9-苄基-9-氮杂双环[3.3.1]壬烷-3-醇的合成工艺优化

利用Mannich反应合成9-苄基-9-氮杂双环[3.3.1]壬烷-3-酮。选择异丙醇铝为催化剂还原9-苄基-9-氮杂双环[3.3.1]壬烷-3-酮。在单因素试验基础上,采用正交试验考察9-苄基-9-氮杂双环[3.3.1]壬烷-3-酮与异丙醇铝物质的量之比、异丙醇的用量、原料滴加速度和反应时间,四个因素对产率的影响。最佳的合成条件为:n(9-苄基-9-氮杂双环[3.3.1]壬烷-3-酮)∶n(异丙醇铝)=1∶0.5,异丙醇30mL,滴加速度为3s滴1滴,反应时间6h,产率为89.6%～90.8%。     

串联式一锅法合成2,6-二氧杂双环[3.3.1]壬烷衍生物

利用6-庚烯-2,4-二醉与不同的醛酮化合物在三氯化锢和浓盐酸存在下,以二氯甲烷做溶剂进行Prins反应,得到一系列3,7-二取代-2,6-二氧杂双环[3.3.1]壬烷衍生物.该反应条件简单,三氯化锢在其中起关键作用.产物的相对构型用NOESY测试进行了表征.     

9-硝基-9-氮杂双环[3.3.1]壬烷-2,6-二醇二硝酸酯的合成与表征

以环辛二烯为原料,经环氧化、胺化成环、硝化等合成了一种新型含能材料9-硝基-9-氮杂双环[3.3.1]壬烷-2,6-二醇二硝酸酯,采用NMR、IR、元素分析对其结构进行了表征;利用热重分析和差示扫描量热法对其热性能进行了分析;利用Kamlet-Jacobs经验公式对其爆轰性能进行了理论计算;研究了硝化反应过程中反应时间、反应温度和物料配比等因素对收率的影响。结果表明,硝酸用量为7倍摩尔当量时,在30℃下反应3h,目标产物收率为83%。9-硝基-9-氮杂双环[3.3.1]壬烷-2,6-二醇二硝酸酯熔点为120℃,起始分解温度为150℃,放热峰温为192℃,表明其具有较好的热稳定性。其爆速、爆压、密度的理论计算值分别为7 580m/s、23.82GPa和1.61g/cm3,有望应用于炸药及推进剂配方中。     

三种稠环硝胺化合物的爆炸性能估算及其硝化母体化合物的合成

以乙二醛、硝基胍为原料,经两步环化反应合成了含能稠环化合物6-硝亚氨基咪唑烷并[4,5-e]呋咱并[3,4-b]哌嗪(化合物4),并优化了其合成条件,总收率52.2%(文献值29.4%)。以乙二醛、尿素为原料,经两步环化反应合成了稠环化合物5-硝亚氨基咪唑烷并[4,5-d]咪唑烷酮(化合物5)。以乙二醛和1,1-二氨基-2,2-二硝基乙烯(FOX-7)为原料,通过两步环化反应得到了一种新型含能稠环化合物6-偕二硝基乙烯基咪唑烷并[4,5-e]呋咱并[3,4-b]哌嗪化合物(化合物6)。用IR、NMR、MS和元素分析对3种稠环和中间体的结构进行了表征。基于化合物4、5、6设计了3种新型稠环硝胺化合物的结构。用Gaussian 98程序和VLW方程计算了3种稠环的理化性能和爆轰性能。结果表明,3种稠环硝胺化合物的计算密度分别为2.03、2.08、2.07g/cm3,理论爆速分别为9 928、9 672、10 109m/s。     

几种新的环脲化合物的合成与硝化

本文报道６，６＇－乙撑二［３、７－二氧代－２、４、６、８－四氮杂双环［３、３、０］辛烷］，７、７＇－乙撑二［８－氧代－２、５、７、９－四氮杂双环［４、３、０］壬烷］和５，１１－二硫代－２、４、６、８、１０、１２－六氮杂三环［７、３、０、０（３．７）］十二烷］三种新环脲化合物的合成与硝化。硝化产物６，６＇－乙撑二［３、７－二氧代－２、４、８－三硝基－２、４、６、８－四氮杂双环［４、３、０］辛烷］，７，７＇－乙撑二［８－氧代－２、５、９－三硝基－２、５、７、９－四氮杂双环［４、３、０］壬烷］是新的环脲硝胺炸药，它们具有相当高的能量和改善的水解安定性。     

DPT的一种新合成法

本文介绍由脲、甲醛、硝酸及氨水等为原料,经中间产物亚甲基二脲和亚甲基二硝基脲合成3,7—二硝基—1,3,5,7—四氮杂二环[3,3,1]壬烷(简称DPT)的新方法。     

硝基吡唑类含能化合物的研究进展

介绍了硝化吡唑类含能材料,包括单硝基吡唑、双硝基吡唑、三硝基吡唑及其衍生物和多氮杂环的硝基吡唑的合成、物理性质和爆轰性能的最新进展,指出富含多氮杂环的硝基吡唑中的一些化合物具有良好的感度以及优异的爆轰性能,可广泛应用于推进剂,具有巨大应用潜力。     

替代光气的硒催化合成新方法

新催化合成方法具有环境友好性和原子经济性,已成为未来化学工业发展的关键技术。含肽化合物是有用的农用和医用化学品,其工业生产方法大都采用光气作羰基化试剂,光气的高毒性和苛刻的操作条件有诸多的不便。以非金属硒作催化剂、CO为羰基化试剂,可一步催化合成非对称脲类化合物或其衍生物。通过硒催化羰基化,还可以合成咪唑啉酮、(?)唑烷酮、环脲等;采用CO/H2O/Se催化体系,可以高选择性制备(取代)苯胺。本文介绍了二级胺、一级胺和4-氨基吡啶为共试剂的硝基化合物的羰基化反应情况。     

苄基脒类光产碱剂合成工艺研究

以1,5-二氮杂双环[4,3,0]-5-壬烯(DBN)为原料,采用氢化铝锂还原,于55℃下反应9 h,产物1,5-二氮杂双环[4,3,0]壬烷最高收率可达87.9%,纯度>95.0%;再将1,5-二氮杂双环[4,3,0]壬烷分别与不同取代苄基化合物反应,合成了系列新型标题化合物,并通过对其工艺条件的考察和优化,可使系列产物最高收率达89.9%,纯度>95.6%。研究中主要还运用了HPLC、LC-MS、1HNMR对产品及中间体进行了定量和定性分析。     

丙酮酸钠合成工艺研究

以空气为氧化剂,9-氮杂双环[3.3.1]壬烷-N-氧基自由基为催化剂,亚硝酸钠为助催化剂,1atm空气催化氧化合成丙酮酸乙酯。丙酮酸乙酯经水解、碳酸氢钠中和制得丙酮酸钠。考察了各种因素对反应的影响,确定了最佳的反应条件。在此条件下,丙酮酸乙酯收率为92%,丙酮酸钠的收率为93%。     

Nitroureas II. Synthesis of Bicyclic Mono- and Dinitrourea Compounds

We report the synthesis and characterization of several bicyclic mono- and dinitrourea compounds as energetic materials and discuss their use as precursors to other energetic compounds. The new nitrolyzing reagent, trifluoromethanesulfonic acid anhydride/20% N₂O₅/nitric acid, will also be described.     

Click Chemistry of Selenium Dihalides: Novel Bicyclic Organoselenium Compounds Based on Selenenylation/Bis-Functionalization Reactions and Evaluation of Glutathione Peroxidase-like Activity

A number of highly efficient methods for the preparation of novel derivatives of 9-selenabicyclo[3.3.1]nonane in high yields based on selenium dibromide and cis,cis-1,5-cyclooctadiene are reported. The one-pot syntheses of 2,6-diorganyloxy-9-selenabicyclo[3.3.1]nonanes using various O-nucleophiles including alkanols, phenols, benzyl, allyl, and propargyl alcohols were developed. New 2,6-bis(1,2,3-triazol-1-yl)-9-selenabicyclo[3.3.1]nonanes were obtained by the copper-catalyzed 1,3-dipolar cycloaddition of 2,6-diazido-9-selenabicyclo[3.3.1]nonane with unsubstituted gaseous acetylene and propargyl alcohol. The synthesis of 2,6-bis(vinylsulfanyl)-9-selenabicyclo[3.3.1]nonane, based on the generation of corresponding dithiolate anion from bis[amino(iminio)methylsulfanyl]-9-selenabicyclo[3.3.1]nonane dibromide, followed by the nucleophilic addition of the dithiolate anion to unsubstituted acetylene, was developed. The glutathione peroxidase-like activity of the obtained water-soluble products was estimated and compounds with high activity were found. Overall, 2,6-Diazido-9-selenabicyclo[3.3.1]nonane exhibits the highest activity among the obtained compounds.     

Anti-bredt monomers

Summary 1-Aza-3-oxabicyclo[3.3.1]nonan-2-one, an N-bridgehead bicyclic urethane, polymerized in bulk under the influence of dibutyltin oxide and p-toluenesulfonic acid. In solution the monomer polymerizes in the presence of phosphoric acid. This is only the second example of ring opening polymerization of a bicyclo[3.3.1]nonane. The driving force in the present case is thought to be the relief of strain energy in the monomer conferred by its chair-boat conformation.     

Transannulare Reaktionen von Cycloalkenen,Cycloalkadienen und Cycloalkatrienen. VIII. Zur elektrophilen Addition von Pseudohalogenen an Cycloocta-1(Z),5(Z)-dien

Transannular Reactions of Cycloalkenes, Cycloalkadienes and Cycloalkatrienes. VIII. The Electrophilic Addition of Pseudohalogenes to Cycloocta-1(Z), 5(Z)-diene The reaction of cycloocta-1(Z), 5(Z)-diene 5 with chlorothiocyanate is described. The main process is the normal anti-addition to produce trans-5-chloro-6-thiocyanato-(Z)-cyclooctene 6 . In addition 2,6-dichloro-9-thiabicyclo [3.3.1] nonane 7 and 2,6-dithiocyanato-9-thiabicyclo[3.3.1] nonane 8 are obtained as products of a transannular reaction.     

氮杂双环硝胺类含能材料的分子结构与性能的关系

使用Gaussian03软件,采用密度泛函理论(DFT)在B3LPY/6-31++G(d,p)计算精度下,计算并研究了9个具有不同官能团以及母环结构的氮杂双环硝胺类含能化合物的分子结构,分析了其结构与性能的关系,优化了几何构型,通过计算得到了分子体积、能量等;以此为基础计算了该系列材料的密度、爆轰性能以及感度等数据。通过比较分子结构,从密度、生成热、爆轰性能以及撞击感度等方面,研究了不同官能团以及环系结构对该类含能材料性能的影响;通过对比得到了对双环硝胺化合物有利的官能团及结构。结果表明,双环硝胺结构有利于稳定结构以及形成紧凑的空间排布,并提高化合物的撞击感度及密度;同时,羰基的引入以及接近零氧平衡是提高该类含能材料爆炸性能的技术途径。     

Regioselectivity of Oxysulfenylations of Cycloocta-1,5-diene

The regioselectivity of transannular O-heterocyclization of cycloocta-1,5-diene ( 1 ) with phenylsulfenyl chloride and methanol or water, respectively, is determined by the oxy-component which acts as nucleophilic partner in the electrophilic three component reaction. The thermodynamically more stable endo, endo-2,6-bis(phenylsulfenyl)-9-oxabicyclo[3.3.1]nonane ( 2 ) is formed almost exclusively in methanol while the isomeric 9-oxabicyclo[4.2.1]nonane ( 3 ) is favored under kinetic control in the presence of water. The oxidation of 2 or 3 yields the bissulfones 4 and 5 , respectively.     

Construction of Functionalized Azapolycyclic Architectures via Formal Amide Insertion at a Low Catalyst Loading of Copper Trifluoroacetylacetonate

A formal amide insertion reaction for the synthesis of nitrogen‐bridged polycyclic frameworks with diverse functionalities was developed using a sustainable copper catalyst as an advantageous alternative to precious rhodium catalysts. The remarkable feature of this methodology is the amount of catalyst loading (0.05 mol%). The optimized reaction conditions enable access to aromatic ring‐fused 8‐azabicyclo[3.2.1]octane, 9‐azabicyclo[3.3.1]nonane, and 6‐azabicyclo[3.2.2]nonane derivatives in moderate to excellent yields.

     

A study on the aliphatic energetic plasticizers containing nitrate ester and nitramine

The aliphatic energetic plasticizers with three and four –CH₂ between nitrate ester and nitramine were synthesized to obtain a plasticizer that is more stable than N-butyl-N-nitratoethyl nitramine (BuNENA) with two –CH₂. First, amino alcohol compounds such as propylamino propanol (PAP) and ethylamino butanol (EAB) as a precursor of energetic plasticizer were synthesized. However, unlike in BuNENA synthesis, various side reactions occurred in the nitration of amino alcohols. Fortunately, it was possible to considerably suppress the formation of side products in the nitration of PAP by using a solvent and an appropriate concentration of nitric acid. In addition, an energetic plasticizer with higher oxygen content was obtained through the nitration of intermediate, amide alcohol, which was formed in the synthesis of EAB.     

Synthesis,Characterization and Thermal Behaviour of 2,4,6,8‐Tetranitro‐2,4,6,8‐Tetraazabicyclo[3.3.1]Nonane‐3,7‐Dione (TNPDU) and one of its Methylene Analogues

2,4,6,8 ‐ Tetranitro – 2,4,6,8 ‐ tetraazabicyclo[3.3.1]nonane‐3,7‐dione (TNPDU) has been synthesized from propane diurea by nitration with nitric acid‐acetic anhydride with a yield of 85 %. The molecular structure of the compound has been determined by elemental analysis, IR and ¹H‐NMR spectroscopy. Some of the properties including thermal and explosion delay behaviour of the compound and its mixtures with high explosives, are reported. An analogous compound 2,5,7,9‐tetranitro‐2,5,7,9‐tetraazabicyclo[4.3.0]nonane–8–one (TNABN) has also been evaluated for some of the explosive properties considering its good stability and insensitiveness as compared to other nitrodiurea derivatives.     

含能增塑剂的研究现状及发展

从含能增塑剂的能量基团种类出发,综述含能增塑剂的合成和应用研究现状,认为含能增塑剂在含能材料配方中起着重要作用,不仅能改进力学性能,而且可以提高安全特性。硝酸酯含能增塑剂是一种极易受摩擦和撞击引爆的敏感炸药,且大多数危险等级为1．1,而新兴的叠氮类、偕二硝基类及硝胺类含能化合物或齐聚物性能优异,是含能增塑剂的主要研究对象。同时分析了国内含能增塑剂研究在合成技术、数量品种及应用等方面存在的差距,建议国内应加强多种类型新含能增塑剂的合成及应用研究。