A kind of synthetic method of aminoisoindole derivative

A technology for indole derivatives and synthesis methods, applied in the field of organic synthesis chemistry, can solve the problems of poor step economy, harsh reaction temperature, incompatibility of secondary aryl amines and the like

Active Publication Date: 2021-09-14
WENZHOU UNIV
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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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  • A kind of synthetic method of aminoisoindole derivative
  • A kind of synthetic method of aminoisoindole derivative
  • A kind of synthetic method of aminoisoindole derivative

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0035] The preparation of Z-1-benzylidene-3-(1-pyrrolidinyl)-isoindole, the structural formula is as follows:

[0036]

[0037] 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%.

[0038] 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.

[0039] The preparation of E-1-benzylidene-3-(1-pyrrolidinyl)-isoindole, the structural formula is as follows:

[0040]

[0041] 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

[0044] The preparation of Z-1-benzylidene-N-methyl-N-phenyl-1H-isoindol-3-amine, the structural formula is as follows:

[0045]

[0046] 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%.

[0047] 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

[0049] The preparation of Z-1-benzylidene-N-methyl-N-benzyl-1H-isoindol-3-amine, the structural formula is as follows:

[0050]

[0051] 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%.

[0052] 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 specifically relates to a synthesis method of aminoisoindole derivatives. The invention realizes the synthesis of structurally diverse aminoisoindole derivatives through the construction of continuous carbon-nitrogen bonds catalyzed by rare earths. Specifically, aminoisoindole derivatives are prepared by using the compound 2-phenylethynylbenzonitrile and secondary amine as raw materials under a rare earth catalyst system. The method of the invention has wide sources of raw materials or easy preparation, simple operation, controllable selectivity, high yield, mild conditions and wide applicability.

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 Patents(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 UNIV
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