Download or read book Deuterium Isotope Effects on the Solvolysis Rates of Cyclopentyl Brosylates and Tosylates written by Jimmie Duane Christen and published by . This book was released on 1968 with total page 190 pages. Available in PDF, EPUB and Kindle. Book excerpt: "The brosylates and tosylates of cyclopentanol and its 1-d1, c̲i̲s̲-2-d1, t̲r̲a̲n̲s̲-2-d1, and 2,2,5,5-d4 analogs have been synthesized and their solvolysis rates measured at 25° in 70% vol. ethanol-water. The solvoylsis reactions were monitored by a conductance method. The isotope effects, k[subscript H]/k[subscript D], observed for the brosylates and tosylates of each of the isotopically substituted cyclopentyl alcohols are as follows: 1-d1-brosylate (1.1869) and 1-31-tosylate (1l1836); c̲i̲s̲-2-d1-brosylate (1.1533) and c̲i̲s̲-2-31-tosylate (1.1577); t̲r̲a̲n̲s̲-2-d1-brosylate (1.1803) and t̲r̲a̲n̲s̲-2-d1-tosylate (1.1765); 2,2,5,5-d4-brosylate (1.8881) and 2,2,5,5-d4-tosylate (1.8863). The closeness in magnitude of the isotope effects for the c̲i̲s̲- and t̲r̲a̲n̲s̲-isomers is important in that it shows the cyclopentyl system to be very nearly planer. If they had been greatly different it would have indicated that the ring was quite puckered. More important, however, is the fact that the t̲r̲a̲n̲s̲-isotope effect is greater than the c̲i̲s̲-isotope effect. this means that specific solvation of the [underscore Beta]-hydrogens, leading to an elimination driving force, is a possible explanation of secondary deuterium isotope effects. The isotope effects for the d4-compounsd were calculated by taking the products of the squares of the c̲i̲s̲- and t̲r̲a̲n̲s̲-isotope effects. The calculated isotope effect was 1.8530 for the d4-brosylate and 1.8552 for the d4-tosylate. These vales are very near the observed values of 1.8881 and 1.8863 for the brosylate and tosylate, respectively. Because of the great precision (~0.1-0.2%) of the technique used in obtaining these results, the difference between the calculated and the observed isotope effects for both the brosylate and tosylate is considered to be a true difference. However, the closeness of the calculated and observed values does indicate an almost cumulative isotope effects which supports the hyperconjugation postulate as a possible explanation of secondary deuterium isotope rate effects. There is a very close agreement between the isotope effects for the brosylate and tosylate of any one given isotopically substituted cyclopentyl alcohol, e.g., the greatest difference exhibited was that of 0.38% for the c̲i̲s̲-compounds. This close agreement tends to indicate that when changing from one leaving group to another structurally similar leaving group there is a negligible influence on the isotope effect. Attempts were made to synthesize 2,2-d2-cyclopentyl alcohol and c̲i̲s̲-2-d1-5,5-d2-cyclopentyl alcohol and the procedures are described in the Experimental section. Unfortunately, these synthetic procedures were unsuccessful"--Abstract, leaves iii-iv.

Download or read book Deuterium Isotope Effects Upon Solvolyses of Alkyl Sulfonates in Dimethyl Sulfoxide written by Keith Douglas Bowersox and published by . This book was released on 1985 with total page 526 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book Nuclear Science Abstracts written by and published by . This book was released on 1970 with total page 998 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book Secondary gb s and gc s Deuterium Isotope Effects in the Solvolyses of Isobutyryl and Pivaloyl Chlorides written by Adan A. Effio Leon and published by . This book was released on 1971 with total page 170 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book Secondary Deuterium Isotope Effects in the Solvolysis of Propionyl D b0 s 2 2 D b2 sand 3 3 3 D b3 schlorides written by Uan Gen Kang and published by . This book was released on 1969 with total page 132 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book Deuterium Isotope Effects in Some Solvolysis Reactions written by Mary S. Feng and published by . This book was released on 1962 with total page 50 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book Deuterium Isotope Effects and Mechanisms of Solvolytic Elimination Reactions written by Dennis Arthur Nollen and published by . This book was released on 1979 with total page 352 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book Inquiry Concerning the Temperature Dependence of gb s secondary Deuterium Isotope Effects written by Thomas Ashlie Evans and published by . This book was released on 1968 with total page 240 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book Secondary Deuterium Isotope Effects on the Rates of Solvolysis of Some Benzyl Derivatives written by Herbert Robert Pinnick and published by . This book was released on 1973 with total page 390 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book Secondary Deuterium Isotope Effects for Ionization and Solvolysis of Trans Dimethylallyl P nitrobenzoate Part I II Solvolysis of CIS dimethylallyl P nitrobenzoate in Aqueous Acetone written by David Alan Holmes and published by . This book was released on 1968 with total page 346 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book Bibliography of Mass Spectroscopy Literature for 1970 written by and published by . This book was released on 1972 with total page 900 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book Temperature Dependence of Some Secondary Kinetic Deuterium Isotope Effects written by Uan Gen Kang and published by . This book was released on 1972 with total page 166 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book Leaving Group Effects in Solvolysis Reactions written by David James Wong Goon and published by . This book was released on 1968 with total page 332 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book Solvolytic Studies of Brendyl Brexyl and Norbornyl Systems written by Thomas David Swartz and published by . This book was released on 1966 with total page 638 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book Advances in Alicyclic Chemistry written by Harold Hart and published by Academic Press. This book was released on 2013-10-22 with total page 329 pages. Available in PDF, EPUB and Kindle. Book excerpt: Advances in Alicyclic Chemistry, Volume 3 covers papers about the advances in alicyclic chemistry. The book presents a paper on the synthetic application of carbocyclic ring contraction reaction, with topics about rearrangements via carbonium ions, ring contractions via anionic intermediates or divalent carbon intermediates, photochemical ring contractions, and thermal rearrangements. The text also provides papers on the conformational analysis of cyclohexane and cyclohexene derivatives and on the review and analysis of modern theory about eliminations from cycloaliphatic derivatives. Chemists will find the book invaluable.

Download or read book Advances in Physical Organic Chemistry APL written by and published by Academic Press. This book was released on 1977-05-19 with total page 384 pages. Available in PDF, EPUB and Kindle. Book excerpt: Advances in Physical Organic Chemistry APL

Download or read book Inquiry Concerning the Temperature Dependence of beta secondary Deuterium Isotope Effects written by Thomas Ashlie Evans and published by . This book was released on 1968 with total page 206 pages. Available in PDF, EPUB and Kindle. Book excerpt: