540-80-7Relevant articles and documents
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McMillan
, p. 2514 (1962)
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Nitrosation of Organic Hydroperoxides by Nitrogen Dioxide/Dinitrogen Tetraoxide
Pryor, William A.,Castle, Laurence,Church, Daniel F.
, p. 211 - 217 (1985)
Cumyl and tert-butyl hydroperoxides react rapidly with NO2/N2O4 in organic solvents in the presence of a base to form the organic nitrate (RONO2) as the major product, together with smaller amounts of the corresponding nitrite (RONO), alcohol, and carbonyl compound (acetophenone or acetone from cumyl and tert-butyl hydroperoxide, respectively).The products from tert-butyl hydroperoxide are similar whether a base is present or not but those from cumyl hydroperoxide are more complex.We have formulated the initial reaction as a nitrosation of the hydroperoxide by N2O4 to give the pernitrite ester.This latter species is unstable and either rearrenges to give the nitrate or dissociates to form alkoxyl radicals and nitrogen dioxide that ultimately give the other observed products.The kinetics of the reaction were studied by stopped flow and are complex, but we conclude the kinetics are consistent with the nitrosation mechenism.The rate constants at 30 deg C are 2.4*104 and 8.1*103 M-1 s-1 for tert-butyl and cumyl hydroperoxides, respectively.We suggest that this facile reaction of NO2/N2O4 with hydroperoxides may have important consequences respect to the pulmonary toxicity of NO2 in smoggy air.
Batt,Milne
, p. 59 (1976)
Laser-Induced Fluorescence Excitation Spectra of terf-Butoxy and 2-Butoxy Radicals
Wang, Chuji,Shemesh, Liat G.,Deng, Wei,Lilien, Michael D.,Dibble, Theodore S.
, p. 8207 - 8212 (1999)
Laser-induced fluorescence (LIF) excitation spectra of t-C4H9O (terf-butoxy) and 2-C4H9O (2-butoxy) radicals were investigated in the wavelength range 335-400 nm. The radicals were formed by laser photolysis of the corresponding butyl nitrites at 355 nm. For tert-butoxy, 16 vibronic bands in two progressions were labeled. The dominant progression corresponds to C-O stretching mode with v′c-o = 521 ± 10 cm-1. The transition origin was tentatively assigned at 25 866 cm-1 (386.6 nm). Numerous bands remain unassigned. The LIF excitation spectrum of 2-butoxy, consisting of 15 vibronic bands in four progressions, was observed for the first time. A C-O stretching frequency v′c-o = 567 ± 10 cm-1 was obtained from the dominant progression. The transition origin was tentatively assigned at 26 185 cm-1 (381.9 nm). Three other progressions are evident, which have different vibrational band intervals: 617 ± 10, 590 ± 10, and 552 ± 10 cm-1. Zero-pressure fluorescence lifetimes for numerous vibronic bands of tert-butoxy and 2-butoxy were determined to be about 150 and 85 ns, respectively. These spectra can be used as a convenient spectroscopic tool for kinetic studies of butoxy radicals and should provide a starting point for investigations of their excited states structure and dynamics.
Method for recycling byproducts in synthesis of diphenyl sulfide compound
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Paragraph 0083-0088; 0092-0095; 0099-0102; 0106-0111, (2021/03/30)
The invention provides a method for recycling byproducts in synthesis of a diphenyl sulfide compound. The byproducts comprise alkyl alcohol and dimethyl disulfide. The method comprises the steps of (1) mixing the byproducts in synthesis of the diphenyl sulfide compound with a sodium nitrite aqueous solution, adding concentrated hydrochloric acid for reaction, and obtaining alkyl nitrite and dimethyl disulfide; and (2) mixing the products obtained in the step (1) with copper powder, adding an aniline compound for reaction, carrying out desolvation treatment on the obtained reaction solution toobtain a diphenyl sulfide compound and byproducts, and returning the byproducts to the step (1). According to the recycling method, the byproducts do not need to be separated, the byproducts serve asraw materials to be directly applied to synthesis of the diphenyl sulfide compound, the process steps are simple and safe, cyclic utilization of the materials is achieved, and the raw material cost ofindustrial production of the diphenyl sulfide compound and the treatment cost of industrial three wastes are remarkably reduced.
Four-Coordinate Copper Halonitrosyl {CuNO}10 Complexes
Bower, Jamey K.,Sokolov, Alexander Yu.,Zhang, Shiyu
supporting information, p. 10225 - 10229 (2019/07/03)
While copper nitrosyl complexes are implicated in numerous biological systems, isolable examples remain limited. In this report, we show that [Cl3CuNO]?, with a {CuNO}10 electron configuration, can be generated by nitrite reduction at a copper(I) dichloride anion or by nitric oxide addition to a copper(II) trichloride precursor. The bromide analogue, [Br3CuNO]? was synthesized analogously, and both copper halonitrosyl complexes were characterized by X-ray diffraction and a variety of spectroscopic methods. Experimental data and multireference (CASSCF/NEVPT2) calculations provide strong evidence for a CuII–NO. ground state. Both [Cl3CuNO]? and [Br3CuNO]? release and recapture NO. reversibly, and exhibit nitrosative reactivities toward a wide range of biological nucleophiles, such as amines, alcohols, and thiols.