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

Azadibenzocyclooctine compounds and preparation methods thereof

A technology of benzocyclooctyne and benzocyclooctyne hydrochloride, which is applied in the field of organic chemical synthesis, can solve problems that have not been reported, and achieve the effects of easy to obtain raw materials, simple raw materials, convenient post-treatment and easy operation

Inactive Publication Date: 2016-07-27
CHENGDU LIKAI CHIRAL TECH
View PDF8 Cites 0 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the currently reported synthetic azadibenzocyclooctyne compounds are all compounds with substituents on nitrogen, and different substituents need to be made from the raw materials at the forefront of the synthetic route, and there is no substitution on the nitrogen atom. The synthesis of azadibenzocyclooctines based on

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
  • Azadibenzocyclooctine compounds and preparation methods thereof
  • Azadibenzocyclooctine compounds and preparation methods thereof
  • Azadibenzocyclooctine compounds and preparation methods thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0058] Synthesis of the following compounds

[0059]

[0060] Add 40g of the compound 5-dibenzocycloheptenone represented by formula (II), 67.4g of hydroxylamine hydrochloride into a 1L round bottom flask, then add 480mL of absolute ethanol, 104mL of pyridine, heat and reflux for 15h; monitor the reaction by TLC After completion, cool to room temperature, dilute the system with 100mL ethyl acetate, add 500mL 1M hydrochloric acid, stir for half an hour; ), the organic phase was dried with anhydrous sodium sulfate, filtered, and concentrated to obtain 41.3 g of the above compound as a white solid, with a yield of 96%.

Embodiment 2

[0062] Synthesis of the following compounds

[0063]

[0064] Add 48g of compound 3,7-difluoro-5-dibenzocycloheptenone and 68g of hydroxylamine hydrochloride to a 1L round-bottomed flask, then add 500mL of absolute ethanol and 104mL of pyridine, heat and reflux for 15h; monitor the reaction by TLC After completion, cool to room temperature, dilute the system with 100mL ethyl acetate, add 500mL 1M hydrochloric acid, stir for half an hour; ), the organic phase was dried with anhydrous sodium sulfate, filtered, and concentrated to obtain 49.1 g of the above compound as a white solid, with a yield of 95%.

Embodiment 3

[0066] Synthesis of the following compounds

[0067]

[0068] Prepare Eaton's reagent: 25g of phosphorus pentoxide is dissolved in 200mL of methanesulfonic acid.

[0069] Add 41.3 g of the compound represented by formula (IIIa) into a 500 mL round bottom flask, and add the above-mentioned Eaton reagent in one batch under the protection of argon. At this point, the system immediately turned dark red, and then it was placed at 100° C. and stirred for half an hour. The reaction solution was directly poured into 1L of ice-water mixture, and a white solid was precipitated. After filtration, the filter cake was washed with water 2 to 3 times, and dried under an infrared lamp to obtain 41.2 g of a white powdery solid, namely the above compound, with a yield of 99.8%.

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 heterocyclic nitrogen-dibenz-cyclooctyne class compound and a preparation method of the heterocyclic nitrogen-dibenz-cyclooctyne class compound, and belongs to the field of organic chemical synthesis. The structural general formula of the compound is shown in the formula I. 5-dibenz cycloheptene ketene serves as a starting material, final end product heterocyclic nitrogen-dibenz-cyclooctyne hydrochloride is obtained through the reactions of oximation, Beckmann rearrangement, amid reduction, protection, addition, debromination, deprotection and the like, and the total yield is higher than 73.6%. The raw material is easy to obtain, after-treatment is convenient and easy to operate, and the total yield is high. The heterocyclic nitrogen-dibenz-cyclooctyne class compound without a substituent on nitrogen atoms is synthezied for the first time, a novel method can be provided for synthesizing a heterocyclic nitrogen-dibenz-cyclooctyne class compound with different substituents on the nitrogen atoms, especially for synthesizing multiple heterocyclic nitrogen-dibenz-cyclooctyne class compounds with the different substituents on the nitrogen atoms, wherein the heterocyclic nitrogen-dibenz-cyclooctyne class compounds are not easy to prepare through other methods, a product of the heterocyclic nitrogen-dibenz-cyclooctyne class compound can serve as the raw material, and H on nitrogen is replaced by the needed R base.

Description

technical field [0001] The invention relates to the field of organic chemical synthesis, in particular to an azadibenzocyclooctyne compound and a preparation method thereof. Background technique [0002] The 1,3-dipolar cycloaddition reaction catalyzed by Cu(I) has attracted extensive attention due to its good selectivity, fast reaction speed and high yield, and is often used in the biomedical field, such as for polyethylene glycol- Synthesis of protein bioconjugates. However, a small amount of Cu(I) often remains in the product of this type of reaction, and the remaining Cu(I) can be attached to the active site of the enzyme, thereby reducing the activity of the enzyme, or even inactivating the enzyme, and further harming the cells. produce toxic effects. At the same time, Cu(I) is prone to disproportionation reaction in aqueous environment, which makes the reaction rate decrease. Therefore, finding new 1,3-dipolar cycloaddition reactions without Cu(I) participation has ...

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): C07D225/08
CPCC07D225/08
Inventor 袁伟成游勇王振华岳登峰徐小英张晓梅
Owner CHENGDU LIKAI CHIRAL TECH
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