CCLV.—The alkaline condensations of nitrohydrazo-compounds. Part III. Influence of ortho-groups on their formation and condensation

Green, Arthur George; Rowe, F. M.

doi:10.1039/ct9120102443

Cited by 11 publications

(5 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…The earlier studies (4, 5) determined the standard potentials of Ru (VIII)/Ru (VII) and Ru(VII)/Ru(VI) couples and touched on the disproportionation reaction of ruthenate (5) and perruthenate (6), but attempts to follow ruthenate reduction reactions failed. Though two other reports (7,8) have appeared recently, the results and conclusions drawn were contradictory because of uncertainties in coulometric results and current-potential profiles. In one (7) it was postulated that ruth~nate reduces first to ruthenium dioxide, then to Ru(III), and finally to the :metal itself; the other (8) proposed that ruthenium * Electrochemical Society Active Member.…”

Section: Department Of Chemistry University Of Regina Regina Saskatch...mentioning

confidence: 93%

“…Though two other reports (7,8) have appeared recently, the results and conclusions drawn were contradictory because of uncertainties in coulometric results and current-potential profiles. In one (7) it was postulated that ruth~nate reduces first to ruthenium dioxide, then to Ru(III), and finally to the :metal itself; the other (8) proposed that ruthenium * Electrochemical Society Active Member.…”

Section: Department Of Chemistry University Of Regina Regina Saskatch...mentioning

confidence: 93%

“…3,3"-Dinitrobenzidine was prepared by a standard method (5), as were 2,2'-dichloroazobenzene and 3,3'-dichloroazobenzene (6). 2,2'-Dicyanoazo benzene and 2,2'-dinitroazobenzene were prepared by a hypochlorite oxidation of the corresponding anilines in neutral aqueous media (7). Hydroquinone (Aldrich), 2-methylhydroquinone (Aldrich), 2-chlorohydroquinone (Pfaltz and Bauer), 2-bromohydroquinone (Pfaltz and Bauer), and catechol (Aldrich) were obtained commercially and used without further purification.…”

Section: Methodsmentioning

confidence: 99%

See 2 more Smart Citations

The Anodic Decomposition Pathways of Ortho‐ and Meta‐substituted Anilines

Hand

Nelson

1978

J. Electrochem. Soc.

120

View full text Add to dashboard Cite

A survey of the anedic electrochemistry of a number of orthoand metasubstituted anilines in 6N H2SO4 at carbon paste and graphite cloth electrodes has been carried out. It was found that the electrogenerated cation radicals decompose to form the correspondingly substituted benzidines and 4-aminodi-.phenylamines by tail-to-tail and head-to-tail coupling routes, respectively, m agreement with previous studies. Steric restraints hinder or exclude benzidine formation in some systems. The 4-aminodiphenylamines undergo hydrolytic degradation by different routes for the orthoand meta-substituted derivatives, but in both cases 2-substituted p-benzoquinones are the end product. The quinones with electron-withdrawing substituents undergo a 1,4-addition of water to form substituted trihydroxybenzene derivatives which are also electroactive. Products and intermediates formed were verified, where possible, by comparison with authentic samples. Preparative-scale electrolyses resulted in substantial yields of some of the substituted p-benzoquinones of a magnitude comparable with chemical oxidations. A reaction mechanism is proposed which is consistent with the electroanalytical data and products formed for the series of compounds.Recent articles have contributed significantly to our understanding of the decomposition pathways of ringsubstituted anilines. Bacon and Adams have found that para-substituted anilines couple head-to-tail to form the corresponding diphenylamines and that aniline and o-toluidine couple head-to-tail and tail-totail to form the corresponding diphenylamines and benzidines in a pH-dependent process (1). Wawzonek and McIntyre have shown that aniline and a number of ring-substituted anilines couple head-to-head to form hydrazo compounds in acetonitrile with pyridine (2) and in aqueous alkaline solutions (3). These various coupling reactions are summarized below

show abstract

Section: Department Of Chemistry University Of Regina Regina Saskatch...mentioning

confidence: 93%

Section: Department Of Chemistry University Of Regina Regina Saskatch...mentioning

confidence: 93%

Section: Methodsmentioning

confidence: 99%

See 1 more Smart Citation

The Anodic Decomposition Pathways of Ortho‐ and Meta‐substituted Anilines

Hand

Nelson

1978

J. Electrochem. Soc.

120

View full text Add to dashboard Cite

show abstract

“…b) . For the latter pathway, Green and Rowe proposed the oxidation of o ‐dinitroanilines to dinitroazobenzenes or the furazan oxides based on synthesis under neutral and alkaline conditions, respectively. However, decomposition by either of these two pathways would require the initial loss of either H 2 or H 2 O which are necessarily multi‐step (Fig.…”

Section: Introductionmentioning

confidence: 99%

Trigger bond analysis of nitroaromatic energetic materials using wiberg bond indices

Shoaf

Bayse

2018

J Comput Chem

View full text Add to dashboard Cite

The identification of trigger bonds, bonds that break to initiate explosive decomposition, using computational methods could help direct the development of novel, "green" and efficient high energy density materials (HEDMs). Comparing bond densities in energetic materials to reference molecules using Wiberg bond indices (WBIs) provides a relative scale for bond activation (%ΔWBIs) to assign trigger bonds in a set of 63 nitroaromatic conventional energetic molecules. Intramolecular hydrogen bonding interactions enhance contributions of resonance structures that strengthen, or deactivate, the CNO trigger bonds and reduce the sensitivity of nitroaniline-based HEDMs. In contrast, unidirectional hydrogen bonding in nitrophenols strengthens the bond to the hydrogen bond acceptor, but the phenol lone pairs repel and activate an adjacent nitro group. Steric effects, electron withdrawing groups and greater nitro dihedral angles also activate the CNO trigger bonds. %ΔWBIs indicate that nitro groups within an energetic molecule are not all necessarily equally activated to contribute to initiation. %ΔWBIs generally correlate well with impact sensitivity, especially for HEDMs with intramolecular hydrogen bonding, and are a better measure of trigger bond strength than bond dissociation energies (BDEs). However, the method is less effective for HEDMs with significant secondary effects in the solid state. Assignment of trigger bonds using %ΔWBIs could contribute to understanding the effect of intramolecular interactions on energetic properties. © 2018 Wiley Periodicals, Inc.

show abstract

“…b) Alkalische Reduktion aromatischer Nitroverbindungen mit Zink [17]. c) Oxydation aromatischer Amine rnit Kaliumferricyanid in alkalischem Milieu (fur sterisch d) Oxydation aromatischer Amine rnit Natriumhypochlorit [19]. e) Kondensation aromatischer Amine mit Nitrosoverbindungen [20].…”

Section: )unclassified

Electronenstruktur und physikalisch‐chemische Eigenschaften von Azo‐Verbindungen, Teil XV. Über die Struktur der protonierten Azobrücke in Azobenzolderivaten

Haselbach

1970

Helvetica Chimica Acta

View full text Add to dashboard Cite

Summary. The pK,-values of a number of pma-and orllzo-substituted azobcnzencs havc been measured. The effects of the substituents have been parametrized using a modified Hammelt-cquation. The results support the classical view that protonation of the azo-bridge takes placc on a distinct N-atom with formation of a N-H a-bond.Einleitung. -Trans-Azobenzol, eine schwache Base, geht in Medien genugend hoher Protonenaktivitat in seine konjugate Saure uber.

show abstract

CCLV.—The alkaline condensations of nitrohydrazo-compounds. Part III. Influence of ortho-groups on their formation and condensation

Cited by 11 publications

References 0 publications

The Anodic Decomposition Pathways of Ortho‐ and Meta‐substituted Anilines

The Anodic Decomposition Pathways of Ortho‐ and Meta‐substituted Anilines

Trigger bond analysis of nitroaromatic energetic materials using wiberg bond indices

Electronenstruktur und physikalisch‐chemische Eigenschaften von Azo‐Verbindungen, Teil XV. Über die Struktur der protonierten Azobrücke in Azobenzolderivaten

Contact Info

Product

Resources

About