Unlock instant, AI-driven research and patent intelligence for your innovation.

A method for preparing 3-phenyl-[1,2,4]triazol[4,3-a]pyridine compounds without metal catalysis

A metal-free catalyst and compound technology, applied in the direction of organic chemistry, can solve the problems of complete removal of toxic catalysts, many reaction steps, and low reaction efficiency, and achieve the prospect of large-scale industrial application, convenient post-processing, and easy-to-obtain raw materials Effect

Active Publication Date: 2021-08-24
JIYANG COLLEGE OF ZHEJIANG A & F UNIV
View PDF6 Cites 0 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the above synthetic methods have the disadvantages of many reaction steps, low reaction efficiency, and the need to completely remove toxic catalysts.

Method used

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
View more

Image

Smart Image Click on the blue labels to locate them in the text.
Viewing Examples
Smart Image
  • A method for preparing 3-phenyl-[1,2,4]triazol[4,3-a]pyridine compounds without metal catalysis
  • A method for preparing 3-phenyl-[1,2,4]triazol[4,3-a]pyridine compounds without metal catalysis
  • A method for preparing 3-phenyl-[1,2,4]triazol[4,3-a]pyridine compounds without metal catalysis

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0023] Embodiment 1: the preparation of product 4a

[0024]

[0025] At room temperature, 395 mg (5 mmol) of pyridine 1a, 390 mg (6 mmol) of sodium azide 2 and 530 mg (5 mmol) of benzaldehyde 3a were added to a 25 mL round-bottomed flask, followed by 15 mL of ether and 900 mg (10 mmol) of tert- Butyl hydroperoxide, stirred at 25°C for 6 hours. After the reaction is complete, add 15 mL of saturated aqueous sodium chloride solution to the system, extract 3 times with ethyl acetate, 10 mL each time, combine the organic phases, dry with anhydrous sodium sulfate, evaporate the solvent, and perform 200-300 mesh silica gel column chromatography The pure product of 4a was obtained (781 mg, 80% yield, pale yellow solid).

[0026] 1 H NMR (400MHz, CDCl 3 ):δ8.56(d,J=7.0Hz,1H),7.91(d,J=6.5Hz,2H),7.81(d,J=9.3Hz,1H),7.59-7.65(m,3H),7.41 -7.45(m,1H), 7.02(t,J=6.7Hz,1H).

[0027] 13 C NMR (100MHz, CDCl 3 ): δ150.0, 146.0, 129.9, 129.2, 128.0, 127.9, 126.6, 123.8, 115.6, 114.4.

Embodiment 2

[0028] Embodiment 2: the preparation of product 4b

[0029]

[0030] At room temperature, 395mg (5mmol) of pyridine 1a, 390mg (6mmol) of sodium azide 2 and 600mg (5mmol) of p-tolualdehyde 3b were added to a 25mL round bottom flask, and then 15mL of ether and 900mg (10mmol) of ) of tert-butyl hydroperoxide, stirred at 25°C for 6 hours. After the reaction is complete, add 15 mL of saturated aqueous sodium chloride solution to the system, extract 3 times with ethyl acetate, 10 mL each time, combine the organic phases, dry with anhydrous sodium sulfate, evaporate the solvent, and perform 200-300 mesh silica gel column chromatography The pure product of 4b was obtained (857 mg, 82% yield, pale yellow solid).

[0031] 1 H NMR (400MHz, CDCl 3 ): δ8.26(d, J=7.1Hz, 1H), 7.82(d, J=9.3 Hz, 1H), 7.72(d, J=8.2Hz, 2H), 7.39(d, J=7.9Hz, 2H ),7.24-7.29(m, 2H),6.85(t,J=6.4Hz,1H),2.47(s,3H).

[0032] 13 C NMR (100MHz, CDCl 3 ): δ140.6, 130.1, 128.3, 127.0, 124.0, 123.9, 122.8, 117.0, ...

Embodiment 3

[0033] Embodiment 3: the preparation of product 4c

[0034]

[0035] At room temperature, add 395mg (5mmol) of pyridine 1a, 390mg (6mmol) of sodium azide 2 and 670mg (5mmol) of 3,4-dimethylbenzaldehyde 3c into a 25mL round bottom flask respectively, and then add 15mL of diethyl ether in sequence and 900 mg (10 mmol) of tert-butyl hydroperoxide, and stirred at 25° C. for 6 hours. After the reaction is complete, add 15 mL of saturated aqueous sodium chloride solution to the system, extract 3 times with ethyl acetate, 10 mL each time, combine the organic phases, dry with anhydrous sodium sulfate, evaporate the solvent, and perform 200-300 mesh silica gel column chromatography The pure product of 4c was obtained (1038 mg, 93% yield, pale yellow solid).

[0036] 1 H NMR (400MHz, CDCl 3):δ8.28(d,J=7.1Hz,1H),7.82(d,J=9.3Hz,1H),7.41(s,1H),7.32-7.35(m,1H),7.25-7.29(m, 1H),7.05(d,J=8.3Hz,1H),6.85(t,J=7.3Hz,1H),3.97(s,3H),3.97(s,3H).

[0037] 13 C NMR (100MHz, CDCl 3 ): δ150.8,...

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

PUM

No PUM Login to View More

Abstract

The invention discloses a method for preparing 3-phenyl-[1,2,4]triazol[4,3-a]pyridine compounds without metal catalysis. The preparation method comprises: pyridine compounds, sodium azide and Benzaldehyde compounds, in an organic solvent medium, without transition metal catalysis, fully react under the promotion of peroxides to produce products, and the products are obtained by post-processing 3-phenyl-[1,2,4 ]triazol[4,3‑a]pyridine compounds; the reaction temperature is 25°C, the formula (I) R 1 One of the following: hydrogen, hydrocarbyl; R 2 It is selected from one of the following: hydrogen, halogen, hydrocarbon group, aryl group, trifluoromethyl group, etc.; the preparation conditions of the present invention are mild, and the reaction is carried out under normal pressure, normal temperature conditions, which saves costs and has low requirements for equipment; Catalyzed by a metal catalyst, the post-treatment is convenient; the solvent diethyl ether used has a low boiling point to save energy and meet environmental protection requirements.

Description

technical field [0001] The invention belongs to the technical field of preparation of pharmaceutical synthesis intermediates, and in particular relates to a method for preparing 3-phenyl-[1,2,4]triazol[4,3-a]pyridine compounds by metal-free catalysis. Background technique [0002] 3-Phenyl-[1,2,4]triazol[4,3-a]pyridine compounds are an important class of pharmaceutical synthesis intermediates, which have wide and important applications in the synthesis and pharmaceutical industries. 2-tert-butyl carbamate benzimidazole compounds and their complexes have good biological activity and can be used as drug intermediates to prepare 3-phenyl-[1,2,4]triazolo[4,3-a ] Pyridine derivatives are used to treat cancer, especially gastric cancer, esophageal cancer, NSCLC, melanoma and pancreatic cancer, and have very important medicinal value. Because of its very special structure, physiological activity and reactivity, etc. Its synthesis and application research has been a hotspot in org...

Claims

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

Application Information

Patent Timeline
no application Login to View More
Patent Type & Authority Patents(China)
IPC IPC(8): C07D487/04
CPCC07D487/04
Inventor 蔡荣荣韩鸿宽韩雨婷
Owner JIYANG COLLEGE OF ZHEJIANG A & F UNIV