Acidity of hydrocarbons. XXXVII. Broensted correlation and hydrogen isotope exchange kinetics of fluorenes, benzfluorenes, and indene with methanolic sodium methoxide

A Streitwieser; W. B Hollyhead; A. H Pudjaatmaka; P. H Owens; T. L Kruger; P. A Rubenstein; R. A MacQuarrie; M. L Brokaw; W. K. C Chu; H. M Niemeyer

doi:10.1021/ja00749a022

Journal article

Acidity of hydrocarbons. XXXVII. Broensted correlation and hydrogen isotope exchange kinetics of fluorenes, benzfluorenes, and indene with methanolic sodium methoxide

A Streitwieser, W. B Hollyhead, A. H Pudjaatmaka, P. H Owens, T. L Kruger, P. A Rubenstein, R. A MacQuarrie, M. L Brokaw, W. K. C Chu and H. M Niemeyer

Journal of the American Chemical Society, Vol.93(20), pp.5088-5096

10/01/1971

DOI: 10.1021/ja00749a022

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Abstract

Kinetic results are reported for tritium exchange of several hydrocarbons related to fluorene with methanolic sodium methoxide. The second-order rate constant for fluorene increases with NaOMe concentration and a comparison with H_ results is presented. Primary isotope effects are high and indicate the absence of significant amounts of internal return, kH, kD, and kT are interrelated for 9-phenylfluorene and 9-methylfluorene. The secondary isotope effect for exchange of nuorene-9,9-d2 is 15%. Tritium exchange rates given as 104k2 (M-1 sec-1) at 45, ΔH* (kcal/mol), and ΔS* (eu) are, respectively, 1,12-o-phenylene-7,12-dihydropleiadene, 5630, 17.13, —5.99; 9-phenyl-3,4-benznuorene, 1030, …, …; 9-phenylnuorene, 173, 21.30, 0.20; 3,4-benzfluorene, 90.3, 20.95, —2.20; indene, 50.0,20.29, —5.43; 1,2-benznuorene, 31.9, 18.49, —11.98; 4,5-methylenephenanthrene, 6.85, 23.66, 1.21; fluorene, 3.95, 23.26, —1.16; 2,3-benzfluorene, 2.15, …, … These rates give a linear Brönsted plot with pK's derived from cesium cyclohexylamide with a slope, a, of 0.37. No curvature is detectable in this correlation. The significance of the value of a is discussed. © 1971, American Chemical Society. All rights reserved.

Details

Title: Subtitle: Acidity of hydrocarbons. XXXVII. Broensted correlation and hydrogen isotope exchange kinetics of fluorenes, benzfluorenes, and indene with methanolic sodium methoxide
Creators: A Streitwieser
W. B Hollyhead
A. H Pudjaatmaka
P. H Owens
T. L Kruger
P. A Rubenstein
R. A MacQuarrie
M. L Brokaw
W. K. C Chu
H. M Niemeyer
Resource Type: Journal article
Publication Details: Journal of the American Chemical Society, Vol.93(20), pp.5088-5096
Publisher: American Chemical Society
DOI: 10.1021/ja00749a022
ISSN: 0002-7863
eISSN: 1520-5126
Language: English
Date published: 10/01/1971
Academic Unit: Stead Family Department of Pediatrics; Biochemistry and Molecular Biology; Internal Medicine
Record Identifier: 9984288734402771

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