The Isonitrile—Nitrile Isomerization<sup>1</sup>

Casanova, Joseph; Werner, Newton D.; Schuster, Ronald E.

doi:10.1021/jo01349a003

Cited by 125 publications

(65 citation statements)

References 2 publications

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“…Likhotvorik et al [5] attempted this measurement for vinylidene 9 with 12 C enrichment, but the small size of the difference signals meant that the authors could only report that both methyl and isopropyl groups migrated, but not their relative rates. The non-monotonic reactivity order is reminiscent of the sequence Me:Et:iPr of 1:1.40:0.47 obtained by Casanova et al [17] in the isoelectronic isonitrile ± nitrile (RNC 3RCN) rearrangement, except that the rate for the isopropyl group is even slower than that for the methyl group.…”

Section: In Memory Of Wolfgang Rothmentioning

confidence: 72%

Alkyl Migration Aptitudes in the Vinylidene–Acetylene Rearrangement and Isotope Effect in the Vinylidene Formation Process from a Deuterium-Labeled Cyclopropene

Schulenburg

Hopf

Walsh

1999

Angew. Chem. Int. Ed.

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The secret of the mechanism of vinylidene rearrangements has been unlocked by the use of specifically labeled cyclopropenes under mild thermal conditions (see the Equations). (13) C labeling gives the surprising 1,2-alkyl migratory aptitude sequence Et>iPr>Me. Deuterium labeling yields the first measurement of the primary kinetic isotope effect in the ring opening of a cyclopropene to form a vinylidene.

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Section: In Memory Of Wolfgang Rothmentioning

confidence: 72%

Alkyl Migration Aptitudes in the Vinylidene–Acetylene Rearrangement and Isotope Effect in the Vinylidene Formation Process from a Deuterium-Labeled Cyclopropene

Schulenburg

Hopf

Walsh

1999

Angew. Chem. Int. Ed.

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“…The CH3NC sample was prepared by the reaction of N-methyl-formamide with a solution of p-toluenesulfochloride (toluene-p-sulphonyl chloride) in Quinoline [6].…”

Section: Methodsmentioning

confidence: 99%

High Resolution Spectrum of the CH₃NCν₂ Fundamental Band¹

Meister

Yamada

Winnewisser

1989

Zeitschrift Für Naturforschung A

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The spectrum of methyl isocyanide (CH3NC) has been measured in the region from 2148 cm" 1 to 2179 cm ~1 using a tunable diode laser spectrometer employing a newly designed signal averaging technique. The P-, Q-and R-branch lines of the v2 fundamental band have been assigned for values of J <25, K< 12. Molecular constants for the v2 state have been determined including the quartic centrifugal distortion parameters.

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“…[29][30][31] We observed that a mixture of the formamide precursor, p-toluenesulfonyl chloride, and tri-n-octylamine in excess at room temperature in a one-necked flask fitted to a vacuum line (0.1-4 mbar) leads, on heating to 80 8C, to pure isocyanides 2, 3, 5, 6, 8, and 9. In contrast to quinoline, which is generally used in the preparation of low-boiling isocyanides, [32,33] trioctylamine is not distilled under these conditions and thus allows the synthesis of kinetically unstable isocyanides with a relatively high boiling point (<100 8C at 0.1 mbar). Yields range from 42 to 80 %.…”

Section: Synthesis Of Unsaturated Isocyanidesmentioning

confidence: 99%

Are Unsaturated Isocyanides so Different from the Corresponding Nitriles?

et al. 2011

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Simple unsaturated and cyclopropylic isocyanides are synthesized by an efficient and simple approach. These compounds with gradually increasing distance between the unsaturated moiety and the isonitrile group are studied by UV photoelectron spectroscopy and quantum chemical calculations, and also compared to the corresponding nitriles. The first photoelectron band of the unsaturated compounds is linked to removal of an electron from the HOMO, which corresponds to CC multiple-bond ionization in antibonding interaction with the π-isocyanide bond (in the same plane) for conjugated systems, or in antibonding interaction with the pseudo-π-CH(2) group for isolated systems. For the 1-ethenyl derivatives, both cyano and isocyano groups act as a π-electron acceptor from the vinyl group, but the isocyano π system is much more strongly destabilized (ionization energies (IEs) shift to smaller values) by vinyl (3.12 eV) than the cyano π system is (2.70 eV). In comparison with the 1-ethynyl derivatives, a less pronounced destabilization (2.69 eV) of π(NC) by the ethynyl system (1.86 eV for π(CN)), and nearly the same order of magnitude of the energetic gap between the total antibonding (π(CC)-π(NC)) and the total bonding (π(CC)+π(NC)) IEs for ethenyl and ethynyl compounds are noted. The huge values of these last-named data for H(2)C=CH-NC (3.85 eV) and for HC≡C-NC (4.04 eV) reflect the strong interaction between the unsaturated carbon-carbon moiety and the isocyanide group, and thus more efficient conjugation than for the corresponding nitriles.

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The Isonitrile—Nitrile Isomerization¹

Cited by 125 publications

References 2 publications

Alkyl Migration Aptitudes in the Vinylidene–Acetylene Rearrangement and Isotope Effect in the Vinylidene Formation Process from a Deuterium-Labeled Cyclopropene

Alkyl Migration Aptitudes in the Vinylidene–Acetylene Rearrangement and Isotope Effect in the Vinylidene Formation Process from a Deuterium-Labeled Cyclopropene

High Resolution Spectrum of the CH₃NCν₂ Fundamental Band¹

Are Unsaturated Isocyanides so Different from the Corresponding Nitriles?

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The Isonitrile—Nitrile Isomerization1

Cited by 125 publications

References 2 publications

Alkyl Migration Aptitudes in the Vinylidene–Acetylene Rearrangement and Isotope Effect in the Vinylidene Formation Process from a Deuterium-Labeled Cyclopropene

Alkyl Migration Aptitudes in the Vinylidene–Acetylene Rearrangement and Isotope Effect in the Vinylidene Formation Process from a Deuterium-Labeled Cyclopropene

High Resolution Spectrum of the CH3NCν2 Fundamental Band1

Are Unsaturated Isocyanides so Different from the Corresponding Nitriles?

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The Isonitrile—Nitrile Isomerization¹

High Resolution Spectrum of the CH₃NCν₂ Fundamental Band¹