Group Title: 1,3-Dipolar cycloadditions of fluorinated allenes and studies of fluorinated trimethylenemethanes /
Title: 1,3-Dipolar cycloadditions of fluorinated allenes and studies of fluorinated trimethylenemethanes
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Title: 1,3-Dipolar cycloadditions of fluorinated allenes and studies of fluorinated trimethylenemethanes
Alternate Title: One, three-dipolar cycloadditions of fluorinated allenes and studies of fluorinated trimethylenemethanes
Physical Description: iv, 291 leaves : ill. ; 28 cm.
Language: English
Creator: Burkholder, Conrad, 1954- ( Dissertant )
Dolbier, William R. ( Thesis advisor )
Jones, William M. ( Reviewer )
Vala, Martin ( Reviewer )
Deyrup, James A. ( Reviewer )
Goldberg, E. P. ( Reviewer )
Publisher: University of Florida
Place of Publication: Gainesville, Fla.
Publication Date: 1984
Copyright Date: 1984
Subjects / Keywords: Ring formation (Chemistry)   ( lcsh )
Allene   ( lcsh )
Trimethylenemethane   ( lcsh )
Chemistry thesis Ph. D
Dissertations, Academic -- Chemistry -- UF
Genre: bibliography   ( marcgt )
non-fiction   ( marcgt )
Abstract: The 1,3-dipolar cycloadditions of 1 ,1-difluoroallene 1_, fluoroallene 2, and 1 ,1-difluoro-3-methyl- 1 ,2-butadiene 3 are reported. Dipoles studied are diazomethane 4, 2-diazopropane 5, diazofluorene 6, diphenyldiazomethane 7, diphenylnitrone 8, C-phenyl- N-methylnitrone 9, triphenylnitrone 10, mesitylnitrile oxide 1_1_, and tetracyanocarbonyl ylide 12^. Reaction of 1_ with 4 is regiospecific giving 4-(difluoromethylene)-1-pyrazoline. Similar regioselectivity is observed for dipoles 5 through 12_ except for 6 and 7, which give mainly 5-(difluoromethylene)-1- pyrazolines. Regiochemistry is controlled by both electronic and steric interactions. Reaction of 2 with 4 gives only 4-(fluoromethylene)- 1-pyrazoline. Reaction of 2 with 8 gives an 86 to 14 ratio of (E)-and (Z)-4-(fluoromethylene)isoxazolidines. Reactions of 3 with 4, 8, and 9 are regiospecific for the 4- (difluoromethylene )-cycloadducts. The deazetations of the fluorinated 4-methylene- 1 -pyrazolones by photolysis and thermolysis are studied in the gas phase and in solution. The kinetic product ratios of fluorinated methylenecyclopropanes are consistent with trimethylenemethane biradical intermediates. Thermodynamic parameters are determined for the gas-phase equilibria of the products. The (difluoromethylene) cyclopropane from 6 gives cycloadducts with oxygen at room temperature and acrylonitrile at 70°. The distribution of products is consistent with formation of a highly stabilized trimethylenemethane biradical which is trapped. Regiochemistry is also studied for reactions of 1 with acrylonitrile 1_3» methacrylonitrile 1_4, 1 ,1-dichloro- 2,2-difluoroethylene 1_5» 1 t 2- bis-( me"tnylene)cyclobutane 16, 2,3-dicyanobutadiene 1_7» and diphenylisobenzofuran. Olefins 13 , 14 . and 1J5 give 1 ,2-cycloadducts with fluorines mainly on the ring, a result consistent with a biradical mechanism. Dienes ±6_ and 1_7 give competing biradical and concerted reactions. Pluoroallene reacts non-regiospecifically with 15 . Allene 3_ with cyclopentadiene gives the Diels-Alder cycloadduct with an exocyclic difluoromethylene group.
Thesis: Thesis (Ph. D.)--University of Florida, 1984.
Bibliography: Bibliography: leaves 284-290.
Statement of Responsibility: by Conrad Burkholder.
General Note: Typescript.
General Note: Vita.
 Record Information
Bibliographic ID: UF00099345
Volume ID: VID00001
Source Institution: University of Florida
Holding Location: University of Florida
Rights Management: All rights reserved by the source institution and holding location.
Resource Identifier: alephbibnum - 000583108
oclc - 14236343
notis - ADB1504


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