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Title: The synthesis and complexation of asymmetrically functionalised macrocycles
Author: Ross, Steven Andrew
Awarding Body: University of Edinburgh
Current Institution: University of Edinburgh
Date of Award: 1994
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An introduction to macrocyclic chemistry is presented, with particular emphasis on 1,4,7-triazacyclononane ([9]aneN3) and the addition of pendent groups to this macrocycle. Reaction of [9]aneN3, with (CH3O)2CHNMe2 yields 1,4,7-triazatricyclo[,10] decane, the single crystal X-ray structure of which is described. Acidic hydrolysis of 1,4,7-triazatricyclo[]decane yields 1-formyl-1,4,7-triazacyclononane (HOC[9]aneN3), the single crystal X-ray structure of which is also described. Further reaction of HOC[9]aneN3, with excess isobutylene oxide affords 1-formyl-4,7-bis(2-hydroxy-2-methylpropyl)-1,4,7-triazacyclononane (L2H2), which yields 1,4-bis(2-hydroxy-2-methylpropyl)-1,4,7-triazacyclononane upon basic hydrolysis. The single crystal X-ray structure of 1,4-bis(2-hydroxy-2-methylpropyl)-1,4,7-triazacyclononane is reported. The reaction of 1,4,7-triazatricyclo[,10]decane with PhCH2Br yields 1-benzyl-1,4,7-triazacyclononane (L4), which reacts further with isobutylene oxide to yield 1-benzyl-4,7-bis(2-hydroxy-2-methylpropyl)-1,4,7-triazacyclononane (L6H2). Reaction of [9]aneN3 with HCOOH and CH3CO2OCH3 yields 1,4,7-triazacyclononane, the single crystal X-ray structure of which is described. Analogously, reaction of [9]aneN3 with PhCOCI yields 1,4,7-tribenzoyl-1,4,7-triazacyclononane, the single crystal X-ray structure of which is also described. The ring conformations of these two molecules are found to be similar, both adopting a [333] conformation. Reaction of Pd(OAc)2 with HOC[9]aneN3 in CH2CI2 affords the species [Ph(HOC[9]aneN3)2][B(C6F5)4]2.2H2O, the single crystal X-ray structure of which shows the cations to form a 'chain' structure with interchelated H2O molecules. Reaction of Ni(BF4)2.6.5CH3CH with excess HOC[9]aneN3 in refluxing CH3CN leads to hydrolysis of the amide function and formation of the previously reported [Ni([9]aneN3)2]2+.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available