Calix[4]thiourea diaminocyclohexane derivatives and method thereof for catalyzing asymmetric Michael addition

A cyclohexanediamine, addition reaction technology, applied in catalytic reactions, chemical instruments and methods, physical/chemical process catalysts, etc., can solve the problems of difficult catalyst preparation, low catalytic efficiency, environmental pollution, etc. The effect of high catalytic efficiency and broad industrial application prospects

Inactive Publication Date: 2018-11-02
CHANGZHOU UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0005] The technical problem to be solved in the present invention is: provide a kind of calix [4] thiourea cyclohexanediamine in order to overcome problems such as difficult preparation of asymmetric Michael addition reaction catalyst, low catalytic efficiency, poor stability and environmental pollution in the prior art Derivative Catalyzed Asymmetric Michael Addition Reaction Method

Method used

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  • Calix[4]thiourea diaminocyclohexane derivatives and method thereof for catalyzing asymmetric Michael addition
  • Calix[4]thiourea diaminocyclohexane derivatives and method thereof for catalyzing asymmetric Michael addition
  • Calix[4]thiourea diaminocyclohexane derivatives and method thereof for catalyzing asymmetric Michael addition

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Experimental program
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Embodiment 1

[0025] This embodiment is the preparation method of calix[4]thiourea cyclohexanediamine derivative catalysts I and II, and the specific synthesis method is as follows:

[0026] 1. Synthesis of calix[4]thiourea cyclohexanediamine derivative catalysts I and II

[0027]

[0028] 1a (0.996g, 1.5mmol) / 1b (0.204g, 0.30mmol), NaOH (0.18g, 4.5mmol / 0.072g, 1.8mmol) in 20mL CH 2 Cl 2 Stir for 15 minutes. Phenylthiochloroformate (0.258g, 1.5mmol / 0.103g, 0.6mmol) was added slowly over 5 minutes. TLC spot plate to track the reaction process, stop the reaction after the disappearance of the raw materials, add 10% HCl to the reaction solution to neutralize the excess NaOH, shake and stand to separate the organic phase, and the aqueous phase with CH 2 Cl 2 Extract, combine the organic phases, wash with saturated brine, and dry over anhydrous sodium sulfate. After evaporation and concentration, the crude product was separated and purified by column chromatography (ethyl acetate:petrole...

Embodiment 2

[0035] In this example, using β-nitrostyrene and acetylacetone as substrates, the activity of the asymmetric Michael addition reaction catalyzed by calix[4]thiourea cyclohexanediamine derivatives I and II was confirmed. The experimental method is: Weigh β-nitrostyrene (0.5mmol, 0.075g), acetylacetone (1mmol, 0.100g) and catalyst (5mol% of β-nitrostyrene) into 0.48mL (V 甲苯 :V 水 =2: 1) in a test tube, stirred at 25°C, and reacted for 4 hours. The reaction was stopped, dichloromethane (2 mL) was added, the organic phase was extracted and separated, the aqueous phase was extracted with dichloromethane (2 mL), the organic phases were combined, washed with saturated brine (2 mL), and dried over anhydrous sodium sulfate. After separation by column chromatography (ethyl acetate:petroleum ether), the Michael addition product was obtained.

[0036] The results are shown in Table 1. It can be seen that when calix[4]thiourea cyclohexanediamine derivatives I and II are used as catalysts,...

Embodiment 3

[0043] In this embodiment, β-nitrostyrene and acetylacetone are used as substrates, and the main influencing factors of the asymmetric Michael addition reaction catalyzed by calix [4] thiourea cyclohexanediamine derivative I are solvent type, water / toluene The volume ratio, substrate ratio, catalyst dosage and reaction temperature were systematically studied.

[0044] The results are shown in Tables 2 and 3, and the experimental results numbered 9 in Table 3 are the best, so the best experimental conditions of the asymmetric Michael addition reaction of the calix [4] thiourea cyclohexanediamine derivative I catalyzed are: The feed ratio of β-nitrostyrene and acetylacetone is 1:2, the catalyst dosage is 5mol%, the volume ratio of toluene to water is 2:1, and the reaction temperature is 25°C.

[0045]

[0046] Table 2 Effects of different solvents on the asymmetric Michael addition reaction catalyzed by calix[4]thiourea cyclohexanediamine derivative I

[0047]

[0048] Ta...

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Abstract

The invention relates to calix[4]thiourea diaminocyclohexane derivatives and a method thereof for catalyzing asymmetric Michael addition. An Michael addition catalytic reaction is performed on nitroolefin and 1,3-dicarbonyl ketone as raw materials, the calix[4]thiourea diaminocyclohexane derivatives as a phase transfer catalyst and water / toluene as a solvent, after the reaction, the solvent is concentrated, and a product is obtained by column chromatographic separation on silica gel. The calix[4]thiourea diaminocyclohexane derivatives adopt mild synthesis process conditions and are high in catalysis efficiency, water / toluene is taken as the solvent for asymmetric Michael addition catalyzed by the derivatives, reaction speed and yield can be increased greatly by water addition, and the catalyst has a phase transfer catalysis function. Better ee value can be obtained by the catalytic reaction at room temperature, and the derivatives have broad application prospect.

Description

technical field [0001] The invention relates to the technical field of catalytic organic synthesis, in particular to a calix[4]thiourea cyclohexanediamine derivative and a method for catalyzing an asymmetric Michael addition reaction thereof. Background technique [0002] In recent years, organic small molecule catalysis has become a hot research topic in the field of asymmetric catalysis because of its mild reaction conditions, environmental friendliness, etc., and meets the requirements of green chemistry. Chiral thiourea catalysts are used in many asymmetric All of them showed excellent catalytic effect. Initially, the weak Bronsted acidity of the thiourea group was used to form a hydrogen bond with the substrate and generate a stable reaction intermediate, thereby generating catalysis. With the in-depth exploration of organic catalytic reactions and inspired by the way of enzyme catalysis, a series of thiourea catalysts with multiple hydrogen bond donors have emerged. ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C335/18B01J31/02C07C201/12C07C205/45C07C205/53
CPCB01J31/0271B01J2231/4205C07C201/12C07C335/18C07C2601/14C07C2603/92C07C205/45C07C205/53
Inventor 李正义童洪笑陈远殷乐肖唐鑫孙小强
Owner CHANGZHOU UNIV
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