927-83-3Relevant academic research and scientific papers
The role of imidoselenium(ii) chlorides in the formation of cyclic selenium imides: Via cyclocondensation
Karhu, Aino J.,Pakkanen, Olli J.,Rautiainen, J. Mikko,Oilunkaniemi, Raija,Chivers, Tristram,Laitinen, Risto S.
, p. 6210 - 6221 (2016)
The third member of the series of imidoselenium(ii) chlorides ClSe[N(tBu)Se]nCl (n = 3) (9) has been isolated from the cyclocondensation reaction of tBuNH2 and SeCl2 in THF in a molar ratio of ca. 3:1 and characterized in the form of two polymorphs 9a and 9b by single crystal X-ray analysis. The unusual structural features of this nine-atom chain are explained satisfactorily in terms of a bonding model that invokes intra-molecular secondary bonding interactions and hyperconjugation. The reaction of the bifunctional reagent ClSe[N(tBu)Se]2Cl (8) with tBuNH2 in THF occurs via concurrent pathways to give 1,3,5-Se3(NtBu)3 (1) and 1,3-Se3(NtBu)2 (3a). The energetics of the reactions of tBuNH2 and SeCl2 in THF have been calculated at the PBE0/def2-TZVPP level of theory in order to assess the feasibility of ClSe[N(tBu)Se]nCl (7-9, n = 1-3) as intermediates in the formation of known cyclic selenium imides. DFT calculations were also employed to explore the energy profile of the pathway of the formation of the first member of the series ClSeN(tBu)SeCl (7) from tBuNH2 and SeCl2 in THF at 298 K. The neutral ligand ClSeN(tBu)SeCl (7) is Se,Se′-coordinated to the metal centre in the unusual adduct [PdCl2{Se,Se′-(SeCl)2N(tBu)}]·[PdCl2{Se,Se′-Se4(NtBu)3}]·MeCN (10·MeCN), which is the first metal complex of an imidoselenium(ii) chloride.
Novel integrated carbon particle based three dimensional anodes for the electrochemical degradation of reactive dyes
Misra, Rohit,Neti, Nageswara Nao,Dionysiou, Dionysios D.,Tandekar, Mahendra,Kanade, Gajanan S.
, p. 10799 - 10808 (2015/02/05)
Three-dimensional carbon bed electrochemical reactors have been recently applied for the degradation of several organic pollutants. However, the carbon particles in such reactors slowly undergo attrition. We fabricated a novel flow-through three-dimensional anode using granular activated carbon (GAC) particles and polyvinylidene fluoride (PVDF) binder that potentially avoids such attrition. Optimization of the composition of GAC and PVDF with respect to mechanical integrity and electrical conductivity is reported. The anodes were tested in the electro oxidation of the reactive dyes: Reactive Orange-16 (RO-16), Reactive Red-2 (RR-2), and Reactive Blue-4 (RB-4). A tentative mechanism of dye degradation was proposed based on the observed role of the supporting electrolyte and the cyclic voltammetric, UV-vis, FT-IR and GC-MS data. The decolorization efficiencies were 75 ± 3, 81 ± 5 and 88 ± 4% for RB-4, RO-16 and RR-2, respectively. The integrated 3-D anodes are advantageous because of the absence of carbon attrition, which is otherwise found when a bed of GAC is used in the electrochemical reactors.
Formation of the tetranuclear, tetrakis-terminal-imido Mn4 IV(NtBu)8 cubane cluster by four-electron reductive elimination of tBuNNtBu. the role of the s-block ion in stabilization of high-oxidation state intermediates
Vaddypally, Shivaiah,Kondaveeti, Sandeep K.,Roudebush, John H.,Cava, Robert J.,Zdilla, Michael J.
supporting information, p. 1061 - 1063 (2014/01/17)
Mn4IV(μ3-NtBu) 4(NtBu)4 is obtained from a previously reported asymmetric MnIV/V-Li-(NR)(N) cluster by the removal of Li from the starting cluster by ion metathesis, which triggers reductive elimination of azo-tert-butane to give a tetranuclear heterocubane cluster.
1-acylsemicarbazides by ring opening of iminodiaziridines with carboxylic acids: Novel, expeditious access to the azapeptide motif
Quast, Helmut,Schmitt, Edeltraud,Ross, Karl-Heinz
experimental part, p. 3358 - 3362 (2010/11/16)
Carboxylic acids react rapidly and quantitatively with iminodiaziridines to afford 1,2,4-trisubstituted 1-acylsemicarbazides in a multistep sequence. In this way, a carboxy group is readily converted into an azapeptide motif. Broad signals in high-field H and C NMR spectra recorded for the products are indicative of dynamic processes. Georg Thieme Verlag Stuttgart New York.
Syntheses and15N NMR Spectra of Iminodiaziridines - Ring-Expansions of 1-Aryl-3-iminodiaziridines to 1H- and 3aH-Benzimidazoles, 2H-Indazoles, and 5H-Dibenzo[d,f] [1,3]diazepines
Quast, Helmut,Ross, Karl-Heinz,Philipp, Gottfried,Hagedorn, Manfred,Hahn, Harald,Banert, Klaus
supporting information; experimental part, p. 3940 - 3952 (2010/03/01)
Iminodiaziridines are synthesized, by (i) 1,3-dehydrochlorination with potassium, teri-butoxide of N-chloroguanidines, generated in situ from. N,N′,N″-substituted guanidines with tert-butyl hypochlorite, and (ii) base-mediated 1,3-elimination of sulfuric acid from N,N',N″- substituted hydroxyguanidine O-sulfonic acids. At elevated temperatures, (alkylimino)diaziridines undergo valence isomerization by 1,3shift, [2+1] cycloelimination to afford isocyanides and diazenes, and ring-opening elimination to yield alkylideneguanidines. N′-Aryl-N-hydroxyguanidine O-sulfonic acids furnish (N-arylimino)diaziridines, but no 1-aryl-3- iminodiaziridines, instead giving rearranged isomere. Precursors containing perdeuterated feri-butyl groups give rearranged products that show complete scrambling. This indicates that l-aryl-3iminodiaziridines are intermediates that undergo very rapid I degenerate valence isomerization. Provided that the ortho aryl positions are substituted, high yields of (arylimino)diaziridines are obtained, along with 2-imino-2,3-dihydro-3aHbenzimidazoles, Otherwise, 2-amino-lH-benzimidazoles and strongly fluorescent 3-amino-2H-indazoles, originating from rearrangements of the elusive l-aryl-3-iminodiaziridines, predominate. N',N″-Diaryl-N-hydroxyguanidine O-sulfonic acids give only rearranged products: a 2-amino-1H-benzimidazole and a 6-amino-5H-dibenzo[d,f][1. 3]diazepine if aryl = phenyl, or a 2-imino-2,3-dihydro-3aH-benzimidazole if aryl = mesityl. 3aH-Benzimidazoles slowly dimerize through Diels-Alder reactions. 15N NMR signals were assigned, to the syn and anti ring nitrogen atoms of iminodiaziridines with the help of a combination of homonuclear NOE and HNHMBC or HN-gHMBC experiments.
Metathesis and reduction reactions of nitroso compounds with metal carbenes and metal carbonyls
Herndon, James W.,McMullen, Leonard A.
, p. 83 - 102 (2007/10/02)
Reaction of nitroso compounds with metal-carbene complexes and metal carbonyls has been investigated.These reactions lead to reduction of the nitroso compounds, primarily to the corresponding azo- and azoxy compounds.Metal-nitrene complexes have been proposed as intermediates in these reactions.These intermediates couple rapidly with the unreacted nitroso compound, or enter into nitrene-like reactions with external or internal trapping agents.Reaction of metal carbonyls with nitrosoarenes and photolysis has been found to be an effective method for the reduction of nitrosoarenes to azoxyarenes, with few problems resulting from overreduction to amines or azo compounds.
HALOGENOCYCLOGERMANAZES: INFLUENCE DES SUBSTITUANTS HAKOGENES SUR L'EXISTENCE D'UN EQUILIBRE CYCLOGERMAZANE ->/<- GERMA-IMINE
Riviere-Baudet, M.,Khallaayoun, A.,Satge, J.
, p. 152 - 159 (2007/10/02)
Studies of ring opening of chlorocyclotrigermazanes in cycloaddition reactions with the nitrones phenyl- and tert-butylbenzylideneamine N-oxide, catalyzed by Lewis bases (HMPA) or Lewis acids (ZnCl2; M(CO)6; M(CO)5*THF; M=Cr,W), show that hexachlorocyclot
Photoreduction of Nitrobenzene by Aliphatic Amines-A Mechanistic Study
Sundararajan, K.,Ramakrishnan, V.,Kuriacose J.C.
, p. 1068 - 1070 (2007/10/02)
Nitrobenzene is photoreduced by aliphatic amines to phenylhydroxylamine.The product pattern for different amines in the photoreduction has been studied and attempt has been made to elucidate the mechanism of the photoreaction.
