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Prolinol derivative induced chiral MOFs material with asymmetric catalysis

A derivative and asymmetric technology, which is applied in the field of chiral catalytic materials, can solve the problems of unobtained crystal structure and high-density catalytic sites, no enantioselectivity, low catalytic efficiency, etc., and is easy to promote on a large scale Application, cheap raw materials, effect of low raw material prices

Active Publication Date: 2012-12-26
DALIAN UNIV OF TECH
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0008] At present, the research on the construction and catalysis of chiral MOFs has been reported internationally. Makoto Fujita (Chem.Commun., 2004, 1586-1587) and R.Long (J.Am.Chem.Soc. 5854-5855) utilize metal-organic frameworks (MOFs) to catalyze the silicocyanation reaction of aldehydes, but without enantioselectivity, Kimoon Kim (J.Am.Chem.Soc.2009, 131, 7524-7525) will proline Acid derivatives were grafted onto MIL-101 to catalyze the Adol reaction through post-modification methods, but the crystal structure and high-density catalytic sites were not obtained, resulting in low catalytic efficiency and unexplained mechanism

Method used

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  • Prolinol derivative induced chiral MOFs material with asymmetric catalysis
  • Prolinol derivative induced chiral MOFs material with asymmetric catalysis
  • Prolinol derivative induced chiral MOFs material with asymmetric catalysis

Examples

Experimental program
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Effect test

Embodiment 1

[0032] Example 1 (Synthesis of catalyst)

[0033] LN-tert-Butoxycarbonylprolinol (11.3g, 56mmol) 100mL pyridine solution was slowly added to p-toluene yellow acyl chloride (13.1g, 68.8mmol) at 0°C and stirred overnight, diluted with 350mL of ethyl acetate and respectively used 1N HCl (200mL×5), saturated NaHCO 3 (150 mL×2) and brine (100 mL×2) were extracted, the organic layer was dried over anhydrous sodium sulfate, and spin-dried to obtain a yellow oil. Take the yellow oily substance (6.6g, 18.6mmol) and add imidazole sodium salt (2.51g, 27.9mmol) to 60mL acetonitrile solution and heat to reflux for 1.5h, cool to room temperature, extract with chloroform, spin dry to obtain a light yellow solid LN-tert Butoxycarbonyl-2-imidazole-1-pyrrolidine (BCIP). 1 H-NMR(300MHz, CDCl 3 ): d 1.27-1.28 (1H, m), 1.48 (9H, s), 1.60-1.75 (2H, br), 1.89-1.94 (1H, m), 3.14-3.37 (2H, m), 3.99-4.08 ( 2H, m), 4.22-4.26 (1H, m), 6.87 (1H, s), 7.04 (1H, s), 7.44 (1H, s).

Embodiment 2

[0034] Example 2 (Synthesis of catalyst)

[0035] In a 1000ml round bottom flask, Isophthalic acid (99g, 0.6mol), 300mL of oleum with a concentration of 50%, and paraformaldehyde (9.3g, 0.3mol) were sequentially added. The mixture was stirred and reacted at 118°C for 6 hours, and then the heating was stopped. After being cooled to room temperature, the reaction mixture was carefully poured into a glass container containing a large amount of ice cubes, stirred with a glass rod for about 20 minutes, and then allowed to stand for a period of time and then filtered with suction, and the light yellow precipitate obtained by the suction filtered was vacuum dried. The yellow solid obtained from the above reaction was dissolved in 300 mL of saturated methanolic HCl solution, and refluxed at 95° C. for 1 h. After cooling to room temperature, the reaction mixture was suction filtered to obtain a yellow crude product. The crude product was dissolved in 300 ml of chloroform, the insoluble m...

Embodiment 3

[0037] Example 3 (Synthesis of catalyst)

[0038] 5,5’-Methylene diisophthalic acid (H 4 MDIP) (0.086g, 0.25mmol), cerium nitrate hexahydrate (0.0217g, 05mmol), LN-tert-butoxycarbonyl-2-imidazole-1-pyrrolidine (0.125g, 0.5mmol) dissolved in water, and triphenylamine Adjust the pH value of the solution to about 6, after stirring evenly, place it in an oven at 100°C for 3 days, close the oven, cool to room temperature, colorless lumpy crystals are produced, filtered and dried, and the yield is 60%. Anal calc.for C 17 H 11 CeO 9 ·H 2 O: C 39.46, H 2.53%; Found: C 38.53, H 2.91%.

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Abstract

The invention discloses a prolinol derivative induced chiral MOFs material with asymmetric catalysis, which belongs to the technical field of a chiral catalytic material. L-BCIP or D-BCIP is used as a chiral source; 5,5'-methylene diiso-phthalic acid, 4,4'-biphenyl acid, 3,3',4,4'-biphenyltetrazole acid or 4,4'-sulfonyl terephthalic acid is used as a connecting ligand; Ln3+ is used as a node; a three-dimensional hole channel structure is constructed by a hydrothermal method; the general formula is as follows: Ln<3+>+L+L-BCIP or D BCIP->Ln-L, wherein Ln<3+> is a rare earth metal ion; L is a connecting ligand; L-BCIP is L-N-tert-butoxycarbonyl-2-imidazole-1-pyrrolidine; and D-BCIP is D-N tert-butoxycarbonyl-2-imidazole-1-pyrrolidine. The material can be used as a heterogeneous catalyst used for an asymmetric silicon cyanation reaction; therefore, the catalyst can be recycled with a yield of 100% and ee value of 99%; and the chiral MOFs material has good application prospect in the aspects of synthesis of pure enantiomer compounds, synthesis of medical intermediates and the like. The material can be recycled after proper treatment.

Description

Technical field [0001] The invention belongs to the technical field of chiral catalytic materials, and relates to the formation of a single chiral metal-organic framework material using a prolinol derivative as an inducer and its catalysis in a heterogeneous asymmetric reaction. Background technique [0002] Metal-organic coordination polymers (MOFs) are organic-inorganic composite microporous materials formed by self-assembly of metal ions and bridging organic ligands through coordination. Since the mid-1990s, these materials have the characteristics of organic and inorganic materials, diverse structures, and excellent performance. As functional materials, they are used in selective catalysis, molecular recognition, gas adsorption, ion exchange, ultra-high purity separation materials, and biological materials. Conductive materials, optoelectronic materials, new semiconductor materials, magnetic materials, and chip development have shown fascinating application prospects. They ha...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07F5/00B01J31/22C07F7/18
CPCY02P20/584
Inventor 段春迎武鹏彦何成谢忠胡晓月王延听
Owner DALIAN UNIV OF TECH
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