三硝基甲烷键离解能和生成焓的理论计算

采用密度泛函(DFT)四种交换/相关函数(B3LYP、B3P86、B3PW91和PBE0)结合不同的基函数,求得了三硝基甲烷C-NO2键的离解能(BDE),并且通过合理选择参考物硝基甲烷,设计等键等电子对反应,计算了气相三硝基甲烷分子的生成焓(HOF).与实验数据进行比较,PBE0/6-31g*计算出的BDE值最好,误差为-2.1 kcal mol-1;PBE0密度泛函结合带极化函数的6-31g基组得到的HOF值与实验值吻合的最好(误差在0.1 kcal mol-1以内).     

Synthesis of N-trinitroethyl derivatives of linear and heterocyclic nitrogen-containing compounds

Earlier unknown N-trinitroethyl derivatives of acetylhydrazine, 4-amino-1,2,4-triazole, and 2,4,6-triamino-1,3,5-triazine, which are potential components for gas-generating formulations, were synthesized. Dedicated to Academician N. K. Kochetkov on the occasion of his 90th birthday. __________ Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1306–1309, May, 2005.     

气相沉积法制备均苯四甲酸二酰亚胺纳米材料及传感应用

以均苯四甲酸二酰亚胺（PMD）为原料,采用真空气相沉积法制得PMD纳米自组装材料,由此建立了测定三硝基甲烷的荧光化学传感新方法。采用真空气相沉积法自组装PMD纳米材料,并用扫描电镜、透射电镜、红外光谱、紫外光谱、差热分析及荧光光谱对材料进行了表征。扫描电镜图像显示,PMD纳米材料呈带状网络结构,长度为30~100 μm;TEM图像表明,PMD纳米带宽度为100~300 nm,其中纳米线直径为120~220 nm。在PMD分子自组装过程中,分子间氢键、π-π等弱相互作用是构筑纳米结构的主要驱动力。一些较低沸点有机分子蒸汽对PMD纳米材料的荧光（λ_ex/λ_em=377 nm/495 nm）有猝灭作用,尤其是PMD纳米材料对三硝基甲烷有灵敏的响应。测定三硝基甲烷的线性范围为2.19×10^-5~1.37×10^-4 mol/L,R²=0.995,检出限为1.02×10^-6 mol/L。     

α-Azidopolynitroalkanes. Synthesis and vibrational spectra

Methods for the preparation of α-azidopolynitroalkanes by reactions of polynitroalkanes or α-(difluoroamino)polynitroalkanes with NaN₃ were developed. In the case of tetranitromethane, one or two nitro groups can be substituted, depending on the reaction conditions. The reaction of 1,1,1-trinitroethane with NaN₃ affords nitro-1,2,3-triazole, together with 1-azido-1,1-dinitroethane. The IR spectra of α-azidopolynitroalkanes were studied. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 338–341, February, 1997.     

Novel transformations of nitraminodiol diacetates

A novel scission reaction of nitraminodiol diacetates of the formula AcO[CH₂N(NO₂) _x CH₂OAc (x = 1–4) in concentrated sulfuric acid to form formaldehyde, nitramide, and 2-nitro-2-azapropane-1,3-diol disulfate was found.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya. No. 3, pp 761–762, March, 1996.     

Vibrational spectra of trinitromethane derivatives

Spectroscopic parameters of trinitromethane derivatives RC(NO₂)₃ (R = F, Cl, Br, I, NC, NF₂, N₃) were determined. Vibrational frequencies and modes were calculated and the assignment of experimental spectra was performed. Spectral features due to the mutual influence of the C(NO₂)₃ group and other atomic groups and particular atoms were revealed.     

Mechanism of formation and monomolecular decomposition of aci-nitromethanes: a quantum-chemical study

A quantum-chemical study of the reactions of formation of aci-nitromethane (aci-NM) and aci-dinitromethane (aci-DNM) and their decomposition with elimination of water was carried out. The methods employed were the ab initio RHF method with inclusion of electron correlation at the MP2 level of theory and the Dunning—Hay double zeta basis set augmented with polarization d-functions on heavy-element atoms, the DFT approach at the B3LYP level, and the semiempirical PM3 method. The formation of aci-NM and aci-DNM was found to be the limiting stage of the mechanism under study. For DNM, the barrier to reaction is substantially lower than for NM. The estimates of the heights of the barriers to formation found from density functional calculations at the B3LYP/6-311++G(df,p) level (258 kJ mol^–1 for aci-NM and 218.5 kJ mol^–1 for aci-DNM) are thought to be the most reliable.     

Phase transfer catalysis in the chemistry of aliphatic nitrocompounds

The methylation of trinitromethane (TNM) Na-salt under phase transfer catalysis (PTC) conditions was studied in a two-phase system (aqueous solution of TNM Na-salt-CH₃I). The obtained data revealed a relationship between the yield of the methylation product (1,1,1-trinitroethane) and the nature of the phase transfer catalyst and the degree of TNM anion transfer to the organic phase. The kinetic measurements showed that higher efficiency of methylation was achieved under PTC conditions than occurs in a homogeneous reaction due to the fact that the reaction proceeded in the CH₃I medium.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1086–1088, June, 1993.     

Reactions of (difluoroamino)trinitromethane with nucleophilic reagents

Reactions of F₂NC(NO₂)₃ with metal fluorides (KF and CsF) in DMF yield a substitution product of the fluorine atom for one nitro group, F₂NC(NO₂)₂F. The reaction of F₂NC(NO₂)₃ with LiBr in ethanol or DMF affords Br(NO₂)C=NF rather than the expected bromo derivative F₂NC(NO₂)₂Br.     

Molecular structures of trinitromethane derivatives

The molecular structures of trinitromethane derivatives XC(NO₂)₃ (X = F, Cl, Br, NC, NF₂, N₃) were studied using the density functional approach. The rules for changing the configurations of substituents in these compounds were revealed. Acceptability of the method employed for the calculations of trinitromethane derivatives is discussed.