Influence des groupes tert-butyle, triméthylsilyle et triméthylgermyle sur la stéréochimie de réactions d'addition en série cyclohexénique. I. Synthèse des alcènes et hydroboration

1974 ◽  
Vol 52 (24) ◽  
pp. 4133-4138 ◽  
Author(s):  
Christian Freppel ◽  
Marc-André Poirier ◽  
Jean-Claude Richer ◽  
Yvette Maroni ◽  
Georges Manuel

Syntheses of 1-tert-butyl-(1a), 1-trimethylsilyl-(1b) and 1-trimethylgermanyl-4,4-dimethylcyclohexene (1c) are described as are those of 6-tert-butyl- (2a), 6-trimethylsilyl- (2b) and 6-trimethylgermanyl-3,3-dimethylcyclohexene (2c). The stereochemistry of the hydroboration of these alkenes is examined. The stereochemistry is governed, on the one hand, by the steric influence of the various substituents and on the other by the steric and electronic effects of the trimethylsilyl and trimethylgermanyl groups. [Journal translation]

2018 ◽  
Vol 71 (4) ◽  
pp. 222
Author(s):  
Matthias Lein

We evaluate the balance of steric and electronic effects in the site selectivity of the binding of [Rh(Me5Cp)]+ ([RhCp·]+) to the three possible coordination sites of the polyaromatic hydrocarbon (PAH) hexa-tert-butyl-hexa-peri-hexabenzocoronene (HBBC). We find that despite the close proximity of sterically demanding tert-butyl groups to the methyl groups of the Cp* ligand, the extent of steric repulsion is minor compared to electronic interaction from bond formation and that the site selectivity is best explained in terms of the electronics of the (poly) aromatic system. This is in contrast to previous investigations on similar systems with a COD ligand where steric influence has been shown to dominate selectivity.


Synthesis ◽  
2020 ◽  
Vol 52 (06) ◽  
pp. 796-806 ◽  
Author(s):  
Si-Zhe Song ◽  
Youren Dong ◽  
Guo-Ping Ge ◽  
Qiang Li ◽  
Wen-Ting Wei

Nitro compounds serve as valuable intermediates for pharmaceuticals, agrochemicals, dyes, and polymers. In recent years, radical nitration using tert-butyl nitrite (t-BuONO) has attracted wide attention and desirable progress has been made. On the one hand, t-BuONO is a potential active nitro radical source and can react with various functional groups. On the other hand, as a green and novel nitration reagent, t-BuONO has relatively low price and can easily produce a radical under mild conditions, which undoubtedly provides a simple and efficient way for nitration reactions. To date, some important reviews are available that summarize the synthesis of nitro compounds. To the best of our knowledge, however, there is still no review that exclusively discusses the synthesis of nitro compounds using t-BuONO through a radical strategy. Therefore, this review aims to highlight the recent advances in radical nitration using t-BuONO as nitration reagent. The main progress in this area has been presented according to the type of reaction substrates. Special attention has been paid discussion of the reaction mechanisms and selected examples of substrates have been given. We hope this paper will be a useful reference and inspiration for those who are exploring the synthesis of nitro compounds using t-BuONO.1 Introduction2 Radical Nitration of Alkenes3 Radical Nitration of Aromatics4 Radical Nitration of Alkynes5 Radical Nitration of 1,n-Enynes6 Radical Nitration of Alkanes7 Summary and Perspective


1975 ◽  
Vol 26 ◽  
pp. 395-407
Author(s):  
S. Henriksen

The first question to be answered, in seeking coordinate systems for geodynamics, is: what is geodynamics? The answer is, of course, that geodynamics is that part of geophysics which is concerned with movements of the Earth, as opposed to geostatics which is the physics of the stationary Earth. But as far as we know, there is no stationary Earth – epur sic monere. So geodynamics is actually coextensive with geophysics, and coordinate systems suitable for the one should be suitable for the other. At the present time, there are not many coordinate systems, if any, that can be identified with a static Earth. Certainly the only coordinate of aeronomic (atmospheric) interest is the height, and this is usually either as geodynamic height or as pressure. In oceanology, the most important coordinate is depth, and this, like heights in the atmosphere, is expressed as metric depth from mean sea level, as geodynamic depth, or as pressure. Only for the earth do we find “static” systems in use, ana even here there is real question as to whether the systems are dynamic or static. So it would seem that our answer to the question, of what kind, of coordinate systems are we seeking, must be that we are looking for the same systems as are used in geophysics, and these systems are dynamic in nature already – that is, their definition involvestime.


Author(s):  
Stefan Krause ◽  
Markus Appel

Abstract. Two experiments examined the influence of stories on recipients’ self-perceptions. Extending prior theory and research, our focus was on assimilation effects (i.e., changes in self-perception in line with a protagonist’s traits) as well as on contrast effects (i.e., changes in self-perception in contrast to a protagonist’s traits). In Experiment 1 ( N = 113), implicit and explicit conscientiousness were assessed after participants read a story about either a diligent or a negligent student. Moderation analyses showed that highly transported participants and participants with lower counterarguing scores assimilate the depicted traits of a story protagonist, as indicated by explicit, self-reported conscientiousness ratings. Participants, who were more critical toward a story (i.e., higher counterarguing) and with a lower degree of transportation, showed contrast effects. In Experiment 2 ( N = 103), we manipulated transportation and counterarguing, but we could not identify an effect on participants’ self-ascribed level of conscientiousness. A mini meta-analysis across both experiments revealed significant positive overall associations between transportation and counterarguing on the one hand and story-consistent self-reported conscientiousness on the other hand.


2005 ◽  
Vol 44 (03) ◽  
pp. 107-117
Author(s):  
R. G. Meyer ◽  
W. Herr ◽  
A. Helisch ◽  
P. Bartenstein ◽  
I. Buchmann

SummaryThe prognosis of patients with acute myeloid leukaemia (AML) has improved considerably by introduction of aggressive consolidation chemotherapy and haematopoietic stem cell transplantation (SCT). Nevertheless, only 20-30% of patients with AML achieve long-term diseasefree survival after SCT. The most common cause of treatment failure is relapse. Additionally, mortality rates are significantly increased by therapy-related causes such as toxicity of chemotherapy and complications of SCT. Including radioimmunotherapies in the treatment of AML and myelodyplastic syndrome (MDS) allows for the achievement of a pronounced antileukaemic effect for the reduction of relapse rates on the one hand. On the other hand, no increase of acute toxicity and later complications should be induced. These effects are important for the primary reduction of tumour cells as well as for the myeloablative conditioning before SCT.This paper provides a systematic and critical review of the currently used radionuclides and immunoconjugates for the treatment of AML and MDS and summarizes the literature on primary tumour cell reductive radioimmunotherapies on the one hand and conditioning radioimmunotherapies before SCT on the other hand.


2017 ◽  
Vol 47 (188) ◽  
pp. 487-494
Author(s):  
Daniel Mullis

In recent years, political and social conditions have changed dramatically. Many analyses help to capture these dynamics. However, they produce political pessimism: on the one hand there is the image of regression and on the other, a direct link is made between socio-economic decline and the rise of the far-right. To counter these aspects, this article argues that current political events are to be understood less as ‘regression’ but rather as a moment of movement and the return of deep political struggles. Referring to Jacques Ranciere’s political thought, the current conditions can be captured as the ‘end of post-democracy’. This approach changes the perspective on current social dynamics in a productive way. It allows for an emphasis on movement and the recognition of the windows of opportunity for emancipatory struggles.


1996 ◽  
pp. 13-23
Author(s):  
Mykhailo Babiy

Political ideological pluralism, religious diversity are characteristic features of modern Ukrainian society. On the one hand, multiculturalism, socio-political, religious differentiation of the latter appear as important characteristics of its democracy, as a practical expression of freedom, on the other - as a factor that led to the deconsocialization of society, gave rise to "nodal points" of tension, confrontational processes, in particular, in political and religious spheres.


2003 ◽  
pp. 15-26
Author(s):  
P. Wynarczyk
Keyword(s):  
The Core ◽  

Two aspects of Schumpeter' legacy are analyzed in the article. On the one hand, he can be viewed as the custodian of the neoclassical harvest supplementing to its stock of inherited knowledge. On the other hand, the innovative character of his works is emphasized that allows to consider him a proponent of hetherodoxy. It is stressed that Schumpeter's revolutionary challenge can lead to radical changes in modern economics.


2018 ◽  
pp. 49-68 ◽  
Author(s):  
M. E. Mamonov

Our analysis documents that the existence of hidden “holes” in the capital of not yet failed banks - while creating intertemporal pressure on the actual level of capital - leads to changing of maturity of loans supplied rather than to contracting of their volume. Long-term loans decrease, whereas short-term loans rise - and, what is most remarkably, by approximately the same amounts. Standardly, the higher the maturity of loans the higher the credit risk and, thus, the more loan loss reserves (LLP) banks are forced to create, increasing the pressure on capital. Banks that already hide “holes” in the capital, but have not yet faced with license withdrawal, must possess strong incentives to shorten the maturity of supplied loans. On the one hand, it raises the turnovers of LLP and facilitates the flexibility of capital management; on the other hand, it allows increasing the speed of shifting of attracted deposits to loans to related parties in domestic or foreign jurisdictions. This enlarges the potential size of ex post revealed “hole” in the capital and, therefore, allows us to assume that not every loan might be viewed as a good for the economy: excessive short-term and insufficient long-term loans can produce the source for future losses.


2009 ◽  
pp. 18-31
Author(s):  
G. Rapoport ◽  
A. Guerts

In the article the global crisis of 2008-2009 is considered as superposition of a few regional crises that occurred simultaneously but for different reasons. However, they have something in common: developed countries tend to maintain a strong level of social security without increasing the real production output. On the one hand, this policy has resulted in trade deficit and partial destruction of market mechanisms. On the other hand, it has clashed with the desire of several oil and gas exporting countries to receive an exclusive price for their energy resources.


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