Method for generating C-N addition organic amine product by photocatalytic olefin addition amination reaction

An amination reaction and organic amine technology, which is applied in the field of photocatalytic olefin addition amination reaction to generate C-N addition organic amine products, can solve the problems of complex steps, low atom economy, low yield and the like, and achieves fast reaction rate , The effect of high product selectivity and high product yield

Active Publication Date: 2020-06-05
ZHEJIANG JIANYE CHEM +1
View PDF1 Cites 0 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Traditional synthesis of benzazepine skeletons involves intramolecular cyclization of substituted aromatics and ring expansion of smaller rings [5,6] , not only the steps are complicated, the yield is low, but also expensive raw materials such as xanthene and boron trifluoride ether and toxic and harmful drugs are used, and a large number of by-products are produced in the synthesis process, and the atom economy is very low

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
  • Method for generating C-N addition organic amine product by photocatalytic olefin addition amination reaction
  • Method for generating C-N addition organic amine product by photocatalytic olefin addition amination reaction
  • Method for generating C-N addition organic amine product by photocatalytic olefin addition amination reaction

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0036] Dissolve phthalimide (199.7mg, 1.36mmol), cyclohexene (1.5mL, 14.6mmol), iron tetraphenylporphyrin (2mg), triethylamine (0.5mL) and water (3mL) in anhydrous acetonitrile (26 mL). The internally cooled photoreaction bottle was kept at 30°C, protected by nitrogen, and reacted for 2 hours under the conditions of a 250W high-pressure mercury lamp. After the reaction is over, the solvent and excess alkene are distilled off under reduced pressure, and the crude product is extracted with dichloromethane, concentrated and then used for column chromatography separation column chromatography (silica gel, 200-300 mesh; developing agent, petroleum ether, ethyl acetate ester) to obtain 272.4mg of 1,3,4,4a,5,11a-hexahydro-6H-dibenzo[b,e]azepine-6,11(2H)-dione, from the HPLC spectral analysis Product yield and selectivity all reach 99.0% (the HPLC before crossing column sees image 3 ), separated by a chromatographic column (of the product 1 H NMR as Figure 4 , 5), the separation...

Embodiment 2

[0040] Phthalimide (200.3mg, 1.36mmol), 4-methyl-1-cyclohexene (0.25mL, 2.04mmol), tetraphenylporphyrin iron (2mg), triethylamine (4.0mL ) and water (3 mL) were dissolved in anhydrous acetonitrile (25 mL). The internally cooled photoreaction bottle was kept at 30°C, protected by nitrogen, and reacted for 2 hours under the conditions of a 250W high-pressure mercury lamp. 1,3,4,4a,5,11a-hexahydro-6H-dibenzo[b,e]azepine-6,11(2H)-dione was obtained, the HPLC yield was 93.1%, and the selectivity was 93.1% (HPLC of crude product such as Figure 6 ).

[0041]

[0042] 2-Methyl-1,3,4,4a,5,11a-hexahydro-6H-dibenzo[b,e]azepine-6,11(2H)-dione

Embodiment 3

[0044] Phthalimide (203.0mg, 1.36mmol), tetramethylethylene (0.25mL, 2.04mmol), tetraphenylporphyrin iron (2mg), triethylamine (4.0mL) and water (3mL) Dissolve in anhydrous acetonitrile (25 mL). The internally cooled photoreaction bottle was kept at 30°C, protected by nitrogen, and reacted for 2 hours under the conditions of a 250W high-pressure mercury lamp. 3,3,4,4-Tetramethyl-3,4-dihydro-1H-benzo[c]azepine-1,5(2H)-dione was obtained with an HPLC yield of 94.3% and a selectivity of 94.3% % (HPLC of crude product such as Figure 7 ,).

[0045]

[0046] 3,3,4,4-Tetramethyl-3,4-dihydro-1H-benzo[c]azepine-1,5(2H)-dione

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 relates to the technical field of organic amine synthesis, in particular to a method for generating a C-N addition organic amine product through a photocatalytic olefin addition amination reaction. The method comprises the steps that phthalimide and olefin react under the illumination condition with metalloporphyrin or phthalocyanine as a photosensitizer and organic amine as a cocatalyst under N2 protection, and the C-N addition product is generated. According to the method, the product selectivity and the product yield are high and can reach 99% at most, the product is only theC-N addition organic amine product, the reaction rate is high, and treatment after reaction is easy.

Description

technical field [0001] The invention relates to the technical field of organic amine synthesis, in particular to a method for generating C-N addition organic amine products through photocatalytic olefin addition amination reaction. Background technique [0002] In the fine chemical research and production process, organic amines are important organic intermediates, mainly used in pesticides, medicines, rubber accelerators, dyes and colorants, mineral flotation agents, polymerization catalysts and stabilizers, etc. The method of using olefins as raw materials to add ammonia or amines to obtain the required new amines has the advantages of high atom utilization and no by-products. However, theory and practice have shown that the activation energy of this type of addition reaction is very high, and the two cannot react directly without destroying other bonds, so a catalyst must be used. At present, the commonly used catalysts are various acids. The raw materials of this proces...

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): C07D223/20C07D223/16
CPCC07D223/16C07D223/20
Inventor 周新锐冯烈朱世豪陈云斌许京伟刘尚文金波
Owner ZHEJIANG JIANYE CHEM
Who we serve
  • R&D Engineer
  • R&D Manager
  • IP Professional
Why Eureka
  • Industry Leading Data Capabilities
  • Powerful AI technology
  • Patent DNA Extraction
Social media
Try Eureka
PatSnap group products

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

© 2024 PatSnap. All rights reserved.Legal|Privacy policy|Modern Slavery Act Transparency Statement|Sitemap