Diaryl acetylene compound and preparation method thereof

A technology for diarylacetylenes and compounds, which is applied in the field of diarylacetylenes and their preparation, can solve the problems of difficulty in controlling the singleness of products, unfavorable long-term storage, unfavorable purification and purification, etc., and achieves a wide range of substrate expansion, The post-processing is simple, efficient and environmentally friendly, and the preparation method is simple and convenient.

Pending Publication Date: 2022-07-15
上海泰坦科技股份有限公司
View PDF0 Cites 0 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Conventional Sonogashira coupling requires the use of various types of aryl acetylenes, and the market price of some of these aryl acetylenes is too high to be suitable for scale-up of the reaction
If such aryl acetylenes are synthesized, it is often necessary to first synthesize aryl acetylenes protected by silicon ethers, and then use an inorganic base to deprotect the two-step reaction, and the synthesized unprotected aryl acetylenes are often unstable to air, which is not conducive to long-term growth. time storage
In the past, the "one-pot" synthesis strategy of diaryl acetylene compounds often produced by-products, especially when synthesizing asymmetric diaryl acetylenes, it was difficult to control the singleness of the product, which was not conducive to the later stage of purification

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
  • Diaryl acetylene compound and preparation method thereof
  • Diaryl acetylene compound and preparation method thereof
  • Diaryl acetylene compound and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

preparation example Construction

[0048]

[0049] The reaction formula of the preparation method of the diarylacetylene compound of the present invention is:

[0050]

[0051] where R 1 and R 2 All are selected from one or more of chlorine, bromine, fluorine, trifluoromethyl, methyl, ethyl, nitro, aldehyde, methoxy, hydrogen, pyridyl, hydroxyl or methyl carboxylate, R 1 , R 2 Can be the same or different.

[0052] Specifically include the following steps:

[0053](1), in DMF, successively add iodoaromatic compounds, trimethylsilyl acetylene, metal catalyst and alkali lye, stir; Then add DBU, water and iodoaromatic compounds successively, raise temperature, continue to stir, get the mixture;

[0054] (2), after the reaction finishes, the mixed solution is filtered through diatomaceous earth to remove unnecessary metals, under stirring, add water and continue to stir, after a large amount of solids are separated out, filter, and the filter cake is washed with a large amount of water to remove residual ...

Embodiment 1

[0074] The preparation method of 1,2-bis(3-bromophenyl)acetylene of the present embodiment comprises the following steps:

[0075] (1), weigh 11.0g of 3-bromoiodobenzene into a 500mL three-necked flask, add 110mL of DMF, then add 4.21g of Trimethyl silyl acetylene, 0.44g of CuI, 0.39g of PdCl 2 (PPh 3 ) 2 and 14.25g of Et 3 N, nitrogen was replaced three times, and stirred at 60 °C for 3 h. Subsequently, 35.6 g of DBU, 0.28 g of deionized water and 11.0 g of 3-bromoiodobenzene were added in sequence, the temperature was raised to 80° C., and stirring was continued for 3 h.

[0076] (2), after the LC-MS monitoring reaction finishes, remove excess metal through diatomaceous earth filtration, under stirring, add twice the volume of water, continue stirring for 15min, after seeing a large amount of solid precipitation, filter, filter cake with After washing with a large amount of water to remove the residual solvent, the solid was vacuum-dried for 2 hours to obtain 10.0 g of ...

Embodiment 2

[0083] The preparation method of 1,2-bis(4-methylbenzene)acetylene of the present embodiment comprises the following steps:

[0084] (1), weigh 8.48g of 4-methyl iodobenzene into a 500mL three-necked flask, add 110mL of DMF, then add 4.21g of Trimethyl silyl acetylene, 0.44g of CuI, 0.39g of PdCl 2 (PPh 3 ) 2 and 14.25g of Et 3 N, nitrogen was replaced three times, and stirred at 60 °C for 3 h. Subsequently, 35.6 g of DBU, 0.28 g of deionized water and 8.48 g of 4-methyl iodobenzene were added in sequence, the temperature was raised to 80° C., and stirring was continued for 3 h.

[0085] (2), after the LC-MS monitoring reaction finishes, remove excess metal through diatomaceous earth filtration, under stirring state, add twice the volume of water, continue stirring for 10min, after seeing a large amount of solid precipitation, filter, filter cake with Wash with a lot of water to remove the residual solvent, and the solid is vacuum-dried for 1 h to obtain 5.8 g of the desi...

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 provides a diarylacetylene compound and a preparation method thereof, and the preparation method comprises the following steps: sequentially adding an iodo aromatic compound, trimethylsilylacetylene, a metal catalyst and alkali liquor into N, N-dimethylformamide, and stirring; then sequentially adding 1, 8-diazabicyclo [5, 4, 0] undec-7-ene, water and an iodo-aromatic hydrocarbon compound, raising the temperature, and continuously stirring to obtain a mixed solution; stirring, filtering, washing, and carrying out vacuum drying on the solid; the preparation method is simple and convenient, a series of symmetric or asymmetric diarylacetylene compounds can be efficiently synthesized through one-pot synthesis, step-by-step synthesis is not needed, use of expensive aryl acetylene raw materials and separation and purification of perishable aryl acetylene intermediates are avoided, the product is unique due to successive control of the feeding sequence, and the method is suitable for industrial production. The post-treatment is simple and environment-friendly.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, in particular to a diarylacetylene compound and a preparation method thereof. Background technique [0002] The alkyne derivative diphenylacetylene occupies an important position in organic synthesis. Many natural products, drug molecules and polymeric materials contain alkyne structures or are synthesized from simple alkyne compounds. Therefore, a large number of alkynes are synthesized. The derivative method came into being. The classical Sonogashira coupling is one of the most commonly used synthetic methods, that is, under the co-catalysis of palladium and copper, the coupling reaction of aryl halides and terminal alkynes to obtain disubstituted alkynes. Conventional Sonogashira coupling requires various types of arylacetylenes, and some of these arylacetylenes are too expensive in the market and are not suitable for scale-up of the reaction. If synthesizing such arylacetylenes, i...

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): C07C25/24C07C17/269C07C15/54C07C1/26C07C67/343C07C69/76C07C22/04C07C47/548C07C45/68C07C39/373C07C37/18C07C201/12C07C205/06C07D213/127C07D213/06
CPCC07C25/24C07C17/269C07C15/54C07C1/26C07C67/343C07C69/76C07C22/04C07C47/548C07C45/68C07C39/373C07C37/18C07C201/12C07C205/06C07D213/127C07D213/06
Inventor 谢应波张庆张华罗桂云曹云董斌
Owner 上海泰坦科技股份有限公司
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