Synthetic method of aminoisoindole derivatives

A technology of indole derivatives and synthetic methods, which is applied in the field of organic synthetic chemistry, can solve the problems of harsh reaction temperature, inconsistency of atom economy and green chemistry development needs, poor compatibility of substrate amines, etc., and achieves wide sources and easy commercialization Purchase or preparation, the effect of mild reaction conditions

Active Publication Date: 2018-12-14
WENZHOU UNIVERSITY
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Problems solved by technology

This method requires pre-selected halogenation of the substrate, requires a wide variety of additives, and has poor step economy, which does not meet the needs of atom economy and green chemistry development.
Literature (Eur.J.Org.Chem.2016,453–458 and J.Am.Chem.Soc.2010,132,11473-11480) reported Zn-catalyzed and titanium-catalyzed 2-alkynyl-substituted benzonitrile derivatives, respectively A method for preparing aminoisoindole derivatives by addition and cyclization reaction with amines. Although this method does not require cumbersome additives, the reaction temperature is harsh and can only be carried out smoothly at 120 degrees, and the compatibility of the substrate amine is poor, and the aryl secondary Amines are not well compatible and have certain limitations

Method used

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  • Synthetic method of aminoisoindole derivatives
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  • Synthetic method of aminoisoindole derivatives

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0036] The preparation of Z-1-benzylidene-3-(1-pyrrolidinyl)-isoindole, the structural formula is as follows:

[0037]

[0038] Under nitrogen protection, add raw material 2-phenylethynyl benzonitrile (0.5mmol), tetrahydropyrrole (0.6mmol) and catalyst La[N(SiMe 3 ) 2 ] 3 (5mol%), toluene (3mL), reacted at 25°C for 6h, and the isolated yield of the product was 98%.

[0039] 1 H NMR (CDCl 3 ,400MHz,ppm):δ8.29(d,J=8.0Hz,2H),7.80(d,J=8.0Hz,1H),7.71(d,J=7.6Hz,1H),7.43-7.38(m, 3H), 7.31(t, J=7.6Hz, 1H), 7.22(t, J=7.6Hz, 1H), 6.62(s, 1H), 3.99(t, 4H), 2.07(s, 4H). 13 C NMR (CDCl 3 ,100MHz,ppm): δ164.0,148.5,145.0,137.8,132.1,130.4,128.4,126.9,126.5,122.2,119.9,112.3,49.7.48.1,26.7,24.4.

[0040] The preparation of E-1-benzylidene-3-(1-pyrrolidinyl)-isoindole, the structural formula is as follows:

[0041]

[0042] Under nitrogen protection, add raw material 2-phenylethynyl benzonitrile (0.5mmol), tetrahydropyrrole (0.6mmol) and catalyst La[N(SiMe 3 ) 2 ] 3 (5mol%), ...

Embodiment 2

[0045] The preparation of Z-1-benzylidene-N-methyl-N-phenyl-1H-isoindol-3-amine, the structural formula is as follows:

[0046]

[0047] Under nitrogen protection, add raw material 2-phenylethynyl benzonitrile (0.5mmol), nitrogen methyl aniline (0.6mmol) and catalyst La[N(SiMe 3 ) 2 ] 3 (5mol%), toluene (3mL), reacted at 25°C for 6h, and the isolated yield of the product was 94%.

[0048] 1 H NMR (CDCl 3,500MHz,ppm):δ8.22(d,J=7.5Hz,2H),7.66(d,J=7.5Hz,1H),7.37-7.31(m,5H),7.25(s,1H),7.20- 7.14(m,3H),6.86(t,J=7.5Hz,1H),6.66(s,1H),6.01(d,J=8.0Hz,1H),3.70(s,3H). 13 C NMR (CDCl 3 ,125MHz,ppm): δ165.3,147.8,145.2,144.7,137.4,131.7,130.8,129.7,128.5,128.1,127.7,127.5,127.2,126.6,123.0,119.5,114.9,41.9.

Embodiment 3

[0050] The preparation of Z-1-benzylidene-N-methyl-N-benzyl-1H-isoindol-3-amine, the structural formula is as follows:

[0051]

[0052] Under nitrogen protection, add raw material 2-phenylethynyl benzonitrile (0.5mmol), nitrogen methyl benzylamine (0.6mmol) and catalyst La[N(SiMe 3 ) 2 ] 3 (5mol%), toluene (3mL), react at 25°C for 6h, and the isolated yield of the product is 90%.

[0053] 1 H NMR (CDCl 3 ,500MHz,ppm):δ8.28(d,J=8.0Hz,2H),7.84(d,J=7.5Hz,1H),7.61(s,1H),7.42-7.36(m,7H),7.31( t,J=7.0Hz,1H),7.26-7.21(m,2H),6.69(s,1H),5.11(s,2H),3.48(s,3H). 13 C NMR (CDCl 3 ,125MHz,ppm): δ166.6,147.7,145.5,137.7,137.6,131.5,130.6,128.9,128.5,128.4,127.6,127.5,127.1,126.9,122.8,120.0,113.5,55.6,38.2.

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Abstract

The invention belongs to the technical field of organic synthesis chemistry, and particularly relates to a synthetic method of aminoisoindole derivatives. According to the invention, continuous carbon-nitrogen bond construction is catalyzed by rare earth, so that synthesis of aminoisoindole derivatives with diversified structures is realized. Specifically, a compound 2-phenylethynyl benzonitrile and secondary amine are used as raw materials, and the aminoisoindole derivatives are prepared under a rare-earth catalysis system. According to the method disclosed by the invention, the raw materialsare wide in source or are easy to prepare, the operation is simple and convenient, selectivity is controllable, the yield is high, conditions are mild, and universality is wide.

Description

technical field [0001] The invention belongs to the field of organic synthesis chemistry, and in particular relates to a synthesis method of aminoisoindole derivatives whose structures are diversified by continuous carbon-nitrogen bond construction. Background technique [0002] Aminoisoindole is an important class of organic compounds. It is not only an important ligand in organometallic catalytic reactions, but also widely used in the dye industry and photosensitive materials. Therefore, the development of diverse and efficient new methods for the synthesis of aminoisoindole has always been an important topic in organic synthetic chemistry. [0003] In the existing technology for preparing aminoisoindole, the traditional method mainly utilizes dehydration condensation of phthalonitrile and ammonia, and then reacts with different amines to prepare aminoisoindole derivatives. This method requires a stepwise reaction, which is inconvenient to operate and has a narrow scope o...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D209/44
CPCC07D209/44
Inventor 邵银林陈久喜叶鹏清程天行沈柯婷谢乐萍王祺
Owner WENZHOU UNIVERSITY
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