A reaction of 3,6-di(tert-butyl)-4-chloro-1,2-benzoquinone with potassium ethyl xanthate. New sulfur-containing o-quinones

In a reaction of 3,6-di(tert-butyl)-4-chloro-1,2-benzoquinone with potassium ethyl xanthate, the halogen atom was replaced by the ethyl xanthate group. Acid hydrolysis of the product gave 4,7-di(tert-butyl)-5,6-dihydroxy-1,3-benzodithiol-2-one containing a pyrocatechol fragment, which was oxidized into the corresponding quinone. When irradiated in solution with visible light, this quinone quantitatively eliminated a CO molecule with contraction of the ring to a five-membered one. The quinones obtained were studied as ligands in coordination spheres of metals by ESR spectroscopy. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 683–686, April, 2006.     

STUDY OF GRAFTING COPOLYMER OF STYRENE AND 2,2,6,6-TETRAMETHYL-4-PIPERIDINYL METHACRYATE ONTO POLYPROPYLENE DURING HEATING

The grafting of copolymer of styrene and 2, 2, 6, 6-tetramethyl-4-piperidinyl methacrylate onto polypropylene during heating was studied by IR and ESR. It is found that the graft reaction is going through the stable free radical > NO mechanism.     

Synthesis and properties of 2-(3,5-di-tert-butyl-4-hydroxyphenyl)-5-nitroindazole

N-(2-Azido-5-nitrobenzylidene)-3,5-di-tert-butyl-4-hydroxyaniline (3a) and N-(2-azido-5-nitrobenzilidene) aniline (3b), when heated in dimethylformamide yielded 2-(3,5-di-tert-butyl-4-hydroxyphenyl)-5-nitroindazole (4a) and 2-phenyl-5-nitroindazole (4b), respectively. The structure of4b was confirmed by X-ray analysis. A stable phenoxyl radical was shown to originate from the oxidation of4a with lead (IV) dioxide.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1095–1097, June, 1994.     

NMR Study of the Hydrogen Bonding of Sterically Hindered Phenols with Alicyclic Ethers and Pyridine

In a preliminary report¹ it was shown that the hydrogen-bond chemical shift, δ_AB, correlates with the change in enthalpy, δH, in the interaction of chloroform with a series of closely related oxygen and nitrogen bases. In this communication, we report the hydrogen bonding parameters for the interaction in cyclohexane medium between 2,4,6-tri-t-butylphenol and tetrahydrofuran, tetrahydropyran and pyridine, and between 2,6-di-1-adamantyl-4-t-butylphenol and pyridine. There is correlation between the δ_AB and δ_AE for the same proton donor (2,4,6-tri-t-butylphenol) and the closely related alicyclic bases, and for the same base (pyridine) and the two closely related sterically hindered phenols. The temperature dependence of the δ_AB in these systems is also reported.     

Thermal studies of Co(II), Ni(II) and Cu(II) complexes of N,N′-<Emphasis Type="Italic">bis</Emphasis>(3,5-Di-<Emphasis Type="Italic">t</Emphasis>-butylsalicylidene)ethylenediamine

The thermal decomposition kinetics of sterically hindered salen type ligand (L) and its metal complexes [M=Co(II), Ni(II), Cu(II)] were investigated by thermogravimetric analysis. A direct insertion probe-mass spectrometer (DIP-MS) was used for the characterization of metal complexes of L and all fragmentations and stable ions were characterized. The thermogravimetry and differential thermogravimetry (TG-DTG) plots of salen type salicylaldimine ligand and complexes showed a single step. The kinetic analysis of thermogravimetric data was performed by using the invariant kinetic parameter method (IKP). The values of the invariant activation energy, E _inv and the invariant pre-exponential factor, A _inv, were calculated by using Coats-Redfern (CR) method. The thermal stabilities and activation energies of metal complexes of sterically hindered salen type ligand (L) were found as Co(II)>Cu(II)>Ni(II)>L and E _Cu>E _Ni>E _Co>L. Also, the probabilities of decomposition functions were investigated. The diffusion functions (D _n) are most probable for the thermal decomposition of all complexes.     

MALDI TOF‐TOF characterization of a light stabilizer polymer contaminant from polypropylene or polyethylene plastic test tubes

Disposable plasticware such as plastic test tubes are routinely used in all proteomics laboratories. Additives in polymers are used to protect them against oxygen or ultraviolet (UV) light degradation. Hindered amine light stabilizers (HALSs) are of utmost importance in modern polyolefin (polypropylene, polyethylene) stabilization. In this article, we demonstrate that the manufacturing polymeric agent: poly‐(N‐β‐hydroxyethyl‐2,2,6,6‐tetramethyl‐4‐hydroxy‐piperidinyl succinate), known as Tinuvin‐622 or Lowilite 62, from the HALS family, leaches from laboratory polypropylene or polyethylene plastic test tubes into the standard solvents for sample preparation. The analysis of these polluted samples by matrix‐assisted laser desorption/ionisation‐time of flight (MALDI‐TOF) mass spectrometry, in the positive mode, shows highly contaminated mass spectra, due to the high sensitivity of this technique. These contaminants have mass range and mass defect similar to those of peptides arising from the digestion of a protein in a conventional proteomics study. Therefore, they can be really harmful for proteomics studies, leading to misattributions, preventing any protein identification. In this article, an MS and MS/MS fingerprint of this pollutant is given and some pieces of advice to avoid it are proposed. Copyright © 2009 John Wiley & Sons, Ltd.     

Hindered rotation of ligands in cis-[PtR2Cl2] complexes

The temperature dependence of the¹H NMR spectra ofcis-[Pt(II)R₂Cl₂] complexes was studied in DMSO at 18–100°C (R is 2-methyl and 2,5-dimethylpyridine). The broadening of the signals from the methyl groups or hydrogen atoms in theortho-positions of heteroaromatic ligands is due to the coexistence of two forms of thecis-complexes in solution. These forms arise from the hindered rotation of asymmetrical ligands around the Pt-N bond.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 424–425, February, 1993.     

Acetyl chloride-3,5-di(tert-butyl)-4-hydroxy-N,N-dimethylbenzylamme salt in the benzylation of organic and inorganic sulfur-containing compounds

The reactions of the quaternary acylammonium salt formed on treatment of3,5-di-tertbutyl-4-hydroxy N,N-dimethylbenzylamine with acetyl chloride, with various organic and inorganic sulfur-containing compounds were studied. The possibility of using this salt for the introduction of a sterically hindered phenol moiety in various sulfur-containing compounds was shown.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 98–102, January, 1994.     

Temperature dependence of EPR spectrum of 2-trifluoromethylnitrobenzene radical anion in acetonitrile

Temperature dependence of the EPR spectrum of 2-trifluoromethylnitrobenzene radical anion in anhydrous acetonitrile in the temperature range 217 K ≤ T ≤ 296 K was studied and simulated. Temperature-dependent dynamic modulation of the fluorine isotropic hyperfine structure is caused by slow hindered rotation of CF₃ group with an activation energy of E _F* = 36.5±0.5 kJ mol⁻¹, which is the highest value for motions in π-type free radicals studied to date. Dedicated to the memory of Academician V. A. Koptyug on the occasion of the 75th anniversary of his birth. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 926–931, June, 2006.