Nuclear magnetic resonance studies of boron trihalide complexes of 1,1-BIS (dimethylamino) ethylene and related bases

Boron tribalide complexes of 1,1-bis(dimethylamino)ethylene (DME) , t etramethylurea (TMU), tetramethylguanidine (TMG) , and pentamethylguanidine (PMG) and also mixed boron t r ihalide adducts of DME have been investigated by 1H and 19F NMR spectroscopy. Both nitrogen and the C-Q-H carbon of DME are possible donor a toms to boron trihal ides but complexation has been found to occur only at carbon of DME. The initial adduct acts as a Bronsted acid and gives up a proton to free DME in solut ion. A side reaction in the DME-BF, system gives rise to trace amounts of a complex aSSigned as (DME)2BF2+. (DME)2BF2+ is produced in much larger quantities in t he DME-BF3-BC13 and DME-BF,-BBr, systems by reaction of free DME with DME:BF2X (X = Cl, Br). Restricted r otation about the C-N bonds of TMUlBC13 and n1U:BBr3 has been observed at low temperatures. This complements previous work in this system and confirms oxygen donation of TMU to boron trihalides . Restricted rotation at low temperatures also has been observed in DMEboron trihalide systems

The mechanism of formation of the mixed boron trihalide adducts of trimenthylamine

Boron trihalide and mixed boron trihalide adducts of trimethylamine have been prepared, and characterized by proton and fluorine N.M.R. spectroscopy. The acceptor power of the boron trihalides was seen to increase in the order BF3 < BC13 < BBr3 < BI3, corroborating previous evidence. The mixed boron trihalides had intermediate Lewis acidities. Solution reactions between adducts and free boron trihalides rapidly led to the formation of mixed adducts when the free boron trihalide is a stronger Lewis acid than that in the adduct. A slower reaction is observed when the free BX3 is a weaker Lewis aoid than that complexed. The mechanism of halogen exchange leading to the mixed (CH3)3NBX3 adducts was investigated. 10B labelling experiments precluded B-N bond rupture as a possible mechanism in solution; results are discussed in terms of halogen-bridged intermediates. Pre-ionization may be important for some systems. At higher temperatures, during gas phase reactions,B-N coordinate bond rupture may be the initial step of reaction. Two mixed adduots, namely (CH3)3NBClBr2 and (CH3)3NBHOIBr were prepared and characterized by Mass Spectrometry

Racemic and Enantioselective Total Syntheses of Mosquito Oviposition Pheromone from a Naturally Available Unsaturated Fatty Acid

The unnatural threo-6-acetoxy-5-hexadecanolide and the natural mosquito oviposition pheromone erythro-6-acetoxy-5-hexadecanolide were synthesized in a diastereodivergent fashion in 44% and 33% overall yield respectively from 5-bromovaleric acid and undecanal. The key step utilized a chemoenzymatic epoxidation-lactonization of a naturally available fatty acid to form the 6-hydroxy-5-hexadecanolide core.17 The epoxidation strategy was later adapted to allow for an asymmetric synthesis. Shi epoxidation afforded highly enantioenriched (5R, 6R)-6-hydroxyhexadecanolide (er = 10) in 70 % overall yield. Other derivatives of the chiral ketone catalyst were also screened. Finally, attempts were made to obtain the correct stereochemistry at C(6) of the target with a dynamic kinetic transformation using lipase and a transfer hydrogenation catalyst. Epimerization of the lactol with the transfer hydrogenation catalyst was successful, but lipase mediated reactions halted at <10 % conversion.

iTunesU - open educational content in audio and video formats available via iTunes

There is a wealth of open educational content in audio and video formats available via iTunes U, one of the services offered especially for education via iTunes. There are details of how to get started as well as an informative video to help you. Details of how to get started with sharing content can be found for developers.

Copyright Questions: Making chapters from a book available to your students

This narrated slideshow (8 minutes) shows how UK copyright law applies to an example book and explores how a tutor can make copies of selected chapters to distribute to students

A guide to making your e-thesis available

This 10-minute presentation introduces e-theses, outlines their benefits and the issues they raise and describes the process requird to create and submit them. It is available as an Adobe Presenter slideshow, as an MP4 video and as a YouTube video with optional captions for accessibility.

What resources are available to assist parents of hearing-impaired children to increase their children's reading abilitites?

This paper discusses the importance of parental efforts in the reading achievement attained by their hearing impaired children and the need for those parents to have the appropriate tools and resources to effectively assist their children.

Lesser Scaup Population Dynamics: What Can Be Learned from Available Data?

Populations of Lesser Scaup (Aythya affinis) have declined markedly in North America since the early 1980s. When considering alternatives for achieving population recovery, it would be useful to understand how the rate of population growth is functionally related to the underlying vital rates and which vital rates affect population growth rate the most if changed (which need not be those that influenced historical population declines). To establish a more quantitative basis for learning about life history and population dynamics of Lesser Scaup, we summarized published and unpublished estimates of vital rates recorded between 1934 and 2005, and developed matrix life-cycle models with these data for females breeding in the boreal forest, prairie-parklands, and both regions combined. We then used perturbation analysis to evaluate the effect of changes in a variety of vital-rate statistics on finite population growth rate and abundance. Similar to Greater Scaup (Aythya marila), our modeled population growth rate for Lesser Scaup was most sensitive to unit and proportional change in adult female survival during the breeding and non-breeding seasons, but much less so to changes in fecundity parameters. Interestingly, population growth rate was also highly sensitive to unit and proportional changes in the mean of nesting success, duckling survival, and juvenile survival. Given the small samples of data for key aspects of the Lesser Scaup life cycle, we recommend additional research on vital rates that demonstrate a strong effect on population growth and size (e.g., adult survival probabilities). Our life-cycle models should be tested and regularly updated in the future to simultaneously guide science and management of Lesser Scaup populations in an adaptive context.

The spatial prediction of soil mineral N and potentially available N using elevation

The precision farmer wants to manage the variation in soil nutrient status continuously, which requires reliable predictions at places between sampling sites. Ordinary kriging can be used for prediction if the data are spatially dependent and there is a suitable variogram model. However, even if data are spatially correlated, there are often few soil sampling sites in relation to the area to be managed. If intensive ancillary data are available and these are coregionalized with the sparse soil data, they could be used to increase the accuracy of predictions of the soil properties by methods such as cokriging, kriging with external drift and regression kriging. This paper compares the accuracy of predictions of the plant available N properties (mineral N and potentially available N) for two arable fields in Bedfordshire, United Kingdom, from ordinary kriging, cokriging, kriging with external drift and regression kriging. For the last three, intensive elevation data were used with the soil data. The mean squared errors of prediction from these methods of kriging were determined at validation sites where the values were known. Kriging with external drift resulted in the smallest mean squared error for two of the three properties examined, and cokriging for the other. The results suggest that the use of intensive ancillary data can increase the accuracy of predictions of soil properties in arable fields provided that the variables are related spatially. (c) 2005 Elsevier B.V. All rights reserved.