三种低熔点二异噁唑含能化合物的合成与表征
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摘要
为研究二异噁唑含能化合物的合成及性能,以二氯乙二肟、炔醇和炔溴为原料,经过[3+2]环化反应、硝化和叠氮化反应合成得到三种低熔点含能化合物:5,5′-二叠氮甲基-3,3′-二异噁唑(2)、3,3′-二异噁唑-5,5′-二亚甲基硝酸酯(4)和3,3′-二异噁唑-4,4′,5,5′-四亚甲基硝酸酯(6),总收率分别为66%,67%和64%。利用红外、核磁和元素分析对目标化合物和中间体进行了结构表征;探讨了—C+=N—O-和C≡C经1,3-偶极环加成反应构建二异噁唑的反应机理。利用DSC和TG研究了化合物(2)、(4)和(6)的热行为。化合物(2)、(4)和(6)的熔点分别为77.46,95.18℃和124.36℃,热分解起始温度分别为179.21,165.34℃和168.69℃。
To research the synthesis and performances of energetic compounds of bisisoxazole,three kinds of energetic com-pounds with low melting point,5,5′-bis(azidomethyl)-3,3′-biisoxazole(2),[3,3′-biisoxazole]-5,5′-diylbis-(methylene)dini-trate(4)and[3,3′-biisoxazole]-4,4′,5,5′-tetrayl-tetrakis(methylene)tetranitrate(6)were synthesized via[3+2]cyclization re-action,nitration and azidation,using dichloroglyoxime,alkynol and propargyl bromide as starting materials,with a yield of 66%,67% and 64%,respectively,and the structures of target compounds and intermediates were characterized by the means of IR,NMR and elemental analysis. The reaction mechanism of constructing bisisoxazole through two reactions of —C+=N—Oand C≡C with 1,3-dipolar cycloaddition was discussed. The thermal behavior of compounds(2),(4)and(6)were studied by DSC and TG. The melting temperature of compounds(2),(4)and(6)are 77.46,95.18 ℃ and 124.36 ℃. The starting tempera-ture of thermal decomposition are 179.21,165.34 ℃ and 168.69 ℃,respectively.
To research the synthesis and performances of energetic compounds of bisisoxazole,three kinds of energetic com-pounds with low melting point,5,5′-bis(azidomethyl)-3,3′-biisoxazole(2),[3,3′-biisoxazole]-5,5′-diylbis-(methylene)dini-trate(4)and[3,3′-biisoxazole]-4,4′,5,5′-tetrayl-tetrakis(methylene)tetranitrate(6)were synthesized via[3+2]cyclization re-action,nitration and azidation,using dichloroglyoxime,alkynol and propargyl bromide as starting materials,with a yield of 66%,67% and 64%,respectively,and the structures of target compounds and intermediates were characterized by the means of IR,NMR and elemental analysis. The reaction mechanism of constructing bisisoxazole through two reactions of —C+=N—Oand C≡C with 1,3-dipolar cycloaddition was discussed. The thermal behavior of compounds(2),(4)and(6)were studied by DSC and TG. The melting temperature of compounds(2),(4)and(6)are 77.46,95.18 ℃ and 124.36 ℃. The starting tempera-ture of thermal decomposition are 179.21,165.34 ℃ and 168.69 ℃,respectively.
引文
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[15]季文文,姜林,藤信焕,等.取代异(噁)唑甲酰基脲的合成及其抑菌活性[J].化学试剂,2010,32(1):63-65.JI Wen-wen,JIANG Lin,TENG Xin-huan,et al.Synthesis and antimicrmatic activities of substituted isoxazolylacylureasderiv-atives[J].Chemical Reagents,2010,32(1):63-65.
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[18]Phillip L P,Timothy U C,Christian G,et al.A click chemistry approach to 5,5′-disubstituted-3,3′-bisisoxazoles from di-chloroglyoxime and alkynes:luminescent organometalic iridi-um and rhenium bisisoxazole complexes[J].The Journal of Organic Chemistry,2013,78(14):7298-7304.
[19]Jiang Longqiang,Gao Tao,Li Zhi,et al.Highly regioselective-dipolar cycloadditions of nitrile oxides withα,β-acetylenical-dehydes[J].Tetrahedron Letters,2016,57(6):712-714.
[20]Kesornpun C,Aree T,Mahidol C,et al.Water-assisted nitrile oxide cycloadditions:synthesis of isoxazoles and stereoselec-tivesyntheses of isoxazolines and 1,2,4-oxadiazoles[J].Angewandte Chemie International Edition,2016,47(30):3997-4001.
[21]Minuti L F,Memeo M G.,Crespi S,et al.Fluorescent probes from stable aromatic nitrile oxides[J].European Journal of Organic Chemistry,2016,2016(4):821-829.
[22]Siadati S A.The effect of position replacement of functional groups on the stepwise character of 1,3-dipolar reaction of a nitrile oxide and an alkene[J].Verlag Helvetica Chimica Acta.2016,99(4):273-280.
[2]汪洪涛,周集义.NTO及其盐的制备、表征与应用[J].化学推进剂与高分子材料,2006,4(5):25-29.WANG Hong-tao,ZHOU Ji-yi.Preparation,characterization and application of NTO and its salts[J].Chemical Propellants&Polymeric Materials,2006,4(5):25-29.
[3]徐容,董海山,孙杰,等.4-氨基-1,2,4-三唑-NTO盐的晶体结构及性能[J].含能材料,2012,20(1):35-39.XU Rong,DONG Hai-shan,SUN Jie,et al.Crystal structure and properties of 4-amino-1,2,4-triazole NTO salt[J].Chinese Journal of Energetic Materials(Hanneng Cailiao),2012,20(1):35-39.
[4]郁卫飞,聂福德,黄辉,等.类球形NTO的制备及其表征[J].含能材料,2005,13(增刊):4-6.YU Wei-fei,NIE Fu-de,HUANG Hui,et al.Preparation and characterization of NTO spherical crystals[J].Chinese Journal of Energetic Materials(Hanneng Cailiao),2005,13(Suppl.):4-6.
[5]毕福强,肖川,许诚,等.1,1′-二羟基-5,5′-联四唑二羟胺盐的合成与性能[J].含能材料,2014,22(2):272-273.BI Fu-qiang,XIAO Chuan,XU Cheng,et al.Synthesis and properties of dihydroxylammonium 5,5′-bistetrazole-1,1′-di-olate[J].Chinese Journal of Energetic Materials(Hanneng Cailiao),2014,22(2):272-273.
[6]葛忠学,毕福强.高能不敏感含能材料-HATO[J].含能材料,2014,22(4):434-435.GE Zhong-xue,BI Fu-qiang.High energy insensitive energy compound-HATO[J].Chinese Journal of Energetic Materials(Hanneng Cailiao),2014,22(2):272-273.
[7]王小军,苏强,陈树森,等.聚能富氮化合物5,5-联四唑-1,1-二氧化物二羟铵合成工艺研究[J].火工品,2014(3):38-41.WANG Xiao-jun,SU Qiang,CHEN Shu-sen,et al.Synthesis of cumulative nitrogen rich compound of dihydro-xylammoni-um 5,5-bistetrazole-1,1-diolate(TKX-50)[J].Initiators&Pyrotechnics,2014(3):38-41.
[8]赵廷兴,田均均,李磊,等.5,5′-联四唑-1,1′-二氧二羟铵(TKX-50)50克量级制备放大工艺[J].含能材料,2014,22(6):744-747.ZHAO Ting-xing,TIAN Jun-jun,LI Lei,et al.Up-sizing 50grams-scale synthesis technology of dihydroxyl-ammonium 5,5′-bistetrazole-1,1′-diolate(TKX-50)[J].Chinese Journal of Energetic Materials(Hanneng Cailiao),2014,22(6):744-747.
[9]居平文,凌亦飞,谷玉凡,等.TKX-50合成方法改进[J].含能材料,2015,23(9):887-891.JU Ping-wen,LING Yi-fei,GU Yu-fan,et al.Improved synthe-sis of TKX-50[J].Chinese Journal of Energetic Materials(Hanneng Cailiao),2015,23(9):887-891.
[10]江玉亮,韩巧荣,周文龙,等.3-(2-羟基-4,6-二甲氧基苯基)-5-芳基异噁唑啉的合成及抑菌活性[J].高等学校化学学报,2013,34(9):2120-2124.JIANG Yu-liang,HAN Qiao-rong,ZHOU Wen-long,et al.Synthseis and antibacterial activities of some 3-(2-hydroxy-4,6-dimethoxyphenyl)-5-aryl-isoxazolines[J].Chemical Journal of Chinese Universities,2013,34(9):2120-2124.
[11]滕信焕,姜林,周少方,等.含异噁唑环的新型2,5-二取代-1,3,4-噁二唑的合成及其杀菌活性[J].合成化学,2012,20(1):73-75.TENG Xin-huan,JIANG Lin,ZHOU Shao-fang,et al.Synthe-sis and fungicidal activities of novel 2,5-disubstituted-1,3,4-oxadiazoles containing isoxazolering[J].Chinese Journal of Synthetic Chemistry,2012,20(1):73-75.
[12]张存彦,刘登科,孙长海,等.新型异噁唑衍生物的合成及其抗菌活性[J].合成化学,2012,20(4):425-429.ZHANG Cun-yan,LIU Deng-ke,SUN Chang-hai,et al.Synthe-sis and antibacterial activities of new isoxazolinederivatives[J].Chinese Journal of Synthetic Chemistry,2012,20(4):425-429
[13]刘冰妮,刘默,刘登科,等.新型异噁唑啉类化合物的合成及其抗肿瘤活性[J].合成化学,2011,19(6):734-736.LIU Bing-ni,LIU Mo,LIU Deng-ke,et al.Synthesis and an-ti-tumor activities of novel isoxazolecompounds[J].Chinese Journal of Synthetic Chemistry,2011,19(6):734-736.
[14]冯菊红,丁涛,荣霞,等.新型含异噁唑环的1,3,5-三嗪类衍生物的合成及其抗真菌活性[J].合成化学,2016,24(7):561-564.FENG Ju-hong,DING Tao,RONG Xia,et al.Synthesis and antifungal activities of novel 1,3,5-triazine derivatives contain-ing isoxazolering[J].Chinese Journal of Synthetic Chemistry,2016,24(7):561-564.
[15]季文文,姜林,藤信焕,等.取代异(噁)唑甲酰基脲的合成及其抑菌活性[J].化学试剂,2010,32(1):63-65.JI Wen-wen,JIANG Lin,TENG Xin-huan,et al.Synthesis and antimicrmatic activities of substituted isoxazolylacylureasderiv-atives[J].Chemical Reagents,2010,32(1):63-65.
[16]WingardL A,Guzman P E,Johnson E C,et al.Synthesis of bi-sisoxazole-bis-methylene dinitrate:a potential nitrate plasticiz-er and melt-castable energetic material[J].Chem Plus Chem,2016,82(2)1:1-5.
[17]Wingard L A,Johnson E C,Guzman P E,et al.Synthesis of bi-isoxazoletetrakis(methyl nitrate):a potential nitrate plasticizer and highly explosive material[J].European Journal of Organic Chemistry,2017,2017(13):1765-1768.
[18]Phillip L P,Timothy U C,Christian G,et al.A click chemistry approach to 5,5′-disubstituted-3,3′-bisisoxazoles from di-chloroglyoxime and alkynes:luminescent organometalic iridi-um and rhenium bisisoxazole complexes[J].The Journal of Organic Chemistry,2013,78(14):7298-7304.
[19]Jiang Longqiang,Gao Tao,Li Zhi,et al.Highly regioselective-dipolar cycloadditions of nitrile oxides withα,β-acetylenical-dehydes[J].Tetrahedron Letters,2016,57(6):712-714.
[20]Kesornpun C,Aree T,Mahidol C,et al.Water-assisted nitrile oxide cycloadditions:synthesis of isoxazoles and stereoselec-tivesyntheses of isoxazolines and 1,2,4-oxadiazoles[J].Angewandte Chemie International Edition,2016,47(30):3997-4001.
[21]Minuti L F,Memeo M G.,Crespi S,et al.Fluorescent probes from stable aromatic nitrile oxides[J].European Journal of Organic Chemistry,2016,2016(4):821-829.
[22]Siadati S A.The effect of position replacement of functional groups on the stepwise character of 1,3-dipolar reaction of a nitrile oxide and an alkene[J].Verlag Helvetica Chimica Acta.2016,99(4):273-280.