Chemical and electrochemical oxidation of thiophene-pyridine and thiophene-pyrimidine co-oligomers in solutions

Chemical and electrochemical oxidation (or p-doping) of three types of pi-conjugated co-oligomers, Py-Th-(Th)n-Th-Py (Py = pyridine unit; Th = thiophene unit; 5a, n = 1; 6a, n = 2), Th-Py-(Th)n-Py-Th (5b: n = 1; 6b: n = 2), and Pym-Th-(Th)n-Th-Pym (Pym = pyrimidine unit; 5c: n = 1; 6c: n = 2), in solution systems has been studied. The chemical oxidation with NOBF(4) proceeded with isosbestic points in the UV-vis spectrum. The UV-vis absorption peak of 5a at 418 nm in CH(2)Cl(2) shifted to 456 nm after oxidation of 5a with NOBF(4). The oxidized 5a was easily reduced by N(2)H(4) to give the original UV-vis spectrum of 5a, and 5b, 6b, and 5c behaved similarly in the oxidation and reduction. In the oxidation by NOBF4, an (oxidized co-oligomer)/(original neutral co-oligomer) ratio of 1 was attained at [NOBF4] = 1.3 x 10(-6), 4 x 10(-6), 7 x 10(-6), and 9 x 10(-6) M for 5a, 6b, 5b, and 5c, respectively. The obtained data are considered to reflect the ease of oxidation of the co-oligomer, which is affected by the electron-accepting nature of the N-containing aromatic unit in the co-oligomer and effective pi-conjugated length of the co-oligomer. The cyclic voltammogram of 5a showed three redox couples with anodic peak current potentials of Epa = 0.75, 1.10, and 1.34 V versus Ag+/Ag, respectively. The first oxidation peak was assigned to one-electron oxidation of 5a, and electronic current of the first anodic peak (i) of 5a and 5c was proportional to (scanning rate)1/2. From the i- (scanning rate)1/2 relationship, diffusion constants, D's, of 5a and 5c were estimated to be 9.6 x 10(-6) and 1.7 x 10(-5) cm2 s(-1), respectively. CV data of 5b with the terminal thiophene units indicated occurrence of electrochemical oxidative polymerization of 5b.     

SCR脱硝过程中SO2催化氧化的原位红外研究

采用工业用V₂O₅-WO₃/TiO₂催化剂,基于傅里叶原位红外光谱(FT-IR)技术考察SO₂的氧化过程及烟气组分对SO₂氧化行为的影响;结果表明,SO₂在催化剂表面氧化主要是首先吸附在催化剂表面V₂O₅活性位上,占据其O原子,以SO^2-₃形式存在,后与催化剂表面V⁵⁺-OH发生反应,生成金属硫酸盐(VOSO₄)中间产物,O₂重新氧化催化氧化过程中由于被SO₂夺取O原子而被还原的V₂O₅物种,使V⁴⁺转化为V⁵⁺,促进金属硫酸盐(VOSO₄)向SO₃转化;SO₂与NO、NH₃的竞争吸附阻碍SO₂在V₂O₅活性点位上的氧化;在SCR中,NO的脱除与SO₂的氧化是相互抑制的关系。     

1,3,4-oxadiazolin-2-ones from carbo-t-butoxyhydrazones

5-Substituted-1,3,4-oxadiazolin-2-ones 2 were synthesized by the oxidation of carbo-t-butoxyhydrazones 1 of aromatic aldehydes with lead tetraacetate or, preferably, iodosobenzene diacetate. In some instances 5-acetoxy-1,3,4-oxadiazoles 3 were obtained along with 2 . The oxidation of carboethoxyhydrazones 4 gave 2-ethoxy-1,3,4-oxadiazoles 5 .     

Heteroorganic furan derivatives. 61. Trimethyl(5-methyl-2-furyl)silane and trimethyl(5-methyl-2-furyl)germane

The transformations of trimethyl(5-methyl-2-furyl)silane and trimethyl(5-methyl-2-furyl)germane were studied upon vapor-phase oxidation by atmospheric oxygen on a V-Mo-Ag-O catalyst. Under these conditions, trimethyl(5-formyl-2-furyl)-silane and trimethyl(5-formyl-2-furyl)germane are formed albeit in only 5–7% yield. This low yield is a consequence of the thermal instability of the starting compounds and the aldehydes formed. The oxidation of 2-methyl-5-tert-butylfuran was studied under comparable conditions. The corresponding aldehyde was obtained in 30% yield. A scheme was proposed for the catalytic oxidation of 5-substituted 2-methylfurans.For Communication 60, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 22–24, January, 1987.     

Catalyzed oxidation of 2-ethyl-5-methylthiophene

2-Ethyl-5-methylthiophene was subjected to liquid-phase oxidation with molecular oxygen in glacial acetic acid in the presence of cobalt acetate and sodium bromide. The effect of the concentrations of the substance undergoing oxidation, cobalt acetate, and sodium bromide on the oxidation was investigated. The chief reaction product — 2-acetyl-5-methylthiophene — was isolated. A difference in the reactivities of 2-ethylthiophene and 2-ethyl-5-methylthiophene is demonstrated.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 51–55, January, 1977.     

Aromatic bromination versus oxidation of indolylmalonates by bromine

The reactions of 5-substituted indolylmalonates (2a-e), carrying an electron-withdrawing group at the N(1) position, with bromine in CCl(4) or AcOH are reported. These substrates undergo oxidation in competition with the well-known aromatic bromination. Under the two sets of conditions, with parent indolylmalonate (2a), chemospecific oxidation is observed, whereas with 5-hydroxyindolylmalonate (2c), bromination at the 4- and 6-position is the dominating reaction. Investigation of the products composition of several 5-substituted indolylmalonates revealed the following trend: with a 5-substituted electron-withdrawing group like fluorine, the indolylmalonate undergoes oxidation rather than bromination. In contrast, with a 5-substituted electron-donating group, like a hydroxyl group, the ring bromination occurs preferentially over the oxidation. When the 5-substituent is an alkoxyl group, a significant amount of brominated-oxidized products is obtained. Monitoring the oxidation reaction by mass spectrometry allowed the characterization of the 2-bromoindolylidenemalonate intermediate. A bromonium ion is considered as possible pathway in the formation of this intermediate. The conformation of unsymmetrical methoxyl and benzyloxyl substituents was determined from (1)H NMR spectra, single-crystal X-ray diffraction and ab initio calculations.     

原位XRD反应装置下H2O对Fe5 C2的物相及F-T反应性能影响的研究

将原位XRD反应装置与在线气相色谱技术结合,研究了不同H_2O含量(4.36%、1.68%、0.56%)条件下单一相Fe_5C_2的氧化速率,并考察了不同Fe_5C_2氧化程度(0、25%、55%、68%)和氧化次数对其费托合成(F-T)反应性能的影响。研究结果表明,Fe_5C_2物相的氧化速率随H_2O含量的提高而逐渐增加,同时H_2O氧化使Fe_5C_2颗粒粒径减小,暴露出更多活性位点,造成F-T反应活性提高,且氧化程度越大,活性提高越明显;随着氧化次数的增加,F-T反应活性逐渐提高,但CH_4选择性增加,C_(5+)选择性逐渐降低。     

Selenium dioxide oxidations of dialkyl-3H-azepines: the first synthesis of 2-azatropone from oxidation of 2, 5-Di-tert-butyl-3H-azepine

Oxidation reactions of 2,5- and 3,6-di-tert-butyl-3H-azepines (1 and 2) with selenium dioxide (SeO(2)) were performed. The oxidation of 1 with SeO(2) gave 3-tert-butyl-7,7-dimethyl-4-oxo-octa-2,5-dienal 3 in 36% yield, 4-tert-butyl-5-(3,3-dimethyl-2-oxo-butylidene)-1, 5-dihydro-pyrrol-2-one 4 in 13% yield, 2, 6-di-tert-butyl-2-pyridinecarbaldehyde 5 in 12% yield, and 4, 7-di-tert-butyl-2H-azepin-2-one (2-azatropone) 6 in 6% yield, respectively. Oxidation of 2 with SeO(2) gave 2, 2-dimethyl-1-[2-(5-tert-butyl)-pyridyl]propanol 7 in 55% yield, and 3,6-di-tert-butyl-2H-azepine 8 in 5% yield, respectively. We found that selenium dioxide oxidation of 1 affords 4-oxo-octa-2,5-dienal 3 by a new ring cleavage reaction of 1, and we described the first synthesis of 2-azatropone 6 from this oxidation of 1. In the case of 2, pyridylpropanol 7 was obtained as the major product. We now report in detail result of these oxidation reactions, which have led to the synthesis of a novel azatropone derivative.     

Probing the effect of local structure on the thermodynamic redox properties of V(+5): a comparison of V2O5 and Mg3(VO4)2

Coulometric titration, an electrochemical method for measuring oxidation isotherms, has been used to characterize the redox properties of V2O5 and Mg3(VO4)2 between 823 and 973 K. V2O5 shows distinct regions in the isotherms corresponding to equilibrium with mixtures of V2O3 and V2O4 and of V2O4 and V2O5. From this data, the enthalpies for oxidation of V2O3 to V2O4 and for V2O4 to V2O5 are shown to be -380 +/- 10 and -285 +/- 20 kJ mol-1 O2, respectively. Oxidation isotherms for Mg3(VO4)2 exhibit a single step between the oxidized sample (all V+5) and a completely reduced sample (all V+3). The enthalpy of oxidation is found to increase with the oxidation state of the sample, from -370 +/- 30 kJ mol-1 O2 at an O:V ratio of 1.5 to -460 +/- 10 kJ mol-1 O2 at an O:V ratio of 2.5.     

Iron-catalyzed selective oxidation of 5-hydroxylmethylfurfural in air: A facile synthesis of 2,5-diformylfuran at room temperature

An iron(Ⅲ)-catalyzed selective oxidation of 5-HMF to 2,5-DFF in air at room temperature was developed.This approach gives 2,5-DFF with good selectivity and yields. Additionally, a two-step process was developed for the oxidation of 2,5-DFF to 2,5-FDCA at remarkably high substrate concentrations. This work demonstrates unequivocally the great potential of iron as a cheap and earth-abundant catalyst for the development of new protocols for the conversion of biomass to value-added chemicals.     

Synthesis of some 1-methyl-3-alkoxy-5-arylpyrrolecarboxylic acids and derivatives

By a combination of hydrolysis, decarboxylation, and methylation diethyl 1-methyl-3-hydroxy-5-phenylpyrrole-2,4-dicarboxylate was converted into 1-methyl-3-methoxy-5-phenyl-pyrrole-2,4-dicarboxylic acid (5) and into the isomeric compounds ethyl 1-methyl-2-phenyl-4-methoxypyrrole-3-carboxylate (4a) and ethyl 1-methyl-3-methoxy-5-phenylpyrrole-2-carboxylate (9a). 1-Methyl-2-phenyl-4-methoxypyrrole-3-carboxylic acid was synthesized both by the selective decarboxylation of 5 and by the hydrolysis of 4a. Hydrolysis of 9a, however, did not give the corresponding acid, but rather an oxidation product, 1-methyl-3-methoxy-5-hydroxy-5-phenyl-3-pyrrolin-2-onc (10a). Compound 10a was shown to arise from the air oxidation of the completely decarboxylated product, 1-methyl-2-phenyl-4-methoxypyrrole. Reduction of 9a with lithium aluminum hydride gave 1-methyl-3-methoxy-5-phenylpyrrole-2-methanol, which yielded 10a upon oxidation with silver oxide.     

Thermogravimetric investigations of new γ-γ′ cobalt-based superalloys

The aim of the study is characterization of high-temperature oxidation behavior of new Co-based superalloys by thermogravimetry (TG). The following alloys have been taken into account: Co–9Al–9W, Co–20–Ni–7Al–7W, Co–10Al–5Mo–2Nb and Co–20Ni–10Al–5Mo–2Nb (at.%). The thermogravimetric analysis was carried out in the temperature range 40–1200 °C of heating rate 5° min^?1. The investigation was performed using the thermal analyzer NETZSCH STA 449 F3 Jupiter. TG–DTG plots showed oxidation behavior up to 1200 °C and indicated the temperatures of further isothermal oxidation examinations. The oxidation behavior of basic Co–9Al–9W (at.%) alloy was compared to W-free Co–10Al–5Mo–2Nb and Co–20Ni–10Al–5Mo–2Nb (at.%) alloys. The obtained data showed different oxidation behavior dependably on the type of alloying elements. Moreover, the effect of Ni addition on oxidation performance was determined. The scales grown on Co-base superalloys after thermogravimetry were evaluated by means of scanning electron microscopy and energy dispersive spectroscopy.     

不同活性焦载体对V2O5/AC催化剂脱硫活性的影响

活性焦载体的选择是制备高活性烟气脱硫催化剂的关键.以四种煤制活性焦(AC)为载体,制得了系列V2O5/AC催化剂.通过脱硫活性评价、催化氧化能力测试和孔结构分析表明,AC表面的高活性氧化位较少,担载V2O5使AC表面产生了新的高活性氧化位,其脱硫活性显著提高;V2O5在具有高比表面积和较大孔容的载体上分散性较好,能够形...     

Chemoselective Oxidation of Alkenes by Metal-Organic Framework-Supported Copper Catalyst

Oxidation of alkenes to carbonyls or diols compounds is important in synthesizing fine chemicals and pharmaceutical intermediates. We report the synthesis and characterization of an aluminum metal-organic framework node-supported copper(II) chloride (DUT-5-CuCl), which is an efficient heterogeneous catalyst for the oxidation of alkenes using H₂O₂ as an oxidizing agent. Styrene and various substituted styrenes were transformed into the corresponding carbonyl compounds in excellent selectivity and yields. DUT-5-CuCl is tolerant with various functional groups and could be recycled and reused at least 5 times in the oxidation of α-methylstyrene. Unlike the oxidation of styrene derivatives, DUT-5-Cu catalyzed oxidation of aliphatic and cyclic alkenes produced 1,2-diols compounds selectively. The mechanism of the DUT-5-Cu catalyzed oxidation of styrene to benzaldehyde was investigated in detail by various experiments such as the determination of reaction intermediates and characterization of the catalyst after catalysis, and computational studies. This work highlights the importance of MOF-supported earth-abundant metal catalysts for oxidation reactions to produce fine chemicals.     

V2O5/TiO2-ZrO2催化剂上甲醇选择氧化制甲缩醛

采用共沉淀法制备TiO2-ZrO2复合氧化物载体、等体积浸渍法制备V2O5/TiO2-ZrO2催化剂,对催化剂在温和条件下甲醇选择氧化生成甲缩醛(DMM)反应进行研究.结果表明,与单一氧化物载体TiO2或ZrO2负载的钒基催化剂相比,V2O5/TiO2-ZrO2对甲醇选择氧化具有较好的催化性能.XRD、NH3-TPD和...     

Oxidation of alkylsilane-based monolayers on gold

The oxidation of alkylsilane monolayers on Au has been studied by X-ray photoelectron spectroscopy, reflection-absorption infrared spectroscopy, contact-angle measurements, and scanning tunneling microscopy. Exposure of the monolayers at 298 K to pure O(2) or H(2)O (>5 x 10(-5) Torr and >150 000 L) does not cause oxidation. Ambient atmosphere only causes oxidation if direct sight lines are maintained to the sample. Ozone exposure results in rapid monolayer oxidation. Oxidation initially occurs only at the Si atom, resulting in formation of a cross-linked siloxane monolayer that retains alkyl surface termination. Prolonged ozone exposures result in the oxidation and subsequent loss of the alkyl chain.     

Synthesis and characterization of the oxidized dGTP lesions spiroiminodihydantoin-2'-deoxynucleoside-5'- triphosphate and guanidinohydantoin-2'-deoxynucleoside-5'- triphosphate

Two convenient synthetic routes to the oxidized guanosine triphosphate lesions spiroiminodihydantoin-2'-deoxynucleoside-5'-triphosphate (dSpTP) and guanidinohydantoin-2'-deoxynucleoside-5'-triphosphate (dGhTP) are reported. Both two-electron oxidation of 2'-deoxy-7,8-dihydro-8-oxoguanosine-5'-triphosphate (dOGTP) using SO4*- generated photolytically from K2S2O8 or four-electron oxidation of 2'-deoxyguanosine-5'-triphosphate (dGTP) from singlet oxygen provide either dSpTP or dGhTP at pH 8.0 or 4.4, respectively. Highly purified triphosphates are obtained by ion pair reversed-phase HPLC.     

Characterization of 2'-deoxyguanosine oxidation products observed in the Fenton-like system Cu(II)/H2O2/reductant in nucleoside and oligodeoxynucleotide contexts

Reactive oxygen species attack both base and sugar moieties in DNA with a preference among the bases for reaction at guanine. In the present study, 2'-deoxyguanosine (dG) was oxidized by a copper-mediated Fenton reaction with the reductants ascorbate or N-acetyl-cysteine, yielding oxidation on both the base and the sugar. The primary oxidized lesions observed in these studies include the 2'-deoxyribonucleosides of 8-oxo-7,8-dihydroguanosine (dOG), spiroiminodihydantoin (dSp), guanidinohydantoin (dGh), oxazolone (dZ), and 5-carboxamido-5-formamido-2-iminohydantoin (d2Ih), as well as the free base guanine. d2Ih was the major product observed in the nucleoside, single- and double-stranded oligodeoxynucleotide contexts and is proposed to arise from oxidation at C5 of guanine. Product distribution studies provide insight into the role of the reductant in partitioning of dG base oxidation along the C5 and C8 pathways.     

Electrochemical evidence for catalytic water oxidation mediated by a high-valent cobalt complex

The pH-dependent electrochemical behavior for a Co(II) complex, [Co(Py5)(OH(2))](ClO(4))(2) (1; Py5 = 2,6-(bis(bis-2-pyridyl)methoxymethane)pyridine), indicates consecutive (proton-coupled) oxidation steps furnish a Co(IV) species that catalyzes the oxidation of water in basic media.     

Selective catalytic oxidation of organosulfur compounds with tert-butyl hydroperoxide

Rates and selectivities for the oxidation of various organosulfur compounds with tert-butyl hydroperoxide were measured on CoAPO-5 (APO = aluminophosphate; Co/P = 0.05), Co/H-Y (Co/Al = 0.15), and MoO(x)/Al2O3 (15 % wt MoO3). Rates increased with increasing electron density at the sulfur atom (methyl phenyl sulfide>diphenyl sulfide>4-methyldibenzothiophene>2,5-dimethyl thiophene). Rates (per metal atom) were significantly higher on CoAPO-5 than on Co/H-Y, MoO(x)/Al2O3, or homogeneous Co acetate catalysts. Small amounts of sulfoxides (1-oxide) were detected on all catalysts at low reactant conversions, together with their corresponding sulfones; at higher conversions, only sulfones (1,1-dioxide) were detected, indicating that the oxidation of sulfoxides is much faster than for organosulfur reactants in the sequential oxidation pathways prevalent on these catalysts. Framework Co cations were not leached from CoAPO-5 during the oxidation of 4-methyldibenzothiophene, but most exchanged Co cations in H-Y and >20 % of Mo cations in MoO(x)/Al2O3 were extracted during these reactions. The fraction of redox-active Co cations in CoAPO-5 and Co/H-Y was measured by reduction-oxidation cycles using H2 and O2 and by UV-visible spectroscopy. This fraction was much larger in CoAPO-5 (0.35) than in Co/H-Y (0.01), consistent with the higher oxidation rates measured on CoAPO-5 and with the involvement of redox-active species in kinetically-relevant steps in catalytic oxidation sequences. Redox-active Co cations at framework positions within accessible channels are required for catalytic activity and structural stability during oxidative desulfurization, whether hydroperoxides are used as reactants or as intermediates (when O2 is used as the oxidant).