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41.
David T. Connor Patricia A. Young Maximillian Von Strandtmann 《Journal of heterocyclic chemistry》1977,14(1):139-141
The reaction of 2-picoline N-Oxide anion with o-substituted henzoates and isatoic anhydrides to give synthetically useful l-(2-methoxyphenyl)-2-(2-pyridinyl)ethanone N-oxides, I-(2-hydroxy-phenyJ)-2-(2-pyridinyl)ethanone N-oxides and I -(2-arninopheny])-2-(2-pyridinyl)ethanone N-oxides is described. 相似文献
42.
An intermolecular alkyl transfer reaction (ATR) leading to ion-pair formation has been observed for internal salts by using laser mass spectrometry (l.m.s.). Positive- and negative-ion spectra both show evidence for alkyl transfer. Both the LAMMA-500 (transmission) and LAMMA-1000 (reflection) laser mass spectrometers were used. The positive-ion laser mass spectra obtained by these two instruments show some significant differences; no significant differences were observed in the negative-ion spectra. Results obtained for quaternary ammoniohexanoates as a function of laser power indicate that the extent of ATR is greater at high laser power. Addition of a small amount of p-toluenesulfonic acid to the ammoniohexanoates reduces fragmentation and enhances the intensity of the quasimolecular ion (M + H)+ relative to ATR. Results from deuterated sultaines were used to confirm intermolecular alkyl transfer and to elucidate some fragmentation processes. Field-desorption (f.d.) mass spectra of internal salts show similarities and differences from l.m.s.; not all internal salts showed the alkyl transfer reaction in f.d. Cluster ion formation was observed in f.d.m.s. but not in l.m.s. 相似文献
43.
Gary W. Schnuelle S. Swaminathan David L. Beveridge 《Theoretical chemistry accounts》1978,48(1):17-27
A theoretical study of ion hydration using the statistical thermodynamic supermolecule-continuum method is described. The cell and shell methods are used for configurational averaging. Enthalpies, free energies and entropies are calculated for Li+, Na+, K+, F– and Cl– each four coordinated with water. The results are in reasonable accord with experiment. A comparison of the site method, cell method and shell method results is presented. The supermolecule-continuum approach to solvent effects seems to be capable of accommodating essential features for the calculation of solvation energy and solvent effects on structure and properties. 相似文献
44.
Relative rates of solvolysis of some N-triorganosilylanilines in mixtures of ethanol and aqueous potassium hydroxide have been determined, with results as follows. (i) For XC6H4NHSiEt3 compounds in MeOH (5 vol) + aq. alkali (2 vol) at 50°: (X =) H, 1.0;p-Me, 0.80;p-OMe, 0.83;m-Me, 0.90; o-Me, 0.87; p-SMe, 1.90; p-F, 1.7; p-Cl, 2.8; o-Cl, 14; m-Cl, 4.2; m-NO2, 18; p-CN, ca. 43; p-NO2, ca. 120. (ii) For PhNHSi(C6H4Y)3 compounds in MeOH (10 vol) + aq. alkali (1 vol) at 50°: (Y =) H, 1.0; p-OMe, 0.12; p-Cl, ca. 32; m-Cl, ca. 84. (iii) For PhNHSiR3 compounds in MeOH (5 vol) + aq. alkali (2 vol) : (R3 =) Et3, 1.0; Et2Me, 18 (at 30°); Me2-i-Pr, 8 (at 30°);Me2-t-Bu, 0.012 (at 50°);i-Pr3, 0.006 (at 50°). In series (i) the relative rates correlate with σ, or where appropriate σ?-constants, with a ? value of 1.6. It is suggested that in the transition state of the rate-determining step the OSi bond is fully formed, or almost so, the SiN bond approximately 20—50% broken, and the bond between the nitrogen atom and a proton from the solvent ca. 10—30% formed. 相似文献
45.
David R. AppletonBrent R. Copp 《Tetrahedron letters》2003,44(50):8963-8965
Kottamide E, a novel alkaloid containing dibrominated indole enamide, oxalic acid diamide and 4-amino-1,2-dithiolane-4-carboxamide moieties, has been isolated from the New Zealand ascidian Pycnoclavella kottae. Characterisation was achieved by interpretation of spectroscopic data. 相似文献
46.
David W. Vahey 《Chemical physics》1975,10(2-3):261-270
Equations are presented for the spectral and orientational distribution of unexcited dye molecules in the field of an intense giant laser pulse. The solute dye molecules are linear oscillators that may be broadened either homogeneously or inhomogeneously, and may reorient by sudden jumps over large angles or by small angular steps (brownian rotational motion). The equations are employed to analyze the intensity dependence of fluorescence polarization observed by Mourou and Denariez-Roberge for the system cryptocyanine-glycerin. Their data are consistent with an excited-state deactivation time T1 = 0.4 ± 1.0 ns and a rotational diffusion constant D = 20/T1 = 5.0 × 109 s−1 相似文献
47.
Shelton DP 《The Journal of chemical physics》2005,123(8):084502
VH and HV depolarized hyper-Rayleigh scattering spectra were measured for liquid solutions of dipolar CH3CN in nondipolar C2Cl4 at T=300 K. The VH spectrum contains a strong narrow peak due to a slowly relaxing longitudinal orientation mode. This peak is absent in the HV spectrum, and it disappears from the VH spectrum when the CH3CN concentration is reduced to 8%. This observation is consistent with a ferroelectric phase transition predicted to occur when rho mu0(2)=9epsilon0kT=49 D2 M. 相似文献
48.
The structures and energetics of Li(6) (+), Li(6) (-) and three isomers of Li(6) are investigated using the coupled-cluster singles, doubles and perturbative triples [CCSD(T)] method with valence and core-valence correlation consistent basis sets of double- to quadruple-zeta quality (cc-pVXZ and cc-pCVXZ, where X=D-Q). These results are compared with qualitatively different predictions by less reliable methods. Our results conclusively show that the D(4h) isomer is the global minimum structure for Li(6). It is energetically favored over the C(5v) and D(3h) structures by about 5.1 and 7.1 kcal mol(-1), respectively, after the inclusion of the zero-point vibrational energy (ZPVE) correction. Our most accurate total atomization energies are 123.2, 117.6, and 115.7 kcal mol(-1) for the D(4h), C(5v), and D(3h) isomers, respectively. Comparison of experimental optical absorption spectra with our computed electronic spectra also indicate that the D(4h) isomer is indeed the most stable structure. The cation, anion, and some higher spin states are investigated using the less expensive cc-pCVDZ basis set. Adiabatic ionization energies and electron affinities are reported and compared with experimental values. Predictions of molecular properties are found to be sensitive to the basis set used and to the treatment of electron correlation. 相似文献
49.
The alkylhalide-halide association ions, [RX2]? that are observed in the negative chemical ionization mass spectra of alkyl halides appear to be directly related to the corresponding SN2 transition states in solution. ‘Frontside’ association of halide ions with bridgehead alkyl halides does not occur in our system. The Change in heats and entropies of association for the chloromethane series is consistent with delocalization in the [RX]2? ions. 相似文献
50.
Balakumar A Lysenko AB Carcel C Malinovskii VL Gryko DT Schweikart KH Loewe RS Yasseri AA Liu Z Bocian DF Lindsey JS 《The Journal of organic chemistry》2004,69(5):1435-1443
A molecular approach to information storage employs redox-active molecules tethered to an electroactive surface. Attachment of the molecules to electroactive surfaces requires control over the nature of the tether (linker and surface attachment group). We have synthesized a collection of redox-active molecules bearing different linkers and surface anchor groups in free or protected form (hydroxy, mercapto, S-acetylthio, and Se-acetylseleno) for attachment to surfaces such as silicon, germanium, and gold. The molecules exhibit a number of cationic oxidation states, including one (ferrocene), two [zinc(II)porphyrin], three [cobalt(II)porphyrin], or four (lanthanide triple-decker sandwich compound). Electrochemical studies of monolayers of a variety of the redox-active molecules attached to Si(100) electrodes indicate that molecules exhibit a regular mode of attachment (via a Si-X bond, X = O, S, or Se), relatively homogeneous surface organization, and robust reversible electrochemical behavior. The acetyl protecting group undergoes cleavage during the surface deposition process, enabling attachment to silicon via thio or seleno groups without handling free thiols or selenols. 相似文献