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Synthesis method of (R)/(S)-6,6'-benzyloxyl-5,5'-biquinoline

A synthetic method, the technology of hydroxyquinoline, applied in the direction of organic chemistry, etc., can solve the problems of time-consuming and troublesome, high disassembly cost, unfavorable large-scale preparation, etc., and achieve the effect of simple steps and high disassembly efficiency

Inactive Publication Date: 2013-10-16
GUANGZHOU UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the method reported in the above-mentioned literature is a resolution in a chiral column, which is time-consuming and troublesome, and the resolution requires an expensive chiral preparation column, which has a high cost of resolution and is not conducive to large-scale preparation.

Method used

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  • Synthesis method of (R)/(S)-6,6'-benzyloxyl-5,5'-biquinoline
  • Synthesis method of (R)/(S)-6,6'-benzyloxyl-5,5'-biquinoline
  • Synthesis method of (R)/(S)-6,6'-benzyloxyl-5,5'-biquinoline

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0019] 1. Preparation of racemic 6,6'-dihydroxy-5,5'-bisquinoline

[0020] 14.5g (0.085mol) CuCl 2 2H 2 O was dissolved in 600ml of methanol solvent, and then 64.3g (0.42mol) of benzylamine was added. After mixing evenly, 10g (about 0.07mol) of 6-hydroxyquinoline was added to the above mixed solution and reacted at room temperature for 72h. Suction filtration obtained a brown solid filter cake, which was washed with methanol and dried. Dissolve the filter cake with 300mL hydrochloric acid solution (concentrated hydrochloric acid: water = 1:1), then add concentrated ammonia water to adjust the pH to 8-9, the solid precipitates out, filter with suction to obtain the filter cake, wash with water and methanol successively, and drain. Vacuum dry. Weighed to obtain 7.79 g of pure tan solid, with a yield of 81.2%.

[0021] Its reaction process is shown in reaction formula (IV):

[0022]

[0023] Take the above brown solid to detect its NMR:

[0024] 1 H-NMR (400MHz, DMSO-d ...

Embodiment 2

[0070] 1. Preparation of racemic 6,6'-dihydroxy-5,5'-bisquinoline

[0071] 14.5g (0.085mol) CuCl 2 2H 2 O was dissolved in 600ml of methanol solvent, then 32.15g (0.21mol) of benzylamine and 25.4g (0.21mol) of phenethylamine were added, after stirring evenly, 10g (about 0.07mol) of 6-hydroxyquinoline was added to the above mixed solution, Reaction at room temperature for 48h. Suction filtration obtained a brown solid filter cake, which was washed with methanol and dried. Dissolve the filter cake with 300mL hydrochloric acid solution (concentrated hydrochloric acid: water = 1:1), then add concentrated ammonia water to adjust the pH to 8.5, the solid precipitates out, filter with suction to obtain the filter cake, wash with water and methanol successively, and drain. Vacuum dry. Weighed to obtain 5.18 g of pure tan solid, yield 54%.

[0072] 2. Preparation of 6,6'-dihydroxy-5,5'-bisquinoline dicamphorsulfonate shown in chemical formula (I)

[0073]Under ice-salt bath, add ...

Embodiment 3

[0083] 1. Preparation of racemic 6,6'-dihydroxy-5,5'-bisquinoline

[0084] 14.5g (0.085mol) CuCl 2 2H 2 O was dissolved in 600ml of methanol solvent, then 9.3g of aniline, 21.4g of p-methylaniline and 12g of cyclohexylamine were added, after stirring evenly, 10g (about 0.07mol) of 6-hydroxyquinoline was added to the above mixed solution, and reacted at room temperature 96h. Suction filtration obtained a brown solid filter cake, which was washed with methanol and dried. Dissolve the filter cake with 300mL hydrochloric acid solution (concentrated hydrochloric acid: water = 1:1), then add concentrated ammonia water to adjust the pH to 8-9, the solid precipitates out, filter with suction to obtain the filter cake, wash with water and methanol successively, and drain. Vacuum dry. Weighed to obtain 7.58 g of pure tan solid, yield 79%.

[0085] 2. Preparation of 6,6'-dihydroxy-5,5'-bisquinoline dicamphorsulfonate shown in chemical formula (I)

[0086] Under ice-salt bath, add 7...

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Abstract

The invention relates to a synthesis method of biquinoline, in particular to a synthesis method of (R) / (S)-6,6'-benzyloxyl-5,5'-biquinoline. The synthesis method comprises the following steps of: adding 6-hydroxyquinoline to a methanol solution containing copric chloride and organic amine to oxidize and couple to obtain racemization 6,6'-benzyloxyl-5,5'-biquinoline, and carrying out a reaction on the racemization 6,6'-benzyloxyl-5,5'-biquinoline and D-(+)-camphorsulfonyl chloride to obtain 6,6'-benzyloxyl-5,5'-biquinoline dicamphor sulfonic acid ester; crystallizing the 6,6'-benzyloxyl-5,5'-biquinoline dicamphor sulfonic acid ester in a mixed solvent containing ethyl acetate, methanol and normal hexane to obtain (R) / (S)-6,6'-benzyloxyl-5,5'-biquinoline dicamphor sulfonic acid ester; and then hydrolyzing the (R) / (S)-6,6'-benzyloxyl-5,5'-biquinoline dicamphor sulfonic acid ester to obtain the (R) / (S)-6,6'-benzyloxyl-5,5'-biquinoline. Chiral column separation is not needed by the synthesis method provided by the invention, and the synthesis method has the advantages of simplicity and convenience for operations and high split yield.

Description

technical field [0001] The invention belongs to the field of organic chemistry, in particular to the synthesis of nitrogen-containing heterocyclic compounds, especially the synthesis of bisquinoline. Background technique [0002] Asymmetric catalytic synthesis of optically pure compounds is a research hotspot in the field of organic synthesis. The success or failure of asymmetric catalysis mainly depends on the choice of chiral ligands. A catalyst formed by an excellent chiral ligand can increase the chiral value-added effect by as much as 100,000 times in asymmetric catalytic reactions. Among many types of chiral catalysts, containing C 2 Axial chiral ligands, such as 1,1'-binaphthol (BINOL) and its derivatives, are chiral ligands with a wide range of research and application. Since Professor Noyori synthesized optically pure BINOL for the first time in 1979 and successfully applied it in asymmetric catalytic reactions, BINOL has been widely used in various asymmetric syn...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D215/20
Inventor 陈亿新梁海波陈国术刘天穗周美兰张睿
Owner GUANGZHOU UNIVERSITY
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