Preparation of cyclopentene from cyclopentadiene

Summary A convenient laboratory method is proposed for the preparation of cyclopentene by the hydrogenation of cyclopentadiene. Yields of up to 70% are obtained.     

玉米芯酸水解残渣的热解特性

在热重分析仪和管式炉热解装置上对玉米芯酸水解残渣（简称残渣）的热解过程进行了研究,并利用气相色谱（GC）,气相色谱-质谱联用(GC-MS)和扫描电镜(SEM)对热解产物进行了分析。热重分析结果表明,残渣的热裂解主要发生在280℃~ 450℃,仅在340.7℃有一个明显的失重峰。管式炉热解实验表明, 随着热解终温的升高,残渣的气相产物产率明显增加,而固相和液相产物产率均有所下降。GC分析结果表明,H₂和CH₄的产率随着热解终温的升高而升高,CO₂产率呈现下降趋势; 与玉米芯热解气相产物相比,残渣热解CO、H₂和CH₄的产率较高,CO₂产率较低。GC-MS结果表明,残渣热解焦油的主要成分为酚类物质和多环芳烃。SEM结果表明,随着热解终温的升高,残渣热解焦炭的表面结构趋于有序化。     

New approaches to syntheses of diethers and haloethers from cyclopentadiene

Cyclopentadiene (CPD) is oxidized by copper(ii) bromide and chloride in alcohol solutions to form dialkoxy- and haloethers and exhibits a higher reactivity than butadiene. Dialkoxy-, chloroalkoxy-, and dichlorocyclopentenes are formed from CPD and CuCl₂ without catalysts. The reaction selectivity (yield of ethers calculated per consumed CuBr₂) reaches 98%. The characteristic feature of the oxidation mechanism is the parallel formation of all reaction products through a common intermediate (presumably, the bromonium cation) and bromine-containing carbocationic intermediates.     

Pyrolytic production of microporous charcoals from different wood resources

A series of porous chars has been obtained by heat treatment of unconventional raw materials, including plants belonging to short rotation woody crops (Salix viminalis, Salix fragilis). The pyrolysis conditions (1–3 h, 600–900 °C) were the same for the production of all chars, e.g., mesoporous and microporous chars. Salix viminalis wood exhibited an advantage over the other materials, because the obtained material had microporous structure such as carbon molecular sieves. Similar properties (surface area, total pore volume, pore size distribution) were observed for charcoals produced from pine wood (Pinus silvestri), but the thermal stability of these properties was inferior. Furthermore, we have also discussed economical and environmental issues associated with the exploitation of wood resources.     

Anharmonic thermochemistry of cyclopentadiene derivatives

This paper focuses on the thermochemistry of some derivatives of cyclopenta‐1,3‐diene, namely, 5‐methylcyclopenta‐1,3‐diene, 5‐ethylcyclopenta‐1,3‐diene, 5‐formylcyclopenta‐1,3‐diene, 5‐methylcyclopenta‐1,3‐diene‐1‐yl radical, 5‐ethylcyclopenta‐1,3‐diene‐1‐yl radical, 5‐carbonylcyclopenta‐1,3‐diene radical, 1‐formylcyclopenta‐2,4‐diene‐1‐yl radical, 5‐methylenecyclopenta‐1,3‐diene radical, 5‐ethylidenecyclopenta‐1,3‐diene radical, and 3,6‐dimethylenecyclohexa‐1,4‐diene. Several different chemistries of these compounds are of interest in combustion modeling. Here, we present gas‐phase thermochemical properties for the above cited species, which are, except for 3,6‐dimethylenecyclohexa‐1,4‐diene, previously unknown. These were obtained from corrected (using bond additivity corrections) high‐level ab initio quantum chemistry calculations validated with well‐known compounds including cyclopentane, cyclopentene, cyclopenta‐1,3‐diene, and cyclopentadienyl radical. Heat capacities and entropies have been corrected for anharmonic molecular motions, in particular for internal rotations. © 2003 Wiley Periodicals, Inc. Int J Chem Kinet 35: 453–463, 2003     

Pyrolytic carbon film electrodes

Home-made pyrolytic carbon film electrodes (PCFE) were tested in voltammetric experiments. Different drugs were analyzed by differential pulse voltammetry. In many cases the reproducibility of the signals is as satisfactory as by using glassy carbon electrodes (GCE). The cleaning procedure is very easy to accomplish by wiping off the electrode surface with a paper tissue dipped into methanol. The peak- to residual current rate is much better at the PCFE than at the GCE. Therefore the detection limit is lowered at the former.     

4-Nitrobenzenediazonium salt and cyclopentadiene

The title reaction, carried out without solvent at ?50°C raised to room temperature, produces the hydrazonic 1:2 adduct 6 and the 1:3 adducts 9a and 9b whereas in methanol at ?10°C the intermediate cyclopentadienone-4-nitrophenylhydrazone (5) adds a solvent molecule; the azo coupling does not require the cyclopentadienide anion, as demonstrated by the behavior of spiro [2.4] heptadiene (12).     

Molecular structure of cyclopentadiene from its NMR spectrum in a nematic solvent

The NMR spectrum of cyclopentadiene partially oriented in a nematic phase has been measured and the proton geometry has been determined. The results are compared with those deduced from microwave spectroscopy.     

Reaction of atomic oxygen with cyclopentadiene

The reaction of 1,3-cyclopentadiene (CPD) with ground-state atomic oxygen O(³P), produced by mercury photosensitized decomposition of nitrous oxide, was studied. The identified products were carbon monoxide and the following C₄H₆ isomers: 3-methylcyclopropene, 1,3-butadiene, 1,2-butadiene, and 1-butyne. The yield of carbon monoxide over oxygen atoms produced (?_CO) was equal to the sum of the yields of C₄H₆ isomers in any experiment. ?_CO was 0.43 at the total pressure of 6.5 torr and 0.20 at 500 torr. We did not succeed in detecting any addition products such as C₅H₆O isomers. It was found that 3-methylcyclopropene was produced with excess energy and was partly isomerized to other C₄H₆ isomers, especially to 1-butyne. The excess energy was estimated to be about 50 kcal/mol. The rate coefficient of the reaction was obtained relative to those for the reactions of atomic oxygen with trans-2-butene and 1-butene. The ratios k_CPD+O/k_{trans-2-butene+O}= 2.34 and k_CPD+O/k_1-butene+O = 11.3 were obtained. Probable reaction mechanisms and intermediates are suggested.     

Pyrolytic carbon film electrodes

Home-made pyrolytic carbon film electrodes (PCFE) were tested in voltammetric experiments. Different drugs were analyzed by differential pulse voltammetry. In many cases the reproducibility of the signals is as satisfactory as by using glassy carbon electrodes (GCE). The cleaning procedure is very easy to accomplish by wiping off the electrode surface with a paper tissue dipped into methanol. The peak- to residual current rate is much better at the PCFE than at the GCE. Therefore the detection limit is lowered at the former.