Abstract/Details

Synthesis and structural study of 9-(alkylphenyl)-9-fluorenols, 9-(alkylphenyl)fluorenes, alkyl -9 -fluorenylsulfones, and <i>N</i>-(<i>o</i>-alkylphenyl)carbazoles


2008 2008

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Abstract (summary)

Several 9-(alkylphenyl)-9-fluorenols and 9-(alkylphenyl)fluorenes have been synthesized and their X-ray crystal structure determined. Their ap or sp rotamers have been studied in solution and the solid phases. In general, compounds that were found to have hydrogen bonds failed to re-solidify after they had melted. NMR was taken of the melts and showed no molecular decomposition had occurred.

A family of alkyl-9-fluorenylsulfones, whose pK a was previously studied by Bordwell, has been re-examined using X-ray crystallography and Gaussian calculations. Bordwell's theory of relief of steric strain was specifically investigated. The evidence found adds support to Bordwell's theory, and leads to a better understanding of the compounds pKa.

Carbazole is isoelectronic to the fluorenyl anion. N-( o-alkylphenyl)carbazoles were compared to the appropriate 9-( o-alkylphenyl)fluorenyl anion. X-ray crystallography and Gaussian calculations showed the compound to be geometrically similar. The rotational barrier about the nitrogen-phenyl bond was investigated. The first way was by adding an isopropyl group to the carbazole ring and looking at the methyl groups in the NMR. The methyl groups in the isopropyl group were diastereotopic suggesting hindered rotation or no rotation. Rotation was also investigated using an L-menthyl ester group and an α-methyl benzyl amide group. In both cases, the compound was found to be a pair of diastereomers, also suggesting hindered or no rotation. Many attempts were made to resolve the diastereomeric pairs, but all failed. The closest separation achieved was using a chiral HPLC column. Partial separation was achieved and showed that if rotation occurred it was on the minute scale.

Indexing (details)


Subject
Organic chemistry
Classification
0490: Organic chemistry
Identifier / keyword
Pure sciences; Alkyl-9-fluorenylsulfones; Alkylphenyl carbazoles; Alkylphenyl fluorenes; Alkylphenyl-9-fluorenols
Title
Synthesis and structural study of 9-(alkylphenyl)-9-fluorenols, 9-(alkylphenyl)fluorenes, alkyl -9 -fluorenylsulfones, and <i>N</i>-(<i>o</i>-alkylphenyl)carbazoles
Author
McLean, Aaron W.
Number of pages
203
Publication year
2008
Degree date
2008
School code
0209
Source
DAI-B 69/12, Dissertation Abstracts International
Place of publication
Ann Arbor
Country of publication
United States
ISBN
9780549922728
Advisor
Meyers, Cal Y.; Dyer, Daniel J.
Committee member
Hou, Yuqing; McCarroll, Matthew E.; Murphy, Laura
University/institution
Southern Illinois University at Carbondale
Department
Chemistry
University location
United States -- Illinois
Degree
Ph.D.
Source type
Dissertations & Theses
Language
English
Document type
Dissertation/Thesis
Dissertation/thesis number
3337335
ProQuest document ID
304164253
Copyright
Database copyright ProQuest LLC; ProQuest does not claim copyright in the individual underlying works.
Document URL
http://search.proquest.com/docview/304164253
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