17619-22-6Relevant articles and documents
Photoelectron spectroscopic and theoretical study of ketene imine, CH2=C=NH, and ketene N-methylimine, CH2=C=NCH3
Kroto, Harold W.,Matti, George Y.,Suffolk, Roger J.,Watts, John D.,Rittby, Magnus,Bartlett, Rodney J.
, p. 3779 - 3784 (1990)
The organic transient molecule ketene imine, CH2=C=NH, which may be important to the chemistry of the interstellar medium, has been produced by thermolysis of 3-hydroxypropionitrile, HOCH2CH2CN, and its He I photoelectron spectrum obtained for the first time. The interpretation of the spectrum is assisted by the calculation of the lowest four vertical ionization energies by a recently developed ab initio multireference coupled-cluster method (MRCC) and the SCF calculation of the vibrational frequencies of the lowest two cationic states. The lowest three observed ionization energies are 9.28, 11.91, and 13.04 eV. A fourth ionization is observed in the range 15-16 eV, but precise measurement is not possible because of contamination of this region of the spectrum by formaldehyde. The MRCC calculations predict ionization energies of 9.18 (a′), 12.03 (a″), 13.17 (a′), and 15.68 (a″) eV. Additional experimental and MRCC results for ketene N-methylimine, CH2=C=NCH3, provide further confirmation of the assignments for ketene imine.
Photochemical fragmentation of unsubstituted tetrazole, 1,2,3-Triazole, and 1,2,4-triazole: First matrix-spectroscopic identification of nitrilimine HCNNH
Maier, Guenther,Eckwert, Juergen,Bothur, Axel,Reisenauer, Hans Peter,Schmidt, Christiane
, p. 1041 - 1053 (2007/10/03)
Equilibria between the tautomers of heterocyclic azoles like 1, 2, and 4 have been studied many times. We here show that the application of density functional methods in combination with matrix IR spectroscopy is a useful tool for determining which protomer is preferred in rare gas matrices and thus also can be assumed to dominate in the gas phase. Photolysis of tetrazole (4) in cryogenic matrices allows the IR-spectroscopic identification of a new CH2N2 isomer, the long sought-after nitrilimine HCNNH (6). Flash pyrolysis of 4 also yielded nitrilimine. Upon irradiation this species is converted to a second, previously unknown "isomer", an HCN/NH complex 13. Nitrilimine (6) can also be generated by photolyzing 1,2,3- (1) and 1,2,4-triazole (2) in Ar matrices. The complex photochemistry of all three heterocyclic precursor compounds was unveiled. Our findings were supported by isotopic substitution experiments and by high-level ab initio calculations. Moreover, the IR bands of iminocyanide HNCN were tentatively assigned. This radical has up to now not been observed in a matrix. VCH Verlagsgesellschaft mbH, 1996.
Hydrogen Cyanide N-Methylide: Preparation, Spectroscopic Identification, and Its Relationship to Other C2H3N Isomers
Maier, Guenther,Schmidt, Christiane,Reisenauer, Hans Peter,Endlein, Edgar,Becker, Dieter
, p. 2337 - 2352 (2007/10/02)
With the intention of isolating 1H-azirene (8) we studied several precursors which should offer an entry into the C2H3N potential energy hypersurface.It was found that in addition to the known isomers 1, 2, 3, and 6 hydrogen cyanide N-methylide (5) - and probably aminoacetylene (4) - can be detected in an argon matrix at 10 K.No spectroscopic evidence for the formation of 1H-azirene (8) was found.In other words, the first six members 1-6 are now all identified.The elucidation of the structure of the new C2H3N species is based on the comparison of the observed IR spectra with those calculated by ab initio methods. - Key Words: Matrix isolation/ Calculations, ab initio/ Flash pyrolysis/ Photochemistry/ Hydrogen cyanide N-methylide
THE PHOTOCHEMISTRY OF 1,4-DIHYDRO-5H-TETRAZOLE DERIVATIVES ISOLATED IN LOW-TEMPERATURE MATRICES
Dunkin, Ian R.,Shields, Charles J.
, p. 259 - 268 (2007/10/02)
Six 1,4-dihydro-5H-tetrazole (tetrazoline) derivatives have been photolysed in Ar and N2 matrices at 12 K.The dimethyltetrazolinone (1a) gave as the major product the same diaziridinone obtained previously from solution photolysis, but it also underwent a novel cleavage to MeNCO and, presumably, methyl azide.Iminotetrazolines (3a) and (3b) gave the corresponding carbodiimides (5a) and (5b), and iminodiaziridines (4a) and (4b); while the tetrazolinethiones (7a) and (7b) gave carbodiimides (8a) and (8b), respectively.Photolysis of the vinyl substituted tetrazolinone (9) proceeded differently in inert ambient-temperature solutions and low-temperature matrices.In the former an imidazolone (10) was the sole isolable product, while in the latter formation of diaziridinone (15) competed with an alternative cleavage giving t-butyl isocyanate and vinyl azide.THese results are best interpreted on the basis of an intermediate biradical, which, however, could not be detected directly by matrix ir. spectroscopy.
SYNTHESE D'IMINES CYCLIQUES NON-STABILISEES PAR REACTIONS GAZ-SOLIDE SOUS VIDE ET THERMOLYSE-ECLAIR (1,2).
Guillemin, Jean-Claude,Denis, Jean-Marc,Lasne, Marie-Claire,Ripoll, Jean-Louis
, p. 4447 - 4456 (2007/10/02)
Unstabilized cyclic imines 1-4 were synthetized in gram-scale by vacuum dehydrochlorination of N-chlorocycloamines.Azirine 5 was prepared by flash vacuum thermolysis of the corresponding vinylazide 19.All the new compounds were characterized at low temperature by 1H, 13C NMR and IR spectroscopy.
Metastable Isomers of Acetonitrile: Syntheses of Vinylideneamine and Δ1-Azirine
Guillemin, Jean-Claude,Denis, Jean-Marc,Lasne, Marie-Claire,Ripoll, Jean-Louis
, p. 238 - 239 (2007/10/02)
The flash vacuum thermolysis and/or gas-solid phase multistep sequences allow the synthesis of vinylideneamine and a safe, preparative-scale synthesis of Δ1-azirine.
