CN113443950A - 一种光照下羰基还原为亚甲基的方法 - Google Patents
一种光照下羰基还原为亚甲基的方法 Download PDFInfo
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- CN113443950A CN113443950A CN202110728579.3A CN202110728579A CN113443950A CN 113443950 A CN113443950 A CN 113443950A CN 202110728579 A CN202110728579 A CN 202110728579A CN 113443950 A CN113443950 A CN 113443950A
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- carbonyl
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- methylene
- reduction
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- 238000000034 method Methods 0.000 title claims abstract description 49
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 title claims abstract description 20
- 238000005286 illumination Methods 0.000 title claims abstract description 19
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 title claims abstract 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- -1 amine compound Chemical class 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 150000001728 carbonyl compounds Chemical class 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 230000009467 reduction Effects 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- 125000001072 heteroaryl group Chemical group 0.000 claims description 8
- 125000000623 heterocyclic group Chemical group 0.000 claims description 7
- 125000001624 naphthyl group Chemical group 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 150000001299 aldehydes Chemical class 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000000304 alkynyl group Chemical group 0.000 claims description 4
- 125000004104 aryloxy group Chemical group 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- 125000000392 cycloalkenyl group Chemical group 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 150000004820 halides Chemical class 0.000 claims description 4
- 125000004404 heteroalkyl group Chemical group 0.000 claims description 4
- 125000005553 heteroaryloxy group Chemical group 0.000 claims description 4
- 125000004366 heterocycloalkenyl group Chemical group 0.000 claims description 4
- 125000000592 heterocycloalkyl group Chemical group 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
- 125000000018 nitroso group Chemical group N(=O)* 0.000 claims description 4
- 125000003107 substituted aryl group Chemical group 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 2
- 125000003172 aldehyde group Chemical group 0.000 claims description 2
- 125000003368 amide group Chemical group 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229940043279 diisopropylamine Drugs 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 2
- QHCCDDQKNUYGNC-UHFFFAOYSA-N n-ethylbutan-1-amine Chemical compound CCCCNCC QHCCDDQKNUYGNC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 claims description 2
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims 2
- 125000003396 thiol group Chemical group [H]S* 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 65
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 239000000376 reactant Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 231100000053 low toxicity Toxicity 0.000 abstract 1
- 231100000419 toxicity Toxicity 0.000 abstract 1
- 230000001988 toxicity Effects 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 79
- 239000000047 product Substances 0.000 description 69
- CCJVYJDZZJLSIJ-UHFFFAOYSA-N 2,9-dihydrofluoren-1-one Chemical compound C1C2=CC=CC=C2C2=C1C(=O)CC=C2 CCJVYJDZZJLSIJ-UHFFFAOYSA-N 0.000 description 39
- 238000005160 1H NMR spectroscopy Methods 0.000 description 24
- 238000012512 characterization method Methods 0.000 description 23
- 238000004440 column chromatography Methods 0.000 description 23
- 238000007405 data analysis Methods 0.000 description 22
- 239000000706 filtrate Substances 0.000 description 22
- 238000000926 separation method Methods 0.000 description 22
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- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 16
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 12
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 11
- 230000008569 process Effects 0.000 description 8
- 239000007788 liquid Substances 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- RKJHJMAZNPASHY-UHFFFAOYSA-N 2-methyl-9h-fluorene Chemical compound C1=CC=C2C3=CC=C(C)C=C3CC2=C1 RKJHJMAZNPASHY-UHFFFAOYSA-N 0.000 description 4
- WPDAVTSOEQEGMS-UHFFFAOYSA-N 9,10-dihydroanthracene Chemical compound C1=CC=C2CC3=CC=CC=C3CC2=C1 WPDAVTSOEQEGMS-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- NPOGRKGIBGKRNI-UHFFFAOYSA-N 1-benzyl-4-chlorobenzene Chemical compound C1=CC(Cl)=CC=C1CC1=CC=CC=C1 NPOGRKGIBGKRNI-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CSABYBOSPVTETQ-UHFFFAOYSA-N 1-(9h-fluoren-3-yl)ethanone Chemical compound C1=CC=C2C3=CC(C(=O)C)=CC=C3CC2=C1 CSABYBOSPVTETQ-UHFFFAOYSA-N 0.000 description 2
- BYTOZNNXTSCVNP-UHFFFAOYSA-N 1-benzyl-3,5-bis(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC(C(F)(F)F)=CC(CC=2C=CC=CC=2)=C1 BYTOZNNXTSCVNP-UHFFFAOYSA-N 0.000 description 2
- OJMXATJXHTWJDR-UHFFFAOYSA-N 1-benzyl-3-methoxybenzene Chemical compound COC1=CC=CC(CC=2C=CC=CC=2)=C1 OJMXATJXHTWJDR-UHFFFAOYSA-N 0.000 description 2
- ORPNRYPRELTIPZ-UHFFFAOYSA-N 1-benzyl-4-tert-butylbenzene Chemical compound C1=CC(C(C)(C)C)=CC=C1CC1=CC=CC=C1 ORPNRYPRELTIPZ-UHFFFAOYSA-N 0.000 description 2
- MYZIJBJPIHILLG-UHFFFAOYSA-N 1-chloro-9h-fluorene Chemical compound C12=CC=CC=C2CC2=C1C=CC=C2Cl MYZIJBJPIHILLG-UHFFFAOYSA-N 0.000 description 2
- BSHACNDVUPQQJN-UHFFFAOYSA-N 2,3,7-trimethyl-9h-fluorene Chemical compound CC1=C(C)C=C2C3=CC=C(C)C=C3CC2=C1 BSHACNDVUPQQJN-UHFFFAOYSA-N 0.000 description 2
- VPGIYLLXBOUILV-UHFFFAOYSA-N 2-benzylthiophene Chemical compound C=1C=CC=CC=1CC1=CC=CS1 VPGIYLLXBOUILV-UHFFFAOYSA-N 0.000 description 2
- KKTCFZXZGSLKNV-UHFFFAOYSA-N 3,6-dimethyl-9h-fluorene Chemical compound C1=C(C)C=C2C3=CC(C)=CC=C3CC2=C1 KKTCFZXZGSLKNV-UHFFFAOYSA-N 0.000 description 2
- JRMXTDCJRYVMRO-UHFFFAOYSA-N 3-(trifluoromethyl)-9H-fluorene Chemical compound FC(F)(F)c1ccc2Cc3ccccc3-c2c1 JRMXTDCJRYVMRO-UHFFFAOYSA-N 0.000 description 2
- PQJUJGAVDBINPI-UHFFFAOYSA-N 9H-thioxanthene Chemical compound C1=CC=C2CC3=CC=CC=C3SC2=C1 PQJUJGAVDBINPI-UHFFFAOYSA-N 0.000 description 2
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 description 2
- CYSPWCARDHRYJX-UHFFFAOYSA-N 9h-fluoren-1-amine Chemical compound C12=CC=CC=C2CC2=C1C=CC=C2N CYSPWCARDHRYJX-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- JNELGWHKGNBSMD-UHFFFAOYSA-N xanthone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3OC2=C1 JNELGWHKGNBSMD-UHFFFAOYSA-N 0.000 description 2
- CKGKXGQVRVAKEA-UHFFFAOYSA-N (2-methylphenyl)-phenylmethanone Chemical compound CC1=CC=CC=C1C(=O)C1=CC=CC=C1 CKGKXGQVRVAKEA-UHFFFAOYSA-N 0.000 description 1
- VMFJVWPCRCAWBS-UHFFFAOYSA-N (3-methoxyphenyl)-phenylmethanone Chemical compound COC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1 VMFJVWPCRCAWBS-UHFFFAOYSA-N 0.000 description 1
- URBLVRAVOIVZFJ-UHFFFAOYSA-N (3-methylphenyl)-phenylmethanone Chemical compound CC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1 URBLVRAVOIVZFJ-UHFFFAOYSA-N 0.000 description 1
- DFYJCXSOGSYMAJ-UHFFFAOYSA-N (4-tert-butylphenyl)-phenylmethanone Chemical compound C1=CC(C(C)(C)C)=CC=C1C(=O)C1=CC=CC=C1 DFYJCXSOGSYMAJ-UHFFFAOYSA-N 0.000 description 1
- PQTAUFTUHHRKSS-UHFFFAOYSA-N 1-benzyl-2-methylbenzene Chemical compound CC1=CC=CC=C1CC1=CC=CC=C1 PQTAUFTUHHRKSS-UHFFFAOYSA-N 0.000 description 1
- KSYQGOYOIKQFNA-UHFFFAOYSA-N 1-benzyl-3-methylbenzene Chemical compound CC1=CC=CC(CC=2C=CC=CC=2)=C1 KSYQGOYOIKQFNA-UHFFFAOYSA-N 0.000 description 1
- HSUVSSHWXMPDAC-UHFFFAOYSA-N 2-methoxy-2,9-dihydrofluoren-1-one Chemical compound COC1C(C=2CC3=CC=CC=C3C=2C=C1)=O HSUVSSHWXMPDAC-UHFFFAOYSA-N 0.000 description 1
- APWAMQGDVJNMRK-UHFFFAOYSA-N 2-methoxy-9h-fluorene Chemical compound C1=CC=C2C3=CC=C(OC)C=C3CC2=C1 APWAMQGDVJNMRK-UHFFFAOYSA-N 0.000 description 1
- RFISEOWYBKAQIR-UHFFFAOYSA-N 2-methyl-2,9-dihydrofluoren-1-one Chemical compound CC1C=CC2=C(CC3=CC=CC=C23)C1=O RFISEOWYBKAQIR-UHFFFAOYSA-N 0.000 description 1
- DGPGIZUJXOLPMC-UHFFFAOYSA-N 3,6-dimethyl-2,9-dihydrofluoren-1-one Chemical compound CC=1CC(C=2CC3=CC=C(C=C3C=2C=1)C)=O DGPGIZUJXOLPMC-UHFFFAOYSA-N 0.000 description 1
- PVUBSZGNXLNTLX-UHFFFAOYSA-N 3-Hydroxyfluorene Chemical compound C1=CC=C2C3=CC(O)=CC=C3CC2=C1 PVUBSZGNXLNTLX-UHFFFAOYSA-N 0.000 description 1
- UGVRJVHOJNYEHR-UHFFFAOYSA-N 4-chlorobenzophenone Chemical compound C1=CC(Cl)=CC=C1C(=O)C1=CC=CC=C1 UGVRJVHOJNYEHR-UHFFFAOYSA-N 0.000 description 1
- 229910000497 Amalgam Inorganic materials 0.000 description 1
- 238000006214 Clemmensen reduction reaction Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000006856 Wolf-Kishner-Huang Minlon reduction reaction Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- RJGDLRCDCYRQOQ-UHFFFAOYSA-N anthrone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3CC2=C1 RJGDLRCDCYRQOQ-UHFFFAOYSA-N 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- 150000008365 aromatic ketones Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- DWYFUJJWTRPARQ-UHFFFAOYSA-N phenyl(thiophen-2-yl)methanone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CS1 DWYFUJJWTRPARQ-UHFFFAOYSA-N 0.000 description 1
- 229920001843 polymethylhydrosiloxane Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/207—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds
- C07C1/2076—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds by a transformation in which at least one -C(=O)- moiety is eliminated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/35—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
- C07C209/78—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton from carbonyl compounds, e.g. from formaldehyde, and amines having amino groups bound to carbon atoms of six-membered aromatic rings, with formation of methylene-diarylamines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/65—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/78—Ring systems having three or more relevant rings
- C07D311/80—Dibenzopyrans; Hydrogenated dibenzopyrans
- C07D311/82—Xanthenes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/08—Hydrogen atoms or radicals containing only hydrogen and carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
- C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D335/10—Dibenzothiopyrans; Hydrogenated dibenzothiopyrans
- C07D335/12—Thioxanthenes
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明属于有机化学合成技术领域,尤其涉及一种光照下羰基还原为亚甲基的方法,包括如下步骤:将羰基化合物和胺化合物按照摩尔比为1:(3~6)混合溶于溶剂中,在380‑456nm的光照下反应12~24h。本发明反应体系毒性低,原子利用率和生产效率高,反应过程安全可控,简化了制备生产过程中操作。同时使得反应的残留物毒性降至最低,减少了生产过程对环境产生的污染,同时简化了反应后除去残留物的步骤和操作。另外,反应物原料非常容易获得,且反应前该类反应物无需进行额外的修饰,可以直接用于制备生产,简化了操作步骤,缩短了反应路线;显著降低了生产本低。
Description
技术领域
本发明属于有机化学合成技术领域,尤其涉及一种光照下羰基还原为亚甲基的方法。
背景技术
还原反应是有机合成和化工领域非常重要的一类反应,其中羰基还原为亚甲基医药、农药、合成工业等领域有广泛的应用和研究基础。传统工业上将羰基还原为亚甲基有两种方法:第一种是Clemmensen还原,醛或酮与锌汞齐和浓盐酸一起回流反应,对还原芳酮的结果较好,但只适用于对酸稳定的化合物。第二种方法是Wolff-Kishner-Huang Minlon还原法,适用于对酸不稳定而对碱稳定的羰基化合物,将醛或酮与肼和氢氧化钾在高沸点溶剂如一缩二乙二醇中一同加热反应。但这两种方法反应所需条件严苛,成本较高且污染严重,不符合绿色化学的环保节能理念。近些年来也有开发出使用含过渡金属如Fe、Ni、Cu作为催化剂来催化羰基还原为亚甲基,但这种催化剂的催化活性低且要求的反应条件高。如Hans Adolfsson课题组报道以Pd/C为催化剂,用聚甲基氢硅氧烷作氢源还原羰基。RabahBoukherroub课题组用PdO NPs/GO作催化剂,在Et3SiH存在下成功将不同羰基化合物如芳香醛、酮和酰氯还原成相应的亚甲基衍生物。然而这些方法需要额外的添加剂,有大量副产物生成,需要复杂的分离纯化手段,仍然达不到经济环保的要求。
发明内容
本发明的目的在于提供克服现有技术中羰基还原方法,反应所需条件严苛,成本较高且污染严重,不符合绿色化学的环保节能理念,有大量副产物生成,需要复杂的分离纯化手段等技术问题,提供一种光照下羰基还原为亚甲基的方法。
本发明的目的通过以下技术方案予以实现:
一种光照下羰基还原为亚甲基的方法,包括如下步骤:将羰基化合物和胺化合物按照摩尔比为1:(3~6)混合溶于溶剂中,在380-456nm的光照下反应12~24h。
优选地,所述羰基化合物为式(I)、式(II)或式(III)的化合物:
其中,A为C、N、O、S原子其中之一;R1为氢、烷基、烷氧基、杂烷基、环烷基、杂环烷基、烯基、杂烯基、环烯基、杂环烯基、炔基、杂炔基、环炔基、杂环炔基、芳基、取代的芳基、杂芳基、取代的杂芳基、芳氧基、杂芳基氧基、卤素、羟基、巯基、醛基、磺酸基、羧基、酰卤基、酯基、酰胺基、氨基、亚氨基、硝基、氰基、亚硝基中相同或不同任一种;
R2和R3为苯基、取代的苯基、杂环、取代的杂环、萘基、取代的萘基;苯基、萘基和杂环上的取代基为烷基、烷氧基、杂烷基、环烷基、杂环烷基、烯基、杂烯基、环烯基、杂环烯基、炔基、杂炔基、环炔基、杂环炔基、芳基、取代的芳基、杂芳基、取代的杂芳基、芳氧基、杂芳基氧基、卤素、羟基、巯基、醛基、磺酸基、羧基、酰卤基、酯基、酰胺基、氨基、亚氨基、硝基、氰基、亚硝基中相同或不同任一种。
上述胺类化合物的结构如下所示:
将谈及化合物(I)、(II)、(III)、胺类化合物加入溶剂的反应体系在光照下进行反应,得到相应羰基化合物的还原产物:
优选地,上述苯基、萘基和杂环上的取代基可在邻位、间位、对位的其中之一或同时在不同的取代位置。
优选地,所述胺化合物三乙胺、二异丙基乙胺、N,N,N',N'-四甲基乙二胺、二异丙胺、N-乙基正丁胺中其中一种。
以三乙胺为例,上述反应的通式为:
优选地,所述溶剂为二甲基甲酰胺、二甲基亚砜、1,2-二氯乙烷、四氢呋喃、乙腈中任意一种。添加量为如羰基化合物加入量为0.2mmol,溶剂则加入0.5mL,加入溶剂量依次增多。
优选地,上述反应磁转子搅拌下反应时间为12h至24h。
优选地,所述溶剂为超干溶剂乙腈。
优选地,所述光照采用的光源为Kessil灯。
优选地,所述光照的波长为390nm。
优选地,反应温度为20℃~80℃。
优选地,所述反应温度为60℃。
本发明与现有技术相比,具有以下技术特征:
1.反应体系简单,可以实现整体反应体系的严格无金属化,反应过程安全可控,简化了制备生产过程中操作;
2.使用蓝色LED作为反应能源,绿色环保且能量利用率高,能高效地实现光能到化学能的转化;
3.反应物选用简单且商业可得原料,价格低廉又非常容易获得,且反应前该类反应物无需进行额外的修饰保护,可以直接用于制备生产,简化了操作步骤,缩短了反应路线;
4.由于上述第1至第3中的优点,工艺简单、对反应条件要求低,且反应过程安全可控,原子利用率和生产效率高,对环境污染压力小,因此,该方法显著降低了生产成本,也极大拓展该类化合物的可设计性及应用前景。
正是由于本发明羰基还原为亚甲基方法的进步性,因此,其可广泛用于医药、农药、合成工业等领域,且能有效降低经济成本,并提供了其对环境的友好性。
具体实施方式
结合以下具体实施例,对本发明作进一步的详细说明。所描述实施例仅为本发明的一部分实施例,而不是全部实施例,实施本发明的过程、条件、实验方法等,均为本领域的普遍知识和公知常识,本发明没有特别限制内容。
本发明实施例中所涉及的化合物及其衍生物均是按照IUPAC(国际纯粹与应用化学联合会)或CAS(化学文摘服务社,位于俄亥俄州哥伦布市)命名系统命名的。
实施例1
本实施例提供了一种9H-芴的结构式如下分子结构式(a)所示:
其制备步骤如下:
在干燥的2mL样品瓶中加入9H-芴酮(0.2mmol,1.0eq)、三乙胺(1.0mmol,5.0eq)和乙腈(0.5mL),样品瓶密封后室温下搅拌均匀,随后搅拌下用390nmLED照射,反应时间为12h~24h。反应完毕后,滤液旋干,柱层析分离,得目标产物,白色固体,产率86.00%。
相关表征分析,其结果为:1H NMR(CDCl3,400MHz)δ3.94(s,2H),7.32-7.36(m,2H),7.39-7.43(m,2H),7.57-7.59(m,2H),7.83(d,J=7.5Hz,2H);13C NMR(CDCl3,100MHz)δ36.9(t),119.8(d),124.9(d),126.6(d),126.7(d),,141.6(s),143.1(s);HRMS calculatedfor C13H10 166.07825,found 166.07742.该结果进一步证实了产物分子结构正如上述分子结构a。
实施例2
本实施例提供了一种9H-芴-3-醇制备方法。该9H-芴-3-醇的结构式如下分子结构式b示:
其制备方法参照实施例1中9H-芴制备方法,不同之处在于采用9H-芴酮-3-醇(0.2mmol)替代9H-芴酮,滤液旋干,柱层析分离,得目标产物,产率82.05%。
将制备的产物b进行表征数据分析,其结果为:1H NMR(CDCl3,400MHz)δ3.83(s,2H),4.73(s,1H),6.79(dd,J=8.1,2.5Hz,1H),7.25(d,J=2.4Hz,1H),7.31(ddd,J=7.4,7.4,1.3Hz,1H),7.32-7.38(m,2H),7.52-7.55(m,1H),7.73(d,J=7.4Hz,1H);13C NMR(CDCl3,100MHz)δ36.1(t),106.6(d),114.0(d),119.8(d),124.9(d),125.6(d),126.6(d),126.8(d),135.4(s),141.3(s),143.2(s),144.2(s),154.6(s);HRMS calculated forC13H10O 182.07317,found 182.07352.该结果进一步证实了产物分子结构正如上述分子结构b。
实施例3
本实施例提供了一种1-氨基-9H-芴制备方法。1-氨基-9H-芴的结构式如下分子结构式c所示:
其制备方法参照实施例1中9H-芴制备方法,不同之处在于采用1-氨基-9H-芴酮(0.2mmol)替代9H-芴酮,滤液旋干,柱层析分离,得目标产物,产率76.43%。
将制备的产物c进行表征数据分析,其结果为:1H NMR(300MHz,Chloroform-d)δ7.36–7.23(m,1H),7.23–7.13(m,1H),7.12–6.95(m,3H),6.87(dd,J=9.5,7.6Hz,3H),4.11(t,J=6.0Hz,1H),3.82(s,3H),2.90(ddq,J=14.4,9.8,5.2Hz,1H),2.25(dddd,J=12.8,9.6,5.6,2.8Hz,1H),2.10–1.35(m,7H),1.01(t,J=7.3,2.1Hz,3H).1H NMR(300MHz,Chloroform-d)δ7.36–7.23(m,1H),7.23–7.13(m,1H),7.12–6.95(m,3H),6.87(dd,J=9.5,7.6Hz,3H),4.06(dd,J=8.1,6.3Hz,1H),3.83(s,3H),2.90(ddq,J=14.4,9.8,5.2Hz,1H),2.10–1.35(m,8H),1.01(td,J=7.3,2.1Hz,2H).13C NMR(101MHz,Chloroform-d)δ157.97,157.90,142.41,142.12,140.07,139.80,139.71,139.63,130.30,130.18,129.83,129.81,128.78,128.42,126.04,125.95,125.68,125.59,113.82,113.69,55.40,55.38,45.42,44.74,39.86,39.53,37.82,37.66,30.03,29.88,25.56,24.64,20.79,20.62,14.49,14.47.HRMS calculated for C20H25O(M+H+):281.1905,found:281.1898.该结果进一步证实了产物分子结构正如上述分子结构c。
实施例4
本实施例提供了一种2-甲氧基-9H-芴的制备方法。的结构式如下分子结构式d所示:
其制备方法参照实施例1中9H-芴制备方法,不同之处在于采用2-甲氧基-9H-芴酮(0.2mmol)替代9H-芴酮,滤液旋干,柱层析分离,得目标产物,产率82.48%。
将制备的产物d进行表征数据分析,其结果为:1H NMR(400MHz,CDCl3)δ7.69-7.66(m,2H),7.50(d,J=7.4Hz,1H),7.34(m,1H),7.24(t,J=7.4Hz,1H),7.10-7.09(m,1H),6.93(dd,J=8.5,2.6Hz,1H),3.86(s,5H);13C NMR(100MHz,CDCl3)δ159.2,145.0,142.6,141.6,134.7,126.7,125.5,124.8,120.5,119.0,112.9,110.5,55.5,36.9;HRMScalculated for C14H12O[M]+:196.0885,found:196.0888.该结果进一步证实了产物分子结构正如上述分子结构d。
实施例5
本实施例提供了一种2-甲基-9H-芴制备方法。2-甲基-9H-芴的结构式如下分子结构式e所示:
其制备方法参照实施例1中9H-芴制备方法,不同之处在于采用2-甲基-9H-芴酮(0.2mmol)替代9H-芴酮,滤液旋干,柱层析分离,得目标产物,产率73.48%。
将制备的产物e进行表征数据分析,其结果为:1H NMR(400MHz,CDCl3)δ7.75(d,J=7.5Hz,1H),7.68(d,J=7.7Hz,1H),7.52(d,J=7.4Hz,1H),7.37-7.29(m,2H),7.26(t,J=6.7Hz,1H),7.24(dd,J=8.0,0.8Hz,1H),3.85(s,2H),2.43(s,3H);13C NMR(100MHz,CDCl3)δ143.5,143.0,141.8,139.0,136.5,127.5,126.6,126.1,125.7,124.9,119.6,119.5,36.7,21.6;IR(Film)ν3020,2961,2851,1738,1548,1394,1260,1017,953,822cm-1;HRMScalculated for C14H12[M]+:165.0705,found:180.0939.该结果进一步证实了产物分子结构正如上述分子结构e。
实施例6
本实施例提供了一种2,3,7-三甲基-9H-芴制备方法。2,3,7-三甲基-9H-芴的结构式如下分子结构式f所示:
其制备方法参照实施例1中9H-芴制备方法,不同之处在于采用2,3,7-三甲基-9H-芴酮(0.2mmol)替代9H-芴酮,滤液旋干,柱层析分离,得目标产物,白色固体,产率74.21%。
将制备的产物f进行表征数据分析,其结果为:1H NMR(600MHz,CDCl3):δ2.33(s,3H),2.35(s,3H),2.42(s,3H),3.79(s,2H),7.15(d,J=7.8Hz,1H),7.29(s,1H),7.33(s,1H),7.52(s,1H),7.61(d,J=8.4Hz,1H)ppm.13C NMR(150MHz,CDCl3):δ20.0,20.1,21.6,36.4,119.1,120.6,125.7,126.1,127.4,134.7,134.8,135.8,139.3,139.6,140.8,143.6ppm.HRMS calculated for 208.2(100),193.3(23.8)。该结果进一步证实了产物分子结构正如上述分子结构f。
实施例7
本实施例提供了一种2,3-二甲氧基-6-甲基-9H-芴制备方法。该2,3-二甲氧基-6-甲基-9H-芴的结构式如下分子结构式g所示:
其制备方法参照实施例1中9H-芴制备方法,不同之处在于采用2,3-二甲氧基-6-甲基-9H-芴酮(0.2mmol)替代9H-芴酮,滤液旋干,柱层析分离,得目标产物,白色固体,产率83.91%。
将制备的产物g进行表征数据分析,其结果为:1H NMR(600MHz,CDCl3):δ2.45(s,3H),3.77(s,2H),3.94(s,3H),3.98(s,3H),7.04(d,J=7.8Hz,1H),7.07(s,1H),7.26(s,1H),7.37(d,J=7.8Hz,1H),7.49(s,1H)ppm.13C NMR(150MHz,CDCl3):δ21.6,36.4,56.1,102.8,108.3,119.4,124.4,126.3,134.2,136.1,136.3,140.4,142.2,148.6,148.7ppm.HRMS calculated for:240.4(100),225.5(7.6),197.5(4.4).该结果进一步证实了产物分子结构正如上述分子结构g。
实施例8
本实施例提供了一种3,6-二甲基-9H-芴制备方法。该3,6-二甲基-9H-芴的结构式如下分子结构式h所示:
其制备方法参照实施例1中9H-芴制备方法,不同之处在于采用3,6-二甲基-9H-芴酮(0.2mmol)替代9H-芴酮,滤液旋干,柱层析分离,得目标产物,白色固体,产率79.41%。
将制备的产物h进行表征数据分析,其结果为:1H NMR(600MHz,CDCl3):δ2.42(s,6H),3.82(s,2H),7.08(d,J=7.8Hz,2H),7.38(d,J=7.8Hz,2H),7.57(s,2H)ppm.13C NMR(150MHz,CDCl3):δ21.5,36.1,120.3,124.7,127.5,136.2,140.7,141.9ppm.HRMScalculated for:194.2(100),179.3(16.2).该结果进一步证实了产物分子结构正如上述分子结构h。
实施例9
本实施例提供了一种1-氯-9H-芴制备方法。该1-氯-9H-芴的结构式如下分子结构式i所示:
其制备方法参照实施例1中9H-芴制备方法,不同之处在于采用1-氯-9H-芴酮(0.2mmol)替代9H-芴酮,滤液旋干,柱层析分离,得目标产物,产率72.42%。
将制备的产物i进行表征数据分析,其结果为:1H NMR(400MHz,CDCl3)δ7.76(d,J=7.2Hz,1H),7.67(d,J=0.6Hz,1H),7.55(m,1H),7.37-7.23(m,4H),3.90(s,2H);13C NMR(100MHz,CDCl3)δ143.5,124.6,141.1,131.1,128.4,127.3,126.9,126.6,126.6,125.1,120.3,118.1,36.6;HRMS calculated for C13H9Cl[M]+:200.0390,found:200.0393.该结果进一步证实了产物分子结构正如上述分子结构i。
实施例10
本实施例提供了一种3-乙酰基-9H-芴制备方法。该3-乙酰基-9H-芴的结构式如下分子结构式j所示:
其制备方法参照实施例1中9H-芴制备方法,不同之处在于采用3-乙酰基-9H-芴酮(0.2mmol)替代9H-芴酮,滤液旋干,柱层析分离,得目标产物,产率69.37%。
将制备的产物j进行表征数据分析,其结果为:1H NMR(400MHz,CDCl3)δ8.33(s,1H),7.90(d,J=1.6Hz,1H),7.88(d,J=1.5Hz,1H),7.59(d,J=7.8Hz,1H),7.54(d,J=7.3Hz,1H),7.39(m,1H),7.34(t,J=6.3Hz,1H),3.92(s,2H),2.66(s,3H);13C NMR(100MHz,CDCl3)δ198.2,148.5,148.1,142.2,140.7,136.1,127.3,127.1,127.0,125.0,124.9,120.2,119.5,37.0,26.8;HRMS calculated for C15H12O[M]+:208.1251,found:208.1252.该结果进一步证实了产物分子结构正如上述分子结构j。
实施例11
本实施例提供了一种3-(三氟甲基)-9H-芴制备方法。该3-(三氟甲基)-9H-芴的结构式如下分子结构式k所示:
其制备方法参照实施例1中9H-芴制备方法,不同之处在于采用3-(三氟甲基)-9H-芴酮(0.2mmol)替代9H-芴酮,滤液旋干,柱层析分离,得目标产物,产率66.83%。
将制备的产物k进行表征数据分析,其结果为:1H NMR(400MHz,CDCl3)δ7.69-7.66(m,2H),7.50(d,J=7.4Hz,1H),7.53(m,2H),7.40(t,J=0.5Hz,1H),7.38(t,J=6.7Hz,1H),7.36(t,J=6.0Hz,1H),3.93(s,2H);13C NMR(100MHz,CDCl3)δ146.7,143.2,142.3,140.4,129.8(q,2JC-F=31.8Hz),127.6,127.0,125.9(q,1JC-F=271.1Hz),125.2,125.1,123.5(q,3JC-F=3.5Hz),120.2,123.5(q,3JC-F=3.9Hz),36.9;HRMS calculated forC14H9F3[M]+:234.0656,found:234.0700.该结果进一步证实了产物分子结构正如上述分子结构k。
实施例12
本实施例提供了一种9,10-二氢蒽制备方法。该9,10-二氢蒽的结构式如下分子结构式l所示:
其制备方法参照实施例1中9H-芴制备方法,不同之处在于采用蒽酮(0.2mmol)替代9H-芴酮,滤液旋干,柱层析分离,得目标产物,产率77.92%。
将制备的产物l进行表征数据分析,其结果为:1H NMR(500MHz,CDCl3)δ3.97(4H,s,CH2x2),7.21-7.24(4H,m,ArH),7.31-7.33(4H,m,ArH);13C NMRδ(100MHz,CDCl3)36.2(CH2),126.1(CH),127.4(CH),136.7(C);HRMS calculated for 180([M]+,100%),179(85),178(60).该结果进一步证实了产物分子结构正如上述分子结构l。
实施例13
本实施例提供了一种9,10-二氢蒽制备方法。该9,10-二氢蒽的结构式如下分子结构式l所示:
其制备方法参照实施例1中9H-芴制备方法,不同之处在于采用蒽醌(0.2mmol)替代9H-芴酮,滤液旋干,柱层析分离,得目标产物,产率61.23%。
将制备的产物l进行表征数据分析,其结果为:1H NMR(500MHz,CDCl3)δ3.97(4H,s,CH2x2),7.21-7.24(4H,m,ArH),7.31-7.33(4H,m,ArH);13C NMRδ(100MHz,CDCl3)36.2(CH2),126.1(CH),127.4(CH),136.7(C);HRMS calculated for 180([M]+,100%),179(85),178(60).该结果进一步证实了产物分子结构正如上述分子结构l。
实施例14
本实施例提供了一种二苯基甲烷制备方法。该二苯基甲烷的结构式如下分子结构式m所示:
其制备方法参照实施例1中9H-芴制备方法,不同之处在于采用二苯甲酮(0.2mmol)替代9H-芴酮,滤液旋干,柱层析分离,得目标产物,产率82.64%。
将制备的产物m进行表征数据分析,其结果为:1H NMR(300MHz,CDCl3)δ=4.00(s,2H),7.19-7.32(m,10H)ppm;13C NMRδ(75MHz,CDCl3)δ=41.9(CH2),126.0(2 x CH),128.4(4 x CH),128.9(4 x CH),141.1(2 x C)ppm;HRMS calculated for C13H12:168.0934[M+];found:168.0934.该结果进一步证实了产物分子结构正如上述分子结构m。
实施例15
本实施例提供了一种1-苄基-2-甲苯制备方法。该1-苄基-2-甲苯的结构式如下分子结构式n所示:
其制备方法参照实施例1中9H-芴制备方法,不同之处在于采用(2-甲基苯基)苯基甲酮(0.2mmol)替代9H-芴酮,滤液旋干,柱层析分离,得目标产物,无色液体,产率82.64%。
将制备的产物n进行表征数据分析,其结果为:1H NMR(400MHz,CDCl3):δ=7.28–7.22(m,2H),7.20–7.08(m,7H),3.98(s,2H),2.23(s,3H);13C NMRδ(100MHz,CDCl3):δ=140.3,138.9,136.5,130.2,129.9,128.7,128.3,126.4,126.0,125.9,39.4,19.6.HRMScalculated for C14H14:182.27[M+];found:182.27.该结果进一步证实了产物分子结构正如上述分子结构n。
实施例16
本实施例提供了一种1-苄基-3-甲苯制备方法。该1-苄基-3-甲苯的结构式如下分子结构式o所示:
其制备方法参照实施例1中9H-芴制备方法,不同之处在于采用(3-甲基苯基)苯基甲酮(0.2mmol)替代9H-芴酮,滤液旋干,柱层析分离,得目标产物,无色液体,产率80.84%。
将制备的产物o进行表征数据分析,其结果为:1H NMR(400MHz,CDCl3):δ=7.30–7.26(m,2H),7.20–7.15(m,4H),7.01–6.98(m,3H),3.94(s,2H),2.31(s,3H);13C NMRδ(100MHz,CDCl3):δ=141.2,141.0,137.9,129.7,128.9,128.4,128.3,126.8,126.0,125.9,41.8,21.3.HRMS calculated for C14H14:182.27
[M+];found:182.27该结果进一步证实了产物分子结构正如上述分子结构o。
实施例17
本实施例提供了一种3-苄基茴香醚制备方法。该3-苄基茴香醚的结构式如下分子结构式p所示:
其制备方法参照实施例1中9H-芴制备方法,不同之处在于采用(3-甲氧基苯基)苯基甲酮(0.2mmol)替代9H-芴酮,滤液旋干,柱层析分离,得目标产物,无色液体,产率78.30%。
将制备的产物p进行表征数据分析,其结果为:1H NMR(400MHz,CDCl3):δ=7.31–7.27(m,2H),7.21–7.18(m,4H),6.80–6.72(m,3H),3.95(s,2H),3.76(s,3H);13C NMRδ(100MHz,CDCl3):δ=159.6,142.6,140.8,129.3,128.8,128.4,126.0,121.3,114.7,111.2,54.9,41.8.HRMS calculated for C14H14O:198.27[M+];found:198.27该结果进一步证实了产物分子结构正如上述分子结构p。
实施例18
本实施例提供了一种1-苄基-4-叔丁基苯制备方法。该1-苄基-4-叔丁基苯的结构式如下分子结构式q所示:
其制备方法参照实施例1中9H-芴制备方法,不同之处在于采用(4-叔丁基苯基)苯基甲酮(0.2mmol)替代9H-芴酮,滤液旋干,柱层析分离,得目标产物,无色液体,产率72.10%。
将制备的产物q进行表征数据分析,其结果为:1H NMR(400MHz,CDCl3):δ=7.31–7.28(m,4H),7.22–7.18(m,3H),7.13–7.10(m,2H),3.95(s,2H),1.29(s,9H);13C NMRδ(100MHz,CDCl3):δ=148.7,141.2,138.0,128.9,128.5,128.4,126.0,125.3,41.4,34.3,31.4.HRMS calculated for C17H20:224.35[M+];found:224.35该结果进一步证实了产物分子结构正如上述分子结构q。
实施例19
本实施例提供了一种1-苄基-4-氯苯制备方法。该1-苄基-4-氯苯的结构式如下分子结构式r所示:
其制备方法参照实施例1中9H-芴制备方法,不同之处在于采用(4-氯苯基)苯基甲酮(0.2mmol)替代9H-芴酮,滤液旋干,柱层析分离,得目标产物,无色液体,产率63.76%。
将制备的产物r进行表征数据分析,其结果为:1H NMR(400MHz,CDCl3):δ=7.32–7.20(m,5H),7.15(d,J=6.8Hz,2H),7.10(d,J=8.4Hz,2H),3.93(s,2H);13C NMRδ(100MHz,CDCl3):δ=140.4,139.5,131.8,130.2,128.8,128.48,128.46,126.2,41.1.HRMScalculated for C13H11Cl:202.68[M+];found:202.68该结果进一步证实了产物分子结构正如上述分子结构r。
实施例20
本实施例提供了一种5-苄基-1,3-双(三氟甲基)苯制备方法。该5-苄基-1,3-双(三氟甲基)苯的结构式如下分子结构式s所示:
其制备方法参照实施例1中9H-芴制备方法,不同之处在于采用(1,3-双(三氟甲基)苯基)苯基甲酮(0.2mmol)替代9H-芴酮,滤液旋干,柱层析分离,得目标产物,无色液体,产率52.91%。
将制备的产物s进行表征数据分析,其结果为:1H NMR(400MHz,CDCl3):δ=7.75–7.72(m,1H),7.63(s,2H),7.34–7.32(m,2H),7.28–7.25(m,1H),7.19–7.16(m,2H),4.10(s,2H);13C NMRδ(100MHz,CDCl3):δ=143.6,138.8,131.9(q,J=32.7Hz),128.9(m),127.3,127.2,126.9,123.4(q,J=270Hz),120.3(m),41.5.HRMS calculated for C15H10F6:304.24[M+];found:304.24该结果进一步证实了产物分子结构正如上述分子结构s。
实施例21
本实施例提供了一种9H-呫吨制备方法。该9H-呫吨的结构式如下分子结构式t所示:
其制备方法参照实施例1中9H-芴制备方法,不同之处在于采用呫吨酮(0.2mmol)替代9H-芴酮,滤液旋干,柱层析分离,得目标产物,产率49.11%。
将制备的产物t进行表征数据分析,其结果为:1H NMR(400MHz,DMSO):δ7.27–7.20(m,4H),7.09–7.04(m,4H),4.04(s,2H);13C NMRδ(100MHz,DMSO):151.31,129.17,127.75,123.23,120.61,116.04,26.90;HRMS calculated for C13H10O,182.073166;found182.072975.该结果进一步证实了产物分子结构正如上述分子结构t。
实施例22
本实施例提供了一种9H-噻吨制备方法。该9H-噻吨的结构式如下分子结构式u所示:
其制备方法参照实施例1中9H-芴制备方法,不同之处在于采用噻吨酮(0.2mmol)替代9H-芴酮,滤液旋干,柱层析分离,得目标产物,产率41.67%。
将制备的产物u进行表征数据分析,其结果为:1H NMR(300MHz,CDCl3):δ7.48–7.41(m,2H),7.36–7.30(m,2H),7.25–7.16(m,4H),3.86(s,2H);13CNMRδ(100MHz,CDCl3):δ136.3,134.0,128.1,127.0,126.7,126.7,39.4;HRMS calculated for(C13H10S)2·107Ag[2M+107Ag]+:m/z=503.0407,found:m/z=503.0405.该结果进一步证实了产物分子结构正如上述分子结构u。
实施例23
本实施例提供了一种2-苄基噻吩制备方法。该2-苄基噻吩的结构式如下分子结构式v所示:
其制备方法参照实施例1中9H-芴制备方法,不同之处在于采用苯基-2-噻吩基甲酮(0.2mmol)替代9H-芴酮,滤液旋干,柱层析分离,得目标产物,产率38.02%。
将制备的产物v进行表征数据分析,其结果为:1H NMR(400MHz,CDCl3)δ(ppm):7.43-7.38(m,2H),7.36-7.31(m,3H),7.23(dd,J=5.1,1.2Hz,1H),7.02(dd,J=5.1,3.4Hz,1H),6.90(dd,J=3.4,1.2Hz,1H),4.25(s,2H);13C NMRδ(100MHz,CDCl3)δ(ppm):144.0,140.3,128.53,128.48,126.7,126.4,125.1,123.9,36.0;HRMS calculated:174[M+](100),97(44).该结果进一步证实了产物分子结构正如上述分子结构v。
以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等,均应包含在本发明的保护范围之内。
Claims (9)
1.一种光照下羰基还原为亚甲基的方法,其特征在于,包括如下步骤:将羰基化合物和胺化合物按照摩尔比为1:(3~6)混合溶于溶剂中,在380-456nm的光照下反应12~24h。
2.根据权利要求1所述光照下羰基还原为亚甲基的方法,其特征在于,所述羰基化合物为式(I)、式(II)或式(III)的化合物:
其中,A为C、N、O、S原子其中之一;R1为氢、烷基、烷氧基、杂烷基、环烷基、杂环烷基、烯基、杂烯基、环烯基、杂环烯基、炔基、杂炔基、环炔基、杂环炔基、芳基、取代的芳基、杂芳基、取代的杂芳基、芳氧基、杂芳基氧基、卤素、羟基、巯基、醛基、磺酸基、羧基、酰卤基、酯基、酰胺基、氨基、亚氨基、硝基、氰基、亚硝基中相同或不同任一种;
R2和R3为苯基、取代的苯基、杂环、取代的杂环、萘基、取代的萘基;苯基、萘基和杂环上的取代基为烷基、烷氧基、杂烷基、环烷基、杂环烷基、烯基、杂烯基、环烯基、杂环烯基、炔基、杂炔基、环炔基、杂环炔基、芳基、取代的芳基、杂芳基、取代的杂芳基、芳氧基、杂芳基氧基、卤素、羟基、巯基、醛基、磺酸基、羧基、酰卤基、酯基、酰胺基、氨基、亚氨基、硝基、氰基、亚硝基中相同或不同任一种。
3.根据权利要求1所述光照下羰基还原为亚甲基的方法,其特征在于,所述胺化合物三乙胺、二异丙基乙胺、N,N,N',N'-四甲基乙二胺、二异丙胺、N-乙基正丁胺中其中一种。
4.根据权利要求1所述光照下羰基还原为亚甲基的方法,其特征在于,所述溶剂为二甲基甲酰胺、二甲基亚砜、1,2-二氯乙烷、四氢呋喃、乙腈中任意一种。
5.根据权利要求1或4所述光照下羰基还原为亚甲基的方法,其特征在于,所述溶剂为超干溶剂乙腈。
6.根据权利要求1所述光照下羰基还原为亚甲基的方法,其特征在于,所述光照采用的光源为Kessil灯。
7.根据权利要求1或6所述光照下羰基还原为亚甲基的方法,其特征在于,所述光照的波长为390nm。
8.根据权利要求1所述光照下羰基还原为亚甲基的方法,其特征在于,反应温度为20℃~80℃。
9.根据权利要求8所述光照下羰基还原为亚甲基的方法,其特征在于,所述反应温度为60℃。
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