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31.
Kubo Y Tokita S Kojima Y Osano YT Matsuzaki T 《The Journal of organic chemistry》1996,61(11):3758-3765
A new family of indoaniline-derived calix[4]arenes has been synthesized for the purpose of developing a new chromogenic receptor. A condensing reaction of calix[4]arene (1) with 4-(diethylamino)-2-methylaniline hydrochloride (2) in the presence of an oxidizing agent under alkaline conditions affords mono- (3), 1,2-bis- (4), 1,3-bis- (5), and tetrakisindoaniline-derived (6) calix[4]arenes after careful column chromatography. Compound 3 is crystallized from a CHCl(3)-MeOH solution, and the crystal structure was determined by X-ray analysis. The crystal is monoclinic, space group P2(1)/n, Z = 4, a = 19.507(6) ?, b = 18.591(6) ?, c = 8.524(2) ?, beta = 94.69(2) degrees. The final R value for 2406 reflections of F(o) > 3sigma(F(o)) is 0.085. A unique intramolecular hydrogen-bonding network involving the carbonyl oxygen of indoaniline for 3 implied that the quinone carbonyl group as an acceptor of the chromophore can easily be subjected to an electrostatic interaction in the lower rim. Indeed, 1,3-bis(indoaniline)-derived 2,4-bis((ethoxycarbonyl)methoxy)calix[4]arene 7, prepared by the reaction of 5 with ethyl bromoacetate in the presence of NaH, is capable of undergoing an efficient ion-dipole interaction between the binding cation and the two quinone carbonyl groups of the chromophores, so that a selective Ca(2+)-induced pronounced color change (wavelength change > 100 nm) occurs with an association constant on the order of 10(6) in 99% EtOH, making 7 of potential use as an optical sensor for Ca(2+) detection. The IR and NMR studies have indicated that Ca(2+) is encapsulated in the cavity made by the distally located OCH(2)CO(2) groups on the lower rim of the cone-shaped calix[4]arene segment. Interestingly, however, the shape of the cavity in which Ca(2+) has been encapsulated does not have a C(2) axis of symmetry, as inferred from the (1)H-(1)H COSY experiment. On the other hand, 1,2-bis(indoaniline)-derived analogue 8 shows no response with metal ions, which can be interpreted to mean the absence of a cavity for encapsulation on the lower rim. 相似文献
32.
Ichikawa S Tada M Iwasawa Y Ikariya T 《Chemical communications (Cambridge, England)》2005,(7):924-926
Chemoselective hydrogenation of halogenated nitrobenzenes over Pt/C catalysts proceeds effectively in supercritical carbon dioxide (scCO2) to produce halogenated anilines with excellent selectivity; the rate of the hydrogenation of nitro groups is markedly enhanced in scCO2 compared to the neat reaction, and the dehalogenation reaction is significantly suppressed. 相似文献
33.
34.
An approach to analysis of pigment release from microcapsules with size distribution 总被引:2,自引:0,他引:2
Takao Yamamoto Toshiaki Dobashi Miho Kimura Chih Pong Chang 《Colloids and surfaces. B, Biointerfaces》2002,25(4):305-311
We have studied the release curve for microcapsules with size distribution. On the basis of an analogy to the relaxation phenomena with multiple characteristic times, we propose a stretched exponential release curve for the system with size distribution and relate the release curve to the size distribution function of the microcapsule. This method was successfully applied to the transfer of azo-pigments from inner medium of dioctyl phthalate to dispersing medium of methanol through poly(ureaurethane) microcapsule membrane. 相似文献
35.
Mugishima T Tsuda M Kasai Y Ishiyama H Fukushi E Kawabata J Watanabe M Akao K Kobayashi J 《The Journal of organic chemistry》2005,70(23):9430-9435
[Structure: see text]. Citrinadin A (2) is a pentacyclic indolinone alkaloid isolated from the cultured broth of a fungus, Penicillium citrinum, which was separated from a marine red alga. The absolute stereochemistry of the pentacyclic core in 2 and its new congener, citrinadin B (1), was elucidated by analysis of the ROESY spectrum for the chlorohydrin derivative (3) of 1 as well as comparison of the electronic circular dichroism (ECD) spectra for 1 and 2 with those of known spirooxiindole alkaloids. On the other hand, the absolute configuration at C-21 bearing an epoxide ring was assigned as S by comparison of the vibrational circular dichroism (VCD) spectra of 1 with those of model compounds 2S- and 2R-2,3-epoxy-3,3-dimethyl-1-phenylpropan-1-one (4a and 4b, respectively). 相似文献
36.
1,3,5,7-Tetramethylcyclotetrasiloxane (H4) was deposited on silica gel at 80°C by utilizing a chemical vapor deposition (CVD) method, where it was catalytically polymerized to form a surface coating of polymethylsiloxane (PMS). Treated silica gel (PMS-Si) increased in weight up to a plateau level, and there was no further increase with increasing reaction time. The film of PMS was partially cross linked; typical values of crosslinking ratio and film thickness were 2% and 0.6 nm, respectively. An anionic ion exchanger containing diethylamino groups was synthesized from PMS-Si by hydrosilylation of allyl glycidyl ether followed by treatment with diethylamine. Its structure was confirmed by13C and29Si CP/MAS NMR spectroscopy and FT-IR spectrophotometry. Characterization of silica gel (DEA-Si) modified with diethylamino group was evaluated by a packing of the column for liquid chromatography. As a mixture of five nucleotides was completely separated, it was recognized that DEA-Si was operated by ion exchange action. Because the surface of the silica gel was covered with hydrophobic PMS, the peak heights and retention times did not change after washing of the column with alkaline solution. 相似文献
37.
The triphenyl phosphite-palladium complex was found to effect catalytic substitution reactions of allylic alcohols via a direct C-O bond cleavage. The dehydrative etherification proceeded efficiently without any cocatalysts and bases to give allylic ethers in good to excellent yields. 相似文献
38.
Tawada Y Tsuneda T Yanagisawa S Yanai T Hirao K 《The Journal of chemical physics》2004,120(18):8425-8433
We apply the long-range correction (LC) scheme for exchange functionals of density functional theory to time-dependent density functional theory (TDDFT) and examine its efficiency in dealing with the serious problems of TDDFT, i.e., the underestimations of Rydberg excitation energies, oscillator strengths, and charge-transfer excitation energies. By calculating vertical excitation energies of typical molecules, it was found that LC-TDDFT gives accurate excitation energies, within an error of 0.5 eV, and reasonable oscillator strengths, while TDDFT employing a pure functional provides 1.5 eV lower excitation energies and two orders of magnitude lower oscillator strengths for the Rydberg excitations. It was also found that LC-TDDFT clearly reproduces the correct asymptotic behavior of the charge-transfer excitation energy of ethylene-tetrafluoroethylene dimer for the long intramolecular distance, unlike a conventional far-nucleus asymptotic correction scheme. It is, therefore, presumed that poor TDDFT results for pure functionals may be due to their lack of a long-range orbital-orbital interaction. 相似文献
39.
The sequential Sonogashira reaction and the cyclization reaction of various 2-iodoanilines and terminal alkynes in the presence of a palladium catalyst and tetrabutylammonium fluoride (TBAF) gave the corresponding 2-substituted indoles in good yields. 相似文献
40.
Kitano H Fukui N Ohhori K Maehara Y Kokado N Yoshizumi A 《Journal of colloid and interface science》1999,212(1):58-64
Macroinitiators were prepared by coupling disuccinimidyl ester of 4,4'-azobis(cyanovaleric acid) with poly(N-isopropylacrylamide) (PIPA), which had an amino group at its end. Styrene was telomerized with the initiators in THF. When the styrene content in the A-B-A block telomer obtained (PIPA-b-PSt-b-PIPA) was high, the telomer formed an irreversible aggregation resulting in microspheres, whereas the telomer with a much shorter styrene block could be dispersed monomolecularly. The telomers dispersed in water were aggregated by raising the temperature above 32 degrees C due to a coil-globule transition of PIPA moieties. The PIPA-b-PSt-b-PIPA could be strongly adsorbed to polystyrene (PSt) solid surfaces to form a layer, and the PSt blocks might lay on the PSt surface and the PIPA blocks might direct to the solution phase. The contact angle of air bubbles on the surface of telomer-coated PSt in the air-in-water system was dependent on temperature; that is, with the increase in temperature the contact angle of air bubbles largely decreased and leveled off above the coil-globule transition temperature (Tc). Correspondingly, the amount of protein Concanavalin A adsorbed to the telomer layer deposited on the PSt surface increased gradually with an increase in temperature and leveled off above the Tc. These phenomena were attributed to the changes in hydrophobicity of the telomer layer below and above the Tc. The usefulness of macroinitiators in preparing various kinds of block telomers which have responsiveness to external stimuli was strongly suggested. Copyright 1999 Academic Press. 相似文献