Rearrangements of free radicals, XI. Sigmatropic and electrocyclic reactions of bicyclo[3.2.0]heptadienyl radicals, 3‐Quadricyclanyl radicals, and 7‐norbornadienyl radical

Sustmann, Reiner; Brandes, Dieter; Lange, Fritz; Nüchter, Ursula

doi:10.1002/cber.19851180907

Cited by 15 publications

(2 citation statements)

References 33 publications

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“…The same authors used ESR to deduce 13 that C 7 in 7-norbornadienyl radical is more pyramidal than the dehydrogenated carbon in cyclopropyl radical. The ESR spectra of radicals produced by X-ray irradiation of quadricyclane in an adamantane matrix appear 14,15 to correspond to the BHD • radical, which subsequently rearranges to CHT • radical. The same studies 14,15 report that 7-norbornadienyl does not rearrange to BHD • under similar conditions.…”

Section: Relevant C 7 H 7 • and C 7 H 8 Studiesmentioning

confidence: 99%

“…The ESR spectra of radicals produced by X-ray irradiation of quadricyclane in an adamantane matrix appear 14,15 to correspond to the BHD • radical, which subsequently rearranges to CHT • radical. The same studies 14,15 report that 7-norbornadienyl does not rearrange to BHD • under similar conditions. In connection with this study, preliminary ab initio calculations have been performed 2, 16 to determine the electron affinities of the QDC • radicals corresponding to the QDCanions in Figure 1.…”

Section: Relevant C 7 H 7 • and C 7 H 8 Studiesmentioning

confidence: 99%

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Ultraviolet Photoelectron Spectroscopy of Some C₇H₇^- Isomers: Quadricyclanide, Norbornadienide, Cycloheptatrienide, and 1,6-Heptadiynide

et al. 1996

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The 351 nm photoelectron spectra of several isomers of C7H7 -, obtained by deprotonating quadricyclane, norbornadiene, 1,6-heptadiyne, and cycloheptatriene, are reported. Quadricyclane can be deprotonated from either of two distinct sites by amide anion. The electron affinities (EAs) of the two corresponding C7H7 • isomers are 0.868(6) and 0.962(6) eV, with one well-resolved vibration observed for each state, at 909(20) and 826(20) cm-1, respectively. Deprotonation of norbornadiene by amide anion leads to formation of one ionic isomer with a binding energy of 1.286(6) eV. Detachment to form an excited state of the neutral is also observed, with a vertical detachment energy (VDE) of 2.8(1) eV. Three vibrational modes are resolved in the ground state region of the spectrum, and one excited state vibration is observed. 1,6-Heptadiyne is deprotonated by hydroxide at two sites, the end carbon (C1) and the third carbon (C3), to produce isomers with binding energies of 3.037(10) and 1.132(6) eV, respectively. One vibration at 500(20) cm-1 is strongly active in the C3-deprotonated portion of the spectrum. Reaction of cycloheptatriene with hydroxide or amide produces a mixture of products at 91 amu which includes the isomer of C7H7 - corresponding to abstraction from the methylene group. The corresponding neutral has an EA ≤ 0.43 eV, in agreement with earlier estimates obtained from thermochemical cycles. The remaining products are assigned to vinyl systems with transitions in the photoelectron spectrum to the ground and first excited states. The measured VDEs of these states are 1.48(1) and 2.97(1) eV, respectively. The spectrum of benzyl anion appears in the spectra of all of the other C7H7 - isomers, probably as a result of toluene contamination in the precursors.

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Section: Relevant C 7 H 7 • and C 7 H 8 Studiesmentioning

confidence: 99%

Section: Relevant C 7 H 7 • and C 7 H 8 Studiesmentioning

confidence: 99%

Ultraviolet Photoelectron Spectroscopy of Some C₇H₇^- Isomers: Quadricyclanide, Norbornadienide, Cycloheptatrienide, and 1,6-Heptadiynide

et al. 1996

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Synthetic Uses of Tosylmethyl Isocyanide (TosMIC)

Leusen

2001

Organic Reactions

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TosMIC is the acronym for 4‐tolylsulfonylmethyl isocyanide or tosylmethyl isocyanide. It is the best‐known member of a series of about 25 sulfonyl‐substituted methyl isocyanides RSO 2 CH 2 NC collected in Chart 1 (p. 426). TosMIC is a multipurpose synthetic reagent. It is by far the most versatile synthon derived from methyl isocyanide. This chapter provides a complete account of the synthetic uses of TosMIC based on a literature search closed in January 1996, and supplemented with further data available to the authors. Also included are applications of some of the more important TosMIC homologs (TosCHRNC). TosMIC is the only commercially available sulfonylmethyl isocyanide. It is a stable, colorless, practically odorless solid, which can be stored at room temperature without decomposition. Four brief review papers on the chemistry of TosMIC have appeared, in 1980, 1987, 1993, and 1995. Several reviews on the chemistry of isocyanides in general are available. An effort has been made to make this chapter as complete as possible, in coverage both by tables and by references, with respect to the immediate objective: a survey of the “Synthetic Uses of TosMIC.” Emphasis is on the primary products derived from reactions of TosMIC and related isocyanides, with limited reference to the further utilization of these products. Thus, the next section gives a complete account of reductive cyanation, the conversion of aldehydes or ketones into cyanides with the use of TosMIC, but for obvious reasons synthetic applications of the product cyanides are not treated in this chapter. One of the subsequent sections describes the application of TosMIC to the synthesis of pyrroles, including 2,3‐divinylpyrroles, which are important precursors in a new synthesis of indoles. This latter transformation, made possible by the easy availability of the precursors through TosMIC chemistry, is afforded brief coverage. As a rule, reference to preliminary papers has been omitted when the same information is available from the corresponding full papers. The patent literature is covered highly selectively and is cited only when providing new and relevant information. Negative results of reactions are reported in the text or tables only when at least some relevant information is available with respect to the conditions of such unsuccessful attempts.

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Rearrangements of Free Radicals, XII¹⁾ ESR Spectroscopic Study of the Ring Opening of the Homobenzvalenyl Radical

et al. 1987

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Rearrangements of free radicals, XI. Sigmatropic and electrocyclic reactions of bicyclo[3.2.0]heptadienyl radicals, 3‐Quadricyclanyl radicals, and 7‐norbornadienyl radical

Cited by 15 publications

References 33 publications

Ultraviolet Photoelectron Spectroscopy of Some C₇H₇^- Isomers: Quadricyclanide, Norbornadienide, Cycloheptatrienide, and 1,6-Heptadiynide

Ultraviolet Photoelectron Spectroscopy of Some C₇H₇^- Isomers: Quadricyclanide, Norbornadienide, Cycloheptatrienide, and 1,6-Heptadiynide

Synthetic Uses of Tosylmethyl Isocyanide (TosMIC)

Rearrangements of Free Radicals, XII¹⁾ ESR Spectroscopic Study of the Ring Opening of the Homobenzvalenyl Radical

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Rearrangements of free radicals, XI. Sigmatropic and electrocyclic reactions of bicyclo[3.2.0]heptadienyl radicals, 3‐Quadricyclanyl radicals, and 7‐norbornadienyl radical

Cited by 15 publications

References 33 publications

Ultraviolet Photoelectron Spectroscopy of Some C7H7- Isomers: Quadricyclanide, Norbornadienide, Cycloheptatrienide, and 1,6-Heptadiynide

Ultraviolet Photoelectron Spectroscopy of Some C7H7- Isomers: Quadricyclanide, Norbornadienide, Cycloheptatrienide, and 1,6-Heptadiynide

Synthetic Uses of Tosylmethyl Isocyanide (TosMIC)

Rearrangements of Free Radicals, XII1) ESR Spectroscopic Study of the Ring Opening of the Homobenzvalenyl Radical

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Ultraviolet Photoelectron Spectroscopy of Some C₇H₇^- Isomers: Quadricyclanide, Norbornadienide, Cycloheptatrienide, and 1,6-Heptadiynide

Ultraviolet Photoelectron Spectroscopy of Some C₇H₇^- Isomers: Quadricyclanide, Norbornadienide, Cycloheptatrienide, and 1,6-Heptadiynide

Rearrangements of Free Radicals, XII¹⁾ ESR Spectroscopic Study of the Ring Opening of the Homobenzvalenyl Radical