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11.
Bonvin Y Callens E Larrosa I Henderson DA Oldham J Burton AJ Barrett AG 《Organic letters》2005,7(21):4549-4552
[reaction: see text] Oxidation of alkyl and cycloalkyl arenes with tert-butyl hydroperoxide catalyzed by bismuth and picolinic acid in pyridine and acetic acid gave the corresponding benzylic ketones (48-99%). Alternatively, oxidation of methyl arenes gave the corresponding substituted benzoic acids (50-95%). Preliminary mechanistic studies were consistent with a radical mechanism rather than a bismuth(III)-bismuth(V) cycle. 相似文献
12.
Nicolai D. Knfel Hannah Rothfuss Pavleta Tzvetkova Bragavie Kulendran Christopher Barner-Kowollik Peter W. Roesky 《Chemical science》2020,11(38):10331
We introduce the formation and characterization of heterometallic single-chain nanoparticles entailing both catalytic and luminescent properties. A terpolymer containing two divergent ligand moieties, phosphines and phosphine oxides, is synthesized and intramolecularly folded into nanoparticles via a selective metal complexation of Pt(ii) and Eu(iii). The formation of heterometallic Eu(iii)/Pt(ii) nanoparticles is evidenced by size exclusion chromatography, multinuclear NMR (1H, 31P{1H}, 19F, 195Pt) as well as diffusion-ordered NMR and IR spectroscopy. Critically, we demonstrate the activity of the SCNPs as a homogeneous and luminescent catalytic system in the amination reaction of allyl alcohol.A bifunctional terpolymer containing two orthogonal ligand moieties was synthesized, giving way to the facile formation of heterometallic Eu(iii)/Pt(ii) single-chain nanoparticles, which display both catalytic and luminescent properties. 相似文献
13.
Lee S Stackow R Trevithick-Sutton C Foote CS Barrett AG Hoffman BM 《Photochemistry and photobiology》2003,77(1):18-21
We report the quantum yields for singlet oxygen production by a series of porphyrazines (pz) of the form M[pz(An;B4-n)] (Scheme 1), where the peripheral substituent A is [S-R]2 with R = (CH2CH2O)3H, B is a fused alpha,alpha'-dialkoxybenzo group and M = 2H, Mg or Zn. These compounds show intense near-IR absorbance/emission (longest wavelength emission, approximately 830 nm). Their solubilities vary with R, whereas their optical properties do not. We show that singlet oxygen sensitization by these luminescent compounds can be "tuned" from essentially off to on by varying n and selection among M = 2H, Mg or Zn. The quantum yields vary ca 60-fold within the set of compounds studied, from phidelta = 0.007 for compound 3 to phidelta = approximately 0.4 for compound 11. 相似文献
14.
[reaction: see text] Regioselective 1,3-dipolar cycloadditions of supported vinyl ethers R(1)C(=CH(2))O-CH(2)-polymer, prepared by the Tebbe olefination of R(1)CO(2)-CH(2)-polymer, with ethyl cyanoformate N-oxide gave supported isoxazoline derivatives. Release from the support under mild acidic conditions gave the isoxazoles ethyl 5-R(1)-isoxazole-3-carboxylates. Alternatively, further on-resin functionalization of the R(1) substituent using Suzuki coupling reactions and release from the support under acidic conditions gave more structurally diverse isoxazoles. 相似文献
15.
Martin Christlieb Hannah J. Claughton Andrew R. Cowley Julia M. Heslop Jonathan R. Dilworth 《Transition Metal Chemistry》2006,31(1):88-92
During the condensation of 4-methyl-4-phenyl-3-thiosemicarbazide (3) with 2,3-butanedione an unexpected by-product, 8a-methyl-6,8a-dihydro-8-methyl-2-[N-methyl-N-phenylamino]-5H-1,3,4-thiadiazolo[3,2-d][1,2,4]triazine-5-thione, (5) was obtained in addition to the desired bis(thiosemicarbazone) (4). An X-ray crystal structure was obtained and is presented together with a proposed mechanism for its formation. A brief investigation
of the coordination chemistry of bicycle (5) was carried out. The formation of cyclic compounds during the synthesis of analogues with extended backbones is also described. 相似文献
16.
We report the synthesis and physical studies of a novel porphyrazine (pz) dimer [1[Ni,Cu]]2, which has Ni(II) ions incorporated into the pz cores and is linked by two Cu(II) ions coordinated to bis(picolinamide) chelates attached to the pz periphery. [1[Ni,Cu]]2 was prepared from precursor pz 2 with a selenodiazole ring fused to the pz core. This ring was deprotected to form the diamino-pz 3, which reacted with 2 mol of picolinoyl chloride hydrochloride to form pz 1[2H,2H], with peripheral bis(picolinamide) chelates; this was metalated to form [1[Ni,Cu]]2. The crystal structures of 1[2H,2H] and [1[Ni,Cu]]2 are presented. The latter is a dimer in which parallel, face-to-face pz's with an average separation of 3.30 angstroms are linked through the peripheral picolinamide ligands by a pair of peripheral Cu(II) ions. Each Cu(II) is coordinated with distorted square-planar geometry by a picolinamide from each pz. In this report, we focus on the interaction of these two peripheral Cu(II) ions. We discuss the preparation and magnetic properties of the pz dimer complex [1[Ni,Cu]]2 with two Cu(II) ions in the peripheral chelate but a diamagnetic metal ion Ni(II) in the pz core. Although [1[Ni,Cu]]2 contains two Cu(II) ions (S = 1/2), we could detect no electron paramagnetic resonance signal, which suggests very strong antiferromagnetic exchange between those two Cu(II) ions. Temperature-dependent magnetic susceptibility measurement gives an exchange splitting between the S = 0 ground state and the excited triplet state of delta = 660 cm(-1). 相似文献
17.
Condensation of allylborane reagents 9 and 12 with aldehydes gave anti-3-[(diphenylmethylene)amino]-1-alken-4-ols 10 and 13 with high relative and absolute stereocontrol. Subsequent deprotection gave the corresponding free anti-3-amino-1-alken-4-ols 11 and 14. Alternatively, reaction of imines 13a, 13f, and 13g with trifluoromethanesulfonic anhydride and acidic methanol gave, via rearrangement, double inversion, and hydrolysis, the isomeric anti-4-amino-1-alken-3-ols 22, 38a, and 38b in good yield. The stereochemistry of the rearrangement products has been established by a single crystal X-ray study of compound 37 and by chemical correlation. 相似文献
18.
Summary.
A coupled semilinear elliptic problem modelling an
irreversible, isothermal chemical reaction is introduced, and
discretised using the usual piecewise linear Galerkin finite element
approximation. An interesting feature of the problem is that a reaction order of
less than one gives rise to a "dead core" region. Initially,
one
reactant is assumed to be acting as a catalyst and is kept constant. It
is shown that error bounds previously obtained for a scheme involving
numerical integration can be improved upon by considering a quadratic regularisation
of the nonlinear term.
This technique is then applied to the full coupled problem, and optimal
and error bounds
are proved in the absence of
quadrature. For a scheme involving numerical integration,
bounds similar to those
obtained for the catalyst problem are shown to hold.
Received May 25, 1993 / Revised version received July 5, 1994 相似文献
19.
No modern theory of polymer excluded volume adequately describes the crossover from poor solvent to good solvent conditions; a fundamental difficulty is a singularity in the binary cluster integral. Mayer expansion techniques are applied to a model with a pair interaction between monomers to clarify the distinction between geometric and solvent contributions to excluded volume. Detailed calculations are undertaken for a hard-core potential and a mimic Lennard-Jones potential. The significance of the singularity in the binary cluster integral for calculations in the crossover regime is discussed. 相似文献
20.