Synthesis of 1,1′-dimethyl-4,4′-azo-1,2,4-triazolium and 3,3′-dimethyl-1,1′-azobenzotriazolium salts

Glover, E. E.; Rowbottom, Kenneth T.

doi:10.1039/p19740001792

Cited by 9 publications

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“…The main reasons for the scarcity of data pertaining to the study of long chain nitrogen systems are due to the highly endothermic nature and instability problems associated with N–N bond-forming reactions. Only a few groups have managed to synthesize and isolate compounds containing at least eight nitrogen atoms. ,− …”

Section: Introductionmentioning

confidence: 99%

Computational Study of Monosubstituted Azo(tetrazolepentazolium)-Based Ionic Dimers

Pimienta

2015

J. Phys. Chem. A

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The structures of monosubstituted azo(tetrazolepentazolium) cations (N11CHR(+)), oxygen-rich anions such as N(NO2)2(-), NO3(-), and ClO4(-), and the corresponding ion pairs are investigated using ab initio quantum chemistry calculations. The substituents (R) used are H, F, CH3, CN, NH2, OH, OCH3, N3, NF2, and C2H3. The stability of the protonated cation is explored by examining the decomposition pathway of the protonated cation (N11CH2(+)) to yield molecular N2 fragments. The heats of formation of these cations, which are based on isodesmic (bond type conserving) reactions, are dependent on the nature of the substituents. Ionic dimer structures are obtained, but side reactions including proton transfer, binding, and hydrogen bonding are observed in the gas phase. Implicit solvation studies are performed to determine the solution properties of the ion pairs.

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Section: Introductionmentioning

confidence: 99%

Computational Study of Monosubstituted Azo(tetrazolepentazolium)-Based Ionic Dimers

Pimienta

2015

J. Phys. Chem. A

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“…Unfortunately, despite their potential significance , to both theory and technology, compounds containing extended chains of nitrogen atoms are not well-known; this arises from both the endothermicities and associated stability problems and the relative scarcity of N−N bond-forming reactions known in the literature (especially when compared with carbon!). For example, the recent publication of 1 marked the discovery of a surprisingly stable compound containing a chain of eight nitrogen atoms, one of the few ,− compounds with such a long nitrogen chain, whereas comparable and longer carbon compounds are plentiful, well-known, and stable.…”

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confidence: 99%

1,1′-Azobis(tetrazole): A Highly Energetic Nitrogen-Rich Compound with a N₁₀Chain

Klapötke¹,

Piercey²

2011

Inorg. Chem.

250

195

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“…t-BuOCl provided the tetrazene 6 (63%) instead of the expected 1,2-diacyl-diazene [50] or of a cyclopentane derivative. It is known that tetrazenes are formed upon oxidation of hydrazines 7 ) with PhSeO 2 H [61], KBrO 3 ¥ HCl [62], KMnO 4 [63], Br 2 [64], MnO 2 [60], and other oxidants [55] [65]. Tetrazenes are considered to result from the dimerization of diazenes (N-aminonitrenes); 6 may, however, result from dimerization of an intermediate N-chlorohydrazide (X-philic substitution followed by elimination).…”

Section: Methodsmentioning

confidence: 99%

Synthesis and Oxidation of N‐Aminoglyconolactams: A Synthesis of Mannostatin A

Vasella

2004

Helvetica Chimica Acta

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The N-amino-ribono-1,5-lactam 4 was prepared in two high-yielding steps from the known methanesulfonate 2. Oxidation of 4 with t-BuOCl in the presence of 2,6-lutidine afforded the tetrazene 6 (63%). Oxidation with MnO 2 gave the deaminated lactam 7 (40%), which was also obtained, together with the lactone 8, upon oxidation of 4 with PhSeO 2 H. Oxidation with Mn(OAc) 3 /Cu(OAc) 2 provided the lactam 7 as the major and the dimer 9 as the minor product. Oxidation of 4 with 3 equiv. of Pb(OAc) 4 in toluene at room temperature gave two cyclopentanes, viz. the acetoxy epoxide 10 and the diazo ketone 11 in a combined yield of 78%. Oxidation with Pb(OBz) 4 provided 11 and the crystalline benzoyloxy epoxide 12. The crystal structure of 12 was established by X-ray analysis. The N-amino-glyconolactams 41, 46, and 51 were prepared similarly to 4. Their oxidation with Pb(OAc) 4 provided the diazo ketones 56, 57, and 58 as the only isolable products. Oxidation of the N-aminomannono-1,5-lactam 55 with Pb(OAc) 4 in the presence of DMSO gave the sulfoximine 59. Mannostatin A, a strong a-mannosidase inhibitor, was synthesized from the acetoxy epoxide 10 (obtained in 48% from 4) in seven steps and in an overall yield of 45%. . This synthesis renewed our interest in the transformation of carbohydrates into cyclopentanes. Carbohydrates indeed appear to be ideal starting materials for the synthesis of highly functionalized, enantiomerically pure cyclopentanes. The first general method for the transformation of monosaccharides to cyclopentanes is based on a fragmentation and intramolecular 1,3-dipolar cycloaddition [18]

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Synthesis of 1,1′-dimethyl-4,4′-azo-1,2,4-triazolium and 3,3′-dimethyl-1,1′-azobenzotriazolium salts

Cited by 9 publications

References 0 publications

Computational Study of Monosubstituted Azo(tetrazolepentazolium)-Based Ionic Dimers

Computational Study of Monosubstituted Azo(tetrazolepentazolium)-Based Ionic Dimers

1,1′-Azobis(tetrazole): A Highly Energetic Nitrogen-Rich Compound with a N₁₀Chain

Synthesis and Oxidation of N‐Aminoglyconolactams: A Synthesis of Mannostatin A

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Synthesis of 1,1′-dimethyl-4,4′-azo-1,2,4-triazolium and 3,3′-dimethyl-1,1′-azobenzotriazolium salts

Cited by 9 publications

References 0 publications

Computational Study of Monosubstituted Azo(tetrazolepentazolium)-Based Ionic Dimers

Computational Study of Monosubstituted Azo(tetrazolepentazolium)-Based Ionic Dimers

1,1′-Azobis(tetrazole): A Highly Energetic Nitrogen-Rich Compound with a N10Chain

Synthesis and Oxidation of N‐Aminoglyconolactams: A Synthesis of Mannostatin A

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1,1′-Azobis(tetrazole): A Highly Energetic Nitrogen-Rich Compound with a N₁₀Chain