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Method for preparing 3-cyanoethyl-2-hydrocarbyl-4H-benzoxazine from bromoacetonitrile under blue light irradiation condition

A technology of irradiation conditions and benzoxazine, which is applied in the field of functionalization/cyclization reaction of alkenyl-containing compounds, can solve problems such as post-processing troubles, achieve mild reaction conditions, wide applicability, and simple and easy-to-obtain reaction raw materials Effect

Active Publication Date: 2019-08-30
CHANGZHOU UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, stoichiometric peroxides and copper salts need to be used in this reaction, which brings great trouble to the post-treatment of the reaction.

Method used

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  • Method for preparing 3-cyanoethyl-2-hydrocarbyl-4H-benzoxazine from bromoacetonitrile under blue light irradiation condition
  • Method for preparing 3-cyanoethyl-2-hydrocarbyl-4H-benzoxazine from bromoacetonitrile under blue light irradiation condition
  • Method for preparing 3-cyanoethyl-2-hydrocarbyl-4H-benzoxazine from bromoacetonitrile under blue light irradiation condition

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0023] Embodiment 1: prepare 4-methyl-2-phenyl-4-nitrile ethyl-(4 H )-1,3-Benzoxazine (3a)

[0024] (3-(4-methyl-2-phenyl-4H-benzo[d][1,3]oxazin-4-yl)propanenitrole)

[0025]

[0026] In the dried Schlenk tube, add the amide raw material N-(2-isopropenylphenyl)benzamide (0.1mmol, 23.7 mg), base: K 3 PO 4 (0.2 mmol, 42.4 mg), catalyst: tris(2-phenylpyridine) iridium Ir(ppy) 3 (0.002 mmol, 1.3 mg), bromoacetonitrile (0.2 mmol, 24 mg), acetonitrile 1 mL, replace the gas in the reaction tube with nitrogen three times, and finally fill the reaction tube with nitrogen, and place the above Schlenk tube in a 16 W blue Under the condition of LED light irradiation, stir for 24h. The reaction was terminated, and the reaction solution was quenched with 2 mL of saturated ammonium chloride, and extracted several times with ethyl acetate (4 mL × 5). The organic phases were combined, and the solvent was removed on a rotary evaporator. Finally, it was separated by silica gel column chrom...

Embodiment 2

[0028] Embodiment 2: Preparation of 4-methyl-2-phenyl-4-nitrile ethyl-(4 H )-1,3-Benzoxazine (3a)

[0029] (3-(4-methyl-2-phenyl-4H-benzo[d][1,3]oxazin-4-yl)propanenitrole)

[0030]

[0031] In the dried Schlenk tube, add the amide raw material N-(2-isopropenylphenyl)benzamide (0.1mmol, 23.7 mg), base: K 2 CO 3 (0.2 mmol, 27.6 mg), catalyst: tris(2-phenylpyridine) iridium Ir(ppy) 3 (0.002 mmol, 1.3 mg), bromoacetonitrile (0.2 mmol, 24 mg), acetonitrile 1 mL, replace the gas in the reaction tube with nitrogen three times, and finally fill the reaction tube with nitrogen, and place the above Schlenk tube in a 16 W blue Under the condition of LED light irradiation, stir for 24h. The reaction was terminated, and the reaction solution was quenched with 2 mL of saturated ammonium chloride, and extracted several times with ethyl acetate (4 mL × 5). The organic phases were combined, and the solvent was removed on a rotary evaporator. Finally, it was separated by silica gel col...

Embodiment 3

[0032] Embodiment 3: Preparation of 4-methyl-4-nitrile ethyl-2-(p-tolyl)-(4 H )-1,3-Benzoxazine (3b)

[0033] (3-(4-methyl-2-(p-tolyl)-4H-benzo[d][1,3]oxazin-4-yl)propanenitrole)

[0034]

[0035] In the dried Schlenk tube, add the amide raw material N-(2-isopropenylphenyl)-p-benzamide (0.1 mmol, 25.1 mg), base: K 3 PO 4 (0.2 mmol, 42.4 mg), catalyst: tris(2-phenylpyridine) iridium Ir(ppy) 3 (0.002 mmol, 1.3 mg), bromoacetonitrile (0.2 mmol, 24 mg), acetonitrile 1 mL, replace the gas in the reaction tube with nitrogen three times, and finally fill the reaction tube with nitrogen, and place the above Schlenk tube in a 16 W blue Stir for 24 h under LED light irradiation. The reaction was terminated, and the reaction solution was quenched with 2 mL of saturated ammonium chloride, and extracted several times with ethyl acetate (4 mL × 5). The organic phases were combined, and the solvent was removed on a rotary evaporator. Finally, after separation by silica gel column chr...

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Abstract

The invention discloses a method for preparing 3-cyanoethyl-2-hydrocarbyl-4H-benzoxazine from bromoacetonitrile under a blue light irradiation condition, and belongs to the technical field of alkenylbifunctionalization. The method comprises: adding tris(2-phenylpyridine)iridium, potassium phosphate or potassium carbonate, N-[2-isoalkenylaryl]amide, bromoacetonitrile and a solvent to a treated Schlenk pipe, placing the Schlenk pipe under blue LED light irradiation in a nitrogen atmosphere while stirring for 24 h, terminating the reaction solution with saturated brine, extracting, and carryingout column chromatography to obtain the product. According to the present invention, the 3-cyanoethyl-2-hydrocarbyl-4H-benzoxazine compound is constructed under the blue light LED light irradiation condition by using bromoacetonitrile as the cyanomethyl source, such that the method has advantages of simple and easily available reaction raw materials, simple and easily available catalyst, no requirement of excessive oxidizing agent and equivalent copper salt, mild reaction conditions, high product yield, simple operation, simple post-treatment and the like.

Description

technical field [0001] The invention relates to the technical field of alkenyl difunctionalization, in particular to the functionalization / cyclization reaction of alkenyl-containing compounds. Background technique [0002] Cyano groups are widely found in natural products, such as crops, dyes, and pharmaceuticals. Secondly, the cyano group is also an important organic intermediate, which can be easily converted into a variety of useful functional groups, for example: the cyano group can be converted into carboxyl, amide, ester, aldehyde, etc. Therefore, this type of compound has important application value in chemistry and biology. The further development of the synthesis method of cyano-containing compound not only has high scientific research value, but also has broad application prospects. (See: (a) Kleemann, A.; Engel, J.; Kutscher, B.; Reichert, D. Pharmaceutical Substance: Synthesis Patents, Applications , Georg Thieme Verlag, Stuttgart, 4th edn, 2001; (b) Z. Rappo...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D265/16C07D413/04
CPCC07D265/16C07D413/04
Inventor 孙松周聪成江于金涛董亚群
Owner CHANGZHOU UNIV
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