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Method for preparing benzodinitrogen compound by using gold complex

A technology of gold complexes and benzodiazepines, which is applied in the field of preparation of benzodiazepines, can solve problems such as catalyst instability, influence on catalytic efficiency, and long reaction time, and achieve simple and green preparation methods, wide application prospects, The effect of low catalyst dosage

Active Publication Date: 2021-07-16
SHANGHAI INST OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

This approach enables a more atom-economical synthesis, but uses a highly toxic mercury-containing catalyst
Liu in 2012 and Luo in 2014 reported the use of gold catalysts to replace mercury catalysts (J.Org.Chem.2012,77,4484; J.Organomet.Chem.2014,751,438), realizing the synthesis of o-phenylenediamine and Direct synthesis of benzodiazepines from alkynes However, they all require a higher reaction temperature, and the gold catalyst is easily deactivated at this temperature, which affects the catalytic efficiency.
In 2020, Liu et al. also reported a gold catalyst with catalytic activity at room temperature, but the catalyst was used in a large amount and had poor stability in the air, requiring higher reaction conditions (Chin.J.Org.Chem.2020 ,40,2520)
[0004] In summary, the synthesis of benzodiazepine Although the methods of compound-like compounds have been reported, each has its defects, such as unstable catalyst, high catalyst equivalent, additives required for reaction, long reaction time, high reaction temperature, etc., which limit its application.

Method used

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  • Method for preparing benzodinitrogen compound by using gold complex
  • Method for preparing benzodinitrogen compound by using gold complex
  • Method for preparing benzodinitrogen compound by using gold complex

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0031] Synthesis of gold complex 1:

[0032] At 0°C, add n-BuLi (2.2mmol) n-hexane solution dropwise to the ortho carborane o-C 2 B 10 h 12 (1.0mmol) in ether solution, continue stirring for 30 minutes after the dropwise addition, slowly rise to room temperature and continue to react for 30 minutes, then add halophosphine ClPPh 2 (2.2mmol), continue to react at room temperature for 2 hours, then add AuBr (1.0mmol) to the reaction system and continue to react at room temperature for 3 hours, after the reaction is over, stand and filter, dry the solvent under reduced pressure, and the crude product obtained is washed with diethyl ether , drained to obtain target product 1 (yield 81%), its reaction formula is:

[0033]

[0034] 1 H NMR (400MHz, CDCl 3 , 25°C): δ=7.69-7.63 (m, 8H), 7.51-7.42 (m, 12H). Elemental Analysis Theoretical Value C 26 B 10 h 30 P 2 AuBr: C 39.56, H 3.83; Found: C 39.51, H 3.90.

Embodiment 2

[0036] Synthesis of gold complex 2:

[0037] At 0°C, n-BuLi (2.5 mmol) in n-hexane was added dropwise to the ortho carborane o-C 2 B 10 h 12 (1.0mmol) ether solution, continue to stir for 30 minutes after the dropwise addition, slowly rise to room temperature and continue to react for 30 minutes, then add halophosphine ClP (4-MeO-C 6 h 4 ) 2 (2.5mmol), continue to react at room temperature for 2 hours, then add AuBr (1.0mmol) to the reaction system and continue to react at room temperature for 5 hours, after the reaction is over, stand and filter, and dry the solvent under reduced pressure, and the crude product obtained is washed with diethyl ether , drained to obtain the target product 2 (yield 83%), the reaction formula is:

[0038]

[0039] 1 H NMR (400MHz, CDCl 3 , 25°C): δ=7.80-7.73 (m, 8H), 7.63-7.55 (m, 8H), 3.37 (s, 12H). Elemental Analysis Theoretical Value C 30 B 10 h 38 o 4 P 2 AuBr: C 39.62, H 4.21; Found: C 39.66, H 4.28.

Embodiment 3

[0041] Synthesis of gold complex 3:

[0042] At 0°C, add n-BuLi (2.3mmol) n-hexane solution dropwise to the ortho carborane o-C 2 B 10 h 12 (1.0mmol) in ether solution, continue stirring for 30 minutes after the dropwise addition, slowly rise to room temperature and continue to react for 30 minutes, then add halophosphine ClP(4-NO 2 -C 6 h 4 ) 2 (3.0mmol), continue to react at room temperature for 2 hours, then AuBr (1.0mmol) is added to the reaction system at room temperature and continue to react for 4 hours, after the reaction is completed, stand and filter, dry the solvent under reduced pressure, and the crude product obtained is washed with ether , drained to obtain the target product 3 (yield 77%), the reaction formula is:

[0043]

[0044] 1 H NMR (400MHz, CDCl 3 , 25°C): δ=7.86-7.77 (m, 8H), 7.69-7.61 (m, 8H). Elemental Analysis Theoretical Value C 26 B 10 h 26 N 4 o 8 P 2 AuBr: C 32.21, H 2.70, N 5.78; Found: C 32.30, H 2.66, N 5.82.

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Abstract

The invention relates to a method for preparing a benzodinitrogen compound by using a gold complex, which comprises the following step of: reacting an o-phenylenediamine compound and alkyne as raw materials with a gold complex containing a diphosphine ortho-carborane ligand as a catalyst at room temperature to obtain the benzodinitrogen compound. Compared with the prior art, the method has the advantages that the gold complex containing the diphosphine ortho-carborane ligand is used as the catalyst to efficiently catalyze the reaction of the o-phenylenediamine compound and the alkyne to synthesize the benzodinitrogen compound, the dosage of the catalyst is low (about 1.0 mol%), the selectivity is good, the reaction condition is mild, the reaction can be carried out at room temperature, additives are not needed, the reaction rate is high, the yield is relatively high, the substrate range is wide, and the method has a wide application prospect in industry.

Description

technical field [0001] The present invention belongs to benzodiazepine The technical field of compound preparation relates to a method for preparing benzodiazepines by using gold complexes method of compounds. Background technique [0002] Benzodiazepine Plasma compounds are an important class of heterocyclic compounds with pharmacological activity. They have functions such as sedative, hypnotic, anti-inflammatory, and anti-neurotic properties. They not only have potential pharmacological activities, but also serve as important synthetic intermediates for some fused ring compounds body. Therefore, the study of simple and efficient benzodiazepine The synthetic method of the compound is of great significance. [0003] The traditional synthesis method is mainly prepared by condensation reaction of o-phenylenediamine and α, β-unsaturated ketone, β-halogenated ketone or ketone compound (Tetrahedron Lett.2008, 49, 5302; Chem.Eur.J. 2009, 15, 8834). However, such condens...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D243/12C07F1/12B01J31/24
CPCC07D243/12C07F1/12B01J31/2409B01J2531/18
Inventor 姚子健王洋石昱高永红
Owner SHANGHAI INST OF TECH
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