CN105665023B - The application of double β-di-imidogen divalent ytterbium complex - Google Patents
The application of double β-di-imidogen divalent ytterbium complex Download PDFInfo
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- CN105665023B CN105665023B CN201610106509.3A CN201610106509A CN105665023B CN 105665023 B CN105665023 B CN 105665023B CN 201610106509 A CN201610106509 A CN 201610106509A CN 105665023 B CN105665023 B CN 105665023B
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- 229910052769 Ytterbium Inorganic materials 0.000 title claims abstract description 21
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 title claims abstract description 21
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 49
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- 239000010452 phosphate Substances 0.000 claims abstract description 49
- 239000003054 catalyst Substances 0.000 claims abstract description 35
- 150000002576 ketones Chemical class 0.000 claims abstract description 21
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 10
- -1 2- acetonaphthones Chemical group 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 150000008365 aromatic ketones Chemical group 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- WYJOVVXUZNRJQY-UHFFFAOYSA-N 2-Acetylthiophene Chemical class CC(=O)C1=CC=CS1 WYJOVVXUZNRJQY-UHFFFAOYSA-N 0.000 claims description 6
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 claims description 6
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical group C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 4
- 239000012965 benzophenone Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical group 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- MOMFXATYAINJML-UHFFFAOYSA-N 2-Acetylthiazole Chemical group CC(=O)C1=NC=CS1 MOMFXATYAINJML-UHFFFAOYSA-N 0.000 claims 1
- 150000002240 furans Chemical class 0.000 claims 1
- 150000002431 hydrogen Chemical group 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 20
- 230000000694 effects Effects 0.000 abstract description 5
- 230000035484 reaction time Effects 0.000 abstract description 2
- 238000012805 post-processing Methods 0.000 abstract 1
- 239000000376 reactant Substances 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 127
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 88
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 42
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 37
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 36
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 32
- 230000015572 biosynthetic process Effects 0.000 description 24
- 238000003786 synthesis reaction Methods 0.000 description 24
- 229910052757 nitrogen Inorganic materials 0.000 description 21
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 20
- 239000000047 product Substances 0.000 description 19
- 239000007787 solid Substances 0.000 description 18
- 238000005160 1H NMR spectroscopy Methods 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 12
- 150000002148 esters Chemical class 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 229910052761 rare earth metal Inorganic materials 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000000741 silica gel Substances 0.000 description 6
- 229910002027 silica gel Inorganic materials 0.000 description 6
- 229960001866 silicon dioxide Drugs 0.000 description 6
- 239000003480 eluent Substances 0.000 description 5
- 150000002910 rare earth metals Chemical class 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 230000005311 nuclear magnetism Effects 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- IEMMBWWQXVXBEU-UHFFFAOYSA-N 2-acetylfuran Chemical class CC(=O)C1=CC=CO1 IEMMBWWQXVXBEU-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001225 Ytterbium Chemical class 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- ZDOYHCIRUPHUHN-UHFFFAOYSA-N 1-(2-chlorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC=C1Cl ZDOYHCIRUPHUHN-UHFFFAOYSA-N 0.000 description 2
- WYECURVXVYPVAT-UHFFFAOYSA-N 1-(4-bromophenyl)ethanone Chemical compound CC(=O)C1=CC=C(Br)C=C1 WYECURVXVYPVAT-UHFFFAOYSA-N 0.000 description 2
- YOMBUJAFGMOIGS-UHFFFAOYSA-N 2-fluoro-1-phenylethanone Chemical compound FCC(=O)C1=CC=CC=C1 YOMBUJAFGMOIGS-UHFFFAOYSA-N 0.000 description 2
- GNKZMNRKLCTJAY-UHFFFAOYSA-N 4'-Methylacetophenone Chemical compound CC(=O)C1=CC=C(C)C=C1 GNKZMNRKLCTJAY-UHFFFAOYSA-N 0.000 description 2
- YQYGPGKTNQNXMH-UHFFFAOYSA-N 4-nitroacetophenone Chemical compound CC(=O)C1=CC=C([N+]([O-])=O)C=C1 YQYGPGKTNQNXMH-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 241001614291 Anoplistes Species 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- RSTZCEHWJCIAAT-UHFFFAOYSA-N C(C)C(=O)CC.FC=1C=CC=CC1 Chemical compound C(C)C(=O)CC.FC=1C=CC=CC1 RSTZCEHWJCIAAT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000002155 anti-virotic effect Effects 0.000 description 1
- 239000002246 antineoplastic agent Substances 0.000 description 1
- 229940041181 antineoplastic drug Drugs 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000008827 biological function Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- UCQFCFPECQILOL-UHFFFAOYSA-N diethyl hydrogen phosphate Chemical compound CCOP(O)(=O)OCC UCQFCFPECQILOL-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 238000006197 hydroboration reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 150000003747 ytterbium compounds Chemical class 0.000 description 1
Classifications
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- 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4056—Esters of arylalkanephosphonic acids
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J31/22—Organic complexes
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- B01J31/2208—Oxygen, e.g. acetylacetonates
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
- C07F9/65515—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a five-membered ring
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
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- C07F9/655345—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having sulfur atoms, with or without selenium or tellurium atoms, as the only ring hetero atoms the sulfur atom being part of a five-membered ring
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
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Abstract
The present invention provides a kind of applications of double β-di-imidogen divalent ytterbium complex, specially in nitrogen atmosphere, using ketone and diethyl phosphite as reactant, double β-di-imidogen divalent ytterbium complex is catalyst, under condition of no solvent, corresponding α-hydroxyl phosphate is prepared.The advantages of double β disclosed by the invention-di-imidogen divalent ytterbium complex can be catalyzed to high activity reacting for ketone and diethyl phosphite under mild conditions, have that the reaction time is short, and reaction condition is mild, and post-processing approach is convenient, simple.
Description
Technical field
The present invention relates to a kind of metal-organic application fields, and in particular to double β-di-imidogen divalent ytterbium cooperation
The application of object.
Background technology
Alpha-hydroxy phosphate is important in some anti-virus formulations, anticancer drug and enzyme as a kind of phosphorus-containing compound
Component part has a variety of biological functions.Meanwhile the molecular science field of the compound ahead of the curve also has a wide range of applications,
Such as high molecular material, nanometer technology, biological detection, medicament research and development and asymmetry catalysis aspect；The compound also is able into one
Step synthesis with more complicated structural unit derivative (referring to：Karasik, A. A.; Sinyashin, O. G.
Phosphorus Compounds: Advanced Tools in Catalysis and Material Science. Vol.
37, Eds.: Peruzzini, M.; Gonsalvi, L, Kazan, 2011, pp. 375-444.;Sikorski, J.
A.; Miller, M. J.; Braccolino, D. S. Phosphorus, Sulfur and Silicon. 1993,76, 115)。
The addition reaction of diethyl phosphite and carbonyls（That is Pudovik reacts）, it is a kind of synthesis α-hydroxyl phosphorus
Acid esters is most direct, the method for most atom economy；What document was reported at present is used for catalysis of carbonyl chemical combination object and diethyl phosphite
Hydrogen phosphating reaction catalyst system and catalyzing species it is more, mainly have inorganic, organic molecule, acid, alkali, metallo-organic compound.Two
Valency rare earth metal complex has larger ionic radius and reproducibility, reduction reaction can occur with many organic molecules,
Generation trivalent rare earth metals compound (referring to：Boncella, J. M.; Tilley, T. D.; Anderson, R. A.J. Chem. Soc., Chem. Commun1984,710), however, the research of its catalytic performance is relatively fewer.β-two is sub-
Amido is widely used in metallo-organic compound as a kind of easy-regulating steric hindrance and the non-cyclopentadienyl assistant ligand of charge effect
Synthesis.But in the prior art, it is fresh as the application of double β-di-imidogen bivalent rare earth coordination of ligand using β-di-imidogen
It has been reported that.It has been reported that rare earth compound catalysis hydrogen phosphating reaction system be mainly trifluoro sulfoacid rare earth compound,
The trivalent rare earths such as ytterbium compound and amide groups divalent rare earth complexes and β-di-imidogen bivalent rare earth hydroboration
System of the object as catalyst is closed, currently without about double β-di-imidogen divalent ytterbium complex catalysis of carbonyl chemical combination object and phosphorous
The report of diethyl phthalate reaction.
Invention content
The goal of the invention of the present invention is to provide the application of double β-di-imidogen divalent ytterbium complexes, can be catalyzed ketone and Asia
Diethyl phosphate prepares α-hydroxyl phosphate, while has higher catalytic activity, reduces catalyst amount, and have good bottom
The object scope of application.
In order to achieve the above objectives, the technical solution adopted by the present invention is：
Double β-di-imidogen divalent ytterbium complex is as catalyst in catalysis ketone and diethyl phosphite synthetic reaction
Using；The chemical structural formula of double β-di-imidogen divalent ytterbium complex is as follows：
Wherein Ar is 2-MeC6H4.The molecular formula of double β-di-imidogen divalent ytterbium complex is represented by： [(2-Me-
C6H4-NC(Me)CHC(Me)N-C6H4-2-Me)]2Yb (THF), abbreviation Yb (L2-Me)2(THF)。
The invention also discloses a kind of methods for preparing α-hydroxyl phosphate, include the following steps, will be double under nitrogen atmosphere
β-di-imidogen divalent ytterbium complex is added in reactor, adds diethyl phosphite, is mixed；Then ketone is added；Reaction
Obtain α-hydroxyl phosphate；The chemical structural formula of double β-di-imidogen divalent ytterbium complex is as follows：
Wherein Ar is 2-MeC6H4。
In above-mentioned technical proposal, the ketone is aromatic ketone or aliphatic ketone.For example aromatic ketone is benzophenone, 2- naphthalene second
Ketone, 2- acetyl furans, 2- acetyl thiophenes；Or the chemical structural formula of the aromatic ketone is, wherein R choosings
From hydrogen, halogen, nitro, methyl or methoxy；Aliphatic ketone is acetone.
In above-mentioned technical proposal, the dosage of double β-di-imidogen divalent ytterbium complex for the mole of ketone 0.2~
1%；The dosage of the diethyl phosphite is 1.2 times of the mole of ketone.
In above-mentioned technical proposal, the temperature of the synthetic reaction is room temperature, and the time is 10~25 minutes；First by double β-two Asias
Amido divalent ytterbium complex mixes 8~12 minutes with diethyl phosphite.The present invention limits charging sequence, this has reaction yield
It is obviously improved；Such as embodiment ten, after diethyl phosphite mixes reaction with catalyst first, add to fluorobenzene
Ethyl ketone carries out addition reaction, can obtain 99% yield.
In preferred technical solution, the dosage of double β-di-imidogen divalent ytterbium complex is the mole of ketone
0.5%；First double β-di-imidogen divalent ytterbium complex is mixed 10 minutes with diethyl phosphite；The temperature of the synthetic reaction
For room temperature, the time is 20 minutes.
In above-mentioned technical proposal, purification processes are carried out after reaction, specially when reaction product is solid, add in second
Acetoacetic ester dissolves, and is then spin-dried for, then washed with n-hexane, obtains α-hydroxyl phosphate；When reaction product is liquid, second is added in
Acetoacetic ester dissolves, and is then spin-dried for, then analyzes through silicagel column to obtain α-hydroxyl phosphate.
The invention also discloses above-mentioned double β-di-imidogen divalent ytterbium complex α-di is being prepared as catalyst
Application in ester.The specific steps are：
（1）In glove box, the double β-di-imidogen divalent ytterbium complexes of catalyst are added under nitrogen protection；Then it uses
Liquid-transfering gun adds in diethyl phosphite, and 8~12min is stirred at room temperature, adds ketone（With liquid-transfering gun add in liquid ketone, with point
Analysis balance adds in solid-state ketone after weighing）, react 5~25 min；
（2）Treat after reaction, quickly to produce glove box, be exposed in air and into reaction system add in right amount go from
Sub- water terminates reaction, for solid product, adds in suitable ethyl acetate dissolved solid, is spin-dried for, then with n-hexane (4 × 5 mL)
Washing, obtains corresponding α-hydroxyl phosphate；Suitable ethyl acetate dissolving is added in for product liquid, is spin-dried for, through silica gel column layer
Analysis（Eluant, eluent：Ethyl acetate：Petroleum ether=1:10）Corresponding α-hydroxyl phosphate is obtained, is weighed, calculates yield.Nuclear-magnetism yield：
After reaction to setting time, glove box is removed rapidly, 1-2 drop reaction solutions is taken to add deuterochloroform in nuclear magnetic tube, measures core
Magnetic (1H NMR), calculate yield.
By taking one type ketone as an example, above-mentioned technical proposal can represent as follows：
The present invention develops a kind of rare earth for the addition reaction synthesis Alpha-hydroxy phosphate for being catalyzed ketone and diethyl phosphite
Compound catalyst, for double β-di-imidogen divalent ytterbium complexes；It, can be in a mild condition due to the use of the catalyst
（Room temperature）Catalysis ketone and diethyl phosphite the synthesis Alpha-hydroxy phosphate of high activity；Compared with existing several catalyst,
In the case of reaching identical yield, catalyst amount only needs 0.2~1 mol%, and the reaction time is 10~25 minutes；And this hair
Bright disclosed catalyst is wider to the scope of application of substrate, suitable for aliphatic ketone and different substituents position, different electronic effects
Aromatic ketone；Industry for Alpha-hydroxy phosphate is combined to provide more more options.
Specific embodiment
With reference to embodiment, the invention will be further described：
One Yb (L of embodiment2-Me)2(THF) acetophenone and diethyl phosphite synthesis α-hydroxyl phosphate are catalyzed
In glove box, catalyst Yb (L are added under nitrogen protection in the reaction bulb of 20mL2-Me)2(THF) (0.01
Mmol, 0.0087 g), then adds in diethyl phosphite (0.771 mL, 6.0 mmol) with liquid-transfering gun, then at room temperature
10 min are stirred, then acetophenone (0.582 mL, 5.0 mmol) is added in liquid-transfering gun, after reacting 20 min at room temperature, with drop
Pipe draws a drop in nuclear magnetic tube, adds in CDCl3Wiring solution-forming.It is computed1H spectrum yields are 64%.Glove box is produced, with acetic acid second
Ester terminates reaction, and is dissolved with suitable ethyl acetate, and revolving removes solvent, and remaining solid is washed with n-hexane (4 × 5 mL),
Obtain corresponding α-hydroxyl phosphate, C6H4C(CH3)(OH)PO(OCH2CH3)2, 0.8245 g, yield 64%.The nuclear-magnetism number of product
According to：1H NMR (CDCl3, 400 MHz) δ:1.17~1.21 (t,J=7 Hz, 3H), 1.24~1.27 (m, 4H),
1.80~1.84 (d,J=15 Hz, 3H), 3.45 (s, 1H), 3.84~4.13 (m, 4H), 7.27~7.30
(m, 1H), 7.33~7.37 (t,J=8 Hz, 2H), 7.59~7.62 (m, 2H).
Two Yb (L of embodiment2-Me)2(THF) acetophenone and diethyl phosphite synthesis α-hydroxyl phosphate are catalyzed
In glove box, catalyst Yb (L are added under nitrogen protection in the reaction bulb of 20mL2-Me)2(THF) (0.01
Mmol, 0.0087 g), then adds in diethyl phosphite (0.308 mL, 2.4 mmol) with liquid-transfering gun, then at room temperature
10 min are stirred, then acetophenone (0.233 mL, 2.0 mmol) is added in liquid-transfering gun, after reacting 20 min at room temperature, with drop
Pipe draws a drop in nuclear magnetic tube, adds in CDCl3Wiring solution-forming.It is computed1H spectrum yields are 86%.Glove box is produced, with acetic acid second
Ester terminates reaction, and is dissolved with suitable ethyl acetate, and revolving removes solvent, and remaining solid is washed with n-hexane (4 × 5 mL),
Obtain corresponding α-hydroxyl phosphate, C6H4C(CH3)(OH)PO(OCH2CH3)2, 0.4432 g, yield 86%.The nuclear magnetic data of product
With embodiment one.
Three Yb (L of embodiment2-Me)2(THF) acetophenone and diethyl phosphite synthesis α-hydroxyl phosphate are catalyzed
In glove box, catalyst Yb (L are added under nitrogen protection in the reaction bulb of 20mL2-Me)2(THF) (0.01
Mmol, 0.0087 g), then adds in diethyl phosphite (0.154 mL, 1.2 mmol) with liquid-transfering gun, then at room temperature
10 min are stirred, then acetophenone (0.116 mL, 1.0 mmol) is added in liquid-transfering gun, after reacting 20 min at room temperature, are used
Dropper draws a drop in nuclear magnetic tube, adds in CDCl3Wiring solution-forming.It is computed1H spectrum yields are 87%.Glove box is produced, uses acetic acid
Ethyl ester terminates reaction, and is dissolved with suitable ethyl acetate, and revolving removes solvent, and remaining solid is washed with n-hexane (4 × 5 mL)
It washs, obtains corresponding α-hydroxyl phosphate, C6H4C(CH3)(OH)PO(OCH2CH3)2, 0.2242 g, yield 87%.The nuclear-magnetism of product
Data consistent with Example one.
Example IV Yb (L2-Me)2(THF) acetophenone and diethyl phosphite synthesis α-hydroxyl phosphate are catalyzed
In glove box, catalyst Yb (L are added under nitrogen protection in the reaction bulb of 20mL2-Me)2(THF) (0.01
Mmol, 0.0087 g), then adds in diethyl phosphite (0.308 mL, 2.4 mmol) with liquid-transfering gun, then at room temperature
10 min are stirred, then acetophenone (0.233 mL, 2.0 mmol) is added in liquid-transfering gun, after reacting 25min at room temperature, with drop
Pipe draws a drop in nuclear magnetic tube, adds in CDCl3Wiring solution-forming.It is computed1H spectrum yields are 84%.Glove box is produced, with acetic acid second
Ester terminates reaction, and is dissolved with suitable ethyl acetate, and revolving removes solvent, and remaining solid is washed with n-hexane (4 × 5 mL),
Obtain corresponding α-hydroxyl phosphate, C6H4C(CH3)(OH)PO(OCH2CH3)2, 0.4329 g, yield 84%.The nuclear magnetic data of product
With embodiment one.
Five Yb (L of embodiment2-Me)2(THF) acetophenone and diethyl phosphite synthesis α-hydroxyl phosphate are catalyzed
In glove box, catalyst Yb (L are added under nitrogen protection in the reaction bulb of 20mL2-Me)2(THF) (0.01
Mmol, 0.0087 g), then adds in diethyl phosphite (0.308 mL, 2.4 mmol) with liquid-transfering gun, then at room temperature
10 min are stirred, then acetophenone (0.233 mL, 2.0 mmol) is added in liquid-transfering gun, after reacting 10 min at room temperature, are used
Dropper draws a drop in nuclear magnetic tube, adds in CDCl3Wiring solution-forming.It is computed1H spectrum yields are 81%.Glove box is produced, uses acetic acid
Ethyl ester terminates reaction, and is dissolved with suitable ethyl acetate, and revolving removes solvent, and remaining solid is washed with n-hexane (4 × 5 mL)
It washs, obtains corresponding α-hydroxyl phosphate, C6H4C(CH3)(OH)PO(OCH2CH3)2, 0.4174 g, yield 81%.The nuclear-magnetism of product
Data consistent with Example one.
Six Yb (L of embodiment2-Me)2(THF) acetophenone and diethyl phosphite synthesis α-hydroxyl phosphate are catalyzed
In glove box, catalyst Yb (L are added under nitrogen protection in the reaction bulb of 20mL2-Me)2(THF) (0.01
Mmol, 0.0087 g), then adds in diethyl phosphite (0.308 mL, 2.4 mmol) with liquid-transfering gun, then at room temperature
Stir 10 min, then tetrahydrofuran (0.399 mL) added in liquid-transfering gun, then with liquid-transfering gun add in acetophenone (0.233 mL,
2.0 mmol), after reacting 20 min at room temperature, a drop is drawn in nuclear magnetic tube with dropper, adds in CDCl3Wiring solution-forming.Through
It calculates1H spectrum yields are 60%.Glove box is produced, is terminated and reacted with ethyl acetate, and is dissolved with suitable ethyl acetate, revolving is removed
Solvent is removed, remaining solid is washed with n-hexane (4 × 5 mL), obtains corresponding α-hydroxyl phosphate, C6H4C(CH3)(OH)PO
(OCH2CH3)2, 0.4174 g, yield 60%.The nuclear magnetic data of product is the same as embodiment one.
Seven Yb (L of embodiment2-Me)2(THF) acetophenone and diethyl phosphite synthesis α-hydroxyl phosphate are catalyzed
In glove box, catalyst Yb (L are added under nitrogen protection in the reaction bulb of 20mL2-Me)2(THF) (0.01
Mmol, 0.0087 g), then adds in diethyl phosphite (0.308 mL, 2.4 mmol) with liquid-transfering gun, then at room temperature
8min is stirred, then acetophenone (0.233 mL, 2.0 mmol) is added in liquid-transfering gun, after reacting 20 min at room temperature, uses dropper
A drop is drawn in nuclear magnetic tube, adds in CDCl3Wiring solution-forming.It is computed1H spectrum yields are 77%.Glove box is produced, uses ethyl acetate
Reaction is terminated, and is dissolved with suitable ethyl acetate, revolving removes solvent, and remaining solid is washed with n-hexane (4 × 5 mL), obtained
To corresponding α-hydroxyl phosphate, C6H4C(CH3)(OH)PO(OCH2CH3)2, 0.3968 g, yield 77%.The nuclear magnetic data of product is same
Embodiment one.
Eight Yb (L of embodiment2-Me)2(THF) acetophenone and diethyl phosphite synthesis α-hydroxyl phosphate are catalyzed
In glove box, catalyst Yb (L are added under nitrogen protection in the reaction bulb of 20mL2-Me)2(THF) (0.01
Mmol, 0.0087 g), then adds in diethyl phosphite (0.308 mL, 2.4 mmol) with liquid-transfering gun, then at room temperature
Stir 10 min, then n-hexane (0.399 mL) added in liquid-transfering gun, then with liquid-transfering gun add in acetophenone (0.233 mL, 2.0
Mmol), after reacting 20 min at room temperature, a drop is drawn in nuclear magnetic tube with dropper, adds in CDCl3Wiring solution-forming.It is computed1H spectrum yields are 84%.Glove box is produced, is terminated and reacted with ethyl acetate, and is dissolved with suitable ethyl acetate, revolving removes molten
Agent, remaining solid are washed with n-hexane (4 × 5 mL), obtain corresponding α-hydroxyl phosphate, C6H4C(CH3)(OH)PO
(OCH2CH3)2, 0.4328 g, yield 84%.The nuclear magnetic data of product is the same as embodiment one.
Nine Yb (L of embodiment2-Me)2(THF) o-chloroacetophenone and diethyl phosphite synthesis α-hydroxyl phosphate are catalyzed
In glove box, catalyst Yb (L are added under nitrogen protection in the reaction bulb of 20mL2-Me)2(THF) (0.01
Mmol, 0.0087 g), then adds in diethyl phosphite (0.308 mL, 2.4 mmol) with liquid-transfering gun, then at room temperature
10 min are stirred, then o-chloroacetophenone (0.259 mL, 2.0 mmol) is added in liquid-transfering gun, after reacting 20 min at room temperature,
Glove box is produced, is terminated and reacted with ethyl acetate, and is dissolved with suitable ethyl acetate, revolving removes solvent, and remaining solid is used
N-hexane (4 × 5 mL) washs, and obtains corresponding α-hydroxyl phosphate, 2-Cl-C6H4C(CH3)(OH)PO(OCH2CH3)2, 0.5373
G, yield 92%.The nuclear magnetic data of product： 1H NMR (CDCl3, 400 MHz) δ:1.20~1.24 (t,J=7 Hz,
3H), 1.27~1.31 (t,J=7 Hz, 3H), 1.97~2.00 (d,J=15 Hz, 3H), 3.14 (s, 1H),
3.95~4.17 (m, 4H), 7.20~7.29 (m, 2H), 7.35~7.37 (d,J=8 Hz, 1H), 7.72~
7.74 (d, J=8 Hz, 1H).
Ten Yb (L of embodiment2-Me)2(THF) catalysis synthesizes α-hydroxyl phosphate to fluoro acetophenone and diethyl phosphite
In glove box, catalyst Yb (L are added under nitrogen protection in the reaction bulb of 20mL2-Me)2(THF) (0.01
Mmol, 0.0087 g), then adds in diethyl phosphite (0.308 mL, 2.4 mmol) with liquid-transfering gun, then at room temperature
It stirs 10 min, then is added in liquid-transfering gun to fluoro acetophenone (0.241 mL, 2.0 mmol), after reacting 20 min at room temperature,
Glove box is produced, is terminated and reacted with ethyl acetate, and is dissolved with suitable ethyl acetate, revolving removes solvent, and remaining solid is used
N-hexane (4 × 5 mL) washs, and obtains corresponding α-hydroxyl phosphate, 4-F-C6H4C(CH3)(OH)PO(OCH2CH3)2, 0.5457
G, yield 99%.The nuclear magnetic data of product：1H NMR (CDCl3, 400 MHz) δ:1.19~1.23 (t,J=7 Hz,
3H), 1.24~1.28 (t,J=7 Hz, 3H), 1.78~1.82 (d,J=15 Hz, 3H), 3.66 (s, 1H),
3.88~4.14 (m, 4H), 7.01~7.05 (t,J=9 Hz, 2H), 7.55~7.60 (m, 2H).
11 Yb (L of embodiment2-Me)2(THF) benzophenone and diethyl phosphite synthesis α-hydroxyl phosphate are catalyzed
In glove box, catalyst Yb (L are added under nitrogen protection in the reaction bulb of 20mL2-Me)2(THF) (0.01
Mmol, 0.0087 g), then adds in diethyl phosphite (0.308 mL, 2.4 mmol) with liquid-transfering gun, then at room temperature
10 min are stirred, benzophenone (0.3636 g, 2.0 mmol) is weighed, after reacting 10 min at room temperature, produces glove box,
It is terminated and reacted with ethyl acetate, and dissolved with suitable ethyl acetate, revolving removes solvent, remaining solid n-hexane (4 × 5
ML it) washs, obtains corresponding α-hydroxyl phosphate, (C6H4)2C (OH)PO(OCH2CH3)2, 0.5944 g, yield 93%.Product
Nuclear magnetic data：1H NMR (CDCl3, 400 MHz) δ:1.13~1.16 (t,J=7 Hz, 6H), 3.84~3.98
(m, 4H), 7.23~7.33 (m, 6H), 7.66~7.68 (d,J=7 Hz, 4H).
12 Yb (L of embodiment2-Me)2(THF) 2- acetonaphthones and diethyl phosphite synthesis α-hydroxyl phosphate are catalyzed
In glove box, catalyst Yb (L are added under nitrogen protection in the reaction bulb of 20mL2-Me)2(THF) (0.01
Mmol, 0.0087 g), then adds in diethyl phosphite (0.308 mL, 2.4 mmol) with liquid-transfering gun, then at room temperature
10 min are stirred, 2- acetonaphthones (0.3396 g, 2.0 mmol) is weighed, glove box is produced after reacting 15 min at room temperature, are used
Ethyl acetate terminates reaction, and is dissolved with suitable ethyl acetate, and revolving removes solvent, remaining solid n-hexane (4 × 5
ML it) washs, obtains corresponding α-hydroxyl phosphate C10H7C(CH3)(OH)PO(OCH2CH3)2, 0.6152 g, yield 95%.Product
Nuclear magnetic data： 1H NMR (CDCl3, 400 MHz) δ: 1.19 (t, J=7 Hz, 6H), 1.26 (t,J=7 Hz,
6H), 1.92 (d, J=15 Hz, 3H), 3.61 (d,J=6 Hz, 1H) 3.85~4.16 (m, 4H), 7.45~
7.49 (m, 2H), 7.73 (dt, J 1 =9 Hz,J 2 =1 Hz, 1H), 7.82~7.87 (m, 3H), 8.09 (s,
1H)。
13 Yb (L of embodiment2-Me)2(THF) p-nitroacetophenone and diethyl phosphite synthesis α-di are catalyzed
Ester
In glove box, catalyst Yb (L are added under nitrogen protection in the reaction bulb of 20mL2-Me)2(THF) (0.01
Mmol, 0.0087 g), then adds in diethyl phosphite (0.308 mL, 2.4 mmol) with liquid-transfering gun, then at room temperature
10 min are stirred, p-nitroacetophenone (0.3295 g, 2.0 mmol) is weighed, after reacting 20 min at room temperature, produces gloves
Case is terminated with ethyl acetate and reacted, and is dissolved with suitable ethyl acetate, and revolving removes solvent, remaining solid n-hexane (4
× 5 mL) washing, obtain corresponding α-hydroxyl phosphate, 4-NO2-C6H4C(CH3)(OH)PO(OCH2CH3)2, 0.5567 g, yield
92%.The nuclear magnetic data of product： 1H NMR (CDCl3, 400 MHz) δ:1.24~1.28 (t,J=7 Hz, 6H),
1.83~1.87 (d,J=15 Hz, 3H), 4.01~4.18 (m, 4H), 4.29 (s, 1H), 7.78~7.81
(d, J=9 Hz, 2H), 8.19~8.21 (d,J=9 Hz, 2H).
14 Yb (L of embodiment2-Me)2(THF) melilotal and diethyl phosphite synthesis α-di are catalyzed
Ester
In glove box, catalyst Yb (L are added under nitrogen protection in the reaction bulb of 20mL2-Me)2(THF) (0.01
Mmol, 0.0087 g), then adds in diethyl phosphite (0.308 mL, 2.4 mmol) with liquid-transfering gun, then at room temperature
10 min are stirred, melilotal (0.2677 g, 2.0 mmol) is weighed, after reacting 20 min at room temperature, produces gloves
Case is terminated with ethyl acetate and reacted, and is dissolved with suitable ethyl acetate, and revolving removes solvent, remaining solid n-hexane (4
× 5 mL) washing, obtain corresponding α-hydroxyl phosphate, 4-Me-C6H4C(CH3)(OH)PO(OCH2CH3)2, 0.4183 g, yield
77%.The nuclear magnetic data of product： 1H NMR (CDCl3, 400 MHz) δ:1.19~1.22 (t,J=6 Hz, 3H),
1.25~1.28 (t,J=7 Hz, 3H), 1.78~1.82 (d,J=15 Hz, 3H), 2.34 (s, 3H), 2.72
(s, 1H), 3.89~4.08 (m, 4H), 7.17~7.15 (d,J=8 Hz, 2H).
15 Yb (L of embodiment2-Me)2(THF) parabromoacetophenone and diethyl phosphite synthesis α-hydroxyl phosphate are catalyzed
In glove box, catalyst Yb (L are added under nitrogen protection in the reaction bulb of 20mL2-Me)2(THF) (0.01
Mmol, 0.0087 g), then adds in diethyl phosphite (0.308 mL, 2.4 mmol) with liquid-transfering gun, then at room temperature
10 min are stirred, parabromoacetophenone (0.3972 g, 2.0 mmol) is weighed, after reacting 20 min at room temperature, produces gloves
Case is terminated with ethyl acetate and reacted, and is dissolved with suitable ethyl acetate, and revolving removes solvent, remaining solid n-hexane (4
× 5 mL) washing, obtain corresponding α-hydroxyl phosphate, 4-Br-C6H4C(CH3)(OH)PO(OCH2CH3)2, 0.6054 g, yield
90%.The nuclear magnetic data of product： 1H NMR (CDCl3, 400 MHz) δ:1.20~1.24 (t,J=7 Hz, 3H),
1.25 (t, J=7 Hz, 3H), 1.77~1.81 (d,J=15 Hz, 3H), 3.49 (s, 1H), 3.90~4.14
(m, 4H), 7.48 (s, 4H)。
16 Yb (L of embodiment2-Me)2(THF) parachloroacetophenone and diethyl phosphite synthesis α-hydroxyl phosphate are catalyzed
In glove box, catalyst Yb (L are added under nitrogen protection in the reaction bulb of 20mL2-Me)2(THF) (0.01
Mmol, 0.0087 g), then adds in diethyl phosphite (0.308 mL, 2.4 mmol) with liquid-transfering gun, then at room temperature
10 min are stirred, parachloroacetophenone (0.259 mL, 2.0 mmol) is weighed, after reacting 20 min at room temperature, produces gloves
Case is terminated with ethyl acetate and reacted, and is dissolved with suitable ethyl acetate, and revolving removes solvent, remaining solid n-hexane (4
× 5 mL) washing, obtain corresponding α-hydroxyl phosphate, 4-Cl-C6H4C(CH3)(OH)PO(OCH2CH3)2, 0.5782 g, yield
99%.The nuclear magnetic data of product：1H NMR (CDCl3, 400 MHz) δ: 1.22 (t, J=7 Hz, 3H), 1.27 (t,J=7 Hz, 3H), 1.80 (d,J=16 Hz, 3H), 3.41 (d,J=6 Hz, 1H), 3.88~4.17 (m,
4H), 7.33 (d, J=8 Hz, 2H), 7.54 (dd,J 1 =9 Hz,J 2 =2 Hz, 2H).
17 Yb (L of embodiment2-Me)2(THF) acetone and diethyl phosphite synthesis α-hydroxyl phosphate are catalyzed
In glove box, catalyst Yb (L are added under nitrogen protection in the reaction bulb of 20mL2-Me)2(THF) (0.01
Mmol, 0.0087 g), then adds in diethyl phosphite (0.308 mL, 2.4 mmol) with liquid-transfering gun, then at room temperature
10 min are stirred, acetone (0.147 mL, 2.0 mmol) is added in liquid-transfering gun, after reacting 20 min at room temperature, is inhaled with dropper
A drop is taken in nuclear magnetic tube, adds in CDCl3Wiring solution-forming.It is computed1H spectrum yields are 98%.Glove box is produced, with ethyl acetate end
It only reacts, and is dissolved with suitable ethyl acetate, revolving removes solvent, through silica gel post separation（Eluant, eluent：Ethyl acetate：Oil
Ether=1:10）Obtain corresponding α-hydroxyl phosphate, CH3C(CH3)(OH)PO(OCH2CH3)2, 0.3837 g, yield 98%.Product
Nuclear magnetic data：1H NMR (CDCl3, 400 MHz) δ:1.14~1.17 (t,J=7 Hz, 6H), 1.31~1.24
(m, 6H), 3.95~4.06 (m, 4H), 4.42 (s, 1H).
18 Yb (L of embodiment2-Me)2(THF) 2- acetyl furans and diethyl phosphite synthesis α-di are catalyzed
Ester
In glove box, catalyst Yb (L are added under nitrogen protection in the reaction bulb of 20mL2-Me)2(THF) (0.01
Mmol, 0.0087 g), then adds in diethyl phosphite (0.308 mL, 2.4 mmol) with liquid-transfering gun, then at room temperature
10 min are stirred, 2- acetyl furans (0.200 mL, 2.0 mmol) is weighed, after reacting 20 min at room temperature, is inhaled with dropper
A drop is taken in nuclear magnetic tube, adds in CDCl3Wiring solution-forming.It is computed1H spectrum yields are 69%.Glove box is produced, with ethyl acetate end
It only reacts, and is dissolved with suitable ethyl acetate, revolving removes solvent, through silica gel post separation（Eluant, eluent：Ethyl acetate：Oil
Ether=1:10）Obtain corresponding α-hydroxyl phosphate, C4H3OC(CH3)(OH)PO(OCH2CH3)2, 0.3417 g, yield 69%.Production
The nuclear magnetic data of object：1H NMR (CDCl3, 400 MHz) δ:1.19~1.22 (t,J=7 Hz, 3H), 1.25~
1.29 (t, J=7 Hz, 3H), 1.71~1.74 (d,J=15 Hz, 3H), 3.94~4.13 (m, 4H), 4.43
(s, 1H), 6.32 (s, 1H), 6.41 (s, 1H), 7.37 (s, 1H)。
19 Yb (L of embodiment2-Me)2(THF) 2- acetyl thiophenes and diethyl phosphite synthesis α-di are catalyzed
Ester
In glove box, catalyst Yb (L are added under nitrogen protection in the reaction bulb of 20mL2-Me)2(THF) (0.01
Mmol, 0.0087 g), then diethyl phosphite (0.308 mL, 2.4 mmol) is added in liquid-transfering gun, then in room temperature
10 min of lower stirring weigh 2- acetyl thiophenes (0.200 mL, 2.0 mmol), after reacting 20 min at room temperature, with drop
Pipe draws a drop in nuclear magnetic tube, adds in CDCl3Wiring solution-forming.It is computed1H spectrum yields are 53%.Glove box is produced, with acetic acid second
Ester terminates reaction, and is dissolved with suitable ethyl acetate, and revolving removes solvent, through silica gel post separation（Eluant, eluent：Ethyl acetate：
Petroleum ether=1:10）Obtain corresponding α-hydroxyl phosphate, C4H3SC(CH3)(OH)PO(OCH2CH3)2, 0.2795 g, yield
53%.The nuclear magnetic data of product：1H NMR (CDCl3, 400 MHz) δ:1.25~1.28 (t,J=6 Hz, 3H),
1.25~1.29 (t,J=7 Hz, 3H), 1.84~1.87 (d,J=15 Hz, 3H), 4.03~4.17 (m,
4H), 6.97~7.00 (t,J=4 Hz, 1H), 7.12~7.14 (t,J=3 Hz, 1H), 7.25~7.26 (d,J=6 Hz, 1H).
20 Yb (L of embodiment2-Me)2(THF) 2- acetyl thiophenes and diethyl phosphite synthesis α-di are catalyzed
Ester
In glove box, catalyst Yb (L are added under nitrogen protection in the reaction bulb of 20mL2-Me)2(THF) (0.01
Mmol, 0.0087 g), then diethyl phosphite (0.308 mL, 2.4 mmol) is added in liquid-transfering gun, then in room temperature
10 min of lower stirring, then with liquid-transfering gun add in toluene (0.399 mL), weigh 2- acetyl thiophenes (0.200 mL, 2.0
Mmol), after reacting 20 min at room temperature, a drop is drawn in nuclear magnetic tube with dropper, adds in CDCl3Wiring solution-forming.It is computed1H spectrum yields are 48%.Glove box is produced, is terminated and reacted with ethyl acetate, and is dissolved with suitable ethyl acetate, revolving removes molten
Agent, through silica gel post separation（Eluant, eluent：Ethyl acetate：Petroleum ether=1:10）Obtain corresponding α-hydroxyl phosphate, C4H3SC(CH3)
(OH)PO(OCH2CH3)2, 0.2531 g, yield 48%.
Above example can be seen that Yb (L2-Me)2(THF) catalyst shows that good substrate is applicable in ability, can be with
Very high yield obtains corresponding Alpha-hydroxy phosphate, it can be found that the electronic effect of benzene ring substituents to the reaction not
Apparent to influence, either fluorine-containing, chlorine, bromine, nitro these electron withdrawing groups are still containing methoxyl group, methyl these donor residues
Group can obtain more than 90% yield, and the steric effect of benzene ring substituents does not also influence the reaction significantly, right
In some substrates with conjugated structure, also there is good catalysis；And the present invention catalyst apply also for aliphatic ketone and
Heterocycle substrate；Preparation method especially disclosed by the invention can still obtain very high yield without solvent.
Claims (3)
1. couple β-di-imidogen divalent ytterbium complex answering in catalysis ketone and diethyl phosphite synthetic reaction as catalyst
With；The chemical structural formula of double β-di-imidogen divalent ytterbium complex is as follows：
Wherein Ar is 2-MeC6H4；
The dosage of double β-di-imidogen divalent ytterbium complex is the 0.2~1% of the mole of ketone；The diethyl phosphite
1.2 times of mole for ketone of dosage；
The temperature of the synthetic reaction is room temperature, and the time is 10~25 minutes；
The synthetic reaction includes the following steps, under nitrogen atmosphere, double β-di-imidogen divalent ytterbium complex is added in reactor
In, diethyl phosphite is added, is mixed；Then ketone is added；α-hydroxyl phosphate is obtained by the reaction.
2. application according to claim 1, it is characterised in that：The ketone is aromatic ketone or aliphatic ketone.
3. application according to claim 2, it is characterised in that：The aromatic ketone is benzophenone, 2- acetonaphthones, 2- acetyl
Base furans or 2- acetyl thiophenes；Or the chemical structural formula of the aromatic ketone is, wherein R is selected from hydrogen, halogen
Element, nitro, methyl or methoxy；The aliphatic ketone is acetone.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810069935.3A CN108250236B (en) | 2016-02-26 | 2016-02-26 | Preparation method of alpha-hydroxy phosphate based on bis-beta-diimine bivalent ytterbium complex |
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|---|---|---|---|---|
| CN101570546A (en) * | 2009-06-12 | 2009-11-04 | 厦门大学 | Method for synthesizing chiral alpha-hydroxyphosphonate |
| CN101817845A (en) * | 2010-01-22 | 2010-09-01 | 苏州大学 | Method for preparing alpha-hydroxy phosphonate through high-efficiency catalysis |
| CN102380419A (en) * | 2011-09-15 | 2012-03-21 | 安徽师范大学 | Catalyst for synthesizing hydroxyl phosphate, preparation and use method thereof |
| CN104140436A (en) * | 2014-07-23 | 2014-11-12 | 苏州大学 | Beta-diketiminate divalent rare earth boron hydrogen complex and preparation method and application thereof |
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|---|---|---|---|---|
| CN101570546A (en) * | 2009-06-12 | 2009-11-04 | 厦门大学 | Method for synthesizing chiral alpha-hydroxyphosphonate |
| CN101817845A (en) * | 2010-01-22 | 2010-09-01 | 苏州大学 | Method for preparing alpha-hydroxy phosphonate through high-efficiency catalysis |
| CN102380419A (en) * | 2011-09-15 | 2012-03-21 | 安徽师范大学 | Catalyst for synthesizing hydroxyl phosphate, preparation and use method thereof |
| CN104140436A (en) * | 2014-07-23 | 2014-11-12 | 苏州大学 | Beta-diketiminate divalent rare earth boron hydrogen complex and preparation method and application thereof |
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| Amido rare-earth complexes supported by an ansabis(amidinate) ligand with a rigid 1,8-naphthalene linker:synthesis, structures and catalytic activity in rac-lactide polymerization and hydrophosphonylation of carbonyl compounds;Marina V.Yakovenko et al.;《New J. Chem.》;20141112;第39卷;第1083-1093页 * |
| Synthesis and characterization of amidate rare-earth metal amides and their catalytic activities toward hydrophosphonylation of aldehydes and unactivated ketones;Lu Zhao et al.;《Polyhedron》;20140420;第83卷;第50-59页 * |
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| CN105665023A (en) | 2016-06-15 |
| CN108250236B (en) | 2020-08-14 |
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