On the mechanism of the N,N‐dimethyl amination of Grignard reagents: a kinetic study

A direct kinetic study is reported for the electrophilic amination of substituted phenylmagnesium bromides with N,N‐dimethyl O‐(mesitylenesulfonyl)hydroxylamine in THF. Rate data, Hammett relationship, and activation entropy are consistent with a S_N2 displacement involving the attack of carbanions to sp³N in the amination reagent (AR). Copyright © 2007 John Wiley & Sons, Ltd.     

Initiation of petroleum formation and antioxidant function – a DFT study of sulfur?sulfur bond dissociation enthalpies

Experimental studies showed that sulfur radicals play the vital role in petroleum formation. 1 Sulfur‐ centered radicals also exhibit activities in antioxidant functions. Here we conduct a theoretical investigation of their precursor‐disulfides. By investigation into substituent effect on sulfur? sulfur bond dissociation enthalpies (S? S BDEs), we would like to find the most effective provider for sulfur radicals. In the present work, 50 alpha‐substituted disulfides and 16 para‐substituted aryl disulfides are studied systematically, with the general formula XS‐SX or HS‐SX. The substituent effect on S? S BDEs is found to be very eminent, ranging from 33.2 to 75.0 kcal/mol for alpha‐substituted disulfide, and from 43.7 to 59.7 kcal/mol for para‐substituted phenyl disulfides. We also evaluate the performance of 44 density functional methods to get an accurate prediction. A further study indicates that substituents play a major role in radical energies, instead of molecule energies, which is substantiated by the good linearity between XS‐SX bond dissociation enthalpy (BDE) and HS‐SX BDE. Copyright © 2007 John Wiley & Sons, Ltd.     

Correlation of substituted aromatic β‐diketones' characteristic protons chemical shifts with Hammett substituent constants

Influence of dibenzoylmethane's substituents in meta and para positions on chemical shift values of tautomers' characteristic protons was investigated in four solvents with ¹H NMR spectroscopy: acetone‐d₆, benzene‐d₆, CDCl₃ and deuterated dimethyl sulfoxide (DMSO‐d₆). It was proved that the influence of substituents on chemical shifts strongly depends on the kind of the solvent; the greatest changes were observed in benzene‐d₆ and the smallest in CDCl₃. In acetone‐d₆ and DMSO‐d₆, the influence of substituents on chemical shifts is similar and the most regular. It allowed a fair correlation of chemical shifts of para‐substituted dibenzoylmethane derivatives' characteristic protons with Hammett substituent constants in these solvents. In CDCl₃, characteristic protons' chemical shifts were near ¹H NMR spectroscopy measurement error limits, and, therefore, correlation with Hammett substituent constants in this solvent was unsatisfactory. In benzene, although the changes of chemical shifts are the most evident, the changes are also the most irregular, and, therefore, correlation in this solvent failed completely. Results of meta‐substituted derivatives were much more irregular, and their correlation with Hammett substituent constants was poor in all investigated solvents. Copyright © 2013 John Wiley & Sons, Ltd.     

Kinetics and Mechanism of Dehydrochlorination of 3‐Chloro‐1,5‐diarylformazans and Their Mass Spectra

In aqueous dioxane containing triethylamine the title 3‐chloroformazans 1 are converted into the corresponding 1,4‐bis(arylazo)‐3,6‐diaryl‐1,2,4,5‐tetrazines 3 via head‐to‐tail dimerization of the intitially formed 1,3‐dipolar ions 2. The kinetics of triethylamine‐catalyzed dehydrochlorination of 1 in 70% dioxane at 27°C and ionic strength of 0.1 were studied. The rate data were linearly correlated with enhanced Hammett substituent constants σ_x^? and an overall ρ value of 0.2 was determined for the variation of the N‐aryl substituent. These results were interpreted in terms of a two‐step mechanism. Also, the mechanisms of the unimolecular fragmentation of 1 and 3 in the mass spectrometer are discussed.     

Impact of M1A1 main battle tank disturbance on soil quality, invertebrates, and vegetation characteristics

Military training commonly results in land degradation, but protocols for assessing and predicting long-term environmental impact are lacking. An ability to assess the impact of repeated disturbance and subsequent recovery is needed to balance training requirements against environmental quality. To develop methodology for assessing soil quality, a study evaluating disturbance resulting from tank maneuvers was initiated on Fort Riley Military Installation, Kansas. The objectives were to identify and quantify soil-quality indicators on two soil types exposed to controlled tank traffic. We examined physical, chemical, and biotic indicators after treatments were applied during wet and dry soil conditions. A randomized complete-block design, with three blocks per soil type and three treatments per block, was used. Treatments consisted of disturbance created by a 63-ton M1A1 tank making five passes in a figure-8 pattern during either dry or wet soil conditions. The M1A1 was operated at a speed of approximately 8 km/h. Control plots received no tank traffic. Soil-quality indicators evaluated were soil compaction, soil penetration resistance, rut depth, soil bulk density, soil texture, soil chemical composition, plant biomass, soil microbial diversity, and nematode and earthworm taxa. Soil-quality indicators were sampled within one week after tank disturbance. Preliminary data indicate soil-texture-dependent treatment effects (p  0.05) for bulk density and porosity. Bulk density increased and porosity decreased on trafficked areas, in the silt loam soil, but showed no change in the silty clay loam soil. Disturbance during wet soil conditions raised penetrometer resistance and gravimetric water content more than disturbance during dry soil conditions (p  0.05). A significant difference in disturbance was measured between the outside and inside portion of the same track (p  0.01 and 0.001, respectively). The outside track caused the greatest amount of disturbance, as measured by the height of the disturbed soil ridge above the track bed. Tank disturbance significantly reduced total vegetative biomass (p  0.05) compared with that of un-trafficked areas. Disturbance under wet soil conditions significantly reduced grass biomass (p = 0.040), whereas disturbance under dry soil conditions significantly reduced forb biomass (p = 0.0247) compared to un-trafficked areas. Total earthworm abundance (p = 0.011) was reduced by 82% when disturbance occurred during wet soil conditions regardless of soil type.     

Investigation of Lewis Acid versus Lewis Base Catalysis in Asymmetric Cyanohydrin Synthesis

The asymmetric addition of trimethylsilyl cyanide to aldehydes can be catalysed by Lewis acids and/or Lewis bases, which activate the aldehyde and trimethylsilyl cyanide, respectively. It is not always apparent from the structure of the catalyst whether Lewis acid or Lewis base catalysis predominates. To investigate this in the context of using salen complexes of titanium, vanadium and aluminium as catalysts, a Hammett analysis of asymmetric cyanohydrin synthesis was undertaken. When Lewis acid catalysis is dominant, a significantly positive reaction constant is observed, whereas reactions dominated by Lewis base catalysis give much smaller reaction constants. [{Ti(salen)O}₂] was found to show the highest degree of Lewis acid catalysis, whereas two [VO(salen)X] (X=EtOSO₃ or NCS) complexes both displayed lower degrees of Lewis acid catalysis. In the case of reactions catalysed by [{Al(salen)}₂O] and triphenylphosphine oxide, a non‐linear Hammett plot was observed, which is indicative of a change in mechanism with increasing Lewis base catalysis as the carbonyl compound becomes more electron‐deficient. These results suggested that the aluminium complex/triphenylphosphine oxide catalyst system should also catalyse the asymmetric addition of trimethylsilyl cyanide to ketones and this was found to be the case.     

Life cycle assessment and sustainability analysis of products, materials and technologies. Toward a scientific framework for sustainability life cycle analysis

There are many approaches to study the environmental and sustainability aspects of production and consumption. Some of these reside at the level of concepts, e.g., industrial ecology, design for environment, and cleaner production. Other approaches are based on the use of quantitative models, e.g., life cycle assessment, material flow accounting and strategic environmental assessment. This paper focuses on the development of a framework that is able to incorporate different models for environmental analysis, with the option of a broader scope that also includes economic and social aspects, thus covering the three pillars of sustainability. This framework builds on the ISO-framework for life cycle assessment, but takes a broader view, and allows us to move from micro questions on specific products, via meso questions on life styles up to macro questions in which the entire societal structure is part of the analysis.     

Synthetic indicators of mutual funds’ environmental responsibility: An application of the Reference Point Method

Socially Responsible Investing (SRI) is broadly defined as an investment process that integrates not only financial but also social, environmental, and ethical (SEE) considerations into investment decision making. SRI has grown rapidly around the world in the last decades. In the last years, given the causes of the 2008 financial crisis, ethical, social, environmental and governance concerns have become even more relevant investment decision criteria. However, while a diverse set of models have been developed to support investment decision-making based on financial criteria, models including also social responsibility criteria are rather scarce.     

基于信息显著性差异的绿色产业评价指标筛选模型及实证

依据广义的绿色产业内涵,通过信息显著性差异与信息冗余分析定量筛选指标,建立了包括绿色生产指标层、绿色生态环境指标层、绿色消费方式指标层的大连市绿色产业评价指标体系。本文的创新与特色一是通过负载系数大小差异进行信息显著性分析,删除负载系数小、对综合评价结果影响弱的指标。克服了现有研究先进行相关分析剔除冗余指标,再利用负载系数大小差异筛选出反映信息显著性大的指标的弊端。事实上,指标间较高的相关性是计算负载系数的必要前提。因此,利用负载系数筛选指标前是不可进行指标的相关分析降低指标间的相关性的。二是通过结合专家知识经验辨析指标的实际含义,仅对反映信息可能重复的指标使用相关分析,剔除同指标层内相关系数较大的两个指标中反映指标层信息能力相对较弱的指标。克服了仅仅通过相关系数不能准确衡量指标间信息重复程度的弊端。研究结果表明,最终建立的指标体系通过25．68％的指标反映了97．09％的原始信息。通过与同类的指标体系进行对比,对大连市绿色产业评价指标体系的合理性做了进一步的分析。