Reaction of 3-chloro-3-methyldiazirines with hydrogen atoms

Burkholder, C. D.; Jones, W. E.; Wasson, John S.; Liu, M. T. H.

doi:10.1021/ja00528a059

Cited by 3 publications

(5 citation statements)

References 7 publications

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“…Attempts to identify 3-fluoro-3-( p -nitrophenoxy)diazirine ( 9 ) using EI + and ESI + mass spectrometry were unsuccessful. There is little literature precedent for exact mass identification of halodiazirines, as these molecules commonly undergo complex fragmentation pathways once ionized . Attempts to interpret fragmentation data were further complicated by contamination with p -fluoronitrobenzene ( 7 ).…”

Section: Methodsmentioning

confidence: 99%

Attempted Isolation and Characterization of Diazirinone (N₂CO)

et al. 2010

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Stimulated and intrigued by the report of the synthesis of diazirinone (1), a metastable adduct of N(2) and CO, we carried out further experimental and theoretical studies aimed at the detailed spectroscopic characterization of this species. Our attempts to generate and detect diazirinone (1) in either the condensed phase (using matrix isolation spectroscopy) or in the gas phase (using millimeter-wave rotational spectroscopy), however, have been unsuccessful. Trapping the volatile products produced from the reaction of 3-chloro-3-(p-nitrophenoxy)diazirine (5) with tetrabutylammonium fluoride (TBAF) under matrix-isolation conditions affords chlorofluorodiazirine (8) and carbon monoxide but fails to provide evidence for diazirinone (1). Moreover, sophisticated ab initio calculations of the structure and fundamental vibrational frequencies of diazirinone (1) produce an estimate for the fundamental band origin of the C=O stretch (2046 cm(-1)) that is ca. 100 cm(-1) lower in frequency than the experimental value previously attributed to this band. This discrepancy lies well outside any expected solvent shift or calculation error at this level of theory. In an effort to reconcile our findings with the earlier reports concerning diazirinone (1), we reconsidered the infrared spectral evidence upon which the original claim of diazirinone synthesis was based. New experiments demonstrate that these spectra may be explained and reproduced with a combination of solution-phase and gas-phase absorptions of CO, without recourse to invoke diazirinone (1).

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Section: Methodsmentioning

confidence: 99%

Attempted Isolation and Characterization of Diazirinone (N₂CO)

et al. 2010

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“…How can the formation of 18 and 19 be accounted for? Recently, it was suggested [27] that in the gas phase a rare species, diazoethene (20), can form acetonitrile radicals (21) by dimerization and loss of N2 (Scheme 18). If one molecule of Et2NH substitutes3) an ethoxy group in 1 and another abstracts the vinylic proton, a diazoethene derivative 22 may be formed (Scheme 19).…”

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confidence: 99%

“…The main reaction of this species would be polymerization leading to the tarry products observed. If, however, some 22 dimerizes as described [27], a cyano radical 23 can be formed to give 18 and 19 (Scheme 20). Diazoethenes are very elusive species4) and except for [27], none of the groups reporting syntheses [29-321 observed the formation of nitriles.…”

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confidence: 99%

“…If, however, some 22 dimerizes as described [27], a cyano radical 23 can be formed to give 18 and 19 (Scheme 20). Diazoethenes are very elusive species4) and except for [27], none of the groups reporting syntheses [29-321 observed the formation of nitriles. Therefore the proposed scheme should be considered more as a speculation than an indication about the mechanism, more so since the reaction took place in solution and not, as in the earlier study, in the gas phase [27].…”

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confidence: 99%

“…Diazoethenes are very elusive species4) and except for [27], none of the groups reporting syntheses [29-321 observed the formation of nitriles. Therefore the proposed scheme should be considered more as a speculation than an indication about the mechanism, more so since the reaction took place in solution and not, as in the earlier study, in the gas phase [27]. The first step in Scheme 19 corresponds to a known reaction of ketene acetals [33] [34], for example 24, i.e.…”

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Reactions of Alkenediazonium Salts. Part 1. 2,2‐Diethoxyethene‐diazonium hexachloroantimonate: A diazonium, a carbenium or an oxonium salt?

Szele¹,

Tencer²,

Zollinger³

1983

Helvetica Chimica Acta

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SummaryReactions of the title compound 1 with various nucleophiles have been studied. The salt behaves like an alkylating agent towards ethers, alcohols and water forming ethyl diazoacetate (2), which reacts further with excess of the nucleophile. A solvent cage mechanism accounting for the observed products is proposed. Thermal decomposition in inert solvents leads to the alkylation of the counter-ion, i.e. formation of chloroethane, and in anisole, alkylation and chlorination of the solvent are also observed.With a standard coupling component, 2-naphtholate ion, no azo coupling reaction of 1 is observed, but instead 14-methyl-14H-dibenzo [a,j]xanthene (17) is formed. The products of the reaction with diethylamine are diethylcyanoformamide (18) and ethyl diethylcarbamate (19). None of the chemistry of salt 1 is explained by the intervention of vinyl cations expected to be formed in a heterolytic dediazoniation. The predominant pathways seem to involve reactions of an oxonium salt (alkylating properties) or, in the case of diethylamine, a carbenium salt (primary nucleophilic attack on the p-C-atom of 1).The free energy barrier to C=C rotation in 1 is estimated to be 75 to 77 kJ/mol (18.0 to 18.5 kcal/mol), a value which falls between those expected for a double and a single bond.Introduction. -In the context of our investigations on the dediazoniation mechanism of aromatic diazonium ions'), comparisons with the reactivity of vinyldiazonium ions are interesting. Owing to their electronic similarity vinyldiazonium ions might be reagents for the formation of vinyl cations.The unsubstituted vinyldiazonium ion, H,C=CH-N,+, is not yet known. Therefore a theoretical study on the vinyldiazonium ion in the gas phase and in aqueous solution is a worthwhile undertaking. With others, we recently made such a study [2] for the gas phase by ab initio (STO-3G and 4-31G), and for solution by CND0/2 methods. This investigation is a continuation of previous theoretical

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