Structural Investigation of Sigma Complexes of Aromatic Amines with 1,3,5-Trinitrobenzene

1974 ◽  
Vol 52 (4) ◽  
pp. 630-639 ◽  
Author(s):  
Erwin Buncel ◽  
John G. K. Webb
Keyword(s):  
Dimethyl Sulfoxide ◽  
Aromatic Amine ◽  
Aromatic Amines ◽  
Structural Investigation ◽  
Structural Factors ◽  
Dmso Solution ◽  
Visible Spectroscopy ◽  
Sigma Complexes ◽  
Methoxide Ion ◽  
Characteristic Manner

Reaction of the 1,3,5-trinitrobenzene (TNB) – methoxide ion adduct 1 with a series of substituted arylamines in dimethyl sulfoxide (DMSO) solution yields new 1,3,5-trinitrobenzene – aromatic amine σ-complexes (2). The parent TNB–anilide complex is also obtained in the reaction of TNB with potassium anilide in DMSO. Identification of the complexes is effected by n.m.r. and visible spectroscopy. The n.m.r. parameters of the complexes are influenced in characteristic manner by substituents in the aryl-amine moiety. An analysis of electronic and structural factors in these systems is given, with emphasis on the following aspects: structural implications of NH–Hβ′ coupling; aromatic protons on the arylamine moiety; amino protons in free and complexed arylamines.

ChemInform Abstract: STRUCTURAL INVESTIGATION OF SIGMA COMPLEXES OF AROMATIC AMINES WITH 1,3,5-TRINITROBENZENE

1974 ◽  
Vol 5 (18) ◽  
pp. no-no
Author(s):  
ERWIN BUNCEL ◽  
JOHN G. K. WEBB
Keyword(s):  
Aromatic Amines ◽  
Structural Investigation ◽  
Sigma Complexes

An Aromatic Amine—1,3,5-Trinitrobenzene σ-Complex

1972 ◽  
Vol 50 (1) ◽  
pp. 129-131 ◽  
Author(s):  
E. Buncel ◽  
J. G. K. Webb
Keyword(s):  
Complex Formation ◽  
Aromatic Amine ◽  
Dmso Solution ◽  
Spectral Changes ◽  
Methoxide Ion

Interaction between aniline and the 1,3,5-trinitrobenzene–methoxide ion adduct 1 in DMSO solution results in spectral changes which are characteristic of σ-complex formation, the first such case involving an aromatic amine.

scholarly journals P.2.20 Epidemic of bladder cancer in japanese male workers exposed mainly to ortho-toluidine

2019 ◽  
Vol 76 (Suppl 1) ◽  
pp. A93.1-A93
Author(s):  
Makiko Nakano ◽  
Kazuyuki Omae ◽  
Yoko Eitaki ◽  
Satoko Iwasawa ◽  
Kota Fukai ◽  
...  
Keyword(s):  
Bladder Cancer ◽  
Aromatic Amine ◽  
Aromatic Amines ◽  
Organic Dyes ◽  
Cross Sectional Study ◽  
International Agency ◽  
Gross Hematuria ◽  
Cross Sectional ◽  
Exposed Workers ◽  
Medical Histories

BackgroundIn 2012, ortho-toluidine (OT) was listed as a Group 1 carcinogen by the International Agency for Research on Cancer, based on epidemiologic observations in workers co-exposed to OT and aromatic amines. Between 2014 and 2017, 10 cases of bladder cancer (BC) were identified in Japanese males working at two plants of the same company manufacturing intermediates of organic dyes and pigments.ObjectiveTo describe the features of the BC epidemic at the plants.MethodsWe conducted a cross-sectional study of 76 OT and/or aromatic amine-exposed workers including the 10 BC cases at the plants in 2017. The co-exposed aromatic amines were para-toluidine, ortho-anisidine, aniline, 2,4-dimethylaniline, and/or ortho-chloroaniline. Details of each worker’s job-site histories were obtained from the company records. Past medical symptoms and histories were checked in physician interviews. The subjects were divided into the BC group (n=10) and the non-BC group (n=66) and compared. No quantitative exposure data were available. The surrogate level of exposure to each aromatic amine was calculated as the summed job-weight-month in each process in each job-year.ResultsThe mean ages of the non-BC and BC groups were 50 and 56 years and the durations of employment were 23 and 20 years, respectively. The smoking rate in both groups was 80%. Significantly higher rates of gross hematuria (70%) and cystitis (70%) were identified in the BC group’s past medical histories. In the BC group, the surrogate levels of exposure to OT were higher than those of exposures to other aromatic amines. The surrogate levels were high in the job processes of filtering, rinsing, drying and packing products.ConclusionsThe subjects with BC were associated with a high surrogate level of exposure to OT. OT-exposed workers with past histories of gross hematuria and cystitis need a careful follow-up.

Interaction of heterocycles and nucleophiles. II. Sigma complexes formed from methoxide ion and Methoxy-3,5-dinitropyridines in dimethyl sulphoxide

1970 ◽  
Vol 23 (5) ◽  
pp. 957 ◽  
Author(s):  
MEC Biffin ◽  
J Miller ◽  
AG Moritz ◽  
DB Paul
Keyword(s):  
Dimethyl Sulphoxide ◽  
No Conversion ◽  
Solvation Effects ◽  
Sigma Complexes ◽  
Sigma Complex ◽  
Methoxide Ion ◽  
Rearrangement Reactions

Contrasting behaviour is observed when 2- and 4-methoxy-3,5-dinitropyridine interact with methoxide ion in dimethyl sulphoxide. The 4-methoxy compound affords both methine and acetal sigma complexes, the latter being thermodynamically more stable. The interconversion is catalysed by methanol. Labelling experiments have established that the sigma complex from the 2-methoxypyridine is formed by addition at C6; no conversion into the acetal could be effected. These observations are rationalized in terms of differential steric and solvation effects. Demethylation and rearrangement reactions of 4-methoxy-3,5-dinitropyridine are reported.

The ambident reactivity of aromatic amines in their reactions with N-2-(2,4,6-trinitrophenyl)-4,6-dinitrobenzotriazole-1-oxide, a new heterocyclic super-electrophile

1983 ◽  
Vol 61 (7) ◽  
pp. 1690-1691 ◽  
Author(s):  
Erwin Buncel ◽  
Richard A. Renfrow ◽  
Michael J. Strauss
Keyword(s):  
Aromatic Amine ◽  
Title Compound ◽  
Aromatic Amines

Reaction between the title compound 2 and 2,6-dimethylaniline, or N,N-dimethylaniline, gives rise to spectrally observable Meisenheimer type σ-complexes in which bonding has occurred between the para carbon of the aromatic amine and the benzotriazole moiety of 2; however, aniline reacts at the picryl moiety to give the product of displacement 5, via the aniline nitrogen as the nucleophilic atom.

Synthesis of aromatic amine phosphonato ester derivatives from the stereoselective reaction between triphenyl phosphite and dimethyl acetylenedicarboxylate in the presence of derivatives of aromatic amines

2009 ◽  
Vol 20 (4) ◽  
pp. 240-245 ◽  
Author(s):  
Malek Taher Maghsoodlou ◽  
Reza Heydari ◽  
Nourallah Hazeri ◽  
Sayyed Mostafa Habibi-Khorassani ◽  
Mahmoud Nassiri ◽  
...  
Keyword(s):  
Aromatic Amine ◽  
Aromatic Amines ◽  
Triphenyl Phosphite ◽  
Dimethyl Acetylenedicarboxylate ◽  
Stereoselective Reaction ◽  
Derivatives Of

scholarly journals trans-Bis(dimethyl sulfoxide-κO)bis(3-nitrobenzohydroxamato-κ2 O,O′)zinc(II)

IUCrData ◽  
2019 ◽  
Vol 4 (7) ◽  
Author(s):  
Bruna Lisboa Gonçalves ◽  
Samantha Oliveira Monteiro ◽  
Roberta Cargnelutti ◽  
Juliano Rosa de Menezes Vicenti
Keyword(s):  
Hydrogen Bonding ◽  
Dimethyl Sulfoxide ◽  
Single Crystals ◽  
Crystal Packing ◽  
Three Dimensional ◽  
Title Complex ◽  
Dmso Solution ◽  
Asymmetric Unit ◽  
Dimensional Crystal

Single crystals of the title complex, [Zn(C7H5N2O4)2(C2H6OS)2] or [Zn(NBZH)2(DMSO)2], were isolated from a dimethyl sulfoxide (DMSO) solution containing [Zn(NBZH)2]·2H2O (NBZH = 3-nitrobenzohydroxamate anion). The asymmetric unit comprises of one O,O′-chelating NBZH anion, one O-bound DMSO ligand and one zinc(II) cation localized on an inversion centre. The three-dimensional crystal packing includes N—H...O and C—H...O hydrogen bonding, as well as O...H and H...H contacts identified by Hirshfeld isosurface analysis.

scholarly journals Predicting Aromatic Amine Mutagenicity with Confidence: A Case Study Using Conformal Prediction

Biomolecules ◽  
2018 ◽  
Vol 8 (3) ◽  
pp. 85 ◽  
Author(s):  
Ulf Norinder ◽  
Glenn Myatt ◽  
Ernst Ahlberg
Keyword(s):  
Aromatic Amine ◽  
Aromatic Amines ◽  
Conformal Prediction ◽  
Additional Information ◽  
Primary Aromatic Amines

The occurrence of mutagenicity in primary aromatic amines has been investigated using conformal prediction. The results of the investigation show that it is possible to develop mathematically proven valid models using conformal prediction and that the existence of uncertain classes of prediction, such as both (both classes assigned to a compound) and empty (no class assigned to a compound), provides the user with additional information on how to use, further develop, and possibly improve future models. The study also indicates that the use of different sets of fingerprints results in models, for which the ability to discriminate varies with respect to the set level of acceptable errors.

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