Alkylations of isoquinoline via lithium aluminium hydride.

Bibliographic Details
Main Author: Trujillo, David Anthony
Other Authors: Lunsford, J. H. (degree committee member.), Merkle, M. G. (degree committee member.), Presley, B. (degree committee member.)
Format: Thesis Book
Language:English
Published: 1983.
Subjects:
Online Access:Link to ProQuest Copy
Link to OAKTrust copy
Description
Abstract:Lithium aluminium hydride (LAH) in tetrahydrofuran (THF) reacted rapidly with isoquinoline to give lithium tetrakis dihydroisoquinoline aluminate (LTDA). Proton and ('13)C NMR spectra indicated the presence of only 1,2- but not 1,4-dihydro isomer. Unlike isoquinoline, pyridine or quinoline was less reactive and gave the corresponding 1,2- as well as 1,4-dihydro ligands. In THF, the isoquinoline-LAH intermediate (LTDA) reacted with methyl iodide, ethyl bromide, n-propyl bromide, allyl bromide, n-butyl bromide and benzyl chloride but not sec- and tert-butyl bromides to give the corresponding 4-substituted isoquinolines. In diethyl ether (Et(,2)O), all of these alkyl halides reacted. The yields of products ranged from 25 to 64% in THF, and 43 to 61% in Et(,2)O. For most reactions, yields of alkylated products were substantially higher in Et(,2)O than in THF: a one-electron transfer mechanism was proposed. ('1)H NMR and mass spectra for the 4-substituted isoquinolines were reported. These reactions also gave other minor products including 1,2,3,4-tetrahydroisoquinoline, monoalkylated tetrahydroisoquinolines and dialkylated tetrahydroisoquinolines.
Item Description:"Major subject: Chemistry."
Typescript (photocopy).
Vita.
Physical Description:xii, 178 leaves : illustrations ; 29 cm
Bibliography:Includes bibliographical references (leaves 110-115).