2-叠氮基-1,1-二硝基乙基取代苯衍生物的合成

详细研究了2-叠氮基-1,1-二硝基乙基取代苯衍生物的合成方法。由苯基二硝基甲烷钾盐经羟甲基化，磺酰酯化和叠氮化得到目标化合物：3-硝基-(2-叠氮基-1,1-二硝基乙基)苯(4b)，4-硝基-(2-叠氮基-1,1-二硝基乙基)苯(4c)，m-二(2-叠氮基-1,1-二硝基乙基)苯(10)和p-二(2-叠氮基-1,1-二硝基乙基)苯(15)。     

（1，1－二硝基－2－叠氮基乙基）苯的合成及其热稳定性

（１，１－二硝基－２－叠氮基乙基）苯的合成及其热稳定性阎红，管晓培，陈博仁（北京工业大学化学与环境工程学系北京１０００２２）（北京理工大学化工与材料学院北京）关键词　叠氮化合物，偕二硝基化合物，含能材料有机叠氮化合物是一类重要的含能材料，近年来受到广...     

1-氨基-1-肼基-2,2-二硝基乙烯(AHDNE)的合成、 晶体结构和理论计算

利用1,1-二氨基-2,2-二硝基乙烯(FOX-7)和水合肼在水体系中合成了1-氨基-1-肼基-2,2-二硝基乙烯(AHDNE), 并在甲醇溶液中培养出可用于X射线衍射的单晶. 晶体属正交晶系, 空间群为Pnma, 晶胞参数为: a＝0.6283(4) nm, b＝0.7713(5) nm, c＝1.2280(8) nm, a＝b＝g＝90°, V＝0.5950(7) nm3, Dc＝1.821 g/cm3, μ＝0.171 mm－1, F(000)＝336, Z＝4, R1＝0.0489, wR2＝0.1456. 选取标题化合物的一个结构单元作为初始模型, 运用Gaussian 03程序, 在6-311＋G(d)的基组水平上, 用HF, MP2以及B3LYP三种计算方法对标题化合物进行了几何全优化, 并对其成键情况及自然键轨道(NBO)进行了分析.     

二苯并-18-冠-6-硝化产物异构体的分离及顺式化合物的结构测定

在改进的条件下,二苯并-18-冠-6硝化反应的产率达90％以上。提出一种分离二硝基二苯并-18-冠-6的顺、反异构体的方法。反应产物经元素分析和红外光谱鉴定,异角X射线衍射法测定了顺式二硝基二苯并-18-冠-6的晶体结构。晶体空间群为P2_1/n,α=15.95i(7),b=20.411(9),c=8.173(4),β=101.09(4)°,Z=4。结构用直接法解出,R=0.067。     

2-取代-5,5-二硝基嘧啶-4,6-二酮的合成和反应

研究了2-取代嘧啶-4,6-二酮的硝化反应, 产物为2-取代-5,5-二硝基嘧啶-4,6-二酮(3), 收率＞80%, 3与亲核试剂反应形成开环产物. 2-位取代基为烷基时, 嘧啶环5-位和侧链的α-位都发生反应, 当取代基为甲基时, 硝化产物为2-(二硝基亚甲基)-5,5-二硝基嘧啶-4,6-二酮(1), 1的水解产物为1,1-二氨基-2,2-硝基乙烯 (FOX-7) 和二硝基甲烷(2). 2-位取代基为羟基时, 硝化产物为5,5-二硝基巴比妥酸(7b), 7b水解可制得偕二硝基乙酰基脲(9b), 9b与KOH作用生成偕二硝基乙酰基脲钾盐(10b)和二硝基甲烷钾盐(11). 2-位取代基为氨基时, 硝化开环生成偕二硝基乙酰基胍(9a), 9a与KOH作用生成偕二硝基乙酰基胍钾盐(10a)和11. 当2-位无取代基时, 硝化产物无法分离, 结构推测为7c. 考察了亲核试剂对FOX-7收率的影响并对FOX-7的三种合成方法进行了评价, 对反应机理进行了探讨.     

FOX-7的合成和反应机理研究

以2-甲基咪唑为原料合成出1,1-二氨基-2,2-二硝基乙烯(FOX-7)并进行了结构表征,从中间体过滤母液中分离出副产物2-甲基-4(5)-硝基咪唑和仲班酸.直接合成的2-甲基-4(5)-硝基咪唑和仲班酸,最佳收率分别为67.3%和63.3%.首次提出了一个较为完整而详细的合成FOX-7的反应机理,硝基重排成亚硝酸酯是反应的关键步骤.FOX-7主要是通过2-甲基咪唑→2-甲基-4(5)-二氢-5-咪唑啉酮→2-(二硝基亚甲基)-5,5-二硝基-4-咪唑烷二酮→2-(二硝基亚甲基)-4,5-咪唑烷二酮→FOX-7步骤形成.论述了各中间体形成的详细过程并进行了证明,应用该机理解释了硝化过程中主产物和副产物的变化规律.     

3,3-二硝基氮杂环丁烷和1,1''''-亚甲基-双(3,3-二硝基-1-氮杂环丁烷)的合成研究

3,3-二硝基氮杂环丁烷(DNAZ)的含能盐及衍生物是一类重要的高能量密度材料,因此DNAZ的合成和应用受到了密切关注.采用新的合成方法,以1-叔丁基-3,3-二硝基氮杂环丁烷为起始原料,以76.3%的总收率得到了DNAZ,然后以DNAZ为原料,与多聚甲醛反应,得到了1,1'-亚甲基-双(3,3-二硝基-1-氮杂环丁烷)(DNAZ-CH2-DNAZ).用红外和核磁共振光谱等对各化合物的结构进行了表征.     

4,4＇-二硝基二苯乙烷(烯)的合成

二硝基二苯乙烯;硝基甲苯;氧化二聚反应;4;4＇-二硝基二苯乙烷(烯)的合成     

1,3-偶极环加成反应合成1-(取代苄基)-1,2,3-三唑类化合物

利用苄氯和取代苄氯与叠氮化钠的亲核取代反应合成了一系列苯环上带有不同取代基团的苄基叠氮化合物,亲核取代反应速率受苯环上取代基的影响:吸电子基团的存在,可以促使反应更容易进行.合成的叠氮化合物与苯乙炔经1,3-偶极环加成反应得到了相应的取代苄基1,2,3-三唑类化合物,反应条件温和.这些1,2,3-三唑类目标化合物具有对热稳定的优点.用红外、核磁、元素分析、质谱等对合成的叠氮化合物和1,2,3-三唑类化合物的结构进行了表征,重点研究了1,3-环加成反应的规律.加成反应速率取决于叠氮化合物(偶极物)的极性,即与取代基的电负性有关:苯乙炔(亲偶极物)易于与缺电子的叠氮反应,反之亦然.同时在反应过程中观察到空间位阻效应:反应可以生成两种同分异构体,其中4-苯基-1,2,3-三唑是主要产物.     

1-[2′,4′-二氟-(1,1′-联苯)-4-基苯基甲基]-咪唑的合成

以2,4-二氟联苯为起始原料,经酰化反应制得2′,4′-二氟-(1,1′-联苯)-4-基苯基甲酮(2);2经NaBH4还原得2′,4′-二氟-(1,1′-联苯)-4-基苯基甲醇(3);3经氯代得2′,4′-二氟-(1,1′-联苯)-4-基苯基氯甲烷(4);4与咪唑发生亲核取代反应合成了1-[2′,4′-二氟-(1,1′-联苯)-4-基苯基甲基]-咪唑(5). 2～5为新化合物,其结构经1H NMR, IR, MS和元素分析确证.     

Synthesis and Characteristics of Bis(2, 2‐dinitroethyl‐N‐nitro)ethylenediamine‐Based Energetic Salts

New energetic bis(2, 2‐dinitroethyl‐N‐nitro)ethylenediamine‐based salts exhibiting moderate physical properties, good detonation properties, and relatively low impact sensitivities were synthesized in high yield by direct reactions of bis(2, 2‐dinitroethyl‐N‐nitro)ethylenediamine with organic bases. The resulting salts were fully characterized by multinuclear NMR spectroscopy (¹H and ¹³C), vibrational spectroscopy (IR), differential scanning calorimetry (DSC), and elemental analysis. Solid‐state ¹⁵N NMR spectroscopy was used as an effective technique to further determine the structure of some products. Thermal decomposition kinetics and several thermodynamic parameters of some salts were obtained under non‐isothermal conditions by DSC. The densities of the energetic salts paired with organic cations were in the range 1.60–1.89 g · cm^–3 as measured with a gas pycnometer. Based on the measured densities and calculated heats of formation, detonation pressures and velocities were calculated using Explo 5.05 and found to be 23.6–44.8 GPa and 7790–9583 m · s^–1, respectively, which make them potentially useful as energetic materials.     

Preparation and certification of a fish oil natural matrix reference material for organochlorine pesticides

The mass fractions of six organochlorine pesticides in a fish oil certified reference material (CRM) have been determined using multiple methods of analysis. Fish oil was extracted from the filet of Tilapia fish collected from the River Nile, and this CRM was recently issued by the National Institute of Standards (NIS). It can be used as natural matrix CRM for organochlorine pesticides determination in fish and for marine environmental measurement purposes. The analytical methods used are described, and the obtained results were combined to calculate the mass fractions of the six detected organochlorine pesticides and their associated uncertainty values. It has been concluded that mass fractions of four pesticides are certified values. These are 1,1-(dichloroethylidene)bis[4-chlorobenzene](4,4′-DDE), 1,1-(2,2,-dichloroethylidene)bis[4-chlorobenzene] (4,4′-DDD), 1-chloro-2-[2,2,2-trichloro-1-(4-chlorophenyl)ethyl]benzene (2,4′-DDT) and 1,1-(2,2,2-trichloroethylidene)bis[4-chlorobenzene] (4,4′-DDT). Meanwhile, mass fractions of two pesticides were reference values. These are heptachlor and 1-chloro-2-[2,2-dichloro-1-(4-chlorophenyl)ethyl]benzene (2,4′-DDD).     

3,3-二{2,2-二[4-(N,N-二取代氨基)苯基]乙烯基}-4,5,6,7-四氯-2-苯并[c]呋喃酮的合成

在对甲苯磷酸存在下,采用1,1-二[4-(N,N-二取代氨基)苯基]乙烯(3)和四氯苯酐在乙酸酐溶液中的缩合反应合成了3,3-二{2,2-二[4-(N,N-二取代氨基)苯基]乙烯基}-4,5,6,7-四氯-2-苯并[c]呋喃酮(4),产率89～93％。3由4,4＇-二(N,N-二取代氨基)二苯甲酮(1)与甲基碘化镁进行Grignard反应的产物经水解再脱水制得,产率85％～88.5％(以1为基准)。     

Substituent effects in the conversion of azido- and diazidotrinitrobenzenes to benzofuroxans and difuroxans

The preparation of a number of substituted dinitrobenzofurazan oxides (dinitrobenzofuroxans) and nitrobenzobis(oxadiozoles) (nitrobenzodifuroxans), in which the substituents were amino, fluoro, formamido, hydroxy, and ureido groups, by thermolysis of azido precursors is described. The ease of thermolysis appears to be an inverse function of the angle of twist of the nitro groups ortho to the azido group from the plane of the benzene ring. Amino- and hydroxy-substituted dinitrobenzofuroxans and nitrobenzodifuroxans were found to be much more stable than their non-nitro-substituted counterparts.     

Synthesis of Podands of the 3,4-dihydroisoquinoline series

Podands containing 3,4-dihydroisoquinoline fragments were synthesized by reactions of 1,1′-{ethane-1,2-diylbis[oxy(3-methoxybenzene-4,1-diyl)]}bis(2-methylpropan-1-ol) and 1-(2-ethoxyethoxy)-2-methoxy-4-(2-methylprop-1-en-1-yl)benzene with ethyl cyanoacetate and methyl thiocyanate in concentrated sulfuric acid. Likewise, 1-substituted 3,4-dihydroisoquinolines having a crown ether fragment were obtained from 4-acetylbenzo-12-crown-4.     

Conformational polymorphism of (E,E)‐N,N′‐bis(4‐nitrobenzylidene)benzene‐1,4‐diamine

Two polymorphs of (E,E)‐N,N′‐bis(4‐nitrobenzylidene)benzene‐1,4‐diamine, C₂₀H₁₄N₄O₄, (I), have been identified. In each case, the molecule lies across a crystallographic inversion centre. The supramolecular structure of the first polymorph, (I‐1), features stacking based on π–π interactions assisted by weak hydrogen bonds involving the nitro groups. The second polymorph, (I‐2), displays a perpendicular arrangement of molecules linked via the nitro groups, combined with weak C—H...O hydrogen bonds. Both crystal structures are compared with that of the carbon analogue (E,E)‐1,4‐bis[2‐(4‐nitrophenyl)ethenyl]benzene, (II).     

海绵Spongia sp.化学成分的研究（Ⅰ）

应用气相色谱－质谱联用技术从海绵Spongia sp. 中分离鉴定出4个化学成分： 1－氯－2,2－二对氯苯基乙烯(DDMU,Ⅰ)、 1,1－二氯－2,2－二对氯苯基乙烯(DDE,Ⅱ)、 1,1－二氯－2,2－二对氯苯乙烷(DDD, Ⅲ)和角鲨烯（Ⅳ）。前3个化合物是首次从Spongia属海绵中分离得到。     

Synthesis, structure, and biological activity of ferrocenyl carbohydrate conjugates

Seven ferrocenyl carbohydrate conjugates were synthesized. Coupling reactions of monosaccharide derivatives with ferrocene carbonyl chloride produced {6-N-(methyl 2,3,4-tri-O-acetyl-6-amino-6-deoxy-alpha-D-glucopyranoside)}-1-ferrocene carboxamide (3), {1-O-(2,3,4,6-tetra-O-benzyl-D-glucopyranose)}-1-ferrocene carboxylate (4), and {6-O-(1,2,3,4-tetra-O-acetyl-beta-D-glucopyranose)}-1-ferrocene carboxylate (5). Similarly, 1,1'-bis(carbonyl chloride)ferrocene was coupled with the appropriate sugars to produce the disubstituted analogues bis{6-N-(methyl 2,3,4-tri-O-acetyl-6-amino-6-deoxy-alpha-D-glucopyranoside)}-1,1'-ferrocene carboxamide (8), bis{1-O-(2,3,4,6-tetra-O-benzyl-D-glucopyranose)}-1,1'-ferrocene carboxylate (9), and bis{6-O-(1,2,3,4-tetra-O-acetyl-beta-D-glucopyranose)}-1,1'-ferrocene carboxylate (10). {6-N-(Methyl-6-amino-6-deoxy-alpha-D-glucopyranoside)}-1-ferrocene carboxamide monohydrate (12) was synthesized via amide coupling of an activated ferrocenyl ester with the corresponding carbohydrate. All compounds were characterized by elemental analysis, 1H NMR spectroscopy, and mass spectrometry. X-ray crystallography confirmed the solid-state structure of three ferrocenyl carbohydrate conjugates: 2-N-(1,3,4,6-tetra-O-acetyl-2-amino-2-deoxy-D-glucopyranose)-1-ferrocene carboxamide (1), 1-S-(2,3,4,6-tetra-O-acetyl-1-deoxy-1-thio-D-glucopyranose)-1-ferrocene carboxylate (2), and 12. The above compounds, along with bis{2-N-(1,3,4,6-tetra-O-acetyl-2-amino-2-deoxy-D-glucopyranose)}-1,1'-ferrocene carboxamide (6), bis{1-S-(2,3,4,6-tetra-O-acetyl-1-deoxy-1-thio-D-glucopyranose)}-1,1'-ferrocene carboxylate (7), and 2-N-(2-amino-2-deoxy-D-glucopyranose)-1-ferrocene carboxamide (11) were examined for cytotoxicity in cell lines (L1210 and HTB-129) and for antimalarial activity in Plasmodium falciparum strains (D10, 3D7, and K1, a chloroquine-resistant strain). In general, the compounds were nontoxic in the human cell line tested (HTB-129), and compounds 4, 7, and 9 showed moderate antimalarial activity in one or more of the P. falciparum strains.     

海绵Spongia sp.化学成分的研究（I）

应用气相色谱－质谱联用技术从海绵Ｓｐｏｎｇｉａ ｓｐ．中分离鉴定出４个化学成分：１．－氯－２,２－二对氯苯基乙烯（ＤＤＭＵ,Ｉ）、１,１－二氯－２,２－二对氯苯基乙烯（ＤＤＥ,Ⅱ）、１,１－二氯－２,２－二对氯苯乙烷（ＤＤＤ,Ⅲ）和角鲨烯（Ⅳ）。前３个化合物是首次从Ｓｐｏｎｇｉａ属海绵中分离得到。