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81.
Stuart Lang Neil Muir Franziska Schönebeck Andrew H. Payne 《Tetrahedron letters》2005,46(23):4027-4030
The phosphorus based radical precursors N-ethylpiperidine hypophosphite (EPHP) and diethylphosphine oxide (DEPO) are efficient reagents for carrying out the formation of seven- and eight-membered rings. Esters and amides were successfully converted into the corresponding eight-membered lactones and seven- and eight-membered lactams in good to excellent yields. 相似文献
82.
A series of near infrared (NIR) absorbing dinuclear ruthenium dicarbonylhydrazine complexes (DCH-Ru),[{Ru(bpy)_2)_2μ-DCH]~(n ) (where bpy = 2,2'-bipyridinc and n = 2, 3 or 4), were prepared. The DCH-Ru complexes areelectrochromic in the NIR region with a high absorption coefficient at 1550-1600 nm typically over 10000 M~(-1)cm~(-1). DCH-Ru complex polymers with good NIR electrochromic properties were also obtained and processed to make a device foroptical attenuation at a wavelength of 1550 nm. The potential of these DCH-Ru polymers for use in a variable opticalattenuator has been demonstrated with an attenuating power at the 1550-nm telecommunication wavelength over 7.0 dB permicron of polymer film thickness. Other classes of NIR active materials are the pentacenediquinones and the correspondingpoly(ether pentacenediquinone)s. These polymers can be electrochemically reduced to the corresponding semiquinone(radical anion) having NIR absorption within a telecom window (e. g., 1310 nm). 相似文献
83.
An electrochemical synthesis of oxazol‐2‐ones and imidazol‐2‐ones has been developed via 5‐exo‐dig cyclization of propargylic carbamates‐ and ureas‐derived amidyl radicals. The electrosynthesis relies on the dual function of 2,2,6,6‐tetramethylpiperidin‐ 1‐yl)oxyl (TEMPO) as a redox mediator for amidyl radical formation and an oxygen atom donor. The reactions are conducted under mild conditions using a simple setup and provide convenient access to functionalized oxazol‐2‐ones and imidazol‐2‐ones from readily available materials. 相似文献
84.
2-Trifluoroacetyl-4,5-dihydrofurans were obtained by manganese(III) acetate mediated radical cyclization of trifluoromethyl-1,3-dicarbonyl compounds (1a-c) with conjugated alkenes (2a-h). The reaction of 1,1,1-trifluoropentane-2,4-dione (1a) with propenylbenzene and 1,1-diphenyl-1-butene surprisingly yielded 3-(dihydrofuran-2(3H)-ylidene)-1,1,1-trifluoroacetones besides 3-trifluoroacetyl-4,5-dihydrofurans. 相似文献
85.
Trifluoromethylation of alkyl radicals is emerging as a powerful tool for C(sp3)–CF3 bond formations. Based on the hypothesis of CF3 group transfer from Cu(II)–CF3 to alkyl radicals, a number of trifluoromethylation reactions have been developed, including trifluoromethylation of alkyl halides, decarboxylative trifluoromethylation of aliphatic carboxylic acids, C(sp3)–H trifluoromethylation, amino‐ and carbo‐trifluoromethylation of alkenes, etc. Challenges in this intriguing field are also discussed. 相似文献
86.
Tullio Caronna Bruno M. Vittimberga Matthew E. Kornn W. Grant McGimpsey 《Journal of photochemistry and photobiology. A, Chemistry》1995,90(2-3):137-140
The photochemistry of a variety of dicyanopyridines (2,3-, 2,4-, 2,5-, 2,6-, 3,4- and 3,5-dicyanopyridine) in solution at room temperature was investigated. Pulsed UV (308 nm) laser irradiation in deoxygenated acetonitrile yields the triplet state with lifetimes between 4 and 10 μs and absorption bands in the 400 and 320 nm regions. In the presence of added HCl an air-insensitive transient (τ ≈ 10–12 μs, λmax ≈ 360–380 nm) was observed, suggesting the formation of a protonated excited state.
Irradiation in the presence of amines resulted in the production of the pyridyl radical anion (τ ≈ 40–80 μs, air sensitive, λmax ≈ 360–380 nm) formed by electron transfer from the amine to the pyridine triplet excited state. Stern-Volmer analysis gave electron transfer rate constants in the range (1–8) × 10−8 M−1 s−1.
In methanol solvent, irradiation yielded an air-insensitive transient assigned as the neutral pyridyl radical (τ ≈ 30–200 μs, λmax ≈ 370–385 nm). The formation of these transients is discussed in the context of previous photochemical electron spin resonance and product studies. 相似文献
87.
The FT-infrared spectra of two sexithiophenes having their end ,′-positions substituted by n-hexyl or -thiohexyl groups, in neutral and doped states, are studied with the main aim of deriving information about the π-electrons delocalization and about the electronic structure of the charged defects created upon doping with iodine. The analysis of the experimental data is aided by Density Functional Theory calculations. The modifications in the electronic structure of the sexithiophene backbone induced by the n-thiohexyl encapsulation are discussed from the point of view of single molecule interactions in thiol-terminated π-conjugated oligomers bound to metallic or cluster electrodes. 相似文献
88.
《代数通讯》2013,41(6):2883-2896
Abstract In 1945, N. Jacobson has introduced the definition of radical of a ring A (which is known as “Jacobson radical”, and is denoted J = J(A)). Later the concept of (Jacobson) radical of a left (or right) A-module M, J(M), has been defined as the intersection of all submodules N ≤ M such that M/N is simple. Thus one may consider the left radical J l = J( A A) and the right radical J r = J(A A ) of A, which are bilateral ideals of A, and are contained in J(A). If A has identity, one has J = J l = J r , but this equality is not valid in general. Dual, it is possible to define left socle S l and right socle S r of A. We shall establish relations between J, J l , J r , S l and S r , and for artinian algebras we shall obtain expressions for J l (A) and J r (A), S l (A) and S r (A). In particular, if A is a finite dimensional algebra over a field we display J l = J( A A) (and J r ? J(A A )) in a matrix representation. 相似文献
89.
《高分子科学杂志,A辑:纯化学与应用化学》2013,50(5-6):667-679
Polystyrenes, polyacrylates and poly(methyl methacrylate) prepared by atom transfer radical polymerization (ATRP) have predictable molecular weights, low polydispersities and well-defined halogen end groups. The halogen end groups have been substituted by other functionalities such as azides and amines. In order to predict the feasibility and selectivity of nucleophilic substitution reactions, the reactivities of the end groups of the different polymers were studied. First, model studies with benzyl halide (BzX), 1-phenylethyl halide (1-PEX), methyl 2-halopropionate (MXP), ethyl 2-bromoisobutyrate (EBiB) and 2-halopropionitrile (2-XPN) were performed. The models compounds were dissolved in DMF and after adding sodium azide (1.1 eq.), the reaction mixtures were stirred at 25°C. The relative magnitude of the rate constants for the reactions with the chlorinated substrates were found to be BzCl > MClP > 1-PECl ≈ 2-ClPN:22 > 6 > 1. Increased substitution at the carbon center decreased the rate of reaction, benzyl chloride reacted 22 times faster than 1-phenylethyl chloride. The brominated substrates reacted very fast. The rate constant of 1-PEBr, determined by competition experiments, was 4.5 times higher than the rate constant of benzyl chloride. Based on these results, the bromine end groups of different polymers were substituted under reaction conditions simular to those used for the model reactions. The end-functionalized polymers were characterized by 1H-NMR, IR and MALDI-TOFMS. 相似文献
90.
Copper(I) catalyzed radical benzylation and cyclization reaction of tertiary enamides was investigated and 3,3-disubstituted N-Alkyl isoindolin-1-ones were obtained in moderate to good yields. In this reaction, two new C–C bonds were formed in one step with high atom economy. Possible reaction pathway for the formation of the products was also discussed in this paper. 相似文献