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Metal complex of novel double piperidine derivative with symmetric structure

A metal complex, symmetrical structure technology, applied in the direction of organic compound/hydride/coordination complex catalyst, copper organic compound, zinc organic compound, etc., can solve the synthesis method of metal complex without bipiperidine derivatives, etc. problem, to achieve the effect of good catalytic performance

Inactive Publication Date: 2012-07-18
HEBEI UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, there is no report on the synthesis method of metal complexes of bispiperidine derivatives with symmetrical structures

Method used

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  • Metal complex of novel double piperidine derivative with symmetric structure
  • Metal complex of novel double piperidine derivative with symmetric structure
  • Metal complex of novel double piperidine derivative with symmetric structure

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0039] Embodiment 1: the synthesis of bispiperidine ligand 1b

[0040] The structural formula of bispiperidine ligand 1b is:

[0041]

[0042] N 2 Under protection, add 1g (7.94mmol) of bispiperidine and 15ml of acetone into the reaction flask, stir until it dissolves, and cool down to 0°C, add 4.4g (32mmol) of anhydrous potassium carbonate as an ancidic agent, and then slowly add chlorine 2ml (32mmol) of acetonitrile was dropped within 0.5h, and the reaction was carried out at room temperature, and the progress of the reaction was detected by TLC (color development with iodine). After detecting that no bispiperidine remains, remove potassium carbonate by filtration, concentrate the filtrate, and recrystallize the residue with ethyl acetate to obtain bispiperidine ligand 1b as a white solid, 1.2 g, melting point: 130.9-132.0°C, yield 74% . 1 HNMR (CDCl 3 , 400MHz) δ: 1.60 (s, 2H, CH 2 bridge), 2.09(s, 2H, CH), 2.70~2.74(m, 4H, cycl.NCH 2ax ), 2.85~2.88 (m, 4H, cycl.NC...

Embodiment 2

[0043] Embodiment 2: the synthesis of bispiperidine ligand 2b

[0044] The structural formula of bispiperidine ligand 2b is:

[0045]

[0046] N 2Under protection, add 40.8g (6.7mmol) of bispiperidine, 15ml of acetone, and 2.78g (20.1mmol) of anhydrous potassium carbonate into the reaction flask as an acid application agent, drop to 0°C, and slowly add 2.16ml of ethyl chloroacetate (20.1mmol), dropwise finished within 0.5h, raised to room temperature, TLC detection of reaction progress (iodine color). After detecting that there is no remaining bispiperidine, remove potassium carbonate by filtration, dry the filtrate with molecular sieves, concentrate to remove the solvent and excess ethyl chloroacetate, and add 10ml of methanol to the obtained yellow sticky substance, stir until it dissolves, and then add 40% NaOH solution 4ml, heated to reflux. TLC detection of reaction progress (iodine color development), after detection of no intermediate remaining, lower to room temp...

Embodiment 3

[0047] Embodiment 3: the synthesis of bispiperidine ligand 3b

[0048] The structural formula of bispiperidine ligand 3b is:

[0049]

[0050] Under nitrogen protection and ice-water bath cooling, add (R)-mandelic acid 3.07g (20.2mmol) and N-hydroxysuccinimide 2.32g (20.2mmol) successively in a three-necked flask equipped with 50mL THF (tetrahydrofuran), and react After the substance was completely dissolved, 3.87 g (20.2 mmol) of EDCI was added, stirred for 30 min, raised to room temperature for reaction, and TLC was used to detect the reaction progress. After detecting that there is no remaining (R)-mandelic acid, add 0.8 g (6.7 mmol) of bispiperidine dropwise to the above reaction solution under cooling in an ice-water bath, and complete the dropping within 0.5 h, stir for 30 min, rise to room temperature for reaction, and detect by TLC reaction process. After detecting that there is no remaining bispiperidine, wash with saturated sodium chloride, dry over anhydrous so...

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Abstract

The invention belongs to the field of synthesis of a metal complex, and particularly relates to a metal complex of a novel double piperidine derivative with a symmetric structure. According to the complex, under the protection of nitrogen gas, salt of corresponding metal is added into a reaction bottle provided with a reflux condensing tube; methanol is used as a solvent; the salt and the solvent are stirred until the salt is dissolved to obtain clear solution; double piperidine ligand is added and is heated under stirring until reflux occurs; after the double piperidine ligand is not available in the solution to be reacted, the solution is cooled to room temperature; the solvent is removed under reduced pressure; and residues are recrystallized to obtain the metal complex of the corresponding double piperidine derivative. The metal complex of the double piperidine derivative shows better catalytic performance in catalytic reaction such as epoxidation of olefin, asymmetric epoxidation of olefin, asymmetric addition of benzaldehyde and diethyl zinc and cyclopropanation of styrene.

Description

technical field [0001] The invention belongs to the field of synthesis of metal complexes, in particular to the metal complexes of novel bispiperidine derivatives with symmetrical structures. Background technique [0002] Bispiperidine derivatives are a very important class of compounds. European Patent EP103833, U.S. Patent US4550112, U.S. Patent US5164401, Chinese Patent CN1822833A, etc. report that bispiperidine derivatives (structure shown below) have satisfactory antiarrhythmic activity or Diuretic effect. [0003] [0004] Bispiperidine derivatives [0005] In 1942, Petrenkokrischenko discovered 3,7-diazabicyclo[3.3.1]nonane (ie, bispiperidine) in the by-product when using ketones, aldehydes and amines as raw materials to synthesize piperidin-4-one. In 1955, someone obtained bispiperidine from pyridine-3,5-dicarboxylate as a raw material through a six-step reaction. Since then, people have obtained bispiperidine derivatives through various methods, but almost all...

Claims

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Application Information

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IPC IPC(8): C07F1/08C07F3/06C07F15/06C07F15/04C07F11/00C07F15/00C07F13/00C07D471/08B01J31/22C07D301/12C07D303/04C07C29/40C07C33/20C07C13/28C07C2/86
Inventor 张月成赵继全魏娇娇
Owner HEBEI UNIV OF TECH
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