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Synthesis method of B (4, 5) alkenyl substituted carborane derivative

A synthesis method, carborane technology, applied in the field of carborane synthesis, to achieve the effects of good compatibility, good universality, reaction selectivity and high yield

Active Publication Date: 2020-06-19
XIAN MODERN CHEM RES INST
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0005] The present invention proposes a synthetic method of B(4,5) alkenyl substituted carborane derivatives to solve the problem of how to synthesize B(4,5) alkenyl with high selectivity, high yield and good universality of reactants Technical Problems of Substituted Carborane Derivatives

Method used

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  • Synthesis method of B (4, 5) alkenyl substituted carborane derivative
  • Synthesis method of B (4, 5) alkenyl substituted carborane derivative

Examples

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Effect test

Embodiment 12

[0027] The synthesis of embodiment 12-n-hexyl-4,5-bis(methyl acrylate)-1,2-carborane

[0028] Take a 20mL Schlenk tube and put it into a magnet, add 55mg (0.2mmol) of 1-carboxy-2-n-hexyl-o-carborane, 4mg (0.02mmol) of palladium acetate, 133mg of silver acetate (0.8mmol), and 41mg of methyl acrylate (0.48mmol), then add 5mL of 1,2-dichloroethane, and react at 70°C on an electromagnetic heating stirrer for 18 hours. After the reaction, the solvent is evaporated and purified by column chromatography to obtain 2-n-hexyl 70 mg of yl-4,5-bis(methyl acrylate)-1,2-carborane, and the yield was 88%.

[0029] Structure Identification:

[0030] 1 H NMR (500MHz, deuterated chloroform, δ / ppm) δδ6.91(d, J=17.8Hz, 2H), 6.21(d, J=17.8Hz, 2H), 3.74(s, 7H), 2.26–2.17( m,2H),1.46–1.41(m,2H),1.30–1.23(m,6H),0.88(t,J=6.9Hz,3H). 13 C NMR (126MHz, deuterated chloroform, δ / ppm) δ166.12, 133.38, 75.38, 61.15, 51.67, 38.05, 31.20, 29.16, 28.49, 22.36, 13.88. 11 B NMR (160 MHz, deuterated chloroform...

Embodiment 2～13

[0034] Examples 2-13 Synthesize 2-n-hexyl-4,5-bis(methyl acrylate)-1,2-carborane according to the same method as in Example 1, and study by adjusting parameters such as additives, solvents and time The influence of reaction conditions on product yield, experimental result sees the following table:

[0035] Example additive solvent temperature time Yield 2 Silver oxide (0.8mmol) 1,2-Dichloroethane 70℃ 18h 58％ 3 Silver carbonate (0.8mmol) 1,2-Dichloroethane 70℃ 18h 73％ 4 Silver trifluoroacetate (0.8mmol) 1,2-Dichloroethane 70℃ 18h 65％ 5 Silver acetate (0.8mmol) 1,2-Dichloroethane 70℃ 18h 88％ 6 Copper acetate (0.8mmol) 1,2-Dichloroethane 70℃ 18h 35％ 7 Silver acetate (0.8mmol) N,N-Dimethylformamide 70℃ 18h <5％

Embodiment 14～27

[0037] Examples 14-27 Synthesize B(4,5) alkenyl-substituted carboranes according to the same method as in Example 2, and study the reaction conditions by adjusting the types of α, β unsaturated esters, ketones, and amides alkenylating reagents To the influence of product yield, experimental result sees the following table:

[0038] Example α, β unsaturated esters, ketones, amides alkenylating reagents Yield 14 ethyl acrylate 82 15 n-butyl acrylate 80％ 16 tert-butyl acrylate 85％ 17 Phenyl acrylate 77％ 18 benzyl acrylate 80％ 19 methyl vinyl ketone 72％ 20 1-octen-3-one 65％ 21 1-phenyl-2-propenyl-1-one 57％ 22 1-(4-Methyl-phenyl)-2-propenyl-1-one 42％ 23 1-(3-Methyl-phenyl)-2-propenyl-1-one 43％ 24 1-(2-Methyl-phenyl)-2-propenyl-1-one 55％ 25 1-(4-Methoxy-phenyl)-2-propenyl-1-one 63％ 26 N, N-2 methacrylamide 78％ 27 N-tert-butylacrylamide 82％

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Abstract

The invention provides a synthesis method of a B (4, 5) alkenyl substituted carborane derivative, which comprises the following steps of in the presence of a catalyst and an additive, carrying out decarboxylation cross-coupling reaction with 1-carboxyl-2-(substituted) o-carborane, alpha, beta unsaturated ester, ketone and an amide alkenylation reagent used as raw materials in a solvent to generateB (4, 5) alkenyl substituted o-carborane. The reactants involved in the invention have very good universality, and the functional groups of the substrate have very good compatibility; alpha, beta unsaturated esters, ketones and amides which are simple and easy to obtain are used as alkenylation reagents, so that the relative cost is relatively low; the method is high in reaction selectivity and yield, single in reaction system composition, simple in post-treatment and easy to implement.

Description

technical field [0001] The invention belongs to the technical field of carborane synthesis, and in particular relates to a synthesis method of B(4,5) alkenyl-substituted carborane derivatives. Background technique [0002] Carborane is a polyhedral closed cage structure, which has the characteristics of high calorific value, high boron content, good thermal stability and chemical stability, and is a kind of high burning rate catalyst with excellent performance. In addition, carboranes are used as metal ligands and neutron absorbing materials in the field of coordination chemistry and medicine; this type of compound is liquid at room temperature, and they not only play a role in regulating the burning rate in solid propellants, but also have Function of plasticizer. [0003] At present, the commonly used carborane burning rate catalysts include n-butyl carborane, n-hexyl carborane (NHC) and carboryl methyl propionate. The most studied is NHC, whose heat of combustion reache...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F5/02
CPCC07F5/027
Inventor 王谦吕剑张楚宜张建伟李娇毅杜咏梅
Owner XIAN MODERN CHEM RES INST
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