Regioselectivity in the rhodium catalysed 1,4-hydrosilylation of isoprene. Aspects on reaction conditions and ligands

The regioselectivity in the Rh catalysed 1,4-hydrosilylation of isoprene was investigated. Variation of solvents and temperature did not significantly affect the isomer distribution between tail-product (I) and head-product (II). The choice of ligands had the greater influence, where Rh^I-based catalysts with the strong electron withdrawing ligand CO favoured production of isomer II, while Rh^I catalysts with strong electron donating ligands (for example triarylphosphines) gave isomer I as the main product. In contrast to the square planar carbonyl complex RhCl(CO)(PPh₃)₂, the square planar thiocarbonyl complex RhCl(CS)(PPh₃)₂, gave I as the major isomer.     

Effect of phase change materials on the hydration reaction and kinetic of PCM-mortars

The phase change materials are considered an attractive way to reduce energy consumption thanks to their heat storage capacity. Their incorporation in the construction materials allows the energy to be an integral part of the building structure. Even though PCMs have shown their reliability from a thermal point of view, some drawbacks linked to their use were emphasized such as the loss of the compressive strength of the PCM-material. This paper attempts to provide an explanation by the investigation of the hydration kinetic of PCM-mortars. The semi-adiabatic Langavant test was adapted to this case. The numerical diffuse element method was used for the computation of the heat flux, which is a compulsory step for the determination of the hydration degree. The results showed a lower heat released by the PCM mortars compared to a control mortar as well as a delay in the hydration progress with the addition of PCMs.     

Substituent effects in acid-catalyzed hydration of alkenes, measured under consistent reaction conditions

A set of convenient conditions for the title reaction is used to determine directly relative reactivities of alkenes with widely-varying steric requirements. Previous determinations did not use one set of conditions for all alkenes, but developed parameters in order to compare alkene reaction rates run in different solvents and in different concentrations; such an indirect reactivity comparison can introduce errors. Relative rates established under this common set of reaction conditions are compared to those previously calculated by using correction parameters. Comparison reveals that the approximate method overestimated effects of some groups attached to CC, such as methyl and chloro.     

Effect of reaction conditions on the rearrangement of radicals in solution

Russian Chemical Bulletin -     

A DFT study on the regioselectivity of the reaction of dichloropropynylborane with isoprene

This theoretical study deals with the reaction of isoprene and dichloropropynylborane. We report the results of the DFT calculations applied to the two processes involved, Diels-Alder cycloaddition and 1,4-alkynylboration. The boron influences both the chemoselectivity and the regioselectivity of this reaction through secondary orbital interactions (SOI hereafter) that give rise to transition structures with strong [4 atom + 3 atom] character. The "meta" regioselectivity observed experimentally for the reaction between 2-substituted 1,3-dienes and alkynyldihaloboranes has been explained as a result of the higher stabilization of these transition structures with "meta" orientation. Intrinsic reaction coordinate calculations were performed to determine connectivities and established the remarkable result that the geometrically very similar transition structures leading to both regioisomeric 1,4-alkynylboration products correspond to different pathways. For the "meta" orientation a direct alkynylboration of the diene through a concerted transition structure was found.     

反应条件对悬浮床加氢裂化过程的影响

在间歇式反应釜中,考察了氢分压3MPa～28MPa对叔丁基苯和正丁基苯裂化反应的影响。结果表明,氢分压变化对不同分子结构的反应物有不同的影响。叔丁基苯的转化率随氢分压的升高而提高,正丁基苯的转化率随氢分压的升高而降低。氢分压的提高促进了与芳香环连接的碳键的断裂,与反应物的分子结构无关。在此基础上,考察了初氢压的变化对轮古常压渣油（LGAR）和克拉玛依常压渣油（KMAR）悬浮床加氢裂化的影响,讨论了温度和反应时间对悬浮床加氢过程的影响,初氢压的提高对渣油的转化和甲苯不溶物的生成都有促进作用。     

Effect of the reaction conditions on the degree of substitution of carboxymethyl cellulose

Cellulosic fabric composed of 84 % cotton and 16 % viscose rayon fiber was carboxymethylated. The influence of the reaction parameters (concentration of the reagents, time of reaction) on the degree of substitution was studied in the process, applying sodium hydroxide and monochloroacetic acid in one bath. Two kinds of regression equations were used to calculate approximately the degree of substitution. These polynomials can be used for the selection of reaction parameters to obtain a sample of a given degree of substitution.     

Effect of reaction conditions on hydrothermal degradation of cornstalk lignin

Cornstalk lignin was hydrothermally depolymerized at mild conditions in ethanol–water for producing value-added phenolics. The effects of residence time (from 30 min to 180 min), reaction temperature (from 498 K to 573 K) and concentration of ethanol (from 0% to 95% vol.) on yields of liquid products and phenolic compounds were studied in detail. The optimal conditions of 523 K, 90 min and 65% vol. ethanol–water resulted in the highest yield of liquid products (∼70 wt.%). The liquid products were analyzed by gas chromatography–mass spectrometry (GC–MS) to confirm the presence of primarily heterocycle (2,3-dihydrobenzofuran) and phenolics (such as ethylphenol, guaiacol, ethylguaiacol and syringol). Reaction conditions had significant effects on yield and composition of liquid products.     

Selective hydroformylation-hydrogenation tandem reaction of isoprene to 3-methylpentanal

The hydroformylation of isoprene catalysed by rhodium phosphine complexes usually yields a broad mixture of the monoaldehydes, the isomeric methylpentenals, as well as the dialdehyde 3-methyl-1,6-hexandial. Under usual reaction conditions the products of a consecutive hydrogenation are only formed as minor by-products. Surprisingly we discovered now a selective auto-tandem reaction consisting of a hydroformylation and a hydrogenation step if a rhodium complex with the chelate ligand bis(diphenylphosphino)ethane is used as catalyst. If branched aromatic solvents like cumene are applied the conversion of isoprene is nearly quantitatively and the yield of the tandem product 3-methylpentanal amounts to 85%.     

Unusual regioselectivity in a Diels-Alder reaction of isoprene with levoglucosenone

The ZnCl₂-catalyzed [4+2]-cycloaddition of isoprene with levoglucosenone is highly regio- and stereoselective.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 2047–2049, August, 1996.     

Temperature and crosslinking effects on the swelling of poly(isoprene) in isopiestic conditions

Isopiestic measurements of solvent uptake have been made in the synthetic isoprene/benzene system for both crosslinked and uncrosslinked polymers in order to revisit the question of the swelling activity parameter S. Both the nonzero value of S at zero swelling and the appearance of a peak in S vs. degree of swelling have been observed in some solvent/rubber pairs and we here investigate both the crosslink and temperature dependencies of these phenomena. The data analysis is an extension of prior work from this laboratory using continuum thermodynamics concepts and avoiding molecular models in an attempt to establish the fundamental phenomenology of the process and the validity or lack of validity of the hypothesis that the mixing and elastic contributions to the free energy of networks are separable. We present results from measurements in benzene vapors at temperatures between 10 and 55°C for an uncrosslinked rubber and rubbers crosslinked with 1, 5, 10, and 15 parts per hundred dicumyl peroxide. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 817–826, 1997     

Effect of hydration on the FH... NH3 proton transfer reaction: Comparison of some quantum chemical approximations

The proton transfer energy curve for the hydrogen fluoride-ammonia system was studied by semi-empirical methodsin vacuo and in a hydrated form. It was found that the simple point-charge approximation cannot be used to estimate the Coulombic interaction term rather the molecular electrostatic potential has to be considered. Furthermore, even inclusion of the mutual polarization term is insufficient if quantitative agreement with CNDO/2 supermolecule results is desired since charge transfer plays an important role.     

Effect of ZnO on the hydration of Portland cement

ZnO added to the system Portland cement — water changes the kinetics of the hydration process substantially. Amorphous zinc hydroxide is formed and inhibits the reaction of tricalcium silicate with water, resulting in an induction period prolongation. This effect depends on the amount of ZnO added to the hydrated paste. The transformation of zinc hydroxide into calcium hydrozincate provokes the further hydration.

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Zusammenfassung Durch den Zusatz von ZnO zum System Portlandzement-Wasser wird die Kinetik des Hydratationsprozesses grundlegend verändert. Amorphes Zinkhydroxid wird gebildet, was einen Inhibitor für die Tricalciumsilikatreaktion mit Wasser darstellt, wodurch die Induktionsperiode verlängert wird. Dieser Effekt hängt von der Menge ZnO ab, die dem Zementbrei zugesetzt wurde. Die Umwandlung von Zinkhydroxid zu Calciumhydrozinkat führt eine weitere Hydratation herbei.

     

Atmospheric photooxidation of isoprene part II: The ozone-isoprene reaction

A series of experiments have been performed to study the ozone-isoprene reaction in a smog chamber by adding externally produced O₃ to the hydrocarbon in the dark. A chemical tracer, methyl cyclohexane, was added to probe the OH formation in the system. O(³P) formation was also examined using the known distribution of products that are unique to the O(³P)-isoprene reaction (part I). The results provide clear evidence that both OH and O(³P) are produced by the O₃-isoprene reaction directly in large quantities; about 0.68 ± 0.15 and 0.45 ± 0.20 per O₃-isoprene reaction, respectively. These additional radicals severely complicate the analysis of the O₃ reaction, hence, computer kinetic modeling was necessary to ascertain the products of the O₃ reaction itself, corrected for OH and O(³P) reactions. The product distribution, which differs dramatically from that published previously, is: 67 ± 9% methacrolein, 26 ± 6% methyl vinyl ketone, and 7 ± 3% propene, accounting for 100 ± 10% of the reacted isoprene. Applicability of these results to the gas-phase O₃ reaction with other unsaturated hydrocarbons is briefly discussed.     

Effect of initiation conditions on the direct polycondensation reaction using triphenyl phosphite and pyridine

In a model reaction of terephthalic acid with aniline by using triphenyl phosphite in a mixed solvent of pyridine and N-methylpyrrolidone (NMP), mono- and dianilides were produced with relative yields varying with the content of pyridine in the solvent. The polycondensation of terephthalic acid with aromatic diamines was found to proceed more favorably via monoamidation, and highmolecular-weight polyterephthalamides were prepared by controlling initiation conditions (selective activation of carboxylic groups), such as initial solvent systems, including the amount and kind of pyridines and initiation temperatures.     

Effect of reaction conditions on synthesis and properties of multiarm star-branched polyisobutylenes

A series of multiarm star-branched polyisobutylenes was synthesized from narrow polydispersity arms with molecular weights ranging from 12,000 to 60,000 g/mol, via living carbocationic polymerization using the cumyl chloride/TiCl₄/pyridine initiating system and divinylbenzene (DVB) as core-forming comonomer. The effect on star development of arm molecular weight, temperature, solvent composition, and DVB concentration was studied. The rate of star formation and the weight-average number of arms per star polymer, N̄_w, were found to scale inversely with arm molecular weight; N̄_w = 60 was attained for 13,100 g/mol arms, but N̄_w = 2.5 for 60,000 g/mol arms. It was established that star formation was much faster at −80°C compared to 23°C, regardless of solvent composition. For hexane : methyl chloride (MeCl) solvent compositions containing from 40 to 60 vol % MeCl, star–star coupling was observed at −80°C, but not at 23°C, even after 312 h; for the most polar 40 : 60 hexane : MeCl composition, star–star coupling was so extensive at −80°C that gelation was observed after only 44 h. The rate of star formation was found to be substantially higher in 60 : 40 hexane : MeCl compared to 60 : 40 hexane : methylene chloride (MeCl₂). Some reactions containing MeCl were immediately warmed to 23°C after DVB addition, and the MeCl thus volatilized was replaced with either MeCl₂ or hexane for the duration of the star-forming reaction. Slightly higher rates were consistently observed when MeCl₂ was the replacement solvent. The strong influence of initial MeCl content on rate of star formation was found to persist throughout the star-forming reaction, even when the solvent was immediately converted to 100% hexane. The fraction of arms that remained unlinked into stars was found to be higher at the higher temperature and at lower solvent polarity. Regardless of solvent or temperature, the residual arm fraction was approximately the same at a given stage of star development as measured by the average number of arms per star. One star sample was produced with the UV-transparent 2-chloro-2,4,4-trimethylpentane initiator; analysis showed that the residual arm fraction had approximately the same UV absorbance as the star fraction, indicating efficient crossover to DVB and the potential for approximately quantitative arm incorporation given sufficient time. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36 : 471–483, 1998     

异戊二烯与OH自由基光化学反应的二次有机气溶胶的生成

利用烟雾箱模拟装置,研究了异戊二烯与OH自由基反应的二次有机气溶胶(SOA)的生成.反应中生成的气相产物通过质子转移反应质谱仪(PTR-MS)测定,SOA的浓度及粒径谱分布通过高分辨率粒径谱仪(EEPS3090)测定.研究表明:甲基丙烯醛(MAC)/甲基乙烯基酮(MVK)、乙醛、甲醛、甲醇、甲酸/乙醇、乙醇醛、甲基乙二醛、丙酮/丙醛等为主要气相产物,各组实验中MAC/MVK和乙醛浓度达到最大时,其产率分别介于13.78%～37.72%和5.38%～9.34%(以C计)范围内;SOA生成量及其中值粒径随异戊二烯反应量的增加而增加,气相物质稳定后,SOA产率在5.6%～11.7%范围内,粒径在22～165nm范围内.     

Radiation-induced emulsion polymerization of ethylene. I. Effect of reaction conditions on the polymerization

The effect of reaction conditions on the rate of radiation-induced emulsion polymerization of ethylene was studied by use of a 500-ml autoclave. Among various kinds of emulsifiers, a series of potassium salts of fatty acids gave high rates of the polymerization. The polymerization was inhibited by the presence of oxygen, but the rate of polymerization followed by the induction period was not influenced by the initial presence of oxygen. Stirring rate and the monomer: water ratio did not affect the rate of polymerization. The rate of polymerization was maximum at about 80°C, and number-average molecular weight was influenced by the temperature in a similar manner as the rate of polymerization. This suggests that the change of mobility of propagating radical in the polymer particle changes the rate of termination reaction. The rate of polymerization was proportional to the 1.7 power of the reaction pressure.