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31.
m-Phenylene-coupled carbenonitrenes [(3-nitrenophenyl)methylene (2-H), (3-nitrenophenyl)fluoromethylene (2-F), (3-nitrenophenyl)chloromethylene (2-Cl), (3-nitrenophenyl)bromomethylene (2-Br)] have been investigated computationally (with B3LYP, MCSCF, CASPT2, ROMP2, and QCISD(T) methods) and experimentally (with IR, UV, and ESR spectroscopy). For each species, five electronic states were considered. At the highest level of theory explored, the parent compound (2-H) has a quintet ground state, but its halogen derivatives (2-X, X = F, Cl, and Br) have triplet ground states. A linear relationship between the Q[bond]T energy gap of 2-X and the T-S gap of the corresponding phenylcarbenes 8-X is found, which can be helpful in rationalizing and predicting ground-state multiplicities in m-phenylene-linked carbenonitrenes and similar species. Precursors for the photochemical generation of 2-X (X = H, F, Cl, and Br) were synthesized and photolyzed in matrixes (Ar, triacetin) at low temperatures. IR (Ar, 13 K) and ESR (triacetin, 77 K) data are compatible with the generation of triplet halocarbenonitrenes 2-X, (X = F, Cl, and Br). All four compounds upon further irradiation undergo isomerization to substituted cyclopropenes 5-X (X = H, F, Cl, and Br), as suggested by their IR spectra. 相似文献
32.
A system involving two polymer-supported reagents for the selective and organocatalytic oxidation of alcohols to aldehydes or ketones has been developed in which both polymeric reagents can be recovered and reused. 相似文献
33.
Kenjiro Hattori Tomoko Takeuchi Mika Ogata Ayumi Takanohashi Katsuhiko Mikuni Katsuyoshi Nakanishi Hideo Imata 《Journal of inclusion phenomena and macrocyclic chemistry》2007,57(1-4):339-342
We obtained the association constants Ka of estrogen (E2) and environmental chemicals by the surface plasmon resonance (SPR) assay using the immobilized mono-6-O-α-maltosyl-β-CD (G2βCD) compared with the immobilized β-CD and the immobilized estrogen receptor (ER). The association behavior of G2βCD was shown as a ER model compound. The calibration curve was determined by the initial rate of association depending on
the various concentrations, and the minimum detectable concentrations in the order of parts per billion were calculated. The
SPR assay has advantages that the pre-treatment of the sample is not necessary and the immobilized ligand is stable and useful
for the repeated measurement. 相似文献
34.
Methane partial oxidation to formaldehyde with oxygen over SiO2-supported molybdenum oxide catalysts
Hideo Orita Takashi Hayakawa Masao Shimizu Katsuomi Takehira 《Reaction Kinetics and Catalysis Letters》1993,51(1):87-93
The formation rate of formaldehyde increases with increasing surface area of SiO2 support, but the selectivity does not. From the characterization of catalysts using XRD, SEM and Raman spectroscopy, highly dispersed molybdenum oxide was considered to be much more active for the formation of formaldehyde than crystallite forms of MoO3. 相似文献
35.
We have studied on the solubilization of single-walled carbon nanotubes (SW-CNTs) into aqueous and organic media by the use of a variety of nanometer size-controlled fluorinated self-assemblies, which were formed by the aggregations of end-capped fluoroalkyl segments in fluoroalkyl end-capped acrylic acid oligomers [RF-(ACA)n-RF], N,N-dimethylacrylamide oligomers [RF-(DMAA)n-RF], acryloylmorpholine oligomers [RF-(ACMO)n-RF], and N-(1,1-dimethyl-3-oxobutyl)acrylamide oligomers [RF-(DOBAA)n-RF]. Fluorinated self assemblies formed in organic media (colorless solutions) could solubilize SW-CNTs into organic media to afford the transparent pale yellow solutions. The dynamic light scattering measurements showed that the size of fluorinated self-assemblies increased after the solubilization of SW-CNTs into organic media. It was suggested that the solubilization of SW-CNTs into organic media is due to the encapsulation of SW-CNTs into fluorinated assemblies. Fluorinated assemblies were also able to solubilize SW-CNTs into water to give the transparent gray solutions. Among a variety of fluorinated assemblies, fluorinated assemblies formed by RF-(ACMO)n-RF [RF = CF(CF3)OC6F13] oligomer was more effective for the solubilization of SW-CNTs into both aqueous and organic media. Contact angle measurements of dodecane and the fluorescence spectra for poly(methyl methacrylate) cast film modified by fluorinated self-assemblies—SW-CNTs complexes showed that SW-CNTs are dispersed above the PMMA surface. 相似文献
36.
Hideo Hirai Kozo Sawada Matsuhiko Aratani Masashi Hashimoto 《Tetrahedron letters》1985,26(14):1739-1742
A stereoselective kinetic protonation of the azetidinone enolate was studied and an efficient synthesis of(cis) was achieved via aldol reaction of with acetone followed by the kinetic protonation with Ph3SnH as proton source. 相似文献
37.
Kakiuchi K Okada H Kanehisa N Kai Y Kurosawa H 《The Journal of organic chemistry》1996,61(9):2972-2979
Acid-catalyzed rearrangement of 5-cyclopentylidenecyclooctanone derivatives 9a-c was examined to obtain polyspiropolyquinanes 11a-c, considered to have a unique helical structure, through cascade rearrangement pathways consisting of continuous transannular cyclization followed by successive 1,2-alkyl shifts. The substrates were prepared easily by use of the Wittig or McMurry reaction. Reaction of the 5-cyclopentylidenecyclooctanone (9a) with acid gave the expected dispirotriquinane ketone 11a in high yield. The precise mechanism was elucidated by a deuterium-labeling experiment. In the case of the ketone 9b, having another spiroannulated cyclopentane ring attached on 9a, the trispirotetraquiane 11b was not obtained but the bis-propellane-type tetrahydrofuran 25 was produced exclusively. The 5-(5'-cyclopentylidenecyclooctylidene)cyclooctanone (9c) afforded the polycyclic compounds 27-31, depending on the acid used, instead of the desired tetraspiropentaquinane 11c. The structures of the products were determined by NMR spectral data including 2D (13)C INADEQUATE spectra and X-ray crystallographic analyses. The unexpected rearrangement pathways are also discussed. 相似文献
38.
Enyo T Arai N Nakane N Nicolaides A Tomioka H 《The Journal of organic chemistry》2005,70(19):7744-7754
[reaction: see text] Computations find that o-phenylene(halo)carbenonitrenes 2-XN, X = F, Cl, Br, have quinoidal singlet biradical ground states such as the parent o-phenylenecarbenonitrene (2-HN). Compared to the parent 2-HN, halogen substitution stabilizes the A' states relative to the A' ones. Halogen substitution also affects the barrier and exothermicity of the ring-opening reaction (to form unsaturated nitriles 4-XN, X = F, Cl, Br), but it has a smaller effect on the ring-closing reaction (to form benzo(aza)cyclobutadiene 3-XN, X = F, Cl, Br). Attempts to generate and observe the o-phenylene(halo)carbenonitrenes 2-XN, X = F, Cl, Br, using matrix isolation spectroscopy under conditions similar to those of the successful observation of 2-HN failed. Instead, the observed photoproducts were a mixture of 3-XN and 4-XN. In each case, the major product of the mixture appears to be the thermodynamically more stable one. In the case of X = Br, the observed mixture contains an additional component that is postulated to be Z-6-BrN. o-Phenylenechlorocarbenocarbene is also computed to have a quinoidal singlet biradical ground state and relatively stabilized A' excited states. Attempts to generate the biscarbene under matrix isolation conditions led to the detection of benzochlorocyclobutadiene (3-ClC), small amounts of the ring-open product (dienediyne 4-ClC), and cycloalkyne 5-ClC. Computations suggest that the formation of 5-ClC implies the generation of Z-6-ClC, which is analogous to the formation of Z-6-BrN from 2-BrN. 相似文献
39.
Tetsuji Kametani Shiroshi Shibuya Hideo Sugi Keiichiro Fukumoto 《Journal of heterocyclic chemistry》1973,10(4):451-453
The absolute configuraiton at the C1-position of 1,2,3,4-tetrahydro-1-phenylisoquinolines can be deduced from the CD curves of either the free base or its methiodide. Furthermore, the absolute con figuration of (+)-2-amino-1-(3-hydroxyphenyl)ethanol (V) was revised and found to have R-configuration at the C1 -position. 相似文献
40.
Water-swellable polyelectrolyte microgels polymerized in an inverse microemulsion using a nonionic surfactant 总被引:5,自引:0,他引:5
A series of poly(dimethylacrylamide-co-2-acrylamido-2-methyl-1-propanesulfonic acid) microgels slightly crosslinked by methylene-bis-acrylamide (MBA) were polymerized in a novel inverse microemulsion polymerization (IMEP) system. To determine a suitable composition of the IMEP system, the phase diagram of a pseudoternary system was made. The pseudoternary polymerization system consisted of n-hexane, a nonionic surfactant (polyoxyethylene oleyl ether, C18En), and an aqueous monomer solution. Polymerization was performed in a single-phase reversed micelle solution. The reversed micelles were about 50 nm in diameter, as determined by FF-TEM. The viscometric characteristics of the polymers extracted from the IMEP system were studied in 3 mM sodium chloride aqueous solution. The intrinsic viscosity values for the noncrosslinked and crosslinked (0.1 mol% MBA was incorporated) samples were 25 and 7.4 dl/g, respectively. The overlap concentration (c*) of crosslinked polymer microgel occurred at c[eta] = 1 in the solvent. When the volume fraction (phi) of the microgel was 0.7, the value of the apparent yield stress of the microgel solution was observed. These results show that the microgel has a significant thickening effect above c* due to friction between the microgel particles. It is assumed that the microgels polymerized in a confined space retain the shape or size of the nanosized reactor with a diameter on the order of 50 nm. 相似文献