Synthesis of derivatives of 4H-cyclopenta[ def]phenanthren-4-one and development of synthetic strategies for the polycyclic aromatic hydrocarbons with carbon frameworks represented on the surface of C60

A derivative of 4H-cyclopenta[def]phenanthren-4-one, 51, was synthesized from the protected ninhydrin 54 and 2 equivalents of 1-(2-ethynylphenyl)-2-phenylethyne. Condensation of the diketone 54 with the lithium acetylide 55 furnished the trans propargylic alcohol 56a and the cis propargylic alcohol 56b. Treatment of 56a with thionyl chloride promoted a sequence of reactions presumably with an initial formation of the chlorinated benzoenyne-allene 58. Two cycles of a C2--C6 biradical cyclization reaction followed by a radical-radical coupling then afforded the formal [4+2] Diels-Alder cycloaddition adduct 60, which in turn underwent tautomerization to give 61. Reduction with tri-n-butyltin hydride then gave the ketal 62 in 46% overall yield from 56a. Hydrolysis of the ketal 62 gave the ketone 51 in 97% yield.;Another derivative of 4H-cyclopenta[def]phenanthren-4-one, 87, was also synthesized from 54 and 2 equivalents of 1-(2-ethynylphenyl)-2-(4-tert-octylphenyl)ethyne ( 78) by using the same procedure. The dichloride 90 was also synthesized by using the ketone 87 as the precursor. Efforts are being made to synthesize polycyclic aromatic hydrocarbons with carbon frameworks represented on the surface of C60 via the dichloride 90.;The chloride 85 was converted to the corresponding diketone 93. The presence of two carbonyl groups allowed a second condensation with the lithium acetylide 79 to afford the propargylic alcohols 94 and 95. Treatment of 94 with thionyl chloride using the same procedure as described for 56a and 80 afforded the two isomeric 1H-cyclobut[a]indenes 97a and 97b via the [2+2] cycloaddition reaction of the chlorinated benzoenyne-allene.

Name thesis:degree_name

MS

Level thesis:degree_level

Thesis

Discipline thesis:degree_discipline

Chemistry

Year dc:date.available

2001

Author dc:creator

• Han, Xiaoqing

Contributors dc:contributor

• Kung K. Wang.

• Organic chemistry

Identifier

https://researchrepository.wvu.edu/etd/1287

OAI identifier oai:identifier

oai:researchrepository.wvu.edu:etd-2290