CN113443972A - Aryl C-F bond functionalization preparation method - Google Patents
Aryl C-F bond functionalization preparation method Download PDFInfo
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- CN113443972A CN113443972A CN202110727229.5A CN202110727229A CN113443972A CN 113443972 A CN113443972 A CN 113443972A CN 202110727229 A CN202110727229 A CN 202110727229A CN 113443972 A CN113443972 A CN 113443972A
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- Prior art keywords
- aryl
- alkyl
- preparation
- bond
- reaction
- Prior art date
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- 238000002360 preparation method Methods 0.000 title claims abstract description 62
- 238000007306 functionalization reaction Methods 0.000 title claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 239000012038 nucleophile Substances 0.000 claims abstract description 5
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 63
- -1 fluorobenzene compound Chemical class 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 32
- 239000003054 catalyst Substances 0.000 claims description 23
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 125000001072 heteroaryl group Chemical group 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 13
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- HYWCXWRMUZYRPH-UHFFFAOYSA-N trimethyl(prop-2-enyl)silane Chemical compound C[Si](C)(C)CC=C HYWCXWRMUZYRPH-UHFFFAOYSA-N 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 239000003446 ligand Substances 0.000 claims description 8
- 125000000592 heterocycloalkyl group Chemical group 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 150000001450 anions Chemical class 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 125000006735 (C1-C20) heteroalkyl group Chemical group 0.000 claims description 4
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 claims description 4
- 125000003358 C2-C20 alkenyl group Chemical group 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 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
- 239000002131 composite material Substances 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 125000005553 heteroaryloxy group Chemical group 0.000 claims description 4
- 125000003107 substituted aryl group Chemical group 0.000 claims description 4
- 125000000392 cycloalkenyl group Chemical group 0.000 claims description 3
- 125000004366 heterocycloalkenyl group Chemical group 0.000 claims description 3
- 239000012450 pharmaceutical intermediate Substances 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 claims description 2
- 229940006461 iodide ion Drugs 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims 2
- SNOOUWRIMMFWNE-UHFFFAOYSA-M sodium;6-[(3,4,5-trimethoxybenzoyl)amino]hexanoate Chemical compound [Na+].COC1=CC(C(=O)NCCCCCC([O-])=O)=CC(OC)=C1OC SNOOUWRIMMFWNE-UHFFFAOYSA-M 0.000 claims 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 150000001345 alkine derivatives Chemical class 0.000 claims 1
- 125000005594 diketone group Chemical group 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims 1
- 125000001424 substituent group Chemical group 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 239000011941 photocatalyst Substances 0.000 abstract description 4
- 150000002894 organic compounds Chemical class 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 57
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 40
- DTUQWGWMVIHBKE-UHFFFAOYSA-N phenylacetaldehyde Chemical compound O=CCC1=CC=CC=C1 DTUQWGWMVIHBKE-UHFFFAOYSA-N 0.000 description 40
- 229940100595 phenylacetaldehyde Drugs 0.000 description 20
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 19
- 238000005160 1H NMR spectroscopy Methods 0.000 description 19
- 238000012512 characterization method Methods 0.000 description 19
- 238000004440 column chromatography Methods 0.000 description 19
- 239000000706 filtrate Substances 0.000 description 19
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 19
- 238000000926 separation method Methods 0.000 description 19
- 238000009987 spinning Methods 0.000 description 19
- 238000007405 data analysis Methods 0.000 description 18
- 125000005842 heteroatom Chemical group 0.000 description 15
- GSOHKPVFCOWKPU-UHFFFAOYSA-N 3-methylpentane-2,4-dione Chemical compound CC(=O)C(C)C(C)=O GSOHKPVFCOWKPU-UHFFFAOYSA-N 0.000 description 11
- 230000008569 process Effects 0.000 description 10
- 150000003254 radicals Chemical class 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- 125000002950 monocyclic group Chemical group 0.000 description 7
- 239000003814 drug Substances 0.000 description 6
- 150000002430 hydrocarbons Chemical group 0.000 description 6
- 229940079593 drug Drugs 0.000 description 5
- 125000003367 polycyclic group Chemical group 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- OHSOXYBIKPSCSK-UHFFFAOYSA-N 1-cyclopropyl-4-methylbenzene Chemical compound C1=CC(C)=CC=C1C1CC1 OHSOXYBIKPSCSK-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 239000008204 material by function Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- HEIXPNNBTVAWDD-UHFFFAOYSA-N 1,3,5-trimethyl-2-prop-2-enylbenzene Chemical compound CC1=CC(C)=C(CC=C)C(C)=C1 HEIXPNNBTVAWDD-UHFFFAOYSA-N 0.000 description 2
- WFWKNGZODAOLEO-UHFFFAOYSA-N 1-(4-Methoxyphenyl)-2-propanone Chemical compound COC1=CC=C(CC(C)=O)C=C1 WFWKNGZODAOLEO-UHFFFAOYSA-N 0.000 description 2
- WEJRYKSUUFKMBC-UHFFFAOYSA-N 1-(4-chlorophenyl)propan-2-one Chemical compound CC(=O)CC1=CC=C(Cl)C=C1 WEJRYKSUUFKMBC-UHFFFAOYSA-N 0.000 description 2
- APWPLZAFFOTPRO-UHFFFAOYSA-N 1-(4-propan-2-ylphenyl)propan-2-one Chemical compound CC(C)C1=CC=C(CC(C)=O)C=C1 APWPLZAFFOTPRO-UHFFFAOYSA-N 0.000 description 2
- UIPDPUXNQIWJLF-UHFFFAOYSA-N 1-[4-(trifluoromethyl)phenyl]propan-2-one Chemical compound CC(=O)CC1=CC=C(C(F)(F)F)C=C1 UIPDPUXNQIWJLF-UHFFFAOYSA-N 0.000 description 2
- LIGHOIDTGDLAKK-UHFFFAOYSA-N 1-bromo-4-prop-2-enylbenzene Chemical compound BrC1=CC=C(CC=C)C=C1 LIGHOIDTGDLAKK-UHFFFAOYSA-N 0.000 description 2
- VGUNPRNQXXTCCL-UHFFFAOYSA-N 1-chloro-4-prop-2-enylbenzene Chemical compound ClC1=CC=C(CC=C)C=C1 VGUNPRNQXXTCCL-UHFFFAOYSA-N 0.000 description 2
- BTQZKHUEUDPRST-UHFFFAOYSA-N 1-fluoro-3-methylbenzene Chemical compound CC1=CC=CC(F)=C1 BTQZKHUEUDPRST-UHFFFAOYSA-N 0.000 description 2
- WRWPPGUCZBJXKX-UHFFFAOYSA-N 1-fluoro-4-methylbenzene Chemical compound CC1=CC=C(F)C=C1 WRWPPGUCZBJXKX-UHFFFAOYSA-N 0.000 description 2
- RUYZJEIKQYLEGZ-UHFFFAOYSA-N 1-fluoro-4-phenylbenzene Chemical group C1=CC(F)=CC=C1C1=CC=CC=C1 RUYZJEIKQYLEGZ-UHFFFAOYSA-N 0.000 description 2
- SVIHJJUMPAUQNO-UHFFFAOYSA-N 1-methyl-2-prop-2-enylbenzene Chemical compound CC1=CC=CC=C1CC=C SVIHJJUMPAUQNO-UHFFFAOYSA-N 0.000 description 2
- JVQAREFZPKBHPG-UHFFFAOYSA-N 1-methyl-3-prop-2-enylbenzene Chemical compound CC1=CC=CC(CC=C)=C1 JVQAREFZPKBHPG-UHFFFAOYSA-N 0.000 description 2
- WAEOXIOXMKNFLQ-UHFFFAOYSA-N 1-methyl-4-prop-2-enylbenzene Chemical compound CC1=CC=C(CC=C)C=C1 WAEOXIOXMKNFLQ-UHFFFAOYSA-N 0.000 description 2
- HJQPEDHRZNHTCW-UHFFFAOYSA-N 1-phenyl-4-prop-2-enylbenzene Chemical group C1=CC(CC=C)=CC=C1C1=CC=CC=C1 HJQPEDHRZNHTCW-UHFFFAOYSA-N 0.000 description 2
- RJFCFNWLPJRCLR-UHFFFAOYSA-N 1-prop-2-enylnaphthalene Chemical compound C1=CC=C2C(CC=C)=CC=CC2=C1 RJFCFNWLPJRCLR-UHFFFAOYSA-N 0.000 description 2
- FLZUYXUBDVKWPO-UHFFFAOYSA-N 4-(2-oxopropyl)benzoic acid Chemical compound CC(=O)CC1=CC=C(C(O)=O)C=C1 FLZUYXUBDVKWPO-UHFFFAOYSA-N 0.000 description 2
- PATYHUUYADUHQS-UHFFFAOYSA-N 4-methylpropiophenone Chemical compound CCC(=O)C1=CC=C(C)C=C1 PATYHUUYADUHQS-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- 239000007818 Grignard reagent Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- FFSAXUULYPJSKH-UHFFFAOYSA-N butyrophenone Chemical compound CCCC(=O)C1=CC=CC=C1 FFSAXUULYPJSKH-UHFFFAOYSA-N 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 150000004795 grignard reagents Chemical class 0.000 description 2
- 125000001041 indolyl group Chemical group 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000012434 nucleophilic reagent Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- QCCDLTOVEPVEJK-UHFFFAOYSA-N phenylacetone Chemical compound CC(=O)CC1=CC=CC=C1 QCCDLTOVEPVEJK-UHFFFAOYSA-N 0.000 description 2
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 description 2
- 125000003373 pyrazinyl group Chemical group 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- GEWWCWZGHNIUBW-UHFFFAOYSA-N 1-(4-nitrophenyl)propan-2-one Chemical compound CC(=O)CC1=CC=C([N+]([O-])=O)C=C1 GEWWCWZGHNIUBW-UHFFFAOYSA-N 0.000 description 1
- JRDNBWVMEFUNCQ-UHFFFAOYSA-N 1-bromo-4-cyclopropylbenzene Chemical compound C1=CC(Br)=CC=C1C1CC1 JRDNBWVMEFUNCQ-UHFFFAOYSA-N 0.000 description 1
- AITNMTXHTIIIBB-UHFFFAOYSA-N 1-bromo-4-fluorobenzene Chemical compound FC1=CC=C(Br)C=C1 AITNMTXHTIIIBB-UHFFFAOYSA-N 0.000 description 1
- RJCGZNCCVKIBHO-UHFFFAOYSA-N 1-chloro-4-fluorobenzene Chemical compound FC1=CC=C(Cl)C=C1 RJCGZNCCVKIBHO-UHFFFAOYSA-N 0.000 description 1
- MMZYCBHLNZVROM-UHFFFAOYSA-N 1-fluoro-2-methylbenzene Chemical compound CC1=CC=CC=C1F MMZYCBHLNZVROM-UHFFFAOYSA-N 0.000 description 1
- UNNNAIWPDLRVRN-UHFFFAOYSA-N 1-fluoro-4-(trifluoromethyl)benzene Chemical compound FC1=CC=C(C(F)(F)F)C=C1 UNNNAIWPDLRVRN-UHFFFAOYSA-N 0.000 description 1
- WFQDTOYDVUWQMS-UHFFFAOYSA-N 1-fluoro-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(F)C=C1 WFQDTOYDVUWQMS-UHFFFAOYSA-N 0.000 description 1
- XZISOEPNTDOUEA-UHFFFAOYSA-N 1-fluoro-4-propan-2-ylbenzene Chemical compound CC(C)C1=CC=C(F)C=C1 XZISOEPNTDOUEA-UHFFFAOYSA-N 0.000 description 1
- ZLGPNBBJPOBSLY-UHFFFAOYSA-N 2-fluoro-1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=C(F)C(C)=C1 ZLGPNBBJPOBSLY-UHFFFAOYSA-N 0.000 description 1
- BAGQBTMEEISJLK-UHFFFAOYSA-N 2-fluoronaphthalene Chemical compound C1=CC=CC2=CC(F)=CC=C21 BAGQBTMEEISJLK-UHFFFAOYSA-N 0.000 description 1
- BBYDXOIZLAWGSL-UHFFFAOYSA-N 4-fluorobenzoic acid Chemical compound OC(=O)C1=CC=C(F)C=C1 BBYDXOIZLAWGSL-UHFFFAOYSA-N 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- 238000005577 Kumada cross-coupling reaction Methods 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 125000003725 azepanyl group Chemical group 0.000 description 1
- 125000002393 azetidinyl group Chemical group 0.000 description 1
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000004619 benzopyranyl group Chemical group O1C(C=CC2=C1C=CC=C2)* 0.000 description 1
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000004541 benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 238000006664 bond formation reaction Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000298 cyclopropenyl group Chemical group [H]C1=C([H])C1([H])* 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000004404 heteroalkyl group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 125000003392 indanyl group Chemical group C1(CCC2=CC=CC=C12)* 0.000 description 1
- 125000003453 indazolyl group Chemical group N1N=C(C2=C1C=CC=C2)* 0.000 description 1
- 125000003387 indolinyl group Chemical group N1(CCC2=CC=CC=C12)* 0.000 description 1
- 125000003406 indolizinyl group Chemical group C=1(C=CN2C=CC=CC12)* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 125000001977 isobenzofuranyl group Chemical group C=1(OC=C2C=CC=CC12)* 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000000904 isoindolyl group Chemical group C=1(NC=C2C=CC=CC12)* 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
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([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
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000002757 morpholinyl group Chemical group 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000004593 naphthyridinyl group Chemical group N1=C(C=CC2=CC=CN=C12)* 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000001979 organolithium group Chemical group 0.000 description 1
- 125000002734 organomagnesium group Chemical group 0.000 description 1
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- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000004592 phthalazinyl group Chemical group C1(=NN=CC2=CC=CC=C12)* 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001042 pteridinyl group Chemical group N1=C(N=CC2=NC=CN=C12)* 0.000 description 1
- 125000000561 purinyl group Chemical group N1=C(N=C2N=CNC2=C1)* 0.000 description 1
- 125000004309 pyranyl group Chemical group O1C(C=CC=C1)* 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 Chemical group 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
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 description 1
- 125000005888 tetrahydroindolyl group Chemical group 0.000 description 1
- 125000003039 tetrahydroisoquinolinyl group Chemical group C1(NCCC2=CC=CC=C12)* 0.000 description 1
- 125000001712 tetrahydronaphthyl group Chemical group C1(CCCC2=CC=CC=C12)* 0.000 description 1
- 125000001412 tetrahydropyranyl group Chemical group 0.000 description 1
- 125000000147 tetrahydroquinolinyl group Chemical group N1(CCCC2=CC=CC=C12)* 0.000 description 1
- 125000004632 tetrahydrothiopyranyl group Chemical group S1C(CCCC1)* 0.000 description 1
- 125000001113 thiadiazolyl group Chemical group 0.000 description 1
- 125000005307 thiatriazolyl group Chemical group S1N=NN=C1* 0.000 description 1
- 125000001984 thiazolidinyl 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
- 125000004568 thiomorpholinyl group Chemical group 0.000 description 1
- 150000003624 transition metals Chemical group 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 125000001834 xanthenyl group Chemical group C1=CC=CC=2OC3=CC=CC=C3C(C12)* 0.000 description 1
Classifications
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- 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
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
- C07C45/455—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation with carboxylic acids or their derivatives
-
- 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
- C07C1/26—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only halogen atoms as hetero-atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
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- 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
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/373—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of functional groups containing oxygen only in doubly bound form
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of organic compound synthesis, in particular to a preparation method of aryl C-F bond functionalization. The invention adopts the photocatalyst, the reaction process is safe and controllable, and the operation in the preparation production process is simplified; the purple LED is used as a reaction energy source, so that the environment is protected, the energy utilization rate is high, and the conversion from light energy to chemical energy can be efficiently realized; the reaction efficiently and greenly produces a very wide range of target products by using simple nucleophiles to attack free radical cationic species generated under visible light catalysis. The invention simplifies the operation steps and shortens the reaction route; and the forward reaction rate is high, and the production efficiency is obviously improved.
Description
Technical Field
The invention relates to the technical field of organic compound synthesis, in particular to a preparation method of aryl C-F bond functionalization.
Background
The fluorine-containing organic compound is widely applied to the fields of medicine, biochemistry, catalysis, material science and the like. In view of the increasing importance of C-F bond formation, C-F bond functionalization is also of great interest, and it is desired to synthesize organic small molecules with novel and diverse structures by functionalizing the C-F bond of fluorine-containing compounds. The bond energy of the inert C-F bond is very high and difficult to activate, so that the carbon-fluorine bond can be modified in the last step of the drug synthesis by utilizing the characteristic, thereby synthesizing the target compound required by people. Since 1973, the Kumada group reported that nickel-catalyzed cross-coupling reactions of aromatic fluorides with Kumada-Corriu were followed by more and more organolithium or organomagnesium reactions with aryl-, alkenyl-, or alkyl-halohydrocarbons under nickel and palladium catalysis. However, these methods still have some disadvantages, such as: 1) the compatibility with functional groups in the Kumada coupling reaction is poor. The strong basicity and nucleophilicity of the grignard reagent may react with many functional groups and thus is not suitable for halogenated hydrocarbons that are unstable in the presence of the grignard reagent. 2) The price of the palladium catalyst is expensive, the amount of the palladium catalyst is a precondition for realizing industrial production, and a recyclable palladium catalyst 3) some metal complexes are sensitive to water and air, which not only complicates the operation, but also causes a safety problem. In addition, in the pharmaceutical and material industries, some tedious processes and special equipment are often required to solve the "transition metal residue problem", and additional resources are consumed to reduce the metal content to a certain level.
How to efficiently and environmentally break, activate and functionalize the carbon-fluorine bonds of different fluorine-containing compounds is a very important research subject of fluorine chemistry, organic synthesis and organometallic chemistry. Therefore, there is a need for a new method to overcome the deficiencies of the prior art, particularly those described above. In recent years, the development of the visible light catalytic chemistry field is changing day by day, and a new path is provided for the construction of aryl C-F bond functionalization.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provides a preparation method of aryl C-F bond functionalization, so as to overcome the technical problems of limited application range, harsh preparation conditions, low yield, complex process, environmental friendliness and the like of the existing method.
The purpose of the invention is realized by the following technical scheme:
a method for preparing aryl C-F bond functionalization comprises the following steps: reacting a fluorobenzene compound with a nucleophilic reagent under the action of a composite catalyst, wherein the composite catalyst is formed by mixing a visible light catalyst and a metal catalyst;
the visible light catalyst comprises one or more of the following structural formulas of formula (I), (II) and (III):
wherein R is6、R7、R8、R9、R10、R11、R12、R13、R14、R15Are identical or different C1-C20Alkyl radical, C1-C20Heteroalkyl group, C3-C20Cycloalkyl radical, C3-C20Heterocycloalkyl radical, C2-C20Alkenyl radical, C2-C20Heteroalkenyl, C1-C20Perfluoroalkyl radical, C3-C20Cycloalkenyl radical, C3-C20Heterocycloalkenyl, C2-C20Alkynyl, C2-C20Heteroalkynyl, C3-C20Cycloalkynyl radical、C3-C20Heterocycloalkynyl, C1-C20Alkoxy, aryl, substituted aryl, heteroaryl, substituted heteroaryl, aryloxy, heteroaryloxy, aryl (C)1-C20) Alkyl, heteroaryl (C)1-C20) Alkyl radical, C2-C20Alkenyl (C)1-C20) Alkyl radical, C2-C20Alkynyl (C)1-C20) Alkyl, cyano (C)1-C20) Alkyl, alkyloxycarbonylalkyl; z is an anion; a is a nitrogen atom or a carbon atom.
Preferably, the metal catalyst is Cu2+Or Cu+A complex with ligand (I) or ligand (II), wherein the structures of ligand (I) and ligand (II) are:
preferably, the nucleophiles comprise: one or more of allyl trimethylsilane, vinyl ethyl ether, 3-methyl-2, 4-pentanedione, and acetic anhydride.
Preferably, the molar ratio of the visible-light-driven photocatalyst, the metal catalyst and the fluorobenzene compound is (0.05-5): (0.2-20): 1-100).
Preferably, the anion Z is a boron tetrafluoride anion, a chloride ion, an iodide ion, a perchlorate ion or a hexafluorophosphate ion.
Preferably, the reaction takes one or more of acetonitrile, diethyl ether, tetrahydrofuran and dichloromethane as a solvent.
Preferably, the visible light catalyst, the metal catalyst and the fluorobenzene compound are mixed to react at the temperature of 25-80 ℃ by taking the purple LED as a reaction energy source
Preferably, the structural formula of the fluorobenzene compound is as follows:
wherein R is1、R2、R3、R4And R5Are identical or different C1-C20Alkyl radical, C1-C20Heteroalkyl group, C3-C20Cycloalkyl radical, C3-C20Heterocycloalkyl radical, C2-C20Alkenyl radical, C2-C20Heteroalkenyl, C3-C20Cycloalkenyl radical, C3-C20Heterocycloalkenyl, C2-C20Alkynyl, C2-C20Heteroalkynyl, C3-C20Cycloalkynyl group, C3-C20Heterocycloalkynyl, C1-C20Alkoxy, aryl, substituted aryl, heteroaryl, substituted heteroaryl, aryloxy, heteroaryloxy, aryl (C)1-C20) Alkyl, heteroaryl (C)1-C20) Alkyl radical, C2-C20Alkenyl (C)1-C20) Alkyl radical, C2-C20Alkynyl (C)1-C20) Alkyl, cyano (C)1-C20) Any one of alkyl, alkyloxycarbonylalkyl, halogen, and hydrogen atom substituent.
The aryl C-F bond functionalized compound prepared by the aryl C-F bond functionalized preparation method.
The application of the aryl C-F bond functionalized compound in the preparation of a drug intermediate.
The bond energy of the inert C-F bond is very high and difficult to activate, and the carbon-fluorine bond can be modified in the last step of the drug synthesis by utilizing the characteristic, so that the target compound required by people can be synthesized. Therefore, the method can be widely used for synthesizing pharmaceutical intermediates and preparing functional materials, thereby enhancing the application of the pharmaceutical intermediates in the pharmaceutical field.
Compared with the prior art, the invention has the following technical effects:
1. the photocatalyst is adopted, the reaction process is safe and controllable, and the operation in the preparation production process is simplified;
2. the purple LED is used as a reaction energy source, so that the environment is protected, the energy utilization rate is high, and the conversion from light energy to chemical energy can be efficiently realized;
3. the reaction efficiently and greenly produces a very wide range of target products by using simple nucleophiles to attack free radical cationic species generated under visible light catalysis.
4. The reactants are selected from simple and commercially available nucleophilic reagents as reactants and commercially available catalysts, the raw materials are low in price and very easy to obtain, and the reactants before reaction can be directly used for preparation production without additional modification protection, so that the operation steps are simplified, and the reaction route is shortened; the forward reaction rate is high, and the production efficiency is obviously improved;
5. the method has the advantages of simple process, low requirement on reaction conditions, safe and controllable reaction process, high atom utilization rate and production efficiency and low environmental pollution pressure, thereby remarkably reducing the production cost and greatly expanding the designability and application prospect of the compounds.
The aryl C-F bond functionalized compound has a typical high-functionalization structure and the advancement of the preparation method, so the aryl C-F bond functionalized compound can be widely used for synthesis of drug intermediates and preparation of functional materials, can effectively reduce the economic cost for preparation of the drug intermediates and the functional materials, and provides the environment-friendly property.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below with reference to specific examples and comparative examples. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
The compounds and derivatives thereof referred to in the examples of the present invention are named according to the IUPAC (International Union of pure and applied chemistry) or CAS (chemical abstracts service, Columbus, Ohio) naming system. Accordingly, the groups of compounds specifically referred to in the examples of the present invention are illustrated and described as follows:
with respect to "hydrocarbon group," the minimum and maximum values of the carbon atom content in a hydrocarbon group are indicated by a prefix, e.g., the prefix (Ca-Cb) alkyl indicates any alkyl group containing from "a" to "b" carbon atoms. Thus, for example, (C1-C6) alkyl refers to alkyl groups containing one to six carbon atoms.
"alkoxy" refers to a straight or branched, monovalent, saturated aliphatic chain bonded to an oxygen atom and includes, but is not limited to, groups such as methoxy, ethoxy, propoxy, butoxy, isobutoxy, t-butoxy, and the like. (Ca-Cb) alkoxy means any straight or branched, monovalent, saturated aliphatic chain having an alkyl group containing from "a" to "b" carbon atoms bonded to an oxygen atom.
"alkyl" refers to a straight or branched, monovalent, saturated aliphatic chain including, but not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl, and the like.
"heteroalkyl" means a straight or branched, monovalent, saturated aliphatic chain attached to at least one heteroatom, such as, but not limited to, methylaminoethyl or other similar groups.
"alkenyl" refers to straight or branched chain hydrocarbons having one or more double bonds, including but not limited to, groups such as ethenyl, propenyl, and the like.
"Heteroalkenyl" means a straight or branched chain hydrocarbon with one or more double bonds attached to at least one heteroatom, including but not limited to, for example, vinylaminoethyl or other similar groups.
"alkynyl" refers to a straight or branched chain hydrocarbon with one or more triple bonds, including but not limited to, for example, ethynyl, propynyl, and the like.
"Heteroalkynyl" means a straight or branched chain hydrocarbon with one or more triple bonds attached to at least one heteroatom, including but not limited to, groups such as ethynyl, propynyl, and the like.
"aryl" refers to a cyclic aromatic hydrocarbon including, but not limited to, phenyl, naphthyl, anthryl, phenanthryl, and the like.
"heteroaryl" refers to a monocyclic or polycyclic or fused ring aromatic hydrocarbon in which one or more carbon atoms have been replaced with a heteroatom such as nitrogen, oxygen, or sulfur. If the heteroaryl group contains more than one heteroatom, these heteroatoms may be the same or different. Heteroaryl groups include, but are not limited to, groups such as benzofuranyl, benzothienyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, benzopyranyl, furanyl, imidazolyl, indazolyl, indolizinyl, indolyl, isobenzofuranyl, isoindolyl, isoquinolyl, isothiazolyl, isoxazolyl, naphthyridinyl, oxadiazolyl, oxazinyl, oxazolyl, phthalazinyl, pteridinyl, purinyl, pyranyl, pyrazinyl, pyrazolyl, pyridazinyl, pyridine [3,4-b ] indolyl, pyridyl, pyrimidinyl, pyrrolyl, quinolizinyl, quinolyl, quinoxalinyl, thiadiazolyl, thiatriazolyl, thiazolyl, thienyl, triazinyl, triazolyl, xanthenyl, and the like.
"cycloalkyl" refers to a saturated monocyclic or polycyclic alkyl group, possibly fused to an aromatic hydrocarbon group. Cycloalkyl groups include, but are not limited to, groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, indanyl, tetrahydronaphthyl, and the like.
"Heterocycloalkyl" means a saturated monocyclic or polycyclic alkyl group, possibly fused to an aromatic hydrocarbon group, in which at least one carbon atom has been replaced by a heteroatom such as nitrogen, oxygen or sulfur. If the heterocycloalkyl group contains more than one heteroatom, these heteroatoms may be the same or different. Heterocycloalkyl groups include, but are not limited to, groups such as azepanyl, azetidinyl, indolinyl, morpholinyl, pyrazinyl, piperidinyl, pyrrolidinyl, tetrahydrofuryl, tetrahydroquinolinyl, tetrahydroindazolyl, tetrahydroindolyl, tetrahydroisoquinolinyl, tetrahydropyranyl, tetrahydroquinoxalinyl, tetrahydrothiopyranyl, thiazolidinyl, thiomorpholinyl, thioxanthyl, and the like.
"cycloalkenyl" refers to an unsaturated, monocyclic or polycyclic alkenyl group with one or more double bonds, possibly fused to an aromatic hydrocarbon group, including, but not limited to, cyclic ethenyl, cyclopropenyl, or other similar groups.
"Heterocycloalkenyl" means an unsaturated, monocyclic or polycyclic alkenyl radical having one or more double bonds, possibly condensed with an aromatic hydrocarbon radical, in which at least one carbon atom is replaced by a heteroatom such as nitrogen, oxygen or sulfur. If the heterocycloalkyl group contains more than one heteroatom, these heteroatoms may be the same or different.
"cycloalkynyl" refers to an unsaturated, monocyclic or polycyclic alkynyl group having one or more triple bonds, possibly fused to an aromatic hydrocarbon group, including, but not limited to, cycloalkynyl, cyclopropynyl, or the like.
"Heterocycloalkynyl" means an unsaturated, monocyclic or polycyclic alkynyl radical having one or more triple bonds, possibly condensed with an aromatic hydrocarbon radical, in which at least one carbon atom has been replaced by a heteroatom such as nitrogen, oxygen or sulfur. If the heterocycloalkyl group contains more than one heteroatom, these heteroatoms may be the same or different.
Example 1
This example provides a method for producing phenylacetaldehyde. The structural formula of phenylacetaldehyde is shown as the following molecular structural formula I1:
the preparation method comprises the following steps:
a dry 4mL test tube was charged with mesitylene-substituted acridinium salt photocatalyst (0.05eq), CuCl2(0.2eq), bipyridine (0.2eq) and 0.5mL of anhydrous acetonitrile, 0.2mmol of acetic anhydride (1eq) and 0.2mmol of fluorobenzene were added, argon gas was substituted three times, and reaction time was 24 hours under 390nm Kessil lamp irradiation. After the reaction is finished, the filtrate is dried by spinning, and the target product is obtained by column chromatography separation, wherein the yield is 71 percent.
The result of the correlation characterization analysis is as follows:1H NMR(400MHz；CDCl3)δ＝9.70(1H,t,J＝2Hz),7.30–7.10(5H,m),3.60(2H,d,J＝2Hz)；13C NMR(100MHz；CDCl3)＝199.9,132.3,130.0,129.9,129.4,129.3,127.8,51.0；MS(EI)m/z 120(M) +; HRMS (ES) calculated for C8H8O (M) +120.0570, found 120.0568(M) +. this result further confirms the molecular structure of the product as described above for molecular structure I1.
Example 2
This example provides a process for the preparation of 1-allyl-4-methylbenzene. The structural formula of the 1-allyl-4-methylbenzene is shown as the following molecular structural formula I2:
the preparation method refers to the preparation method of phenylacetaldehyde in example 1, and is characterized in that p-methylfluorobenzene (0.2mmol) is adopted to replace fluorobenzene, allyl trimethylsilane (1eq) 0.2mmol is adopted to replace acetic anhydride (1eq) 0.2mmol, filtrate is dried by spinning, and column chromatography separation is carried out to obtain a target product, wherein the yield is 77%. The product I2 prepared was subjected to characterization data analysis, which resulted in:1H NMR(CDCl3,300MHz)δ7.10(s,4H),6.03-5.89(m,1H),5.11-5.03(m,2H),3.35(d,2H,J＝6.6),2.32(s,3H)ppm；13C NMR(CDCl3,75MHz)δ137.7,136.9,135.5,129.1,128.4,115.5,39.8,21.0ppm；IR 2920,2849,1658,1632,1469cm-1；MS calculated for C10H12(m/z)(％):132(59)[M+]this result further confirmed the molecular structure of the product as described above for molecular structure I2 (117).
Example 3
This example provides a process for the preparation of 1-allyl-3-methylbenzene. The structural formula of the 1-allyl-3-methylbenzene is shown as the following molecular structural formula I3:
the preparation method refers to the preparation method of phenylacetaldehyde in example 1, and is characterized in that m-methylfluorobenzene (0.2mmol) is adopted to replace fluorobenzene, 0.2mmol of allyltrimethylsilane (1eq) is adopted to replace 0.2mmol of acetic anhydride (1eq), the filtrate is dried by spinning, and column chromatography separation is carried out to obtain the target product, wherein the yield is 58%. The product I3 prepared was subjected to characterization data analysis, which resulted in:1H NMR(CDCl3,300MHz)δ7.26-7.17(m,1H),7.04-3.99(m,3H),6.04-5.90(m,1H),5.12-5.05(m,2H)3.35(d,2H,J＝6.6),2.33(s,3H)ppm；13CNMR(CDCl3,75MHz)δ140.0,138.0,137.6,129.3,128.3,126.8,125.6,115.6,40.2,21.4ppm；IR 2953,2923,2854,1459,1376,1027cm-1；MS calculated for C10H12:(m/z)(％):132(62)[M+]this result further confirmed the molecular structure of the product as described above for molecular structure I3 (117).
Example 4
This example provides a process for the preparation of 1-allyl-2-methylbenzene. The structural formula of the 1-allyl-2-methylbenzene is shown as the following molecular structural formula I4:
the preparation method refers to the preparation method of phenylacetaldehyde in example 1, and is characterized in that o-methylfluorobenzene (0.2mmol) is adopted to replace fluorobenzene, 0.2mmol of allyltrimethylsilane (1eq) is adopted to replace 0.2mmol of acetic anhydride (1eq), the filtrate is dried by spinning, and column chromatography separation is carried out to obtain the target product, wherein the yield is 50%. The product I4 prepared was subjected to characterization data analysis, which resulted in:1H NMR(CDCl3,300MHz)δ7.14(s,4H),6.02-5.89(m,1H),5.08-4.96(m,2H)3.36(d,2H,J＝6.6),2.28(s,3H)ppm；13C NMR(CDCl3,75MHz)δ138.1,136.6,136.3,130.1,129.1,126.2,126.0,115.6,37.7,19.3ppm；IR 2953,2924,2855,1458cm-1；MS calculated for C10H12:(m/z)(％):132(56)[M+]this result further confirmed the molecular structure of the product as described above for molecular structure I4 (117).
Example 5
This example provides a method for preparing 2-allyl-1, 3, 5-trimethylbenzene. The structural formula of the 2-allyl-1, 3, 5-trimethylbenzene is shown as the following molecular structural formula I5:
the preparation method refers to the preparation method of the phenylacetaldehyde in the embodiment 1, and is characterized in that 1, 3, 5-trimethylfluorobenzene (0.2mmol) is adopted to replace fluorobenzene, 0.2mmol of allyltrimethylsilane (1eq) is adopted to replace 0.2mmol of acetic anhydride (1eq), the filtrate is dried by spinning, and the column chromatography separation is carried out to obtain the target product, wherein the yield is 75%.
The product I5 prepared was subjected to characterization data analysis, which resulted in:1H NMR(CDCl3,300MHz)δ6.85(s,2H),5.95-5.82(m,1H),5.00-4.82(m,2H)3.37-3.34(m,2H),2.25(s,9H)ppm；13C NMR(CDCl3,75MHz)δ136.5,135.5,135.3,133.0,128.7,126.9,33.3,20.8,19.7ppm；IR 2921,2851,1639,1443,1260cm-1；MS calculated for C12H16:(m/z)(％):160(51)[M+]this result further confirmed the molecular structure of the product as described above for molecular structure I5.
Example 6
This example provides 4-allylbiphenyl and a method of making the same. The structural formula of the 4-allyl biphenyl is shown as the following molecular structural formula I6:
the preparation method refers to the preparation method of phenylacetaldehyde in example 1, and is characterized in that 4-fluorobiphenyl (0.2mmol) is adopted to replace fluorobenzene, 0.2mmol of allyltrimethylsilane (1eq) is adopted to replace 0.2mmol of acetic anhydride (1eq), the filtrate is dried by spinning, and column chromatography separation is carried out, so that the target product is obtained, and the yield is 52%.
The product I6 prepared was subjected to characterization data analysis, which resulted in:1H NMR(CDCl3,200MHz)δ7.60-7.24(m,9H),6.10-5.90(m,1H),6.02-5.89(m,1H)5.17-5.06(m,2H),3.42(d,2H,J＝7.0)ppm；13C NMR(CDCl3,50MHz)δ141.1,139.2,139.1,137.4,129.0,128.8,127.2,127.1,116.0,39.8ppm；IR 3057,1638,1486cm-1；MS calculated for C15H14:(m/z)(％):194(100)[M+]this result further confirmed the molecular structure of the product as described above for molecular structure I6.
Example 7
This example provides a process for the preparation of 1-allyl-4-chlorobenzene. The structural formula of the 1-allyl-4-chlorobenzene is shown as the following molecular structural formula I7:
the preparation method refers to the preparation method of phenylacetaldehyde in example 1, and is characterized in that 4-chlorofluorobenzene (0.2mmol) is adopted to replace fluorobenzene, 0.2mmol of allyltrimethylsilane (1eq) is adopted to replace 0.2mmol of acetic anhydride (1eq), the filtrate is dried by spinning, and column chromatography separation is carried out to obtain a target product, wherein the yield is 63%.
The product I7 prepared was subjected to characterization data analysis, which resulted in:1H NMR(CDCl3,300MHz)δ7.24(d,1H,J＝8.4),7.09(d,1H,J＝8.4),5.98-5.85(m,1H),5.09-5.03(m,2H),3.32(d,2H,J＝6.6)ppm；13C NMR(CDCl3,75MHz)δ138.4,136.8,131.8,129.9,128.4,116.2,39.4ppm；IR 2954,2924,2855,1456,1377,1091cm-1；MS calculated for C9H9Cl:(m/z)(％):152(50)[M+]this result further confirmed the molecular structure of the product as described above for molecular structure I7 (117).
Example 8
This example provides a method for preparing 1-allyl-4-bromobenzene. The structural formula of the 1-allyl-4-bromobenzene is shown as the following molecular structural formula I8:
the preparation method refers to the preparation method of phenylacetaldehyde in example 1, and is characterized in that 4-bromofluorobenzene (0.2mmol) is adopted to replace fluorobenzene, 0.2mmol of allyltrimethylsilane (1eq) is adopted to replace 0.2mmol of acetic anhydride (1eq), the filtrate is dried by spinning, and column chromatography separation is carried out, so that the target product is obtained, and the yield is 67%. The product I8 prepared was subjected to characterization data analysis, which resulted in:1H NMR(CDCl3,300MHz)δ7.42(d,1H,J＝8.4),7.07(d,1H,J＝8.4),6.02-5.87(m,1H),5.14-5.05(m,2H),3.34(d,2H,J＝6.9)ppm；13C NMR(CDCl3,75MHz)δ138.9,136.7,131.4,130.3,119.8,116.2,39.5ppm；IR 2953,2924,2853,1488,1460,1024cm-1；MS calculated for C9H9Br:(m/z)(％):196(56)[M+]this result further confirmed the molecular structure of the product as described above for molecular structure I8 (117).
Example 9
This example provides a process for the preparation of 1-allylnaphthalene. The structural formula of the 1-allyl naphthalene is shown as the following molecular structural formula I9:
the preparation method refers to the preparation method of the phenylacetaldehyde in the embodiment 1, and is characterized in that 2-fluoronaphthalene (0.2mmol) is adopted to replace fluorobenzene, 0.2mmol of allyltrimethylsilane (1eq) is adopted to replace 0.2mmol of acetic anhydride (1eq), the filtrate is dried by spinning, and the column chromatography separation is carried out, so that the target product is obtained, and the yield is 72%. The product I9 prepared was subjected to characterization data analysis, which resulted in:1H NMR(CDCl3,300MHz)δ8.00(d,2H,J＝9.0),7.83-7.80(m,1H),7.70(d,1H,J＝8.1),7.47-7.43(m,2H),7.37(d,2H,J＝8.1),7.31(d,2H,J＝7.2),6.16-6.02(m,1H),5.11-5.04(m,2H),3.80(d,2H,J＝6.3)ppm；13C NMR(CDCl3,75MHz)δ136.9,136.0,131.9,128.6,127.8,126.9,126.2,125.8,125.5,124.0,116.1,37.2ppm；IR 2976,1638,1597,1510,1396,993,913cm-1；MS calculated for C13H12:(m/z)(％):168(100)[M+]this result further confirmed the molecular structure of the product as described above for molecular structure I9 (153 (87)).
Example 10
This example provides a method for preparing 1-phenyl-2-propanone. The structural formula of the 1-phenyl-2-acetone is shown as the following molecular structural formula I10:
the preparation method refers to the preparation method of the phenylacetaldehyde in the example 1, and is characterized in that 0.2mmol of 3-methyl-2, 4-pentanedione (1eq) is adopted to replace 0.2mmol of acetic anhydride (1eq), the filtrate is dried by spinning, and column chromatography separation is carried out, so that the target product is obtained, and the yield is 40%.
The product I10 prepared was subjected to characterization data analysis, which resulted in:1H NMR(600MHz,CDCl3):δ7.33-7.30(t,J＝7.5Hz,2H),7.26-7.24(t,J＝7.2Hz,1H),7.20-7.18(d,J＝7.8Hz,2H),3.67(s,2H),2.13(s,3H)；13C NMR(150MHz,CDCl3):δ206.21,134.09,129.31,129.14,128.64,128.47,126.96,126.77,50.80,29.09.MS calculated for C9H10134.18 in% (m/z), and the results confirmed that the molecular structure of the product was the same as that of the above-mentioned molecular structure I10.
Example 11
This example provides a method for preparing p-methoxyphenylacetone. The structural formula of the p-methoxy phenyl acetone is shown as the following molecular structural formula I11:
the preparation method refers to the preparation method of the phenylacetaldehyde in the embodiment 1, and is characterized in that 0.2mmol of 3-methyl-2, 4-pentanedione (1eq) is adopted to replace 0.2mmol of acetic anhydride (1eq), 0.2mmol of p-anisole is adopted to replace fluorobenzene, the filtrate is dried by spinning, and the column chromatography separation is carried out to obtain the target product with the yield of 72%.
The product I11 prepared was subjected to characterization data analysis, which resulted in:1H NMR(600MHz,CDCl3):δ7.11-7.10(d,J＝8.4Hz,2H),6.87-6.85(d,J＝8.4Hz,2H),3.77(s,3H),3.61(s,2H),2.12(s,3H)；13C NMR(150MHz,CDCl3):δ206.67,158.46,130.30,130.14,126.10,114.02,113.91,55.10,49.86,28.92.HRMS(ESI/[M+H+])calcd.for C10H13O2165.0910.Found:165.0904. the results further confirm that the molecular structure of the product is as described above for molecular structure I11.
Example 12
This example provides a process for the preparation of p-trifluoromethylphenylacetone. The structural formula of the p-trifluoromethylphenyl acetone is shown as the following molecular structural formula I12:
the preparation method refers to the preparation method of the phenylacetaldehyde in the embodiment 1, and is characterized in that 0.2mmol of 3-methyl-2, 4-pentanedione (1eq) is adopted to replace 0.2mmol of acetic anhydride (1eq), 0.2mmol of p-fluorotrifluorotoluene is adopted to replace fluorobenzene, the filtrate is dried by spinning, and the column chromatography separation is carried out to obtain the target product with the yield of 57%. The product I12 prepared was subjected to characterization data analysis, which resulted in:1H NMR(600MHz,CDCl3):δ7.60-7.59(d,J＝7.8Hz,2H),7.32-7.31(d,J＝7.8Hz,2H),3.78(s,2H),2.20(s,3H)；13C NMR(150MHz,CDCl3):δ205.13,138.00,129.87,129.71,129.46,129.25,125.61,125.49,124.97,123.17,50.32,29.61.HRMS(ESI/[M+H+])calcd.for C10H10F3o203.0678 Found 203.0683 the results further confirm that the molecular structure of the product is as described above for molecular structure I12.
Example 13
This example provides a method for preparing 4-methyl propiophenone. The structural formula of the 4-methyl propiophenone is shown as the following molecular structural formula I13:
the preparation method refers to the preparation method of the phenylacetaldehyde in the embodiment 1, and is characterized in that 0.2mmol of 3-methyl-2, 4-pentanedione (1eq) is adopted to replace 0.2mmol of acetic anhydride (1eq), 0.2mmol of p-fluorotoluene is adopted to replace fluorobenzene, the filtrate is dried by spinning, and the column chromatography separation is carried out to obtain the target product with the yield of 61%.
The product I13 prepared was subjected to characterization data analysis, which resulted in:1H NMR(600MHz,CDCl3):δ7.14-7.13(d,J＝7.8Hz,2H),7.09-7.07(d,J＝8.4Hz,2H),3.64(s,2H),2.32(s,3H),2.12(s,3H)；13C NMR(150MHz,CDCl3):δ206.68,136.63,131.16,129.51,129.32,129.20,129.14,50.60,29.15,21.09.HRMS calcd.for C10H12o. 148.2.Found:148.2. this result further confirms the molecular structure of the product as in the above molecular structure I13.
Example 14
This example provides a method for preparing 3-methyl propiophenone. The structural formula of the 3-methyl propiophenone is shown as the following molecular structural formula I14:
the preparation method refers to the preparation method of the phenylacetaldehyde in the embodiment 1, and is characterized in that 0.2mmol of 3-methyl-2, 4-pentanedione (1eq) is adopted to replace 0.2mmol of acetic anhydride (1eq), 0.2mmol of 3-fluorotoluene is adopted to replace fluorobenzene, the filtrate is dried by spinning, and the column chromatography separation is carried out to obtain the target product with the yield of 57%.
The product I14 prepared was subjected to characterization data analysis, which resulted in:1H NMR(600MHz,CDCl3):δ7.25-7.21(q,J＝8.8Hz,1H),7.09-7.07(d,J＝7.2Hz,1H),7.02-6.99(t,J＝6.6Hz,2H),3.65(s,2H),2.34(s,3H)2.14(s,3H)；13C NMR(150MHz,CDCl3):δ206.57,138.33,134.05,130.11,129.96,128.64,128.49,127.81,127.66,126.39,126.24,50.93,29.17,21.32.HRMS calcd.for C10H12o. 148.2.Found:148.2. this result further confirms the molecular structure of the product as in the above molecular structure I14.
Example 15
This example provides a process for the preparation of 4-isopropylphenylacetone. The structural formula of the 4-isopropyl phenylacetone is shown as the following molecular structural formula I15:
the preparation method refers to the preparation method of the phenylacetaldehyde in the embodiment 1, and is characterized in that 0.2mmol of 3-methyl-2, 4-pentanedione (1eq) is adopted to replace 0.2mmol of acetic anhydride (1eq), 0.2mmol of 4-fluoroisopropylbenzene is adopted to replace fluorobenzene, the filtrate is dried by spinning, and the column chromatography separation is carried out to obtain the target product with the yield of 50%. The product I15 prepared was subjected to characterization data analysis, which resulted in:1H NMR(300MHz,CDCl3):δ7.12-7.03(m,4H),3.57(s,2H),2.85-2.76(m,1H),2.06(s,3H),1.17(s,3H),1.15(s,3H)；13C NMR(75MHz,CDCl3):δ207.04,147.86,131.70,129.52,127.05,50.85,33.96,29.50,24.20.HRMS calcd.for C12H16o. 176.25.Found:176.25. this result further confirmed the molecular structure of the product as described above for molecular structure I15.
Example 16
This example provides a method for preparing 4-chlorophenyl propanone. The structural formula of the 4-chlorophenylacetone is shown as the following molecular structural formula I16:
the preparation method refers to the preparation method of the phenylacetaldehyde in the embodiment 1, and is characterized in that 0.2mmol of 3-methyl-2, 4-pentanedione (1eq) is adopted to replace 0.2mmol of acetic anhydride (1eq), 0.2mmol of 4-fluorobenzene is adopted to replace fluorobenzene, the filtrate is dried by spinning, and the column chromatography separation is carried out to obtain the target product with the yield of 51%.
The product I16 prepared was subjected to characterization data analysis, which resulted in:1H NMR(600MHz,CDCl3):δ7.30-7.29(d,J＝7.8Hz,2H),7.13-7.12(d,J＝7.8Hz,2H),3.67(s,2H),2.16(s,3H)；13C NMR(150MHz,CDCl3):δ205.59,132.89,132.49,130.76,130.61,128.81,128.66,49.93,29.34.HRMS calcd.for C9H9ClO:168.62.Found:168.62. the results further confirm that the molecular structure of the product is as described above for molecular structure I16.
Example 17
This example provides a method for preparing 4-nitrophenylacetone. The structural formula of the 7-methoxy-1- (3-chloro-phenyl) -fluorobenzene is shown as the following molecular structural formula I17:
the preparation method refers to the preparation method of the phenylacetaldehyde in the embodiment 1, and is characterized in that 0.2mmol of 3-methyl-2, 4-pentanedione (1eq) is adopted to replace 0.2mmol of acetic anhydride (1eq), 0.2mmol of 4-fluoronitrobenzene is adopted to replace fluorobenzene, the filtrate is dried by spinning, and the column chromatography separation is carried out to obtain the target product with the yield of 48%. The product I17 prepared was subjected to characterization data analysis, which resulted in: 1H NMR (400 MH)z,CDCl3):δ8.21-8.19(d,J＝8.4Hz,2H),7.38-7.36(d,J＝8.8Hz,2H),3.87(s,2H),2.25(s,3H)；13C NMR(100MHz,CDCl3):δ204.40,141.38,130.42,123.69,115.57,49.96,29.81.HRMS calcd.for C9H9NO3179.17 Found 179.17 the results further confirm that the molecular structure of the product is as described above for molecular structure I17.
Example 18
This example provides a method for preparing 4- (2-oxopropyl) benzoic acid. The structural formula of the 4- (2-oxopropyl) benzoic acid is shown as the following molecular structural formula I18:
the preparation method refers to the preparation method of the phenylacetaldehyde in the embodiment 1, and is characterized in that 0.2mmol of 3-methyl-2, 4-pentanedione (1eq) is adopted to replace 0.2mmol of acetic anhydride (1eq), 0.2mmol of 4-fluorobenzoic acid is adopted to replace fluorobenzene, the filtrate is dried by spinning, and the column chromatography separation is carried out to obtain the target product, wherein the yield is 41%. The product I18 prepared was subjected to characterization data analysis, which resulted in:1H NMR(400MHz,d6-DMSO):δ7.86-7.84(d,J＝8.0Hz,2H),7.26-7.24(d,J＝8.0Hz,2H),3.81(s,2H),2.10(s,3H)；13C NMR(100MHz,d6-DMSO):δ205.85,167.74,140.55,130.37,129.75,129.55,49.82,30.13.HRMS calcd.for C10H10O3178.18 Found 178.18 the results further confirm that the molecular structure of the product is as described above under I18.
Example 19
This example provides a method for preparing 4-biphenylacetone. The structural formula of the 4-biphenylacetone is shown as the following molecular structural formula I19:
the preparation method refers to the preparation method of the phenylacetaldehyde in the embodiment 1, and is characterized in that 0.2mmol of 3-methyl-2, 4-pentanedione (1eq) is adopted to replace 0.2mmol of acetic anhydride (1eq), 0.2mmol of 4-fluorobiphenyl is adopted to replace fluorobenzene, the filtrate is dried by spinning, and the column chromatography separation is carried out to obtain the target product, wherein the yield is 57%.
The product I19 prepared was subjected to characterization data analysis, which resulted in:1H NMR(600MHz,CDCl3):δ7.58-7.55(q,J＝6.2Hz,4H),7.43-7.41(t,J＝7.8Hz,2H),7.34-7.32(t,J＝7.2Hz,1H),7.26-7.25(d,J＝7.8Hz,2H),3.72(s,2H),2.17(s,3H)；13C NMR(150MHz,CDCl3):δ206.25,140.59,139.90,133.14,129.82,129.66,128.76,128.61,127.43,127.31,126.99,126.89,126.57,50.48,29.33,29.29.HRMS calcd.for C15H14o210.27107, Found 210.27107, this result further confirmed the molecular structure of the product as described above for molecular structure I19.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
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| CN103951694A (en) * | 2014-04-14 | 2014-07-30 | 上海大学 | Acridine or benzacridine derivative and synthesis method thereof |
| CN104151243A (en) * | 2014-07-22 | 2014-11-19 | 清华大学 | Method for preparing multi-substituted acridine derivative with high efficiency |
| CN112125840A (en) * | 2020-08-11 | 2020-12-25 | 河南师范大学 | Based on CO2Method for preparing diaryl ether compound by participated C-F bond activation |
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| CN103951694A (en) * | 2014-04-14 | 2014-07-30 | 上海大学 | Acridine or benzacridine derivative and synthesis method thereof |
| CN104151243A (en) * | 2014-07-22 | 2014-11-19 | 清华大学 | Method for preparing multi-substituted acridine derivative with high efficiency |
| CN112125840A (en) * | 2020-08-11 | 2020-12-25 | 河南师范大学 | Based on CO2Method for preparing diaryl ether compound by participated C-F bond activation |
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