The regioselectivity of the formation of 2-pyrazolylthiazoles and their precursors from the reaction of 2-hydrazinothiazoles with 4,4,4-trifluoro-1-hetaryl-1,3-butanediones

Reaction of 2-hydrazinothiazoles 1 with 1-thienyl- and 1-furyl-1,3-butanediones 2a,b in methanol in the presence of hydrochloric acid mainly leads to a mixture of pyrazoles 3 and pyrazolines 4 or pyrazoles 3 and 5 in strong acidic conditions. Isomeric hydrazones 6 and pyrazolines 4 were formed and isolated in these reactions in the absence of hydrochloric acid. It has been shown that the regioselectivity in the reaction of diketones 2 with hydrazine 1 is governed by both the concentration of acid and the nature of substituents in the 1,3-diketones 2. Cyclization of hydrazones 6 is shown to occur under milder conditions than dehydration for pyrazolines 4. The new heterocyclic compounds were prepared and fully characterized by NMR spectra and by X-ray analysis for 3c.     

Gas chromatographic conditions for the linearity of the relationship between σT,t and tR in open tubes

The linearity of the relationship between σ_T,t² and (1 + k)² is studied with the view of using it for the evaluation of GC equipment. Based on appropriate analytical expressions it is concluded that in general this relationship is not linear and that practical procedures for column evaluation should be developed that take this non-linearity into account.     

On the applicability of the “abt” concept

Kaiser's “abt” concept rests on the experimental establishment of a linear relation between band width at half height, b_0.5, and capacity ratio, k, according to His column specification quantity, h_real, is dependent on the square of the slope a, obtained from a linear regression analysis based on this relation. It is shown in the present paper that an improvement of the experimental conditions leading to a lower extra-column contribution to band broadening, b, introduces a tendency towards a negative curvature in the plot at low k values. The mean slope increases, and an uncritical linear regression would yield an h_real-value which is higher than before and which would be in the opposite direction to the requirements of a reliable column specification. Generally the linear regression analysis has to be moved to higher k regions in cases of curvature, especially as it is also shown that h_real is an estimation of the traditional HETP value, H∞, that would be obtained when k approaches infinity. This theoretically expected relation is a strong motivation for the use of h_real as a column specification, since the b_0.5-value associated with H∞ is expected to be practically independent of b.     

Small-angle X-ray study of air-dried elastoidin using three- and one- dimensional correlation functions obtained from slit-smeared intensity

In the present paper an isotropic sample of air-dried elastoidin has been studied considering it to be a non-ideal two-phase densely packed system after the theories by Vonk [1]. The relevant important physical parameters obtained for the sample areE, the width of the transition layer,D, the average periodicity transverse to the layers, S/V, the specific inner surface ₁ and ₂, the volume fraction of two phases, i. e. matter and void,l ₁ andl ₂ the transversal lengths,l _r, the range of inhomogeneity,l _c, the length of coherence and 2E/D, the volume fraction of the transition layer. The values ofE obtained by two approches as given by Vonk [1] and Ruland [2] show but a small difference indicating the correctness of the analysis.     

Practical capillary gas chromatography—a systematic approach

Capillary gc is now rapidly expanding. Naturally, initiation is most often attempted on the basis of the experience acquired with packed columns. However, such an extrapolation is successful only if a number of essential peculiarities of capillary gc are considered. Based on practical examples this paper discusses six essential details: 1) design and maintenance of the gas flow paths, 2) the greatly increased importance of sampling technique, which should not be confined just to stream splitting, 3) the problems in quantitative analysis arising from small sample size, 4) specific sources of trouble related to small amounts of liquid phase, 5) specific arguments for the choice of the carrier gas, clearly pointing to hydrogen as the ideal carrier and, 6) the different way to approach column production. Figures for all selected examples are given.     

热动力学对比进度法II. 2-2型可逆反应

在第Ⅰ报中,我们建立了可逆反应动力学的数学模型,提出了可逆反应热动力学的对比进度研究法.为了进一步验证和完善该数学模型及对比进度法,在前文基础上研究了2-硝基丙烷与吗啡啉的反应,测定了该反应在25.0℃及30.0℃时的正逆速率常数和平衡常数.并对热动力学对比进度法及实验结果进行了讨论.     

Molecular structure and spectral properties of thionaphthalimides

The molecular structure and absorption spectra of monothio- and dithio-naphthalimides were compared to their naphthalimide analogues using AM1, PM3 and ZINDO/S semiempirical quantum chemical methods. The substitution of the 4R-naphthalimide oxygen atoms by sulphur atoms resulted in a red-shift of the absorption spectra by Δλ_max60-65 and 100-140 nm, respectively. The thionated naphthalimide derivatives do not show observable fluorescence due to intersystem crossing to the triplet -states localised at the CS groups. The -absorption bands of monothioimides are located at 525-580 nm (ε=60-80) and those for dithioimides at 535-560 nm (ε=140-390) and 628-686 nm (ε=34-68). None of these transitions are solvent sensitive. The -transitions of N-phenylthioimides have also a small contribution from -states due to a partial conjugation between CS group and π-electronic system of the N-phenyl ring. As a result, the bands of aromatic substituted N-phenylthioimides are red-shifted as compared to those of the aliphatic N-methyl-thioimides.     

双级矩阵变换器驱动异步电动机的特性分析

分析了双级矩阵变换器的拓朴结构特点;推导出双级矩阵变换器整流级的脉宽调制算法和逆变级的空间矢量调制策略,并阐述了零电流换流的原理.在MATLAB/SIMULINK平台上建立了双级矩阵变换器的仿真模型,并针对其驱动异步电动机起动、运行的开环系统进行仿真.仿真结果验证了所提出的控制策略的可行性和正确性,表明双级矩阵变换器输入电压和电流为正弦脉冲,且基本同相位;输出线电压为正弦脉冲宽度调制且基波分量为绝对主要成分,具有优良的输入和输出特性.