Synthetic applications of diethyl cyanomalonate.
| dc.contributor.author | Cook, Matthew C. | en_US |
| dc.contributor.degree | Ph.D. | en_US |
| dc.date.accessioned | 2014-10-21T12:38:31Z | |
| dc.date.available | 2007 | |
| dc.date.issued | 2007 | en_US |
| dc.description | Diethyl cyanomalonate was prepared in high yield from ethyl cyanoacetate and ethyl chloroformate in refluxing acetone/anhydrous K2CO 3 and converted to its salts by titration with alkali metal and tetraalkylammonium hydroxides. These stable, non-hygroscopic salts were soluble in a variety of organic solvents and were reactive towards alkylation by electrophiles under neutral conditions. Under optimized conditions (Bu4N + salt, DMSO, 80°C), diethyl cyanomalonate was monoalkylated exclusively on carbon by a variety of 1° and 2° alkyl bromide and iodide electrophiles, as well as electrophiles containing base-sensitive or acidic groups. The highly functionalized alkylation products were isolated using a simple work up procedure. | en_US |
| dc.description | GABA, an o-amino acid and important neurotransmitter, was synthesized from diethyl cyanomalonate and ethyl bromoacetate via alkylation, decarboethoxylation, ester hydrolysis and nitrite reduction reactions. While selective deuterium incorporation was not achieved during the decarboethoxylation reaction, a selective nitrite-mediated, base-catalyzed deuterium exchange method was developed and used to prepare [3,3-2H2]-3-cyanopropanoate and [4,4-2H2]-4-cyanobutanoic acid. [3,3- 2H2]GABA was obtained upon reduction of the former, and the latter was used to demonstrate a gas-phase McLafferty-type rearrangement of carboxylate ions. | en_US |
| dc.description | Alkylation of diethyl cyanomalonate by halogenated esters and acids, followed by ester hydrolysis and monodecarboxylation provided a homologous series of 2-cyanodicarboxylic acids which, after nitrite reduction, provided a similar series of 2-(aminomethyl)dicarboxylic acids (beta 2-amino acids). The two series of compounds inhibited enzymes of amino acid metabolism and also were valuable substrates for an ESI-MS study to elucidate the collision-induced fragmentation processes of substituted dicarboxylic acids. | en_US |
| dc.description | Thesis (Ph.D.)--Dalhousie University (Canada), 2007. | en_US |
| dc.identifier.other | AAINR27190 | en_US |
| dc.identifier.uri | http://hdl.handle.net/10222/54896 | |
| dc.language | eng | en_US |
| dc.publisher | Dalhousie University | en_US |
| dc.publisher | en_US | |
| dc.subject | Chemistry, Organic. | en_US |
| dc.title | Synthetic applications of diethyl cyanomalonate. | en_US |
| dc.type | text | en_US |
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