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Beta-diketiminate divalent rare earth boron hydrogen complex and preparation method and application thereof

A -diimine-based divalent rare earth, -diimine technology, applied in the field of rare earth metal complexes, can solve the problem of low reduction potential of divalent rare earth metal ions, limiting the catalytic application of divalent rare earth complexes, and divalent rare earth complex complex preparation and other problems, to achieve the effect of simple and controllable reaction process, easy purification, and stable storage.

Active Publication Date: 2014-11-12
HUAWEI TEHCHNOLOGIES CO LTD
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Problems solved by technology

[0005] In the rare earth metal catalytic system, rare earth borohydride complexes have catalytic activity due to the presence of Ln-H bonds, and have been widely used to catalyze the polymerization of various types of polymers; but there is no rare earth metal borohydride complex in the prior art. Report on Synthesis of α-Hydroxy Phosphates Catalyzed by Addition Reaction of Phosphite and Carbonyl Compounds as Catalysts
[0006] In addition, the reduction potential of divalent rare earth metal ions is small and has strong reducing ability; divalent rare earth complexes are different from trivalent rare earth complexes in terms of structure and reaction performance, and they have shown many advantages as single-electron reducing agents. Unique advantages, such as good solubility, can provide a larger reaction site, high reactivity, redox reactions can occur, and can also be used as an efficient catalyst for organic synthesis; but the catalytic application of divalent rare earth complexes is still very limited.
This is due to the complex preparation of divalent rare earth complexes, the low success rate of the conventional reduction method and the potassium (sodium) method, and the difference in the structure of the ligands greatly increases the surprise of the reaction; and because of its strong reducibility, it can Reduction reaction with many small organic molecules can easily generate trivalent rare earth metal complexes
These all limit the catalytic application of divalent rare earth complexes
[0007] So far, there have been no reports on the application of the divalent rare earth borohydride complex catalyst system in the addition reaction of phosphite and carbonyl compounds. Therefore, a divalent rare earth borohydride complex was designed and synthesized, and used as a The catalyst catalyzes the addition reaction of phosphite and carbonyl compounds has important application value

Method used

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  • Beta-diketiminate divalent rare earth boron hydrogen complex and preparation method and application thereof

Examples

Experimental program
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Effect test

Embodiment 1

[0039] Example one: [2,6- i pr 2 -(C 6 H 3 )-NC(Me)CHC(Me)N-(C 6 H 3 )-2,6- i pr 2 ] Yb-BH 4 . Synthesis of 2THF

[0040] In the dehydrated and deoxygenated reaction flask, use a syringe to take β-diimine ligand sodium salt ([2,6- i pr 2 -(C 6 H 3 )-NC(Me)CHC(Me)N-(C 6 H 3 )-2,6- i pr 2 ] Na) and equimolar amount of YbCl 3 The THF slurry was reacted with THF slurry at room temperature and stirred for 24 hours to obtain β-diimine ytterbium dichloride quantitatively. The β-diimine ytterbium dichloride (4.30 mmol) and an equimolar amount of sodium borohydride (4.30 mmol) ) After reacting at room temperature for 24 hours, add 1.2 equivalents of sodium potassium alloy with a molar ratio of 9:1, and react at room temperature for 24 hours. The precipitate was removed by centrifugation, the clear solution was transferred to another crystallization flask, concentrated appropriately, the flask was sealed, and crystallized at room temperature to obtain black crystals of 2.36 (3.14 mmol) with...

Embodiment 2

[0041] Example two: [2,6- i pr 2 -(C 6 H 3 )-NC(Me)CHC(Me)N-(C 6 H 3 )-2,6- i pr 2 ] Sm-BH 4 . Synthesis of 2THF

[0042] In the dehydrated and deoxygenated reaction flask, use a syringe to take β-diimine ligand sodium salt ([2,6- i pr 2 -(C 6 H 3 )-NC(Me)CHC(Me)N-(C 6 H 3 )-2,6- i pr 2 ] Na) and equimolar amount of SmCl 3 The THF slurry was reacted with THF slurry at room temperature and stirred for 24 hours to obtain β-diimine samarium dichloride quantitatively. The β-diimine samarium dichloride (4.84 mmol) and an equimolar amount of sodium borohydride (4.84 mmol) ) After 24 hours of reaction at room temperature, 1.2 equivalents of sodium potassium alloy with a molar ratio of 9:1 are added, and the reaction is performed at room temperature for 24 hours. The precipitate was removed by centrifugation, the clear solution was transferred to another crystallization flask, concentrated appropriately, the flask was sealed, and crystallized at room temperature to obtain 2.76 g (3.78 mmo...

Embodiment 3

[0043] Embodiment Three: [2,6- i pr 2 -(C 6 H 3 )-NC(Me)CHC(Me)N-(C 6 H 3 )-2,6- i pr 2 ] Sm-BH 4 . 2THF-catalyzed synthesis of α-hydroxy phosphate from benzaldehyde and diethyl phosphite

[0044] In the reaction flask that has been dehydrated and deoxygenated, the catalyst is added under the protection of argon [2,6- i pr 2 -(C 6 H 3 )-NC(Me)CHC Me)N-(C 6 H 3 )-2,6- i pr 2 ] Sm-BH 4 . 2THF (0.01 mmol, 0.0073 g), then use a syringe to add diethyl phosphite (1.55 mL, 12 mmol), then stir at room temperature for 10 minutes, then use a syringe to add benzaldehyde (1.01 mL, 10 mmol), and react for 5 minutes After that, the reaction was terminated with ethyl acetate and dissolved with an appropriate amount of ethyl acetate. The solvent was removed by rotary evaporation. The remaining solid was washed with n-hexane (4×5 mL) to obtain the corresponding α-hydroxy phosphate, C 6 H 4 CHOHPO(OCH 2 CH 3 ) 2 , 2.2213 g, 91% yield.

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Abstract

The invention discloses a beta-diketiminate divalent rare earth boron hydrogen complex and a preparation method and application thereof. In the method, a beta-diimine rare earth dichloride and NaBH4 have a reaction in a tetrahydrofuran solvent and are reduced through in-situ Na / K to obtain the beta-diketiminate divalent rare earth boron hydrogen complex with the molecular structural formula being [2,6-ipr2-(C6H3)-NC(Me) CHC (Me) N-(C6H3)-2,6-ipr2] Ln-BH4.2THF. The beta-diketiminate divalent rare earth boron hydrogen complex can highly actively catalyze the reaction between aldehyde and phosphite ester under the mild condition and has the advantages that the reaction time is short, the reaction condition is mild, and a follow-up treatment method is easy and convenient to implement.

Description

Technical field [0001] The invention relates to a rare earth metal complex, in particular to a beta-diimide divalent rare earth borohydride complex and its application as a catalyst for the addition reaction of a phosphite and a carbonyl compound. Background technique [0002] Alpha-hydroxy phosphate is a class of biologically active substances, and such compounds containing alpha-hydroxy phosphate structural units have been widely used in the synthesis of drugs and biologically active compounds. Alpha-hydroxy phosphate derivatives have been found to have inhibitory effects on hypertensive proteinogenase, EPSP synthase, HIV protease and other enzymes, thus exhibiting a variety of biological and physiological activities, such as antihypertensive, antiviral, and weeding , Sterilization, plant growth regulation activity, etc. [0003] The addition reaction of phosphites and carbonyl compounds (such as aldehydes) (ie Pudovik reaction) is the most direct and atomically economical metho...

Claims

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Application Information

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IPC IPC(8): C07F5/00B01J31/22C07F9/40
Inventor 薛明强沈琪洪玉标
Owner HUAWEI TEHCHNOLOGIES CO LTD
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