Unlock instant, AI-driven research and patent intelligence for your innovation.

Preparation method of 1,7-m-carborane dihydroxyl substituted derivatives

A carborane and dihydroxyl technology, which is applied in the field of preparation of 1,7-m-carborane dihydroxyl substituted derivatives, can solve problems such as expensive raw materials, difficult post-processing, incomplete reaction, etc.

Active Publication Date: 2021-11-16
ZHENGZHOU SIGMA CHEM
View PDF6 Cites 0 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] 1,7-m-carborane dihydroxyl substituted derivatives have high application value, but the existing synthesis methods have the following problems: ① raw materials are expensive, resulting in high cost
②The reaction is not complete and the yield is low
③There are many reaction by-products, difficult post-processing and low yield
Literature Xin Huang, Qiuhong Zhang, Zheng Meng, Jiangjiang Gu, Xudong Jia, Kai Xi, Greatly Enhanced Thermo-oxidative Stability of Polybenzoxazine Thermoset by Incorporation of m-Carborane (J.Polym.Sci.Pol.Chem.2015,53(8) , 973-980) reported the method of synthesizing 1,7-bismethylol-m-carborane with m-carborane, butyllithium and paraformaldehyde as raw materials. The raw materials used in this method are expensive and not suitable for industrialization
Document B.A.Izmaylov, V.A.Vasnev, G.D.Markova, On the reactions of haloidmagnesiummethyl m-carboranes with organoalkoxysilanes and chlorosilanes (Inorg.Chim.Acta, 2018, 471, 475-480) reported m-carborane, butyllithium and paraformaldehyde as The method for synthesizing 1,7-bishydroxymethyl-m-carborane from raw materials, the reaction is not complete and there are by-products, the post-processing is difficult and the yield is low
The problems existing in the existing synthetic methods limit the industrial production and application of 1,7-m-carborane dihydroxyl substituted derivatives

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
  • Preparation method of 1,7-m-carborane dihydroxyl substituted derivatives
  • Preparation method of 1,7-m-carborane dihydroxyl substituted derivatives
  • Preparation method of 1,7-m-carborane dihydroxyl substituted derivatives

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0033] The preparation method of the 1,7-bishydroxymethyl-m-carborane of the present embodiment comprises the following steps:

[0034]

[0035] (1) Add 12.2 g of decaborane and 25 g of acetonitrile into a reactor with a reflux device, stir and raise the temperature, and under reflux conditions, add 18.3 g of 1,4-diacetoxy-2-butyne shown in formula VIa , the reaction was carried out at 80°C, and the end point of the reaction was determined by thin-layer chromatography (developing agent: PE (petroleum ether): EA (ethyl acetate) = 5:1, Rf was 0.4), and the reaction was completed after 4 hours. Petroleum ether was extracted three times, and the compound represented by formula IIIa (26.5 g, yield 92.0%) was obtained after recovering petroleum ether.

[0036]

[0037] (2) In an inert environment, 26.5 g of the compound represented by formula IIIa was added into the rearrangement reactor at a constant rate, and the reaction was completed after reacting at 200° C. for 5 hours, ...

Embodiment 2

[0046]The preparation method of the 1,7-bishydroxymethyl-m-carborane of the present embodiment comprises the following steps:

[0047]

[0048] (1) Add 122.3 g of decaborane and 245 g of acetonitrile into a reactor with a reflux device, stir and raise the temperature, and under reflux conditions, add 367 g of 1,4-diacetoxy-2-butyne shown in formula VI, The reaction was carried out at 50°C, and the end point of the reaction was determined by thin-layer chromatography (developing agent: PE: EA = 5: 1, Rf 0.4). After 8 hours of reaction, the reaction was terminated, extracted three times with 150 mL of petroleum ether, and the solvent was recovered to obtain the formula Compound indicated by III (269.5 g, yield 93.5%).

[0049]

[0050] (2) In an inert environment, 269.5 g of the compound represented by formula III was heated to 270° C., and the reaction was completed after 4 hours of reaction, and separated by column chromatography.

[0051] The separation conditions of t...

Embodiment 3

[0058] The preparation method of the 1,7-bishydroxymethyl-m-carborane of the present embodiment comprises the following steps:

[0059]

[0060] (1) Add 122.3 g of decaborane and 611.5 g of dimethyl sulfide into a reactor with a reflux device, stir and raise the temperature, and under reflux conditions, add 1,4-diacetoxy-2- Butyne 611.5g, reacted at 60°C, determined the end point of the reaction by thin-layer chromatography (developer: PE:EA=5:1, Rf 0.4), ended the reaction after 10 hours, extracted 300mL*3 with petroleum ether , after recovering the solvent, the compound represented by formula III (270.9 g, yield 94.0%) was obtained.

[0061]

[0062] (2) In an inert environment, heat up 270.9 g of the compound shown in formula III to 300° C., finish the reaction after 1.5 hours of reaction, and separate by column chromatography (the conditions for column chromatography separation are the same as in Example 2) to obtain the compound obtained by formula IIa. For the com...

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 a preparation method of a 1,7-m-carborane dihydroxyl substituted derivative, belonging to the technical field of organic synthesis of carborane derivatives. The present invention provides a method for preparing 1,7-m-carborane dihydroxyl substituted derivatives, comprising the following steps: (1) reacting decaborane with a compound represented by formula VI, and isolating and obtaining a compound represented by formula III (2) in an inert environment, the compound shown in formula III is subjected to a rearrangement reaction at 200-400 ° C, and the compound shown in formula II is isolated; (3) the compound shown in formula II is subjected to ester hydrolysis reaction, separated The 1,7-m-carborane dihydroxy-substituted derivative represented by formula I is obtained. The method uses cheap and easy-to-obtain raw materials to prepare 1,7-m-carborane dihydroxyl-substituted derivatives, which can significantly reduce the production cost of 1,7-m-carborane dihydroxyl-substituted derivatives, and the reaction process is smooth and easy to control. The yield of the product is high, and it has good industrial application value.

Description

technical field [0001] The invention relates to a preparation method of 1,7-m-carborane dihydroxyl substituted derivatives, belonging to the technical field of organic synthesis of carborane derivatives. Background technique [0002] Carboranes can greatly improve the thermo-oxidative stability of polymers. Carborane-containing polymers such as polyetherketones, polysilanes, and polysiloxanes are advanced materials with unique thermal stability. Among the icosahedral carboranes, m-carboranes and p-carboranes were modified to synthesize different polymers. 1,7-m-carborane dihydroxyl-substituted derivatives are important intermediates of carborane polymers and have received more and more attention. [0003] 1,7-m-carborane dihydroxy-substituted derivatives have high application value, but the existing synthesis methods have the following problems: ① The raw materials are expensive, resulting in high costs. ②The reaction is not complete and the yield is low. ③There are many...

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): C07F5/05
CPCC07F5/05
Inventor 武小军胡孝伦杨勇申丽坤王英豪高永棋
Owner ZHENGZHOU SIGMA CHEM