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Synthetic method of dihydropyrrole and pyrrole compounds

A technology of dihydropyrrole and synthesis method, applied in the direction of organic chemistry and the like, achieves the effects of high atom economy, environmental friendliness and simple synthesis method

Inactive Publication Date: 2016-06-29
SHAANXI NORMAL UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0008] The technical problem to be solved by the present invention is to overcome the shortcomings of existing dihydropyrrole compound synthesis methods, and provide a method for synthesizing dihydropyrrole and pyrrole compounds with simple operation, environmental friendliness and atom economy

Method used

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  • Synthetic method of dihydropyrrole and pyrrole compounds
  • Synthetic method of dihydropyrrole and pyrrole compounds
  • Synthetic method of dihydropyrrole and pyrrole compounds

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0021] Taking the synthesis of the dihydropyrrole compound shown in III-1 and the pyrrole compound shown in IV-1 as an example, its synthetic route and specific synthetic method are as follows:

[0022]

[0023] Add 87.9mg (0.462mmol) α, β-unsaturated ester shown in formula I-1, 79.1mg (0.462mmol) p-toluenesulfonamide, 5.4mg (0.00924mmol) trifluoromethanesulfonate successively in 10mL round bottom flask Lanthanum acid, 14.1mg (0.0925mmol) DBU, 49.0mg (0.462mmol) benzaldehyde, 0.25mL isopropanol, stirred at room temperature for 12 hours, then added 164.5mg (0.924mmol) NBS, stirred at room temperature for 2 hours, then added 51.2 mg (0.1386mmol) TBAI and 1.386mL1mmol / L potassium carbonate aqueous solution, heated to reflux for 3 hours to stop the reaction, cooled the reaction system to room temperature, filtered under reduced pressure, washed the solid with a small amount of dichloromethane several times, and combined the filtrate , and pour it into water, let stand to separa...

Embodiment 2

[0030] Taking the synthesis of the dihydropyrrole compound shown in III-2 and the pyrrole compound shown in IV-2 as an example, its synthetic route and specific synthetic method are as follows:

[0031]

[0032] In Example 1, the benzaldehyde used was replaced with equimolar p-tolualdehyde, and the other steps were the same as in Example 1 to obtain a white solid 4,5-dihydro-2-phenyl-5-(4-methanol Base) phenyl-1-(4-methylphenyl)sulfonyl-4-pyrrole-α-ethyl acetate (dihydropyrrole compound shown in formula III-2), its yield is 68%, structure The characterization data are as follows:

[0033] 1 HNMR (300MHz, CDCl 3 )δ: 7.29-7.35 (m, 4H, Ph), 7.15 (d, J = 8.1Hz, 2H, Ph), 7.03 (d, J = 7.8Hz, 2H, Ph), 6.91-6.99 (m, 5H, Ph), 6.66 (t, J=1.5Hz, 1H, CH), 5.91 (dd, J=5.4, 0.6Hz, 1H, CH), 5.84 (dd, J=5.4, 1.8Hz, 1H, CH), 3.96 -4.14(m, 2H, CH 2 ), 2.35(s, 3H, CH 3 ), 2.34 (s, 3H, CH 3 ), 1.12(t, J=7.2Hz, 3H, CH 3 ).

[0034] 13 CNMR (100MHz, CDCl 3 )δ: 162.01, 142.15, 139.12, ...

Embodiment 3

[0039] Taking the synthesis of the dihydropyrrole compound shown in III-3 and the pyrrole compound shown in IV-3 as an example, its synthetic route and specific synthetic method are as follows:

[0040]

[0041] In Example 1, the benzaldehyde used was replaced with equimolar p-methoxybenzaldehyde, and the other steps were the same as in Example 1 to obtain a white solid 4,5-dihydro-2-phenyl-5-(4- Methoxy) phenyl-1-(4-methylphenyl) sulfonyl-4-pyrrole-α-ethyl acetate (dihydropyrrole compound shown in formula III-3), its yield is 62% , the structural characterization data are as follows:

[0042] 1 HNMR (300MHz, CDCl 3 )δ: 7.29-7.41 (m, 5H, Ph), 7.16 (d, J = 8.4Hz, 2H, Ph), 6.93-7.01 (m, 4H, Ph), 6.75 (d, J = 8.4Hz, 2H, Ph), 6.66 (bs, 1H, CH), 5.93 (d, J=5.4Hz, 1H, CH), 5.82 (d, J=5.4Hz, 1H, CH), 3.99-4.14 (m, 2H, CH 2 ), 3.82 (s, 3H, OCH 3 ), 2.34 (s, 3H, CH 3 ), 1.12(t, J=7.2Hz, 3H, CH 3 ).

[0043] 13 CNMR (100Hz, CDCl 3 )δ: 162.03, 159.47, 142.17, 139.06, 138.36,...

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Abstract

The invention discloses a synthetic method of dihydropyrrole and pyrrole compounds. The method comprises: reacting Alpha,Beta-unsaturated ester as raw material with para toluene sulfonamide and aldehydes under the action of an organic small-molecular catalyst 1,8-diazabicycloundercane-7-ene or 1,5-diazabycyclo[4,3,0]one-5-ene without separating an intermediate product, directly adding N-bromosuccinimide and alkali, and enabling intramolecular cyclization under mild reaction conditions so as to produce multi-group substituted dihydropyrrole compounds difficult to prepare by a conventional method, with high yield and good stereoselectivity. The synthetic method is simple, environment-friendly and high in atomic economy, enables dihydropyrrole compounds to be quickly and efficiently synthesized with one kettle, and the synthesized dihydropyrrole compounds are dehydrogenized under the action of dichloro dicyane benzoquinone to directly obtain pyrrole compounds.

Description

technical field [0001] The invention belongs to the technical field of synthesis of dihydropyrroles and pyrrole compounds, and specifically relates to a method of constructing dihydropyrroles and pyrrole compounds using α, β-unsaturated esters as raw materials and under the action of organic small molecule tertiary amine catalysts Methods. Background technique [0002] Dihydropyrrole and its derivatives are the core skeleton structures of many natural products and active molecules, as well as reaction intermediates in many organic synthesis reactions. Therefore, its synthetic method has been widely concerned by chemists, and the common synthetic methods can be roughly divided into three categories: cycloaddition method, intramolecular cyclization method and other synthetic methods. [0003] The first [3+2] cycloaddition method to synthesize dihydropyrrole rings was proposed by Lu's research group in 1997. The reaction uses methyl 2,3-butadienoate as C 3 synthon, imine is ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D207/48
CPCC07D207/48
Inventor 柴永海刘爱云张敏康磊张琦冯颖乐
Owner SHAANXI NORMAL UNIV
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