CN111807971A - 一种原位催化醇类的烷基化合成方法 - Google Patents
一种原位催化醇类的烷基化合成方法 Download PDFInfo
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- CN111807971A CN111807971A CN202010658851.0A CN202010658851A CN111807971A CN 111807971 A CN111807971 A CN 111807971A CN 202010658851 A CN202010658851 A CN 202010658851A CN 111807971 A CN111807971 A CN 111807971A
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- alkylation
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- 238000001308 synthesis method Methods 0.000 title claims abstract description 45
- 238000005804 alkylation reaction Methods 0.000 title claims abstract description 27
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 19
- 230000029936 alkylation Effects 0.000 title claims abstract description 14
- 150000001298 alcohols Chemical class 0.000 title claims abstract description 12
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 6
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 75
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 73
- -1 VIB group metal complex Chemical class 0.000 claims abstract description 33
- 239000003446 ligand Substances 0.000 claims abstract description 24
- 239000000758 substrate Substances 0.000 claims abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 15
- 230000000269 nucleophilic effect Effects 0.000 claims abstract description 15
- 150000002576 ketones Chemical class 0.000 claims abstract description 10
- 238000003442 catalytic alkylation reaction Methods 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 230000002152 alkylating effect Effects 0.000 claims abstract description 8
- 150000001412 amines Chemical group 0.000 claims abstract description 8
- 230000003197 catalytic effect Effects 0.000 claims abstract description 8
- 150000003333 secondary alcohols Chemical class 0.000 claims abstract description 8
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 239000012298 atmosphere Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 65
- 238000000034 method Methods 0.000 claims description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 14
- 229910052750 molybdenum Inorganic materials 0.000 claims description 14
- 239000011733 molybdenum Substances 0.000 claims description 14
- 238000000605 extraction Methods 0.000 claims description 11
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical group [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 10
- 229910052804 chromium Inorganic materials 0.000 claims description 10
- 239000011651 chromium Substances 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 125000001424 substituent group Chemical group 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- FQNHWXHRAUXLFU-UHFFFAOYSA-N carbon monoxide;tungsten Chemical group [W].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] FQNHWXHRAUXLFU-UHFFFAOYSA-N 0.000 claims description 6
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 6
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 238000007126 N-alkylation reaction Methods 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 2
- 239000002168 alkylating agent Substances 0.000 claims 2
- 229940100198 alkylating agent Drugs 0.000 claims 2
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 204
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 49
- 238000005160 1H NMR spectroscopy Methods 0.000 description 49
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 33
- 239000007787 solid Substances 0.000 description 32
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 24
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- 239000003921 oil Substances 0.000 description 16
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 14
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 12
- 235000019445 benzyl alcohol Nutrition 0.000 description 11
- MSHFRERJPWKJFX-UHFFFAOYSA-N 4-Methoxybenzyl alcohol Chemical compound COC1=CC=C(CO)C=C1 MSHFRERJPWKJFX-UHFFFAOYSA-N 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- 238000004440 column chromatography Methods 0.000 description 9
- KMTDMTZBNYGUNX-UHFFFAOYSA-N 4-methylbenzyl alcohol Chemical compound CC1=CC=C(CO)C=C1 KMTDMTZBNYGUNX-UHFFFAOYSA-N 0.000 description 8
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 8
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 8
- 125000006575 electron-withdrawing group Chemical group 0.000 description 8
- 125000000623 heterocyclic group Chemical group 0.000 description 8
- 238000004293 19F NMR spectroscopy Methods 0.000 description 7
- GTWJETSWSUWSEJ-UHFFFAOYSA-N n-benzylaniline Chemical compound C=1C=CC=CC=1CNC1=CC=CC=C1 GTWJETSWSUWSEJ-UHFFFAOYSA-N 0.000 description 7
- XPNGNIFUDRPBFJ-UHFFFAOYSA-N (2-methylphenyl)methanol Chemical compound CC1=CC=CC=C1CO XPNGNIFUDRPBFJ-UHFFFAOYSA-N 0.000 description 6
- NGIPUQZQWOTHPZ-UHFFFAOYSA-N C1(=CC=CC=C1)C(CC[C-]1C=CC=C1)=O.[CH-]1C=CC=C1.[Fe+2] Chemical compound C1(=CC=CC=C1)C(CC[C-]1C=CC=C1)=O.[CH-]1C=CC=C1.[Fe+2] NGIPUQZQWOTHPZ-UHFFFAOYSA-N 0.000 description 6
- 239000012230 colorless oil Substances 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- QLNHWQQSIRBHAT-UHFFFAOYSA-N 3-(4-fluorophenyl)-1-phenylpropan-1-one Chemical compound C1=CC(F)=CC=C1CCC(=O)C1=CC=CC=C1 QLNHWQQSIRBHAT-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 125000000304 alkynyl group Chemical group 0.000 description 4
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 125000004093 cyano group Chemical group *C#N 0.000 description 4
- QGGZBXOADPVUPN-UHFFFAOYSA-N dihydrochalcone Chemical compound C=1C=CC=CC=1C(=O)CCC1=CC=CC=C1 QGGZBXOADPVUPN-UHFFFAOYSA-N 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 4
- 125000004346 phenylpentyl group Chemical group C1(=CC=CC=C1)CCCCC* 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- 125000000101 thioether group Chemical group 0.000 description 4
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- 239000010937 tungsten Substances 0.000 description 4
- NLXWIEOJEBAXRH-UHFFFAOYSA-N 3-(2-methylphenyl)-1-phenylpropan-1-one Chemical compound CC1=CC=CC=C1CCC(=O)C1=CC=CC=C1 NLXWIEOJEBAXRH-UHFFFAOYSA-N 0.000 description 3
- MHNUDVYKHUVNCC-UHFFFAOYSA-N 3-(4-bromophenyl)-1-phenylpropan-1-one Chemical compound C1=CC(Br)=CC=C1CCC(=O)C1=CC=CC=C1 MHNUDVYKHUVNCC-UHFFFAOYSA-N 0.000 description 3
- RHAMWHONYCOKTQ-UHFFFAOYSA-N 3-(4-chlorophenyl)-1-phenylpropan-1-one Chemical compound C1=CC(Cl)=CC=C1CCC(=O)C1=CC=CC=C1 RHAMWHONYCOKTQ-UHFFFAOYSA-N 0.000 description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical group OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- LIJJGMDKVVOEFT-UHFFFAOYSA-N n-benzyl-4-methoxyaniline Chemical compound C1=CC(OC)=CC=C1NCC1=CC=CC=C1 LIJJGMDKVVOEFT-UHFFFAOYSA-N 0.000 description 3
- PTHGDVCPCZKZKR-UHFFFAOYSA-N (4-chlorophenyl)methanol Chemical compound OCC1=CC=C(Cl)C=C1 PTHGDVCPCZKZKR-UHFFFAOYSA-N 0.000 description 2
- GEZMEIHVFSWOCA-UHFFFAOYSA-N (4-fluorophenyl)methanol Chemical compound OCC1=CC=C(F)C=C1 GEZMEIHVFSWOCA-UHFFFAOYSA-N 0.000 description 2
- JJFFOBOHMGOFJM-UHFFFAOYSA-N 1-phenyl-3-thiophen-2-ylpropan-1-one Chemical compound C=1C=CC=CC=1C(=O)CCC1=CC=CS1 JJFFOBOHMGOFJM-UHFFFAOYSA-N 0.000 description 2
- XHLHPRDBBAGVEG-UHFFFAOYSA-N 1-tetralone Chemical compound C1=CC=C2C(=O)CCCC2=C1 XHLHPRDBBAGVEG-UHFFFAOYSA-N 0.000 description 2
- LWBKNBIUKKTGEJ-UHFFFAOYSA-N 2-benzyl-3,4-dihydro-2h-naphthalen-1-one Chemical compound C1CC2=CC=CC=C2C(=O)C1CC1=CC=CC=C1 LWBKNBIUKKTGEJ-UHFFFAOYSA-N 0.000 description 2
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- VBMLYDUTYXBITB-UHFFFAOYSA-N 3-(4-methylphenyl)-1-phenylpropan-1-one Chemical compound C1=CC(C)=CC=C1CCC(=O)C1=CC=CC=C1 VBMLYDUTYXBITB-UHFFFAOYSA-N 0.000 description 2
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- 239000006227 byproduct Substances 0.000 description 2
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- 150000004696 coordination complex Chemical class 0.000 description 2
- QETISSZVCNFQBN-UHFFFAOYSA-N cyclopentane;cyclopentylmethanol;iron Chemical compound [Fe].[CH]1[CH][CH][CH][CH]1.OC[C]1[CH][CH][CH][CH]1 QETISSZVCNFQBN-UHFFFAOYSA-N 0.000 description 2
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- AZLKZLKCCRFAAE-UHFFFAOYSA-N n-benzyl-4-bromoaniline Chemical compound C1=CC(Br)=CC=C1NCC1=CC=CC=C1 AZLKZLKCCRFAAE-UHFFFAOYSA-N 0.000 description 2
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- HHAISVSEJFEWBZ-UHFFFAOYSA-N 1-[4-(trifluoromethyl)phenyl]ethanone Chemical compound CC(=O)C1=CC=C(C(F)(F)F)C=C1 HHAISVSEJFEWBZ-UHFFFAOYSA-N 0.000 description 1
- CDRQOYRPWJULJN-UHFFFAOYSA-N 1-naphthalen-1-ylethanol Chemical group C1=CC=C2C(C(O)C)=CC=CC2=C1 CDRQOYRPWJULJN-UHFFFAOYSA-N 0.000 description 1
- TWBPWBPGNQWFSJ-UHFFFAOYSA-N 2-phenylaniline Chemical compound NC1=CC=CC=C1C1=CC=CC=C1 TWBPWBPGNQWFSJ-UHFFFAOYSA-N 0.000 description 1
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- YKFROQCFVXOUPW-UHFFFAOYSA-N 4-(methylthio) aniline Chemical compound CSC1=CC=C(N)C=C1 YKFROQCFVXOUPW-UHFFFAOYSA-N 0.000 description 1
- MOOUWXDQAUXZRG-UHFFFAOYSA-N 4-(trifluoromethyl)benzyl alcohol Chemical compound OCC1=CC=C(C(F)(F)F)C=C1 MOOUWXDQAUXZRG-UHFFFAOYSA-N 0.000 description 1
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- WDFQBORIUYODSI-UHFFFAOYSA-N 4-bromoaniline Chemical compound NC1=CC=C(Br)C=C1 WDFQBORIUYODSI-UHFFFAOYSA-N 0.000 description 1
- QSNSCYSYFYORTR-UHFFFAOYSA-N 4-chloroaniline Chemical compound NC1=CC=C(Cl)C=C1 QSNSCYSYFYORTR-UHFFFAOYSA-N 0.000 description 1
- KRZCOLNOCZKSDF-UHFFFAOYSA-N 4-fluoroaniline Chemical compound NC1=CC=C(F)C=C1 KRZCOLNOCZKSDF-UHFFFAOYSA-N 0.000 description 1
- WRDWWAVNELMWAM-UHFFFAOYSA-N 4-tert-butylaniline Chemical compound CC(C)(C)C1=CC=C(N)C=C1 WRDWWAVNELMWAM-UHFFFAOYSA-N 0.000 description 1
- WREVVZMUNPAPOV-UHFFFAOYSA-N 8-aminoquinoline Chemical compound C1=CN=C2C(N)=CC=CC2=C1 WREVVZMUNPAPOV-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- TWQNSHZTQSLJEE-UHFFFAOYSA-N [2-(trifluoromethyl)phenyl]methanol Chemical compound OCC1=CC=CC=C1C(F)(F)F TWQNSHZTQSLJEE-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- CNUDBTRUORMMPA-UHFFFAOYSA-N formylthiophene Chemical compound O=CC1=CC=CS1 CNUDBTRUORMMPA-UHFFFAOYSA-N 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- HUDSSSKDWYXKGP-UHFFFAOYSA-N n-phenylpyridin-2-amine Chemical compound C=1C=CC=NC=1NC1=CC=CC=C1 HUDSSSKDWYXKGP-UHFFFAOYSA-N 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 description 1
- VEDDBHYQWFOITD-UHFFFAOYSA-N para-bromobenzyl alcohol Chemical compound OCC1=CC=C(Br)C=C1 VEDDBHYQWFOITD-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- ZPHGMBGIFODUMF-UHFFFAOYSA-N thiophen-2-ylmethanol Chemical compound OCC1=CC=CS1 ZPHGMBGIFODUMF-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 150000003657 tungsten Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一种原位催化醇类的烷基化合成方法,是以VIB族金属络合物、辅助配体和碱为催化反应体系,以醇为烷基化试剂,在溶剂和惰性气体氛围中,对亲核底物进行原位催化的烷基化反应,所述亲核底物为胺、酮或二级醇。本发明的催化体系对底物的适应范围广,能够在较温和的条件下,催化不同结构的C‑N和C‑C键化合物的合成;可绿色合成得到一系列有价值的N‑烷基化和C‑烷基化化合物。
Description
技术领域
本发明属于化学合成领域,具体涉及一种原位催化醇类的烷基化合成方法。
背景技术
烷基化反应是一类构建C-N和C-C键的重要反应之一,在活性天然产物、药物以及功能材料的合成方面有着广泛的应用。传统的N-烷基化和C-烷基化反应需要使用毒性较大的有机卤试剂、金属有机试剂和过量的碱,且伴随产生大量的副产物和废弃物,造成较大的环境污染。因此,直接以绿色的可再生来源的醇作为烷基化试剂,采用过渡金属催化剂催化的“借氢反应”策略进行烷基化反应在绿色合成和选择性方面显现巨大的优势。该策略通过金属催化剂催化非活化醇脱氢为醛/酮类亲电合成子;然后醛/酮和亲核试剂反应得到含C=N或者C=C的不饱和双键的缩合中间体;最后催化剂再原位将C=N或C=C双键还原形成C-N或者C-C键的烷基化产物。该方法的优点是使用便宜易得的醇底物作为烷基化试剂,且原子效率高,副产物只有水,环境友好,并且可以避免过度烷基化,选择性高。但是,该方法主要集中在钌、铑、铱等贵金属催化剂上,成本较高。近年来,非贵金属如铁、钴、锰、镍等催化剂也得到发展,但是,目前大部分应用于这类反应的非贵金属催化剂结构中均含有磷,环境不友好,并且反应底物适用性也受限。因此,开发简单高效、环境友好的新型非贵金属催化剂,具有广阔应用前景。VIB族的铬、钼、钨作为地球上蕴藏量巨大的一类廉价金属,具有来源广、价格低廉,环境友好等优点,其在有机金属、电池能源储存以及发光金属材料等领域应用广泛,若能将其应用于催化醇类的烷基化合成反应,是非常符合可持续发展和绿色合成需求,具有极大的应用价值。
发明内容
本发明的目的在于克服现有技术中存在的缺点,提供一种环境友好、成本低、操作简单、反应底物适用性广的原位催化醇类的烷基化合成方法。
本发明的目的通过下述技术方案实现:
一种原位催化醇类的烷基化合成方法,是以VIB族金属络合物、辅助配体和碱为催化反应体系,以醇(结构式为式1)为烷基化试剂,在溶剂和惰性气体氛围中,对亲核底物(结构式为式2,包括胺、酮或二级醇等)进行原位催化的烷基化反应,反应温度为80~150℃。
其中,烷基化试剂醇(式1)的R3、R4为H、脂肪取代基(包含大位阻基团)、芳香取代基或杂环取代基;亲核试剂(式2)为胺、酮或二级醇。烷基化试剂和亲核底物的摩尔比为1:1~1.5:1;优选为1.2:1。
所述烷基化试剂醇(式1)的R3、R4中,所述脂肪取代基优选含芳环长链脂肪烃;所述大位阻基团优选2-甲基、2-乙基、2-丙基或2-叔丁基;所述芳香取代基优选苯环衍生物或杂环芳香化合物,可含供电子基团、吸电子基团、或者氰基/烯基/炔基等官能团,所述供电子基团优选烷基、烷氧基或硫醚基,所述吸电子基团优选卤素或三氟甲基;所述杂环取代基为含氮杂环、含氧杂环或含硫杂环。所述含芳环长链脂肪烃优选为苯丁基、苯戊基、苯己基、苯庚基和苯辛基。
更为具体的,当亲核底物为胺时,进行N-烷基化反应,得到N-烷基化产物,其反应通式为:
其中,胺的取代基R1为H,R2是脂肪取代基(包含大位阻基团)、芳香取代基、杂环取代基或磺酰取代基。所述脂肪取代基优选含芳环长链脂肪烃;所述大位阻基团优选2-甲基、2-乙基、2-丙基或2-叔丁基;所述芳香取代基优选苯环衍生物或杂环芳香化合物,可含供电子基团、吸电子基团、或者氰基/烯基/炔基等官能团,所述供电子基团优选烷基、烷氧基或硫醚基,所述吸电子基团优选卤素或三氟甲基;所述杂环取代基为含氮杂环、含氧杂环或含硫杂环;所述磺酰取代基为对烷基苯磺酰基。所述含芳环长链脂肪烃优选为苯丁基、苯戊基、苯己基、苯庚基和苯辛基。
更为具体的,当亲核底物为酮时,进行C-烷基化反应,得到C-烷基化产物,其反应通式为:
其中,酮的取代基R1和R2为脂肪取代基(包含大位阻基团)、芳香取代基或杂环取代基。所述脂肪取代基优选含芳环长链脂肪烃;所述大位阻基团优选2-甲基、2-乙基、2-丙基或2-叔丁基;所述芳香取代基优选苯环衍生物或杂环芳香化合物,可含供电子基团、吸电子基团、或者氰基/烯基/炔基等官能团,所述供电子基团优选烷基、烷氧基或硫醚基,所述吸电子基团优选卤素或三氟甲基;所述杂环取代基为含氮杂环、含氧杂环或含硫杂环。所述含芳环长链脂肪烃优选为苯丁基、苯戊基、苯己基、苯庚基和苯辛基。
更为具体的,当亲核底物为二级醇时,进行C-烷基化反应,得到C-烷基化产物,其反应通式为:
其中,二级醇的取代基R1和R2为脂肪取代基(包含大位阻基团)、芳香取代基或杂环取代基。所述脂肪取代基优选含芳环长链脂肪烃;所述大位阻基团优选2-甲基、2-乙基、2-丙基或2-叔丁基;所述芳香取代基优选苯环衍生物或杂环芳香化合物,可含供电子基团、吸电子基团、或者氰基/烯基/炔基等官能团,所述供电子基团优选烷基、烷氧基或硫醚基,所述吸电子基团优选卤素或三氟甲基;所述杂环取代基为含氮杂环、含氧杂环或含硫杂环。所述含芳环长链脂肪烃优选为苯丁基、苯戊基、苯己基、苯庚基和苯辛基。
所述VIB族金属络合物为铬、钼或钨络合物;优选为零价含羰基的铬、钼或钨络合物;更优选为六羰基铬、六羰基钼或六羰基钨。
所述VIB族金属催化剂与亲核底物的摩尔比为0.005:1~0.15:1;优选为0.02:1~0.1:1。
所述辅助配体为以下结构L1~L7中的一种:
所述辅助配体与VIB族金属催化剂的摩尔比为1:1~1.5:1;优选为1.2:1。
所述碱为NaOH、KOH、NaOtBu、KOtBu、NaH或KH;所述碱与烷基化试剂醇的摩尔比为0.3:1~1.5:1;优选为0.5:1~1:1。
所述溶剂为苯、甲苯、二氧六环、THF、t-AmOH、正己烷、环己烷中的一种或两种。
所述惰性气体为氮气或者氩气。
所述烷基化的反应时间为6~24h,反应结束后,萃取、分离纯化、干燥,得到烷基化产物。
本发明的原理是:借助借氢策略、巧妙利用零价VIB族金属催化剂的低电负性和金属-氢负离子中间体的高活性,成功实现高效绿色、原位简便、经济实惠的醇类烷基化反应。
本发明与现有技术相比具有如下优点和效果:
(1)本发明采用VIB族非贵金属络合物作为催化剂,提供了一种新型的原位催化醇类的烷基化合成方法,反应直接以醇为原料,反应物易得,绿色可再生。
(2)本发明的催化剂原料易得,成本低廉,无需使用含磷配体,低毒性,对环境友好,反应操作简单。
(3)本发明的催化体系对底物的适应范围广,能够在较温和的条件下,催化不同结构的C-N和C-C键化合物的合成;可绿色合成得到一系列有价值的N-烷基化和C-烷基化化合物。
具体实施方式
为了便于理解本发明,下面将结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明,但是,不以任何形式限制本发明。应该指出的是,对本领域的技术人员来说,在不脱离本发明构思的前提下,本发明还可以做出若干变形和改进,这些都属于本发明的保护范围。
实施例1:合成N-苄基苯胺
向带有搅拌子的10mL Schlenk管中,氮气保护下分别加入苯胺(1eq.),苯甲醇(1.2eq.),六羰基钨(10%eq.),辅助配体L4(R5=H,R6=H,12%eq.),KOtBu(1eq.),1,4-dixoane(2mL),130℃反应24h。反应完全后,乙酸乙酯萃取,旋干,柱层析,干燥,即得无色油状物N-苄基苯胺,其产率为94%。
1H NMR(400MHz,CDCl3)δ7.46(q,J=7.7Hz,4H),7.41–7.36(m,1H),7.32–7.25(m,2H),6.84(t,J=7.3Hz,1H),6.74(d,J=7.9Hz,2H),4.41(s,2H),4.10(s,1H)。13C NMR(100MHz,CDCl3)δ148.05,139.36,129.15,128.51,127.38,127.10,117.42,112.74,48.16。
实施例2:合成N-苄基-4-甲基苯胺
向带有搅拌子的10mL Schlenk管中,氮气保护下分别加入4-甲基苯胺(1eq.),苯甲醇(1.2eq.),六羰基铬(5%eq.),辅助配体L3(R5=Me,X=Br,6%eq.),KOtBu(0.5eq.),甲苯(2mL),120℃反应24h。反应完全后,乙酸乙酯萃取,旋干,柱层析,干燥,即得淡黄色油状N-苄基-4-甲基苯胺,其产率为95%。
1H NMR(400MHz,CDCl3)δ7.44–7.37(m,4H),7.32(t,J=6.8Hz,1H),7.05(d,J=8.2Hz,2H),6.62(d,J=8.4Hz,2H),4.35(s,2H),3.70(s,1H),2.30(s,3H)。13C NMR(100MHz,CDCl3)δ145.86,139.61,129.68,128.53,127.43,127.08,126.66,112.94,48.57,20.35。
实施例3:合成N-苄基-4-甲氧基苯胺
向带有搅拌子的10mL Schlenk管中,氮气保护下分别加入4-甲氧基苯胺(1eq.),苯甲醇(1.2eq.),六羰基钼(2%eq.),辅助配体L1(R5=Me,X=Br,3%eq.),KOtBu(0.5eq.),正己烷(2mL),130℃反应24h。反应完全后,乙酸乙酯萃取,旋干,柱层析,干燥,即得淡黄色油状物N-苄基-4-甲氧基苯胺,其产率为97%。
1H NMR(400MHz,CDCl3)δ7.43–7.33(m,4H),7.29(t,J=6.8Hz,1H),6.80(d,J=8.9Hz,2H),6.63(d,J=8.9Hz,2H),4.30(s,2H),3.76(s,3H),3.42(s,1H)。13C NMR(100MHz,CDCl3)δ152.12,142.39,139.63,128.53,127.48,127.10,114.85,114.06,55.74,49.18。
实施例4:合成N-苄基-4-甲硫基苯胺
按照实施例1中的合成方法,用4-甲硫基苯胺(1eq.)代替苯胺,其他操作条件同实施例1,反应结束后得到黄色油状物N-苄基-4-甲硫基苯胺,其产率为88%。
1H NMR(400MHz,CDCl3)δ7.38–7.32(m,4H),7.31–7.27(m,1H),7.22(d,J=8.6Hz,2H),6.58(d,J=8.6Hz,2H),4.31(s,2H),4.09(s,1H),2.40(s,3H)。13CNMR(100MHz,CDCl3)δ146.89,139.08,131.35,128.57,127.34,127.20,124.35,113.38,48.18,19.01。
实施例5:合成N-苄基-4-叔丁基苯胺
按照实施例2中的合成方法,用4-叔丁基苯胺(1eq.)代替苯胺,其他操作条件同实施例2,反应结束后得到黄色油状物N-苄基-4-叔丁基苯胺,其产率为89%。
1H NMR(400MHz,CDCl3)δ7.40(dt,J=14.8,7.3Hz,4H),7.32(t,J=7.0Hz,1H),7.26(d,J=8.7Hz,2H),6.65(d,J=8.6Hz,2H),4.35(s,2H),3.76(s,1H),1.33(s,9H)。13CNMR(100MHz,CDCl3)δ145.82,140.27,139.66,128.55,127.51,127.12,125.98,112.53,48.59,33.82,31.52.
实施例6:合成N-苄基-4-乙基苯胺
按照实施例3中的合成方法,用4-乙基苯胺(1eq.)代替苯胺,其他操作条件同实施例3,反应结束后得到淡黄色油状物N-苄基-4-乙基苯胺,其产率为91%。
1H NMR(400MHz,CDCl3)δ7.49–7.40(m,4H),7.36(t,J=6.9Hz,1H),7.12(d,J=8.4Hz,2H),6.68(d,J=8.4Hz,2H),4.39(s,2H),3.96(s,1H),2.65(q,J=7.6Hz,2H),1.30(t,J=7.6Hz,3H)。13C NMR(100MHz,CDCl3)δ146.08,139.62,133.29,128.51,128.49,127.44,127.07,112.90,48.55,27.88,15.92。
实施例7:合成N-苄基-4-溴苯胺
按照实施例1中的合成方法,用4-溴苯胺(1eq.)代替苯胺,其他操作条件同实施例1,反应结束后得到黄色油状物N-苄基-4-溴苯胺,其产率为91%。
1H NMR(400MHz,CDCl3)δ7.44–7.38(m,4H),7.37–7.33(m,1H),7.29(d,J=8.8Hz,2H),6.55(d,J=8.8Hz,2H),4.34(s,2H),4.10(s,1H)。13C NMR(100MHz,CDCl3)δ146.97,138.79,131.85,128.63,128.19,127.32,114.36,109.02,48.14。
实施例8:合成N-苄基-4-氯苯胺
按照实施例2中的合成方法,用4-氯苯胺(1eq.)代替苯胺,其他操作条件同实施例2,反应结束后得到黄色油状物N-苄基-4-氯苯胺,其产率为83%。
1H NMR(400MHz,CDCl3)δ7.36(d,J=4.4Hz,4H),7.30(dd,J=8.9,4.4Hz,1H),7.12(d,J=8.8Hz,2H),6.56(d,J=8.8Hz,2H),4.31(s,2H),4.09(s,1H)。13CNMR(100MHz,CDCl3)δ146.58,138.88,129.03,128.67,127.38,127.34,122.08,113.90,48.32。
实施例9:合成N-苄基-4-氟苯胺
按照实施例3中的合成方法,用4-氟苯胺(1eq.)代替苯胺,其他操作条件同实施例3,反应结束后得到黄色油状物N-苄基-4-氟苯胺,其产率为87%。
1H NMR(400MHz,CDCl3)δ7.39(dd,J=6.7,3.8Hz,4H),7.34–7.29(m,1H),6.91(t,J=8.8Hz,2H),6.58(dd,J=9.0,4.4Hz,2H),4.31(s,2H),3.70(s,1H)。13C NMR(100MHz,CDCl3)δ155.83(d,J=234.9Hz),144.40,139.17,128.57(d,J=8.7Hz),128.21,127.34(d,J=18.2Hz),115.60(d,J=22.3Hz),113.61(d,J=7.4Hz),48.87。
19F NMR(377MHz,CDCl3)δ-127.85.
实施例10:合成N-苄基-2-甲硫基苯胺
按照实施例1中的合成方法,用2-甲硫基苯胺(1eq.)代替苯胺,其他操作条件同实施例1,反应结束后得到淡黄色油状物N-苄基-2-甲硫基苯胺,其产率为90%。
1H NMR(400MHz,CDCl3)δ7.53–7.30(m,6H),7.20(t,J=7.7Hz,1H),6.73(t,J=7.4Hz,1H),6.65(d,J=8.1Hz,1H),5.44(s,1H),4.46(s,2H),2.40(s,3H)。13C NMR(100MHz,CDCl3)δ148.02,139.14,133.93,129.36,128.57,127.15,127.10,119.72,117.14,110.32,47.92,18.05。
HRMS(ESI):Calculated for[C14H16NS]+230.0998;Found 230.0997。
实施例11:合成N-苄基-2-甲基苯胺
按照实施例2中的合成方法,用2-甲基苯胺(1eq.)代替苯胺,其他操作条件同实施例2,反应结束后得到浅黄色固体N-苄基-2-甲基苯胺,其产率为90%。
1H NMR(400MHz,CDCl3)δ7.41(dt,J=14.8,7.3Hz,4H),7.33(t,J=7.0Hz,1H),7.14(dd,J=12.7,7.1Hz,2H),6.72(t,J=7.3Hz,1H),6.66(d,J=8.0Hz,1H),4.42(s,2H),3.91(s,1H),2.21(s,3H)。13C NMR(100MHz,CDCl3)δ146.02,139.46,130.02,128.62,127.50,127.21,127.12,121.87,117.14,109.93,48.27,17.52。
实施例12:合成N-苄基-2-苯基苯胺
按照实施例3中的合成方法,用2-苯基苯胺(1eq.)代替苯胺,其他操作条件同实施例3,反应结束后得到浅黄色固体N-苄基-2-苯基苯胺,其产率为93%。
1H NMR(400MHz,CDCl3)δ7.64–7.53(m,4H),7.50–7.40(m,6H),7.38–7.21(m,3H),6.91(t,J=7.4Hz,1H),6.79(d,J=8.1Hz,1H),4.53(s,1H),4.43(s,2H)。13C NMR(100MHz,CDCl3)δ144.79,139.40,130.13,129.29,128.84,128.63,128.48,128.17,127.57,127.15,126.93,117.10,110.69,48.01。
实施例13:合成N-2-甲基苄基-2-甲硫基苯胺
按照实施例1中的合成方法,用2-甲硫基苯胺(1eq.)代替苯胺,用2-甲基苯甲醇(1.2eq.)代替苯甲醇,其他操作条件同实施例1,反应结束后得到淡黄色油状物N-2-甲基苄基-2-甲硫基苯胺,其产率为97%。
1H NMR(400MHz,CDCl3)δ7.50(dd,J=7.6,1.5Hz,1H),7.39(d,J=6.7Hz,1H),7.30–7.23(m,4H),6.75(td,J=7.5,1.1Hz,1H),6.67(d,J=8.1Hz,1H),5.25(s,1H),4.40(d,J=4.6Hz,2H),2.45(s,3H),2.39(s,3H)。13C NMR(100MHz,CDCl3)δ148.14,136.64,136.09,134.00,130.34,129.43,127.80,127.27,126.09,119.63,117.06,110.14,46.15,18.90,18.09。
HRMS(ESI):Calculated for[C15H18NS]+244.1154;Found 244.1154.
实施例14:合成N-苄基-3-乙烯基苯胺
按照实施例2中的合成方法,用3-乙烯基苯胺(1eq.)代替苯胺,其他操作条件同实施例2,反应结束后得到淡黄色油状物N-苄基-3-乙烯基苯胺,其产率为89%。
1H NMR(400MHz,CDCl3)δ7.57–7.34(m,5H),7.24(t,J=7.8Hz,1H),6.92(d,J=7.6Hz,1H),6.84–6.70(m,2H),6.63(dd,J=8.0,1.9Hz,1H),5.80(dd,J=17.6,0.8Hz,1H),5.31(dd,J=10.9,0.7Hz,1H),4.41(s,2H),4.08(s,1H)。13CNMR(100MHz,CDCl3)δ148.24,139.29,138.44,137.20,129.29,128.54,127.41,127.14,115.73,113.39,112.41,110.53,48.19。
实施例15:合成4-(苄基氨基)苯甲腈
按照实施例3中的合成方法,用4-氨基苯甲腈(1eq.)代替苯胺,其他操作条件同实施例3,反应结束后得到无色油状物4-(苄基氨基)苯甲腈,其产率为93%。
1H NMR(400MHz,CDCl3)δ7.44–7.29(m,7H),6.59(d,J=8.6Hz,2H),4.78(s,1H),4.38(d,J=5.5Hz,2H)。13C NMR(100MHz,CDCl3)δ151.08,137.75,133.55,128.72,127.51,127.15,120.38,112.28,98.66,47.26。
实施例16:合成N-4-甲硫基苄基苯胺
按照实施例1中的合成方法,用4-甲硫基苯甲醇(1.2eq.)代替苯甲醇,其他操作条件同实施例1,反应结束后得到淡黄色油状物N-4-甲硫基苄基苯胺,其产率为96%。
1H NMR(400MHz,CDCl3)δ7.35–7.27(m,4H),7.21(t,J=7.8Hz,2H),6.76(t,J=7.3Hz,1H),6.65(d,J=8.2Hz,2H),4.31(s,2H),4.03(s,1H),2.50(s,3H)。13C NMR(100MHz,CDCl3)δ147.98,137.10,136.37,129.18,127.94,126.94,117.55,112.80,47.77,15.95。
实施例17:合成N-4-甲基苄基苯胺
按照实施例2中的合成方法,用4-甲基苯甲醇(1.2eq.)代替苯甲醇,其他操作条件同实施例2,反应结束后得到浅黄色固体N-4-甲基苄基苯胺,其产率为90%。
1H NMR(400MHz,CDCl3)δ7.38(d,J=8.0Hz,2H),7.33–7.24(m,4H),6.84(t,J=7.3Hz,1H),6.75(dd,J=8.5,0.8Hz,2H),4.39(s,2H),4.05(s,1H),2.47(s,3H)。13C NMR(100MHz,CDCl3)δ148.14,136.73,136.30,129.22,129.16,127.42,117.38,112.75,47.96,21.03。
实施例18:合成N-4-甲氧基苄基苯胺
按照实施例3中的合成方法,用4-甲氧基苯甲醇(1.2eq.)代替苯甲醇,其他操作条件同实施例3,反应结束后得到淡黄色油状物N-4-甲氧基苄基苯胺,其产率为94%。
1H NMR(400MHz,CDCl3)δ7.32(d,J=8.7Hz,2H),7.24–7.18(m,2H),6.92(d,J=8.7Hz,2H),6.75(t,J=7.3Hz,1H),6.67(dd,J=8.6,1.0Hz,2H),4.28(s,2H),3.98(s,1H),3.83(s,3H)。13C NMR(100MHz,CDCl3)δ158.80,148.16,131.37,129.18,128.73,117.42,113.97,112.78,55.23,47.73。
实施例19:合成N-苄基-2-吡啶苯胺
按照实施例1中的合成方法,用2-吡啶苯胺(1.0eq.)代替苯胺,其他操作条件同实施例1,反应结束后得到白色固体N-苄基-2-吡啶苯胺,其产率为86%。
1H NMR(400MHz,CDCl3)δ8.07(dd,J=5.0,1.1Hz,1H),7.43–7.32(m,5H),7.30–7.24(m,1H),6.63–6.51(m,1H),6.36(d,J=8.4Hz,1H),5.44(s,1H),4.50(d,J=5.8Hz,2H)。13C NMR(100MHz,CDCl3)δ158.59,147.93,139.09,137.24,128.39,127.19,126.96,112.77,106.51,46.05。
实施例20:合成N-苄基喹啉-8-胺
按照实施例2中的合成方法,用8-胺基喹啉(1.0eq.)代替苯胺,其他操作条件同实施例2,反应结束后得黄色油状物N-苄基喹啉-8-胺,其产率为79%。
1H NMR(400MHz,CDCl3)δ8.78(dd,J=4.1,1.5Hz,1H),8.09(dd,J=8.3,1.4Hz,1H),7.50(d,J=7.4Hz,2H),7.44–7.37(m,4H),7.33(t,J=7.2Hz,1H),7.11(d,J=8.1Hz,1H),6.71(d,J=7.5Hz,2H),4.61(d,J=5.8Hz,2H)。13C NMR(100MHz,CDCl3)δ146.81,144.48,139.14,138.13,135.90,128.52,127.68,127.31,127.03,121.31,114.05,105.03,47.59。
实施例21:合成N-苄基-9H-芴-2-胺
按照实施例3中的合成方法,用99H-芴-2-胺(1.0eq.)代替苯胺,其他操作条件同实施例3,反应结束后得到浅黄色固体N-苄基-9H-芴-2-胺,其产率为86%。
1H NMR(400MHz,CDCl3)δ7.63(dd,J=7.5,1.5Hz,1H),7.55(dd,J=8.0,1.8Hz,1H),7.38–7.27(m,6H),7.17–7.08(m,2H),6.69(dd,J=8.0,1.5Hz,1H),6.50(s,1H),4.16(t,J=7.5Hz,1H),3.53(s,2H),3.10(d,J=7.6Hz,2H)。13C NMR(100MHz,CDCl3)δ148.67,145.86,145.52,141.17,139.91,131.88,129.48,128.18,126.94,126.23,124.93,124.52,120.52,118.43,114.16,111.67,48.41,40.17。
实施例22:合成1,3-二苯基-1-丙酮
向带有搅拌子的10mL Schlenk管中,氮气保护下分别加入苯乙酮(1eq.),苯甲醇(1.2eq.),六羰基钨(5%eq.),辅助配体L5(R5=H,6%eq.),NaOH(0.5eq.),甲苯(2mL),140℃反应12h。反应完全后,二氯甲烷萃取,旋干,柱层析,干燥,即得白色固体1,3-二苯基-1-丙酮,其产率为93%。
1H NMR(400MHz,CDCl3)δ7.97(d,J=7.3Hz,2H),7.56(t,J=7.4Hz,1H),7.46(t,J=7.6Hz,2H),7.34–7.26(m,4H),7.22(t,J=7.0Hz,1H),3.48–3.25(m,2H),3.15–2.96(m,2H).13C NMR(100MHz,CDCl3)δ199.20,141.24,136.80,133.02,128.56,128.48,128.38,127.99,126.09,40.41,30.09.
实施例23:合成1-苯基-3-对甲苯基-1-丙酮
向带有搅拌子的10mL Schlenk管中,氮气保护下分别加入苯乙酮(1eq.),对甲基苯甲醇(1.2eq.),六羰基铬(3%eq.),辅助配体L7(X=Br,3.6%eq.),KOH(0.5eq.),甲苯(2mL),140℃反应12h。反应完全后,二氯甲烷萃取,旋干,柱层析,干燥,即得白色固体1-苯基-3-对甲苯基-1-丙酮,其产率为91%。
1H NMR(400MHz,CDCl3)δ7.97(d,J=7.2Hz,2H),7.56(t,J=7.4Hz,1H),7.46(t,J=7.6Hz,2H),7.15(q,J=8.1Hz,4H),3.44–3.21(m,2H),3.16–2.87(m,2H),2.34(s,3H).13CNMR(100MHz,CDCl3)δ199.30,138.14,136.84,135.57,132.98,129.16,128.54,128.25,127.99,40.56,29.68,20.96.
实施例24:合成3-对甲氧苯基-1-苯基-1-丙酮
向带有搅拌子的10mL Schlenk管中,氮气保护下分别加入苯乙酮(1eq.),对甲氧基苯甲醇(1.2eq.),六羰基钼(2%eq.),辅助配体L2(R5=H,R6=Me,X=Br,2.4%eq.),KOH(0.5eq.),正己烷(2mL),130℃反应12h。反应完全后,二氯甲烷萃取,旋干,柱层析,干燥,即得白色固体3-对甲氧苯基-1-苯基-1-丙酮,其产率为94%。
1H NMR(400MHz,CDCl3)δ7.96(d,J=7.1Hz,2H),7.56(t,J=7.4Hz,1H),7.45(t,J=7.6Hz,2H),7.18(d,J=8.6Hz,2H),6.85(d,J=8.6Hz,2H),3.79(s,3H),3.27(t,J=7.6Hz,2H),3.02(t,J=7.6Hz,2H).13C NMR(100MHz,CDCl3)δ199.36,157.93,136.83,133.25,132.98,129.29,128.54,127.98,113.88,55.21,40.65,29.23.
实施例25:合成3-对氟代苯基-1-苯基-1-丙酮
按照实施例22中的合成方法,用4-氟代苯甲醇(1.2eq.)代替苯甲醇,其他操作条件同实施例22,反应结束后,得白色固体3-对氟代苯基-1-苯基-1-丙酮,其产率为88%。
1H NMR(400MHz,CDCl3)δ7.95(d,J=7.1Hz,2H),7.56(t,J=7.4Hz,1H),7.46(t,J=7.6Hz,2H),7.21(dd,J=8.6,5.4Hz,2H),6.98(t,J=8.7Hz,2H),3.28(t,J=7.5Hz,2H),3.05(t,J=7.5Hz,2H).13C NMR(100MHz,CDCl3)δ199.01,136.77,133.10,129.83,129.76,128.60,127.98,115.32,115.11,40.39,29.24.19FNMR(376MHz,CDCl3)δ-117.27.
实施例26:合成3-对氯代苯基-1-苯基-1-丙酮
按照实施例23中的合成方法,用4-氯代苯甲醇(1.2eq.)代替对甲基苯甲醇,其他操作条件同实施例23,反应结束后,得白色固体3-对氯代苯基-1-苯基-1-丙酮,其产率为83%。
1H NMR(400MHz,CDCl3)δ7.95(d,J=7.1Hz,2H),7.56(t,J=7.4Hz,1H),7.46(t,J=7.6Hz,2H),7.30–7.23(m,2H),7.18(d,J=8.4Hz,2H),3.28(t,J=7.5Hz,2H),3.05(t,J=7.5Hz,2H).13C NMR(100MHz,CDCl3)δ198.83,139.70,136.71,133.14,131.84,129.79,128.61,128.56,127.98,40.11,29.35.
实施例27:合成3-对溴代苯基-1-苯基-1-丙酮
按照实施例24中的合成方法,用4-氯代苯甲醇(1.2eq.)代替对甲氧基苯甲醇,其他操作条件同实施例24,反应结束后,得白色固体3-对氯代苯基-1-苯基-1-丙酮,其产率为80%。
1H NMR(400MHz,CDCl3)δ7.95(d,J=8.0Hz,2H),7.56(t,J=6.8Hz,1H),7.50–7.37(m,4H),7.17–7.05(m,2H),3.28(t,J=7.5Hz,2H),3.03(t,J=7.4Hz,2H).13C NMR(100MHz,CDCl3)δ198.77,140.21,136.68,133.13,131.50,130.19,128.60,127.96,119.83,40.01,29.38.
实施例28:合成3-对三氟甲基苯基-1-苯基-1-丙酮
按照实施例24中的合成方法,用4-三氟甲基代苯甲醇(1.2eq.)代替对甲氧基苯甲醇,其他操作条件同实施例24,反应结束后,得白色固体3-对三氟甲基苯基-1-苯基-1-丙酮,其产率为89%。
1H NMR(400MHz,CDCl3)δ7.96(d,J=7.5Hz,2H),7.56(dd,J=11.2,7.7Hz,3H),7.46(t,J=7.7Hz,2H),7.37(d,J=8.0Hz,2H),3.33(t,J=7.5Hz,2H),3.14(t,J=7.4Hz,2H).13C NMR(100MHz,CDCl3)δ198.52,145.42,136.62,133.21,128.78,128.63,127.96,125.40,125.37,122.91,39.78,29.73.19F NMR(376MHz,CDCl3)δ-62.35.
实施例29:合成3-邻三氟甲基苯基-1-苯基-1-丙酮
按照实施例22中的合成方法,用2-三氟甲基苯甲醇(1.2eq.)代替苯甲醇,其他操作条件同实施例22,反应结束后,得白色固体3-邻三氟甲基苯基-1-苯基-1-丙酮,其产率为90%。
1H NMR(400MHz,CDCl3)δ7.96(d,J=7.2Hz,2H),7.65(d,J=7.8Hz,1H),7.56(t,J=7.4Hz,1H),7.52–7.43(m,3H),7.40(d,J=7.6Hz,1H),7.32(t,J=7.6Hz,1H),3.51–2.95(m,4H).13C NMR(100MHz,CDCl3)δ198.58,140.13,136.65,133.14,131.95,131.33,128.61,128.44,128.01,126.31,126.11,126.05,123.24,40.52,27.07.19F NMR(376MHz,CDCl3)δ-59.68.
实施例30:合成3-邻甲基苯基-1-苯基-1-丙酮
按照实施例23中的合成方法,用邻甲基苯甲醇(1.2eq.)代替对甲基苯甲醇,其他操作条件同实施例23,反应结束后,得白色固体3-邻甲基苯基-1-苯基-1-丙酮,其产率为89%
1H NMR(400MHz,CDCl3)δ7.99(d,J=7.2Hz,2H),7.58(t,J=7.4Hz,1H),7.47(t,J=7.6Hz,2H),7.24–7.11(m,4H),3.43–3.20(m,2H),3.15–2.94(m,2H),2.37(s,3H).13C NMR(100MHz,CDCl3)δ199.31,139.32,136.79,135.93,133.03,130.29,128.67,128.56,127.98,126.27,126.12,39.06,27.46,19.30.
实施例31:合成3-(2,6-二甲基)苯基-1-苯基-1-丙酮
按照实施例24中的合成方法,用2,6-二甲基苯甲醇(1.2eq.)代替对甲氧基苯甲醇,其他操作条件同实施例24,反应结束后,得白色固体3-(2,6-二甲基)苯基-1-苯基-1-丙酮,其产率为92%。
1H NMR(400MHz,CDCl3)δ8.03(d,J=7.8Hz,2H),7.61(t,J=7.0Hz,1H),7.51(t,J=7.7Hz,2H),7.10(s,3H),3.30–2.91(m,4H),2.41(s,6H).13C NMR(100MHz,CDCl3)δ199.29,137.79,136.65,136.00,132.97,128.50,128.18,127.89,125.95,37.54,23.92,19.71.HRMS(ESI)m/z calcd for C17H19O[M+H]+:239.14304,found:239.14309.
实施例32:合成1-苯基-3-(噻吩-2-基)-1-丙酮
按照实施例22中的合成方法,用2-噻吩甲醇(1.2eq.)代替苯甲醇,其他操作条件同实施例22,反应结束后,得白色固体1-苯基-3-(噻吩-2-基)-1-丙酮,其产率为89%。
1H NMR(400MHz,CDCl3)δ7.98(d,J=7.1Hz,2H),7.57(t,J=7.4Hz,1H),7.47(t,J=7.6Hz,2H),7.13(dd,J=5.1,1.2Hz,1H),6.93(dd,J=5.1,3.4Hz,1H),6.87(dd,J=3.3,0.9Hz,1H),3.40–3.34(m,2H),3.33–3.27(m,2H).13C NMR(100MHz,CDCl3)δ198.55,143.84,136.69,133.13,128.60,127.99,126.81,124.64,123.34,40.51,24.18.
实施例33:合成1-苯基-3-二茂铁基-1-丙酮
按照实施例23中的合成方法,用二茂铁基甲醇(1.2eq.)代替对甲基苯甲醇,其他操作条件同实施例23,反应结束后,得黄色固体1-苯基-3-二茂铁基-1-丙酮,其产率为89%。
1H NMR(400MHz,CDCl3)δ7.97(d,J=7.4Hz,2H),7.57(t,J=7.3Hz,1H),7.47(t,J=7.6Hz,2H),4.19–4.03(m,9H),3.39–3.07(m,2H),2.95–2.57(m,2H).13C NMR(100MHz,CDCl3)δ199.48,136.85,132.97,128.55,127.99,87.95,68.55,68.50,68.08,67.31,40.30,24.06.
实施例34:合成3-(呋喃-2-基)-1-苯基-1-丙酮
按照实施例24中的合成方法,用2-呋喃甲醇(1.2eq.)代替对甲氧基苯甲醇,其他操作条件同实施例24,反应结束后,得淡黄色固体3-(呋喃-2-基)-1-苯基-1-丙酮,其产率为85%。
1H NMR(400MHz,CDCl3)δ7.72(d,J=3.7Hz,1H),7.65(d,J=4.9Hz,1H),7.38–7.21(m,5H),7.16–7.11(m,1H),3.26(t,J=7.7Hz,2H),3.13–3.06(m,2H).13C NMR(100MHz,CDCl3)δ192.11,144.12,140.95,133.51,131.77,128.50,128.38,128.04,126.17,41.10,30.35.
实施例35:合成1-(2,6-二甲基)苯基-3-苯基--1-丙酮
按照实施例22中的合成方法,用2,6-二甲基苯乙酮(1.0eq.)代替苯乙酮,其他操作条件同实施例22,反应结束后,得淡黄色油状物1-(2,6-二甲基)苯基-3-苯基-1-丙酮,其产率为89%。
1H NMR(400MHz,CDCl3)δ7.29(qd,J=14.2,6.9Hz,5H),7.19(t,J=7.6Hz,1H),7.04(d,J=7.5Hz,2H),3.25–2.92(m,4H),2.20(s,6H).13C NMR(100MHz,CDCl3)δ209.39,142.12,140.83,132.41,128.49,128.45,128.43,127.70,126.11,46.16,29.34,18.97.HRMS(ESI)m/z calcd for C17H18ONa[M+H+Na]+:261.12499,found:261.12492.
实施例36:合成3-苯基-1-(2-三氟甲基)苯基-1-丙酮
按照实施例23中的合成方法,2-三氟甲基苯乙酮(1.0eq.)代替苯乙酮,其他操作条件同实施例23,反应结束后,得白色固体3-苯基-1-(2-三甲基)苯基-1-丙酮,其产率为82%。
1H NMR(400MHz,CDCl3)δ7.71(d,J=7.0Hz,1H),7.61–7.51(m,2H),7.35–7.28(m,3H),7.27–7.19(m,3H),3.23–3.15(m,2H),3.10–3.02(m,2H).13C NMR(100MHz,CDCl3)δ203.38,140.58,131.78,129.96,128.51,128.34,126.79,126.67,126.62,126.21,44.83,29.81.19F NMR(376MHz,CDCl3)δ-58.06.HRMS(ESI)m/z calcd for C16H12OF3[M-H]-:277.08457,found:277.08459.
实施例37:合成2-苄基-3,4-二氢-1(2H)-萘酮
按照实施例24中的合成方法,用3,4-二氢-1(2H)-萘酮(1.0eq.)代替苯乙酮,其他操作条件同实施例24,反应结束后,得淡黄色油状物2-苄基-3,4-二氢-1(2H)-萘酮,其产率为88%。
1H NMR(400MHz,CDCl3)δ8.08(dd,J=7.8,1.0Hz,1H),7.47(td,J=7.5,1.4Hz,1H),7.36–7.28(m,3H),7.28–7.18(m,4H),3.50(dd,J=13.6,3.9Hz,1H),3.03–2.85(m,2H),2.81–2.71(m,1H),2.65(dd,J=13.6,9.6Hz,1H),2.12(dq,J=13.4,4.5Hz,1H),1.80(dddd,J=13.3,11.6,10.1,5.6Hz,1H).13C NMR(100MHz,CDCl3)δ199.38,144.00,140.00,133.24,132.43,129.23,128.68,128.37,127.51,126.59,126.10,49.42,35.64,28.59,27.63.
实施例38:合成1,3-二苯基-1-丙酮
向带有搅拌子的10mL Schlenk管中,氮气保护下分别加入苯乙醇(1eq.),苯甲醇(1.2eq.),六羰基钨(10%eq.),辅助配体L4(R5=H,R6=H,12%eq.),KOtBu(1eq.),t-AmOH(2mL),130℃反应24h。反应完全后,二氯甲烷萃取,旋干,柱层析,干燥,即得白色固体1,3-二苯基-1-丙酮,其产率为88%。
1H NMR(400MHz,CDCl3)δ7.97(d,J=7.1Hz,2H),7.56(t,J=7.4Hz,1H),7.46(t,J=7.6Hz,2H),7.30(dd,J=14.9,7.9Hz,4H),7.21(t,J=7.0Hz,1H),3.31(t,J=7.6Hz,2H),3.10–3.06(m,2H).13C NMR(100MHz,CDCl3)δ199.21,141.26,136.83,133.04,128.58,128.51,128.40,128.02,126.11,40.44,30.12.
实施例39:合成1-苯基-3-对甲基苯基-1-丙酮
向带有搅拌子的10mL Schlenk管中,氮气保护下分别加入苯乙醇(1eq.),对甲基苯甲醇(1.2eq.),六羰基铬(5%eq.),辅助配体L7(X=Br,6%eq.),NaOH(0.5eq.),t-AmOH(2mL),130℃反应24h。反应完全后,二氯甲烷萃取,旋干,柱层析,干燥,即得白色固体1-苯基-3-对甲基苯基-1-丙酮,其产率为86%。
1H NMR(400MHz,CDCl3)δ7.96(d,J=7.2Hz,2H),7.56(t,J=7.4Hz,1H),7.45(t,J=7.6Hz,2H),7.21–7.09(m,4H),3.29(t,J=7.7Hz,2H),3.03(t,J=7.7Hz,2H),2.33(s,3H).13C NMR(100MHz,CDCl3)δ199.32,138.17,136.88,135.61,133.00,129.18,128.57,128.27,128.02,40.60,29.71,20.99.
实施例40:合成3-对甲氧基苯基-1-苯基-1-丙酮
向带有搅拌子的10mL Schlenk管中,氮气保护下分别加入苯乙醇(1eq.),对甲氧基苯甲醇(1.2eq.),六羰基钼(3%eq.),辅助配体L3(R5=Me,X=Br,3.6%eq.),NaOH(0.5eq.),甲苯(2mL),130℃反应24h。反应完全后,二氯甲烷萃取,旋干,柱层析,干燥,即得白色固体3-对甲氧基苯基-1-苯基-1-丙酮,其产率为90%。
1H NMR(400MHz,CDCl3)δ7.97(d,J=7.8Hz,2H),7.56(t,J=7.3Hz,1H),7.46(t,J=7.6Hz,2H),7.18(d,J=8.4Hz,2H),6.86(d,J=8.4Hz,2H),3.79(s,3H),3.28(t,J=7.7Hz,2H),3.03(t,J=7.6Hz,2H).13C NMR(100MHz,CDCl3)δ199.29,157.92,136.83,133.23,132.94,129.27,128.51,127.95,113.87,55.18,40.61,29.21.
实施例41:合成3-苯基-1-对三氟甲基苯基-1-丙酮
按照实施例38中的合成方法,对三氟甲基苯乙酮(1.0eq.)代替苯乙酮,其他操作条件同实施例38,反应结束后,得白色固体3-苯基-1-对三氟甲基苯基-1-丙酮,其产率为82%。
1H NMR(400MHz,CDCl3)δ7.96(d,J=7.9Hz,2H),7.61–7.52(m,3H),7.46(t,J=7.6Hz,2H),7.37(d,J=8.0Hz,2H),3.33(t,J=7.5Hz,2H),3.14(t,J=7.4Hz,2H).13C NMR(100MHz,CDCl3)δ198.53,145.42,136.65,133.21,128.78,128.63,128.32,127.97,125.39(q,J=3.8Hz),122.91,39.78,29.74.19F NMR(376MHz,CDCl3)δ-62.36.
实施例42:合成3-对氟代苯基-1-苯基-1-丙酮
按照实施例39中的合成方法,对氟代苯甲醇(1.2eq.)代替对甲基苯甲醇,其他操作条件同实施例39,反应结束后,得白色固体3-对氟代苯基-1-苯基-1-丙酮,其产率为86%。
1H NMR(400MHz,CDCl3)δ7.95(d,J=7.2Hz,2H),7.56(t,J=7.4Hz,1H),7.46(t,J=7.6Hz,2H),7.21(dd,J=8.5,5.5Hz,2H),6.98(t,J=8.7Hz,2H),3.28(t,J=7.6Hz,2H),3.05(t,J=7.5Hz,2H).13C NMR(100MHz,CDCl3)δ199.00,133.11,129.76(t,J=8.4Hz),128.58(d,J=6.8Hz),128.00,127.70,125.87,115.23(d,J=21.2Hz),114.97,40.41,29.27.19F NMR(376MHz,CDCl3)δ-117.29.
实施例43:合成3-对溴代苯基-1-苯基-1-丙酮
按照实施例40中的合成方法,对溴代苯甲醇(1.2eq.)代替对甲氧基苯甲醇,六羰基钼(5%eq.),辅助配体L3(R5=Me,X=Br,6%eq.),其他操作条件同实施例40,反应结束后,得白色固体3-对溴代苯基-1-苯基-1-丙酮,其产率为86%。
1H NMR(400MHz,CDCl3)δ7.95(d,J=7.7Hz,2H),7.56(t,J=7.3Hz,1H),7.49–7.38(m,4H),7.13(d,J=8.2Hz,2H),3.28(t,J=7.5Hz,2H),3.03(t,J=7.5Hz,2H).13C NMR(100MHz,CDCl3)δ198.73,140.21,136.68,133.11,131.49,130.18,128.59,127.95,119.83,39.99,29.38.
实施例44:合成3-(2-甲基苯基)-1-苯基-1-丙酮
按照实施例38中的合成方法,2-甲基苯甲醇(1.2eq.)代替苯甲醇,其他操作条件同实施例38,反应结束后,得白色固体3-(2-甲基苯基)-1-苯基-1-丙酮,其产率为91%。
1H NMR(400MHz,CDCl3)δ8.00(d,J=7.8Hz,2H),7.58(t,J=7.3Hz,1H),7.48(t,J=7.6Hz,2H),7.24–7.12(m,4H),3.38–3.23(m,2H),3.18–3.01(m,2H),2.38(s,3H).13C NMR(100MHz,CDCl3)δ199.27,139.31,136.78,135.91,133.01,130.27,128.66,128.55,127.97,126.25,126.11,39.04,27.45,19.29.
实施例45:合成3-(萘-2-基)-1-苯基-1-丙酮
按照实施例39中的合成方法,萘-2-基甲醇(1.2eq.)代替对甲基苯甲醇,其他操作条件同实施例39,反应结束后,得白色固体3-(萘-2-基)-1-苯基-1-丙酮,其产率为88%。
1H NMR(400MHz,CDCl3)δ8.00(d,J=7.6Hz,2H),7.82(t,J=7.8Hz,3H),7.71(s,1H),7.57(t,J=7.3Hz,1H),7.50–7.38(m,5H),3.41(t,J=7.6Hz,2H),3.31–3.19(m,2H).13C NMR(100MHz,CDCl3)δ199.10,138.74,136.80,133.58,133.04,132.05,128.57,128.08,128.00,127.58,127.41,127.13,126.46,125.97,125.28,40.30,30.22.
实施例46:合成1-苯基-3-二茂铁基-1-丙酮
按照实施例40中的合成方法,二茂铁基甲醇(1.2eq.)代替对甲氧基苯甲醇,六羰基钼(5%eq.),辅助配体L3(R5=Me,X=Br,6%eq.),其他操作条件同实施例40,反应结束后,得黄色固体1-苯基-3-二茂铁基-1-丙酮,其产率为87%。
1H NMR(400MHz,CDCl3)δ7.97(d,J=7.2Hz,2H),7.56(d,J=6.9Hz,1H),7.47(t,J=6.9Hz,2H),4.11(d,J=23.4Hz,9H),3.20(t,J=7.3Hz,2H),2.80(t,J=7.2Hz,2H).13CNMR(100MHz,CDCl3)δ199.43,136.83,132.94,128.52,127.96,87.93,68.48,68.06,67.29,40.27,24.03.
实施例47:合成3-苯基-1-间三氟甲基苯基-1-丙酮
按照实施例38中的合成方法,间三氟甲基苯乙醇(1.0eq.)代替苯乙醇,其他操作条件同实施例38,反应结束后,得白色固体3-苯基-1-间三氟甲基苯基-1-丙酮,其产率为82%。
1H NMR(400MHz,CDCl3)δ8.19(s,1H),8.13(d,J=7.8Hz,1H),7.81(d,J=7.6Hz,1H),7.59(t,J=7.8Hz,1H),7.34–7.29(m,2H),7.27–7.19(m,3H),3.33(t,J=7.6Hz,2H),3.09(t,J=7.5Hz,2H).13C NMR(100MHz,CDCl3)δ197.76,140.85,137.33,131.41,131.12,129.44(dd,J=7.1,3.6Hz),129.28,128.93,128.58,128.40,126.28,124.87(q,J=3.7Hz),40.55,29.91.19F NMR(377MHz,CDCl3)δ-62.82.
实施例48:合成1-(萘-1-基)-1-苯基-1-丙酮
按照实施例39中的合成方法,萘-1-基乙醇(1.0eq.)代替苯乙醇,其他操作条件同实施例39,反应结束后,得白色固体1-(萘-1-基)-1-苯基-1-丙酮,其产率为83%。
1H NMR(400MHz,CDCl3)δ8.55(d,J=8.4Hz,1H),7.98(d,J=8.2Hz,1H),7.88(d,J=7.8Hz,1H),7.82(d,J=7.1Hz,1H),7.56(dt,J=14.8,7.1Hz,2H),7.47(t,J=7.7Hz,1H),7.32(dd,J=19.8,12.2Hz,2H),7.17(ddd,J=21.7,14.5,7.0Hz,3H),3.39(t,J=7.7Hz,2H),3.15(t,J=7.6Hz,2H).13C NMR(100MHz,CDCl3)δ203.54,141.09,135.99,133.95,132.55,130.11,129.09,128.52,128.44,127.86,127.36,126.43,126.15,125.76,124.33,43.82,30.59.
实施例49:合成1-苯基-3-二茂铁基-1-丙酮
按照实施例40中的合成方法,邻甲基苯乙醇(1.0eq.)代替苯乙醇,六羰基钼(5%eq.),辅助配体L3(R5=Me,X=Br,6%eq.),其他操作条件同实施例40,反应结束后,得淡黄色油状物1-苯基-3-二茂铁基-1-丙酮,其产率为82%。
1H NMR(400MHz,CDCl3)δ7.64(d,J=8.0Hz,1H),7.40(t,J=7.4Hz,1H),7.34(t,J=7.5Hz,2H),7.26(dd,J=17.5,6.9Hz,5H),3.27(t,J=7.6Hz,2H),3.09(t,J=7.6Hz,2H),2.52(s,3H).13C NMR(100MHz,CDCl3)δ203.32,141.13,138.01,137.86,131.90,131.18,128.44,128.36,128.30,126.06,125.60,43.16,30.28,21.18.
实施例50
按照实施例1中的合成方法,所用辅助配体L4(R5=H,R6=H,10%eq.),其他操作条件同实施例1,反应结束后得到无色油状物N-苄基苯胺,其产率为89%。
实施例51
按照实施例1中的合成方法,所用辅助配体L4(R5=H,R6=H,15%eq.),其他操作条件同实施例1,反应结束后得到无色油状物N-苄基苯胺,其产率为95%。
实施例52
按照实施例1中的合成方法,六羰基钨(15%eq.),辅助配体L4(R5=H,R6=H,18%eq.),其他操作条件同实施例1,反应结束后得到无色油状物N-苄基苯胺,其产率为96%。
实施例53
按照实施例1中的合成方法,苯甲醇用量为1.0eq.,其他操作条件同实施例1,反应结束后得到无色油状物N-苄基苯胺,其产率为86%。
实施例54
按照实施例1中的合成方法,苯甲醇用量为1.5eq.,其他操作条件同实施例1,反应结束后得到黄无色油状物N-苄基苯胺,其产率为95%。
实施例55
按照实施例3中的合成方法,金属络合物六羰基钼用量为(1%eq.),辅助配体L1(R5=Me,X=Br,1.2%eq.),其他操作条件同实施例3,反应结束后得到淡黄色油状物N-苄基-4-甲氧基苯胺,其产率为85%。
实施例56
按照实施例40的合成方法,碱NaOH用量为1.0eq.,其他操作条件同实施例40,反应结束后,得白色固体3-对甲氧基苯基-1-苯基-1-丙酮,其产率为91%。
实施例57
按照实施例40的合成方法,碱NaOH用量为1.5eq.,其他操作条件同实施例40,反应结束后,得白色固体3-对甲氧基苯基-1-苯基-1-丙酮,其产率为92%。
以上所述仅为本发明的实施例,但本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均为等效的置换方式,都包含在本发明的保护范围之内。
Claims (10)
5.根据权利要求1~4任一项所述的原位催化醇类的烷基化合成方法,其特征在于:所述VIB族金属络合物为六羰基铬、六羰基钼或六羰基钨。
6.根据权利要求1~4任一项所述的原位催化醇类的烷基化合成方法,其特征在于:所述VIB族金属催化剂与亲核底物的摩尔比为0.005:1~0.15:1。
8.根据权利要求1~4任一项所述的原位催化醇类的烷基化合成方法,其特征在于:所述碱为NaOH、KOH、NaOtBu、KOtBu、NaH或KH;所述碱与烷基化试剂醇的摩尔比为0.3:1~1.5:1。
9.根据权利要求1~4任一项所述的原位催化醇类的烷基化合成方法,其特征在于:所述溶剂为苯、甲苯、二氧六环、THF、t-AmOH、正己烷、环己烷中的一种或两种。
10.根据权利要求1~4任一项所述的原位催化醇类的烷基化合成方法,其特征在于:所述惰性气体为氮气或者氩气;所述烷基化的反应时间为6~24h,反应结束后,萃取、分离纯化、干燥,得到烷基化产物。
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JIAHAO LIU ET AL.: "Selective C-alkylation Between Alcohols Catalyzed by N-Heterocyclic Carbene Molybdenum", 《CHEM ASIAN J.》 * |
XIAO-BING LAN ET AL.: "Nonbifunctional Outer-Sphere Strategy Achieved Highly Active α‑Alkylation of Ketones with Alcohols by N‑Heterocyclic Carbene Manganese (NHC-Mn)", 《ORGANIC LETTERS》 * |
XIAO-BING LAN ET AL.: "Tungsten-Catalyzed Direct N-Alkylation of Anilines with Alcohols", 《CHEMSUSCHEM》 * |
张彩莉: "廉价金属镍催化的基于借氢策略的N-烷基化反应", 《山东师范大学硕士论文》 * |
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