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Chiral 6, 6'-2 carbazole base binaphthol

A technology of carbazolyl binaphthol and brominated binaphthol is applied in the field of chiral 6,6'-dicarbazolyl binaphthol, which can solve the problems of optical rotation characterization, lack of relevant characterization data, and non-existence.

Inactive Publication Date: 2015-05-13
CHENGDU UNIVERSITY OF TECHNOLOGY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the molecule mentioned in the patent does not involve chirality, and there is no research work on the synthesis and characterization of the molecule, and there is no characterization of the possible chiral parameters such as the optical rotation of the molecule. Therefore, the patent The reported 6,6'-dicarbazolyl binaphthol can only be counted as racemate
In addition, the compound mentioned in the patent has no synthetic procedures and no relevant characterization data, so, in fact, the molecule has never existed

Method used

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  • Chiral 6, 6'-2 carbazole base binaphthol

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0011] Add R configuration 6,6'-dibromobinaphthol (1.0 mmol), carbazole (1.0 mmol), tris(dibenzylideneacetone) dipalladium (18.3 mg , 0.02 mmol), 2-(di-tert-butylphosphine) biphenyl (8.95 mg, 0.03 mmol), potassium carbonate (414 mg, 3.0 mmol). The ground-mouth test tube was sealed with an inversion rubber stopper, then replaced with high-purity argon for 3 times, and then injected with 5 ml of toluene through the syringe. Put the sealed ground-mouth test tube in a preheated oil bath at 100°C, and stir for 24 hours to react. The test tube was cooled to room temperature, and the acidity of the reaction mixture was carefully adjusted to pH 5-6 with 2 mol / L dilute hydrochloric acid. After quenching, the reaction mixture was extracted three times with ethyl acetate, and the combined organic phases were dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The obtained crude product was separated and purified by silica gel column chromatograph...

Embodiment 2

[0013] Use S configuration 6,6'-dibromobinaphthol instead of R configuration 6,6'-dibromobinaphthol in Example 1 to obtain S configuration 6,6'-dicarbazolyl binaphthol . Yield: 386.1 mg, yield: 63%, yellow solid. Mp. 193-195 ℃; [α] D 25 = -108.1 (c = 0.45, THF).

Embodiment 3

[0015] Use racemic 6,6'-dibromo-binaphthol to replace the R-configuration 6,6'-dibromo-binaphthol in Example 1 to obtain racemic 6,6'-dicarbazolyl-binaphthol . Yield: 376.5 mg, yield: 61%, yellow solid. Mp. 207-209℃.

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Abstract

A chiral binaphthol and chiral ligand adopting the chiral binaphthol as a framework show good chiral induction capability in unsymmetrical catalysis and obtain high enantioselectivity in a plurality of catalytic reactions. A membrane reactor can recycle homogeneous phase catalysts, and for expensige homogeneous phase chiral catalysts, recycling the chiral catalysts has more important values. The invention discloses a chiral compound 6,6'-2 carbazole base binaphthol derived from binaphthol with large molecular dimensions, and the 6,6'-2 carbazole base binaphthol is hopeful for being used as the chiral ligand of the membrane reactor. Chiral 6, 6'-2 carbazole base binaphthol is obtained by synthetizing 6,6'-carbazole base binaphthol, carbazole, palladium and alkali at a next step. The chiral compound can serve as the chiral ligand and used for unsymmetrical catalytic addition reaction of aryl acetylene and aromatic aldehyde.

Description

Technical field [0001] The patent involves the research field of organic synthesis, hand synthesis, and fine chemicals. Specifically, it is from hand 6,6' -dietine phenol and pagazole synthesis 6,6' -two pagazoleBackenol. Background technique [0002] Lianxinphenol is a molecular skeleton with good hand -induced capabilities.Lianxinol itself is a good hand ligand, which is used for a variety of asymmetric catalytic reactions.Double 衍 ligand BinaP ( Acc. Chem. Res. 1990, 23, 345 -350 ;; Chirrality inde. 1992, 313-323), nitrogen gyrus ligand Map (2 -amino -2' -two phenyl -based cymbal -1,1' -couplet, J. org. Chem. 1998, 63, 7738-7748), Monophos (US 6989461 B2) and so on. [0003] Membrane separation technology and membrane reactor are important technologies to promote green production, which are generally valued by scientists from various countries.The essence of the nanofilled membrane reactor circulation is used, which is due to the "screen" effect of the membrane, so that the p...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D209/86
Inventor 曾庆乐董俊宇裘德智
Owner CHENGDU UNIVERSITY OF TECHNOLOGY
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