LXIV.—The formation and stability of associated alicyclic systems. Part I. A system of nomenclature, and some derivatives of methane-II-cyclopropane and of methane-III-cyclopropane

Beesley, Richard Moore; Thorpe, Jocelyn Field

doi:10.1039/ct920170591b

Cited by 14 publications

(4 citation statements)

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“…The first suggestion of bent bonds appeared in an unusual context. In 1913, a paper by Beesley and Thorpe reported the preparation of a bicyclobutane and a tricyclobutane via elimination reactions carried out under vigorous conditions (Scheme ) . It is now known that even if the compounds had been formed, they would not have survived the workup conditions that were described.…”

Section: Cyclopropane and Related Compoundsmentioning

confidence: 99%

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Bent Bonds in Organic Compounds

1996

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Section: Cyclopropane and Related Compoundsmentioning

confidence: 99%

“…Woodward managed to locate Beesley in Mexico working for an oil company. He informed Woodward that he had not done the work, and had been sent by Thorpe to the war because “he did not have the proper academic frame of mind” . It is now clear that the report is fraudulent.…”

Section: Cyclopropane and Related Compoundsmentioning

confidence: 99%

Bent Bonds in Organic Compounds

1996

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“…The relatively few cases where proportionality exists between the corresponding effects of substituents on free energies are definitely determined by the nature of the above-mentioned variables.2a The failure of eq. ( 1) to apply to this important class of reactions must depend on one or both of the (2)…”

Section: Received March 20 1953mentioning

confidence: 99%

“Acetylenic” Strained Hydrocarbons

Weltner¹

1953

J. Am. Chem. Soc.

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Acetylene, C4H4, and CsHs form a series of strained hydrocarbons analogous to the ethylene, cyclopropane, cyclobutane senes. The "caged" structures of the two higher members of this series are formed from tetrahedral and cubic configurations of CH groups, respectively. Assuming that these two molecules possess bond lengths corresponding to paraffinic hydrocarbons, the strain energies are calculated by the procedure of Dunitz, Schomaker and Pauling, and by the electron pairing approximation of VB theory, and a comparison made of the results by the two methods. The heats of formation at 0 "K. thus derived are compared with the energies of certain isomers of CnH4 and C8HS, namely, vinylacetylene, cyclobutadiene (as yet unsynthesized), and cycloiictatetraene. Tetrahedral C~H I is found to have a strain energy of about 90 kcal./mole as compared to 59 kcal./mole in vinylacetylene and about 50 kcal. /mole in a hypothetical non-resonating model of cyclobutadiene.The true tetrahedral C4H4 probably has carbon-carbon bond lengths near 1.48 A. a t which distance the strain energy may be reduced to a value comparable with that of vinylacetylene. Cycloijctatetraene is found to be about 80 kcal./mole more stable than the cubic CsHs. (1) R. M. Beesley and J. F. Thorpe, PYOC. Ckem. SOL., 29, 346 (1913). (2) R. M. Beesley and J. F. Thorpe, Trans. Chem. Sac., 117, 591 (1920). (3) The full names for these compounds are tricyclo[l.l.0.0~~*]butane and tricyclo [4.2.0.0~*5.0~~80~~~]8ctane according to the system specified in A. M. Patterson and L. T. Capell, "The Ring Index," Reinhold Publ. Corp., New York, N. Y., 1940. (4) See, for example, a review of cyclobutadiene chemistry by W. Baker, J. Chem. Sac., 259 (1945). ( 5 ) C. A. Coulson and W. E. Moffitt, Phil. Mag., 40, 1 (1949). Dr.Moffitt bas, however, pointed out that theapplication of the Jahn-Teller theorem to account for the instability of cyclobutadiene is only Possible in the zeroth order where the MO configuration is degenerate. In first-order theory no degeneracy is present and the Jahn-Teller theorem does not apply.

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“…At that time, the structures of the cage compound 4 (Scheme ) reported by Beesley and Thorpe appeared to contain this ring system,and Woodward assigned one of his students (Harold O. Larson) to attempt repetition of its synthesis ( 1 > 4 , in brackets ) . However, Professor Woodward clearly doubted the validity of the intermediate 3 .…”

mentioning

confidence: 99%