JP2021505572A - 有機化合物における、または、それに関連する改善 - Google Patents
有機化合物における、または、それに関連する改善 Download PDFInfo
- Publication number
- JP2021505572A JP2021505572A JP2020530550A JP2020530550A JP2021505572A JP 2021505572 A JP2021505572 A JP 2021505572A JP 2020530550 A JP2020530550 A JP 2020530550A JP 2020530550 A JP2020530550 A JP 2020530550A JP 2021505572 A JP2021505572 A JP 2021505572A
- Authority
- JP
- Japan
- Prior art keywords
- mixture
- rotundone
- guaiene
- iii
- iron
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 150000002894 organic compounds Chemical class 0.000 title 1
- 239000000203 mixture Substances 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 39
- 230000003647 oxidation Effects 0.000 claims abstract description 32
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 32
- 239000002904 solvent Substances 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 150000002576 ketones Chemical class 0.000 claims abstract description 16
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims abstract description 13
- 125000000746 allylic group Chemical group 0.000 claims abstract description 12
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910001882 dioxygen Inorganic materials 0.000 claims abstract description 11
- 150000004032 porphyrins Chemical class 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 43
- NUWMTBMCSQWPDG-SDDRHHMPSA-N Rotundone Chemical compound C1([C@H](CC[C@H](C2)C(C)=C)C)=C2[C@@H](C)CC1=O NUWMTBMCSQWPDG-SDDRHHMPSA-N 0.000 claims description 34
- NUWMTBMCSQWPDG-UHFFFAOYSA-N Rotundone Natural products C1C(C(C)=C)CCC(C)C2=C1C(C)CC2=O NUWMTBMCSQWPDG-UHFFFAOYSA-N 0.000 claims description 34
- ADIDQIZBYUABQK-UHFFFAOYSA-N alpha-Guaiene Natural products C1C(C(C)=C)CCC(C)C2=C1C(C)CC2 ADIDQIZBYUABQK-UHFFFAOYSA-N 0.000 claims description 29
- XURCUMFVQKJMJP-UHFFFAOYSA-N Dihydro-alpha-guaien Natural products C1C(C(C)C)CCC(C)C2=C1C(C)CC2 XURCUMFVQKJMJP-UHFFFAOYSA-N 0.000 claims description 28
- ADIDQIZBYUABQK-RWMBFGLXSA-N alpha-guaiene Chemical compound C1([C@H](CC[C@H](C2)C(C)=C)C)=C2[C@@H](C)CC1 ADIDQIZBYUABQK-RWMBFGLXSA-N 0.000 claims description 28
- 229930000038 α-guaiene Natural products 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 4
- GDIUQZNEUVFHHD-UHFFFAOYSA-N [Fe+3].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical group [Fe+3].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 GDIUQZNEUVFHHD-UHFFFAOYSA-N 0.000 claims description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 150000007942 carboxylates Chemical class 0.000 claims description 2
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims description 2
- 230000005670 electromagnetic radiation Effects 0.000 claims description 2
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 claims description 2
- 229940011051 isopropyl acetate Drugs 0.000 claims description 2
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 claims description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- BTIJJDXEELBZFS-UHFFFAOYSA-K hemin Chemical compound [Cl-].[Fe+3].[N-]1C(C=C2C(=C(C)C(C=C3C(=C(C)C(=C4)[N-]3)C=C)=N2)C=C)=C(C)C(CCC(O)=O)=C1C=C1C(CCC(O)=O)=C(C)C4=N1 BTIJJDXEELBZFS-UHFFFAOYSA-K 0.000 claims 1
- YNHJECZULSZAQK-UHFFFAOYSA-N tetraphenylporphyrin Chemical group C1=CC(C(=C2C=CC(N2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3N2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 YNHJECZULSZAQK-UHFFFAOYSA-N 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 27
- 238000004817 gas chromatography Methods 0.000 description 13
- 238000004821 distillation Methods 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 208000033962 Fontaine progeroid syndrome Diseases 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 6
- RGRYQUWGSJPMMK-SBJFKYEJSA-N Epoxyguaiene Natural products C(=C)(C)[C@H]1C[C@@]23[C@@H](C)CC[C@@]2([C@@H](C)CC1)O3 RGRYQUWGSJPMMK-SBJFKYEJSA-N 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- RGRYQUWGSJPMMK-UHFFFAOYSA-N epoxyguaiene Chemical compound CC1CCC2(C(CCC(C3)C(C)=C)C)C13O2 RGRYQUWGSJPMMK-UHFFFAOYSA-N 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-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
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
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- 238000007664 blowing Methods 0.000 description 3
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- 230000001590 oxidative effect Effects 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- -1 propenyl-3,8-dimethyl-3,4,5,6,7,8-hexahydro-1 (2H) -azulenone Chemical compound 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- SHXWCVYOXRDMCX-UHFFFAOYSA-N 3,4-methylenedioxymethamphetamine Chemical compound CNC(C)CC1=CC=C2OCOC2=C1 SHXWCVYOXRDMCX-UHFFFAOYSA-N 0.000 description 2
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 241000110847 Kochia Species 0.000 description 2
- JQRLYSGCPHSLJI-UHFFFAOYSA-N [Fe].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Fe].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 JQRLYSGCPHSLJI-UHFFFAOYSA-N 0.000 description 2
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
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- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000001927 guaiacum sanctum l. gum oil Substances 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
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- 238000002955 isolation Methods 0.000 description 2
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- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 2
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- LEHBURLTIWGHEM-UHFFFAOYSA-N pyridinium chlorochromate Chemical compound [O-][Cr](Cl)(=O)=O.C1=CC=[NH+]C=C1 LEHBURLTIWGHEM-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229930004725 sesquiterpene Natural products 0.000 description 2
- 150000004354 sesquiterpene derivatives Chemical class 0.000 description 2
- 239000011877 solvent mixture Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- ADIDQIZBYUABQK-UPJWGTAASA-N (1r,4r,7s)-1,4-dimethyl-7-prop-1-en-2-yl-1,2,3,4,5,6,7,8-octahydroazulene Chemical compound C1([C@@H](CC[C@@H](C2)C(C)=C)C)=C2[C@H](C)CC1 ADIDQIZBYUABQK-UPJWGTAASA-N 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- FAMLQSCGIQGDPV-UHFFFAOYSA-N 3,4-dihydroxy-6-[4-hydroxy-5-(hydroxymethyl)-2-(sulfooxymethyl)oxolan-3-yl]oxy-5-sulfooxyoxane-2-carboxylic acid Chemical compound OC1C(CO)OC(COS(O)(=O)=O)C1OC1C(OS(O)(=O)=O)C(O)C(O)C(C(O)=O)O1 FAMLQSCGIQGDPV-UHFFFAOYSA-N 0.000 description 1
- UTRBHXSKVVPTLY-UHFFFAOYSA-N 4,5,6,7-tetrachloro-2-hydroxyisoindole-1,3-dione Chemical compound ClC1=C(Cl)C(Cl)=C(Cl)C2=C1C(=O)N(O)C2=O UTRBHXSKVVPTLY-UHFFFAOYSA-N 0.000 description 1
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- YHUYPIGAOHTVJU-WDEREUQCSA-N C[C@@H]1C=2CCC(C=2C[C@@H](CC1)C(=C)C)=O Chemical compound C[C@@H]1C=2CCC(C=2C[C@@H](CC1)C(=C)C)=O YHUYPIGAOHTVJU-WDEREUQCSA-N 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
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- 238000005481 NMR spectroscopy Methods 0.000 description 1
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- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical group [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 1
- 238000010352 biotechnological method Methods 0.000 description 1
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- 125000000068 chlorophenyl group Chemical group 0.000 description 1
- QAEKNCDIHIGLFI-UHFFFAOYSA-L cobalt(2+);2-ethylhexanoate Chemical compound [Co+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O QAEKNCDIHIGLFI-UHFFFAOYSA-L 0.000 description 1
- XSWKLHINRKWMTD-UHFFFAOYSA-L cobalt(2+);3-(3-ethylcyclopentyl)propanoate Chemical compound [Co+2].CCC1CCC(CCC([O-])=O)C1.CCC1CCC(CCC([O-])=O)C1 XSWKLHINRKWMTD-UHFFFAOYSA-L 0.000 description 1
- FCEOGYWNOSBEPV-FDGPNNRMSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FCEOGYWNOSBEPV-FDGPNNRMSA-N 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
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- 238000007710 freezing Methods 0.000 description 1
- 108700039708 galantide Proteins 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229940091561 guaiac Drugs 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000003919 heteronuclear multiple bond coherence Methods 0.000 description 1
- 238000005570 heteronuclear single quantum coherence Methods 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
-
- 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
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Abstract
Description
Xは、Cl、BrおよびIから選択され;ならびに
Rは、フェニル、ペンタフルオロフェニル、p−メトキシフェニル、ジクロロフェニル、ベンゼンスルホナート、ブロモフェニル、クロロフェニル、およびメチルフェニルから選択される、
で表される、鉄(III)ポルフィリン錯体である。
ある態様において、触媒の濃度は、α−グアイエンのモル数に基づき、0.01〜10mol%、好ましくは0.5〜2mol%、例として、1.1mol%を包含する1〜1.5mol%の範囲にあってもよい。
加えて、または、代替的に、対象のプロセスにおいて使用されるサステナブル溶媒は、シクロヘキサン、ヘプタン、トルエン、メチルシクロヘキサン、メチルt−ブチルエーテル、イソオクタン、アセトニトリル、キシレン、ジメチルスルホキシド、酢酸、エチレングリコールおよびそれらの混合物からなる群から選択されてもよい。
極性GCMS:35℃/2min、50℃まで10℃/min、240℃まで2.5℃/min、240℃/5min。Thermo Scientific TSQ8000evo + Trace 1310 system。極性カラム:Varian VF-WAX(極性、PEG相)。カラム寸法:30m長さ、0.25mmID、0.25mフィルム厚。インジェクタ:スプリットレス。流量:1.2ml/min。キャリアガス:ヘリウム。注入体積:1μl。インジェクタ温度:230℃。移送ライン:250℃。MS−四重極(quadrupol):160℃。MS−供給:230℃。イオン化モード:70 eVでの電子衝撃(EI)。この方法によって、GC変換および生成物分布を測定し、主構成成分1〜7の相対的なピーク面積を%において与える。
クロロ(テトラフェニルポルフィリナト)鉄(III)(34mg、0.05mmol)およびイミダゾール(6.7mg、0.1mmol)を、攪拌下、1:1エタノール/水混合物(20ml)中α−グアイエン91%(1g、4.5mmol)へ添加した。酸素を緑色を帯びた濁った混合物中へ吹き込み、完全な変換を検知するまで(8〜16時間)、300 W Osram Ultra Vitalux lumpでの光照射下、45℃で攪拌した。生成物分布には、ロタンドン2(31%)、ケトン5(9%)、ヒドロキシ−ロタンドン6(16%)およびコリンボロン7(1%)が含まれていた。緑褐色の濁った混合物を減圧下で部分的に蒸発させ、残渣をtert-ブチルメチルエーテルを用いて抽出した。合わせた有機層をMgSO4上で乾燥させ、濾過し、蒸発させた。残余の褐色の油(1.22g)を、150〜230℃/0.045mbarでバルブ・ツー・バルブ蒸留することによって、45%GC純度(29%corr.収率)の0.63g ロタンドン2および0.39gの残渣が与えられた。
クロロ(テトラフェニルポルフィリナト)鉄(III)(34mg、0.05mmol)およびイミダゾール(6.7mg、0.1mmol)を、攪拌下、1:1エタノール/水混合物(20ml)中α−グアイエン91%(1g、4.5mmol)へ添加した。酸素を、45℃で緑色を帯びた濁った混合物中へ吹き込んだ。反応フラスコをアルミニウム箔で包んで、光を排除した。8時間後、GCMSによってロタンドン2(25%)、ロツンドール3(1%)、エポキシ−グアイエン4(4%)、ケトン5(5%)、およびヒドロキシ−ロタンドン6(20%)を含む混合物への完全な変換が示された。緑褐色の濁った混合物を減圧下で部分的に蒸発させ、残渣をtert−ブチルメチルエーテルを用いて抽出した。合わせた有機層を、MgSO4上で乾燥させ、濾過し、蒸発させた。残余の褐色の油(1.22g)を、150〜230℃/0.045mbarでバルブ・ツー・バルブ蒸留することによって、43%GC純度の0.77g ロタンドン2(34%corr.収率)および0.24gの残渣が与えられた。
空気を、攪拌下および45℃で、1:1エタノール/水混合物(20ml)中クロロ(テトラフェニルポルフィリナト)鉄(III)(34mg、0.05mmol)、イミダゾール(6.7mg、0.1mmol)およびα−グアイエン91%(1g、4.5mmol)の緑色を帯びた濁った混合物中へ吹き込んだ。49時間後、GSMSによって、ロタンドン2(21%)、エポキシ−グアイエン4(5%)、ケトン5(4%)、ヒドロキシ−ロタンドン6(10%)、およびコリンボロン7(1%)を含む混合物への96%変換が示された。減圧下でエタノールの蒸発後、暗色の混合物を水に対してtert−ブチルメチルエーテルを用いて抽出した。合わせた有機層をMgSO4上で乾燥させ、濾過し、1.3gの褐色の残渣まで蒸発させ、それを150〜230℃/0.025mbarでバルブ・ツー・バルブ蒸留によって精製することによって、41%GC純度をもつ0.76gのロタンドン2および0.28gの残渣が得られた。
例4から12は、1%((クロロ(テトラフェニルポルフィリナト)鉄(III)))および2%イミダゾールを有する混合物中1g α−グアイエン1(91%)のケトン(ロタンドン2)へのアリル酸化を実証している。
通常の条件に、45℃での20ml溶媒または溶媒の混合物の使用が包含されている。他に指し示されない限り、混合物の意図的な照射がないか、光排除であった。
化合物:α−グアイエン1、ロタンドン2、ロツンドール3、エポキシ−グアイエン4、ケトン5、ヒドロキシ−ロタンドン6、およびコリンボロン7。
例13〜15は、異なる置換されたポルフィリンリガンドを有する鉄ポルフィリン触媒を用いる、α−グアイエン1のケトン(ロタンドン2)へのアリル酸化を実証している。通常の条件に、45℃で、分子酸素が流入口を通して1:1のモル比での20mlのEtOH/H2O溶媒混合物へ導入されると共に、1g α−グアイエン1(91%)、1mol%鉄ポルフィリン触媒、2mol%イミダゾールを混合することが包含されている。化合物1〜7のパーセンテージを、単離後GCMSによって決定した。
例16から19は、様々な温度条件での1%Fe−ポルフィリンおよび2%イミダゾールを有する混合物中、1g α−グアイエン1(91%)のケトン(ロタンドン2)へのアリル酸化を実証している。通常の条件に、20ml溶媒EtOH/H2O(1:1)中混合物の1000rpmの混合と共に、30分、O2を流入口を通して吹き込むこと、次いでバルーンを用いてO2雰囲気を提供することが包含される。化合物1〜7のパーセンテージを、GCMSによって決定した。
酸素を、攪拌下および45℃で、1:1エタノール/水混合物(200ml)中クロロ(テトラフェニルポルフィリナト)−鉄(III)(172mg、0.245mmol)、イミダゾール(67mg、1mmol)およびα−グアイエン91%(10g、45mmol)の緑色を帯びた濁った混合物中へ吹き込んだ。1h後、酸素流入口を、酸素バルーンによって置き換えた。45℃でさらに7h攪拌した後、GCMSによってロタンドン2(30%)、エポキシ−グアイエン4(3%)、ケトン5(7%)、ヒドロキシ−ロタンドン6(13%)、およびコリンボロン7(1%)を含む混合物への定量的な変換が指し示された。減圧下でのエタノールの蒸発後、暗褐色の混合物を水に対してtert−ブチルメチルエーテルを用いて抽出した。合わせた有機層を、MgSO4上で乾燥させ、濾過し、蒸発して、14.3gの茶褐色の残渣を与え、それを150〜230℃/0.1mbaでバルブ・ツー・バルブ蒸留によって精製することによって、38%GC純度(33%corr.収率)をもつ8.6gのロタンドンおよび2.3gの褐色の残渣を与えられた。
Claims (8)
- アリル酸化プロセスであって、以下:
α−グアイエンおよび鉄(III)−Xポルフィリン錯体触媒を含有する混合物をサステナブル溶媒中に形成すること、
ここでXは、Cl、Br、I、メシラート、トリフラート、およびカルボキシラートからなる群から選択され、
分子酸素を混合物中へ導入すること、ならびに
アリル酸化を生じさせ、α,β−不飽和ケトンであるロタンドンを生成すること、
を含む、前記プロセス。 - 混合物が、塩基配位化合物をさらに含有する、請求項1に記載のプロセス。
- 混合物を電磁放射線に曝露することを包含する、請求項1または2に記載のプロセス。
- サステナブル溶媒が、水、アセトン、エタノール、2−プロパノール、酢酸エチル、イソプロピルアセタート、メタノール、メチルエチルケトン、1−ブタノール、t−ブタノールおよびそれらの混合物からなる群から選択される、請求項1〜3のいずれか一項に記載のプロセス。
- サステナブル溶媒が、シクロヘキサン、ヘプタン、トルエン、メチルシクロヘキサン、メチルt−ブチルエーテル、イソオクタン、アセトニトリル、キシレン、ジメチルスルホキシド、酢酸、エチレングリコールおよびそれらの混合物からなる群から選択される、請求項1〜4のいずれか一項に記載のプロセス。
- 触媒が、塩化物対イオンを有する鉄(III)ポルフィリン錯体触媒である、請求項1〜5のいずれか一項に記載のプロセス。
- ポルフィリン錯体が、テトラフェニルポルフィリン錯体である、請求項1〜6のいずれか一項に記載のプロセス。
- 触媒が、クロロ(テトラフェニルポルフィリナト)鉄(III)およびヘミン塩化物である、請求項1〜7のいずれか一項に記載のプロセス。
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