CN106632434B - A kind of tert-butoxy rare earth/miscellaneous bimetal complexes of sodium and its preparation method and application - Google Patents
A kind of tert-butoxy rare earth/miscellaneous bimetal complexes of sodium and its preparation method and application Download PDFInfo
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- CN106632434B CN106632434B CN201611203067.0A CN201611203067A CN106632434B CN 106632434 B CN106632434 B CN 106632434B CN 201611203067 A CN201611203067 A CN 201611203067A CN 106632434 B CN106632434 B CN 106632434B
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- butoxy
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- -1 tert-butoxy rare earth Chemical class 0.000 title claims abstract description 39
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 title claims abstract description 22
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 22
- 239000011734 sodium Substances 0.000 title claims abstract description 22
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 71
- 239000003054 catalyst Substances 0.000 claims abstract description 38
- 150000002576 ketones Chemical class 0.000 claims abstract description 19
- 150000001345 alkine derivatives Chemical class 0.000 claims abstract description 14
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 4
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 claims description 76
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 57
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 48
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 46
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 39
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 38
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 36
- 239000002904 solvent Substances 0.000 claims description 36
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 28
- 238000000926 separation method Methods 0.000 claims description 24
- 229910052786 argon Inorganic materials 0.000 claims description 23
- 238000004440 column chromatography Methods 0.000 claims description 23
- 230000018044 dehydration Effects 0.000 claims description 23
- 238000006297 dehydration reaction Methods 0.000 claims description 23
- 239000007789 gas Substances 0.000 claims description 23
- 238000006555 catalytic reaction Methods 0.000 claims description 20
- 239000003480 eluent Substances 0.000 claims description 19
- 239000000284 extract Substances 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- AXQNJCVTWOBBNH-UHFFFAOYSA-N 2-methoxyethynylbenzene Chemical group COC#CC1=CC=CC=C1 AXQNJCVTWOBBNH-UHFFFAOYSA-N 0.000 claims description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 claims description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 12
- 238000005905 alkynylation reaction Methods 0.000 claims description 9
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 8
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 claims description 6
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 5
- 239000012965 benzophenone Substances 0.000 claims description 5
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical group [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 claims description 3
- NMWSKOLWZZWHPL-UHFFFAOYSA-N 3-chlorobiphenyl Chemical group ClC1=CC=CC(C=2C=CC=CC=2)=C1 NMWSKOLWZZWHPL-UHFFFAOYSA-N 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 239000000758 substrate Substances 0.000 abstract description 4
- 239000000654 additive Substances 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract description 2
- 239000003426 co-catalyst Substances 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 68
- 239000012074 organic phase Substances 0.000 description 28
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 21
- 239000007788 liquid Substances 0.000 description 21
- 239000003208 petroleum Substances 0.000 description 18
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 17
- 238000005160 1H NMR spectroscopy Methods 0.000 description 17
- 238000000605 extraction Methods 0.000 description 15
- 239000002585 base Substances 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 12
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 6
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 238000005935 nucleophilic addition reaction Methods 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- CPLWKNRPZVNELG-UHFFFAOYSA-N (3-chlorophenyl)-phenylmethanone Chemical class ClC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1 CPLWKNRPZVNELG-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- 229910052772 Samarium Inorganic materials 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 229910052769 Ytterbium Inorganic materials 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 2
- HTMYMRSLEMVHNX-UHFFFAOYSA-N 1-bromo-2-phenylethanol Chemical compound OC(Br)CC1=CC=CC=C1 HTMYMRSLEMVHNX-UHFFFAOYSA-N 0.000 description 1
- QYLFHLNFIHBCPR-UHFFFAOYSA-N 1-ethynylcyclohexan-1-ol Chemical compound C#CC1(O)CCCCC1 QYLFHLNFIHBCPR-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 229910017544 NdCl3 Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229930013930 alkaloid Natural products 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000008365 aromatic ketones Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- ICXXXLGATNSZAV-UHFFFAOYSA-N butylazanium;chloride Chemical compound [Cl-].CCCC[NH3+] ICXXXLGATNSZAV-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- QILSFLSDHQAZET-UHFFFAOYSA-N diphenylmethanol Chemical compound C=1C=CC=CC=1C(O)C1=CC=CC=C1 QILSFLSDHQAZET-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- BVWCFOXBDSMXEP-UHFFFAOYSA-N espeletone Natural products COC1=CC=C(C(C)=O)C=C1C(=O)CC(C)C BVWCFOXBDSMXEP-UHFFFAOYSA-N 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- VBZWSGALLODQNC-UHFFFAOYSA-N hexafluoroacetone Chemical compound FC(F)(F)C(=O)C(F)(F)F VBZWSGALLODQNC-UHFFFAOYSA-N 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical class CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000012485 toluene extract Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/003—Compounds containing elements of Groups 3 or 13 of the Periodic Table without C-Metal linkages
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
- C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
- C07C29/42—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones with compounds containing triple carbon-to-carbon bonds, e.g. with metal-alkynes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
- B01J2231/4266—Sonogashira-type, i.e. RY + HC-CR' triple bonds, in which R=aryl, alkenyl, alkyl and R'=H, alkyl or aryl
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Molecular formula the invention discloses a kind of tert-butoxy rare earth/miscellaneous bimetal complexes of sodium and its preparation method and application, wherein tert-butoxy rare earth/miscellaneous bimetal complexes of sodium is：LnNa8[OC(CH3)3]10(OH), Ln represents rare earth metal.Tert-butoxy rare earth of the present invention/miscellaneous bimetal complexes of sodium can be used for being catalyzed end position alkynes and the reaction of ketone generates alkynol compound, the reaction condition is mild, co-catalyst and additive are not needed, atom utilization is high and catalyst amount is relatively low, and the scope of application of substrate is wider.
Description
One, technical field
The present invention relates to a kind of tert-butoxy rare earth/miscellaneous bimetal complexes of sodium and its preparation method and application.
Two, background technology
In synthesis chemistry, alkynol compound is a kind of important organic synthesis intermediate, and is widely used in synthesis
Drug, natural products and some other important organic compounds.Since it includes that alkynyl and this two class of hydroxyl are vivaciously variable
Functional group so that it in terms of molecular diversity also have prodigious potential using value.Alkynol can pass through hydrogenation, ring
The reactions such as change, coupling are transformed into the molecule (Fig. 1) of other functional groups.And it is anti-to the nucleophilic addition of aldehyde, ketone by alkynyl zinc reagent
It should be one of structure alkynol most efficient method.Although being achieved in alkynes is to the asymmetric reduction reaction field of aldehyde at present excellent
It is different as a result, but for inactive ketone, the yield of addition compound product propargyl alcohol compound is relatively low.Therefore, researchers
The nucleophilic addition for having developed many catalyst to be catalyzed alkynes to ketone.
The zinc alkyl such as Jun-An Ma in 2011, Ti (OiPr)4, alkaloids ligand and additive B aF2It is catalyzed fluoroform
The alkynylation reaction of base ketone, temperature carry out (- 20 DEG C) under the conditions of extremely low, and alkynes, zinc alkyl, Ti (OiPr)4It is both needed to significantly
Excessive (2.5 times, 3.0 times, 2.0 times).(Angew.Chem.Int.Ed.2011,50,3538-3541) the same year, Venkat
The reports such as Reddy Chintareddy are catalyzed the addition of trialkyl silyl alkynes and aldehydes or ketones using tetrabutyl ammonium fluoride (TBAF),
Mild condition, but raw material trialkyl silica alkynes needs are previously prepared, and catalyst TBAF dosages are also excessive (10-20mol%), Er Qiesan
Alkyl silyl alkynes also needs 2 times excessive.(J.Org.Chem.2011,76,4482-4485) Ling Song in 2012 etc. are with four
The nucleophilic addition of butyl ammonium chloride and KOH catalysis phenylacetylene and aromatic ketone, however phenylacetylene and KOH are both needed to serious offense in reacting
Amount is that 2 times and 10 times of ketone are measured, and the reaction time grows (3 days) respectively.(Tetra.Lett.2012,53,2160-2163)2014
Year, Makoto Nakajima et al. report a kind of using dinaphthol lithium salts as catalyst, the nucleophilic of catalysis ketone and alkynyl lithium
The method that addition prepares alkynol, reaction needs carry out under the conditions of -78, and use excessive highly basic butyl lithium.
(J.Org.Chem.2014,79,4817-4825) the metallic copper catalyst trifluoromethyl ketone of Ning Liu et al. in 2015
Alkynylation reaction, alkynes need excessive 2 times, while a large amount of alkali (20mol%) need to be added and catalyst amount is larger
(10mol%).(RSC Adv.2015,5,10089-10092)
In addition, somebody is catalyzed alkynes and carbonyls using potassium tert-butoxide and metallic aluminium, titanium, zinc, copper, lithium etc.
Nucleophilic addition.However, some catalyst systems still have many disadvantages, previously prepared alkynyl zinc is such as needed, alkynes is excessive, instead
Long between seasonable, catalyst amount is big, and substrate limitation is big, low yield etc..
Three, invention content
The present invention is intended to provide a kind of tert-butoxy rare earth/miscellaneous bimetal complexes of sodium and its preparation method and application.This
Invention tert-butoxy rare earth/miscellaneous bimetal complexes of sodium can be used as the alkynylation reaction of catalyst ketone to prepare alkynol, and
And there is higher catalytic activity, the reaction time can be shortened and reduce catalyst amount, expand the general applicability of substrate.
The tert-butoxy rare earth of the present invention/miscellaneous bimetal complexes of sodium, is using the tert-butyl alcohol as ligand, molecular formula is：
LnNa8[OC(CH3)3]10(OH),
Wherein Ln represents rare earth metal, such as scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium
Deng preferably neodymium, samarium, ytterbium.
The preparation method of tert-butoxy rare earth of the present invention/miscellaneous bimetal complexes of sodium, includes the following steps：
Weigh the anhydrous LnCl of 3mmol3It is placed in the processed centrifugal bottle of dehydration and deoxidation, solvent THF is added, is stirred at room temperature 24
Hour, mixed liquor is added to the (CH of NaOC containing 30mmol3)3THF solution in, add 3mmol NaOH, stirred at 40 DEG C
Reaction 24 hours is mixed, precipitation is centrifuged off after reaction, clear liquid is pumped into solvent THF, toluene extraction is added, centrifuges, turn
It moves in clear liquid to Schlenk reaction bulbs, low temperature crystallization under protection of argon gas after concentration is precipitated crystal as target product.
The temperature of the low temperature crystallization is -10 DEG C.
The tert-butoxy rare earth of the present invention/miscellaneous bimetal complexes of sodium, makees during the alkynylation reaction of ketone prepares alkynol
For catalyst application.
Tert-butoxy rare earth of the present invention/miscellaneous bimetal complexes of sodium as catalyst ketone alkynylation reaction process such as
Under：
Catalyst LnNa is added into the processed reaction bulb of dehydration and deoxidation under protection of argon gas8[OC(CH3)3]10(OH)、
Alkynes and carbonyls, are stirred to react 24 hours at 30 DEG C, after reaction column chromatography for separation (eluent be petroleum ether/
Ethyl acetate=10~20:1, v/v) target product alkynol compound is obtained.
The alkynes is for phenylacetylene or to Methoxy-phenylacetylene.
The carbonyls is acetone, cyclohexanone, benzophenone, 2 pentanone, propione, 3- espeletons or 3- chlorine two
Benzophenone.
The molar ratio of catalyst, alkynes and carbonyls is 0.04：1：1.
The alkynylation reaction that the present invention is catalyzed ketone can carry out in the absence of a solvent, can also be in the condition for having solvent
Lower progress.If adding solvent, solvent of first going out after reaction, then column chromatography for separation, target product is obtained；The solvent packet
Include dimethyl sulfoxide (DMSO), toluene or tetrahydrofuran (THF) etc..
If solvent is dimethyl sulfoxide (DMSO) (DMSO), addition deionized water is needed to be quenched after reaction, and use dichloromethane
Reaction solution is extracted, column chromatography for separation obtains target product alkynol compound after removing solvent.
Beneficial effects of the present invention are embodied in：
1, catalyst amount of the invention is less, can be reacted under different solvents.
2, due to the use of catalyst, which need not be added activator, and simultaneous reactions object need not be excessive, alkynes and ketone
Ratio is 1：1.
3, catalyst of the invention is wider to the scope of application of substrate.
Four, it illustrates
Fig. 1 is the possibility transformation routes schematic diagram of alkynol functional group.
Five, specific implementation mode
With reference to embodiment, the invention will be further described：
Embodiment 1：NdNa8[OC(CH3)3]10(OH) synthesis of complex
Weigh 0.75g (3mmol) anhydrous NdCl3It is placed in the processed centrifugal bottle of dehydration and deoxidation, solvent THF, room is added
Temperature stirring 24 hours, (the CH of NaOC containing 30mmol are added to by mixed liquor3)3THF solution in, add 0.12g's (3mmol)
NaOH, is stirred to react 24 hours at 40 DEG C, is centrifuged off precipitation after reaction, and clear liquid is pumped solvent THF, adds first
Benzene extracts, and centrifugation is shifted in clear liquid to Schlenk reaction bulbs, is precipitated in -10 DEG C of low temperature crystallizations 2 days under argon gas protection after concentration
Light blue crystal 2.90g (yield 71%).
Embodiment 2：SmNa8[OC(CH3)3]10(OH) synthesis of complex
Weigh 0.77g (3mmol) anhydrous SmCl3It is placed in the processed centrifugal bottle of dehydration and deoxidation, solvent THF, room is added
Temperature stirring 24 hours, (the CH of NaOC containing 30mmol are added to by mixed liquor3)3THF solution in, add 0.12g's (3mmol)
NaOH, is stirred to react 24 hours at 40 DEG C, is centrifuged off precipitation after reaction, and clear liquid is pumped solvent THF, adds first
Benzene extracts, and centrifugation is shifted in clear liquid to Schlenk reaction bulbs, is precipitated in -10 DEG C of low temperature crystallizations 2 days under argon gas protection after concentration
Light yellow crystal 2.60g (yield 80%).
Embodiment 3：YbNa8[OC(CH3)3]10(OH) synthesis of complex
Weigh 0.84g (3mmol) anhydrous YbCl3It is placed in through in the processed centrifugal bottle of dehydration and deoxidation, solvent THF is added,
It is stirred at room temperature 24 hours, mixed liquor is added to the (CH of NaOC containing 30mmol3)3THF solution in, add 0.12g (3mmol)
NaOH, be stirred to react at 40 DEG C 24 hours, be centrifuged off precipitation after reaction, clear liquid is pumped into solvent THF, is added
Toluene extracts, and centrifugation is shifted in clear liquid to Schlenk reaction bulbs, in -10 DEG C of low temperature crystallizations 2 days, analysis under argon gas protection after concentration
Go out white crystal 2.24g (yield 78%).
Embodiment 4：NdNa8[OC(CH3)3]10(OH) catalysis phenylacetylene is reacted with acetone
Catalyst n dNa is added into the processed reaction bulb of dehydration and deoxidation under protection of argon gas8[OC(CH3)3]10(OH)
0.01mmol, phenylacetylene 1mmol, acetone 1mmol and 0.5mL DMSO, are stirred to react 24 hours at 30 DEG C, after reaction
Deionized water is added to be quenched, extracts reaction solution with dichloromethane, extraction three times, merges organic phase, organic phase anhydrous sodium sulfate
It is dry, solvent is removed, (eluant, eluent is petroleum ether to column chromatography for separation：Ethyl acetate=12:1, v/v) target product phenylacetylene is obtained
Base propyl alcohol is yellow liquid, yield 52.7%.
1H NMR(400MHz,CDCl3)δ7.41(s,2H),7.31(s,3H),1.94(br,1H),1.62(s,6H)ppm
；13C NMR(101MHz,CDCl3)δ131.64,128.25,122.74,93.76,82.15,65.64,31.50ppm。
Embodiment 5：NdNa8[OC(CH3)3]10(OH) catalysis phenylacetylene is reacted with acetone
Catalyst n dNa is added into the processed reaction bulb of dehydration and deoxidation under protection of argon gas8[OC(CH3)3]10(OH)
0.04mmol, phenylacetylene 1mmol, acetone 1mmol and 0.5mL DMSO, are stirred to react 24 hours at 30 DEG C, after reaction
Deionized water is added to be quenched, extracts reaction solution with dichloromethane, extraction three times, merges organic phase, organic phase anhydrous sodium sulfate
It is dry, solvent is removed, (eluant, eluent is petroleum ether to column chromatography for separation：Ethyl acetate=12:1, v/v) target product phenylacetylene is obtained
Base propyl alcohol is yellow liquid, yield 100%.
1H NMR(400MHz,CDCl3)δ7.41(s,2H),7.31(s,3H),1.94(br,1H),1.62(s,6H)ppm
；13C NMR(101MHz,CDCl3)δ131.64,128.25,122.74,93.76,82.15,65.64,31.50ppm。
Embodiment 6：NdNa8[OC(CH3)3]10(OH) catalysis phenylacetylene is reacted with acetone
Under protection of argon gas to through catalyst n dNa is added in the processed reaction bulb of dehydration and deoxidation8[OC(CH3)3]10(OH)
0.04mmol, phenylacetylene 1mmol, acetone 1mmol and 0.5mL THF, are stirred to react 24 hours at 30 DEG C, remove after reaction
Solvent is removed, (eluant, eluent is petroleum ether to column chromatography for separation：Ethyl acetate=12:1, v/v) target product phenylacetylene base propyl alcohol is obtained,
For yellow liquid, yield 79.3%.
1H NMR(400MHz,CDCl3)δ7.41(s,2H),7.31(s,3H),1.94(br,1H),1.62(s,6H)ppm
；13C NMR(101MHz,CDCl3)δ131.64,128.25,122.74,93.76,82.15,65.64,31.50ppm。
Embodiment 7：NdNa8[OC(CH3)3]10(OH) catalysis phenylacetylene is reacted with acetone
Under protection of argon gas to through catalyst n dNa is added in the processed reaction bulb of dehydration and deoxidation8[OC(CH3)3]10(OH)
0.04mmol, phenylacetylene 1mmol, acetone 1mmol and 0.5mL toluene, are stirred to react 24 hours, after reaction at 30 DEG C
Solvent is removed, (eluant, eluent is petroleum ether to column chromatography for separation：Ethyl acetate=12:1, v/v) target product phenylacetylene base third is obtained
Alcohol is yellow liquid, yield 40.4%.
1H NMR(400MHz,CDCl3)δ7.41(s,2H),7.31(s,3H),1.94(br,1H),1.62(s,6H)ppm
；13C NMR(101MHz,CDCl3)δ131.64,128.25,122.74,93.76,82.15,65.64,31.50ppm。
Embodiment 8：NdNa8[OC(CH3)3]10(OH) catalysis phenylacetylene is reacted with acetone
Catalyst n dNa is added into the processed reaction bulb of dehydration and deoxidation under protection of argon gas8[OC(CH3)3]10(OH)
0.04mmol, phenylacetylene 1mmol, acetone 1mmol are stirred to react 24 hours, after reaction column layer at solvent-free lower 30 DEG C
(eluant, eluent is petroleum ether for analysis separation：Ethyl acetate=12:1, v/v) target product phenylacetylene base propyl alcohol is obtained, is yellow liquid,
Yield is 88.9%.
1H NMR(400MHz,CDCl3)δ7.41(s,2H),7.31(s,3H),1.94(br,1H),1.62(s,6H)ppm
；13C NMR(101MHz,CDCl3)δ131.64,128.25,122.74,93.76,82.15,65.64,31.50ppm。
Embodiment 9：SmNa8[OC(CH3)3]10(OH) catalysis phenylacetylene is reacted with acetone
Catalyst SmNa is added into the processed reaction bulb of dehydration and deoxidation under protection of argon gas8[OC(CH3)3]10(OH)
0.04mmol, phenylacetylene 1mmol, acetone 1mmol and 0.5mL DMSO, are stirred to react 24 hours at 30 DEG C, and reaction terminates
Deionized water is added afterwards to be quenched, extracts reaction solution with dichloromethane, extraction three times, merges organic phase, organic phase anhydrous slufuric acid
Sodium is dried, and removes solvent, (eluant, eluent is petroleum ether to column chromatography for separation：Ethyl acetate=12:1, v/v) target product benzene second is obtained
Alkynyl propyl alcohol is yellow liquid, yield 65.4%.
1H NMR(400MHz,CDCl3)δ7.41(s,2H),7.31(s,3H),1.94(br,1H),1.62(s,6H)ppm
；13C NMR(101MHz,CDCl3)δ131.64,128.25,122.74,93.76,82.15,65.64,31.50ppm。
Embodiment 10：YbNa8[OC(CH3)3]10(OH) catalysis phenylacetylene is reacted with acetone
Catalyst YbNa is added into the processed reaction bulb of dehydration and deoxidation under protection of argon gas8[OC(CH3)3]10(OH)
0.04mmol, phenylacetylene 1mmol, acetone 1mmol and 0.5mL DMSO, are stirred to react 24 hours at 30 DEG C, and reaction terminates
Deionized water is added afterwards to be quenched, extracts reaction solution with dichloromethane, extraction three times, merges organic phase, organic phase anhydrous slufuric acid
Sodium is dried, and removes solvent, (eluant, eluent is petroleum ether to column chromatography for separation：Ethyl acetate=12:1, v/v) target product benzene second is obtained
Alkynyl propyl alcohol is yellow liquid, yield 55.1%.
1H NMR(400MHz,CDCl3)δ7.41(s,2H),7.31(s,3H),1.94(br,1H),1.62(s,6H)ppm
；13C NMR(101MHz,CDCl3)δ131.64,128.25,122.74,93.76,82.15,65.64,31.50ppm。
Embodiment 11：NdNa8[OC(CH3)3]10(OH) catalysis phenylacetylene and hexamethylene reactive ketone
Catalyst n dNa is added into the processed reaction bulb of dehydration and deoxidation under protection of argon gas8[OC(CH3)3]10(OH)
0.04mmol, phenylacetylene 1mmol, cyclohexanone 1mmol and 0.5mL DMSO are stirred to react 24 hours, reaction knot at 30 DEG C
Deionized water is added after beam to be quenched, extracts reaction solution with dichloromethane, extraction three times, merges organic phase, the anhydrous sulphur of organic phase
Sour sodium drying, removes solvent, (eluant, eluent is petroleum ether to column chromatography for separation：Ethyl acetate=16:1, v/v) target product benzene is obtained
Ethynylcyclohexanol is faint yellow solid, yield 94.6%.
1H NMR(400MHz,CDCl3) δ 7.43 (m, 2H), 7.30 (m, 3H), 2.02 (m, 2H), 1.60~1.75 (m,
7H),1.30(br,1H)ppm；13C NMR(101MHz,CDCl3)δ131.69,128.25,128.20,126.69,122.95,
92.84,84.38,69.13,40.11,25.25,23.43ppm。
Embodiment 12：NdNa8[OC(CH3)3]10(OH) catalysis phenylacetylene is reacted with benzophenone
Catalyst n dNa is added into the processed reaction bulb of dehydration and deoxidation under protection of argon gas8[OC(CH3)3]10(OH)
0.04mmol, phenylacetylene 1mmol, benzophenone 1mmol and 0.5mL DMSO are stirred to react 24 hours at 30 DEG C, reaction
After deionized water be added be quenched, extract reaction solution with dichloromethane, extraction three times, merges organic phase, and organic phase is with anhydrous
Sodium sulphate is dried, and removes solvent, (eluant, eluent is petroleum ether to column chromatography for separation：Ethyl acetate=16:1, v/v) target product is obtained
Phenylacetylene base benzhydrol is faint yellow solid, yield 80.2%.
1H NMR(400MHz,CDCl3) δ 7.67 (d, 4H), 7.50 (m, 2H), 7.25~7.36 (m, 9H), 2.89 (s, 1H)
ppm；13C NMR(10MHz,CDCl3)δ145.14,131.71,128.60,128.35,127.84,127.76,125.85,
122.34,91.53,87.09,74.98ppm。
Embodiment 13：NdNa8[OC(CH3)3]10(OH) catalysis phenylacetylene is reacted with 2 pentanone
Catalyst n dNa is added into the processed reaction bulb of dehydration and deoxidation under protection of argon gas8[OC(CH3)3]10(OH)
0.04mmol, phenylacetylene 1mmol, 2 pentanone 1mmol and 0.5mL DMSO are stirred to react 24 hours, reaction knot at 30 DEG C
Deionized water is added after beam to be quenched, extracts reaction solution with dichloromethane, extraction three times, merges organic phase, the anhydrous sulphur of organic phase
Sour sodium drying, removes solvent, (eluant, eluent is petroleum ether to column chromatography for separation：Ethyl acetate=20:1, v/v) target product benzene is obtained
Acetenyl -2- amylalcohols are weak yellow liquid, yield 74.7%.
1H NMR(400MHz,CDCl3)δ7.41(m,2H),7.29(m,3H),2.22(br,1H),1.73(m,2H),1.57
~1.62 (m, 5H), 0.99 (t, 3H) ppm；13C NMR(101MHz,CDCl3)δ131.67,128.25,128.22,122.84,
93.02,83.29,68.63,46.06,29.87,18.15,14.28ppm。
Embodiment 14：NdNa8[OC(CH3)3]10(OH) catalysis phenylacetylene is reacted with propione
Catalyst n dNa is added into the processed reaction bulb of dehydration and deoxidation under protection of argon gas8[OC(CH3)3]10(OH)
0.04mmol, phenylacetylene 1mmol, propione mmol and 0.5mL DMSO, are stirred to react 24 hours at 30 DEG C, and reaction terminates
Deionized water is added afterwards to be quenched, extracts reaction solution with dichloromethane, extraction three times, merges organic phase, organic phase anhydrous slufuric acid
Sodium is dried, and removes solvent, (eluant, eluent is petroleum ether to column chromatography for separation：Ethyl acetate=20:1, v/v) target product benzene second is obtained
Alkynyl -3- amylalcohols are weak yellow liquid, yield 80.7%.
1H NMR(400MHz,CDCl3) δ 7.42 (m, 2H), 7.29 (m, 3H), 2.15 (br, 1H), 1.69~1.83 (m,
4H),1.10(t,6H)ppm；13C NMR(101MHz,CDCl3)δ131.72,128.26,128.20,122.93,91.74,
84.50,72.61,34.50,8.71ppm。
Embodiment 15：NdNa8[OC(CH3)3]10(OH) catalysis phenylacetylene is reacted with 3- espeletons
Under protection of argon gas to through catalyst n dNa is added in the processed reaction bulb of dehydration and deoxidation8[OC(CH3)3]10(OH)
0.04mmol, phenylacetylene 1mmol, 3- espeleton 1mmol and 0.5mL DMSO, are stirred to react 24 hours, instead at 30 DEG C
Deionized water is added after answering to be quenched, extracts reaction solution with dichloromethane, extraction three times, merges organic phase, organic phase nothing
Aqueous sodium persulfate is dried, and removes solvent, (eluant, eluent is petroleum ether to column chromatography for separation：Ethyl acetate=20:1, v/v) target production is obtained
Object phenylacetylene base 3- methyl butanols are weak yellow liquid, yield 80.4%.
1H NMR(400MHz,CDCl3)δ7.43(m,2H),7.30(m,3H),1.90(m,1H),1.54(s,3H),1.09
(dd,6H)ppm；13C NMR(101MHz,CDCl3)δ131.67,128.24,128.19,122.89,92.04,83.97,
72.10,39.15,27.20,17.97,17.54ppm。
Embodiment 16：NdNa8[OC(CH3)3]10(OH) catalysis phenylacetylene is reacted with 3- chlorobenzophenones
Catalyst n dNa is added into the processed reaction bulb of dehydration and deoxidation under protection of argon gas8[OC(CH3)3]10(OH)
0.04mmol, phenylacetylene 1mmol, 3- chlorobenzophenone 1mmol and 0.5mL DMSO, are stirred to react 24 hours at 30 DEG C,
Deionized water is added after reaction to be quenched, extracts reaction solution with dichloromethane, extraction three times, merges organic phase, and organic phase is used
Anhydrous sodium sulfate is dried, and removes solvent, (eluant, eluent is petroleum ether to column chromatography for separation：Ethyl acetate=16:1, v/v) target is obtained
Product phenylacetylene base -3- chlorodiphenyl methanol is faint yellow solid, yield 55.4%.
1H NMR(400MHz,CDCl3) δ 7.69 (m, 2H), 7.66 (s, 1H), 7.53 (m, 3H), 7.27~7.38 (m, 8H)
ppm；13C NMR(101MHz,CDCl3)δ147.05,144.46,128.49,128.41,128.06,127.89,126.27,
126.02,124.35,122.11,90.97,87.69,74.41ppm。
Embodiment 17：NdNa8[OC(CH3)3]10(OH) Methoxy-phenylacetylene is reacted in catalysis with acetone
Catalyst n dNa is added into the processed reaction bulb of dehydration and deoxidation under protection of argon gas8[OC(CH3)3]10(OH)
0.04mmol, to Methoxy-phenylacetylene 1mmol, acetone 1mmol and 0.5mL DMSO, 24 hours are stirred to react at 30 DEG C,
Deionized water is added after reaction to be quenched, extracts reaction solution with dichloromethane, extraction three times, merges organic phase, and organic phase is used
Anhydrous sodium sulfate is dried, and removes solvent, (eluant, eluent is petroleum ether to column chromatography for separation：Ethyl acetate=16:1, v/v) target is obtained
Product is weak yellow liquid, yield 98.2% to Methoxy-phenylacetylene base propyl alcohol.
1H NMR(400MHz,CDCl3)δ7.35(d,2H),6.83(d,2H),3.80(s,3H),1.61(s,6H)ppm；13C NMR(101MHz,CDCl3)δ159.31,133.21,114.85,113.44,92.14,82.06,65.75,55.14,
31.31ppm。
Embodiment 18：NdNa8[OC(CH3)3]10(OH) catalysis is to Methoxy-phenylacetylene and hexamethylene reactive ketone
Catalyst n dNa is added into the processed reaction bulb of dehydration and deoxidation under protection of argon gas8[OC(CH3)3]10(OH)
0.04mmol, to Methoxy-phenylacetylene 1mmol, cyclohexanone 1mmol and 0.5mL DMSO, be stirred to react at 30 DEG C 24 small
When, deionized water is added after reaction and is quenched, extracts reaction solution with dichloromethane, extraction three times, merges organic phase, organic phase
It is dried with anhydrous sodium sulfate, removes solvent, (eluant, eluent is petroleum ether to column chromatography for separation：Ethyl acetate=10:1, v/v) mesh is obtained
Product is marked to Methoxy-phenylacetylene base to bromophenethyl alcohol, is faint yellow solid, yield 95.1%.
1H NMR(400MHz,CDCl3)δ7.36(d,2H),6.83(d,2H),3.81(s,3H),2.00(m,2H),1.58
~1.75 (m, 8H) ppm；13C NMR(101MHz,CDCl3)δ159.53,133.10,115.01,113.87,91.35,84.21,
69.16,55.29,40.14,25.25,23.44ppm。
Embodiment 19：NdNa8[OC(CH3)3]10(OH) Methoxy-phenylacetylene is reacted in catalysis with 2 pentanone
Catalyst n dNa is added into the processed reaction bulb of dehydration and deoxidation under protection of argon gas8[OC(CH3)3]10(OH)
0.04mmol, to Methoxy-phenylacetylene 1mmol, 2 pentanone 1mmol and 0.5mL DMSO, be stirred to react at 30 DEG C 24 small
When, deionized water is added after reaction and is quenched, extracts reaction solution with dichloromethane, extraction three times, merges organic phase, organic phase
It is dried with anhydrous sodium sulfate, removes solvent, (eluant, eluent is petroleum ether to column chromatography for separation：Ethyl acetate=20:1, v/v) mesh is obtained
Product is marked to Methoxy-phenylacetylene base -2- amylalcohols, is weak yellow liquid, yield 63.1%.
1H NMR(400MHz,CDCl3)δ7.35(d,2H),6.83(d,2H),3.80(s,3H),1.72(m,2H),1.56
~1.62 (m, 5H), 0.99 (t, 3H) ppm；13C NMR(101MHz,CDCl3)δ159.54,133.08,114.93,113.87,
91.54,83.15,68.66,55.27,46.12,29.95,18.15,14.27ppm。
Embodiment 20：NdNa8[OC(CH3)3]10(OH) Methoxy-phenylacetylene is reacted in catalysis with propione
Catalyst n dNa is added into the processed reaction bulb of dehydration and deoxidation under protection of argon gas8[OC(CH3)3]10(OH)
0.04mmol, to Methoxy-phenylacetylene 1mmol, propione 1mmol and 0.5mL DMSO, be stirred to react at 30 DEG C 24 small
When, deionized water is added after reaction and is quenched, extracts reaction solution with dichloromethane, extraction three times, merges organic phase, organic phase
It is dried with anhydrous sodium sulfate, removes solvent, (eluant, eluent is petroleum ether to column chromatography for separation：Ethyl acetate=20:1, v/v) mesh is obtained
Product is marked to Methoxy-phenylacetylene base -3- amylalcohols, is weak yellow liquid, yield 74.3%.
1H NMR(400MHz,CDCl3) δ 7.36 (d, 2H), 6.83 (d, 2H), 3.80 (s, 3H), 1.68~1.82 (m,
4H),1.10(t,6H)ppm；13C NMR(101MHz,CDCl3)δ159.50,133.13,114.99,113.86,90.21,
84.35,72.64,55.29,34.53,8.73ppm。
Claims (5)
1. a kind of purposes of tert-butoxy rare earth/miscellaneous bimetal complexes of sodium, it is characterised in that：Tert-butoxy rare earth/the sodium
Miscellaneous bimetal complexes are during the alkynylation reaction of ketone prepares alkynol as catalyst application；
The molecular formula of the tert-butoxy rare earth/miscellaneous bimetal complexes of sodium is：LnNa8[OC(CH3)3] 10(OH), wherein Ln is
Rare earth metal.
2. special using tert-butoxy rare earth/miscellaneous bimetal complexes of sodium as the method for the alkynylation reaction of catalyst ketone
Sign is to include the following steps：
Catalyst LnNa is added into the processed reaction bulb of dehydration and deoxidation under protection of argon gas8[OC(CH3)3] 10(OH), alkynes
And carbonyls, it is stirred to react at 30 DEG C 24 hours, column chromatography for separation, obtains target product alkynol chemical combination after reaction
Object；
The alkynes is for phenylacetylene or to Methoxy-phenylacetylene；
The carbonyls is acetone, cyclohexanone, benzophenone, 2 pentanone, propione, 3- espeletons or 3- chlorodiphenyl first
Ketone；
The molar ratio of catalyst, alkynes and carbonyls is 0.04：1：1；
The molecular formula of the tert-butoxy rare earth/miscellaneous bimetal complexes of sodium is：LnNa8[OC(CH3)3] 10(OH), wherein Ln is
Rare earth metal.
3. according to the method described in claim 2, it is characterized in that：
The alkynylation reaction of the catalysis ketone carries out in the system for having solvent, first removes solvent, then column chromatography after reaction
Separation obtains target product；The solvent is selected from dimethyl sulfoxide, toluene or tetrahydrofuran.
4. according to the method described in claim 3, it is characterized in that：
The solvent is dimethyl sulfoxide, and deionized water is added into reaction solution after reaction is quenched, and is then extracted with dichloromethane
It extracts reaction solution, column chromatography for separation obtains target product after removing solvent.
5. according to the method described in claim 2, it is characterized in that：
Eluent when column chromatography for separation is petrol ether/ethyl acetate=10 ~ 20:1, v/v.
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