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Method for synthesizing (E)-benzylidene spiropyrazole pyrrolizinone compound

A benzylidene spiropyrazole pyrroleazinone and compound technology are applied in the field of organic synthesis and can solve the problems of single compound type and the like

Inactive Publication Date: 2020-10-27
YANGZHOU UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

It can be seen from the analysis of the published literature that although there are many reports on the synthesis of pyrazolone derivatives, the reported synthesis methods and the types of synthesized compounds are relatively single

Method used

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  • Method for synthesizing (E)-benzylidene spiropyrazole pyrrolizinone compound
  • Method for synthesizing (E)-benzylidene spiropyrazole pyrrolizinone compound
  • Method for synthesizing (E)-benzylidene spiropyrazole pyrrolizinone compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0028] To prepare (E)-7'-benzylidene-3-methyl-1,2',3'-triphenyl-2',3',5',6',7',7a' with the following structural formula - Hexahydrospiro[pyrazole-4,1'-pyrrolazin]-5(1H)-ketone is an example, and its preparation method is as follows:

[0029]

[0030] Add 0.1311g (0.5mmol) 4-benzylidene-5-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one, 0.1590g (1.5mmol ) benzaldehyde, 0.0710g (1mmol) tetrahydropyrrole, then add 15mL toluene, then add 0.1200g (1mmol) acetic acid, react under the condition of heating and reflux for 14 hours, after the reaction is finished, the solvent is evaporated and concentrated, and the column is carried out by using a silica gel column. Pure (E)-7'-benzylidene-3-methyl-1,2',3'-triphenyl-2',3',5',6',7' can be obtained by chromatographic purification ,7a'-hexahydrospiro[pyrazole-4,1'-pyrrolazin]-5(1H)-one, its isolated yield is 58%, and its structural characterization data are as follows:

[0031] 1 H NMR (400MHz, CDCl 3 )δ: 7.46(d, J=7.6Hz, 3H, ArH), 7....

Embodiment 2

[0033] To prepare (E)-7'-(4-methylbenzylidene)-2',3'-bis(4-methylphenyl)-3-methyl-1-phenyl-2' with the following structural formula ,3',5',6',7',7a'-hexahydrospiro[pyrazole-4,1'-pyrrolazin]-5-(1H)-one as an example, its preparation method is as follows:

[0034]

[0035] In Example 1, the 4-benzylidene-5-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one used was used with an equimolar amount of 4-(4-methyl benzylidene)-5-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one replacement, the benzaldehyde used is replaced with p-tolualdehyde in an equimolar amount, the catalyst Acetic acid was replaced with p-toluenesulfonic acid, the dosage was 1mmol, and the other steps were the same as in Example 1 to obtain (E)-7'-(4-methylbenzylidene)-2',3'-bis(4-methylbenzene base)-3-methyl-1-phenyl-2',3',5',6',7',7a'-hexahydrospiro[pyrazole-4,1'-pyrrolizine]-5-( 1H)-ketone, its isolated yield is 10%, and the structural characterization data are as follows:

[0036] 1 H NMR (400MHz, CDCl 3 )δ:7.49...

Embodiment 3

[0038] To prepare (E)-7'-(2-methylbenzylidene)-2',3'-bis(2-methylphenyl)-3-methyl-1-phenyl-2' with the following structural formula ,3',5',6',7',7a'-hexahydrospiro[pyrazole-4,1'-pyrrolazin]-5-(1H)-one as an example, its preparation method is as follows:

[0039]

[0040] In Example 1, the 4-benzylidene-5-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one used was used with an equimolar amount of 4-(2-methyl 1.5 mmol of benzaldehyde used was replaced with 1 mmol of 2-methylbenzaldehyde, Reaction under the condition of heating and reflux for 16 hours, other steps are the same as Example 1, to obtain (E)-7'-(2-methylbenzylidene)-2',3'-bis(2-methylphenyl) -3-Methyl-1-phenyl-2',3',5',6',7',7a'-hexahydrospiro[pyrazole-4,1'-pyrrolizine]-5-(1H) -ketone, its isolated yield is 50%, and the structural characterization data are as follows:

[0041] 1 H NMR (400MHz, CDCl 3 )δ:7.49(d,J=7.6Hz,2H,ArH),7.30-7.27(m,1H,ArH), 7.25-7.22(m,2H,ArH),7.12-7.08(m,4H,ArH), 7.06-7.03(m,4H,ArH),7.01-6....

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Abstract

The invention discloses a method for synthesizing a (E)-benzylidene spiropyrazole pyrrolizinone compound. The method comprises the following step of: carrying out one-step reaction on tetrahydropyrrole, various substituted aromatic aldehydes and pyrazolone acetal in the presence of an organic solvent and a catalyst to obtain the (E)-benzylidene spiropyrazole pyrrolizinone compound. According to the method, an effective strategy of subjecting azomethine ylide which is generated by tetrahydropyrrole and benzaldehyde in situ and 4-benzal-5-methyl-2-phenyl-2, 4-dihydro-3H-pyrazole-3-one to 1, 3-dipolar cycloaddition to synthesize a complex spiro compound is adopted. Specifically, the azomethine ylide has a special [1, 3]hydrogen migration phenomenon, and can form the azomethine ylide with benzylidene substitution with excessive benzaldehyde. The raw materials used in the method are easy to obtain, anaerobic reaction conditions are not needed, a transition metal catalyst is not needed either, operation is easy and convenient, and an efficient, economical and applicable method is provided for synthesizing the (E)-benzylidene spiropyrazole pyrrolizinone compound.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, and relates to a method for synthesizing (E)-7'-benzylidene-hexahydrospiro[pyrazole-4,1'-pyrrolazin]-5(1H)-one. Background technique [0002] Pyrazoles and their derivatives represent a very important class of nitrogen-containing five-membered heterocyclic rings, which are widely used in medicinal chemistry, synthetic chemistry, coordination chemistry, dyes and functional materials (Fustero S., Sanchez-Roselio M., Barrio, P., et al. [J] Chem Rev., 2011, 111, 6984-7034). At the same time, among numerous synthetic pyrazole derivatives, many compounds have important medicinal value. Pyrazolodihydropyran derivative 1 has antibacterial, analgesic and antiplatelet activities, and celecoxib 2 is a COX-2 inhibitor (Mandha S.R., Siliveri S., Alla M., et al.[J] Bioorg. Med. Chem. Lett., 2012, 22, 5272-5278). [0003] [0004] Pyrazolin-5-one (ie, pyrazolone), as a very important member of t...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D487/20
CPCC07D487/20
Inventor 颜朝国方惠琳韩莹孙晶
Owner YANGZHOU UNIV
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