Die reaktion von azoestern mit tetraalkyl-tetrazenen-(2)

Effenberger, Franz; Fischer, Peter

doi:10.1016/s0040-4020(01)92884-4

Cited by 10 publications

(4 citation statements)

References 12 publications

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“…The neutral oil (142 mg) could not b e separated by preparative vpc and exhibited tti/e peaks at 182 (M+, 92), 167(100), 165 (38), 152 (15), 141(4), 128(6), 104(36), 91 (19), and 77 (10) and ir peaks at 3028, 1604, 1516, 1031, 791(w), 769(w), 746, 729(s), 698(s), and 600 cm-'. The nmr spectrum showed two sets of singlets at r 6.05 and 7.79 for o-benzyltoluene 22 and at r 6.10 and 7.71 forp-benzyltoluene in a ratio of 37:63.…”

Section: Decottipositiot~ Of T M T It1 H2s04 In the Presence Of Tolrrenementioning

confidence: 99%

“…A number of mechanisms proposed so far may be summarized as shown in eqs. [l-31 (6,(8)(9)(10). Thermolysis or photolysis of TMT to generate the dimethylamine radical (eq.…”

Section: Introductionmentioning

confidence: 99%

“…[2] (or its ion pairs with the existing anions) (8,9). However, other investigators also suggest an intramolecular cyclic proton transfer to account for the decomposition (10). In concentrated sulfuric acid the diprotonated tetraphenyl-2-tetrazene is suggested to homolytically decompose to yield diphenylaminum radicals (1 1).…”

Section: Introductionmentioning

confidence: 99%

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Decomposition of tetramethyl-2-tetrazene under acidic conditions

Madgzinski¹,

Pillay²,

Richard³

et al. 1978

Can. J. Chem.

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Can. J. Chem. 56, 1657Chem. 56, (1978.Decompositions of tetramethyl-2-tetrazene (TMT) under acidic conditions were investigated by product analysis and by nmr and esr spectroscopic monitors. Photolysis in acetonitrile containing trifluoroacetic acid generated the dimethylaminium radical which added efficiently to an olefinic double bond. Some adducts contained a (CH3),NCH2-moiety, the immediate precursor of which could be CH2=N(CH3),+ species. Photolytic addition of TMT to norbornenes generated 2-norbornyl radicals that underwent coupling through the exo or endo side to give the dimers. Thermal decomposition in sulfuric acid in the presence of toluene gave N,N-dimethyltoluidines, N-methylphenethylamine, benzyltoluenes, and a plethora of other minor products in addition to a large amount of formylidene methylamine. The last compound was the major product when thermal decomposition of T M T was carried out in trifluoroacetic acid in the presence of toluene or anisol; amination products of aromatic substrates were low and contained only ortllo and porn isomers. TMT dissolved in these solvents exhibited the esr signal of the stable T M T t (the tetrazene cation radical) which did not react with cyclohexene. In concentrated sulfuric acid, T M T was decomposed in less than 15 min giving formylidene methylamine and dimethylamine as shown by nmr. In trifluoroacetic acid, the esr signal of tetramethylhydrazine cation radical ( T M H t ) emerged after the TMT solution was irradiated ; no dimethylaminium radical signal could be detected. The relationship of TMTf and TMHC with formation of the observed products remains unclear. Chem. 56, 1657Chem. 56, (1978.On a Ctudie, a I'aide de I'analyse des produits et par etudes spectroscopiques rmn et rpe la decomposition de la tetrarnethyltetrazene-2 (TMT) dans des conditions acides. La photolyse dans I'acetonitrile contenant de I'acide trifluoroacetique conduit a la formation de radical dimethylaminium qui s'additionne d'une f a~o n efficace a la double liaison olkfinique. Quelques produits contenaient une portion (CH3),NCH2-dont le prkcurseur immkdiat serait I'espece CH2N(CH3),+. L'addition photolytique du TMT aux norbornenes conduit a des radicaux norbornyl-2 qui subissent des couplages par les faces exo ou erldo pour conduire a des dimeres. La decomposition thermique dans I'acide sulfurique en presence de toluene conduit aux N,N-dimethyltoluidines, a la N-methylphenethylamine, aux benzyltoluenes et a toute une strie d'autres produits mineurs en plus d'une grande quantitt de formylidene methylamine. Ce dernier conrposk est le produit majeur lorsque la dCcomposition therrnique du TMT est effectuee dans I'acide trifluoroacetique en presence du toluene ou d'anisol; les produits d'amination des substrats aromatiques sont faibles et contiennent uniquement les isomeres orflro et pnrn. Lorsque le TMT est dissous dans ces solvants, il presente un signal rpe correspondant a I'entite T M T t (le radical cation tetraztne) qui ne rtagit pas avec le cyclohexene. Dans l'acide sulfurique co...

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Section: Decottipositiot~ Of T M T It1 H2s04 In the Presence Of Tolrrenementioning

confidence: 99%

“…A number of mechanisms proposed so far may be summarized as shown in eqs. [l-31 (6,(8)(9)(10). Thermolysis or photolysis of TMT to generate the dimethylamine radical (eq.…”

Section: Introductionmentioning

confidence: 99%

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Decomposition of tetramethyl-2-tetrazene under acidic conditions

Madgzinski¹,

Pillay²,

Richard³

et al. 1978

Can. J. Chem.

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“…Propyne has a first IP of 10.37 eV ['*]; the appearance of the PE spectra obtained at high temperatures is consistent with the presence of this molecule. Thermolysis of the tricyclic cis-tetrazene 13 affords only a single product besides molecular nitrogen which is easily identified as 2,3,4,5tetrahydropyridine (26). This reaction can be explained as a [2 + 2 + 21 cycloreversion.…”

mentioning

confidence: 99%

Electronic Structure and Gas‐Phase Thermolysis of 2‐Tetrazenes with Acyclic or Cyclic Amino Groups Studied by Photoelectron Spectroscopy

et al. 1994

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The electronic structures and the gas‐phase thermolyses of the 2‐tetrazenes 2–13 have been studied by He(I) photoelectron spectroscopy. The compounds are characterized by at least three ionization potentials with energies less than 10 eV which are assigned to the molecular orbitals π3 (HOMO), n+, π2, and n‐. In the thermolyses either the formal disproportionation products (amine and imine) of the respective aminyl radical are found, or the latter is stabilized by loss of an alkyl radical affording also an imine. Further products which can be explained by radical reactions are detected in flash vacuum pyrolyses. The tricyclic cis‐2‐tetrazene 13 is cleaved by [2 + 2 + 2] cycloreversion. The methoxymethylsubstituted compound 8 exhibits a more complex cleavage pattern.

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Umpolung der Reaktivität von Aminen. Nucleophile α‐sek.‐Aminoalkylierung über metallierte Nitrosamine

Seebàch¹,

Enders²

1975

Angewandte Chemie

124

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Es gibt prinzipiell zwei Arten von Heteroatomen in organischen Molekiilen: Die einen machen das mit ihnen verbundene Kohlenstoffatom zu einem elektrophilen, die anderen zu einem nucleophilen Zentrum. Die Entwicklung von Methoden zum Uberwechseln zwischen den beiden darauf beruhenden Kategorien von Reagentien ist eine wichtige Aufgabe der modernen organischen Synthese. Moglichkeiten dieser Umpolung der Reaktivitat funktioneller Gruppen werden am Beispiel der Amine diskutiert. Eine Methode zur Herstellung von maskierten a-sek.-Aminocarbanionen besteht darin, daD man das sekundare Amin nitrosiert, das entstandene Nitrosamin in a-Stellung zum Stickstoff metalliert, mit Elektrophilen umsetzt und entnitrosiert. Fur jeden dieser Schritte wird eine Anzahl von Beispielen gegeben, die die groBe Anwendungsbreite der synthetischen Gesamtoperation (elektrophile Substitution am a-C-Atom des sekundaren Amins) belegen. Erste Anwendungen und ein Verfahren zur Umgehung des Hantierens von Nitrosaminen werden vorgestellt, und zum SchluD wird die Bedeutung der Nitrosamine fur die Carcinogenese-und Mutageneseforschung kurz erortert.

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Die reaktion von azoestern mit tetraalkyl-tetrazenen-(2)

Cited by 10 publications

References 12 publications

Decomposition of tetramethyl-2-tetrazene under acidic conditions

Decomposition of tetramethyl-2-tetrazene under acidic conditions

Electronic Structure and Gas‐Phase Thermolysis of 2‐Tetrazenes with Acyclic or Cyclic Amino Groups Studied by Photoelectron Spectroscopy

Umpolung der Reaktivität von Aminen. Nucleophile α‐sek.‐Aminoalkylierung über metallierte Nitrosamine

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