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71.
The gas‐phase acidities (GA) of various aryl‐substituted fluoroalkanes, XC6H4CH(R1)R2, were calculated at the B3LYP/6‐311 + G(d,p)//B3LYP/6‐311 + G(d,p). The acidity values of alkanes having a common substituent X varied significantly with the change of R1 and R2. Their changes in acidity of 1 and 2 having two strong electron‐withdrawing groups (CF3 or C2F5) at the deprotonation site and 8 , 9 , 10 , 11 having no fluorine atom at β‐position were linearly correlated with the corrected number of fluorine atoms contained in the fluorinated alkyl group (R2 > 0.999). On the other hand, the GA values of β‐fluorine substituted alkanes ( 3 , 4 , 5 , 6 , 7 ) deviated in a stronger acid direction from the line. The enhanced acidity was attributed to the additional stabilization of the conjugate anion caused by the β‐fluorine negative hyperconjugation. The magnitude of β‐fluorine negative hyperconjugation of the fluorinated alkyl group (ΔGoβ‐F) given by the deviations from the line decreased with increasing electron‐withdrawing ability of substituent X on the benzene ring, indicating that β‐fluorine negative hyperconjugation competes with the electronic effect of the substituent X. The GAel values obtained by subtraction ΔGoβ‐F from the apparent GA value were successfully correlated in terms of the Yukawa–Tsuno equation. The obtained ρel and r?el values were linearly related to the GAel value of the respective phenyl‐substituted fluoroalkanes, supporting our previous conclusion that the ρ and r? values for the substituent effect caused by the electronic effects of the substituent on the acidity are determined by the thermodynamic stability of the parent ion (ring substituent = H). Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
72.
The vectorial Debye integral shows that tightly focused Laguerre-Gaussian (LG) beams have a residual intensity at the focal point for linear polarization, for a topological charge of m=1 and 2. We measured the shapes of linearly and circularly polarized LG beams and found that a central intensity appeared at m=1 and 2 for linear and right-handed circular polarization, however, it is completely canceled for left-handed circular polarization. In general, when the orbital angular momentum of the LG beam is parallel to the spin angular momentum of the photons, zero intensity is always achieved at the focus. 相似文献
73.
Masaaki Yamabe 《Macromolecular Symposia》1992,64(1):11-18
Perfluoro(vinyl ether) derivatives are extremely versatile monomers in preparing a variety of functional fluoropolymers. In this paper, two challenging topics in the development of novel fluoropolymers will be introduced. Carboxylated perfluoro(vinyl ether) can be copolymerized with tetrafluoroethylene to afford perfluorinated ion-exchange membranes, which realize the innovative process for pollution-free and energy-saving chlor-alkali production. Another topic includes the discovery of selective cyclo-polymerization of specially designed difunctional perfluoromonomers such as perfluoro(allyl vinyl ether) which is readily derived from the carboxylated perfluoro(vinyl ether). The novel perfluoropolymer with a cyclic structure in the main chain is characterized by an exceptional transparency, and has been commercialized with expectation of major applications in electronics industries. 相似文献
74.
75.
Chlorine isotope fractionation factor was determined by strongly basic anion-exchange chromatography with 0.1 mol/l HCl at 25 °C. The magnitude of the factor was calculated as a single-stage separation factor of 1.00030 with analytical precision of 0.00006 (1σ). The results showed that the lighter isotope () was preferentially fractionated into the resin phase, while the heavier one () enriched into the aqueous phase. This trend suggested that the hydrated Cl− ions in the aqueous phase were slightly more stable than the hydrated Cl− ions electrostatically interacting with the ion-exchange groups of the resin. 相似文献
76.
77.
78.
Sekiguchi A Ishida Y Fukaya N Ichinohe M Takagi N Nagase S 《Journal of the American Chemical Society》2002,124(7):1158-1159
Dark red crystals of the halogen-substituted cyclotrigermenes [(tBu3Si)3Ge3X; X = Cl, Br, I] were obtained in good yields by the reaction of [(tBu3Si)3Ge3]+.TTFPB- (TTFPB- = tetrakis(2,3,5,6-tetrafluorophenyl)borate) with potassium halides (KCl, KBr, or KI) in diethyl ether. The crystal structures of the halogen-substituted cyclotrigermenes reveal a cis-bent Ge=Ge double bond, caused by the introduction of the electronegative halogen atom on the sp3 germanium atom of cyclotrigermene. In solution, an intramolecular halogen migration over the three-membered ring skeleton was observed. Facial stereoselectivity in the Diels-Alder reaction of new cyclotrigermenes with 2,3-dimethyl-1,3-butadiene is also reported. 相似文献
79.
80.
Munetaka Nakata Masaaki Sugie Harutoshi Takeo Chi Matsumura Tsutomu Fukuyama Kozo Kuchitsu 《Journal of Molecular Spectroscopy》1981,86(1):241-249
The microwave spectra of four isotopic species of dichlorine monoxide (OCl2) have been observed, and the rotational constants have been obtained. The rm structure for each isotopic species has been determined by Watson's method. The equilibrium structure has been estimated by taking proper averages of rm structures to be and ∠eClOCl = 110.886(6)°. The general applicability and the merit of the present method for estimating the equilibrium structure are pointed out. 相似文献