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Method for performing ring-opening for cyclohexylaziridine by carboxylic acid

A technology of heterocyclopropane and cyclohexane nitrogen, applied in the field of organic synthesis, can solve problems such as large excess input of potassium acetate, and achieve the effects of reduced price, low price and mild reaction conditions

Active Publication Date: 2013-01-16
TAIYUAN UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, in order to prevent side reactions, the input of potassium acetate is relatively large

Method used

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  • Method for performing ring-opening for cyclohexylaziridine by carboxylic acid
  • Method for performing ring-opening for cyclohexylaziridine by carboxylic acid
  • Method for performing ring-opening for cyclohexylaziridine by carboxylic acid

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0025] Add 50 mg of tosyl-activated cyclohexaneaziridine, 4.5 mg of KOH, 14 μL of acetic acid, and 1.0 mL of dimethyl sulfoxide into the test tube, heat to 35° C. and stir for 12 h. After the reaction, with 5% K 2 CO 3 The remaining acid was removed from the solution, and extracted three times with dichloromethane. The organic phases were combined, washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and evaporated to dryness under reduced pressure to obtain a crude product. After the crude product was purified by silica gel chromatography, the ring-opened product A was obtained with a yield of 98%.

[0026]

[0027] NMR spectrometer: Bruker AVANCE III 600MHz, solvent CDCl 3 , internal standard TMS. 1 H NMR data were collected at 600MHz, chemical shifts are in ppm, where CDCl 3 chemical shift( δ ) 7.27, coupling constant unit Hz; 13 C NMR data were collected at 150MHz under fully decoupled conditions, where CDCl 3 chemical shift( δ ) 77.0. ...

Embodiment 2

[0030] Add 50 mg of tosyl-activated cyclohexaneaziridine, 4.5 mg of KOH, 9 μL of formic acid, and 1.5 mL of N-methylpyrrolidone into the test tube, heat to 45° C. and stir for 4 h. After the reaction, with 5% K 2 CO 3The remaining acid was removed from the solution, and extracted three times with dichloromethane. The organic phases were combined, washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and evaporated to dryness under reduced pressure to obtain a crude product. After the crude product was purified by silica gel chromatography, the ring-opened product B was obtained with a yield of 64%.

[0031]

[0032] 1 H NMR (600MHz, CDCl 3 ): δ 1.11-1.24 (m, 4H), 1.66-1.70 (m, 2H), 2.00-2.02 (m, 2H), 2.42 (s, 3H), 3.23-3.28 (m, 1H), 4.64-4.68 ( td, J=10.2, 5.4Hz, 1H), 4.90 (m, 1H), 7.28-7.29 (d, J=8.4Hz, 2H), 7.53 (s, 1H), 7.73-7.74 (d, J=7.8Hz , 2H )ppm.

Embodiment 3

[0034] Add 50 mg of tosyl-activated cyclohexaneaziridine, 4 mg of NaOH, 36.6 mg of benzoic acid, and 1.2 mL of dimethyl sulfoxide into the test tube, heat to 55° C. and stir for 2 h. After the reaction, with 5% K 2 CO 3 The remaining acid was removed from the solution, and extracted three times with dichloromethane. The organic phases were combined, washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and evaporated to dryness under reduced pressure to obtain a crude product. After the crude product was purified by silica gel chromatography, the ring-opened product C was obtained with a yield of 98%.

[0035]

[0036] 1 H NMR (600MHz, CDCl 3 ): δ 1.28-1.48 (m, 4H), 1.69-1.76 (m, 3H), 2.00-2.04 (m, 1H), 2.18 (s, 3H), 2.22-2.24 (m, 1H), 3.31-3.32 ( m, 1H), 4.79-4.84 (td, J=10.2, 4.2 Hz, 1H), 5.04-5.05 (d, J=7.2, 1H), 6.90-6.92 (d, J=7.8, 2H), 7.35-7.38 (t, J=7.8 Hz, 2H), 7.53-7.58 (m, 3H), 7.75-7.76 (m, 2H)ppm.

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Abstract

The invention discloses a method for performing ring-opening for cyclohexylaziridine by a carboxylic acid. The method includes that in a polar aprotic solvent system, alkali metal type inorganic base is utilized as a catalyst, a monocarboxylic acid is utilized as a nucleophilic reagent, and the cyclohexylaziridine which is activated by tosyl is subjected to a ring-opening reaction. The method has the advantages that the ring-opening reaction is simple in process, the reaction condition is mild, the solvent is environment-friendly, the carboxylic acid is utilized as the nucleophilic reagent, atom economical requirement of green chemistry is met, the catalytic agent is cheap, and the catalytic activity is high.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, and relates to a ring-opening method of aziridine compounds. Background technique [0002] Aziridine is a widely used intermediate in organic synthesis, and its cyclopropane structure can undergo a series of nucleophilic ring-opening reactions for the synthesis of β - Substituted amino compounds, and then synthesize many amino alcohols, amino acids, alkaloids and β - Various biologically active compounds such as lactam, this property makes aziridine widely valued by researchers. [0003] Although ring-opening reactions of aziridines with various nucleophiles have been reported by several investigators, the ring-opening reactions of carboxylic acids with aziridines are surprisingly less reported. Exploring cheap and efficient ring-opening reactions of carboxylic acids and aziridines is still a considerable challenge for organic synthesis workers. [0004] In fact, stronger organic aci...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C311/20C07C303/40
Inventor 张朝峰李兴张帆常宏宏
Owner TAIYUAN UNIV OF TECH
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