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Bivalent copper complex containing diphosphine ortho-position carborane ligand, preparation method and application thereof

A technology of copper complexes and carboranes, applied in the field of divalent copper complexes and their preparation, can solve the problems of difficult control, harsh reaction conditions, complex reactions, etc., achieve fast reaction rate, mild reaction conditions, and simple preparation method Effect

Active Publication Date: 2020-09-08
SHANGHAI INST OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] The traditional synthetic methods of β-carbonyl phosphine oxide mainly include Arbuzov reaction, acylation reaction of alkyl phosphonate under strong acid or strong base conditions, etc., but the reaction conditions are harsh and difficult to control.
In recent years, the addition reaction and hydration reaction of phosphorus-centered radicals to prepare such compounds have also been developed, but these reactions usually include two steps (addition and hydration), and expensive reagents are used for the reaction. substances such as alkynes and their derivatives, multi-substituted alkenes or allenes, etc.; at the same time, this type of reaction also requires the participation of oxidants, and the reaction is complex

Method used

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  • Bivalent copper complex containing diphosphine ortho-position carborane ligand, preparation method and application thereof
  • Bivalent copper complex containing diphosphine ortho-position carborane ligand, preparation method and application thereof
  • Bivalent copper complex containing diphosphine ortho-position carborane ligand, preparation method and application thereof

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Experimental program
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Effect test

Embodiment 1

[0029] Example 1: Synthesis of copper complex 1 and its application in the catalytic synthesis of β-carbonylphosphine oxides

[0030] At 0°C, add n-BuLi (2.2mmol) n-hexane solution dropwise to the ortho carborane o-C 2 B 10 h 12 (1.0mmol) in ether solution, continue stirring for 30 minutes after the dropwise addition, slowly rise to room temperature and continue to react for 30 minutes, then add halophosphine ClPPh 2 (2.2mmol), continue to react at room temperature for 2 hours, then Cu(OAc) 2 (1.0mmol) was added to the reaction system at room temperature and continued to react for 3 hours. After the reaction was completed, it was left to stand and filtered, and the solvent was drained under reduced pressure. The obtained crude product was washed with ether and drained to obtain the target product 1 (yield 80%). The formula is:

[0031]

[0032] Elemental Analysis Theoretical Value C 30 B 10 h 36 o 4 P 2 Cu: C 51.90, H 5.23; Found: C 51.79, H 5.26.

[0033] Dissolv...

Embodiment 2

[0038] Embodiment 2: the synthesis of copper complex 2

[0039] At 0°C, n-BuLi (2.5 mmol) in n-hexane was added dropwise to the ortho carborane o-C 2 B 10 h 12 (1.0mmol) ether solution, continue to stir for 30 minutes after the dropwise addition, slowly rise to room temperature and continue to react for 30 minutes, then add halophosphine ClP (4-MeO-C 6 h 4 ) 2 (2.5mmol), continue to react at room temperature for 2 hours, then Cu(OAc) 2 (1.0mmol) was added to the reaction system at room temperature and continued to react for 5 hours. After the reaction was over, it was left to stand and filtered, and the solvent was drained under reduced pressure. The obtained crude product was washed with ether and drained to obtain the target product 2 (yield 86%), the reaction formula for:

[0040]

[0041] Elemental Analysis Theoretical Value C 34 B 10 h 44 o 8 P 2 Cu: C 50.15, H 5.45; Found: C 50.23, H 5.51.

Embodiment 3

[0042] Embodiment 3: the synthesis of copper complex 3

[0043] At 0°C, add n-BuLi (2.3mmol) n-hexane solution dropwise to the ortho carborane o-C 2 B 10 h 12 (1.0mmol) in ether solution, continue stirring for 30 minutes after the dropwise addition, slowly rise to room temperature and continue to react for 30 minutes, then add halophosphine ClP(4-NO 2 -C 6 h 4 ) 2 (3.0mmol), continue to react at room temperature for 2 hours, then Cu(OAc) 2 (1.0mmol) was added to the reaction system at room temperature to continue the reaction for 4 hours. After the reaction was over, it was left to stand and filtered, and the solvent was drained under reduced pressure. The obtained crude product was washed with ether and drained to obtain the target product 3 (yield 81%), the reaction formula for:

[0044]

[0045] The product is paramagnetic, so there is no NMR data. Elemental Analysis Theoretical Value C 30 B 10 h 32 N 4 o 12 P 2 Cu: C 41.22, H 3.69, N 6.41; found: C 41.29, ...

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Abstract

The invention relates to a bivalent copper complex containing a diphosphine ortho-position carborane ligand, a preparation method and application thereof. The copper complex is prepared by the following method of: adding an n-BuLi solution dropwise into an ortho-position carborane o-C2B10H12 solution, and carrying out stirring reaction, then adding halogenated phosphine for continuous reaction, adding copper acetate Cu(OAc)2 into the reaction system for continuous reaction, after the reaction is finished, performing separating to obtain the diphosphine ortho-position carborane ligand, and applying the copper complex to catalytic synthesis of a beta-carbonyl phosphine oxide compound. Compared with the prior art, the synthesis process has excellent selectivity and high yield, the copper complex can catalyze alpha-haloketone and phosphite to react to synthesize the beta-carbonyl phosphine oxide compound under the room temperature condition, and the reaction is efficient, green and environmentally friendly.

Description

technical field [0001] The invention relates to the field of complex synthesis, in particular to a divalent copper complex containing a bisphosphine ortho-carborane ligand and a preparation method and application thereof. Background technique [0002] As an important class of phosphorus-containing organic compounds, β-carbonylphosphine oxides have been widely used in many fields such as organic chemistry, coordination chemistry, and biochemistry. Such compounds are important ligands in coordination chemistry; they are used in the preparation of various β-aminophosphonic acids, chiral β-hydroxyphosphonic acids and other compounds in organic synthesis; in addition, β-carbonylphosphine oxygen derivatives Drugs also have a wide range of biological activities, such as anti-cancer effects, promoting bone metabolism and inhibiting the activity of β-lactamase. [0003] The traditional synthetic methods of β-carbonyl phosphine oxide mainly include Arbuzov reaction, acylation reactio...

Claims

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Application Information

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IPC IPC(8): C07F9/6596B01J31/24C07F9/40
CPCC07F9/6596B01J31/2452C07F9/4087C07F9/4075B01J2531/16B01J2231/4277
Inventor 姚子健邓维
Owner SHANGHAI INST OF TECH
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