4074-25-3Relevant articles and documents
Dichloro-Cycloazatriphosphane: The Missing Link between N2P2 and P4 Ring Systems in the Systematic Development of NP Chemistry
Bresien, Jonas,Hinz, Alexander,Schulz, Axel,Suhrbier, Tim,Thomas, Max,Villinger, Alexander
supporting information, p. 14738 - 14742 (2017/10/12)
A dichloro-cycloazatriphosphane that incorporates a cyclic NP3 backbone could be synthesized using knowledge gained from the chemistry of N2P2 and P4 ring systems. It fills the gap between the congeneric compounds [ClP(μ-NR)]2 and [ClP(μ-PR)]2 (R=sterically demanding substituent), and thus contributes to the systematic development of nitrogen–phosphorus chemistry in general. The title compound was studied with respect to its formation via a labile aminodiphosphene, which readily underwent different rearrangement reactions depending on the solvent. All compounds were fully characterized by experimental and computational methods.
SUBSTITUTED NITROBENZENE DERIVATIVES AS MEDICINES AND OTHER USEFUL USES THEREOF
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, (2008/06/13)
The present invention relates to a use of substituted nitrobenzene derivatives of general Formula I in medicine and health food, the pharmaceutical compositions comprising substituted nitrobenzene derivatives of general Formula I and the methods thereof for the prophylaxis and treatment of diseases.
Catalytic oxidation of a trialkyl-substituted phenol and aniline with biomimetic schiff base complexes
Knaudt, Jutta,Foerster, Stefan,Bartsch, Ulrich,Rieker, Anton,Jaeger, Ernst-G.
, p. 86 - 93 (2007/10/03)
The catalytic oxidation of 2,4,6-tri-tert-butylphenol and 2,4,6-tri-tert-butylaniline with molecular oxygen and tert-butylhydroperoxide was investigated using biomimetic Mn-, Fe- and Co-complexes as catalysts. The catalytic activity and product distribution were determined and compared with those observed in the reactions of the well-known Co(salen) complex.
Cobalt schiff base complex-catalyzed oxidation of anilines with tert-butyl hydroperoxide
Foerster, Stefan,Rieker, Anton,Maruyama, Kazushige,Murata, Kunihiko,Nishinaga, Akira
, p. 3320 - 3326 (2007/10/03)
Cobalt Schiff base complexes [Co(SB)] catalyze the oxidation of anilines (1) with tert-butyl hydroperoxide to give nitrobenzenes 2 and 4-(tert-butylperoxy)-2,5-cyclohexadien-1-imine derivatives 3 in yield distributions depending on the substitution mode of the substrate. 4-Alkyl- and 4-aryl-2,6-di-tert-butylanilines gave mixtures of 2 and 3, where the higher the bulkiness of the 4-substituent, the higher the yield of 2. With 2,4,6-trimethylaniline, the ratio of oxidations of the nitrogen and C-4 atoms was almost the same; but a hydrolyzed product 5 of the imine was obtained. 2,4,6-Triphenylaniline gave only 2. Nitrobenzene derivatives were also obtained from 2,6-dialkylanilines and 4-substituted anilines. The catalytic activity of Co(SB) depended on the nature of the SB ligand: the formal potential E° and steric factors seem to affect the reaction rate. Kinetic studies showed that the key step may involve hydrogen abstraction from the aniline, presumably by t-BuO? generated from homolytic decomposition of initially formed CoIII(SB)(OO-t-Bu). A precursor of 2 was found to be the nitrosobenzene derivative.
Ozone-mediated Nitration of Alkylbenzenes and Related Compounds with Nitrogen Dioxide
Suzuki, Hitomi,Murashima, Takashi,Kozai, Iku,Mori, Tadashi
, p. 1591 - 1598 (2007/10/02)
In the presence of ozone, nitrogen dioxide exhibits a strong nitrating ability for alkylbenzenes at low temperatures, converting them into the corresponding nitro derivatives in high yield.The addition of a protonic acid as catalyst enhances considerably the ability of this nitrating system and leads to a good yield of polynitro compounds.The reaction is clean and proceeds rapidly without any accompanying side-chain substitution or aryl-aryl coupling.It shows no kinetic dependence on the concentration of substrates and, as far as can be judged from relative reactivities and isomer distributions of products, it gives the appearance of being an electrophilic aromatic process.A possible role for nitrogen trioxide has been suggested as the initial electrophilic agent for the nitration of alkylbenzenes.
Co(salen) catalyzed oxidation of 2,4,6-trisubstituted anilines with tert-butylhydroperoxide
Nishinaga,Forster,Eichhorn,Speiser,Rieker
, p. 4425 - 4428 (2007/10/02)
Co(salen) catalyzed oxidation of 2,4,6-trisubstituted (preferentially 2,6-di-tert-butylated) anilines with tert-butylhydroperoxide gives 4-tert-butylperoxy-2,5-cyclohexadien-1-imine and nitrobenzene derivatives. The relative ratio of the products depends on the nature of the substituents in the substrate.
Picosecond Laser Photolysis Studies of Hydrogen Atom Transfer Reaction via Heteroexcimer State in Pyrene-Primary and Pirene-Secondary Aromatic Amine Systems: Role of "Hydrogen-Bonding" Interaction between Amino Group of Donor and ? Electron Acceptor in the Heteroexcimer
Okada, Tadashi,Karaki, Ichiro,Mataga, Noboru
, p. 7191 - 7195 (2007/10/02)
The mechanism of charge transfer followed by proton transfer in the hydrogen atom transfer reaction of excited pyrene-primary and -secondary amine systems has been directly demonstrated by means of a picosecond laser photolysis method.In the case of pyrene-N-ethylamine heteroexcimer system in hexane, for example, it has been observed that the 1-hydro-1-pyrenyl radical and the pyrene triplet state are produced simultaneously in the time region of subnanosecond to nanosecond.The deuteration of the NH group of the amine affects considerably the rate of formation of the 1-hydro-1-pyrenyl radical but not the rate of intersystem crossing from the heteroexcimer.On the basis of the results obtained for various pyrene-primary and -secondary aromatic amine heteroexcimer systems, the nature of the interaction between donor and acceptor in these heteroexcimers and their conformation in relation to the mechanism of the hydrogen atom transfer reaction via heteroexcimer have been elucidated.
Kinetics and Thermodynamics of Ion Pair Dissociation to Yield Free Solvated Ions. Effect of Steric Hindrance
Kokosinski, Jeanette D.,Forch, Brad E.,Stevenson, Gerald R.,Echegoyen, Luis,Castillo, Carlos A.
, p. 793 - 798 (2007/10/02)
The kinetics and thermodynamics of ion pair dissociation involving the anion radicals of ninhydrin, nitrobenzene, and trialkyl-substituted nitrobenzenes ion associated with Na+, K+, Cs+, or (Bu)4N+ in hexamethylphosphoramide (HMPA) were studied via ESR spectroscopy.The large alkyl groups on the (Bu)4N+ cation were found to sterically inhibit the close approach of the positive nitrogen to the anion radical.However, this loose ion pair dissociates less exothermically and exoenergetically than tighter ion pairs involving the other cations due to the poorer solvation of this large cation by the HMPA.The alkyl groups in the ortho positions of the nitrobenzene anion radical also prevent close approach of a solvated cation to yield intimate ion pairs.These loose ion pairs have lower free energies of activation for ion pair disociation.The observed rates and thermodynamics of ion pair dissociation and formation are explained in terms of ion solvation and steric inhibition to ion association.
