2,4,6-三硝基-2,4,6-三氮杂环己酮生成历程的~(15)N NMR研究

由DPT与脲或硝基脲在硝化剂中反应可以合成2,4,6-三硝基-2,4,6-三氮杂环己酮。本文用~(15)N示踪原子对DPT分子中不同位置的氮原子分别进行标记,用~(15)N NMR谱图来考察~(15)N标记的反应物和产物分子中标记原子的位置及丰度。结果表明,与脲或硝基脲缩合的DPT硝解碎片为非硝基取代的N,N-二羟甲基胺,硝基脲上硝基与硝化剂之间存在着交换反应。     

1,3,3-三硝基氮杂环丁烷合成研究的现状与进展

叙述近年来国外对新的高能量密度材料１，３，３－三硝基氮杂环丁烷合成研究的情况与进展，介绍了六种新的合成路线并进行了评论。     

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.     

N-乙酰基-3,3-二硝基氮杂环丁烷的合成

多硝基氮杂环丁烷及其衍生物因其四元杂环所具有很高的环张力能,赋予这类化合物优良的爆轰性能,从而成为一类重要的高能量密度材料,其中1,3,3-三硝基氮杂环丁烷(TNAZ)成为最具有应用前景的含能材料之一。N-乙酰基-3,3-二硝基氮杂环丁烷(ADNAZ),为白色或无色晶体,可溶于丙酮,二氯甲烷等有机溶剂。     

1,3,3-三硝基氮杂环丁烷及其衍生物的热解机理的AM1研究

用ＳＣＦ－ＭＯ－ＡＭ１方法计算研究了１，３，３－三硝基氮杂环丁烷和它的三个衍生物的分子几何构型，电子结构和热解机理，分子中连结偕二硝基的两个Ｃ－Ｎ键级较小，均裂该建所需活化能较低，可能是优先发生的主要热解引发反应，四个标题物均裂该键的活化能和该键的Ｗｉｂｅｒｇ键级之间存在良好的线性关系，线性相关系数为０．９９。     

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．     

N-硝基-2,4,6-三硝基苯基脲的合成及生物活性研究

在甲苯溶液中，将N-硝基-2,4,6-三硝基苯胺与固体光气反应, 得到酰氯中间体, 该中间体无需分离, 然后直接与其它取代苯胺反应合成了13个未见文献报道的N-硝基-2,4,6-三硝基苯基脲类化合物, 其结构经¹H NMR, IR, MS和元素分析确证. 初步测试结果表明: 当浓度为500 mg/L时, 部分化合物具有较好的抑制稗草生长活性.     

1,3,3-三硝基氮杂环丁烷的合成

1,3,3-三硝基氮杂环丁烷（TNAZ）作为高能量密度材料，其合成和应用研究受 到了广泛重视。本文用硝基甲烷、多聚甲醛、叔丁胺等作为起始原料，经过五步反 应合成出了TNAZ，总收率为34%，用红外光谱、核磁共振氢谱及碳谱和质谱等对其 及中间体结构进行了表征。大部分反应使用水作为反应介质，降低了合成成本，污 染明显减少。讨论了反应条件和影响反应产物收率的主要因素，获得了制备TNAZ合 适条件。     

一种可用于检测2,4,6-三硝基苯酚的杂环芳族卤化物小分子荧光探针

以2,6-二甲氧基苯甲酸为起始原料得到氨基噻二唑衍生物,通过Gattermann反应合成一种杂环芳族卤化物2-氯-5-(3-氯-2,6-二甲氧基苯基)-1,3,4-噻二唑(L),利用核磁共振波谱仪(NMR)和高分辨率质谱仪(HRMS)等测试手段确定了结构,并将其用作小分子荧光探针检测2,4,6-三硝基苯酚(TNP),系统地研究了其荧光特性,并且结合理论计算,探究了其可能的猝灭机制。 研究结果表明,探针L对TNP具有高选择性、高灵敏度、抗干扰能力强,在较宽的pH值范围内,仍然表现出良好的荧光性能。 具有较低的检测限(4.2×10^-7 mol/L),可用于实际水样中TNP的检测。     

Synthesis and crystal structure of ethyl 1-benzyl-2-hydroxy-5-methyl-3-oxo-2-phenacyl-2,3-dihydropyrrole-4-carboxylate

Reaction of 5-phenyl-2,3-dihydro-2,3-furandione with ethyl 3-benzylamino-2-butenoate, resulting in ethyl 1-benzyl-2-hydroxy-5-methyl-3-oxo-2-phenacyl-2,3-dihydropyrrole-4-carboxylate and benzylamide ofN-benzoylpyruvic acid, was studied. The structure of the pyrrole derivative was confirmed by X-ray analysis.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1552–1555, August, 1995.     

Crystal and molecular structure of 1-chloromethyl-1-oxo-1,3-dihydro-2,1-benzoxaphosphole

The crystal and molecular structure of 1-chloromethyl-1-oxo-1,3-dihydro-2,1-benzoxaphosphole was determined by x-ray diffraction structural analysis. This compound has an almost planar bicyclic unit with extruding phosphorus atoms and atrans Cl-C-P=O fragment.Institute of Physiologically Active Compounds, Russian Academy of Sciences, 142432 Chernogolovka. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 7, pp. 1670–1673, July, 1992.     

Molecular and crystal structure of 4,6,6-trimethyl-2-oxo-5,6-dihydro-2H-pyran-3-carbonitrile and 4,6,6-trimethyl-2-oxo-1,2,5,6-tetrahydropyridine-3-carbonitrile

Single crystals of 4,6,6-trimethyl-2-oxo-5,6-dihydro-2H-pyran-3-carbonitrile and 4,6,6-trimethyl-2-oxo-1,2,5,6-tetrahydropyridine-3-carbonitrile were prepared and submitted to X-ray diffraction analysis. Both compounds have a molecular structure belonging to the C₁ symmetry group. The heterocyclic rings are in a distorted envelope conformation. The crystals belong to the monoclinic system and each contain four molecules in the unit cell. In the crystal the pyridine derivative exists in the form of centrosymmetric dimers stabilized by intermolecular hydrogen bonds between the oxygen atoms of the carbonyl group and the hydrogen atom at the nitrogen atom of the ring. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1620–1624, November, 2007.     

Reaction of 2-substituted 4-oxo-5, 6-benzo-1, 3, 2-dioxaphosphorinanes with ethyl pyruvate

The reaction of 2-substituted 4-oxo-5, 6-benzo-1, 3, 2-dioxaphosphorinanes with ethyl pyruvate affords ring-expansion products, i.e., diastereomeric 2-substituted 2, 5-dioxo-6, 7benzo-1, 3, 2-dioxaphosphepanes.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 565–567, March, 1993.The authors are grateful to Ye.I.Gol'dfarb for recording the 31_P-(1_H) NMR spectra.     

对氯苯基硫脲和2,4,6-三溴苯基硫脲的晶体结构和分子结构

本文报道对氯苯基硫脲(Ⅰ)和2,4,6-三溴苯基硫脲(Ⅱ)的晶体结构和分子结构,(Ⅰ)属单斜晶系,空间群P2_1/a,a=10.671(1),b=8.912(1),c=9.128(1),β=106.85(1)°,Z=4,D_c=1.492g/cm~(-3),最后的偏离因子R=0.029,R_w=0.031;(Ⅱ)属正交晶系,空间群Pcab,a=9.997(2),b=7.876(4),c=27.920(3),Z=8,D_c=2.35g/cm~(-3),最后的偏离因子R=0.047,R_w=0.047。晶体结构测定结果表明,硫脲部分的四个原子组成平面三角形,苯环平面与硫脲平面的夹角分别为70.1°和80.3°。     

水介质中1,6-二氧-5-氧代-1,4,5,6-四氢化菲衍生物的三组分一锅合成

水介质中在氯化三乙基苄基铵(TEBA)催化下, 芳醛与丙二腈和4-羟基香豆素三组分一锅反应合成了2-氨基-4-芳基-3-氰基-1,6-二氧-5-氧代-1,4,5,6-四氢化菲, 该反应具有产率高、污染少、操作简单、环境友好等优点.     

Nucleophilic reactions of 1-methyl-2-methoxy-2-phenyl-3-oxo-2,3-dihydroindole

The title compound (1) was prepared via methylene blue (MB)-sensitized photooxy-genation of l-methyl-2-phenylindole (2d) in methanol. Acid-catalyzed nucleophilic substitution of 1 with nucleophiles gave 1,2,2-trisubstituted 3-oxo-2,3-dihydroindoles (3-6). Reduction of 1 with lithium aluminum hydride, followed by acidic workup yielded 4d and 2d, whereas the same reduction reaction of 1, followed by neutral workup gave l-methyl-2-phenyl-3-hydroxy-2,3-dihydroindole (15), together with 3. The reaction pathways of nucleophilic substitution and reduction of 1 were discussed.     

2,4,6-三甲氧基苯-1-O-D葡萄糖苷的核磁共振谱的理论研究

The 1H and 13C-NMR of 2,4,6-trimethoxyphenol-1-O-D-glucopyranoside(Compound 1) isolated from Celastrus angulatus (Celastraceae) was calculated theoretically at the both levels HF/6-311+G(2d,p)//B3LYP/6-31G(d) and HF/6-311+G(2d,p)//B3LYP/6-31G(d,p) using the GIAO (gauge-independent atomic orbital) method. Statistical error analysis for theoretically predicted δH and δC values versus those experimentally observed for compound 1 was discussed. The results show that the theoretically predicted δH and δC values of β conformer of compound 1 are more close to the experimentally observed values than α conformer, and the β conformer of compound 1 is more stable than α conformer according to molecular energy theoretically calculated. So compound 1 is assigned to be 2,4,6-trimethoxyphenol-1-O-β-D-glucopyranoside, which is in good consistence with the conclusion deduced by the anomeric proton signal (δH=4.80, J=7.3 Hz) experimentally observed.     

Synthesis and Crystal Structure of Ethyl 3-（4-Chlorophenyl）-3,4-dihydro-6-methyl-4-oxo-2- （pyrrolidin-1-yl）furo[2,3-d]pyrimidine-5-carboxylate

The crystal structure of the title compound ethyl 3-（4-chlorophenyl）-3,4-dihydro-6- methyl-4-oxo-2-（pyrrolidin-1-yl）furo[2,3-d]pyrimidine-5-carboxylate （C20H20ClN3O4, Mr= 401.84） has been prepared and determined by single-crystal X-ray diffraction. The crystal is of monoclinic, space group P21/n with a = 20.6215（9）, b = 8.5311（4）, c = 21.6886（9） A^°, β = 91.607（1）°, V = 3814.0（3）A^°^3, Z = 8, Dc = 1.400 g/cm^3, F（000） = 1680, μ = 0.233 mm^-1, R = 0.0718 and wR = 0.1545 for 6717 observed reflections with I 〉 2σ（I）. X-ray diffraction analysis reveals two crystallographically independent molecules in the asymmetric unit.     

利用二氢吡啶光诱导芳香化反应合成3,5-二氰基-2,4,6-三甲基吡啶

3,5-二氰基-2,4,6-三甲基吡啶在新型光电功能材料的合成中有重要的应用价值.本文在CCl₄中光照1,4-二氢-3,5-二氰基-2,4,6-三甲基吡啶,高产率地合成了3,5-二氰基-2,4,6-三甲基吡啶.