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21.
Mohamed Brakta Denis Sinou Michel Becchi Joseph Banoub 《Journal of mass spectrometry : JMS》1992,27(5):621-624
A series of anomeric unsaturated C-glycosides were studied by negative ion mass spectrometry following keV ion bombardment The compounds bearing an acidic hydrogen show a prominent [M ? H]? peak; in the other cases, the [M ? H]? peak is of very low intensity. A retro-Diels–Alder fragmentation and the abstraction of a hydrogen atom from the aglycon residue are observed in all cases. 相似文献
22.
Molar excess mixing enthalpies h
E
, Gibbs free energies g
E
and hence entropies s
E
have been obtained using calorimetry and the vapor sorption method at 25°C for hexane isomers+2,2,4,4,6,8,8-heptamethylnonane, a highly branched C
16
. The h
E
and g
E
are negative while Ts
E
are positive, but small. The values are explained by the Prigogine-Flory theory through negative free volume contributions to h
E
and Ts
E
, counterbalanced in the case of Ts
E
by the positive combinatiorial Ts
E
for mixing molecules of different size. No contribution is seen from the interaction between methyl and methylene groups. The excess quantities are also obtained for hexane and heptane isomers mixed with n-hexadecane. Values of h
E
and Ts
E
are now strongly positive, while those of g
E
are only slightly less negative. The interpretation requires two recently advanced contributions in addition to those of the Prigogine-Flory theory: 1) a decrease of order when correlations of orientations between n-C
16
molecules in the pure liquid are replaced in the solution by weaker correlations whose strengths depend on the shapes of the lower alkane isomers. For lower alkane isomers of the same shape, but highly sterically hindered, h
E
and Ts
E
are small, manifesting, 2) a negative contribution, ascribed to a rotational ordering of n-C
16
segments on the sterically-hindered molecule. Enthalpy-entropy compensation is observed for these new contributions, arising from their rapid fall-off with increase of temperature. 相似文献
23.
Yolande MespliÉ Michel Bergon Jean-Pierre Calmon 《Journal of heterocyclic chemistry》1984,21(4):985-993
The alkaline hydrolysis of propargyl 3-chlorocarbanilates was investigated kinetically using uv spectropotometry. The cyclization to 4-methoylene-2-oxazolisinones proceeds via the numcleophilic attack of the substrate anion concomitantly with that of the hydroxide ion on the triple bond. The nucleophilic attack leads directly to the heterocycle whereas the hydroxide ion attack gives rise to a ketocarbamate which is then cyclized to the oxazolidione. 相似文献
24.
We present in this paper two new effects observed in the state of molecular iodine: a very high diamagnetic correction in the vibrational level υ′ = 62 and an important orientation of the optically excited molecules due to predissociation. Both effects can be interpreted by taking into consideration the perturbation of the B state by other electronic states. 相似文献
25.
Charles W. Jefford Manuel Jimenez Estrada Giacomo Barchietto Tho Berclaz Michel Geoffroy 《Helvetica chimica acta》1990,73(6):1653-1658
The photo-oxygenation of adamantylideneadamantane ( 1 ) on siliceous supports using admixed granules of ion-exchange resin fixed to methylene blue (MB) and rose bengal (RB) gave exclusively the corresponding dioxetane derivative 2 for the former sensitizer, while the latter gave 2 and traces of the epoxide 3. RB and the charge-transfer complex produced from N-ethylcarbazole and 2,4,5,6-tetranitrofluoren-9-one both reacted with chemically generated singlet oxygen to give superoxide radical anion. Trapping of the latter with 5,5-dimethyl-1-pyrroline 1-oxide gave an adduct exhibiting a characteristic ESR spectrum. The treatment of 1 in MeOH with 30% aqueous H2O2 for 22 h at 60° gave 3 in 100% yield. Repetition of this experiment in the presence of 2,6-di(tert-butyl)-p-cresol caused no significant change. These results indicate that singlet oxygen reacts with 1 , in the presence of RB, by two different processes. The first leads to dioxetane formation. The second process involves conversion of singlet oxygen by RB to superoxide radical anion which subsequently gives H2O2 so producing epoxide 3 from 1 . 相似文献
26.
Chin W Dognon JP Piuzzi F Tardivel B Dimicoli I Mons M 《Journal of the American Chemical Society》2005,127(2):707-712
Laser desorption of model peptides coupled to laser spectroscopic techniques enables the gas-phase observation of genuine secondary structures of biology. Spectroscopic evidence for the formation of beta-turns in gas-phase peptide chains containing glycine and phenylalanine residues establishes the intrinsic stability of these forms and their ability to compete with other stable structures. The precise characterization of local minima on the potential energy surface from IR spectroscopy constitutes an acute assessment for the state-of-the-art quantum mechanical calculations also presented. The observation of different types of beta-turns depending upon the residue order within the sequence is found to be consistent with the residue propensities in beta-turns of proteins, which suggests that the prevalence of glycine in type II and II' turns stems essentially from an energetic origin, already at play under isolated conditions. 相似文献
27.
A general approach for the allylation of aldehydes using stable, air-tolerant camphor-based chiral allylboronates under Sc(OTf)3 catalysis is described. This practical methodology provides both syn and anti propionate units and other homoallylic alcohols with very high levels of diastereo- and enantioselectivity for several substrates, including functionalized aliphatic aldehydes useful toward the elaboration of complex natural products. 相似文献
28.
Heterocyclic nitronate anions prepared from 3-ethyl-5-hydroxymethyl-5-nitrotetra-hydro-1,3-oxazine are found to be suitable nucleophiles for SRN1 reactions. Base-promoted nitrous acid elimination from C-alkylation product gives rise to new tetrahydro-1,3 oxazines with a trisubstituted ethylenic double bond in the 5 position. 相似文献
29.
Patrick Dallemagne Michel Boulouard Sylvain Rault Max Robba 《Journal of heterocyclic chemistry》1993,30(3):799-802
Synthesis of thieno[2′,3′:5,4]cyclopenta[3,2-d]oxazole and thiazole derivatives are achieved by insertion of carbon dioxide and disulfide into 4-amino-5-chloro-5,6-dihydro-4H-cyclopenta[b]thiophen-6-one. 相似文献
30.
A recently suggested scheme for relating ionisation potentials (IP) to excitation energies (E) has been applied to pyrazine and 2,6-dimethylpyrazine. The results indicate that in these systems the energy gap (ΔE) between the two lowest lying 1n,π*-states is significantly smaller than that (ΔIP) between the corresponding 2n-states of the parent radical cations. The values estimated for ΔE on the basis of ΔIP, measurable by photoelectron spectroscopy, disagree with those calculated theoretically but seem to be supported by the experimental evidence available. Since ΔE = ΔIP would normally be expected, the relationship ΔE < ΔIP actually present in these systems is discussed and related to the different shape of the n-MO's involved in the ionization and excitation processes. 相似文献