミノカルボニル基、ジ(C1-6アルキル)アミノカルボニル基、ジ(C3-6シクロアルキル)アミノカルボニル基、(C1-12アルキル)カルボニルオキシ基、(C3-12シクロアルキル)カルボニルオキシ基、(C1-12アルキル)カルボニルチオ基、(C3-12シクロアルキル)カルボニルチオ基、(C1-12アルキル)カルボニルアミノ基、(C3-12シクロアルキル)カルボニルアミノ基、ジ(C1-12アルキルカルボニル)アミノ基、ジ(C3-12シクロアルキルカルボニル)アミノ基、C1-6ハロアルキル基、C3-6ハロシクロアルキル基、C2-6アルケニル基、C3-6シクロアルケニル基、C2-6ハロアルケニル基、C3-6ハロシクロアルケニル基、C2-6アルキニル基、C2-6ハロアルキニル基、Raで置換されていてもよいベンジル基、Raで置換されていてもよいベンジルオキシ基、Raで置換されていてもよいベンジルチオ基、Raで置換されていてもよいベンジルアミノ基、Raで置換されていてもよいジベンジルアミノ基、Raで置換されていてもよいベンジルカルボニル基、Raで置換されていてもよいベンジルオキシカルボニル基、Raで置換されていてもよいベンジルチオカルボニル基、Raで置換されていてもよいベンジルアミノカルボニル基、Raで置換されていてもよいジベンジルアミノカルボニル基、Raで置換されていてもよいベンジルカルボニルオキシ基、Raで置換されていてもよいベンジルカルボニルチオ基、Raで置換されていてもよいベンジルカルボニルアミノ基、Raで置換されていてもよいジ(ベンジルカルボニル)アミノ基、Raで置換されていてもよいアリール基、Raで置換されていてもよいアリールオキシ基、Raで置換されていてもよいアリールチオ基、Raで置換されていてもよいアリールアミノ基、Raで置換されていてもよいジアリールアミノ基、Raで置換されていてもよいアリールカルボニル基、Raで置換されていてもよいアリールオキシカルボニル基、Raで置換されていてもよいアリールチオカルボニル基、Raで置換されていてもよいアリールアミノカルボニル基、Raで置換されていてもよいジアリールアミノカルボニル基、Raで置換されていてもよいアリールカルボニルオキシ基、Raで置換されていてもよいアリールカルボニルチオ基、Raで置換されていてもよいアリールカルボニルアミノ基、及びRaで置換されていてもよいジ(アリールカルボニル)アミノ基からなる群から選ばれる1以上の置換基を表し、置換基の数が2以上である場合は、それぞれの置換基は同じでも異なっていてもよい。Raは、ハロゲン、C1-6アルキル基、C1-6ハロアルキル基、C3-6シクロアルキル基、C1-6アルコキシ基、C1-6アルコキシC1-6アルキル基、C1-6アルキルスルフェニルC1-6アルキル基、C1-6ハロアルコキシ基、C1-6アルキルスルフェニル基、C1-6アルキルスルフィニル基、C1-6アルキルスルホニル基、C1-6ハロアルキルスルフェニル基、C1-6ハロアルキルスルフィニル基、C1-6ハロアルキルスルホニル基、C2-6アルケニル基、C2-6ハロアルケニル基、C2-6アルケニルオキシ基、C2-6ハロアルケニルオキシ基、C2-6アルケニルスルフェニル基、C2-6アルケニルスルフィニル基、C2-6アルケニルスルホニル基、C2-6ハロアルケニルスルフェニル基、C2-6ハロアルケニルスルフィニル基、C2-6ハロアルケニルスルホニル基、C2-6アルキニル基、C2-6ハロアルキニル基、C2-6アルキニルオキシ基、C2-6ハロアルキニルオキシ基、C2-6アルキニルスルフェニル基、C2-6アルキニルスルフィニル基、C2-6アルキニルスルホニル基、C2-6ハロアルキニルスルフェニル基、C2-6ハロアルキニルスルフィニル基、C2-6ハロアルキニルスルホニル基、−NO2、−CN、ホルミル基、−OH、−SH、−NH2、−SCN、C1-6アルコキシカルボニル基、C1-6アルキルカルボニル基、C1-6ハロアルキルカルボニル基、C1-6アルキルカルボニルオキシ基、フェニル基、C1-6アルキルアミノ基またはジC1-6アルキルアミノ基であって、置換するRaの数は1〜5個であり、Raが2個以上の場合は、それぞれの置換基は同じでも異なっていてもよい。Xは、水素原子又はアシル基、カルバモイル基、スルホンアミド基、アルキル基、アリル基、ベンジル基、アリール基、シリル基、水酸基、アルコキシ基、酸素原子から選択される基を表す。)
で表わされるヒドラゾノアザビシクロ[3.3.1]ノナン化合物を閉環せしめてアザノルアダマンタン環を形成せしめ、得られた上記式(2)で表わされるアザノルアダマンタン化合物を酸化する工程を少なくとも経由することを特徴とする上記式(1)で表される9−アザノルアダマンタンN−オキシル化合物の製造方法。
(6)式(4):
(上式中、R1、R2及びXは上記と同義である。)
で表わされるケトアザビシクロ[3.3.1]ノナン化合物をフェニルヒドラジンと縮合せしめ、得られた上記式(3)で表わされるヒドラゾノアザビシクロ[3.3.1]ノナンを閉環処理せしめてアザノルアダマンタン環を形成せしめ、得られた上記式(2)で表わされるアザノルアダマンタン化合物を酸化する工程を少なくとも経由することを特徴とする上記式(1)で表される9−アザノルアダマンタンN−オキシル化合物の製造方法。
(7)グルタリルクロリドをジワインレブアミドとした後、メチル化によって得られる2、6−ヘプタンジオンと塩化アンモニウム、アセトンジカルボン酸の縮合によってケトビシクロアミン体を合成した後に、ヒドラジンとの縮合によりヒドラゾンとした後、塩基性条件下にアザノルアダマンタン骨格を形成し、アミノ基を酸化することを特徴とする上記式(1)で表わされるアザノルアダマンタンN-オキシル化合物を製造する方法。
(8)上記(1)に記載の9−アザノルアダマンタンN−オキシル化合物の存在下に、アルコール類を酸化せしめて、対応するオキソ体を合成することを特徴とするアルコール類の酸化方法。
(9)共酸化剤の存在下で酸化が行われることを特徴とする上記(8)に記載の方法。
(10)アルコール類が第1級アルコール及び/又は第2級アルコールを有する化合物であることを特徴とする上記(8)に記載の方法。
(11)アルコール類が第1級アルコール及び第2級アルコールを有する化合物であって、前記第1級アルコールを選択的に酸化せしめることを特徴とする上記(8)に記載の方法。
(12)前記9−アザノルアダマンタンN−オキシル化合物の添加量が、アルコールに対して0.001mol%〜1000mol%の範囲であることを特徴とする上記(8)〜(11)の何れか一に記載の方法。
(13)共酸化剤が、過酸素酸、過酸化水素、次亜ハロゲン酸及びその塩、過ハロゲン酸及びその塩、過硫酸塩、ハロゲン化物、ハロゲン化剤、トリハロゲン化イソシアヌル酸類、ジアセトキシヨードアレン類、酸素及び空気からなる群から選ばれる酸化剤であることを特徴とする上記(9)〜(12)の何れか一に記載の方法。
で表わされるヒドラゾノアザビシクロ[3.3.1]ノナン化合物を閉環せしめてアザノルアダマンタン環を形成せしめることで合成することができる。
(E)−メチル 6−エチル−5−ヒドロキシ−6−(ヒドロキシメチル)−2−オクテネートの酸化
2,2−ジメチル−5−フェニルペンタン−1,3−ジオールの酸化
オレアノ−12−エン−11−オキソ−3β,30−ジオールの酸化
2,2,4−トリメチルペンタン−1,3−ジオールの酸化
2,2,4−トリメチルペンタン−1,3−ジオール(44.4mg、0.304mmol)を実施例7−1に記載の方法と同様の方法により酸化し,目的化合物をメチルエステル(48.7mg、92%)として得た。
Claims (13)
- 請求項1に記載の9−アザノルアダマンタンN−オキシル化合物を含有することを特徴とする有機分子酸化触媒。
- 第1級アルコール選択性を有することを特徴とする請求項2に記載の触媒。
- 式(3):
(上式中、R1及びR2は、上記と同義である。R3は、水素原子、ハロゲン原子、ニトロ基、シアノ基、ヒドロキシ基、メルカプト基、アミノ基、ホルミル基、カルボキシル基、スルホ基、直鎖または分岐鎖であるC1-12アルキル基、C3-12シクロアルキル基、(C1-12アルキル)オキシ基、(C3-12シクロアルキル)オキシ基、(C1-12アルキル)チオ基、(C3-12シクロアルキル)チオ基、(C1-12アルキル)アミノ基、(C3-12シクロアルキル)アミノ基、ジ(C1-6アルキル)アミノ基、ジ(C3-6シクロアルキル)アミノ基、C1-12アルキルカルボニル基、C3-12シクロアルキルカルボニル基、(C1-12アルキル)オキシカルボニル基、(C3-12シクロアルキル)オキシカルボニル基、(C1-12アルキル)チオカルボニル基、(C3-12シクロアルキル)チオカルボニル基、(C1-12アルキル)アミノカルボニル基、(C3-12シクロアルキル)アミノカルボニル基、ジ(C1-6アルキル)アミノカルボニル基、ジ(C3-6シクロアルキル)アミノカルボニル基、(C1-12アルキル)カルボニルオキシ基、(C3-12シクロアルキル)カルボニルオキシ基、(C1-12アルキル)カルボニルチオ基、(C3-12シクロアルキル)カルボニルチオ基、(C1-12アルキル)カルボニルアミノ基、(C3-12シクロアルキル)カルボニルアミノ基、ジ(C1-12アルキルカルボニル)アミノ基、ジ(C3-12シクロアルキルカルボニル)アミノ基、C1-6ハロアルキル基、C3-6ハロシクロアルキル基、C2-6アルケニル基、C3-6シクロアルケニル基、C2-6ハロアルケニル基、C3-6ハロシクロアルケニル基、C2-6アルキニル基、C2-6ハロアルキニル基、Raで置換されていてもよいベンジル基、Raで置換されていてもよいベンジルオキシ基、Raで置換されていてもよいベンジルチオ基、Raで置換されていてもよいベンジルアミノ基、Raで置換されていてもよいジベンジルアミノ基、Raで置換されていてもよいベンジルカルボニル基、Raで置換されていてもよいベンジルオキシカルボニル基、Raで置換されていてもよいベンジルチオカルボニル基、Raで置換されていてもよいベンジルアミノカルボニル基、Raで置換されていてもよいジベンジルアミノカルボニル基、Raで置換されていてもよいベンジルカルボニルオキシ基、Raで置換されていてもよいベンジルカルボニルチオ基、Raで置換されていてもよいベンジルカルボニルアミノ基、Raで置換されていてもよいジ(ベンジルカルボニル)アミノ基、Raで置換されていてもよいアリール基、Raで置換されていてもよいアリールオキシ基、Raで置換されていてもよいアリールチオ基、Raで置換されていてもよいアリールアミノ基、Raで置換されていてもよいジアリールアミノ基、Raで置換されていてもよいアリールカルボニル基、Raで置換されていてもよいアリールオキシカルボニル基、Raで置換されていてもよいアリールチオカルボニル基、Raで置換されていてもよいアリールアミノカルボニル基、Raで置換されていてもよいジアリールアミノカルボニル基、Raで置換されていてもよいアリールカルボニルオキシ基、Raで置換されていてもよいアリールカルボニルチオ基、Raで置換されていてもよいアリールカルボニルアミノ基、及びRaで置換されていてもよいジ(アリールカルボニル)アミノ基からなる群から選ばれる1以上の置換基を表し、置換基の数が2以上である場合は、それぞれの置換基は同じでも異なっていてもよい。Raは、ハロゲン、C1-6アルキル基、C1-6ハロアルキル基、C3-6シクロアルキル基、C1-6アルコキシ基、C1-6アルコキシC1-6アルキル基、C1-6アルキルスルフェニルC1-6アルキル基、C1-6ハロアルコキシ基、C1-6アルキルスルフェニル基、C1-6アルキルスルフィニル基、C1-6アルキルスルホニル基、C1-6ハロアルキルスルフェニル基、C1-6ハロアルキルスルフィニル基、C1-6ハロアルキルスルホニル基、C2-6アルケニル基、C2-6ハロアルケニル基、C2-6アルケニルオキシ基、C2-6ハロアルケニルオキシ基、C2-6アルケニルスルフェニル基、C2-6アルケニルスルフィニル基、C2-6アルケニルスルホニル基、C2-6ハロアルケニルスルフェニル基、C2-6ハロアルケニルスルフィニル基、C2-6ハロアルケニルスルホニル基、C2-6アルキニル基、C2-6ハロアルキニル基、C2-6アルキニルオキシ基、C2-6ハロアルキニルオキシ基、C2-6アルキニルスルフェニル基、C2-6アルキニルスルフィニル基、C2-6アルキニルスルホニル基、C2-6ハロアルキニルスルフェニル基、C2-6ハロアルキニルスルフィニル基、C2-6ハロアルキニルスルホニル基、−NO2、−CN、ホルミル基、−OH、−SH、−NH2、−SCN、C1-6アルコキシカルボニル基、C1-6アルキルカルボニル基、C1-6ハロアルキルカルボニル基、C1-6アルキルカルボニルオキシ基、フェニル基、C1-6アルキルアミノ基またはジC1-6アルキルアミノ基であって、置換するRaの数は1〜5個であり、Raが2個以上の場合は、それぞれの置換基は同じでも異なっていてもよい。Xは、水素原子又はアシル基、カルバモイル基、スルホンアミド基、アルキル基、アリル基、ベンジル基、アリール基、シリル基、水酸基、アルコキシ基、酸素原子から選択される基を表す。)
で表わされるヒドラゾノアザビシクロ[3.3.1]ノナン化合物を閉環せしめてアザノルアダマンタン環を形成せしめ、得られた上記式(2)で表わされるアザノルアダマンタン化合物を酸化する工程を少なくとも経由することを特徴とする上記式(1)で表される9−アザノルアダマンタンN−オキシル化合物の製造方法。 - グルタリルクロリドをジワインレブアミドとした後、メチル化によって得られる2、6−ヘプタンジオンと塩化アンモニウム、アセトンジカルボン酸の縮合によってケトビシクロアミン体を合成した後に、ヒドラジンとの縮合によりヒドラゾンとした後、塩基性条件下にアザノルアダマンタン骨格を形成し、アミノ基を酸化することを特徴とする上記式(1)で表わされるアザノルアダマンタンN-オキシル化合物を製造する方法。
- 請求項1に記載の9−アザノルアダマンタンN−オキシル化合物の存在下に、アルコール類を酸化せしめて、対応するオキソ体を合成することを特徴とするアルコール類の酸化方法。
- 共酸化剤の存在下で酸化が行われることを特徴とする請求項8に記載の方法。
- アルコール類が第1級アルコール及び/又は第2級アルコールを有する化合物であることを特徴とする請求項8に記載の方法。
- アルコール類が第1級アルコール及び第2級アルコールを有する化合物であって、前記第1級アルコールを選択的に酸化せしめることを特徴とする請求項8に記載の方法。
- 前記9−アザノルアダマンタンN−オキシル化合物の添加量が、アルコールに対して0.001mol%〜1000mol%の範囲であることを特徴とする請求項8〜11の何れか一項に記載の方法。
- 共酸化剤が、過酸素酸、過酸化水素、次亜ハロゲン酸及びその塩、過ハロゲン酸及びその塩、過硫酸塩、ハロゲン化物、ハロゲン化剤、トリハロゲン化イソシアヌル酸類、ジアセトキシヨードアレン類、酸素及び空気からなる群から選ばれる酸化剤であることを特徴とする請求項9〜12の何れか一項に記載の方法。
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