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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.
Cycloheptatrienes were obtained by the reaction of 2-substituted allylic alcohols with alkynes in the presence of catalytic amounts of palladium complexes and p-toluenesulfonic acid. 相似文献
33.
Yasuyuki Takeda Chihiro Takagi 《Journal of inclusion phenomena and macrocyclic chemistry》1994,17(1):93-97
The theory is derived to determine the dimer-formation constant,K
2, of a crown ethermetal salt 111 complex in organic solvents of low dielectric constant by solvent extraction. The theoretical predictions are verified experimentally by extraction of sodium picrate (NaA) with 15-crown-5 (15C5) into carbon tetrachloride. All the experiments were conducted at 25°C. The logK
2 value of the Na(15C5)A complex in carbon tetrachloride has been determined to be 4.05±0.11. Moreover, the partition constant of the complex is calculated. 相似文献
34.
Highly Selective Separation of Rhodopsin from Bovine Rod Outer Segment Membranes Using Combination of Divalent Cation and Alkyl(thio)glucoside 总被引:1,自引:0,他引:1
The micellization process of bovine rod outer segment (ROS) membranes is investigated utilizing a series of neutral detergents. It is found that when alkyl(thio)glucosides with an appropriate hydrophilic–lipophilic balance (e.g. octylthioglucoside) are used in combination with a divalent cation, rhodopsin is selectively extracted from ROS membranes at a specific detergent-to-membrane ratio. This allows remarkable purification of rhodopsin by a single-step solubilization, because the residual membranes are heavily aggregated in the presence of divalent cation and are therefore easily sedimented by low-speed centrifugation. The absorption spectrum of the supernatant reproducibly exhibits an A280 /A500 value of 1.6, an excellent value that could rarely be obtained by chromatographic purification. The degree of purification also depends on the type of divalent cation included in the solubilization solution; specific binding of IIB-series cations (Zn2+ and Cd2+ ) to ROS membranes is suggested to play an important role in the solubilization process. The present result represents a unique example of selective solubilization of a specific membrane protein from highly aggregated membranes. 相似文献
35.
H. Budzikiewicz K. Takeda K. Schreiber 《Monatshefte für Chemie / Chemical Monthly》1970,101(4):1003-1012
Zusammenfassung Der Einfluß von Substituenten in Ring D und F auf das Fragmentierungsverhalten von Spirostan-Derivaten wird diskutiert.
Mit 10 Abbildungen 相似文献
Mass spectrometric investigation of substituted steroid sapogenins
The influence of substitutents in ring D and F on the fragmentation behavior of spirostane derivatives is discussed.
Mit 10 Abbildungen 相似文献
36.
37.
Ihara M Katsumata A Setsu F Tokunaga Y Fukumoto K 《The Journal of organic chemistry》1996,61(2):677-684
[Ni(cyclam)](ClO(4))(2)-catalyzed indirect electroreduction of olefinic bromides produced six-membered compounds in low to high yields. The synthetic intermediate 49 of Ipecac and Corynanthe alkaloids was obtained in 88% yield in a highly stereoselective manner. Lactam 66, the synthetic precursor of tacamonine, was prepared in 49% yield as a mixture of two diastereoisomers. The electrolysis of the bromoacetates gave the debrominated compounds in good yields. 相似文献
38.
T. Minamisono S. Fukuda T. Ohtsubo M. Tanigaki A. Kitagawa M. Fukuda K. Matsuta Y. Nojiri S. Takeda 《Hyperfine Interactions》1993,78(1-4):191-194
Quadrupole effects in -NMR spectra of41Sc(I
=7/2–,T
1/2=0.596 s) implanted in a TiO2 single crystal were detected by use of a modified -NMR technique. Using the field gradient in the crystal determined by the pulsed-Fourier-transformed NMR of45Sc in TiO2, the quadrupole moment of41Sc has been determined as |Q(41Sc; 7/2–)|=166±8 mb. 相似文献
39.
Isolation of lignan glucosides and neolignan sulfate from the leaves of Glochidion zeylanicum (Gaertn) A. Juss 总被引:2,自引:0,他引:2
Six lignan and neolignan derivatives (1-6) were isolated from the n-BuOH-soluble fraction of a MeOH extract of the leaves of Glochidion zeylanicum. On the basis of spectral data, their structures were elucidated to be (+)-isolarisiresinol 3a-O-beta-glucopyranoside (1), dihydrodehydrodiconiferyl alcohol 4-, 9- and 9'-O-beta-D-glucopyranosides (2-4, respectively), (+)-isolarisiresinol 2a-O-beta-D-glucopyranoside (5), and dihydrodehydrodiconiferyl alcohol 9-O-sulfate (6), and 5 and 6 were new compounds. 相似文献
40.