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Title:Synthetic methods and studies of some 10-Y-5 and 12-Y-6 hypervalent main group element species of group IIIB
Author(s):Hoglen, Dean Kent
Doctoral Committee Chair(s):Martin, J.C.
Department / Program:Chemistry
Degree Granting Institution:University of Illinois at Urbana-Champaign
Subject(s):Chemistry, Organic
Abstract:p-t-Butylhexafluorocumylthiol and N,N-dimethylhexafluorocumylamine were synthesized and found not to undergo ortho-lithiation. p-t-Butylhexafluorocumylthiol forms several products upon treatment with an alkyllithium reagent and N,N-dimethylhexafluorocumylamine undergoes meta-lithiation upon treatment with sec-butyllithium in the presence of TMEDA. Evidence for the formation of stable hypervalent phosphorus and silicon species using 1,3-bis(2$\sp\prime$-pyridylimino)isoindoline as a tridentate ligand was obtained.
New synthetic routes were developed for 4-t-butyl-2,6-bis(1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl)pyridine and 2-amino-4-(t-butyl)pyridine which allowed their synthesis on a large scale, with reasonable amounts formed. The former was synthesized by ortho-lithiation of 4-t-butyl-2-(1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl)-pyridine-1-oxide and treatment with hexafluoroacetone. The latter was synthesized by nucleophilic aromatic substitution on 2-bromo-4-t-butylpyridine using sodium amide as nucleophile.
Because a new melting point reflecting a new crystal structure for 10-t-butyl-1-chloro-3,3,7,7-tetrakis(trifluoromethyl)-4,6-benzo-5-azonia-1-borata-2,8-dioxabicyclo- (3,3,0) octane resulted in a change in solubility and reactivity, new routes to hypervalent 12-B-6 and 10-B-5 species were explored, and were not successful.
N,N,N-tributylbutanaminium(OC-6-11$\sp\prime$)-bis (4-(1,1-dimethylethyl)-$\alpha,\alpha,\alpha\sp\prime\alpha\sp\prime$-tetrakis(trifluoromethyl)-2,6-pyridinedimethanolato(2-)N1,O$\alpha$,O$\alpha\sp\prime$) aluminum, a 12-Al-6 anionic species was synthesized and experimentally examined. Neutral mono-protonated and mono-methylated products of this anion were synthesized and studied. X-ray crystallography was used to establish the structure of the octahedral 12-Al-6 species and its protonated analogue. The protonated species was a distorted octahedral species with the proton hydrogen-bonding two of the apical oxygens.
Issue Date:1990
Rights Information:Copyright 1990 Hoglen, Dean Kent
Date Available in IDEALS:2011-05-07
Identifier in Online Catalog:AAI9026207
OCLC Identifier:(UMI)AAI9026207

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