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Axial chiral styrene tertiary amine thiourea catalyst as well as preparation method and application thereof

A styrene-based, tertiary thiourea technology, applied in the direction of organic chemical methods, chemical instruments and methods, physical/chemical process catalysts, etc., can solve the problems of poor catalytic effect and poor control of stereoselectivity, and achieve good stereo Selectivity, excellent catalytic effect, suitable for large-scale industrial production

Pending Publication Date: 2021-01-26
XUZHOU NORMAL UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The stereoselective control of these axial chiral tertiary thiourea urea catalysts in the prior art is not good, and the catalytic effect is poor

Method used

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  • Axial chiral styrene tertiary amine thiourea catalyst as well as preparation method and application thereof
  • Axial chiral styrene tertiary amine thiourea catalyst as well as preparation method and application thereof
  • Axial chiral styrene tertiary amine thiourea catalyst as well as preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0027] The synthetic route of the present embodiment is as follows:

[0028]

[0029] The specific steps are

[0030] Add 0.2mmol of the compound of formula 1 to 2ml of dichloromethane, then add 0.3mmol of pyridine and 0.24mmol of carbon dichloride in turn, react at 25°C for 1 hour, follow the reaction to the end by TLC, add 2ml of dichloromethane after concentration , 0.3mmol(S)-N 1 ,N 1 , 3-trimethylbutane-1,2-diamine, reacted at 25°C for 0.5 hours, TLC tracked the reaction to the end, concentrated and passed through silica gel column chromatography (dichloromethane with a volume ratio of 50:1 was used to remove the agent) / methanol mixture) to separate compounds of formula 3a and formula 4a.

[0031] The structural characterization data of product 3a are as follows:

[0032] yield:28% (34.3mg); yellow solid; m.p.81.6–81.9℃; [α] D 20 =+43.8(c 0.03, acetone); 1 H NMR(400MHz,DMSO)δ13.94(s,1H),8.50(s,1H),8.12–8.04(m,1H),7.61–7.56(m,2H),7.49–7.43(m,3H), 7.41–7.33(m,4H...

Embodiment 5

[0041] Add 0.1 mmol of p-methoxyphenyl-substituted o-methylenebenzoquinone (formula 5) and 0.006 mmol of catalyst 3d (the product in Example 4) to 1 ml of toluene, and lower the temperature to -50°C. Add 0.1 mmol of malononitrile, react at -50°C for 4 hours, follow the reaction to the end by TLC, concentrate and separate by silica gel column chromatography (the deagent uses a dichloromethane / methanol mixture with a volume ratio of 50:1), That is, the compound of formula 6 is obtained.

[0042] The structural characterization data of product 6 are as follows:

[0043] Yield: 90% (49.0mg); Yellow solid, m.p.102-103°C; [α] D 20 = -39.5(c 0.35, Acetone); 1 H NMR (400MHz, CDCl 3 )δ7.10(d, J=8.6Hz, 2H), 6.85(d, J=8.6Hz, 2H), 6.50(s, 1H), 6.34(s, 1H), 5.92(s, 1H), 5.89( s,1H),4.58(s,1H),4.54(s,2H),3.78(s,3H); 13 C NMR (100MHz, CDCl 3 )δ159.0,158.9,147.2,144.9,143.0,136.9,129.0,120.0,115.3,114.3,107.9,101.7,97.9,60.9,55.4,40.5; IR:2924,2189,1684,1507,1371,135,7cm -1 ;ESI FTMS ...

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Abstract

The invention discloses an axial chiral styrene tertiary amine thiourea catalyst as well as a preparation method and application thereof. The chemical structures of the axial chiral styrene tertiary amine thiourea catalyst are shown as formulas 3 and 4. The preparation method comprises the following steps: (1) putting a compound shown as a formula 1 and carbon dichloride sulfide serving as raw materials into dichloromethane, adding pyridine, stirring for reaction at 25 DEG C, and performing TLC tracking reaction until the reaction is finished; (2) concentrating the product obtained in the step(1), adding dichloromethane and a compound shown in a formula 2, stirring for reaction at 25 DEG C, and performing TLC tracking reaction until the reaction is finished; and (3) concentrating and purifying the product obtained in the step (2) to obtain the compound shown in the formula 3 and the formula 4. The catalyst disclosed by the invention is relatively good in stereoselectivity control andrelatively good in catalytic effect. The preparation method disclosed by the invention is simple in steps, the cost is reduced, and two catalysts with different configurations can be obtained in one step; and the method is mild in reaction condition, and the enantioselectivity is improved.

Description

technical field [0001] The invention relates to the field of organic synthesis chemistry, in particular to an axial chiral styrene-type tertiary thiourea amine catalyst, a preparation method and application thereof. Background technique [0002] Chiral tertiary thioaminourea catalysts are a class of widely used catalysts that can be used to catalyze various organic chemical reactions. For example, the document Org.Biomol.Chem., 2010,8,2117 reported the asymmetric [3+2] cyclization reaction catalyzed by a chiral tertiary thiocarbamide catalyst; the document Angew.Chem., Int.Ed., 2012, 51,2084 reported the asymmetric [4+2] cyclization reaction catalyzed by a chiral tertiary thiocarbamide catalyst. However, most of the chiral tertiary thioaminourea catalysts are carbon chiral central tertiary thioaminourea catalysts, and the axial chiral tertiary thioaminourea catalysts are rarely reported, and are limited to biaryl axial chiral tertiary thioaminourea catalysts. For example, ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/02C07D209/34C07D453/04C07D493/04
CPCB01J31/0244C07D209/34C07D453/04C07D493/04C07B2200/07
Inventor 石枫张宇辰谭伟刘思嘉陈科伟
Owner XUZHOU NORMAL UNIVERSITY
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