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Schroeder Lr.Pdf (4.749Mb) The Institute of Paper Chemistry Appleton, Wisconsin Doctor's Dissertation The Alcoholysis of 2,3,4,6,Tetra-OAcetyl-aCD Glucopyranosyl Bromide Leland R. Schroeder June, 1965 THE ALCOHOLYSIS OF 2,3,4,6-TETRA-O-ACETYL-a-D- GLUCOPYRANOSYL BROMIDE A thesis submitted by Leland R. Schroeder A.B. 1960, Ripon College M.S. 1962,.Lawrence College in.partial fulfillment of the requirements of The Institute of Paper Chemistry for the degree of Doctor of Philosophy from Lawrence University, Appleton, Wisconsin June, 1965 SUMMARY iv Comparison of Specific Rate Constant with Literature Values. 73 Thermodynamic Functions of Activation 76 TABLE OF CONTENTS Page SUMMARY- 1 INTRODUCTION 4 Koenigs-Knorr Reaction 4 Glycosyl Halides: Reaction:Mechanism Studies 5 Nucleophilic Substitution Reactions 6 Bimolecular Nucleophilic Substitution (S2) 7 Unimolecular Nucleophilic Substitution (SN1) 7 Solvolysis Reactions 8 .Reactions of Glycosyl Halides: Literature Survey 10 Reactivity and Stability 10 Effect of C1 and C2 Substituent Steric Configuration 11 Effect of the Glycosyl.Moiety - 1 Mechanistic Classification 14 Reactions with Hydroxylic Compounds 17 EXPERIMENTAL PROCEDURES AND RESULTS 18 Theory of Calculation of Rate Constants from.Polarimetry 18 Preparation of Compounds 20 Penta-O-Acetyl-P-D-Glucopyranose 20 2,3,4,6-Tetra-O-Acetyl-a-D-Glucopyranosyl Bromide 20 Alkyl 2,5,4,6-Tetra-O-Acetyl-P-D-Glucopyranosides 21 Alkyl 2,3,4,6-Tetra-O-Acetyl-c-D-Glucopyranosides 23 Purification of Solvents 25 Chloroform 25 Methanol, Ethanol, and n-Butanol 25 n-Propanol and iso-Propanol 25 Cyclohexanol 26 Alcohol Storage and Water Content 26 -2- Acetylated alkyl D-glucosides were prepared for use as reference compounds in the product analyses. Acetylated alkyl P-D-glucosides were prepared by a modified Koenigs-Knorr reaction utilizing mercuric oxide (yellow) and mercuric bromide. Acetylated alkyl a-D-glucosides were prepared from the P-anomer by rearrangement with titanium tetrachloride in chloroform. Gas-chromatographic analyses of solutions of acetylated alkyl P-D-glucosides in alcoholic hydrogen bromide verified that acid-catalyzed transglycosidation (anomerization) did not cause the observed a-glucoside formation. Analyses of the same systems indicated that deacetylation of the reactant and products by acid-catalyzed transesterification was not important at 15% reaction. Lithium perchlorate caused a positive salt effect in all the alcoholyses. The relative effect for the iso-propanolysis was larger than expected on the basis of dielectric constant. The fraction of a-glucoside formed in the iso- propanolysis was affected by the salt; the primary-alcoholyses were unaffected. Lithium bromide increased the reaction rate and the fraction of a-glucoside for all the alcoholyses. For the iso-propanolysis, both effects were large relative to the primary-alcoholyses. The lithium bromide data suggested the possibility of a reactive intermediate in the formation of part of the glucosidic products when bromide ions are added to the alcoholyses. The enthalpies and entropies of activation were significantly different for the primary- and secondary-alcoholyses. The primary-alcoholyses had enthalpies of activation ranging from 19 to 21 kcal. per mole; the entropies ranged from -18 to -16 e.u. The iso-propanolyses exhibited an enthalpy of activation of 12 kcal. per mole and an entropy of -48 e.u. Thermodynamic func- tions of activation were not determined for the cyclohexanolyses.- .Effect of Deacetylation on the.Experimental Specific Rate Constant 69 -3- The polarimetric kinetic data indicated that electrophilic catalysis of the alcoholyses by the liberated hydrogen bromide can become important at less than 25% reaction. Analysis of the data indicated that the methanolyses, ethanolyses, n-propan- olyses, and n-butanolyses of 2,3,4,6-tetra-O-acetyl-a-D-glucopyranosyl bromide occurred by an SN1 reaction mechanism. The iso-propanolyses and cyclohexanolyses exhibited characteristics of SN2 reaction mechanisms. -4- INTRODUCTION KOENIGS-KNORR REACTION The Koenigs-Knorr reaction, in which an O-acyl-glycosyl halide* reacts with an alcohol or phenol, e.g., Equation (1), has been employed successfully for the preparation of numerous glycosides and oligosaccharides (1-6). Since its earliest application in the preparation of. methyl P-D-glucopyranoside (7) the reaction, as a preparative tool, has been improved considerably by the use of additives. The generation of a hydrohalic acid in the Koenigs-Knorr reaction facili- tates detrimental reactions such as transesterification and transglycosidation, resulting in deesterified and Cl-racemized glycosidic products. To alleviate this problem an acid acceptor is employed in the reaction system, the most common being silver oxide or silver carbonate. An additional advantage in the use of the silver salts is that they are also thought to act as catalysts for the reaction. Amines and mercuric salts have also been employed as acid accep- tors and/or catalysts for the Koenigs-Knorr reaction (8). *Unless specified otherwise the discussion of sugars will pertain to the pyranose form; terms such as glycosyl and glycopyranosyl will be used interchangeably. -5- Employment of acid acceptors in the reaction system causes additional compli- cations however. Silver oxide has been reported to cause the decomposition of glycosyl halides under the conditions normally employed in the Koenigs-Knorr reaction (9). Iodine, generally considered to be a catalyst for the reaction, suppresses this side reaction but also suppresses glycoside formation. However, because the iodine suppresses the side reaction more effectively than glycoside formation, an increased yield of the glycoside is obtained. Desiccants are employed in the Koenigs-Knorr reaction to combine with traces of water present initially in the system and also to combine with the water formed when the hydrohalic acid is neutralized by the acid acceptor, e.g.,.Equation (2). Ag20 + 2HBr -- 2AgBr + H20 (2) If the reaction system is not desiccated, the water reacts with the glycosyl halide to form a reducing sugar rather than the preferred glycoside. Evans and Reynolds (10) found that use of Drierite (anhydrous calcium sulfate) in a Koenigs-Knorr reaction producing gentiobiose increased the yield from 25 to 80%. GLYCOSYL HALIDES: REACTION MECHANISM STUDIES The earliest mechanistic studies of the reactions of glycosyl halides were made by Frush and Isbell (11-13) utilizing reactions employing Drierite and/or silver carbonate, as in the preparative Koenigs-Knorr reaction. The studies did not utilize kinetic measurements and consisted of reconciling the isolated products with the postulated mechanism. Mechanistic studies involving rate measurements normally do not employ additives such as Drierite and the silver salts. Rate measurements for glycosyl halide reactions are normally made by polar- imetric, titrimetric, or conductimetric techniques. The heterogeneity resulting -6- from the use of insoluble desiccants and acid acceptors prohibits practical utilization of polarimetry for reaction rate measurements. Titration of the liberated hydrohalic acid is impossible when an acid acceptor is employed. A homogeneous reaction medium amenable to polarimetric and conductimetric kinetic measurements can be achieved by employing a soluble amine as the acid acceptor, but the possibility of a side reaction between the glycosyl halide and the amine exists (4, 14). In addition to the above considerations it is known that complicated kinetic results can be obtained when silver salts are employed in reactions involving scission of a carbon-halogen bond (19, p. 55). This is probably related to a surface catalytic effect and would therefore be dependent on the available surface area (particle size), the age and previous history of the surface (activity), etc. The probability of consistently duplicating these character- istics is small. Due to the preceding complications mechanistic studies of the reaction of glycosyl halides are frequently made without the additives normally employed in the preparative Koenigs-Knorr reaction. The results obtained are sometimes extrapolated, with some uncertainty, to the preparative reaction. NUCLEOPHILIC SUBSTITUTION REACTIONS The reactions of glycosyl halides with hydroxylic compounds [Equation (1)] belong to the class of reactions known as nucleophilic substitutions. As such the reactions are normally discussed in terms of Hughes' and Ingold's (15-18) mechanistic spectrum in which the terms SN1 (substitution, nucleophilic, uni- molecular) and SN2 (substitution, nucleophilic, bimolecular) refer to mechanisms at the extremes of the spectrum. A brief discussion of the SN1 and SN2 -7- mechanistic concepts follows. More detailed discussions of the nucleophilic substitution mechanisms, including the spectrum intermediate of SN1 and SN2, are available in several sources (18-21). BIMOLECULAR NUCLEOPHILIC SUBSTITUTION (SN2) The SN2 mechanism is described as a one-step reaction in which one nucleo- phile (Lewis base) displaces another from a carbon atom. Bond formation between the attacking nucleophile and the carbon atom is simultaneous with the breaking of the initial bond between the carbon atom and the leaving group. In the transition state the attacking group and leaving group are both partially bonded to the carbon atom. Formation of the transition state is the rate-controlling as well as the product-controlling step for the reaction [Equation (3)]. Y: + R:X Y...R... X --- Y:R + :X (3) Reactants
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