Aziridinimine, Diaziridinimine, Diaziridinone und Carbodiimide durch Photolyse von 2‐Tetrazolinen

Quast, Helmut; Bieber, Lothar W.

doi:10.1002/ange.19750871116

Cited by 37 publications

(3 citation statements)

References 15 publications

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“…The photochemically induced opening of the tetrazole ring has been found to be an easy process. − ,− As mentioned in the Introduction, tetrazole itself easily eliminates molecular nitrogen, leading to production of nitrilimine, which then undergoes secondary photoreactions, such as isomerization to carbodiimide, cyanamide, or a hydrogen cyanide/nitrene complex . In the case of 2MTA, the weakest bonds of the tetrazole ring are N1−N2, N2−N3, and N4−C5, which correspond to the formal single bonds and can then be expected to undergo easier photochemical cleavage.…”

Section: Resultsmentioning

confidence: 99%

Molecular Structure, Vibrational Spectra and Photochemistry of 2-Methyl-2H-Tetrazol-5-Amine in Solid Argon

et al. 2005

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In this work, the molecular structure, infrared spectrum and UV photochemistry of 2-methyl-2H-tetrazol-5-amine (2MTA) isolated in solid argon (10 K) were investigated. The experimental studies were supported by extensive DFT(B3LYP)/6-311++G(d,p) calculations. The infrared spectrum of matrix-isolated 2MTA was fully assigned and correlated with structural properties. Taking into consideration the observed frequency of the NH 2 wagging mode, it is suggested that, in the matrixes, the amine group becomes slightly more planar than in the gas phase, due to matrix-packing effects. In situ UV irradiation (λ > 235 nm) of the matrixisolated 2MTA monomer is shown to induce three main primary photochemical processes: (1) tautomerization to mesoionic 3-methyl-1H-tetrazol-3-ium-5-aminide; (2) nitrogen elimination, with production of 1-methyl-1H-diazirene-3-amine; (3) ring cleavage leading to production of methyl azide and cyanamide. Following the primary photoproducts, secondary reactions were observed, leading to spectroscopic observation of methylenimine and isocyanidric acid.

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Section: Resultsmentioning

confidence: 99%

Molecular Structure, Vibrational Spectra and Photochemistry of 2-Methyl-2H-Tetrazol-5-Amine in Solid Argon

et al. 2005

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“…Outlined below are the results of our initial foray into this promising territory, with emphasis on the coordination chemistry of gold as a particularly "carbophilic" and catalytically relevant Lewis acid. [5,6] Although compound 1 has been investigated in some detail, [2,3,7] the parent 1,3-dimethyl-2-methyleneimidazoline (3) itself has not been isolated in pure form. Gratifyingly, we found that this particular compound is readily obtained as an air-sensitive solid by deprotonation of imidazolium iodide 2 with KH in Et 2 O (Scheme 2).…”

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confidence: 99%

Coordination Chemistry of Ene‐1,1‐diamines and a Prototype “Carbodicarbene”

et al. 2008

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Carbophilic Lewis acids can polarize a coordinated π‐bond by a slippage mechanism. A series of stable ylid‐ or enolate gold complexes of ene‐1,1‐diamines not only emulate this property, but also reveal the exceptional donor capacity of such electron‐rich olefin ligands. Moreover, the first metal complex of a tetraaminoallene is reported, which features a prototype “carbodicarbene” ligand bound to a transition‐metal template.

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“…C 60.52 H 10.87 N 20.58 b) Man ruhrte 20 rng (0.07 mmol) 14b und 22 mg (0.15 mmol) Caesiumfluorid 0.5 h in 0.6 ml [D3]Acetonitril bei 2 0 -2 5 T , filtrierte und erhielt quantitativ 14a ('H-NMR). [1][2][3][4][5][6][7][8][9][10][11][12]2,: Nach der Vorschrift fur 14a aus 11 mmol 13'5' und 16 ml einer 0.76 M Losung von [(Trimethyl-~ilyl)methyl]lithium~~) in Pentan (12 mmol 12,2, ( N-(2,2-Dimethylpropyl~-2,2-dimethyl-l-c und der Fehler von (kE + kZ) dienten zur Berechnung der angegebenen Fehler von kE und k,.…”

Section: Photolyse Und Thermolyse Des Dihydroj-methylen-123-triazolunclassified

Synthese, Photolyse und Thermolyse eines 1,4,4‐Trialkyl‐4,5‐dihydro‐5‐methylen‐1H‐1,2,3‐triazols. Hoch diastereoselektive Bildung des (E)‐2,2‐Dimethyl‐N‐neopentyl‐1‐cyclopropanimins

Quast

Meichsner

1987

Chem. Ber.

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Das 3,5-Dihydro-4H-l,2,3-triazol-4-on 13 reagiert glatt rnit Organolithiumverbindungen zu den tertiiren Alkoholen 14. Peterson-Olcfinierung oder -vicl bcsscr -Wittig-Olcfinicrung von 13 ergeben das erstc Dihydromethylen-l,2,3-triazol 17. Bcim Bestrahlcn ( h 2 320 nm) eliminiert 17 Stickstoff und bildet quantitativ und diastereoselektiv ( > 98% d.e.) das Cyclopropanimin (E)-22. Bei 70 C isomerisiert diescs rnit den Geschwindigkeitskonstanten k t L = 9.0. l O -' s -' und kll. = 15.0. . s-I).Obviously, the geometry of the H2C=k-N-CH2 group fixcd by the ring in 17 is retained to a large extent in the cyclopropanimine 22 formed, no matter whcther the molecular nitrogen is eliminated photochemically or thermally. The results are interpreted in terms of identical or very similar diradical intermediates on both routes, e.g. (E)-27, (E)-28, SdE)-30. In a way, these diradicals possess the partial structure of an (E)-1-azaallyl radical or a C = N double bond, respectively. which exhibits configurational stability. triazole 9 zu untersuchen. Wir berichten daher hier iiber die Synthese des ersten 5-Alkyliden-4,5-dihydro-l H-1,2,3-triazols 17, seine Thermolyse und das iiberraschende Ergebnis der photochemischen Stickstoff-Eliminierung.Synthese des 5-Methylen-4,5-dihydrolH-1,2,3-triazols 17 5-Alkylidendihydro-1,2,3-triazole 9 konnen prinzipiell als [3 + 21-Cycloaddukte von Allenen und Aziden 'OJ') oder von Keteniminen und Diazoverbindungen121 betrachtet werden. Umsetzungen dieser Verbindungen sind zwar wiederholt beschrieben worden, doch wurden dabei nie 5-Alkylidendihydro-l,2,3-triazole vom Typ 9 isoliert. So haben bereits 1968 Bleiholder und Shechter mit der gleichen Zielsetzung, die der vorliegenden Arbeit zugrunde Iiegt, elektronegativ substituierte Azide an Tetramethylallen addiert und die zum Teil (Ila-c) thermisch uberraschend stabilen, zu 9 isomeren Alkylidendihydro-1,2,3-triazole 11 erhalten. Deren photochemische (11 a) und thermische (11 d) Stickstoff-Eliminierung fuhrte jedoch nicht zu Alkylidenaziridinen 7 oder Cyclopropaniminen 8, sondern zu anderen Produkten (10 bzw. 12)")Chem.

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Aziridinimine, Diaziridinimine, Diaziridinone und Carbodiimide durch Photolyse von 2‐Tetrazolinen

Abstract: gen) entwickelten Filmwaage bei konstanter Spreitflache ein Schub-Zeitdiagramm auf, so ermittelt man fur (2) den Spreitungsdruck p= 28.5 und fiir ( I ) nur 2.

Cited by 37 publications

References 15 publications

Molecular Structure, Vibrational Spectra and Photochemistry of 2-Methyl-2H-Tetrazol-5-Amine in Solid Argon

Molecular Structure, Vibrational Spectra and Photochemistry of 2-Methyl-2H-Tetrazol-5-Amine in Solid Argon

Coordination Chemistry of Ene‐1,1‐diamines and a Prototype “Carbodicarbene”

Synthese, Photolyse und Thermolyse eines 1,4,4‐Trialkyl‐4,5‐dihydro‐5‐methylen‐1H‐1,2,3‐triazols. Hoch diastereoselektive Bildung des (E)‐2,2‐Dimethyl‐N‐neopentyl‐1‐cyclopropanimins

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