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

Synthesis method of 1, 4, 7-triazacyclononane

A synthetic method, nonane technology, applied in the direction of organic chemistry, can solve the problems of low total yield, low three-step molar yield, pollution, etc., and achieve the effect of avoiding side reactions

Pending Publication Date: 2021-08-31
仪征市海帆化工有限公司
View PDF2 Cites 0 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0009] The first method has long steps, and the final deprotection needs to be carried out in a large amount of concentrated sulfuric acid at high temperature for a long time. The reaction generates a large amount of high-concentration waste sulfuric acid, and the waste sulfuric acid contains impurities such as p-toluenesulfonic acid that have been removed, which cannot be applied mechanically and causes pollution. serious
Although the conversion rate of each step reaction can reach more than 80%, the total yield is low, and the utilization rate of atoms is extremely low, and the production efficiency is low
[0010] The second method has short steps, but the reagent DMF-DMA used is expensive, and the three-step molar yield is very low
very expensive to produce

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
  • Synthesis method of 1, 4, 7-triazacyclononane
  • Synthesis method of 1, 4, 7-triazacyclononane
  • Synthesis method of 1, 4, 7-triazacyclononane

Examples

Experimental program
Comparison scheme
Effect test

example 1

[0024] In a 500ml four-neck flask equipped with a mechanical stirrer, an air condenser, a thermometer, a dropping funnel and a dry ice acetone bath, add 25.8g of N,N'-di(2-chloroethyl)ethylenediamine hydrochloride in sequence (0.1mol), 51.6g of carbon tetrachloride. Start stirring, and cool down to minus 50°C with a dry ice acetone bath.

[0025] Slowly add 48.8g (0.4mol) of DMAP in batches. When DMAP is added into the bottle, the system will exotherm. Control the feeding speed to ensure that the temperature does not exceed minus 40°C. After adding DMAP, when the temperature dropped to minus 50°C again, start to slowly add 5.7g (0.095mol) of anhydrous ethylenediamine dropwise, and control the rate of addition to ensure that the temperature does not exceed minus 45°C. After the dropwise addition was completed, the temperature was kept at minus 50°C to minus 45°C for 3 hours. After the heat preservation was completed, the cooling bath was removed, and the reaction was stirred ...

example 2

[0029] In a 500ml four-neck flask equipped with a mechanical stirrer, an air condenser, a thermometer, a dropping funnel and a dry ice acetone bath, add 25.8g of N,N'-di(2-chloroethyl)ethylenediamine hydrochloride in sequence (0.1mol), 51.6g of carbon tetrachloride. Start stirring, and cool down to minus 50°C with a dry ice acetone bath.

[0030] Slowly add 48.8g (0.4mol) of DMAP in batches. When DMAP is added into the bottle, the system will exotherm. Control the feeding speed to ensure that the temperature does not exceed minus 40°C. After the addition of DMAP, when the temperature dropped to minus 50°C again, slowly add 6 g (0.1 mol) of anhydrous ethylenediamine dropwise, and control the rate of addition to ensure that the temperature did not exceed minus 45°C. After the dropwise addition was completed, the temperature was kept at minus 35°C to minus 30°C for 3 hours. After the heat preservation was completed, the cooling bath was removed, and the reaction was stirred at ...

example 3

[0033] In a 2000ml four-necked flask equipped with a mechanical stirrer, an air condenser, a thermometer, a dropping funnel and a dry ice acetone bath, 200 g of N,N'-bis(2-chloroethyl)ethylenediamine hydrochloride ( 0.78mol), 400g carbon tetrachloride. Start stirring, and cool down to minus 50°C with a dry ice acetone bath.

[0034] Slowly add 380g (3.1mol) DMAP in batches. When DMAP is added into the bottle, the system will exotherm. Control the feeding speed to ensure that the temperature does not exceed minus 40°C. After adding DMAP, when the temperature dropped to minus 50°C again, start to slowly add 45g (0.75mol) of anhydrous ethylenediamine dropwise, and control the rate of addition to ensure that the temperature does not exceed minus 45°C. After the dropwise addition was completed, the temperature was kept at minus 50°C to minus 45°C for 3 hours. After the heat preservation was completed, the cooling bath was removed, and the reaction was stirred at room temperature ...

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 synthesis method of 1, 4, 7-triazacyclononane. The preparation method comprises the step of: carrying out condensation ring-closure reaction on N, N'-bis (2-chloroethyl) ethylenediamine hydrochloride and ethylenediamine at low temperature to obtain 1, 4, 7-triazacyclononane. According to the method, the reaction temperature ranges from -50 DEG C to -30 DEG C, and the molar ratio of N, N'-bis (2-chloroethyl) ethylenediamine hydrochloride to ethylenediamine is 1: (0.95-1). 4-dimethylaminopyridine (DMAP) is adopted as an acid-binding agent, and the molar ratio of the DMAP to the N, N'-bis (2-chloroethyl) ethylenediamine hydrochloride is (3.9-4.1): 1. Carbon tetrachloride is selected as a reaction solvent, and the mass ratio of the carbon tetrachloride to the N, N'-bis (2-chloroethyl) ethylenediamine hydrochloride is 2: 1. According to the process, other side reactions can be effectively avoided, the highest reaction yield can reach 78% or above, and the product purity can reach 94% or above.

Description

technical field [0001] The invention proposes a synthesis method of 1,4,7-triazacyclononane. Background technique [0002] 1,4,7-Triazacyclononane is an important coordination compound intermediate, which itself is a widely used organic intermediate and ligand. Important synthetic intermediates. At present, there is no published literature reporting this type of compound and its synthesis method. [0003] The molecular structural formula of 1,4,7-triazacyclononane is: [0004] [0005] There are many publicly reported synthesis methods of 1,4,7-triazacyclononane, which are basically classified into two methods according to the principle of the route. The first method is to prepare N-protected (p-toluenesulfonyl (Ts) or methylsulfonyl (Ms) or benzyl (Bn)) 1,4,7-triazacyclononane at high temperature in sulfuric acid Deprotection and neutralization give the product. Represented by the 5-step reaction described in PCT patent WO86 / 02352, the synthetic route is as follows:...

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): C07D255/02
CPCC07D255/02
Inventor 张燕邹从伟李付李靓牛伟
Owner 仪征市海帆化工有限公司
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