WO2023016459A1 - 一种新型有机醇盐团聚物及其制备方法和应用 - Google Patents
一种新型有机醇盐团聚物及其制备方法和应用 Download PDFInfo
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- WO2023016459A1 WO2023016459A1 PCT/CN2022/111179 CN2022111179W WO2023016459A1 WO 2023016459 A1 WO2023016459 A1 WO 2023016459A1 CN 2022111179 W CN2022111179 W CN 2022111179W WO 2023016459 A1 WO2023016459 A1 WO 2023016459A1
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 150000004703 alkoxides Chemical class 0.000 title abstract description 6
- 239000013078 crystal Substances 0.000 claims description 179
- 150000001875 compounds Chemical class 0.000 claims description 164
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 83
- -1 ether compound Chemical class 0.000 claims description 82
- 238000006243 chemical reaction Methods 0.000 claims description 75
- 125000003118 aryl group Chemical group 0.000 claims description 74
- 125000000217 alkyl group Chemical group 0.000 claims description 71
- 125000003342 alkenyl group Chemical group 0.000 claims description 68
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 64
- 239000011734 sodium Substances 0.000 claims description 59
- 229910052757 nitrogen Inorganic materials 0.000 claims description 40
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 claims description 35
- 125000005842 heteroatom Chemical group 0.000 claims description 33
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 29
- 229910052736 halogen Inorganic materials 0.000 claims description 28
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 27
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 26
- 229910052708 sodium Inorganic materials 0.000 claims description 26
- 229910052783 alkali metal Inorganic materials 0.000 claims description 24
- 239000000460 chlorine Substances 0.000 claims description 24
- 125000001313 C5-C10 heteroaryl group Chemical group 0.000 claims description 23
- 150000002367 halogens Chemical class 0.000 claims description 22
- 125000000392 cycloalkenyl group Chemical group 0.000 claims description 21
- 125000000592 heterocycloalkyl group Chemical group 0.000 claims description 20
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 20
- 229910052801 chlorine Inorganic materials 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- 229910052799 carbon Inorganic materials 0.000 claims description 18
- 229910052760 oxygen Inorganic materials 0.000 claims description 16
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 16
- 150000001340 alkali metals Chemical class 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 15
- AZQWKYJCGOJGHM-UHFFFAOYSA-N para-benzoquinone Natural products O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- 229910052717 sulfur Inorganic materials 0.000 claims description 15
- 125000003545 alkoxy group Chemical group 0.000 claims description 14
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 14
- 125000005915 C6-C14 aryl group Chemical group 0.000 claims description 13
- 239000003153 chemical reaction reagent Substances 0.000 claims description 13
- 238000006482 condensation reaction Methods 0.000 claims description 13
- 239000011780 sodium chloride Substances 0.000 claims description 13
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 12
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 12
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 12
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 12
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 12
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 12
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 11
- 125000006717 (C3-C10) cycloalkenyl group Chemical group 0.000 claims description 10
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 claims description 10
- 229910052794 bromium Inorganic materials 0.000 claims description 10
- 125000004366 heterocycloalkenyl group Chemical group 0.000 claims description 10
- 238000000634 powder X-ray diffraction Methods 0.000 claims description 10
- UIXPTCZPFCVOQF-UHFFFAOYSA-N ubiquinone-0 Chemical compound COC1=C(OC)C(=O)C(C)=CC1=O UIXPTCZPFCVOQF-UHFFFAOYSA-N 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 9
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 9
- 235000009518 sodium iodide Nutrition 0.000 claims description 9
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 8
- 239000002585 base Substances 0.000 claims description 8
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 8
- 125000005843 halogen group Chemical group 0.000 claims description 8
- 125000001624 naphthyl group Chemical group 0.000 claims description 8
- 150000004053 quinones Chemical class 0.000 claims description 8
- 239000011775 sodium fluoride Substances 0.000 claims description 8
- 235000013024 sodium fluoride Nutrition 0.000 claims description 8
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 claims description 7
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 claims description 7
- 230000002140 halogenating effect Effects 0.000 claims description 7
- QIXDHVDGPXBRRD-UHFFFAOYSA-N 2,3,5-trimethylcyclohexa-2,5-diene-1,4-dione Chemical compound CC1=CC(=O)C(C)=C(C)C1=O QIXDHVDGPXBRRD-UHFFFAOYSA-N 0.000 claims description 6
- AIACLXROWHONEE-UHFFFAOYSA-N 2,3-dimethylcyclohexa-2,5-diene-1,4-dione Chemical compound CC1=C(C)C(=O)C=CC1=O AIACLXROWHONEE-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 6
- 125000001072 heteroaryl group Chemical group 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 claims description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical group ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 6
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 claims description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 5
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 5
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 5
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 5
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 5
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 4
- VTWDKFNVVLAELH-UHFFFAOYSA-N 2-methylcyclohexa-2,5-diene-1,4-dione Chemical compound CC1=CC(=O)C=CC1=O VTWDKFNVVLAELH-UHFFFAOYSA-N 0.000 claims description 4
- 125000006374 C2-C10 alkenyl group Chemical group 0.000 claims description 4
- MJVAVZPDRWSRRC-UHFFFAOYSA-N Menadione Chemical compound C1=CC=C2C(=O)C(C)=CC(=O)C2=C1 MJVAVZPDRWSRRC-UHFFFAOYSA-N 0.000 claims description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 229930002875 chlorophyll Natural products 0.000 claims description 4
- 235000019804 chlorophyll Nutrition 0.000 claims description 4
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 229910052740 iodine Inorganic materials 0.000 claims description 4
- KQPYUDDGWXQXHS-UHFFFAOYSA-N juglone Chemical compound O=C1C=CC(=O)C2=C1C=CC=C2O KQPYUDDGWXQXHS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 claims description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 3
- LGMPVUDVTHHFDR-UHFFFAOYSA-N 4-chloro-2-methylbut-1-ene Chemical group CC(=C)CCCl LGMPVUDVTHHFDR-UHFFFAOYSA-N 0.000 claims description 3
- NZHXEWZGTQSYJM-UHFFFAOYSA-N [bromo(diphenyl)methyl]benzene Chemical group C=1C=CC=CC=1C(C=1C=CC=CC=1)(Br)C1=CC=CC=C1 NZHXEWZGTQSYJM-UHFFFAOYSA-N 0.000 claims description 3
- ZDVDCDLBOLSVGM-UHFFFAOYSA-N [chloro(phenyl)methyl]benzene Chemical group C=1C=CC=CC=1C(Cl)C1=CC=CC=C1 ZDVDCDLBOLSVGM-UHFFFAOYSA-N 0.000 claims description 3
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical group ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 claims description 3
- 229940073608 benzyl chloride Drugs 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 claims description 3
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 claims description 3
- 230000026030 halogenation Effects 0.000 claims description 3
- 238000005658 halogenation reaction Methods 0.000 claims description 3
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 2
- 229940005561 1,4-benzoquinone Drugs 0.000 claims description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 2
- LWHDQPLUIFIFFT-UHFFFAOYSA-N 2,3,5,6-tetrabromocyclohexa-2,5-diene-1,4-dione Chemical compound BrC1=C(Br)C(=O)C(Br)=C(Br)C1=O LWHDQPLUIFIFFT-UHFFFAOYSA-N 0.000 claims description 2
- JKLYZOGJWVAIQS-UHFFFAOYSA-N 2,3,5,6-tetrafluorocyclohexa-2,5-diene-1,4-dione Chemical compound FC1=C(F)C(=O)C(F)=C(F)C1=O JKLYZOGJWVAIQS-UHFFFAOYSA-N 0.000 claims description 2
- QQQCWVDPMPFUGF-ZDUSSCGKSA-N alpinetin Chemical compound C1([C@H]2OC=3C=C(O)C=C(C=3C(=O)C2)OC)=CC=CC=C1 QQQCWVDPMPFUGF-ZDUSSCGKSA-N 0.000 claims description 2
- 125000001047 cyclobutenyl group Chemical group C1(=CCC1)* 0.000 claims description 2
- 125000000298 cyclopropenyl group Chemical group [H]C1=C([H])C1([H])* 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 2
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 2
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 125000002298 terpene group Chemical group 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
- 125000000739 C2-C30 alkenyl group Chemical group 0.000 claims 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims 2
- 239000000463 material Substances 0.000 claims 2
- WOGWYSWDBYCVDY-UHFFFAOYSA-N 2-chlorocyclohexa-2,5-diene-1,4-dione Chemical group ClC1=CC(=O)C=CC1=O WOGWYSWDBYCVDY-UHFFFAOYSA-N 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 60
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- 239000000203 mixture Substances 0.000 description 38
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- 239000007787 solid Substances 0.000 description 30
- 229910000104 sodium hydride Inorganic materials 0.000 description 28
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 17
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- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 16
- 238000000034 method Methods 0.000 description 16
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- 238000005160 1H NMR spectroscopy Methods 0.000 description 13
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- 238000002474 experimental method Methods 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- SENUUPBBLQWHMF-UHFFFAOYSA-N 2,6-dimethylcyclohexa-2,5-diene-1,4-dione Chemical compound CC1=CC(=O)C=C(C)C1=O SENUUPBBLQWHMF-UHFFFAOYSA-N 0.000 description 6
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 5
- DMBSOGFSLXMORC-UHFFFAOYSA-N CC(C)=CCC1=C(C)C(=O)C(C)=CC1=O Chemical compound CC(C)=CCC1=C(C)C(=O)C(C)=CC1=O DMBSOGFSLXMORC-UHFFFAOYSA-N 0.000 description 5
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
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- 125000001246 bromo group Chemical group Br* 0.000 description 3
- ACTIUHUUMQJHFO-UPTCCGCDSA-N coenzyme Q10 Chemical compound COC1=C(OC)C(=O)C(C\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CCC=C(C)C)=C(C)C1=O ACTIUHUUMQJHFO-UPTCCGCDSA-N 0.000 description 3
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- SHUZOJHMOBOZST-UHFFFAOYSA-N phylloquinone Natural products CC(C)CCCCC(C)CCC(C)CCCC(=CCC1=C(C)C(=O)c2ccccc2C1=O)C SHUZOJHMOBOZST-UHFFFAOYSA-N 0.000 description 3
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- BJVUJIDTICYHLL-UHFFFAOYSA-N 1-chloro-3,7,11-trimethyldodeca-2,6,10-triene Chemical compound CC(C)=CCCC(C)=CCCC(C)=CCCl BJVUJIDTICYHLL-UHFFFAOYSA-N 0.000 description 2
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- 101000860835 Homo sapiens Ubiquinone biosynthesis protein COQ9, mitochondrial Proteins 0.000 description 2
- FKUYMLZIRPABFK-UHFFFAOYSA-N Plastoquinone 9 Natural products CC(C)=CCCC(C)=CCCC(C)=CCCC(C)=CCCC(C)=CCCC(C)=CCCC(C)=CCCC(C)=CCCC(C)=CCC1=CC(=O)C(C)=C(C)C1=O FKUYMLZIRPABFK-UHFFFAOYSA-N 0.000 description 2
- 102100028230 Ubiquinone biosynthesis protein COQ9, mitochondrial Human genes 0.000 description 2
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000012454 non-polar solvent Substances 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- FKUYMLZIRPABFK-IQSNHBBHSA-N plastoquinone-9 Chemical compound CC(C)=CCC\C(C)=C\CC\C(C)=C\CC\C(C)=C\CC\C(C)=C\CC\C(C)=C\CC\C(C)=C\CC\C(C)=C\CC\C(C)=C\CC1=CC(=O)C(C)=C(C)C1=O FKUYMLZIRPABFK-IQSNHBBHSA-N 0.000 description 2
- 230000008092 positive effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 125000003003 spiro group Chemical group 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 description 2
- UUGXJSBPSRROMU-WJNLUYJISA-N ubiquinone-9 Chemical compound COC1=C(OC)C(=O)C(C\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CCC=C(C)C)=C(C)C1=O UUGXJSBPSRROMU-WJNLUYJISA-N 0.000 description 2
- 239000011712 vitamin K Substances 0.000 description 2
- 235000019168 vitamin K Nutrition 0.000 description 2
- 150000003721 vitamin K derivatives Chemical class 0.000 description 2
- 229940046010 vitamin k Drugs 0.000 description 2
- WLAUCMCTKPXDIY-JXMROGBWSA-N (2e)-1-chloro-3,7-dimethylocta-2,6-diene Chemical compound CC(C)=CCC\C(C)=C\CCl WLAUCMCTKPXDIY-JXMROGBWSA-N 0.000 description 1
- YNGDWRXWKFWCJY-UHFFFAOYSA-N 1,4-Dihydropyridine Chemical compound C1C=CNC=C1 YNGDWRXWKFWCJY-UHFFFAOYSA-N 0.000 description 1
- LOYZVRIHVZEDMW-UHFFFAOYSA-N 1-bromo-3-methylbut-2-ene Chemical compound CC(C)=CCBr LOYZVRIHVZEDMW-UHFFFAOYSA-N 0.000 description 1
- YXZFFTJAHVMMLF-UHFFFAOYSA-N 1-bromo-3-methylbutane Chemical compound CC(C)CCBr YXZFFTJAHVMMLF-UHFFFAOYSA-N 0.000 description 1
- MBWXNTAXLNYFJB-UHFFFAOYSA-N 2-methyl-3-(3,7,11,15-tetramethylhexadec-2-enyl)naphthalene-1,4-dione Chemical compound C1=CC=C2C(=O)C(CC=C(C)CCCC(C)CCCC(C)CCCC(C)C)=C(C)C(=O)C2=C1 MBWXNTAXLNYFJB-UHFFFAOYSA-N 0.000 description 1
- UVPKEFBKRJZCNA-UHFFFAOYSA-N 2-methyl-3-(3-methylbut-3-enyl)naphthalene-1,4-dione Chemical compound CC(CCC(C(C1=CC=CC=C11)=O)=C(C)C1=O)=C UVPKEFBKRJZCNA-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- KAKIDRZCDBPEDK-RMKNXTFCSA-N CC(C(C(C)=C1C/C=C/C2=CC=CC=C2)=O)=CC1=O Chemical compound CC(C(C(C)=C1C/C=C/C2=CC=CC=C2)=O)=CC1=O KAKIDRZCDBPEDK-RMKNXTFCSA-N 0.000 description 1
- QTUUMVCFSUJVTH-UHFFFAOYSA-N CC(C)=CCCC(C)=CCCC(C)=CCC(C(C=C1C)=O)=C(C)C1=O Chemical compound CC(C)=CCCC(C)=CCCC(C)=CCC(C(C=C1C)=O)=C(C)C1=O QTUUMVCFSUJVTH-UHFFFAOYSA-N 0.000 description 1
- DTTGLDIFUNZRTR-UHFFFAOYSA-N CCOC(C1)=C(C)NC(C)=C1OCC Chemical compound CCOC(C1)=C(C)NC(C)=C1OCC DTTGLDIFUNZRTR-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- DIIWSYPKAJVXBV-UHFFFAOYSA-N Hantzch dihydropyridine Natural products CCOC(=O)C1=CC(C(=O)OCC)=C(C)N=C1C DIIWSYPKAJVXBV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- ABSPRNADVQNDOU-UHFFFAOYSA-N Menaquinone 1 Natural products C1=CC=C2C(=O)C(CC=C(C)C)=C(C)C(=O)C2=C1 ABSPRNADVQNDOU-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- 125000004604 benzisothiazolyl group Chemical group S1N=C(C2=C1C=CC=C2)* 0.000 description 1
- 125000004603 benzisoxazolyl group Chemical group O1N=C(C2=C1C=CC=C2)* 0.000 description 1
- 150000004054 benzoquinones Chemical class 0.000 description 1
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 230000003851 biochemical process Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 125000002837 carbocyclic group Chemical group 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 125000002720 diazolyl group Chemical group 0.000 description 1
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 1
- LJXTYJXBORAIHX-UHFFFAOYSA-N diethyl 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1 LJXTYJXBORAIHX-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 125000003453 indazolyl group Chemical group N1N=C(C2=C1C=CC=C2)* 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910001502 inorganic halide Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000005956 isoquinolyl group Chemical group 0.000 description 1
- 125000001786 isothiazolyl group Chemical group 0.000 description 1
- 125000000842 isoxazolyl group Chemical group 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000001208 nuclear magnetic resonance pulse sequence Methods 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- MBWXNTAXLNYFJB-NKFFZRIASA-N phylloquinone Chemical compound C1=CC=C2C(=O)C(C/C=C(C)/CCC[C@H](C)CCC[C@H](C)CCCC(C)C)=C(C)C(=O)C2=C1 MBWXNTAXLNYFJB-NKFFZRIASA-N 0.000 description 1
- 239000011772 phylloquinone Substances 0.000 description 1
- 235000019175 phylloquinone Nutrition 0.000 description 1
- 229960001898 phytomenadione Drugs 0.000 description 1
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 1
- 238000001144 powder X-ray diffraction data Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 125000004151 quinonyl group Chemical group 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000000373 single-crystal X-ray diffraction data Methods 0.000 description 1
- 238000000235 small-angle X-ray scattering Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 125000001113 thiadiazolyl group Chemical group 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- YXFVVABEGXRONW-JGUCLWPXSA-N toluene-d8 Chemical compound [2H]C1=C([2H])C([2H])=C(C([2H])([2H])[2H])C([2H])=C1[2H] YXFVVABEGXRONW-JGUCLWPXSA-N 0.000 description 1
- 150000003613 toluenes Chemical class 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- JBWKIWSBJXDJDT-UHFFFAOYSA-N triphenylmethyl chloride Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(Cl)C1=CC=CC=C1 JBWKIWSBJXDJDT-UHFFFAOYSA-N 0.000 description 1
- SOECUQMRSRVZQQ-UHFFFAOYSA-N ubiquinone-1 Chemical compound COC1=C(OC)C(=O)C(CC=C(C)C)=C(C)C1=O SOECUQMRSRVZQQ-UHFFFAOYSA-N 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000011728 vitamin K2 Substances 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
- 229940041603 vitamin k 3 Drugs 0.000 description 1
Images
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- 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
-
- C—CHEMISTRY; METALLURGY
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- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B37/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving either the formation of a carbon-to-carbon bond between two carbon atoms not directly linked already or the disconnection of two directly linked carbon atoms
- C07B37/04—Substitution
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- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/68—Preparation of metal alcoholates
- C07C29/70—Preparation of metal alcoholates by converting hydroxy groups to O-metal groups
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- C07C31/28—Metal alcoholates
- C07C31/30—Alkali metal or alkaline earth metal alcoholates
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- C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C33/02—Acyclic alcohols with carbon-to-carbon double bonds
- C07C33/025—Acyclic alcohols with carbon-to-carbon double bonds with only one double bond
- C07C33/03—Acyclic alcohols with carbon-to-carbon double bonds with only one double bond in beta-position, e.g. allyl alcohol, methallyl alcohol
-
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C33/05—Alcohols containing rings other than six-membered aromatic rings
- C07C33/14—Alcohols containing rings other than six-membered aromatic rings containing six-membered rings
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C33/18—Monohydroxylic alcohols containing only six-membered aromatic rings as cyclic part
- C07C33/20—Monohydroxylic alcohols containing only six-membered aromatic rings as cyclic part monocyclic
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- C07C33/18—Monohydroxylic alcohols containing only six-membered aromatic rings as cyclic part
- C07C33/24—Monohydroxylic alcohols containing only six-membered aromatic rings as cyclic part polycyclic without condensed ring systems
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07—ORGANIC CHEMISTRY
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- C07C35/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring
- C07C35/02—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring monocyclic
- C07C35/08—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring monocyclic containing a six-membered rings
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- C07C35/22—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring polycyclic, at least one hydroxy group bound to a condensed ring system
- C07C35/37—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring polycyclic, at least one hydroxy group bound to a condensed ring system with a hydroxy group on a condensed system having three rings
- C07C35/38—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring polycyclic, at least one hydroxy group bound to a condensed ring system with a hydroxy group on a condensed system having three rings derived from the fluorene skeleton
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- C—CHEMISTRY; METALLURGY
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- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/64—Preparation of O-metal compounds with O-metal group bound to a carbon atom belonging to a six-membered aromatic ring
- C07C37/66—Preparation of O-metal compounds with O-metal group bound to a carbon atom belonging to a six-membered aromatic ring by conversion of hydroxy groups to O-metal groups
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- C07C39/235—Metal derivatives of a hydroxy group bound to a six-membered aromatic ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07C46/00—Preparation of quinones
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C50/00—Quinones
- C07C50/02—Quinones with monocyclic quinoid structure
- C07C50/06—Quinones with monocyclic quinoid structure with unsaturation outside the quinoid structure
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C50/00—Quinones
- C07C50/10—Quinones the quinoid structure being part of a condensed ring system containing two rings
- C07C50/14—Quinones the quinoid structure being part of a condensed ring system containing two rings with unsaturation outside the ring system, e.g. vitamin K1
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C50/00—Quinones
- C07C50/26—Quinones containing groups having oxygen atoms singly bound to carbon atoms
- C07C50/28—Quinones containing groups having oxygen atoms singly bound to carbon atoms with monocyclic quinoid structure
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D323/00—Heterocyclic compounds containing more than two oxygen atoms as the only ring hetero atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/54—Organic compounds
Definitions
- the invention relates to a novel organic alkoxide aggregate and its preparation method and application.
- Coenzyme Q10, vitamin K, plastoquinone and other compounds containing quinone functional groups are electron transfer carriers in eukaryotic respiration, photosynthesis and other biochemical processes.
- coenzyme Q10 and vitamin K family are indispensable vitamins in the human body and have positive effects on organs and tissues such as the heart and bones.
- the food sources of these vitamins are limited, so chemical synthesis is an important source of them, and the successful synthesis method The market potential is huge.
- the classic method of synthesizing quinone compounds generally starts with raw materials such as phenol and aryl ether, and carries out side chain modification through functionalization reactions such as Lewis acid and metal-catalyzed coupling, and then deprotects and oxidizes the aryl ether.
- the reaction uses more catalysts, protecting group reagents and oxidants, and the steps are longer and the efficiency is not high.
- the technical problem to be solved by the present invention is the defect that the existing catalysts for catalyzing the synthesis of alkenyl quinone compounds have fewer types. Therefore, the present invention provides a novel organic alkoxide aggregate and its preparation method and application. Under the catalysis of the novel organic alkoxide aggregate of the invention, quinone compounds containing alkenyl side chains can be prepared in high yield.
- the present invention provides a compound as shown in formula I:
- R is adamantyl, C 6-14 aryl, C 6-14 aryl substituted by one or more R -1 , 5-10 membered heteroaryl, substituted by one or more R -2 5-10 membered heteroaryl or
- the heteroatoms in the 5-10 membered heteroaryl group or the heteroatoms in the 5-10 membered heteroaryl group substituted by one or more R -2 are one or more of N, S and O, The number is 1, 2 or 3;
- R -1 and R -2 are independently C 1-6 alkyl
- R 1 , R 2 and R 3 are independently H, C 1-10 alkyl, C 1-10 alkyl substituted by one or more R 1-1 (when there are multiple R 1-1 , R 1 - 1 is the same or different), C 6-14 aryl, C 6-14 aryl substituted by one or more R 1-2 (when R 1-2 is multiple, R 1-2 is the same or different) , C 3-6 cycloalkyl, C 3-6 cycloalkenyl, C 3-6 cycloalkenyl substituted by one or more R 1-3 (when there are multiple R 1-3 , R 1-3 same or different), C 2-40 alkenyl, C 1-10 alkoxy, 5-10 membered heteroaryl, 3-6 membered heterocycloalkyl or 3-6 membered heterocycloalkenyl; the 5 - the heteroatoms in the 10-membered heteroaryl, the heteroatoms in the 3-6-membered heterocycloalkyl and the heteroatoms in the 3-6-membered heterocycl
- the heteroatoms in , the heteroatoms in the 3-6 membered heterocycloalkyl and the heteroatoms in the 3-6 membered heterocycloalkenyl are independently one or more of N, S and O, and the number is 1 , 2 or 3;
- R 1-1-1 , R 1-1-2 , R 1-1-3 , R 1-1-4 and R 1-1-5 are independently H or C 1-6 alkyl;
- any two of R 1 , R 2 and R 3 together form a C 3-6 cycloalkyl group, a C 3-6 cycloalkyl group substituted by one or more R 1-4 , 3-6 Membered heterocycloalkyl, or 3-6 membered heterocycloalkyl substituted by one or more R 1-5 ; said 3-6 membered heterocycloalkyl and or substituted by one or more R 1-5
- the heteroatoms in the 3-6 membered heterocycloalkyl group are independently one or more of N, S and O, and the number is 1, 2 or 3;
- the heteroatoms in the 3-6 membered heterocycloalkyl group and the heteroatoms in the 3-6 membered heterocyclenyl group are independently one or more of N, S and O, and the number is 1, 2 or 3 ;
- R 1-4-1 , R 1-4-2 , R 1-4-3 , R 1-4-4 and R 1-4-5 are independently H or C 1-6 alkyl;
- Z is an alkali metal
- Y is an alkali metal or an ether compound-alkali metal complex (the ether compound-alkali metal complex is a complex formed between an ether compound and an alkali metal);
- the ether compound in the ether compound-alkali metal complex is a C 2-18 ether compound or a C 12-18 crown ether compound;
- Q is independently H, halogen or -B(C 6-14 aryl) 4 (when Q is 2, Q can be the same or different);
- n and n are 1 or 2 independently.
- O is an oxygen atom.
- the compound represented by formula I is an agglomeration compound (also called a cluster compound).
- the compound shown in formula I can be described as the compound shown in formula I or the solution containing the compound shown in formula I (for example, can contain the compound shown in formula I The reaction solution of the indicated compound was used as it is).
- the compound represented by formula I has an icosahedral three-dimensional structure.
- the compound shown in formula I forms the following three-dimensional structure: the O atom is at the apex of the regular icosahedron, and Q is located at the regular icosahedron At the body center of the icosahedron, Y is located at the face center of the icosahedron (Y can migrate on different face centers of the icosahedron, and the position of Y is not fixed on a certain face center of the icosahedron) .
- the compound shown in formula I forms the following three-dimensional structure: the O atom is at the apex of the regular icosahedron, and one Q is located at the regular two The body center of the decahedron, the other is located outside the icosahedron, and Y is respectively located at the face centers of any two of the icosahedrons (Y can migrate on different face centers of the icosahedron, The position of Y is not fixed on the face center of a regular icosahedron).
- the C 6-14 aryl group and the C 6-14 aryl group in the C 6-14 aryl group substituted by one or more R -1 are independently benzene base, naphthyl, anthracenyl or
- the C 1-6 alkyl groups are independently methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, iso Butyl or tert-butyl.
- the C 6-14 aryl in the C 6-14 aryl substituted by one or more R -1 is
- the C 1 in the C 1-10 alkyl and the C 1-10 alkyl substituted by one or more R 1-1 -10 alkyl is independently C1-7 alkyl, and can also be methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl , n-hexyl or n-heptyl.
- C 6 in the C 6-14 aryl group and the C 6-14 aryl group substituted by one or more R 1-2 -14Aryl is independently phenyl, naphthyl or anthracenyl.
- the C 3-6 cycloalkyl is independently cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
- in the C 3-6 cycloalkenyl and the C 3-6 cycloalkenyl substituted by one or more R 1-3 C 3-6 cycloalkenyl is independently cyclopropenyl, cyclobutenyl, cyclopentenyl or cyclohexenyl.
- the C 2-40 alkenyl is independently a C 5-40 alkenyl, which may further be
- the C 6-14 aryl groups are independently phenyl, naphthyl or anthracenyl.
- the C 1-6 alkyl groups are independently methyl, ethyl, n-propyl, isopropyl, n-butyl base, sec-butyl, isobutyl or tert-butyl.
- the C 1-6 alkane are independently methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl.
- the C 1-10 alkyl substituted by one or more R 1-1 is
- the C 3-6 cycloalkenyl substituted by one or more R 1-3 is
- R 1 , R 2 and R 3 when any two of R 1 , R 2 and R 3 together form a C 3-6 cycloalkyl group or a C 3-6 cycloalkane substituted by one or more R 1-4 with its attached C
- the C 3-6 cycloalkyl group and the C 3-6 cycloalkyl group in the C 3-6 cycloalkyl group substituted by one or more R 1-4 are independently cyclopropyl , cyclobutyl, cyclopentyl or cyclohexyl.
- the C 1-6 alkyl is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl , isobutyl or tert-butyl.
- R 1 , R 2 and R 3 when any two of R 1 , R 2 and R 3 form a C 3-6 cycloalkyl group substituted by one or more R 1-4 together with the C to which they are attached, said one or multiple R 1-4 substituted C 3-6 cycloalkyl groups are
- the alkali metal is Li, Na or K, such as Na.
- the alkali metal in the alkali metal and the ether compound-alkali metal complex is independently Li, Na or K, such as Na.
- n 1
- m is 2 and n is 2.
- the C2-8 ether compound is methyl ether, diethyl ether, n-propyl ether or n-butyl ether, For example methyl ether.
- the C 12-18 crown ether compound is 12-crown (ether)-4, 15- Crown(ether)-5 or 18-crown(ether)-6, eg 15-crown(ether)-5.
- the halogen is F, Cl, Br or I.
- the C 6-14 aryl in -B(C 6-14 aryl) 4 is independently phenyl, naphthyl or phenanthrenyl, such as phenyl.
- the -B(C 6-14 aryl) 4 is -B(phenyl) 4 .
- R is adamantyl, C 6-14 aryl, C 6-14 aryl substituted by one or more R -1 or
- R -1 is C 1-6 alkyl.
- R 1 , R 2 and R 3 are independently H, C 1-10 alkyl, C 1-10 alkyl substituted by one or more R 1-1 , C 6-14 aryl , C 6-14 aryl substituted by one or more R 1-2 , C 3-6 cycloalkyl, C 3-6 cycloalkenyl, C 3-6 substituted by one or more R 1-3 Cycloalkenyl or C 2-40 alkenyl;
- any two of R 1 , R 2 and R 3 together with their attached C form a C 3-6 cycloalkyl group or a C 3-6 cycloalkyl group substituted by one or more R 1-4 .
- R 1-1 is C 6-14 aryl or hydroxy.
- R 1-2 is C 1-6 alkyl.
- R 1-3 is C 1-6 alkyl.
- R 1-4 is C 1-6 alkyl.
- Q is independently halogen, H, or -B(C 6-14 aryl) 4 .
- the general formula of the compound shown in formula I is as shown in formula I-1:
- the general formula of the compound shown in formula I is as shown in formula I-1:
- Y is an ether compound-alkali metal complex
- Q is independently halogen or H.
- the general formula of the compound shown in formula I is formula I-2:
- Y is alkali metal; one of Q is -B(C 6-14 aryl) 4 , and the other is H or halogen.
- R is adamantyl, C 6-14 aryl, C 6-14 aryl substituted by one or more R -1 or
- R -1 is C 1-6 alkyl
- R 1 , R 2 and R 3 are independently H, C 1-10 alkyl, C 1-10 alkyl substituted by one or more R 1-1 , C 6-14 aryl, one or more C 6-14 aryl substituted by R 1-2 , C 3-6 cycloalkyl, C 3-6 cycloalkenyl, C 3-6 cycloalkenyl substituted by one or more R 1-3 or C 2 -40 alkenyl, and R 1 , R 2 and R 3 are not H at the same time; or, any two of R 1 , R 2 and R 3 form a C 3-6 cycloalkyl group together with the C connected to it or are replaced by one or Multiple R 1-4 substituted C 3-6 cycloalkyl;
- R 1-1 is C 6-14 aryl or hydroxyl
- R 1-2 is C 1-6 alkyl
- R 1-3 is C 1-6 alkyl
- R 1-4 is C 1-6 alkyl
- Q is independently halogen, H or -B(C 6-14 aryl) 4 .
- the compound represented by formula I is any one of the following compounds:
- the present invention provides a preparation method of a compound shown in formula I, which comprises the following steps: in the presence of NaH or a halogenating agent, compound ZOR and compound II are reacted in a solvent according to the following formula to obtain the A compound as shown in formula I;
- the halogenation reagent is tetrahalobenzoquinone, methyl halide substituted by 1, 2 or 3 R 4 , carbon tetrahalide, C 3-6 cycloalkenyl methyl halide or sodium halide;
- R 4 is phenyl or phenyl C 2-30 alkenyl (such as C 2-4 alkenyl, such as isobutylene) substituted by 1, 2 or 3 R 4-1 ;
- R 4-1 is halogen, C 1-10 alkyl or C 1-10 alkoxy
- the compound II is a C 2-18 ether compound, a C 12-18 crown ether compound, Z[Ph 4 B] or does not exist;
- the temperature of the reaction is 60-300°C;
- the tetrahaloquinone is preferably tetrachlorobenzoquinone, tetrabromobenzoquinone, tetraiodobenzoquinone or tetrafluorobenzoquinone.
- the methyl halide substituted by 1, 2 or 3 R4 is preferably trityl bromide, benzhydryl chloride, benzyl chloride or isopentenyl chloride.
- said carbon tetrahalide is carbon tetrachloride or carbon tetrabromide.
- the sodium halide is preferably sodium chloride, sodium bromide, sodium iodide or sodium fluoride.
- the molar ratio of the "NaH or halogenating reagent" to the compound ZOR can be the conventional molar ratio of this type of reaction in the art.
- Z is Na
- the ratio of NaH to ZOR does not need additional restrictions.
- the molar ratio of the ZOR to the halogen atom in the halogenation reagent is preferably 20:1-1:1, for example 10:8.
- the compound II in the presence of NaH, is a C 2-18 ether compound, a C 12-18 crown ether compound, Z[Ph 4 B].
- the compound II in the presence of a halogenating agent, is a C 2-18 ether compound, a C 12-18 crown ether compound or does not exist.
- the molar ratio of the compound II to the compound ZOR can be a conventional molar ratio for this type of reaction in the art, preferably 1:5-1:20, such as 0.2:1.
- the solvent may be a conventional solvent for this type of reaction in the art, preferably a non-polar solvent.
- a non-polar solvent is preferably aromatic hydrocarbon solvent (such as chlorobenzene or toluene), alkane solvent (such as n-hexane, n-octane or cyclohexane), ether solvent (such as THF or DME) and organic amines
- aromatic hydrocarbon solvent such as chlorobenzene or toluene
- alkane solvent such as n-hexane, n-octane or cyclohexane
- ether solvent such as THF or DME
- organic amines such as triethylamine or pyridine
- solvents such as triethylamine or pyridine
- the temperature of the reaction is preferably 80-120°C.
- the progress of the reaction can be monitored by conventional methods in the art (such as nuclear magnetic resonance (such as carbon spectrum, hydrogen spectrum, sodium spectrum, fluorine spectrum), TLC, GC-MS, LC-MS).
- the reaction time is preferably 1-600 hours, such as 5 hours, 8 hours or 48 hours.
- the present invention also provides a compound represented by formula I prepared according to the above-mentioned preparation method of the compound represented by formula I.
- the structure of the single crystal of the compound represented by formula I-a is preferably basically as shown in FIG. 1 .
- the structure of the single crystal of the compound represented by formula I-b is preferably as shown in FIG. 2 .
- the structure of the single crystal of the compound shown in formula I-c is preferably basically as shown in Figure 3;
- the X-ray powder diffraction pattern of the single crystal of the compound represented by formula I-c is preferably substantially as shown in FIG. 13 .
- the structure of the single crystal of the compound represented by formula I-d is preferably as shown in FIG. 5 .
- the structure of the single crystal of the compound represented by formula I-e is preferably as shown in FIG. 6 .
- the structure of the single crystal of the compound represented by formula I-f is preferably as shown in FIG. 7 .
- the structure of the single crystal of the compound represented by formula I-g is preferably as shown in FIG. 8 .
- the structure of the single crystal of the compound represented by formula I-h is preferably as shown in FIG. 9 .
- the structure of the single crystal of the compound represented by formula I-i is preferably shown in FIG. 10 .
- the present invention also provides the application of a substance A as a catalyst in the preparation of quinone compounds;
- the substance A is selected from the above-mentioned compound shown in formula I, the above-mentioned single crystal of the compound shown in formula Ia, The above-mentioned single crystal of the compound shown in formula Ib, the above-mentioned single crystal of the compound shown in formula Ic, the above-mentioned single crystal of the compound shown in formula Id, the above-mentioned single crystal of the compound shown in formula Ie crystal, the above-mentioned single crystal of the compound represented by the formula If, the above-mentioned single crystal of the compound represented by the formula Ig, the above-mentioned single crystal of the compound represented by the formula Ih and the above-mentioned compound represented by the formula Ii One or more of the single crystals; the quinone compound contains an alkenyl side chain (the side chain refers to the substituent on the parent body of the quinone compound, for example ,
- the preparation method of the quinone compound includes the following steps: under the catalysis of the above-mentioned substance A, the compound shown in formula IV and the compound shown in formula V are condensed to obtain the compound shown in formula
- the quinone compounds shown in III (abbreviated formula III compound) get final product
- R 1a , R 2a and R 3a are independently hydrogen, C 1-10 alkyl, C 2-10 alkenyl or C 1-10 alkoxy;
- R 2a , R 3a and the carbon atoms connected to them together form a C 6-10 aryl group, a C 6-10 aryl group substituted by one or more hydroxyl groups, or a 5-10 membered heteroaryl group;
- the heteroatoms in the heteroaryl group are selected from one or more of N, O and S, and the number of heteroatoms is 1, 2 or 3;
- R 6a is C 3-100 alkenyl, C 3-100 alkenyl substituted by one or more R 6a-1 , or, C 3-10 cycloalkenyl;
- R 6a-1 is independently a C 6-10 aryl group or a 5-10 membered heteroaryl group; the heteroatom in the heteroaryl group is selected from one or more of N, O and S, and the heteroatom The number of is 1, 2 or 3;
- X is halogen
- the C 1-10 alkyl groups are independently methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, Isobutyl or tert-butyl, eg methyl.
- the C 2-10 alkenyl is independently a C 2-5 alkenyl, such as 3-methyl-2-buten-1-yl
- the C 1-10 alkoxy group is independently methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy , sec-butoxy, isobutoxy or tert-butoxy, such as methoxy.
- the C 6-10 aryl group is phenyl
- the C 6-10 aryl group is phenyl.
- the C 3-100 alkenyl and the C 3-100 alkenyl in the C 3-100 alkenyl substituted by one or more R 6a-1 independently contain 1 ⁇ 15 double bonds, can also contain 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 double bonds;
- one of the double bonds is located between the ⁇ -position and the ⁇ -position of X.
- the C 3-100 alkenyl and the C 3-100 alkenyl in the C 3-100 alkenyl substituted by one or more R 6a-1 are independently C 5
- the terpene group of -100 can also be n is 0 ⁇ 19 (such as 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18 or 19, also such as 0 , 1, 2, 3, 4, 5, 6, 7, 8 or 9)".
- the C 3-100 alkenyl and the C 3-100 alkenyl in the C 3-100 alkenyl substituted by one or more R 6a-1 are independently C 3 ⁇ C 50 alkenyl, can also be C 3 alkenyl, C 4 alkenyl, C 5 alkenyl, C 6 alkenyl, C 7 alkenyl, C 8 alkenyl, C 9 alkenyl C 10 alkenyl, C 15 alkenyl, C 20 alkenyl, C 30 alkenyl, C 40 alkenyl, C 45 alkenyl or C 50 alkenyl, more can be allyl , 2-buten-1-yl 3-Methyl-2-buten-1-yl 2-Hexen-1-yl (All-E)-3,7-Dimethyl-2,6-octadien-1-yl (All-E)-3,7,11-trimethyl-2,6,10-dodecatrien-1-yl Chlorophyll
- the C 3-10 cycloalkenyl is a C 3-10 cycloalkenyl, and may also be 2-cyclohexen-1-yl
- the number of C 3-100 alkenyl groups substituted by one or more R 6a-1 is 2 or 3.
- the C 6-10 aryl is phenyl.
- the C 3-100 alkenyl substituted by one or more R 6a-1 is a C 3 -C 50 alkenyl substituted by one R 6-1 , and it can also be 3-phenyl-2-propen-1-yl
- the C 3-10 cycloalkenyl group contains 1 to 5 double bonds, and may also contain 1, 2, 3, 4 or 5 double bonds;
- one of the double bonds is located between the ⁇ -position and the ⁇ -position of X.
- the C 3-10 cycloalkenyl is a C 3 -C 6 cycloalkenyl, such as 2-cyclohexen-1-yl
- the halogen is chlorine, bromine or iodine, and can also be chlorine or bromine.
- R 1a is hydrogen, C 1-10 alkyl, or C 1-10 alkoxy.
- R 2a is hydrogen, C 1-10 alkyl, or C 1-10 alkoxy
- R 3a is hydrogen, C 1-10 alkyl or C 1-10 alkoxy
- R 2a , R 3a and the carbon atoms connected to them together form a C 6-10 aryl group, or a C 6-10 aryl group substituted by one or more hydroxyl groups.
- R 6a is C 3-100 alkenyl.
- R 6a is chlorophyll or n is 0 to 9 (for example, 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9).
- R 6a-1 is independently C 6-10 aryl.
- R 1a is hydrogen, C 1 -C 10 alkyl, or C 1 -C 10 alkoxy
- R 2a is hydrogen, C 1 -C 10 alkyl or C 1 -C 10 alkoxy
- R 3a is hydrogen, C 1 -C 10 alkyl or C 1 -C 10 alkoxy
- R 2a , R 3a and the carbon atoms connected to them together form a C 6-10 aryl group, or a C 6-10 aryl group substituted by one or more hydroxyl groups;
- R 6a is C 3-100 alkenyl
- X is halogen
- the compound represented by formula II is 1,4-benzoquinone, 2-methyl-1,4-benzoquinone, 2,3-dimethyl-1,4-benzoquinone , 2,3,5-trimethyl-1,4-benzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2-methyl-1,4-naphthoquinone or 5-hydroxy-1,4-naphthoquinone.
- R 6a is 3-methyl-2-buten-1-yl (All-E)-3,7-Dimethyl-2,6-octadien-1-yl (All-E)-3,7,11-trimethyl-2,6,10-dodecatrien-1-yl Chlorophyll (All-E)-3,7,11,15-Tetramethyl-2,6,10,14-Hexadecatetraen-1-yl (All-E)-3,7,11,15,19,23,27-heptamethyl-2,6,10,14,18,22,26-octadecaheptaen-1-yl (All-E)-3,7,11,15,19,23,27,31,35-nonamethyl-2,6,10,14,18,22,26,30,34-hexadecyl Nonen-1-yl or (all-E)-3,7,11,15,19,23,27,31,35,39-decamethyl-2,6,10,14,
- the compound shown in formula III is any of the following structures:
- the molar ratio of the substance A to the compound represented by formula IV is (0.05-0.30):1, such as 0.15:1.
- the condensation reaction is carried out in an alkaline reagent (such as sodium hydride (60% sodium hydride-mineral oil)) and in presence.
- an alkaline reagent such as sodium hydride (60% sodium hydride-mineral oil)
- the condensation reaction can have the following reaction parameters: the condensation reaction is carried out in the presence of a protective gas (such as nitrogen); the condensation reaction is carried out in an alkaline reagent (such as sodium hydride (60 % sodium hydride-mineral oil)) exists, the molar ratio of the alkaline reagent and the compound shown in formula IV is (1-3): 1 (for example 1: 1) described condensation
- the reaction is carried out in an organic solvent, and the organic solvent is a halogenated aromatic hydrocarbon solvent (such as chlorobenzene or o-dichlorobenzene), and the molar volume ratio of the compound shown in formula IV to the organic solvent is 0.1mol/L ⁇ 0.3mol/L; the condensation reaction is still carried out in the presence of the The molar ratio to the compound shown in formula IV is (0.025 ⁇ 0.10): 1 (for example (0.05 ⁇ 0.10): 1); the molar ratio of the compound shown in formula V to the compound shown in formula IV The ratio is (0.2-2.0): 1
- each term has the following meanings:
- plurality refers to 2, 3, 4 or 5 species.
- halogen refers to fluorine, chlorine, bromine or iodine.
- hydrocarbyl refers to a group formed by the loss of one hydrogen atom of a hydrocarbon.
- alkyl refers to a saturated straight or branched chain hydrocarbon group containing 1 or more carbon atoms.
- An alkyl group containing n carbon atoms is represented by C n , and C m to C n represent that the alkyl group contains at least m and at most n carbon atoms.
- Representative saturated straight-chain alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, n-butyl, n-pentyl, etc.; representative saturated branched-chain alkyl groups include isopropyl, isobutyl, sec-butyl Base, tert-butyl, isopentyl, neopentyl, etc.
- cycloalkyl refers to a saturated monocyclic or polycyclic (eg, spiro, fused or bridged) alkyl group, which may have 3-10 ring carbon atoms, or may have 3-6 ring carbon atoms.
- cycloalkyl groups include, but are not limited to, adamantyl, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.
- alkoxy refers to -O-(alkyl), wherein “alkyl” is an alkyl group as defined above.
- alkenyl refers to an unsaturated straight or branched chain hydrocarbon group containing one or more double bonds and multiple carbon atoms.
- Representative straight chain alkenyl groups include, but are not limited to, ethenyl, propenyl, allyl, and the like.
- cycloalkenyl refers to an unsaturated (but not aromatic), monocyclic or polycyclic (e.g. spiro, fused or bridged) ring containing one or more double bonds and multiple carbon atoms Hydrocarbyl.
- Representative cycloalkenyl groups include, but are not limited to, cyclopentenyl, cyclohexenyl, and the like.
- aryl refers to an aromatic carbocyclic group of 6-14 carbon atoms, having a single ring (eg, phenyl) or multiple fused rings (eg, naphthyl or anthracenyl). When it is polycyclic, at least one ring is aromatic, for example
- heteroaryl refers to an aromatic group containing 1, 2 or 3 5-6 membered monocyclic or 9-10 membered bicyclic rings (such as fused or bridged rings) independently selected from nitrogen, oxygen and sulfur , when it is bicyclic, at least one ring is aromatic, including but not limited to furyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, thienyl, isoxazolyl, oxazolyl, diazolyl, imidazolyl, pyrrolyl, pyrazolyl, triazolyl, thiazolyl, isothiazolyl, thiadiazolyl, benzimidazolyl, indolyl, indazolyl, benzothiazolyl, benzisothiazolyl, Benzazolyl, benzisoxazolyl, quinolinyl, isoquinolyl, etc.
- the reagents and raw materials used in the present invention are all commercially available.
- the positive and progressive effect of the present invention is that: the catalyst of the present invention can be used to obtain alkenyl-containing quinone compounds in high yield.
- Fig. 1 is the X-ray single crystal diffraction figure of embodiment 1.
- Figure 2 is the X-ray single crystal diffraction pattern of Example 2.
- Figure 3 is the X-ray single crystal diffraction pattern of Example 3.
- Fig. 4 is the diffusion order spectrogram of embodiment 3.
- FIG. 5 is an X-ray single crystal diffraction pattern of Example 4.
- FIG. 6 is an X-ray single crystal diffraction pattern of Example 5.
- FIG. 7 is an X-ray single crystal diffraction pattern of Example 6.
- FIG. 8 is an X-ray single crystal diffraction pattern of Example 7.
- FIG. 9 is an X-ray single crystal diffraction pattern of Example 8.
- FIG. 10 is an X-ray single crystal diffraction pattern of Example 9.
- FIG. 11 is the diffusion sequence diagram of Example 10.
- FIG. 12 is a diffusion sequence diagram of Example 11.
- Fig. 13 is the PXRD spectrogram of embodiment 3; Wherein, figure a represents the PXRD test spectrogram of embodiment 3, and figure b is the PXRD simulation of embodiment 3.
- the compound shown in formula I can be characterized by the following means: X-ray single crystal diffraction, infrared spectrum, Raman spectrum, ultraviolet spectrum, solid nuclear magnetic, diffusion sequence nuclear magnetic resonance spectrum, thermogravimetric analysis, powder X-ray diffraction , Small angle X-ray scattering.
- Diffusion sequence NMR spectroscopy (DOSY) measurements were performed on a Bruker Avance 500MHz spectrometer equipped with a 1/10 large pulsed gradient unit and a 298K direct probe.
- the parameters of the LED pulse sequence (ledbpgp2s) used for the diffusion experiment are as follows: the duration of the sinusoidal pulse gradient is 1.5-2.0ms, the value of ⁇ (P30) gradually increases from 0.842 to 40.014Gcm-1, and the measurement step is 16 or 21 steps .
- the pulse gradient interval ⁇ (D20) is 50ms, the disturbance gradient (P19) is 600 ⁇ s, and the eddy current delay (D21) is 5ms.
- (NaOt-Bu) 12 NaH Heat a small amount of NaH in 0.1ml DME until the solution boils and then cool, then add 0.20g NaOt-Bu (2.08mmol, 1.0eq.), 2.5mL anhydrous PhCl into the above 4mL vial and seal it . The vial was then heated to 100°C for 30 minutes until all solids were substantially dissolved. Then the temperature was raised to 120° C. and DME was distilled off, and then left to stand until crystals precipitated.
- 1,4-tetrafluorobenzoquinone, 1,4-tetrachlorobenzoquinone, 1,4-tetrabromobenzoquinone, 1,4-tetraiodobenzoquinone in the above-mentioned examples 1-4 can be aryl methyl halide (such as trityl haloalkane, benzhydryl haloalkane, benzyl haloalkane, etc.), carbon tetrahalide, allyl haloalkane (such as isopentenyl haloalkane, geranyl haloalkane, phytyl haloalkane, 2- Cyclohexenyl halide, etc.), sodium halide and other organic and inorganic halides are substituted to prepare (NaOt-Bu) 12 NaX containing the corresponding halogen X.
- aryl methyl halide such as trityl haloalkan
- the temperature may be 60-300° C., and the time may be 0.5-6 hours.
- Trityl chloride NaOt-Bu
- Trityl bromide NaOt-Bu
- Benzhydryl chloride NaOt-Bu 12 NaCl Benzyl chloride (NaOt-Bu) 12 NaCl Isopentenyl chloride (NaOt-Bu) 12 NaCl carbon tetrachloride (NaOt-Bu) 12 NaCl carbon tetrabromide (NaOt-Bu) 12 NaBr Sodium chloride (NaOt-Bu) 12 NaCl sodium bromide (NaOt-Bu) 12 NaBr sodium iodide (NaOt-Bu) 12 NaI sodium fluoride (NaOt-Bu) 12 NaF
- Embodiment 6 is a diagrammatic representation of Embodiment 6
- [DME-Na][(NaOt-Bu) 12 H] Heat a small amount of NaH in 0.1ml DME until the solution boils and cool, then add 0.20g NaOt-Bu (2.08mmol, 1.0eq.), 2.5mL anhydrous PhCl was added to the above 4 mL vial and sealed. The vial was then heated to 100°C for 30 minutes until all solids were substantially dissolved. After X-ray crystallography, the structural formula of the obtained crystal is [DME-Na][(NaOt-Bu) 12 H], wherein the O atom is at the apex of the icosahedron, and the H is at the body center of the icosahedron.
- Embodiment 7 is a diagrammatic representation of Embodiment 7:
- the structure is [15-crown-5-Na][(NaOt-Bu) 12 H], in which the O atom is at the apex of the regular icosahedron, and the H is at the apex of the regular icosahedron.
- the compound shown in formula I is prepared first.
- the amount of the compound shown in formula I is determined by the amount of alcohol used in the compound shown in formula I.
- the cluster solution is prepared by heating with alcohol, NaH, halogen source, and solvent, add 2,6-di Methyl-3,5-bis(ethoxyacyl)-1,4-dihydropyridine (Hantzsch Ester, HE), quinone, allyl haloalkane, react at a suitable temperature to obtain the product.
- HE 2,6-di Methyl-3,5-bis(ethoxyacyl)-1,4-dihydropyridine
- quinone allyl haloalkane
- reaction solution was placed in a centrifuge tube and centrifuged at 10,000 rpm for 2 minutes, and the supernatant was taken and subjected to column chromatography with petroleum ether: ethyl acetate mixture to obtain 2,6-dimethyl-3-(3- Methyl-2-buten-1-yl)-p-benzoquinone 97 mg, yield 95%. Yellow oily liquid.
- the cluster compound formed in Table 12 is used as a catalyst to prepare 2,6-dimethyl-3-(3-methyl-2-buten-1-yl)-p-benzoquinone, and other reaction conditions and operations are implemented with the application example 1.
- the cluster compound formed in Table 15 is used as a catalyst to prepare 2,6-dimethyl-3-(3-methyl-2-buten-1-yl)-p-benzoquinone, and other reaction conditions and operations are implemented with the application example 1.
- the cluster compound formed in Table 16 is used as a catalyst to prepare 2,6-dimethyl-3-(3-methyl-2-buten-1-yl)-p-benzoquinone, and other reaction conditions and operations are implemented with the same application example 1.
- Example 1 Using Example 1 to obtain the catalyst, the following examples investigate the catalytic effect of the catalyst on different substrates.
- reaction solution was placed in a centrifuge tube and centrifuged at 10,000 rpm for 2 minutes, and the supernatant was taken and subjected to column chromatography with petroleum ether: ethyl acetate mixture to obtain 2,6-dimethyl-3-(3, 111.4 mg of 7-dimethyl-2,6-diocten-1-yl)-p-benzoquinone, yield 82%. Yellow oily liquid.
- reaction solution was placed in a centrifuge tube and centrifuged at 10,000 rpm for 2 minutes, and the supernatant was taken and subjected to column chromatography with petroleum ether: ethyl acetate mixture to obtain 2,6-dimethyl-3-(3, 7,11-trimethyl-2,6,10-dodecatrien-1-yl)-p-benzoquinone 136.9 mg, yield 80%. Yellow oily liquid.
- reaction solution was placed in a centrifuge tube and centrifuged at 10,000 rpm for 2 minutes, and the supernatant was taken and subjected to column chromatography with petroleum ether: ethyl acetate mixture to obtain 3,5-dimethyl-2-((2E ,7R,11R)-3,7,11,15-tetramethyl-2-hexadecen-1-yl)-p-benzoquinone 119.8 mg, yield 58%. Yellow oily liquid.
- reaction solution was placed in a centrifuge tube and centrifuged at 10,000 rpm for 2 minutes, and the supernatant was subjected to column chromatography with petroleum ether: ethyl acetate mixture to obtain 3,5-dimethyl-2-(trans -3-phenyl-2-propen-1-yl)-p-benzoquinone 118.3 mg, yield 94%. Yellow oily liquid.
- reaction solution was placed in a centrifuge tube and centrifuged at 10,000 rpm for 2 minutes, and the supernatant was taken and subjected to column chromatography with petroleum ether: ethyl acetate mixture to obtain 2,3,5-trimethyl-6-( (2E,7R,11R)-3,7,11,15-tetramethyl-2-hexadecen-1-yl)-p-benzoquinone 138.8 mg, yield 65%. Brown oily liquid.
- reaction solution was placed in a centrifuge tube and centrifuged at 10,000 rpm for 2 minutes, and the supernatant was taken and subjected to column chromatography with petroleum ether: ethyl acetate mixture to obtain 2-methyl-3-(3,7,11 ,15-tetramethyl-2-hexadecen-1-yl)-1,4-naphthoquinone (vitamin K1) 157.9 mg, yield 78%. Yellow oily liquid.
- reaction solution was placed in a centrifuge tube and centrifuged at 10,000 rpm for 2 minutes, and the supernatant was taken and subjected to column chromatography with petroleum ether: ethyl acetate mixture to obtain 2-methyl-3-isopentenyl-1 ,4-naphthoquinone 65.3 mg, yield 54%. Yellow oily liquid.
- reaction solution was placed in a centrifuge tube and centrifuged at 10,000 rpm for 2 minutes, and the supernatant was subjected to column chromatography with petroleum ether: ethyl acetate mixture to obtain 2,3-dimethoxy-5-methyl -6-(3-methyl-2-buten-1-yl)-p-benzoquinone 72.6 mg, yield 58%.
- Orange oily liquid
- reaction solution was placed in a centrifuge tube and centrifuged at 10,000 rpm for 2 minutes, and the supernatant was taken and carried out column chromatography with petroleum ether: ethyl acetate mixture to obtain 124.9 mg of coenzyme Q9 (CoQ9), with a yield of 63% ( Calculated as solanyl chloride). yellow solid.
- reaction solution was placed in a centrifuge tube and centrifuged at 10,000 rpm for 2 minutes, and the supernatant was taken and carried out column chromatography with petroleum ether: ethyl acetate mixture to obtain 97.7 mg of coenzyme Q10 (CoQ10) with a yield of 45% ( Calculated as 1-chloro-decamethyl-tetradecacene). Orange solid.
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Abstract
公开了一种新型有机醇盐团聚物及其制备方法和应用。团聚物具有如下分子式:(ZOR) 12Y mQ n。新型有机醇盐团聚物具有良好的催化活性,应用前景良好。
Description
本申请要求申请日为2021年8月9日的中国专利申请2021109103874的优先权。本申请引用上述中国专利申请的全文。
本发明涉及一种新型有机醇盐团聚物及其制备方法和应用。
苯醌类化合物具有独特的结构功能特点,广泛存在于自然界中并发挥重要作用。含有醌官能团的辅酶Q10、维生素K、质体醌等化合物是真核生物呼吸作用、光合作用等生化过程中的电子转移载体。有研究表明,辅酶Q10、维生素K族是人体中不可或缺的维生素,对心脏、骨骼等器官组织有积极作用,但这些维生素的食物来源有限,因此化学合成是它们重要来源,成功的合成方法市场潜力巨大。
经典的合成醌类化合物的方法,一般采用苯酚、芳基醚等原料出发,经路易斯酸、金属催化偶联等官能化反应进行侧链修饰,再将芳基醚脱保护、氧化的方式,这些反应使用较多催化剂、保护基团试剂和氧化剂,步骤较长,效率不高。
因此,开发简便、高效、广泛适用催化剂以合成的醌类化合物具有重要意义。
发明内容
本发明所要解决的技术问题是现有的催化合成含烯基醌类化合物的催化剂种类较少的缺陷。为此,本发明提供了一种新型有机醇盐团聚物及其制备方法和应用。在本发明的新型有机醇盐团聚物催化下,可以高收率地制备含烯基侧链的醌类化合物。
本发明提供了一种如式I所示的化合物:
(ZOR)
12Y
mQ
n
I
其中,R为金刚烷基、C
6-14芳基、被一个或多个R
-1取代的C
6-14芳基、5-10元杂芳基、被一个或多个R
-2取代的5-10元杂芳基或
所述的5-10元杂芳基中的杂原子或被一个或多个R
-2取代的5-10元杂芳基中的杂原子为N、S和O中的1种或多种,个数为1、2或3个;
R
-1和R
-2独立地为C
1-6烷基;
R
1、R
2和R
3独立地为H、C
1-10烷基、被一个或多个R
1-1取代的C
1-10烷基(当R
1-1为多个时,R
1-
1相同或不同)、C
6-14芳基、被一个或多个R
1-2取代的C
6-14芳基(当R
1-2为多个时,R
1-2相同或不同)、C
3-6环烷基、C
3-6环烯基、被一个或多个R
1-3取代的C
3-6环烯基(当R
1-3为多个时,R
1-3相同或不同)、 C
2-40烯基、C
1-10烷氧基、5-10元杂芳基、3-6元杂环烷基或3-6元杂环烯基;所述的5-10元杂芳基中的杂原子、所述的3-6元杂环烷基中的杂原子和所述的3-6元杂环烯基中的杂原子独立地为N、S和O中的1种或多种,个数为1、2或3个;
R
1-1和R
1-2和R
1-3独立地为C
6-14芳基、羟基、卤素、C
1-6烷基、C
3-6环烷基、5-10元杂芳基、3-6元杂环烷基、3-6元杂环烯基、巯基、C
1-6烷氧基、-S-C
1-6烷基、-NR
1-1-1R
1-1-2、-C(=O)R
1-1-3、-C(=O)OR
1-
1-4或-C(=O)NR
1-1-5,所述的5-10元杂芳基中的杂原子、3-6元杂环烷基中的杂原子和3-6元杂环烯基中的杂原子独立地为N、S和O中的1个或多个,个数为1、2或3个;
R
1-1-1、R
1-1-2、R
1-1-3、R
1-1-4和R
1-1-5独立地为H或C
1-6烷基;
或者,R
1、R
2和R
3中任意两个与其相连的C一起形成C
3-6环烷基、被一个或多个R
1-4取代的C
3-6环烷基、3-6元杂环烷基、或被一个或多个R
1-5取代的3-6元杂环烷基;所述的3-6元杂环烷基和或被一个或多个R
1-5取代的3-6元杂环烷基中的杂原子独立地为N、S和O中的1种或多种,个数为1、2或3个;
R
1-4和R
1-5独立地为C
1-6烷基、C
6-14芳基、羟基、卤素、C
3-6环烷基、5-10元杂芳基、3-6元杂环烷基、3-6元杂环烯基、巯基、C
1-6烷氧基、-S-C
1-6烷基、-NR
1-4-1R
1-4-2、-C(=O)R
1-4-3、-C(=O)OR
1-4-4或-C(=O)NR
1-4-5,所述的5-10元杂芳基中的杂原子、3-6元杂环烷基中的杂原子和3-6元杂环烯基中的杂原子独立地为N、S和O中的1种或多种,个数为1、2或3个;
R
1-4-1、R
1-4-2、R
1-4-3、R
1-4-4和R
1-4-5独立地为H或C
1-6烷基;
Z为碱金属;
Y为碱金属或醚类化合物-碱金属的配合物(醚类化合物-碱金属的配合物为醚类化合物与碱金属形成的配合物);
所述的醚类化合物-碱金属配合物中的醚类化合物为C
2-18醚类化合物或C
12-18冠醚类化合物;
Q独立地为H、卤素或-B(C
6-14芳基)
4(当Q为2个时,Q可以相同或不同);
m和n独立地为1或2。
所述的如式I所示的化合物的分子式((ZOR)
12Y
mQ
n)中O为氧原子。
所述的如式I所示的化合物为团聚化合物(还可以称之团簇化合物)。
所述的如式I所示的化合物在使用时可以所述的如式I所示的化合物、或含有所述的如式I所示的化合物的溶液(例如可以将含有所述的如式I所示的化合物的反应液直接使用)的形式使用。
在一些实施方案中,所述的如式I所示的化合物具有正二十面体立体结构。
在一些实施方案中,当m和n为1时;所述的如式I所示的化合物形成如下的立体结构:O原子处于正二十面体的顶点处,Q位于所述的正二十面体的体心处,Y位于所述的正二十面体的面心处(Y可以在正二十面体的不同面心上迁移,Y的位置不固定在某一个正二十面体的面心上)。
在一些实施方案中,当m和n为2时;所述的如式I所示的化合物形成如下的立体结构:O原子处于正二十面体的顶点处,其中一个Q位于所述的正二十面体的体心处,另一个位于正二十面体体外,Y各自位于所述的正二十面体中的任意两个的面心处(Y可以在正二十面体的不同面心上迁移, Y的位置不固定在某一个正二十面体的面心上)。
在一些实施方案中,R
-1和R
-2中,所述的C
1-6烷基独立地为甲基、乙基、正丙基、异丙基、正丁基、仲丁基、异丁基或叔丁基。
在一些实施方案中,R
1、R
2和R
3中,所述的C
1-10烷基和所述的被一个或多个R
1-1取代的C
1-10烷基中的C
1-10烷基独立地为C
1-7烷基,还可以为甲基、乙基、正丙基、异丙基、正丁基、仲丁基、异丁基、叔丁基、正戊基、正己基或正庚基。
在一些实施方案中,R
1、R
2和R
3中,所述的C
6-14芳基和所述的被一个或多个R
1-2取代的C
6-14芳基中的C
6-14芳基独立地为苯基、萘基或蒽基。
在一些实施方案中,R
1、R
2和R
3中,所述的C
3-6环烷基独立地为为环丙基、环丁基、环戊基或环己基。
在一些实施方案中,R
1、R
2和R
3中,所述的C
3-6环烯基和所述的被一个或多个R
1-3取代的C
3-6环烯基中的C
3-6环烯基独立地为环丙烯基、环丁烯基、环戊烯基或环己烯基。
在一些实施方案中,R
1-1和R
1-2和R
1-3中,所述的C
6-14芳基独立地为苯基、萘基或蒽基。
在一些实施方案中,R
1-1、R
1-2和R
1-3中,所述的C
1-6烷基独立地为甲基、乙基、正丙基、异丙基、正丁基、仲丁基、异丁基或叔丁基。
在一些实施方案中,R
1-1-1、R
1-1-2、R
1-1-3、R
1-1-4和R
1-1-5中,所述的C
1-6烷基独立地为甲基、乙基、正丙基、异丙基、正丁基、仲丁基、异丁基或叔丁基。
在一些实施方案中,当R
1、R
2和R
3中任意两个与其相连的C一起形成C
3-6环烷基或被一个或多个R
1-4取代的C
3-6环烷基时,所述的C
3-6环烷基和所述的被一个或多个R
1-4取代的C
3-6环烷基中的C
3-6环烷基独立地为环丙基、环丁基、环戊基或环己基。
在一些实施方案中,R
1-4和R
1-5中,所述的C
1-6烷基独立地为甲基、乙基、正丙基、异丙基、正丁基、仲丁基、异丁基或叔丁基。
在一些实施方案中,Z中,所述的碱金属为Li、Na或K,例如Na。
在一些实施方案中,Y中,所述的碱金属和醚类化合物-碱金属配合物中的碱金属独立地为Li、Na或K,例如Na。
在一些实施方案中,m为1,n为1。
在一些实施方案中,m为2,n为2。
在一些实施方案中,Y中,当所述的醚类化合物为C
2-8醚类化合物时,所述的C
2-8醚类化合物为甲醚、乙醚、正丙醚或正丁醚,例如甲醚。
在一些实施方案中,Y中,当所述的醚类化合物为C
12-18冠醚类化合物时,所述的C
12-18冠醚类化合物为12-冠(醚)-4、15-冠(醚)-5或18-冠(醚)-6,例如15-冠(醚)-5。
在一些实施方案中,Q中,所述的卤素为F、Cl、Br或I。
在一些实施方案中,Q中,所述的-B(C
6-14芳基)
4中的C
6-14芳基独立地为苯基、萘基或菲基,例如苯基。
在一些实施方案中,Q中,所述的-B(C
6-14芳基)
4为-B(苯基)
4。
在一些实施方案中,R
-1为C
1-6烷基。
在一些实施方案中,R
1、R
2和R
3独立地为H、C
1-10烷基、被一个或多个R
1-1取代的C
1-10烷基、C
6-14芳基、被一个或多个R
1-2取代的C
6-14芳基、C
3-6环烷基、C
3-6环烯基、被一个或多个R
1-3取代的C
3-6环烯基或C
2-40烯基;
或者,R
1、R
2和R
3中任意两个与其相连的C一起形成C
3-6环烷基或被一个或多个R
1-4取代的C
3-6环烷基。
在一些实施方案中,R
1-1为C
6-14芳基或羟基。
在一些实施方案中,R
1-2为C
1-6烷基。
在一些实施方案中,R
1-3为C
1-6烷基。
在一些实施方案中,R
1-4为C
1-6烷基。
在一些实施方案中,Q独立地为卤素、H或-B(C
6-14芳基)
4。
在一些实施方案中,所述的如式I所示的化合物的通式为如式I-1所示:
(ZOR)
12YQ
I-1;
其中,Y为碱金属;Q独立地为卤素。
在一些实施方案中,所述的如式I所示的化合物的通式为如式I-1所示:
(ZOR)
12YQ
I-1;
其中,Y为醚类化合物-碱金属配合物;Q独立地为卤素或H。
在一些实施方案中,所述的如式I所示的化合物的通式为如式I-2:
[(ZOR)
12Y
2Q]Q
I-2
其中,Y为碱金属;Q中一个为-B(C
6-14芳基)
4,另一个为H或卤素。
R
-1为C
1-6烷基;
R
1、R
2和R
3独立地为H、C
1-10烷基、被一个或多个R
1-1取代的C
1-10烷基、C
6-14芳基、被一个或多个R
1-2取代的C
6-14芳基、C
3-6环烷基、C
3-6环烯基、被一个或多个R
1-3取代的C
3-6环烯基或C
2-40烯基,且R
1、R
2和R
3不同时为H;或者,R
1、R
2和R
3中任意两个与其相连的C一起形成C
3-6环烷基或被一个或多个R
1-4取代的C
3-6环烷基;
R
1-1为C
6-14芳基或羟基;
R
1-2为C
1-6烷基;
R
1-3为C
1-6烷基;
R
1-4为C
1-6烷基;
Q独立地为卤素、H或-B(C
6-14芳基)
4。
在一些实施方案中,所述的如式I所示的化合物为如下任一化合物:
本发明提供了还一种如式I所示的化合物的制备方法,其包括以下步骤:在NaH或卤化试剂存在下,将化合物ZOR和化合物II在溶剂中进行如下式的反应,得到所述的如式I所示的化合物;
其中,所述的卤化试剂为四卤苯醌、被1、2或3个R
4取代的卤甲烷、四卤化碳、C
3-6环烯基卤代甲烷或卤化钠;
R
4为苯基或被1、2或3个R
4-1取代的苯基C
2-30烯基(例如C
2-4烯基,例如异丁烯);
R
4-1为卤素、C
1-10烷基或C
1-10烷氧基;
所述的化合物II为C
2-18醚类化合物、C
12-18冠醚类化合物、Z[Ph
4B]或者不存在;
所述的反应的温度为60-300℃;
其中,Z、R、Y、Q、m、n、C
2-18醚类化合物和C
12-18冠醚类化合物的定义均同前所述。
本发明中,所述的四卤代醌优选为四氯苯醌、四溴苯醌、四碘苯醌或四氟苯醌。
本发明中,所述的被1、2或3个R
4取代的卤甲烷优选为三苯甲基溴、二苯甲基氯、苯甲基氯或异戊烯氯。
本发明中,所述的四卤化碳为四氯化碳或四溴化碳。
本发明中,所述的卤化钠优选为氯化钠、溴化钠、碘化钠或氟化钠。
本发明中,所述的“NaH或卤化试剂”与所述的化合物ZOR的摩尔比可以为本领域此类反应常规的摩尔比,当Z为Na时,NaH与ZOR的比例无需额外限制。我们定义卤化试剂能提供的最大卤离子数量为其卤化当量,例如,四卤苯醌的卤化当量为4,而三苯基卤甲烷的卤化当量为1。所述的ZOR与卤化试剂中的卤原子摩尔比优选20:1-1:1,例如10:8。
本发明中,当在NaH存在下,所述的化合物II为C
2-18醚类化合物、C
12-18冠醚类化合物、Z[Ph
4B]。当卤化试剂存在下,所述的化合物II为C
2-18醚类化合物、C
12-18冠醚类化合物或不存在。
本发明中,所述的化合物II与所述的化合物ZOR的摩尔比可以为本领域此类反应常规的摩尔比,优选1:5-1:20,例如0.2:1。
本发明中,所述的溶剂可以为本领域此类反应常规的溶剂,优选非极性溶剂。所述的非极性溶剂优选为芳烃类溶剂(例如氯苯或甲苯)、烷烃类溶剂(例如正己烷、正辛烷或环己烷)、醚类溶剂(例如THF或DME)和有机胺类溶剂(例如三乙胺或吡啶)中的一种或多种,例如芳烃类溶剂。
本发明中,所述的反应的温度优选80-120℃。
所述的反应的进程可以采用本领域常规的方法进行监测(例如核磁共振(例如碳谱,氢谱,钠谱、氟谱)、TLC、GC-MS、LC-MS)。所述的反应时间优选为1-600小时,例如5小时、8小时或48小时。
本发明还提供了一种按照上述的如式I所示的化合物的制备方法制得的如式I所示的化合物。
(NaOt-Bu)
12NaF
I-a。
所述的如式I-a所示的化合物的单晶的结构优选基本如图1所示。
(NaOt-Bu)
12NaCl
I-b。
所述的如式I-b所示的化合物的单晶的结构优选如图2所示。
或者,所述的如式I-c所示的化合物的单晶,其以2θ角度表示的X-射线粉末衍射图在7.9±0.2°、9.1±0.2°、18.8±0.2°、19.4±0.2°、21.0±0.2°和32.8±0.2°处有特征峰;
(NaOt-Bu)
12NaBr
I-c。
所述的如式I-c所示的化合物的单晶的结构优选基本如图3所示;
所述的如式I-c所示的化合物的单晶的X-射线粉末衍射图优选基本如图13所示。
(NaOt-Bu)
12NaI
I-d。
所述的如式I-d所示的化合物的单晶的结构优选如图5所示。
(NaOt-Bu)
12NaH
I-e。
所述的如式I-e所示的化合物的单晶的结构优选如图6所示。
[DME-Na][(NaOt-Bu)
12H]
I-f。
所述的如式I-f所示的化合物的单晶的结构优选如图7所示。
[15-冠-5-Na][(NaOt-Bu)
12H]
I-g。
所述的如式I-g所示的化合物的单晶的结构优选如图8所示。
[15-冠-5-Na][(NaOt-Bu)
12F]
I-h。
所述的如式I-h所示的化合物的单晶的结构优选如图9所示。
[15-冠-5-Na][(NaOt-Bu)
12Cl]
I-i。
所述的如式I-i所示的化合物的单晶的结构优选如图10所示。
本发明还提供了一种物质A作为催化剂在制备醌类化合物中的应用;所述的物质A选自上述的如式I所示的化合物、上述的如式I-a所示的化合物的单晶、上述的如式I-b所示的化合物的单晶、上述的如式I-c所示的化合物的单晶、上述的如式I-d所示的化合物的单晶、上述的如式I-e所示的化合物的单晶、上述的如式I-f所示的化合物的单晶、上述的如式I-g所示的化合物的单晶、上述的如式I-h所示的化合物的单晶和上述的如式I-i所示的化合物的单晶中的一种或多种;所述的醌类化合物为含有烯基侧链(侧链指的是醌类化合物的母体上的取代基,例如
中,标记1(甲基)、2(甲基)和3
的取代基均为侧链,标记3的烯基侧链)的醌类化合物。
在一些实施方案中,所述的醌类化合物的制备方法包括如下步骤:在上述的物质A催化下,将如式IV所示的化合物和如式V所示的化合物进行缩合反应,得到如式III所示的醌类化合物(简称式III化合物)即可
其中,R
1a、R
2a和R
3a独立地为氢、C
1-10烷基、C
2-10烯基或C
1-10烷氧基;
或者,R
2a、R
3a以及与之相连的碳原子一起形成C
6-10芳基、被一个或多个羟基取代的C
6-10芳基、或、5-10元的杂芳基;所述的杂芳基中的杂原子选自N、O和S中的一种或多种,杂原子的个数为1个、2个或3个;
R
6a为C
3-100烯基、被一个或多个R
6a-1取代的C
3-100烯基、或、C
3-10环烯基;
R
6a-1独立地为C
6-10芳基或5-10元的杂芳基;所述的杂芳基中的杂原子选自N、O和S中的一种或多种,杂原子的个数为1个、2个或3个;
X为卤素。
在一些实施方案中,R
1a、R
2a和R
3a中,所述的C
1-10烷基独立地为甲基、乙基、正丙基、异丙基、正丁基、仲丁基、异丁基或叔丁基,例如甲基。
在一些实施方案中,R
1a、R
2a和R
3a中,所述的C
1-10烷氧基独立地为甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、仲丁氧基、异丁氧基或叔丁氧基,例如甲氧基。
在一些实施方案中,当R
2a、R
3a以及与之相连的碳原子一起形成C
6-10芳基时,所述的C
6-10芳基为苯基。
在一些实施方案中,当R
2a、R
3a以及与之相连的碳原子一起形成被一个或多个羟基取代的C
6-10芳基时,所述的C
6-10芳基为苯基。
在某一方案中,R
6a中,所述的C
3-100烯基和被一个或多个R
6a-1取代的C
3-100烯基中的C
3-100烯基独立地含有1~15个双键,还可以含有1个、2个、3个、4个、5个、6个、7个、8个、9个或10个双键;
较佳地,其中的一双键为位于所述的X的β位和γ位中间。
在某一方案中,R
6a中,所述的C
3-100烯基和被一个或多个R
6a-1取代的C
3-100烯基中的C
3-100烯基独立地为C
5-100的萜烯基,还可以为
n为0~19(例如0、1、2、3、4、5、6、7、8、9、10、11、12、13、14、15、16、17、18或19,还例如0、1、2、3、4、5、6、7、8或9)”。
在某一方案中,R
6a中,所述的C
3-100烯基和被一个或多个R
6a-1取代的C
3-100烯基中的C
3-100烯基独立地为C
3~C
50的烯基,还可以为C
3的烯基、C
4的烯基、C
5的烯基、C
6的烯基、C
7的烯基、C
8的烯基、C
9的烯基、C
10的烯基、C
15的烯基、C
20的烯基、C
30的烯基、C
40的烯基、C
45的烯基或C
50的烯基,更可以为烯丙基、2-丁烯-1-基
3-甲基-2-丁烯-1-基
2-己烯-1-基
(全-E)-3,7-二甲基-2,6-辛二烯-1-基
(全-E)-3,7,11-三甲基 -2,6,10-十二烷三烯-1-基
叶绿基
(全-E)-3,7,11,15-四甲基-2,6,10,14-十六碳四烯-1-基
(全-E)-3,7,11,15,19,23,27-七甲基-2,6,10,14,18,22,26-二十八碳七烯-1-基
(全-E)-3,7,11,15,19,23,27,31,35-九甲基-2,6,10,14,18,22,26,30,34-三十六碳九烯-1-基
或(全-E)-3,7,11,15,19,23,27,31,35,39-十甲基-2,6,10,14,18,22,26,30,34,38-四十碳十烯-1-基
在一些实施方案中,R
6a中,所述的被一个或多个R
6a-1取代的C
3-100烯基中的多个为2个或3个。
在一些实施方案中,R
6a-1中,所述的C
6-10芳基为苯基。
在一些实施方案中,R
6a中,所述的C
3-10环烯基含有1~5个双键,还可以含有1个、2个、3个、4个或5个双键;
较佳地,其中的一双键为位于所述的X的β位和γ位中间。
在一些实施方案中,X中,所述的卤素为氯、溴或碘,还可以为氯或溴。
在一些实施方案中,R
1a为氢、C
1-10烷基或C
1-10烷氧基。
在一些实施方案中,R
2a为氢、C
1-10烷基或C
1-10烷氧基;
R
3a为氢、C
1-10烷基或C
1-10烷氧基;
或者,R
2a、R
3a以及与之相连的碳原子一起形成C
6-10芳基、或、被一个或多个羟基取代的C
6-10芳基。
在一些实施方案中,R
6a为C
3-100的烯基。
在一些实施方案中,R
6a-1独立地为C
6-10芳基。
在一些实施方案中,R
1a为氢、C
1~C
10烷基或C
1~C
10烷氧基;
R
2a为氢、C
1~C
10烷基或C
1~C
10烷氧基;
R
3a为氢、C
1~C
10烷基或C
1~C
10烷氧基;
或者,R
2a、R
3a以及与之相连的碳原子一起形成C
6-10芳基、或、被一个或多个羟基取代的C
6-10芳基;
R
6a为C
3-100烯基;
X为卤素。
在一些实施方案中,所述的如式II所示的化合物为1,4-苯醌、2-甲基-1,4-苯醌、2,3-二甲基-1,4-苯醌、2,3,5-三甲基-1,4-苯醌、2,3-二甲氧基-5-甲基-1,4-苯醌、2-甲基-1,4-萘醌或5-羟基-1,4-萘醌。
在一些实施方案中,R
6a为3-甲基-2-丁烯-1-基
(全-E)-3,7-二甲基-2,6-辛二烯-1-基
(全-E)-3,7,11-三甲基-2,6,10-十二烷三烯-1-基
叶绿基
(全-E)-3,7,11,15-四甲基-2,6,10,14-十六碳四烯-1-基
(全-E)-3,7,11,15,19,23,27-七甲基-2,6,10,14,18,22,26-二十八碳七烯-1-基
(全-E)-3,7,11,15,19,23,27,31,35-九甲基-2,6,10,14,18,22,26,30,34-三十六碳九烯-1-基
或(全-E)-3,7,11,15,19,23,27,31,35,39-十甲基- 2,6,10,14,18,22,26,30,34,38-四十碳十烯-1-基
在一些实施方案中,所述的如式III所示的化合物为如下任一结构:
在一些实施方案中,所述的物质A与所述的如式IV所示的化合物的摩尔比为(0.05-0.30):1,例如0.15:1。
在一些实施方案中,所述的缩合反应可以具有如下的反应参数:所述的缩合反应在保护气体(例如氮气)的存在下进行;所述的缩合反应在碱性试剂(例如氢化钠(60%氢化钠-矿物油))存在下进行,所述的碱性试剂与所述的如式IV所示的化合物的摩尔比为(1-3):1(例如1:1)所述的缩合反应在有机溶剂中进行,所述的有机溶剂为卤代芳香烃类溶剂(例如氯苯或邻二氯苯),所述的如式IV所示的化合物与所述的有机溶剂的摩尔体积比为0.1mol/L~0.3mol/L;所述的缩合反应还在
的存在下进行,所述的
与如式IV所示的化合物的摩尔比为(0.025~0.10):1(例如(0.05~0.10):1);所述的如式V所示的化合物与如式IV所示的化合物的摩尔比为(0.2~2.0):1(例如(0.2~1.70):1);所述的缩合反应的温度为20℃~100℃(例如70℃~80℃)。
本发明中,如无特别说明,各术语具有以下含义:
术语“多个”是指2个、3个、4个或5个。
术语“多种”是指2种、3种、4种或5种。
术语“卤素”是指氟元素、氯元素、溴元素或碘元素。
术语“烃基”是指碳氢化合物失去1个氢原子形成的基团。
术语“烷基”是指含有1个或多个碳原子的饱和直链或支链烃基。含有n个碳原子的烷基用C
n表示,C
m~C
n表示该烷基含有至少m个,至多n个碳原子。代表性的饱和直链烷基包括但不限于甲基、乙基、正丙基、正丁基、正戊基等;代表性的饱和支链烷基包括异丙基、异丁基、仲丁基、叔丁 基、异戊基、新戊基等。
术语“环烷基”是指饱和的单环或多环(例如螺环、稠环或桥环)烷基,可以具有3-10个环碳原子,也可以具有3-6个环碳原子。环烷基的实例包括但不限于:金刚烷基、环丙基、环丁基、环戊基和环己基。
术语“烷氧基”是指-O-(烷基),其中“烷基”为如上文所定义的烷基。
术语“烯基”是指是指含有一个或多个双键和多个碳原子的不饱和直链或支链烃基。代表性的直链烯基包括但不限于乙烯基、丙烯基、烯丙基等。
术语“环烯基”是指是指含有一个或多个双键和多个碳原子的不饱和(但不具有芳香性)、单环或多环(例如螺环、稠环或桥环)环烃基。代表性的环烯基包括但不限于环戊烯基、环己烯基等。
术语“杂芳基”是指含有1个、2个或3个独立选自氮、氧和硫的5-6元单环或9-10元双环(例如稠环或桥环)的芳香基团,当其为双环时,至少一个环具有芳香性,包括但不限于呋喃基、吡啶基、哒嗪基、嘧啶基、吡嗪基、噻吩基、异唑基、噁唑基、二唑基、咪唑基、吡咯基、吡唑基、三唑基、噻唑基、异噻唑基、噻二唑基、苯并咪唑基、吲哚基、吲唑基、苯并噻唑基、苯并异噻唑基、苯并唑基、苯并异唑基、喹啉基、异喹啉基等。
在不违背本领域常识的基础上,上述各优选条件,可任意组合,即得本发明各较佳实例。
本发明所用试剂和原料均市售可得。
本发明的积极进步效果在于:采用本发明的催化剂,可以高收率地得含有烯基的醌类化合物。
图1为实施例1的X-射线单晶衍射图。
图2为实施例2的X-射线单晶衍射图。
图3为实施例3的X-射线单晶衍射图。
图4为实施例3的扩散序谱图。
图5为实施例4的X-射线单晶衍射图。
图6为实施例5的X-射线单晶衍射图。
图7为实施例6的X-射线单晶衍射图。
图8为实施例7的X-射线单晶衍射图。
图9为实施例8的X-射线单晶衍射图。
图10为实施例9的X-射线单晶衍射图。
图11为实施例10的扩散序谱图。
图12为实施例11的扩散序谱图。
图13为实施例3的PXRD谱图;其中,图a表示实施例3的PXRD测试谱图,图b为实施例3的PXRD模拟。
下面通过实施例的方式进一步说明本发明,但并不因此将本发明限制在所述的实施例范围之中。下列实施例中未注明具体条件的实验方法,按照常规方法和条件,或按照商品说明书选择。
所述的如式I所示的化合物可由以下手段表征:X-射线单晶衍射、红外光谱、拉曼光谱、紫外光谱、固体核磁、扩散序谱核磁共振波谱、热重分析、粉末X射线衍射、小角度X射线散射。
扩散序列核磁共振波谱(DOSY)的测量是在配备了1/10大脉冲梯度单元和298K直接探针的Bruker Avance 500MHz光谱仪上进行的。用于扩散实验的LED脉冲序列(ledbpgp2s)参数如下:正弦形脉冲梯度持续时间为1.5-2.0ms,δ(P30)的值从0.842逐渐增加到40.014Gcm-1,测量步长为16或21步。脉冲梯度间隔Δ(D20)为50ms,扰流梯度(P19)为600μs,涡流延迟(D21)为5ms。样品于甲苯-d8中制备,每个测量实验应至少重复两次。最后的流体力学的半径是通过根据以下的斯托克斯-爱因斯坦方程计算得到的。其中,d为溶剂中流体力学直径,kb为玻尔兹曼常数,η为溶液粘度,对于氘代甲苯,25℃时粘度为0.5137mPa·s。
d=(k_b T)/3πηD
实施例1:
(NaOt-Bu)
12NaF:将0.20g NaOt-Bu(2.08mmol,1.0eq.),1,4-四氟苯醌(0.4mmol,0.2eq.),2.5mL无水PhCl加入一个干燥的4mL小瓶并密封。将小瓶加热至100℃并保持30分钟,直到全部固体基本溶解。混合液趁热使用针头滤膜过滤,之后静置至析出晶体。
经X射线晶体衍射,得到的晶体的结构式为(NaOt-Bu)
12NaF,其中O原子处于正二十面体的顶点处,F位于正二十面体的体心处,Na位于正二十面体的面心处;其晶系属于立方晶系,Pa-3空间群,晶胞参数为
α=β=γ=90°;其单晶参数如表1所示;其X-射线单晶衍射如图1所示。
表1
实施例2
(NaOt-Bu)
12NaCl:将0.20g NaOt-Bu(2.08mmol,1.0eq.),1,4-四氯苯醌(0.4mmol,0.2eq.),2.5mL无水PhCl加入一个干燥的4mL小瓶并密封。将小瓶加热至100℃并保持30分钟,直到全部固体基本溶解。混合液趁热使用针头滤膜过滤,之后静置至析出晶体。经X射线晶体衍射,得到的晶体的结构式为(NaOt-Bu)
12NaCl,其中O原子处于正二十面体的顶点处,Cl位于正二十面体的体心处,Na位于正二十面体的面心处;其晶系属于立方晶系,Pa-3空间群,晶胞参数为
α=β=γ=90°;其单晶参数如表2所示;其X-射线单晶衍射如图2所示。
表2
实施例3
(NaOt-Bu)
12NaBr:将0.20g NaOt-Bu(2.08mmol,1.0eq.),1,4-四溴苯醌(0.4mmol,0.2eq.),2.5mL无水PhCl加入一个干燥的4mL小瓶并密封。将小瓶加热至100℃并保持30分钟,直到全部固体基本溶解。混合液趁热使用针头滤膜过滤,之后静置至析出晶体。
经X射线晶体衍射,得到的晶体的结构式为(NaOt-Bu)
12NaBr,其中O原子处于正二十面体的顶点处,Br位于正二十面体的体心处,Na位于正二十面体的面心处;其晶系属于立方晶系,Pa-3空间群,晶胞参数为
α=β=γ=90°;其单晶参数如表3所示;其X-射线单晶衍射如图3所示。
经核磁检测,得到扩散序谱为图4。
表3
[(NaOt-Bu)
12NaBr]的粉末X射线衍射:
在无水的环境中将上述得到的[(NaOt-Bu)
12NaBr]晶体磨碎,并且彻底抽干溶剂,然后用贴Kapton膜隔绝空气的方式制备粉晶样品。经过铜靶PXRD测试得到这些粉晶样品的衍射谱图,具体见图13,其以2θ角度表示的PXRD图在7.9±0.2°、9.1±0.2°、18.8±0.2°、19.4±0.2°、21.0±0.2°和32.8±0.2°处有特征峰。
该谱图表明,当[(NaOt-Bu)
12NaBr]晶体被磨成粉末并排出溶剂后,样品仍然会以粉晶的形式存在。将实验数据与用团簇的单晶X射线衍射数据模拟得到的模拟谱图相比对,两者高度吻合。由此可见,构成这些粉晶的仍然是[(NaOt-Bu)
12NaBr]团簇。
实施例4
(NaOt-Bu)
12NaI:将0.20g NaOt-Bu(2.08mmol,1.0eq.),1,4-四碘苯醌(0.4mmol,0.2eq.),2.5mL无水PhCl加入一个干燥的4mL小瓶并密封。将小瓶加热至100℃并保持30分钟,直到全部固体基本溶解。混合液趁热使用针头滤膜过滤,之后静置至析出晶体。
经X射线晶体衍射,得到的晶体的结构式为(NaOt-Bu)
12NaI,其中O原子处于正二十面体的顶点处,I位于正二十面体的体心处,Na位于正二十面体的面心处;其晶系属于立方晶系,Pa-3空间群,晶胞参数为
α=β=γ=90°;其单晶参数如表4所示;其X-射线单晶衍射如图5所示。
表4
实施例5
(NaOt-Bu)
12NaH:将少量NaH至于0.1ml DME中加热至溶液沸腾后冷却,随后将0.20g NaOt-Bu(2.08mmol,1.0eq.),2.5mL无水PhCl加入上述4mL小瓶并密封。再将小瓶加热至100℃并保持30分钟,直到全部固体基本溶解。随后升温至120℃并馏出DME,之后静置至析出晶体。
经X射线晶体衍射,得到的晶体的结构式为(NaOt-Bu)
12NaH,其中O原子处于正二十面体的顶点处,H位于正二十面体的体心处,Na位于正二十面体的面心处;其晶系属于立方晶系,Pa-3空间群,晶胞参数为
α=β=γ=90°;其单晶参数如表5所示;其X-射线单晶衍射如图6所示。
表5
上述实施例1-4中的1,4-四氟苯醌、1,4-四氯苯醌、1,4-四溴苯醌、1,4-四碘苯醌,可用芳基甲基卤代烷(如三苯甲基卤代烷、二苯甲基卤代烷、苯甲基卤代烷等)、四卤化碳、烯丙基卤代烷(如异戊烯基卤代烷、香叶基卤代烷、叶绿醇基卤代烷、2-环己烯基卤代烷等)、卤化钠等有机、无机卤代物代替,制备得到含有相应卤素X的(NaOt-Bu)
12NaX。
温度可为60~300℃,时间可为0.5~6小时。
其他条件不变,将四氯苯醌替换为表6中的卤代物,得到相应的产物。
表6
卤代物 | 产物 |
三苯甲基氯 | (NaOt-Bu) 12NaCl |
三苯甲基溴 | (NaOt-Bu) 12NaBr |
二苯甲基氯 | (NaOt-Bu) 12NaCl |
苯甲基氯 | (NaOt-Bu) 12NaCl |
异戊烯氯 | (NaOt-Bu) 12NaCl |
四氯化碳 | (NaOt-Bu) 12NaCl |
四溴化碳 | (NaOt-Bu) 12NaBr |
氯化钠 | (NaOt-Bu) 12NaCl |
溴化钠 | (NaOt-Bu) 12NaBr |
碘化钠 | (NaOt-Bu) 12NaI |
氟化钠 | (NaOt-Bu) 12NaF |
实施例6:
[DME-Na][(NaOt-Bu)
12H]:将少量NaH至于0.1ml DME中加热至溶液沸腾后冷却,随后将0.20g NaOt-Bu(2.08mmol,1.0eq.),2.5mL无水PhCl加入上述4mL小瓶并密封。再将小瓶加热至100℃并保持30分钟,直到全部固体基本溶解。经X射线晶体衍射,得到的晶体的结构式为[DME-Na][(NaOt-Bu)
12H],其中O原子处于正二十面体的顶点处,H位于正二十面体的体心处,Na位于正二十面体的面心处;其晶系属于立方晶系,Fm-3m空间群,晶胞参数为
α=β=γ=90°,其单晶参数如表7所示;其X-射线单晶衍射如图7所示。
表7
实施例7:
[15-冠-5-Na][(NaOt-Bu)
12H]:将0.20g NaOt-Bu(2.08mmol,1.0eq.),NaH(0.4mmol,0.2eq.),15-冠-5(0.4mmol,0.2eq.),2.5mL无水PhCl加入一个干燥的4mL小瓶并密封。将小瓶加热至100℃并保持30分钟,直到全部固体基本溶解。混合液趁热使用针头滤膜过滤,之后静置至析出晶体。X射线晶体衍射实验确认其结构,结构是为[15-冠-5-Na][(NaOt-Bu)
12H],其中O原子处于正二十面体的顶点处,H位于正二十面体的体心处,Na位于正二十面体的面心处;其晶系属于立方晶系,P213空间 群,晶胞参数为
α=β=γ=90°;其单晶参数如表8所示;其X-射线单晶衍射如图8所示。
表8
实施例8
[15-冠-5-Na][(NaOt-Bu)
12F]:将0.20g NaOt-Bu(2.08mmol,1.0eq.),1,4-四氟苯醌(0.4mmol,0.2eq.),15-冠-5(0.4mmol,0.2eq.),2.5mL无水PhCl加入一个干燥的4mL小瓶并密封。将小瓶加热至100℃并保持30分钟,直到全部固体基本溶解。混合液趁热使用针头滤膜过滤,之后静置至析出晶体。X射线晶体衍射实验确认其结构,结构式为[15-冠-5-Na][(NaOt-Bu)
12F],其中O原子处于正二十面体的顶点处,F位于正二十面体的体心处,Na位于正二十面体的面心处;其晶系属于立方晶系,P213空间群,晶胞参数为
α=β=γ=90°;其单晶参数如表9所示;其X-射线单晶衍射如图9所示。
表9
实施例9
[15-冠-5-Na][(NaOt-Bu)
12Cl]:将0.20g NaOt-Bu(2.08mmol,1.0eq.),1,4-四氯苯醌(0.4mmol,0.2eq.),15-冠-5(0.4mmol,0.2eq.),2.5mL无水PhCl加入一个干燥的4mL小瓶并密封。将小瓶加热至100℃并保持30分钟,直到全部固体基本溶解。混合液趁热使用针头滤膜过滤,之后静置至析出晶体。X射线晶体衍射实验确认其结构,结构式为[15-冠-5-Na][(NaOt-Bu)
12F],其中O原子处于正二十面体的顶点处,Cl位于正二十面体的体心处,Na位于正二十面体的面心处;其晶系属于立方晶系,P213空间群,晶胞参数为
α=β=γ=90°;其单晶参数如表10所示;其X-射线单晶衍射如图10所示。
表10
实施例10
[n-C
7H
15C(CH
3)
2ONa]
12NaBr:将0.20g 2-甲基-2-壬醇(n-C
7H
15C(CH
3)
2OH,1.2mmol,1.0eq.),1,4-四溴苯醌(0.2mmol,0.2eq.),2.5mL无水D-8氘代甲苯加入一个干燥的4mL小瓶并密封。将小瓶加热至100℃并保持30分钟,直到全部固体基本溶解。混合液趁热使用针头滤膜过滤,之后静置做NMR DOSY(扩散序列核磁共振波谱)分析,扩散序列数据如表11所示;扩散序列核磁共振波谱如图11所示。
实施例11
[n-C
7H
15C(CH
3)
2ONa]
12NaI:将0.20g 2-甲基-2-壬醇(n-C
7H
15C(CH
3)
2OH,1.2mmol,1.0eq.),1,4-四溴苯醌(0.2mmol,0.2eq.),2.5mL无水D-8氘代甲苯加入一个干燥的4mL小瓶并密封。将小瓶加热至100℃并保持30分钟,直到全部固体基本溶解。混合液趁热使用针头滤膜过滤,之后静置做NMR DOSY(扩散序列核磁共振波谱)分析,扩散序列数据如表11所示;扩散序列核磁共振波谱如图12所示。
表11
实施例12:
[(NaOt-Bu)
12Na
2H]
+[Ph
4B]
-:将0.20g NaOt-Bu(2.08mmol,1.0eq.),NaH(0.4mmol,0.2eq.),Na[Ph
4B](0.4mmol,0.2eq.),2.5mL无水PhCl加入一个干燥的4mL小瓶并密封。将小瓶加热至100℃并保持30分钟,直到全部固体基本溶解。混合液趁热使用针头滤膜过滤,之后静置至析出晶体。X射线晶体衍射实验确认其结构,其结构式为[(NaOt-Bu)
12Na
2H]
+[Ph
4B]
-。
使用如式I所示的化合物催化的反应中,均先制得如式I所示的化合物。如式I所示的化合物的用量以如式I所示的化合物所用醇的量确定团聚物的用量,使用醇、NaH、卤源、溶剂加热制备好团簇溶液后,加入2,6-二甲基-3,5-二(乙氧酰基)-1,4-二氢吡啶(Hantzsch Ester,HE)、醌、烯丙基卤代烷,在合适的温度下反应,获得产物。例如如下实施例:
应用实施例1
于一干燥的10mL烧瓶中按实施例2法制备含有0.15mmol NaOR(0.3当量)的(NaOR)
12NaX,其中ROH为2-甲基-2-壬醇,X为氯。
此后溶液降温至室温,加入磁力搅拌子、2,6-二甲基对苯醌68mg(0.5mmol,1当量)、2,6-二甲基-3,5-二(乙氧酰基)-1,4-二氢吡啶6.3mg(0.025mmol,0.05当量)、1-氯-3-甲基-2-丁烯(异戊烯氯)87mg(0.83mmol,1.66当量)。待固体溶解后,向反应瓶中加入32mg市售60%氢化钠-矿物油混合物(约含24mg氢化钠,1.6当量),随后连接一支空气冷凝管于圆底烧瓶上,置换氮气并持续通氮气泡于反应体系中。加热烧瓶至80℃,搅拌反应48小时。此后,反应液置于离心管中以10000转每分钟离心2分钟,取上清液并用石油醚:乙酸乙酯混合物进行柱层析,制得2,6-二甲基-3-(3-甲基-2-丁烯-1-基)对苯醌97mg,产率95%。黄色油状液体。
1H-NMR(400MHz,CDCl
3)δ(ppm)6.55(d,J=2.2Hz,1H),4.94(t,J=7.1Hz,1H),3.18(d,J=7.0Hz,2H),2.06–2.01(m,6H),1.74(s,3H),1.67(s,3H).
13C-NMR(126MHz,CDCl
3)δ(ppm)188.46,187.19,145.23,143.42,140.71,133.79,133.12,119.23,25.71,25.40,17.97,15.88,12.18.HRMS(ESI)calcd.For C
13H
17O
2
+:205.1223.Found:205.1221(M-H
+)。
应用实施例2-39
采用表12中形成的簇化合物作为催化剂制备2,6-二甲基-3-(3-甲基-2-丁烯-1-基)对苯醌,其它的反应条件和操作均同应用实施例1。
表12
备注:产率:A级:50%以上,B级:30%~50%,C级:5%~30%。
采用表13中形成的簇化合物和当量数制备2,6-二甲基-3-(3-甲基-2-丁烯-1-基)对苯醌,其它的反应条件和操作均同应用实施例1。
表13
采用表14中形成的簇化合物[15-冠-5-Na][(NaOR)
12Cl]和当量数制备2,6-二甲基-3-(3-甲基-2-丁烯-1-基)对苯醌,其它的反应条件和操作均同应用实施例1。
表14
采用表15中形成的簇化合物作为催化剂制备2,6-二甲基-3-(3-甲基-2-丁烯-1-基)对苯醌,其它的反应条件和操作均同应用实施例1。
表15
采用表16中形成的簇化合物作为催化剂制备2,6-二甲基-3-(3-甲基-2-丁烯-1-基)对苯醌,其它的反应条件和操作均同应用实施例1。
表16
采用实施例1得到催化剂,以下实施例考察催化剂对不同的底物的催化效果。
应用实施例70
于一干燥的10mL烧瓶中按实施例1法制备含有0.15mmol NaOR(0.3当量)的(NaOR)
12NaX,其中ROH为2-甲基-2-壬醇,X为氯。此后溶液降温至室温,加入磁力搅拌子、2,6-二甲基对苯醌68mg(0.5mmol,1当量)、2,6-二甲基-3,5-二(乙氧酰基)-1,4-二氢吡啶6.3mg(0.025mmol,0.05当量)、1-氯-3,7-二甲基-2,6-二辛烯(香叶基氯)143mg(0.83mmol,1.66当量)。待固体溶解后,向反应瓶中加入40mg市售60%氢化钠-矿物油混合物(约含24mg氢化钠,2当量),随后连接一支空气冷凝管于圆底烧瓶上,置换氮气并持续通氮气泡于反应体系中。加热烧瓶至80摄氏度,搅拌反应36小时。此后,反应液置于离心管中以10000转每分钟离心2分钟,取上清液并用石油醚:乙酸乙酯混合物进行柱层析,制得2,6-二甲基-3-(3,7-二甲基-2,6-二辛烯-1-基)对苯醌111.4mg,产率82%。黄色油状液体。
1H NMR(400MHz,CDCl
3)δ(ppm)6.55(q,J=1.6Hz,1H),5.07–4.99(m,1H),4.94(tq,J=7.0,1.3Hz,1H),3.19(d,J=6.9Hz,2H),2.03(d,J=1.7Hz,8H),1.97(dd,J=8.9,6.2Hz,2H),1.73(d,J=1.4Hz,3H),1.65(d,J=1.5Hz,3H).
13C NMR(101MHz,CDCl
3)δ(ppm)188.47,187.15,145.23,143.53,140.80,137.32,133.12,131.54,124.02,119.17,39.67,26.53,25.68,25.25,17.68,16.30,15.89,12.18.HRMS(ESI)calcd.For C
18H
25O
2
+:273.1849.Found:273.1844(M-H
+)
应用实施例66
于一干燥的10mL烧瓶中按实施例1法制备含有0.15mmol NaOR(0.3当量)的(NaOR)
12NaX,其中ROH为2-甲基-2-壬醇,X为氯。此后溶液降温至室温,加入磁力搅拌子、2,6-二甲基对苯醌68mg(0.5mmol,1当量)、2,6-二甲基-3,5-二(乙氧酰基)-1,4-二氢吡啶6.3mg(0.025mmol,0.05当量)、1-氯-3,7,11-三甲基-2,6,10-十二烷三烯(法尼基氯)200mg(0.83mmol,1.66当量)。待固体溶解后,向反应瓶中加入40mg市售60%氢化钠-矿物油混合物(约含24mg氢化钠,2当量),随后连接一支空气冷凝管于圆底烧瓶上,置换氮气并持续通氮气泡于反应体系中。加热烧瓶至80摄氏度,搅拌反应36小时。此后,反应液置于离心管中以10000转每分钟离心2分钟,取上清液并用石油醚:乙酸乙酯混合物进行柱层析,制得2,6-二甲基-3-(3,7,11-三甲基-2,6,10-十二烷三烯-1-基)对苯醌136.9mg,产率80%。黄色油状液体。
1H-NMR(400MHz,CDCl
3)δ(ppm)6.47(q,J=1.6Hz,1H),5.07–4.93(m,2H),4.87(t,J=14.8Hz,1H),3.11(d,J=7.0Hz,2H),2.03–1.93(m,10H),1.91(d,J=7.6Hz,2H),1.86(dd,J=9.4,6.2Hz,2H),1.67(d,J=1.4Hz,3H),1.60(t,J=2.7Hz,3H),1.51(s,3H),1.50(s,3H).
13C-NMR(101MHz,CDCl
3)δ(ppm)188.44,187.14,145.22,143.51,140.76,137.36,135.18,133.11,131.29,124.33,123.85,119.15,39.70,39.67,26.75,26.43,25.70,25.27,17.67,16.32,16.02,15.87,12.19.
应用实施例67
于一干燥的10mL烧瓶中按实施例1法制备含有0.15mmol NaOR(0.3当量)的(NaOR)
12NaX,其中ROH为2-甲基-2-壬醇,X为氯。此后溶液降温至室温,加入磁力搅拌子、2,6-二甲基对苯醌68mg(0.5mmol,1当量)、2,6-二甲基-3,5-二(乙氧酰基)-1,4-二氢吡啶6.3mg(0.025mmol,0.05当量)、(2E,7R,11R)-1-氯-3,7,11,15-四甲基-2-十六碳烯(叶绿基氯)259mg(0.83mmol,1.66当量)。待固体溶解后,向反应瓶中加入40mg市售60%氢化钠-矿物油混合物(约含24mg氢化钠,2当量),随后连接一支空气冷凝管于圆底烧瓶上,置换氮气并持续通氮气泡于反应体系中。加热烧瓶至80摄氏度,搅拌反应60小时。此后,反应液置于离心管中以10000转每分钟离心2分钟,取上清液并用石油醚:乙酸乙酯混合物进行柱层析,制得3,5-二甲基-2-((2E,7R,11R)-3,7,11,15-四甲基-2-十六碳烯-1-基)对苯醌119.8mg,产率58%。黄色油状液体。
1H-NMR(400MHz,CDCl
3)δ(ppm)6.55(d,J=1.8Hz,1H),4.98–4.89(m,1H),3.19(d,J=7.0Hz,2H),2.03(d,J=2.5Hz,6H),1.95–1.89(m,2H),1.72(s,3H),1.67–1.62(m,1H),1.52(dt,J=13.3,6.6Hz,1H),1.33(ddt,J=24.5,9.1,4.7Hz,5H),1.28–1.17(m,6H),1.14(ddd,J=9.0,5.7,1.9Hz,3H),1.05(ddt,J=18.0,10.3,7.7Hz,3H),0.86(d,J=6.7Hz,6H),0.83(t,J=6.3Hz,6H).
13C-NMR(126MHz,CDCl
3)δ(ppm)188.45,187.15,145.20,143.56,140.74,137.78,133.12,118.85,40.00,39.38,37.43,37.39,37.30,36.64,32.79,32.65,27.98,25.28,25.26,24.80,24.47,22.73,22.63,19.75,19.72,16.22,15.88,12.20.
应用实施例68
于一干燥的10mL烧瓶中按实施例1法制备含有0.15mmol NaOR(0.3当量)的(NaOR)
12NaX,其中ROH为2-甲基-2-壬醇,X为溴。此后溶液降温至室温,加入磁力搅拌子、2,6-二甲基对苯醌68mg(0.5mmol,1当量)、2,6-二甲基-3,5-二(乙氧酰基)-1,4-二氢吡啶6.3mg(0.025mmol,0.05当量)、烯丙基溴100mg(0.83mmol,1.66当量)。待固体溶解后,向反应瓶中加入40mg市售60%氢化钠-矿物油混合物(约含24mg氢化钠,2当量),随后连接一支空气冷凝管于圆底烧瓶上,置换氮气并持续通氮气泡于反应体系中。加热烧瓶至80摄氏度,搅拌反应48小时。此后,反应液置于离心管中以10000转每分钟离心2分钟,取上清液并用石油醚:乙酸乙酯混合物进行柱层析,制得3,5-二甲基-2-烯丙基对苯醌29.8mg,产率34%。黄色油状液体。
1H-NMR(400MHz,CDCl
3)δ(ppm)6.57(s,1H),5.81-5.63(m,2H),5.09(d,J=9.3Hz,1H),3.24(d,J=6.6Hz,2H),2.05(s,6H).
应用实施例69
于一干燥的10mL烧瓶中按实施例1法制备含有0.15mmol NaOR(0.3当量)的(NaOR)
12NaX,其中ROH为2-甲基-2-壬醇,X为氯。此后溶液降温至室温,加入磁力搅拌子、2,6-二甲基对苯醌68mg(0.5mmol,1当量)、2,6-二甲基-3,5-二(乙氧酰基)-1,4-二氢吡啶6.3mg(0.025mmol,0.05当量)、反式-1-氯-3-苯基-2-丙烯(肉桂基氯)125.5mg(0.83mmol,1.66当量)。待固体溶解后,向反应瓶中加入40mg市售60%氢化钠-矿物油混合物(约含24mg氢化钠,2当量),随后连接一支空气冷凝管于圆底烧瓶上,置换氮气并持续通氮气泡于反应体系中。加热烧瓶至80摄氏度,搅拌反应48小时。此后,反应液置于离心管中以10000转每分钟离心2分钟,取上清液并用石油醚:乙酸乙酯混合物进行柱层析,制得3,5-二甲基-2-(反式-3-苯基-2-丙烯-1-基)对苯醌118.3mg,产率94%。黄色油状液体。
1H-NMR(400MHz,CDCl
3)δ(ppm)7.34–7.23(m,4H),7.26–7.15(m,1H),6.59(q,J=1.6Hz,1H),6.42(dt,J=15.8,1.6Hz,1H),6.11(dt,J=15.9,6.7Hz,1H),3.39(dd,J=6.8,1.6Hz,2H),2.10(s,3H),2.05(d,J=1.7Hz,3H).
13C-NMR(101MHz,CDCl
3)δ(ppm)188.24,186.93,145.52,141.75,141.62,137.03,133.12,131.90,128.52,127.38,126.11,124.91,29.54,15.95,12.25.
应用实施例70
于一干燥的10mL烧瓶中按实施例1法制备含有0.15mmol NaOR(0.3当量)的(NaOR)
12NaX, 其中ROH为2-甲基-2-壬醇,X为氯。此后溶液降温至室温,加入磁力搅拌子、2,3-二甲基对苯醌68mg(0.5mmol,1当量)、2,6-二甲基-3,5-二(乙氧酰基)-1,4-二氢吡啶6.3mg(0.025mmol,0.05当量)、全E式-1-氯-3,7,11,15,19,23,27,31,35-九甲基-2,6,10,14,18,22,26,30,34-三十六碳九烯(茄尼基氯)341mg(0.52mmol,1.05当量)。待固体溶解后,向反应瓶中加入40mg市售60%氢化钠-矿物油混合物(约含24mg氢化钠,2当量),随后连接一支空气冷凝管于圆底烧瓶上,置换氮气并持续通氮气泡于反应体系中。加热烧瓶至80摄氏度,搅拌反应36小时。此后,反应液置于离心管中以10000转每分钟离心2分钟,取上清液并用石油醚:乙酸乙酯混合物进行柱层析,制得产物质体醌187.1mg,产率51%。黄色油状液体。
1H-NMR(400MHz,CDCl
3)δ(ppm)6.49–6.45(m,1H),5.11(t,J=7.2Hz,9H),3.12(d,J=7.2Hz,2H),2.06(t,J=7.2Hz,16H),2.03(s,3H),2.01(s,3H),1.98(dd,J=9.9,5.5Hz,16H),1.68(s,6H),1.62(s,3H),1.60(s,21H).
应用实施例71
于一干燥的10mL烧瓶中按实施例1法制备含有0.15mmol NaOR(0.3当量)的(NaOR)
12NaX,其中ROH为2-甲基-2-壬醇,X为氯。此后溶液降温至室温,加入磁力搅拌子、2,3,5-三甲基对苯醌75mg(0.5mmol,1当量)、2,6-二甲基-3,5-二(乙氧酰基)-1,4-二氢吡啶12.6mg(0.05mmol,0.1当量)、(2E,7R,11R)-1-氯-3,7,11,15-四甲基-2-十六碳烯(叶绿基氯)259mg(0.83mmol,1.66当量)。待固体溶解后,向反应瓶中加入40mg市售60%氢化钠-矿物油混合物(约含24mg氢化钠,2当量),随后连接一支空气冷凝管于圆底烧瓶上,置换氮气并持续通氮气泡于反应体系中。加热烧瓶至80摄氏度,搅拌反应100小时。此后,反应液置于离心管中以10000转每分钟离心2分钟,取上清液并用石油醚:乙酸乙酯混合物进行柱层析,制得2,3,5-三甲基-6-((2E,7R,11R)-3,7,11,15-四甲基-2-十六碳烯-1-基)对苯醌138.8mg,产率65%。棕色油状液体。
1H-NMR(500MHz,CDCl
3)δ(ppm)4.94(t,J=7.0Hz,1H),3.20(d,J=6.9Hz,2H),2.02(s,3H),2.01(s,6H),1.92(td,J=7.4,3.8Hz,2H),1.73(s,3H),1.64(d,J=17.4Hz,1H),1.52(hept,J=6.7Hz,1H),1.43(s,1H),1.40–1.32(m,2H),1.31–1.18(m,10H),1.18–1.09(m,2H),1.09–1.00(m,2H),0.86(d,J=6.7Hz,6H),0.83(t,J=6.3Hz,6H).
13C-NMR(126MHz,CDCl
3)δ(ppm)187.95,187.02,143.24,140.37,140.32,140.25,137.51,119.20,40.02,39.38,37.43,37.39,37.30,36.65,32.79,32.65,27.98,25.57,25.29,24.80,24.47,22.72,22.63,19.74,19.72,16.21,12.38,12.36,12.17.
应用实施例72
于一干燥的10mL烧瓶中按实施例1法制备含有0.15mmol NaOR(0.3当量)的(NaOR)
12NaX,其中ROH为2-甲基-2-壬醇,X为氯。此后溶液降温至室温,加入磁力搅拌子、2-甲基萘醌86mg(0.5mmol,1当量)、2,6-二甲基-3,5-二(乙氧酰基)-1,4-二氢吡啶6.3mg(0.025mmol,0.05当量)、(2E,7R,11R)-1-氯-3,7,11,15-四甲基-2-十六碳烯(叶绿基氯)259mg(0.83mmol,1.66当量)。待固体溶解后,向反应瓶中加入40mg市售60%氢化钠-矿物油混合物(约含24mg氢化钠,2当量),随后连接一支空气冷凝管于圆底烧瓶上,置换氮气并持续通氮气泡于反应体系中。加热烧瓶至80摄氏度,搅拌反应120小时。此后,反应液置于离心管中以10000转每分钟离心2分钟,取上清液并用石油醚:乙酸乙酯混合物进行柱层析,制得2-甲基-3-(3,7,11,15-四甲基-2-十六碳烯-1-基)-1,4-萘醌(维生素K1)157.9mg,产率78%。黄色油状液体。
1H-NMR(500MHz,CDCl
3)δ(ppm)8.07(dq,J=7.0,4.0,3.5Hz,2H),7.68(dd,J=5.8,3.2Hz,2H),5.01(t,J=6.9Hz,1H),3.37(d,J=6.9Hz,2H),2.19(s,3H),1.99–1.90(m,2H),1.78(s,3H),1.66(d,J=21.1Hz,1H),1.55–1.48(m,1H),1.42(s,1H),1.34(tt,J=10.6,4.9Hz,2H),1.30–1.17(m,10H),1.17–1.08(m,2H),1.03(m,2H),0.86(d,J=6.6Hz,6H),0.82(dd,J=6.6,3.9Hz,6H).
13C-NMR(126MHz,CDCl
3)δ(ppm)185.47,184.54,146.22,146.21,143.34,137.96,133.33,133.27,132.21,132.16,126.31,126.19,118.82,40.04,39.38,37.42,37.38,37.30,36.65,32.78,32.65,27.98,26.01,25.29,24.82,24.80,24.46,22.73,22.64,19.74,19.72,16.32,12.70.
应用实施例73
于一干燥的10mL烧瓶中按实施例1法制备含有0.088mmol NaOR(0.175当量)的(NaOR)
12NaX,其中ROH为2-甲基-2-壬醇,X为氯。2-甲基萘醌86mg(0.5mmol,1当量)、2,6-二甲基-3,5-二(乙氧酰基)-1,4-二氢吡啶6.3mg(0.025mmol,0.05当量)、1-氯-3-甲基-2-丁烯(异戊烯氯)87mg(0.83mmol,1.66当量)。待固体溶解后,向反应瓶中加入40mg市售60%氢化钠-矿物油混合物(约含24mg氢化钠,2当量),随后连接一支空气冷凝管于圆底烧瓶上,置换氮气并持续通氮气泡于反应体系中。加热烧瓶至80摄氏度,搅拌反应30小时。此后,反应液置于离心管中以10000转每分钟离心2分钟,取上清液并用石油醚:乙酸乙酯混合物进行柱层析,制得2-甲基-3-异戊烯基-1,4-萘醌65.3mg,产率54%。黄色油状液体。
1H-NMR(500MHz,CDCl
3)δ(ppm)8.08(dt,J=5.3,2.7Hz,2H),7.68(dd,J=5.9,3.3Hz,2H),5.01(d,J=7.2Hz,1H),3.36(d,J=7.0Hz,2H),2.19(s,3H),1.80(s,3H),1.69(s,3H).
13C NMR(101MHz,CDCl
3)δ(ppm)185.50,184.58,146.08,143.30,133.98,133.35,133.30,132.19,132.15,126.31,126.20,119.21,26.15,25.75,18.07,12.68.
应用实施例74
于一干燥的10mL烧瓶中按实施例1法制备含有0.15mmol NaOR(0.3当量)的(NaOR)
12NaX,其中ROH为2-甲基-2-壬醇,X为溴。此后溶液降温至室温,加入磁力搅拌子、2-甲基萘醌86mg(0.5mmol,1当量)、2,6-二甲基-3,5-二(乙氧酰基)-1,4-二氢吡啶6.3mg(0.025mmol,0.05当量)、全E式-1-溴-3,7,11,15,19,23,27,31,35-九甲基-2,6,10,14,18,22,26,30,34-三十六碳九烯(茄尼基溴)139mg(0.2mmol,0.4当量)。待固体溶解后,向反应瓶中加入40mg市售60%氢化钠-矿物油混合物(约含24mg氢化钠,2当量),随后连接一支空气冷凝管于圆底烧瓶上,置换氮气并持续通氮气泡于反应体系中。加热烧瓶至80摄氏度,搅拌反应36小时。此后,反应液置于离心管中以10000转每分钟离心2分钟,取上清液并用石油醚:乙酸乙酯混合物进行柱层析,制得维生素K2-MK9 145.6mg,产率93%(以茄尼基溴计)。黄色固体。
1H-NMR(500MHz,CDCl
3)δ(ppm)8.07(dq,J=6.9,4.1,3.5Hz,2H),7.67(dd,J=5.8,3.3Hz,2H),5.14–4.94(m,9H),3.37(d,J=6.9Hz,2H),2.19(d,J=2.5Hz,3H),2.06(t,J=7.5Hz,16H),2.02–1.95(m,16H),1.79(s,3H),1.68(s,3H),1.60(s,21H),1.56(s,3H)
应用实施例75
于一干燥的10mL烧瓶中按实施例1法制备含有0.25mmol NaOR(0.5当量)的(NaOR)
12NaX,其中ROH为2-甲基-2-壬醇,X为溴。此后溶液降温至室温,加入磁力搅拌子、2,3-二甲氧基-5-甲基对苯醌91mg(0.5mmol,1当量)、2,6-二甲基-3,5-二(乙氧酰基)-1,4-二氢吡啶12.6mg(0.05mmol,0.1当量)、1-溴-3-甲基-2-丁烯(异戊烯溴)123.7mg(0.83mmol,1.66当量)。待固体溶解后,向反应瓶中加入40mg市售60%氢化钠-矿物油混合物(约含24mg氢化钠,2当量),随后连接一支空气冷凝管于圆底烧瓶上,置换氮气并持续通氮气泡于反应体系中。加热烧瓶至80摄氏度,搅拌反应21小时。此后,反应液置于离心管中以10000转每分钟离心2分钟,取上清液并用石油醚:乙酸乙酯混合物进行柱层析,制得2,3-二甲氧基-5-甲基-6-(3-甲基-2-丁烯-1-基)对苯醌72.6mg,产率58%。橙色油状液体。
1H-NMR(400MHz,CDCl
3)δ(ppm)4.94(t,J=7.3Hz,1H),4.00(s,3H),3.98(s,3H),3.17(d,J=7.1Hz,2H),2.02(s,3H),1.74(s,3H),1.68(s,3H).
应用实施例76
于一干燥的10mL烧瓶中按实施例1法制备含有0.15mmol NaOR(0.3当量)的(NaOR)
12NaX,其中ROH为2-甲基-2-壬醇,X为氯。此后溶液降温至室温,加入磁力搅拌子、2,3-二甲氧基-5-甲基对苯醌91mg(0.5mmol,1当量)、2,6-二甲基-3,5-二(乙氧酰基)-1,4-二氢吡啶12.6mg(0.05mmol,0.1当量)、全E式-1-氯-3,7,11,15,19,23,27,31,35-九甲基-2,6,10,14,18,22,26,30,34-三十六碳九烯(茄尼基氯)162mg(0.25mmol,0.5当量)。待固体溶解后,向反应瓶中加入40mg市售60%氢化钠-矿物油混合物(约含24mg氢化钠,2当量),随后连接一支空气冷凝管于圆底烧瓶上,置换氮气并持续通氮气泡于反应体系中。加热烧瓶至100摄氏度,搅拌反应42小时。此后,反应液置于离心管中以10000转每分钟离心2分钟,取上清液并用石油醚:乙酸乙酯混合物进行柱层析,制得辅酶Q9(CoQ9)124.9mg,产率63%(以茄尼基氯计)。黄色固体。
1H-NMR(500MHz,CDCl
3)δ(ppm)5.11(m,8H),4.94(d,J=7.8Hz,1H),3.99(d,J=2.5Hz,3H),3.98(s,3H),3.18(d,J=6.9Hz,2H),2.06(t,J=7.5Hz,16H),2.01(s,3H),1.99(t,J=7.4Hz,16H),1.74(s,3H),1.68(s,3H),1.62(s,3H),1.60(s,21H).
应用实施例77
于一干燥的10mL烧瓶中按实施例1法制备含有0.15mmol NaOR(0.3当量)的(NaOR)
12NaX,其中ROH为2-甲基-2-壬醇,X为氯。此后溶液降温至室温,加入磁力搅拌子、2,3-二甲氧基-5-甲基对苯醌91mg(0.5mmol,1当量)、2,6-二甲基-3,5-二(乙氧酰基)-1,4-二氢吡啶12.6mg(0.05mmol,0.1当量)、全E式-1-氯-3,7,11,15,19,23,27,31,35,39-十甲基-2,6,10,14,18,22,26,30,34,38-四十碳十烯179mg(0.25mmol,0.5当量)。待固体溶解后,向反应瓶中加入40mg市售60%氢化钠-矿物油混合物(约含24mg氢化钠,2当量),随后连接一支空气冷凝管于圆底烧瓶上,置换氮气并持续通氮气泡于反应体系中。加热烧瓶至100摄氏度,搅拌反应42小时。此后,反应液置于离心管中以10000转每分钟离心2分钟,取上清液并用石油醚:乙酸乙酯混合物进行柱层析,制得辅酶Q10(CoQ10)97.7mg,产率45%(以1-氯-十甲基-四十碳十烯计)。橙色固体。
1H-NMR(400MHz,CDCl
3)δ(ppm)1.55(s,3H),1.60(s,21H),1.68(s,6H),1.74(s,3H),1.93–2.02(m,18H),2.01(s,3H),2.02–2.13(m,18H),3.18(d,J=7.2Hz,2H),3.98(s,3H),3.99(s,3H),4.94(t,J=7.1Hz,1H),5.06(t,J=6.8Hz,1H),5.12(t,J=6.8Hz,8H)。
Claims (14)
- 一种如式I所示的化合物:(ZOR) 12Y mQ nI其中,R为金刚烷基、C 6-14芳基、被一个或多个R -1取代的C 6-14芳基、5-10元杂芳基、被一个或多个R -2取代的5-10元杂芳基或 所述的5-10元杂芳基中的杂原子或被一个或多个R -2取代的5-10元杂芳基中的杂原子为N、S和O中的1种或多种,个数为1、2或3个;R -1和R -2独立地为C 1-6烷基;R 1、R 2和R 3独立地为H、C 1-10烷基、被一个或多个R 1-1取代的C 1-10烷基、C 6-14芳基、被一个或多个R 1-2取代的C 6-14芳基、C 3-6环烷基、C 3-6环烯基、被一个或多个R 1-3取代的C 3-6环烯基、C 2-40烯基、C 1-10烷氧基、5-10元杂芳基、3-6元杂环烷基或3-6元杂环烯基;所述的5-10元杂芳基中的杂原子、所述的3-6元杂环烷基中的杂原子和所述的3-6元杂环烯基中的杂原子独立地为N、S和O中的1种或多种,个数为1、2或3个;R 1-1和R 1-2和R 1-3独立地为C 6-14芳基、羟基、卤素、C 1-6烷基、C 3-6环烷基、5-10元杂芳基、3-6元杂环烷基、3-6元杂环烯基、巯基、C 1-6烷氧基、-S-C 1-6烷基、-NR 1-1-1R 1-1-2、-C(=O)R 1-1-3、-C(=O)OR 1- 1-4或-C(=O)NR 1-1-5,所述的5-10元杂芳基中的杂原子、3-6元杂环烷基中的杂原子和3-6元杂环烯基中的杂原子独立地为N、S和O中的1个或多个,个数为1、2或3个;R 1-1-1、R 1-1-2、R 1-1-3、R 1-1-4和R 1-1-5独立地为H或C 1-6烷基;或者,R 1、R 2和R 3中任意两个与其相连的C一起形成C 3-6环烷基、被一个或多个R 1-4取代的C 3-6环烷基、3-6元杂环烷基、或被一个或多个R 1-5取代的3-6元杂环烷基;所述的3-6元杂环烷基和或被一个或多个R 1-5取代的3-6元杂环烷基中的杂原子独立地为N、S和O中的1种或多种,个数为1、2或3个;R 1-4和R 1-5独立地为C 1-6烷基、C 6-14芳基、羟基、卤素、C 3-6环烷基、5-10元杂芳基、3-6元杂环烷基、3-6元杂环烯基、巯基、C 1-6烷氧基、-S-C 1-6烷基、-NR 1-4-1R 1-4-2、-C(=O)R 1-4-3、-C(=O)OR 1-4-4或-C(=O)NR 1-4-5,所述的5-10元杂芳基中的杂原子、3-6元杂环烷基中的杂原子和3-6元杂环烯基中的杂原子独立地为N、S和O中的1种或多种,个数为1、2或3个;R 1-4-1、R 1-4-2、R 1-4-3、R 1-4-4和R 1-4-5独立地为H或C 1-6烷基;Z为碱金属;Y为碱金属或醚类化合物-碱金属的配合物;所述的醚类化合物-碱金属配合物中的醚类化合物为C 2-18醚类化合物或C 12-18冠醚类化合物;Q独立地为卤素、H或-B(C 6-14芳基) 4;m和n独立地为1或2。
- 如权利要求1所述的如式I所示的化合物,其特征在于,所述的如式I所示的化合物满足如下1个或多个条件:(1)所述的如式I所示的化合物具有正二十面体立体结构;(3)R -1和R -2中,所述的C 1-6烷基独立地为甲基、乙基、正丙基、异丙基、正丁基、仲丁基、异丁基或叔丁基;(4)R 1、R 2和R 3中,所述的C 1-10烷基和所述的被一个或多个R 1-1取代的C 1-10烷基中的C 1-10烷基独立地为C 1-7烷基,还可以为甲基、乙基、正丙基、异丙基、正丁基、仲丁基、异丁基、叔丁基、正戊基、正己基或正庚基;(5)R 1、R 2和R 3中,所述的C 6-14芳基和所述的被一个或多个R 1-2取代的C 6-14芳基中的C 6-14芳基独立地为苯基、萘基或蒽基;(6)R 1、R 2和R 3中,所述的C 3-6环烷基独立地为环丙基、环丁基、环戊基或环己基;(7)R 1、R 2和R 3中,所述的C 3-6环烯基和所述的被一个或多个R 1-3取代的C 3-6环烯基中的C 3-6环烯基独立地为环丙烯基、环丁烯基、环戊烯基或环己烯基;(9)R 1-1、R 1-2和R 1-3中,所述的C 6-14芳基独立地为苯基、萘基或蒽基(10)R 1-1-1、R 1-1-2、R 1-1-3、R 1-1-4和R 1-1-5中,所述的C 1-6烷基独立地为甲基、乙基、正丙基、异丙基、正丁基、仲丁基、异丁基或叔丁基;(11)当R 1、R 2和R 3中任意两个与其相连的C一起形成C 3-6环烷基或被一个或多个R 1-4取代的C 3-6环烷基时,所述的C 3-6环烷基和所述的被一个或多个R 1-4取代的C 3-6环烷基中的C 3-6环烷基独立地为环丙基、环丁基、环戊基或环己基;(12)R 1-4和R 1-5中,所述的C 1-6烷基独立地为甲基、乙基、正丙基、异丙基、正丁基、仲丁基、异丁基或叔丁基;(13)Z中,所述的碱金属为Li、Na或K,例如Na;(14)Y中,所述的碱金属和醚类化合物-碱金属配合物中的碱金属独立地为Li、Na或K,例如Na;(15)Y中,当所述的醚类化合物为C 2-8醚类化合物时,所述的C 2-8醚类化合物为甲醚、乙醚、正丙醚或正丁醚,例如甲醚;(16)Y中,当所述的醚类化合物为C 12-18冠醚类化合物时,所述的C 12-18冠醚类化合物为12-冠 (醚)-4、15-冠(醚)-5或18-冠(醚)-6,例如15-冠(醚)-5;(17)Q中,所述的卤素为F、Cl、Br或I(18)Q中,所述的-B(C 6-14芳基) 4中的C 6-14芳基独立地为苯基、萘基或菲基,例如苯基;(19)m为1,n为1;或者,m为2,n为2。
- 如权利要求1所述的如式I所示的化合物,其特征在于,所述的如式I所示的化合物满足如下1个或多个条件:(2)R -1为C 1-6烷基;(3)R 1、R 2和R 3独立地为H、C 1-10烷基、被一个或多个R 1-1取代的C 1-10烷基、C 6-14芳基、被一个或多个R 1-2取代的C 6-14芳基、C 3-6环烷基、C 3-6环烯基、被一个或多个R 1-3取代的C 3-6环烯基或C 2-40烯基;或者,R 1、R 2和R 3中任意两个与其相连的C一起形成C 3-6环烷基或被一个或多个R 1-4取代的C 3-6环烷基;(4)R 1-1为C 6-14芳基或羟基;(5)R 1-2为C 1-6烷基;(6)R 1-3为C 1-6烷基;(7)R 1-4为C 1-6烷基;(8)Q独立地为卤素、H或-B(C 6-14芳基) 4。
- 如权利要求1所述的如式I所示的化合物,其特征在于,所述的如式I所示的化合物为方案1、方案2、方案3或方案4、:方案1:所述的如式I所示的化合物的通式为如式I-1所示:(ZOR) 12YQI-1其中,Y为碱金属;Q独立地为卤素;方案2:所述的如式I所示的化合物的通式为如式I-1所示:(ZOR) 12YQI-1其中,Y为醚类化合物-碱金属配合物;Q独立地为卤素或H;方案3:所述的如式I所示的化合物的通式为如式I-2:[(ZOR) 12Y 2Q]QI-2其中,Y为碱金属;Q中一个为-B(C 6-14芳基) 4,另一个为H或卤素;方案4:R -1为C 1-6烷基;R 1、R 2和R 3独立地为H、C 1-10烷基、被一个或多个R 1-1取代的C 1-10烷基、C 6-14芳基、被一个或多个R 1-2取代的C 6-14芳基、C 3-6环烷基、C 3-6环烯基、被一个或多个R 1-3取代的C 3-6环烯基或C 2-40烯基,且R 1、R 2和R 3不同时为H;或者,R 1、R 2和R 3中任意两个与其相连的C一起形成C 3-6环烷基或被一个或多个R 1-4取代的C 3-6环烷基;R 1-1为C 6-14芳基或羟基;R 1-2为C 1-6烷基;R 1-3为C 1-6烷基;R 1-4为C 1-6烷基;Q独立地为卤素、H或-B(C 6-14芳基) 4。
- 一种如式I所示的化合物的制备方法,其特征在于,其包括以下步骤:在NaH或卤化试剂存在下,将化合物ZOR和化合物II在溶剂中进行如下式的反应,得到所述的如式I所示的化合物;其中,所述的卤化试剂为四卤苯醌、被1、2或3个R 4取代的卤甲烷、四卤化碳、C 3-6环烯基卤甲烷或卤化钠;R 4为苯基、被1、2或3个R 4-1取代的苯基、C 2-30烯基、被1、2或3个羟基取代的C 2-30烯基;R 4-1为卤素、C 1-10烷基或C 1-10烷氧基;所述的化合物II为C 2-18醚类化合物、C 12-18冠醚类化合物、Z[Ph 4B]或者不存在;所述的反应的温度为60-300℃;其中,Z、R、Y、Q、m、n、C 2-18醚类化合物和C 12-18冠醚类化合物的定义均如权利要求1-6中任一项所述。
- 如权利要求7所述的如式I所示的化合物的制备方法,其特征在于,所述的如式I所示的化合物的制备方法满足如下1个或多个条件:(1)所述的四卤代醌为四氯苯醌、四溴苯醌、四碘苯醌或四氟苯醌;(2)所述的被1、2或3个R 4取代的卤甲烷优选为三苯甲基溴、二苯甲基氯、苯甲基氯或异戊烯氯;(3)所述的四卤化碳为四氯化碳或四溴化碳;(4)所述的卤化钠优选为氯化钠、溴化钠、碘化钠或氟化钠;(5)所述的ZOR与卤化试剂中的卤原子摩尔比优选20:1-1:1,例如10:8;(6)当在NaH存在下,所述的化合物II为C 2-18醚类化合物、C 12-18冠醚类化合物或Z[Ph 4B];当卤化试剂存在下,所述的化合物II为C 2-18醚类化合物、C 12-18冠醚类化合物或不存在;(7)所述的化合物II与所述的化合物ZOR的摩尔比为1:5-1:20,例如0.2:1;(8)所述的反应的温度为80-120℃。
- 一种按照权利要求7或8所述的如式I所示的化合物的制备方法制得的如式I所示的化合物。
- 一种如权利要求1-6中任一项所述的如式I所示的化合物的单晶,其特征在于,所述的如式I所示的化合物的单晶为如式I-a所示的化合物的单晶、如式I-b所示的化合物的单晶、如式I-c所示的化合物的单晶、如式I-d所示的化合物的单晶、如式I-e所示的化合物的单晶、如式I-f所示的化合物的单晶、如式I-g所示的化合物的单晶、如式I-h所示的化合物的单晶或如式I-i所示的化合物的单晶;所述的如式I-a所示的化合物的单晶的结构优选基本如图1所示;(NaOt-Bu) 12NaFI-a;(NaOt-Bu) 12NaClI-b;或者,所述的如式I-c所示的化合物的单晶,其以2θ角度表示的X-射线粉末衍射图在7.9±0.2°、9.1±0.2°、18.8±0.2°、19.4±0.2°、21.0±0.2°和32.8±0.2°处有特征峰;所述的如式I-c所示的化合物的单晶的X-射线粉末衍射图优选基本如图13所示;(NaOt-Bu) 12NaBrI-c;(NaOt-Bu) 12NaII-d;(NaOt-Bu) 12NaHI-e;[DME-Na][(NaOt-Bu) 12H]I-f;[15-冠-5-Na][(NaOt-Bu) 12H]I-g;[15-冠-5-Na][(NaOt-Bu) 12F]I-h;[15-冠-5-Na][(NaOt-Bu) 12Cl]I-i。
- 一种物质A作为催化剂在制备醌类化合物中的应用,其特征在于,所述的物质A选自如权利要求1-6中任一项所述的如式I所示的化合物、如权利要求10所述的如式I-a所示的化合物的单晶、如权利要求10所述的如式I-b所示的化合物的单晶、如权利要求10所述的如式I-c所示的化合物的单晶、如权利要求10所述的如式I-d所示的化合物的单晶、如权利要求10所述的如式I-e所示的化合物的单晶、如权利要求10所述的如式I-f所示的化合物的单晶、如权利要求10所述的如式I-g所 示的化合物的单晶、如权利要求10所述的如式I-h所示的化合物的单晶和如权利要求10所述的如式I-i所示的化合物的单晶中的一种或多种;所述的醌类化合物为含有烯基侧链的醌类化合物。
- 如权利要求11所述的应用,其特征在于,所述的醌类化合物的制备方法包括如下步骤:在所述的物质A催化下,将如式IV所示的化合物和如式V所示的化合物进行缩合反应,得到如式III所示的醌类化合物即可;其中,R 1a、R 2a和R 3a独立地为氢、C 1-10烷基、C 2-10烯基或C 1-10烷氧基;或者,R 2a、R 3a以及与之相连的碳原子一起形成C 6-10芳基、被一个或多个羟基取代的C 6-10芳基、或、5-10元的杂芳基;所述的杂芳基中的杂原子选自N、O和S中的一种或多种,杂原子的个数为1个、2个或3个;R 6a为C 3-100烯基、被一个或多个R 6a-1取代的C 3-100烯基、或、C 3-10环烯基;R 6a-1独立地为C 6-10芳基或5-10元的杂芳基;所述的杂芳基中的杂原子选自N、O和S中的一种或多种,杂原子的个数为1个、2个或3个;X为卤素。
- 如权利要求11所述的应用,其特征在于,所述的应用满足如下条件:(1)R 1a、R 2a和R 3a中,所述的C 1-10烷基独立地为甲基、乙基、正丙基、异丙基、正丁基、仲丁基、异丁基或叔丁基;(2)R 1a、R 2a和R 3a中,所述的C 2-10烯基独立地为C 2-5烯基,例如3-甲基-2-丁烯-1-基;(3)R 1a、R 2a和R 3a中,所述的C 1-10烷氧基独立地为甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、仲丁氧基、异丁氧基或叔丁氧基;(4)当R 2a、R 3a以及与之相连的碳原子一起形成C 6-10芳基时,所述的C 6-10芳基为苯基;(5)当R 2a、R 3a以及与之相连的碳原子一起形成被一个或多个羟基取代的C 6-10芳基时,所述的C 6-10芳基为苯基;(6)R 6a中,所述的C 3-100烯基和被一个或多个R 6a-1取代的C 3-100烯基中的C 3-100烯基独立地含有1~15个双键,还可以含有1个、2个、3个、4个、5个、6个、7个、8个、9个或10个双键;较佳地,其中的一双键为位于所述的X的β位和γ位中间;(7)R 6a中,所述的C 3-100烯基和被一个或多个R 6a-1取代的C 3-100烯基中的C 3-100烯基独立地为C 5-100的萜烯基,还可以为“ n为0~19,例如0、1、2、3、4、5、6、7、8、9、10、11、12、13、14、15、16、17、18或19,还例如0、1、2、3、4、5、6、7、8或9”;(8)R 6a中,所述的C 3-100烯基和被一个或多个R 6a-1取代的C 3-100烯基中的C 3-100烯基独立地为C 3~C 50的烯基,还可以为C 3的烯基、C 4的烯基、C 5的烯基、C 6的烯基、C 7的烯基、C 8的烯基、C 9的烯基、C 10的烯基、C 15的烯基、C 20的烯基、C 30的烯基、C 40的烯基、C 45的烯基或C 50的烯基,更可以为烯丙基、2-丁烯-1-基、3-甲基-2-丁烯-1-基、2-己烯-1-基、(全-E)-3,7-二甲基-2,6-辛二烯-1-基、(全-E)-3,7,11-三甲基-2,6,10-十二烷三烯-1-基、叶绿基、(全-E)-3,7,11,15-四甲基-2,6,10,14-十六碳四烯-1-基、(全-E)-3,7,11,15,19,23,27-七甲基-2,6,10,14,18,22,26-二十八碳七烯-1-基、(全-E)-3,7,11,15,19,23,27,31,35-九甲基-2,6,10,14,18,22,26,30,34-三十六碳九烯-1-基或(全-E)-3,7,11,15,19,23,27,31,35,39-十甲基-2,6,10,14,18,22,26,30,34,38-四十碳十烯-1-基;(9)R 6a中,所述的C 3-10环烯基,为C 3-10的环烯基,还可以为2-环己烯-1-基;(10)R 6a中,所述的被一个或多个R 6a-1取代的C 3-100烯基中的多个为2个或3个;(11)R 6a-1中,所述的C 6-10芳基为苯基;(12)R 6a中,所述的C 3-10环烯基含有1~5个双键,还可以含有1个、2个、3个、4个或5个双键;较佳地,其中的一双键为位于所述的X的β位和γ位中间;(13)R 6a中,所述的C 3-10环烯基为C 3~C 6的环烯基,例如2-环己烯-1-基;(14)X中,所述的卤素为氯、溴或碘,还可以为氯或溴;(15)所述的物质A与所述的如式IV所示的化合物的摩尔比为(0.05-0.30):1,例如0.15:1。
- 如权利要求11所述的应用,其特征在于,所述的缩合反应具有如下的反应参数:所述的缩合反应在保护气体的存在下进行;所述的缩合反应在碱性试剂存在下进行,所述的碱性试剂与所述的如式IV所示的化合物的摩尔比为(1-3):1所述的缩合反应在有机溶剂中进行,所述的有机溶剂为卤代芳香烃类溶剂,所述的如式IV所示的化合物与所述的有机溶剂的摩尔体积比为0.1mol/L~0.3mol/L;所述的缩合反应还在 的存在下进行,所述的 与如式IV所示的化合物的摩尔比为(0.025~0.10):1;所述的如式V所示的化合物与如式IV所示的化合物的摩尔比为(0.2~2.0):1;所述的缩合反应的温度为20℃~100℃;和/或,所述的如式II所示的化合物为1,4-苯醌、2-甲基-1,4-苯醌、2,3-二甲基-1,4-苯醌、2,3,5-三甲基-1,4-苯醌、2,3-二甲氧基-5-甲基-1,4-苯醌、2-甲基-1,4-萘醌或5-羟基-1,4-萘醌;和/或,R 6a为3-甲基-2-丁烯-1-基、(全-E)-3,7-二甲基-2,6-辛二烯-1-基、(全-E)-3,7,11-三甲基-2,6,10-十二烷三烯-1-基、叶绿基、(全-E)-3,7,11,15-四甲基-2,6,10,14-十六碳四烯-1-基、(全-E)-3,7,11,15,19,23,27-七甲基-2,6,10,14,18,22,26-二十八碳七烯-1-基、(全-E)-3,7,11,15,19,23,27,31,35-九甲基-2,6,10,14,18,22,26,30,34-三十六碳九烯-1-基或(全-E)-3,7,11,15,19,23,27,31,35,39-十甲基-2,6,10,14,18,22,26,30,34,38-四十碳十烯-1-基。
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