No description available.

A series of salts of the strong fluorocarbon acid bis(trifluoromethylsulfonyl)methane were made: (CF3S02 ) 2CHK, (CF3S02 ) 2CHLi, [ (CF3S02 ) 2CH] 2Ca, [ (CF3S02 ) 2CH] 2Hg, (CF3S02 ) 2CHAg, [ (CF3S02 ) 2CH] 3La. Their reactivity and use as organic intermediates were investigated. The salts were made from their corresponding carbonates, oxides, or hydrides. The reaction times for the salts is generally short, however the purification process was laborious, involving recrystallization from organic solvents and drying under vacuum. The lithium salt is being evaluated as a solid state battery electrolyte. Derivatives of bis(trifluoromethylsulfonyl)methane were made by using the salts as nucleophiles in organic reactions. Reactions with Br2 , CH2=CH2CH2Br, CH3CH2CH2I, and OCH2CHCH2Br were carried out to make: bis(trifluormethylsulfonyl)bromomethane, 4,4-bis(trifluormethylsulfonyl)butene-1, 1,1-bis(trifluormethylsulfonyl)butane, and 4,4-bis(trifluormethylsulfonyl)-1,3-epoxybutane In addition, work was carried out on the synthesis of the polymer -(-O-CH2-C(CH20CF2CF2S02F)H-)n- and the corresponding lithium salt. The polymer was treated with aqueous lithium hydroxide in order to convert the S02F group to a S03-Li+ group. This salt is being investigated as a solid state ion conducting polymer. All products were characterized by infrared spectroscopy, mass spectroscopy, 1H and 19F nuclear magnetic resonance spectroscopy, elemental analysis, and melting points.

Thesis (Ph. D.)--Ohio State University, 2003. / Document formatted into pages; contains xvi, 371 p.; also contains graphics. Includes bibliographical references. Abstract available online via OhioLINK's ETD Center; full text release delayed at author's request until 2005 May 5.

The kinetics of base-catalyzed isomerization and hydration of butadiene sulfones has been studied by using the gas chromatographic method. The reaction has been shown to be first-order with respect to each of the three components, i.e., α-butadiene sulfone, β-butadiene sulfone, and alcohol, in this complex reaction system. It is also first-order with respect to base, and second-order overall. The rate constants and relative rate constants of this reaction system have been obtained in the range of 35 to 55° C. The thermodynamic quantities of the reversible isomerization of β-butadiene sulfone to a-butadiene sulfone have been evaluated. The heat of isomerization obtained in this investigation is consistent with an independent thermochemical measurement. / Master of Science

No description available.

The thesis is concerned with approaches to substituted 2-phenyl- 1,3-oxathiolans and their cycloreversion to olefins. 2-(α-Methoxybenzylthio)acetophenone (l) was prepared by <u>in situ</u> alkylation of the thiolate generated by aminolysis of 0-ethyl-S-phenacyldithiocarbonate with α-chlorobenzyl methyl ether. Reduction of (l) with lithium aluminium hydride gave 2-(α-methoxybenzylthio)—1— phenylethanol which cyclised in the presence of <u>p</u>-toluenesulphonic acid to give 2,5-diphenyl-l,3-oxathiolan. α-(α'-Methoxybenzylthio)acetone (2), was prepared by a similar route to that used for (l). Compounds (1) and (2) and various other a-thiosubstituted ketones were investigated as potential starting materials for the synthesis of substituted β—(α-methoxybenzylthio)alcohols but the transformations attempted were unsuccessful. A reasonably flexible synthesis of substituted oxathiolans and hence the corresponding olefins was developed starting from α—(benzylthio)ketones. The olefins prepared were 2-methyl—3—phenyl—2— butene, 1,2-dimethylcyclohexene and the Z-(3) and E-(4) 3,4—dimethylhex— 3—enes. Alkylation of the a-(benzylthio)ketones proceeded regio— specifically α- to the thio and keto groups. Subsequent reaction with organometallic reagents gave β-benzylthioalcohols. Generally alkyllithiums gave the best yields and higher stereoselectivities in these additions. The benzylthio group was cleaved with sodium/ ammonia to give β-mercaptoalcohols which were condensed with benzaldehyde to give 2-phenyl-l,3-oxathiolans. Treatment of the oxathiolans with lithium diisopropylamide resulted in cycloreversion to olefins in high yields (75-100%). Stereochemical integrity was maintained throughout the reactions used to convert the β-benzylthioalcohols into olefins and consequently the stereoselectivity was determined at the β-benzylthioalcohol forming step. Thus the ratio found for (3) to (4) synthesised from a 3-benzylthioalcohol prepared by reaction of methyllithium with 3-benzylthio-3- methyl-4—hexanone was 3:7, whereas when the β-benzylthioalcohol was prepared from 3-benzylthio-3-methyl-2-pentanone by an ethyllithium reaction the ratio of (3) to (4) subsequently obtained was 6:4.

This thesis describes the synthesis of a number of hydroxy vinylsulphoxides and sulphones by a high pressure modification of the Baylis-Hillman reaction, together with their directed hydrogenation catalysed by rhodium catalysts. A detailed kinetic analysis of a number of the hydrogenation reactions carried out by numerical analysis is also presented. Chapter 1 serves as an introduction to directed hydrogenation and the chemistry of sulphur containing compounds. Chapter 2 details the synthesis of catalysts and substrates used in hydrogenation reactions. The use of high pressures to improve the performance of the Baylis-Hillman reaction is included. Chapter 3 details the products and the selectivity obtained in the hydrogenation of hydroxy vinylsulphoxides and sulphones. The kinetic resolution of 3-phenyl-2-(phenylsulphonyl)- propene-3-ol using a DiPAMP rhodium catalyst is described. Chapter 4 details the numerical analysis of the kinetics of the hydrogenation reactions of a number of hydroxy vinylsulphoxides and sulphones.

Thesis (M.Sc. (Organic Chemistry))--Mahidol University, 1983.

Thesis (Ph. D.)--University of Pittsburgh, 1922. / Vita. Bibliography: [1] p. following p. 14.

Thesis (Ph. D.)--Chemistry and Biochemistry, Georgia Institute of Technology, 2004. / Dr. Suzanne Shuker, Committee Member ; Dr. Niren Murthy, Committee Member ; Dr. Donald Doyle, Committee Member ; Dr. Nicholas Hud, Committee Member ; Dr. James C. Powers, Committee Chair. Includes bibliographical references.