A New Synthesis of Fulminic Acid

Abstract

3] H Liredereck, G. Hagelloch. E. Hambsch, Chem. Ber. 87, 35 (1954): A. H. H C J V I~S K. C. S-vmes. J. Chem. SOC. C 1971, 2331. and references cited therein 141 Trrhalose mixtures were prepared via this method; H Bredereck. E Hamhqch, Chem. Ber. 87, 38 (1954).IS] M Rerchrurh, planned Dissertation, Universitat Konstanr.[6] Investigations are currently being carried out on the application of this synthetic concept to pyranoses and reactions with secondary trifluoromethanesulfonyl groups [ 5 ] . [7] Preparation, see: L. D. Hall, D. C. Miller, Carbohydr. Res. 40, C1 (1975). R. W Binkley, D. G. Hehemann, J. Org. Chem. 43, 3224 (1978). [8] The configuration of the disaccharides (54, (Sb) and (6a)-(6f) were confirmed by comparison with authentic materials [(6e), (Sf)] and by the chemical shift of the protons of the isopropylidene group: K. H. Jung, P. Hermenfin. Dissertations, Universitat Stuttgart 1977 and 1979, resp.; R. R. Schmidt, P. Hermentin. Chem. Ber., in press: K. H. Jung, R. R. Schmidr, Justus Liebigs Ann Chem.. in press. [9J We assume that rapid and preferred formation of the p-anomer (2) or the uanomer (3) takes place on deprotonation of the anomeric mixture (1). 0 Verluy Cliemie, GmhH, 6940 Wr.inheirn, 1979 05 70-0833/ 79/O606-0468 $ 02. S0/0 A J I~~W .

Pyrolysis Nozzles Coupled to a Microwave Spectrometer with Stark Modulation for the Detection of Transients Species in a Supersonic Expansion

“…For gas phase work fulminic acid can be generated by the pyrolysis of mercury fulminate or 3-methyl-4-hydroxy-iminoisoxaline-5-one [27] as shown in Scheme 1. Wentrup et al [27] pyrolysed MHI in an attempt to generate HONC (isofulminic acid) but detected only the isomer HCNO (fulminic acid) and very small amounts of HNCO. Depending on the mechanism, generation of HONC in the gas phase using MHI may be possible if HONC can be stabilized before it isomerises.…”

“…A sample of MHI, synthesised by the method of Wentrup [27], was lowered into the first heating stage 3 , (ca. 200°C) and the nozzle temperature was set to ca.…”

The First Chemical Achievements and Publications by Justus von Liebig (1803−1873) on Metal Fulminates and Some Further Developments in Metal Fulminates and Related Areas of Chemistry

“…[9,26,27] b) From iodoformhydroxime [I(H)CϭCNOH] and base (NEt 3 ); [28] this is obviously a method for preparative work; I(H)CϭNOH has been obtained from NaCNO solutions and HI [34] or more conveniently by Huisgen and Christl (avoiding the highly explosive NaCNO), directly from Hg(CNO) 2 and HI. [28] c) By gas-phase pyrolysis of 3-phenyl-4-oxoiminoisoxazol-5(4H)-one [35] (high yield) for spectroscopic measurements of HCNO. [27] d) In situ preparation of HCNO by hydrolysis of trimethylsilylnitrile oxide Me 3 SiCNO, [36] which is accessible from Hg(CNO) 2 and Me 3 SiBr.…”

Formation of Cumulenes, Triple-Bonded, and Related Compounds by Flash Vacuum Thermolysis of Five-Membered Heterocycles

“…As we shall see below, aryl groups R can undergo 1,2-shifts that can produce other types of products. Thus, the 3-methylisoxazolones generate vinylidenes or isocyanides Z ϭ C:, which afford acetylenes, aminoacetylenes (including those with primary and secondary amine functions), aryl isocyanides, [96] amino isocyanides, fulminic acid [97] (from the oxime 138, Z ϭ NOH), and fulminates, RONC (from 138, Z ϭ NOR). [98,99] This reaction constitutes a practical and highyielding synthesis of many arylacetylenes and heteroarylacetylenes, some of which are not easily obtained in other ways.…”