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Method of catalyzing asymmetric Knoevenagel reaction via trans-1, 2-diaminocyclohexane derivative

A technology of cyclohexanediamine and derivatives, which is applied in the field of synthesis of organic intermediates, can solve the problems of insufficient catalytic effect, low substrate universality, etc., and achieves high steric selectivity and enantioselectivity and improved yield. , the effect of simple synthesis process

Inactive Publication Date: 2015-12-16
JIANGSU UNIV OF SCI & TECH
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the catalytic effect of this method is insufficient, the ee value of the target product is 57%, and the substrate universality is not high

Method used

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  • Method of catalyzing asymmetric Knoevenagel reaction via trans-1, 2-diaminocyclohexane derivative
  • Method of catalyzing asymmetric Knoevenagel reaction via trans-1, 2-diaminocyclohexane derivative
  • Method of catalyzing asymmetric Knoevenagel reaction via trans-1, 2-diaminocyclohexane derivative

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0034] The synthesis of diethyl 2-(2-phenylpropylene) malonate, the synthetic route is:

[0035]

[0036] 2-Phenylpropanal (0.001mol, 0.134g), diethyl malonate (0.0011mol, 0.176g) and pre-prepared Cat (0.0001mol, 0.032g), acetonitrile (2mL) as a solvent, stirred and reacted at 60°C for 168h under a nitrogen atmosphere, then stopped the reaction, added a small amount of 0.1mol / L dilute hydrochloric acid (10mL) to wash the reaction system after cooling, and extracted the aqueous phase three times with ethyl acetate (3× 15mL), the organic phases were combined, and the organic phases were sequentially washed with saturated NaHCO 3 solution (10mL), saturated brine (15mL), washed with anhydrous Na 2 SO 4 After drying and filtering, the filtrate was rotary evaporated under reduced pressure to remove the solvent to obtain a crude product, which was separated by column chromatography to obtain 0.221 g of the target product, with an ee value of 73% and a yield of 80%.

[0037] 1 ...

Embodiment 2

[0039] The synthesis of diethyl 2-(2-(4-fluorophenyl) propylene) malonate, the synthetic route is:

[0040]

[0041] Add p-fluoro 2-phenylpropanal (0.001mol, 0.152g), diethyl malonate (0.0011mol, 0.176g) and pre-prepared Cat (0.0001mol, 0.032g) into a 10mL reaction tube in sequence , acetonitrile (2mL) was used as a solvent, and the reaction was stirred at 60°C for 168h under a nitrogen atmosphere, and then the reaction was stopped. After the reaction system was cooled, a small amount of 0.1mol / L dilute hydrochloric acid (10mL) was added for washing, and the aqueous phase was extracted three times with ethyl acetate ( 3×15mL), the organic phases were combined, and the organic phases were sequentially washed with saturated NaHCO 3 solution (10mL), saturated brine (15mL), washed with anhydrous Na 2 SO 4 After drying and filtering, the filtrate was rotary evaporated under reduced pressure to remove the solvent to obtain a crude product, which was separated by column chromato...

Embodiment 3

[0044] The synthesis of diethyl 2-(2-(4-methoxyphenyl) propylene) malonate, the synthetic route is:

[0045]

[0046] In a 10mL reaction tube, add p-methoxy 2-phenylpropanal (0.001mol, 0.164g), diethyl malonate (0.0011mol, 0.176g) and pre-prepared Cat (0.0001mol, 0.017 g), acetonitrile (2mL) was used as a solvent, and the reaction was stirred at 60°C for 168h under a nitrogen atmosphere, and then the reaction was stopped. After the reaction system was cooled, a small amount of 0.1mol / L dilute hydrochloric acid (10mL) was added for washing, and the aqueous phase was extracted with ethyl acetate Three times (3×15mL), the organic phases were combined, and the organic phases were sequentially washed with saturated NaHCO 3 solution (10mL), saturated brine (15mL), washed with anhydrous Na 2 SO 4 After drying and filtering, the filtrate was rotary evaporated under reduced pressure to remove the solvent to obtain a crude product, which was separated by column chromatography to ob...

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Abstract

The invention provides a method of catalyzing asymmetric Knoevenagel reaction via a trans-1, 2-diaminocyclohexane derivative. A hydratropic aldehyde derivative and an active methylene compound used as raw materials and the trans-1, 2-diaminocyclohexane derivative used as a catalyst are mixed in an organic solvent to obtain a condensation product. A synthetic route is shown below. A synthetic process of the catalyst used in the method is simple, and the catalyst is easy to prepare and is suitable for industrial production; a target product is high in both spatial selectivity and enantioselectivity; the catalyst is reusable; the yield of the target product is increased, up to 80%-92%.

Description

technical field [0001] The invention belongs to the field of synthesis of organic intermediates, and in particular relates to a method for catalyzing asymmetric Knoevenagel reaction by trans-1,2-cyclohexanediamine derivatives. Background technique [0002] The Knoevenagel reaction is a dehydration condensation reaction between carbonyl compounds and active methylene compounds. As a main method for the formation of carbon-carbon double bonds, it has been widely used in many fields such as industry, agriculture, and biological sciences. It is widely used in the synthesis of medicines, cosmetics, perfumes, pharmaceutical intermediates, etc. In recent years, the research on the Knoevenagel reaction mainly tends to improve the catalytic performance of the catalyst and reduce the pollution of the reaction system. However, it is still difficult to synthesize chiral products by using asymmetric Knoevenagel reaction. There are currently two methods for this kind of asymmetric Knoeve...

Claims

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Application Information

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IPC IPC(8): C07B53/00B01J31/02C07C67/343C07C69/618C07C69/65C07C69/734
CPCY02P20/584
Inventor 陆鸿飞唐演谷晓玉
Owner JIANGSU UNIV OF SCI & TECH
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