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71.
6-(Perfluoroalkyl)salicylates were prepared by [3+3] cyclization of 1,3-bis(silyl enol ethers) with 3-ethoxy-1-(perfluoroalkyl)prop-2-en-1-ones. 相似文献
72.
Olaf Heitzsch Karsten Gloe Alfréd Sabela Jiří Koryta Edwin Weber 《Journal of inclusion phenomena and macrocyclic chemistry》1992,13(4):311-319
The complex forming properties with alkali metal and ammonium ions of a series of oligo benzo-condensed 18-crown-6 ethers1–8 having a different gradation of lipophilicity and of molecular rigidity are investigated by voltammetry at the interface of two immiscible electrolyte solutions (ITIES) and by a liquid-liquid extraction technique. The experimental results obtained in the two phase system H2O/nitrobenzene are discussed in relation to the structure of the crown and the cation type. The stability constants for the 1 : 1 complexes of Na+, K+, Rb+, Cs+ and NH
4
+
in nitrobenzene have been determined and compared with the extraction constants for the 1: 1 complexes of Na+ and K+ and for the 1 : 1 and 1 : 2 complexes of Cs+, showing the effect of oligo benzo condensation for the 18-crown-6 system. 相似文献
73.
A homologous series of 2,4-dichlorobenzyl alkyl ethers (DCBEs) have been synthesized and purified for use as retention index calibrants and internal standards. They are stable, sensitive to ECD and FID and ideal for GC-MS, with base peaks at m/z 159/161. The retention index calibration against the n-alkanes for a linear temperature program (LTP) series is given and recommendations made for the most suitable members of the DCBE series for use as internal standards in organochlorine (OC) residue analysis. 相似文献
74.
Xinhao Yang Naresh Kumar Hua Chi D. Brynn Hibbert Peter W. Alexander 《Electroanalysis》1997,9(7):549-553
Three double-armed diazacrown ethers with two thiophene side groups, 7,16-dithenyl-1,4,10,13-tetraoxa-7,16-diazacyclooctadecane (DTDC), 7,16-dithenoyl-1,4,10,13-tetraoxa-7,16-diazacyclooctadecane (DTODC), and 7,16-di-(2-thiopheneacetyl)-1,4,10,13-tetraoxa-7,16-diazacyclooctadecane (DTAODC), have been synthesized and used as novel neutral lead(II) ionophores in ion selective electrode applications. The relationship between the molecular structure of these ionophores and electrochemical properties (linear range, response time, selectivity) of the membrane electrode is discussed. The optimum conditions for the preparation of the electrodes are described. The optimized dithenoyldiazacrown had a detection limit of pPb = 5.7, and Nernstian range with slope 29.2 mV decade−1 from pPb = 5.0 to 2.7. Mercury and silver ions are the major interferences. These electrodes are applied to potentiometric titrations of lead(II) ions and show promise for the determination of lead ions in water samples. 相似文献
75.
[Ni(H2O)6][Cu3Cl8(H2O)2] · (15-crown-5)2 · 2H2O can be conveniently prepared by the interaction of NiCl2 · 6H2O, CuCl2 · 2H2O and 15-crown-5 in water. The X-ray crystal structure reveals an ionic complex involved in a hydrogen-bonded two dimensional network with the [Ni(H2O)6]2+ and [Cu3Cl8(H2O)2]2− ions sandwiched between the 15-crown-5 macrocycles. The magnetic susceptibility data (4–300 K) and magnetisation isotherms (2–5.5 K; 0–5 T) are best interpreted in terms of intra-trimer ferromagnetic coupling within the [Cu3Cl8(H2O)2]2− moieties, with J ∼ 6 cm−1, and antiferromagnetic coupling between the trimers, the latter mediated by H-bonding pathways. Comparisons are made to other reported quaternary ammonium salts of [Cu3Cl8]2− and [Cu3Cl12]6−, most of which display structures that involve close stacking of such Cu(II) trimers, rather than being of the present isolated, albeit H-bonded, types. 相似文献
76.
Judit E. Puskas Sam W. P. Chan Kimberley B. McAuley Sohel Shaikh Gabor Kaszas 《Journal of polymer science. Part A, Polymer chemistry》2005,43(22):5394-5413
This article is a critical analysis of kinetic dataavailable on carbocationic polymerizations. A survey of published propagation rate constant (kp) data revealed several orders of magnitude differences. In this article, an explanation of this apparent discrepancy is offered with a case study involving the carbocationic polymerization of 2,4,6‐trimethylstyrene (TMS). With the polymerization mechanism originally proposed for this system, kp = 1.35 × 104 L mol?1 s?1 was extracted from experimental data with the Predici polyreaction package. The alternative mechanism yielded kp = 1.01 × 107 L mol?1 s?1, close to that predicted by Mayr's Linear Free Energy Relationship (LFER). We propose that true rate constants can only be obtained from direct competition experiments or from kinetic interpretation based on independently proven mechanisms. The second part of this review discusses critical analysis of the temperature and concentration dependence of various living IB systems. Comparison of the temperature dependence in systems initiated with 2‐ chloro‐2,4, 4‐ trimethylpentane (TMPCl)/TiCl4 from various laboratories yielded of ΔH ~?25 and ?34.5 kJ/mol for high and low TMPCl/TiCl4 ratios, respectively. Aromatic (cumyl‐type) initiators show ΔH ~ ?40 kJ/mol, whereas H2O/TiCl4 in the presence of the strong electron‐ pair donor dimethylacetamide gave ΔH = ?12 kJ/mol. The significant differences indicate different underlying mechanisms with complex elementary reactions. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5394–5413, 2005 相似文献
77.
V. P. Tsybyshev V. A. Livshits B. B. Meshkov O. A. Fedorova S. P. Gromov M. V. Alfimov 《Russian Chemical Bulletin》1997,46(7):1239-1244
An amphiphilic crown-containing styryl dye (1) was synthesized, and the effects of irradiation, temperature, and alkali and alkali-earth metal ions on the conductivity
and optical spectra of its solutions in dioctyl phthalate were studied. Compound1 in thetrans-form almost completely exists as ion pairs (IP). Irradiation at a long-wavelength absorption maximum (λmax) results in a reversible increase in the conductivity and, hence, a degree of dissociation of IP (α); these parameters decrease
when complexes with metal ions are formed. The relaxation times for the photoinduced conductivity coincide with a decrease
in the extinction within experimental error in the 20–60°C temperature range. The photoinduced increase in α is caused bytrans—cis-isomerization and an increase in steric hindrances for the interaction of the ClO4
− anion with the N+ atom of benzothiazolium in thecis-form of1. The activation energies for the darkcis—trans-relaxation, absolute α values, and thermodynamic parameters of dissociation of IP in thetrans-form, as well as the α values in a photostationary mixture ofcis—trans-isomers, were estimated. The decrease in α after binding with metal ions is likely caused by the redistribution of the positive
charge to benzothiazolium through the conjugated system of1. Correlations between the decrease in conductivity (decrease in α) and the hypsochromic shift Δλmax after the formation of complexes between1 and metal ions were observed.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1296–1301, July, 1997. 相似文献
78.
The liquid-liquid extraction of copper(I) with 12-, 13-, 15- and 16-membered cyclic tetrathio ethers ([n]aneS4, where n represents the total number of carbon and sulphur atoms in the cyclic ligand ring) was examined stoichiometrically using picrate ion (Pic?) for the formation of the ion pair. Copper(I) was extracted with four ligands (L) into 1,2-dichloroethane as the ion-pair compound, [Cu(I)L]+Pic?. The extraction constant, Kex, with each ligand was determined. As the ring size of cyclic tetrathio ethers increases, the log Kex values, including that previously reported for [14]aneS4, increase from 7.7 to 9.4. The value of Δ log Kex, which represents the increase in log Kex due to the addition of one carbon atom to the macrocyclic ring, was large between [13]aneS4 and [14]aneS4 (Δ log Kex=1.0) and small between [14]aneS4 and [15]aneS4 (Δ log Kex=0.1). 相似文献
79.
Chang-Eun Yeom Young Jong Kim So Young Lee Yong Je Shin B. Moon Kim 《Tetrahedron》2005,61(52):12227-12237
Fast and chemoselective desilylation of silyl-protected alcohols was achieved using a catalytic amount of 1-chloroethyl chloroformate in methanol. With a minimal amount of 1-chloroethyl chloroformate as the source for anhydrous HCl, extremely efficient cleavage of silyl ethers of primary and secondary alcohols was accomplished, and chemoselective deprotection of one silyl ether in the presence of another silyl or other acid-labile group was possible through controlling the amount of the chloroformate and reaction time. 相似文献
80.
Oxolane was fluoroalkylated by its photoadditions under atmospheric pressure. Monofluoro-alkylations were carried out with hexafluoropropene (1) and perfluorovinyl ethers C3F7O-[CF(CF3)CF2O]n-CF = CF2 (24, n = 0–2) by direct photoexcitation of the olefins to give high yields of addition products 9–12 (81–94%). The reactions were completely regioselecti ve at the oxolane molecule and almost completely regioselective (93–99%) at the double bond of fluoro-olefins; no bis-fluoroalkylated oxolanes were detected. The completely selective introduction of a second fluoroalkyl into position 5 of the oxolane molecule was accomplished by acetone-sensitised photoaddition of 2fluoroalkylated oxolanes 9,10 to fluoro-olefins 1 and 2. Byproducts from reactions of the dimethylketyl radical which is formed in the initiation step were isolated and have given some evidence about the reaction mechanism that is discussed. 相似文献