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Method for regulating and controlling structure of o-carborane derivative through preoccupation

A technology of carborane and derivatives, which is applied in the field of regulating the structure of carborane derivatives, can solve the problems of complex reaction system, increase the difficulty of product separation and purification, and reduce chemical selectivity, and achieve the effect of great application prospects

Inactive Publication Date: 2016-11-09
HARBIN INST OF TECH WUXI RES INST OF NEW MATERIALS +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] Due to the high activity of carborane monolithium salt, it is easy to convert into dilithium-substituted intermediates, and then generate disubstituted carborane derivatives, resulting in more complex reaction systems, lower chemoselectivity, and increased difficulty in product separation and purification.

Method used

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  • Method for regulating and controlling structure of o-carborane derivative through preoccupation
  • Method for regulating and controlling structure of o-carborane derivative through preoccupation

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0028] In a nitrogen atmosphere, add 851.2mg (5.902mmol) of 1,2-carborane and 20ml of benzene / ether (2:1) mixed solvent to a 100ml three-necked flask respectively, stir, and add n-butyllithium (11.804 mmol) n-hexane 5.50ml solution, continue stirring for 2h, add dimethyl tert-butylchlorosilane (892.8mg, 5.902mmol), continue stirring at 35°C for 2h, add paraformaldehyde 420.3mg (14.01mmol) at room temperature, 3h Finally, it was acidified with 10% hydrochloric acid solution, the solvent was evaporated by rotary evaporation, extracted with ether, the organic layer was washed three times with deionized water and saturated brine, dried over anhydrous magnesium sulfate, and subjected to column chromatography of petroleum ether: ethyl acetate = 1:1 For purification, dissolve it in 15ml of ether solution at -35°C, add 5.902mmol of tetrabutylammonium fluoride, and stir for 60min. After rotary evaporation of the solvent, the final product was obtained after extraction and vacuum drying...

Embodiment 2

[0031] In a nitrogen atmosphere, add 851.2mg (5.902mmol) of 1,2-carborane and 18ml of benzene / ether (2:1) mixed solvent to a 100ml three-necked flask respectively, stir, and add n-butyllithium (11.804 mmol) n-hexane 5.50ml solution, continue stirring for 4h, add triphenylchlorosilane (1.735g, 5.902mmol), continue stirring at 35°C for 4h, add paraformaldehyde 420.3mg (14.01mmol) at room temperature, after 3h, use 10% hydrochloric acid solution was acidified, the solvent was evaporated by rotary evaporation, extracted with ether, the organic layer was washed three times with deionized water and saturated brine, dried over anhydrous magnesium sulfate, purified by petroleum ether: ethyl acetate = 1:1 column chromatography, in Dissolve it in 15ml of ether solution at 0°C, add 5.902mmol of tetrabutylammonium fluoride, and stir for 30min. After rotary evaporation of the solvent, extraction and vacuum drying gave a colorless solid 1-hydroxymethyl-2-H-carborane with a yield of 70%.

...

Embodiment 3

[0034]In a nitrogen atmosphere, add 851.2 mg (5.902 mmol) of 1,2-carborane and 15 ml of a mixed solvent of benzene / ether (2:1) to a 100 ml three-necked flask, stir, and add n-butyllithium (11.804 mmol) n-hexane 5.50ml solution, continue stirring for 3h, add dimethyl tert-butylchlorosilane (892.8mg, 5.902mmol), continue stirring for 3h at 35°C, add oxetane (0.87ml, 13.20mmol) at room temperature ), after 3 hours, acidify with 10% hydrochloric acid solution, spin evaporate the solvent, extract with ether, wash the organic layer three times with deionized water and saturated brine, dry with anhydrous magnesium sulfate, pass through petroleum ether: ethyl acetate = 1:1 Purify by column chromatography, dissolve it in 15ml of ether solution at -76°C, add 5.902mmol of tetrabutylammonium fluoride, and stir for 30min. After rotary evaporation of the solvent, extraction and vacuum drying gave a colorless solid 1-hydroxypropyl-2-H-carborane with a yield of 70%.

[0035] Infrared analysi...

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Abstract

The invention discloses a method for regulating and controlling the structure of an o-carborane derivative through preoccupation. The method comprises the following steps: (1) subjecting o-carborane to lithiation to form a monolithium salt and then reacting the monolithium salt with a CH group protecting agent so as to quantitatively convert the o-carborane into C-H protected carborane; (2) activating C-H by using butyllithium and then carrying out functionalization of a second carbon position; and (3) carrying out deprotection by using tetrabutyl ammonium fluoride. According to the invention, the CH group protecting agent is introduced at first, then the group is subjected to functionalization, and finally deprotection of the group is carried out, so the structure of the o-carborane derivative is regulated and controlled through preoccupation; and thus, a monosubstituted or disubstituted o-carborane derivative is purposefully and selectively synthesized. The obtained monosubstituted or disubstituted o-carborane derivative can be applied to field of aerospace materials like high-temperature-resistant bonding materials and composite materials and has great application prospect in the fields like biological medicines, catalysts, supramolecular systems and high energy fuels.

Description

technical field [0001] The invention relates to the technical field of elemental organic chemistry, in particular to a method for regulating the structure of carborane derivatives through preoccupancy reactions. Background technique [0002] Carborane is an elemental organic compound composed of boron, hydrogen and carbon. It is generally divided into open type and closed type. Among them, open type has nest shape and network shape, while closed type generally refers to The cage structure is an icosahedron composed of two carbon atoms, ten boron atoms and twelve hydrogen atoms. The carborane structure with the largest number of caged carboranes and the most stable structure is an important raw material for boron chemistry. Brown won the Nobel Prize in Chemistry in 1979 for his discovery of the hydroboration reaction between unsaturated bonds and borane. Williams group and Greenwood group synthesized carborane and metalborane respectively, and Hawthorne et al synthesized met...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F5/02
CPCC07F5/027
Inventor 白永平李宁曲德智李卫东席丹殷晓芬
Owner HARBIN INST OF TECH WUXI RES INST OF NEW MATERIALS
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