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81.
A novel type of heterogenized CuCl2 catalysts was designed for the oxidative carbonylation of methanol to dimethyl carbonate (DMC) taking account of the plausible reaction mechanism and intermediates. To prevent severe corrosion of the reaction equipment materials due to Cl– while keeping the catalytic activity of the homogeneous CuCl2 catalyst, we adopted, as supports (or ligands) of CuCl2, four polymers, bearing a 2,2-bipyridine (bpy) or pyridine (py) unit, namely, poly(2,2-bipyridine-5,5-diyl) (Pbpy), poly(pyridine-2,5-diyl) (Ppy), poly(N,N-bisphenylene-2,2-bipyridine-4,4-dicarboxylic amide) (Bpya), and poly(4-methyl-4-vinyl-2,2-bipyridine) (Pvbpy), together with one chelate compound, 8-quinolinol. The catalytic activity, stability of heterogenized CuCl2 and their corrosivities to stainless steels were examined in the liquid-phase reaction of the oxidative carbonylation of methanol. These polymer-supported catalysts showed considerable catalytic activity and stability for the DMC synthesis. In particular, the Pbpy-CuCl2 and Ppy-CuCl2 catalysts exhibited high DMC yields and selectivity comparable to those of the homogeneous CuCl2 catalyst. This high activity appears to be associated with the presence of the -conjugated system in the polymers, which affect the redox reactions of Cu involved in the catalytic reaction. All of the polymer-supported CuCl2 catalysts could be easily recycled after filtration, and the initial catalytic activity was maintained after three times of use. The corrosive characters of the catalysts were closely related to CuCl2 leaching from the supports, which reflects the ability of supports to coordinate Cu. These experimental results suggest that both the electronic structure and the coordination ability of the polymer supports are key factors for the development of an effective catalytic system. 相似文献
82.
Protocatechuic acid esters (= 3,4‐dihydroxybenzoates) scavenge ca. 5 equiv. of radical in alcoholic solvents, whereas they consume only 2 equiv. of radical in nonalcoholic solvents. While the high radical‐scavenging activity of protocatechuic acid esters in alcoholic solvents as compared to that in nonalcoholic solvents is due to a nucleophilic addition of an alcohol molecule at C(2) of an intermediate o‐quinone structure, thus regenerating a catechol (= benzene‐1,2‐diol) structure, it is still unclear why protocatechuic acid esters scavenge more than 4 equiv. of radical (C(2) refers to the protocatechuic acid numbering). Therefore, to elucidate the oxidation mechanism beyond the formation of the C(2) alcohol adduct, 3,4‐dihydroxy‐2‐methoxybenzoic acid methyl ester ( 4 ), the C(2) MeOH adduct, which is an oxidation product of methyl protocatechuate ( 1 ) in MeOH, was oxidized by the DPPH radical (= 2,2‐diphenyl‐1‐picrylhydrazyl) or o‐chloranil (= 3,4,5,6‐tetrachlorocyclohexa‐3,5‐diene‐1,2‐dione) in CD3OD/(D6)acetone 3 : 1). The oxidation mixtures were directly analyzed by NMR. Oxidation with both the DPPH radical and o‐chloranil produced a C(2),C(6) bis‐methanol adduct ( 7 ), which could scavenge additional 2 equiv. of radical. Calculations of LUMO electron densities of o‐quinones corroborated the regioselective nucleophilic addition of alcohol molecules with o‐quinones. Our results strongly suggest that the regeneration of a catechol structure via a nucleophilic addition of an alcohol molecule with a o‐quinone is a key reaction for the high radical‐scavenging activity of protocatechuic acid esters in alcoholic solvents. 相似文献
83.
The behavior of hexafluoroacetone ethoxycarbonylimine in cyclocondensation with different binucleophiles of the amidine type, viz., amino derivatives of N- and N,S-heterocycles, was studied. A preparative method for the synthesis of previously unknown annelated 2,2-bis(trifluoromethyl)-1,3,5-triazinones was developed. 相似文献
84.
D. Tirzite A. Krauze A. Zubareva G. Tirzitis G. Duburs 《Chemistry of Heterocyclic Compounds》2002,38(7):795-800
The alkylation of 3-cyano-1,4-dihydropyridine-2(3H)-thiones or the condensation of an aromatic aldehyde, cyanothioacetamide, acetylacetone, and methyl iodide in the presence of piperidine has given a series of novel 5-acetyl-2-alkylthio-4-aryl-6-methyl-1,4-dihydropyridine-3-carboxylic acid nitriles. A compound was obtained from 3,5-di(tert-butyl)-4-hydroxybenzaldehyde in the molecule of which were combined the active part of the antioxidant ionol and a 1,4-dihydropyridine ring. It was found that, among the compounds synthesized, the highest antiradical activity occurred in a compound having two hydroxyl groups in the 4-phenyl substituent. 相似文献
85.
86.
Martin Winterwerber Rouzita Geiger Ursula Predoiu Hans-Hartwig Otto 《Monatshefte für Chemie / Chemical Monthly》2006,137(11):1441-1451
Summary. Reactions of cyanomethanesulfonamides with aromatic aldehydes in the presence of AcOH and piperidine produced the addition products, the 1-cyano-2-arylethenesulfonamides, whereas reactions with benzonitrile
yielded the 2-amino-1-cyano-2-phenylethenesulfonamides only when done in THF with BuLi. No addition products were isolated from the analogue reactions with 2-hydroxybenzaldehyde (salicylaldehyde). Instead,
we obtained 2-imino-2H-chromene-3-sulfonamides with good to excellent yields. These 2H-chromene derivatives allowed a number of transformations, from which the reactions with orthoformates opened an approach
to the hitherto unknown benzopyrano[3,2-e] [1,2,4]thiadiazine ring system. 相似文献
87.
The electrochemistry of 1,1′-bis(diphenylphosphino)ferrocene (dppf) derivatives of Ru3(CO)12 was investigated. Two known compounds [Ru3(CO)8(μ-dppf)2 (1) and Ru3(CO)10dppf (2)] and a new compound [Ru3(CO)11(μ-dppf)Ru3(CO)11 (3)] were prepared. Compound 3 was characterized spectroscopically and an X-ray crystal structure was obtained. The reductive electrochemistry of 1 and 2 showed an irreversible reduction and a follow-up oxidation, similar to Ru3(CO)12. The electrochemistry of compound 3 showed two irreversible waves and a follow-up oxidation. A trend in the reduction potential vs. the number of coordinated phosphorus atoms was noted. The oxidative electrochemistry of 1-3 showed a dppf-based chemically reversible wave, and an irreversible wave similar to that of Ru3(CO)12. Trends were also noted between the oxidation potential and the number of coordinated phosphorus atoms. 相似文献
88.
B. S. Fedorov N. I. Golovina L. S. Barinova V. V. Arakcheeva G. V. Lagodzinskaya M. V. Loginova R. F. Trofimova V. Z. Laishev V. F. Lazarev S. P. Smirnov I. Sh. Abdrakhmanov A. I. Firkin L. O. Atovmyan 《Russian Chemical Bulletin》1992,41(12):2185-2188
1,1,4,4-Tetranitrobutane-2,3-diol reacts with formaldehyde, forming 2,2-dinitropropane-1,3-diol or a cyclic ether — 4,4-dinitro-2,3-dihydroxytetrahydrofuran — as a function of the reaction conditions.Institute of Chemical Physics, Chernogolovka, Russian Academy of Sciences, 142432 Chernogolovka. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 12, pp. 2755–2759, December, 1992. 相似文献
89.
Hao Li 《Tetrahedron letters》2007,48(12):2209-2211
2,2′-Disubstituted ferrocenecarboxaldehydes are subjected to zinc-mediated allylation to form homoallylic ferrocenyl alcohols. The effects of ortho-substituted functional groups on facial selectivities of planar chiral aldehydes were studied and it was found that the corresponding homoallylic alcohols were obtained as single diastereomers in excellent yields. 相似文献
90.
The reactions of α-trifluoromethylated α-arylacetates 1 with 3 equiv of hydrazine, methylhydrazine or benzylhydrazine in 1,4-dioxane at reflux for 24 h afforded the corresponding 5-fluoropyrazolin-3-one derivatives 3a-m in high yields. Similarly, treatment of 1 with 3 equiv of PhNLiNH2 in THF at −78 °C, followed by warming to room temperature, resulted in the formation of 3n-s in high yields. 相似文献