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Prolinol derivative induced chiral MOFs material with asymmetric catalysis

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

Active Publication Date: 2010-09-15
DALIAN UNIV OF TECH
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  • Abstract
  • Description
  • Claims
  • Application Information

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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

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Embodiment 1

[0032] Embodiment 1 (synthesis of catalyst)

[0033] L-N-tert-butoxycarbonylprolinol (11.3g, 56mmol) 100mL pyridine solution was slowly added p-toluene chloride (13.1g, 68.8mmol) at 0°C and stirred overnight, diluted with 350mL of ethyl acetate and washed with 1N HCl (200mL×5), saturated NaHCO 3 (150mL×2) and brine (100mL×2) were extracted, the organic layer was dried over anhydrous sodium sulfate, and spin-dried to obtain a yellow oil. Take yellow oil (6.6g, 18.6mmol) and add imidazole sodium salt (2.51g, 27.9mmol) to 60mL of acetonitrile solution, heat to reflux for 1.5h, cool to room temperature, extract with chloroform, spin dry, and obtain light yellow solid L-N-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] Embodiment 2 (synthesis of catalyst)

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

Embodiment 3

[0037] Embodiment 3 (synthesis of catalyst)

[0038] 5,5'-methylene diisophthalic acid (H 4 MDIP) (0.086g, 0.25mmol), cerium nitrate hexahydrate (0.0217g, 05mmol), L-N-tert-butoxycarbonyl-2-imidazole-1-pyrrolidine (0.125g, 0.5mmol) were dissolved in water, and washed with triphenylamine Adjust the pH value of the solution to about 6, stir it evenly, place it in an oven, burn it at 100°C for 3 days, turn off the oven, cool to room temperature, colorless massive crystals are produced, filter and dry, 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 induced by prolinol derivatives as an inducer and its catalysis in heterogeneous asymmetric reactions. Background technique [0002] Metal-organic coordination polymers (metal-organic frameworks, MOFs) are organic-inorganic composite microporous materials formed by self-assembly of metal ions and bridging organic ligands through coordination. Since the mid-1990s, due to the characteristics of both organic and inorganic materials, diverse structures and excellent performance, these materials have been used as functional materials in selective catalysis, molecular recognition, gas adsorption, ion exchange, ultra-high purity separation materials, biological Fields such as conductive materials, optoelectronic materials, new semiconductor materials, magnetic materials and chip development have shown fas...

Claims

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Application Information

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IPC IPC(8): C07F5/00B01J31/22C07F7/18
CPCY02P20/584
Inventor 段春迎武鹏彦何成谢忠
Owner DALIAN UNIV OF TECH
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