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A method for preparing 3-nitrile ethyl-2-hydrocarbyl-4h-benzoxazine by bromoacetonitrile under blue light irradiation conditions

A technology of benzoxazine and irradiation conditions, 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: 2022-04-26
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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  • A method for preparing 3-nitrile ethyl-2-hydrocarbyl-4h-benzoxazine by bromoacetonitrile under blue light irradiation conditions
  • A method for preparing 3-nitrile ethyl-2-hydrocarbyl-4h-benzoxazine by bromoacetonitrile under blue light irradiation conditions
  • A method for preparing 3-nitrile ethyl-2-hydrocarbyl-4h-benzoxazine by bromoacetonitrile under blue light irradiation conditions

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 (0.1 mmol, 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 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, it was separated by silica gel column chromatography (eluen...

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 (0.1 mmol, 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 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, it was separated by silica gel column chromatograp...

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-nitrile ethyl-2-hydrocarbyl-4H-benzoxazine from bromoacetonitrile under the condition of blue light irradiation, and belongs to the technical field of alkenyl difunctionalization. Add tris(2-phenylpyridine)iridium, potassium phosphate or potassium carbonate, N-[2-isoenylaryl]amide, bromoacetonitrile, and solvent to the treated Schlenk tube, and place the Schlenk tube under nitrogen atmosphere. Stir under blue LED light for 24 hours. The reaction solution was terminated by saturated brine, then extracted, and the product was obtained by column chromatography. The present invention uses bromoacetonitrile as the source of nitrile methyl group for the first time, and constructs 3-nitrile ethyl-2-hydrocarbyl-4H-benzoxazine compound under the condition of blue LED light irradiation. The method has the advantages of simple and easy-to-obtain reaction raw materials and catalysts, no need for excessive oxidants and equivalent copper salts, mild reaction conditions, high product yield, simple operation and post-treatment processes, 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 Patents(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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