Looking for breakthrough ideas for innovation challenges? Try Patsnap Eureka!

Synthetic method of benzindole derivative

A technology for benzoindole derivatives and synthesis methods, which is applied in the field of synthesis of benzoindole derivatives, can solve problems such as single catalyst, harsh reaction conditions, etc., and achieves strong substrate applicability, stable raw materials, and high yield Effect

Active Publication Date: 2018-12-21
陕西源之锦生物科技有限公司
View PDF2 Cites 0 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The traditional method of forming benzindole compounds is to use naphthylamine and alkenes through C-H bond activated cyclization [Wang, X.W.; Li, X.T.; Xiao, J.; Jiang, Y.; Li, X.W.synlett2012,23, 1649.], but this type of method often requires harsh reaction conditions, such as the need to react under the protection of an inert gas, and the catalyst used is relatively simple

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
  • Synthetic method of benzindole derivative
  • Synthetic method of benzindole derivative
  • Synthetic method of benzindole derivative

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0063] Preparation of Ethyl 2-acetyl-1,2-dihydrobenzo[c,d]indole-2-carboxylate

[0064] Dissolve 0.1 mmol of naphthylamine in 2 mL of H 2 In the Shrek tube of O, add 0.2mmol ethyl diazoacetoacetate, add 0.3mL good solvent ethanol to promote dissolution, and add 0.005mmol [RuCl 2 (p-cymene)] 2 As a catalyst, 0.025mmol cesium acetate was used as an additive, heated and stirred at 65°C for 16 hours, and the progress of the reaction was monitored by TLC. After the reaction was complete, it was extracted three times with 5mL of dichloromethane, the combined organic phase was concentrated, and separated by silica gel column chromatography. Obtain 19.2mg yellow oily compound, productive rate is 76%, and the product structural formula of gained is as follows:

[0065]

[0066] Such as figure 1 with figure 2 Shown, product NMR characterization: 1 H NMR (400MHz, CDCl 3 )δ=8.91(s,1H),8.24(d,J=8.2Hz,1H),7.92(d,J=8.1Hz,1H),7.73(t,J=7.5Hz,1H),7.62(t, J=7.6Hz, 1H), 7.37(d, J=8.6Hz...

Embodiment 2

[0068] Preparation of Ethyl 2-acetyl-6-bromo-1,2-dihydrobenzo[c,d]indole-2-carboxylate

[0069] Dissolve 0.1 mmol of 4-bromo-1-naphthylamine in 2 mL of H 2 In the Shrek tube of O, add 0.2mmol ethyl diazoacetoacetate, add 0.3mL good solvent ethanol to promote dissolution, and add 0.005mmol [RuCl 2 (p-cymene)] 2 As a catalyst, 0.025mmol cesium acetate was used as an additive, heated and stirred at 65°C for 16 hours, and the progress of the reaction was monitored by TLC. After the reaction was complete, it was extracted three times with 5mL of dichloromethane, the combined organic phase was concentrated, and separated by silica gel column chromatography. Obtain 19.5mg yellow oily compound, productive rate is 59%, and the product structural formula of gained is as follows:

[0070]

[0071] Such as image 3 with Figure 4 Shown, product NMR characterization: 1 H NMR (400MHz, CDCl 3 )δ=9.20(s,1H),8.32(d,J=7.7Hz,1H),8.15(d,J=8.3Hz,1H),7.92(t,J=8.3Hz,1H),7.75(t, J=8.1Hz, 1H...

Embodiment 3

[0073] Preparation of Ethyl 2-acetyl-6-amino-1,2-dihydrobenzo[c,d]indole-2-carboxylate

[0074] Dissolve 0.1 mmol of 4-amino-1-naphthylamine in 2 mL of H 2 In the Shrek tube of O, add 0.2mmol ethyl diazoacetoacetate, add 0.3mL good solvent ethanol to promote dissolution, and add 0.005mmol [RuCl 2 (p-cymene)] 2 As a catalyst, 0.025mmol cesium acetate was used as an additive, heated and stirred at 65°C for 16 hours, and the progress of the reaction was monitored by TLC. After the reaction was complete, it was extracted three times with 5mL of dichloromethane, the combined organic phase was concentrated, and separated by silica gel column chromatography. Obtain 17.7mg yellow oily compound, productive rate is 47%, and the product structural formula of gained is as follows:

[0075]

[0076] Such as Figure 5 with Image 6 Shown, product NMR characterization: 1 H NMR (400MHz, CDCl 3 )δ=8.62(s,1H),7.37(dd,J=8.3,5.5Hz,2H),7.28(t,J=7.8Hz,1H),7.20(s,1H),6.91–6.88(m,1H ),5.85(...

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 synthetic method of a benzindole derivative. The synthetic method comprises the following steps of adding naphthylamine, a diazo compound, a catalyst and an additive in a solvent, then performing separation and purification after C-H bond activation and cyclization to obtain benzindole. The synthetic method provided by the invention uses a ruthenium catalyst in reaction of directing insertion of diazo carbine with a directing gene for the first time, is moderate in condition without protection of inert gas, is environmentally friendly in solvent and has relatively strong substrate applicability and good yield.

Description

technical field [0001] The invention belongs to the field of organic synthesis, and in particular relates to a synthesis method of benzindole derivatives. Background technique [0002] Benzindole compounds are an important class of fused heterocyclic skeletons in organic chemistry, and have important prospects in luminescent materials and medicine. The traditional method of forming benzindole compounds is to use naphthylamine and alkenes through C-H bond activated cyclization [Wang, X.W.; Li, X.T.; Xiao, J.; Jiang, Y.; Li, X.W.synlett2012,23, 1649.], but this kind of method often requires harsh reaction conditions, such as the need to react under the protection of inert gas, and the catalyst used is relatively simple. Contents of the invention [0003] The object of the present invention is to provide a kind of synthetic method of benzindole derivative, to overcome the defective that above-mentioned prior art exists, the present invention is reaction raw material with nap...

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
IPC IPC(8): C07D209/90C07D487/06
CPCC07D209/90C07D487/06
Inventor 张金汪小钢杨秀芳马养民
Owner 陕西源之锦生物科技有限公司
Who we serve
  • R&D Engineer
  • R&D Manager
  • IP Professional
Why Patsnap Eureka
  • Industry Leading Data Capabilities
  • Powerful AI technology
  • Patent DNA Extraction
Social media
Patsnap Eureka Blog
Learn More
PatSnap group products

Browse by: Latest US Patents, China's latest patents, Technical Efficacy Thesaurus, Application Domain, Technology Topic, Popular Technical Reports.

© 2024 PatSnap. All rights reserved.Legal|Privacy policy|Modern Slavery Act Transparency Statement|Sitemap|About US| Contact US: help@patsnap.com