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41.
Hideki Moriishi Osamu Kikuchi Keizo Suzuki Gilles Klopman 《Theoretical chemistry accounts》1984,64(5):319-338
Reaction potential maps (RPM) have been introduced as a new tool for the study of molecular reactivity. The equipotential energy maps, which are created on given planes around a molecule, define reaction contours towards specific counter-reagent models and are evaluated by perturbation theory. Since the calculated interaction energy involves electrostatic, polarization, exchange, and charge transfer energies, the RPM's can be used to predict site selectivity in a variety of chemical reactions. We found that the calculated RPM's of the SCN– anion explained well the experimental observations that it reacts at the S atom with soft electrophiles and at the N atom with hard electrophiles. The difference in reactivity between SCN– and OCN– was clearly shown by the RPM's of these anions. The ambident nucleophilic nature of the NO
2
–
and the CH2CHO– anions was also well represented by their RPM's. 相似文献
42.
The structure of P,P-bis(diisopropylamino)-4-phenyl-1,3,2lambda(5)-diazaphosphete, 1a, has been determined by a single-crystal X-ray diffraction study (C(19)H(33)N(4)P, monoclinic system, space group P2(1), a = 9.482(1) ?, b = 11.374(3) ?, c = 9.668(2) ?, beta = 97.16(1) degrees, Z = 2). According to quantum chemical calculations at an RHF level of optimization utilizing the 6-31g(d,p) basis set, 1a has a zwitterionic structure with the negative charge delocalized on the NCN allylic fragment and the positive charge localized at the phosphorus. Heterocycle 1a reacts with water and benzaldehyde affording N-phosphoranylbenzamidine 3 (95% yield) and the expected aza-Wittig adduct 4 (85% yield), respectively. Addition of 1 equiv of methyl trifluoromethanesulfonate and of 2 equiv of BH(3).THF to 1a affords cyclic phosphonium salt 5 (94% yield) and the bis(borane) adduct 6a (90% yield), respectively. Dimethyl acetylenedicarboxylate slowly reacts with 1a giving rise to 1,3,4lambda(5)-diazaphosphinine, 9, in 70% yield. The X-ray crystal structures of products 2,3, and 6a are reported (2: C(26)H(38)N(5)P, monoclinic system, space group C2/c, a = 16.337(8) ?, b = 19.810(2) ?, c = 8.800(2) ?, beta = 117.68(2) degrees, Z = 4. 3: C(19)H(35)N(4)OP, orthorhombic system, space group P2(1)2(1)2(1), a = 9.090(1) ?, b = 12.955(2) ?, c = 17.860(3) ?, Z = 4. 6a: C(19)H(39)B(2)N(4)P, orthorhombic system, space group P2(1)2(1)2(1), a = 10.340(1) ?, b = 13.247(1) ?, c = 16.996(1) ?, Z = 4). 相似文献
43.
Yockot D Moreau V Demailly G Djedaïni-Pilard F 《Organic & biomolecular chemistry》2003,1(10):1810-1818
The synthesis of branched beta-cyclodextrins substituted with mannosyl mimetic derivatives at one primary hydroxy group is described. It was shown that the self-inclusion phenomenon observed for the target compounds in water did not preclude the inclusion properties of the cyclodextrin moiety. 相似文献
44.
Monique Nanot Francine Queyroux Jean-Claude Gilles 《Journal of solid state chemistry》1979,28(2):137-147
The homologous phases corresponding to the formula AnBnO3n+2 observed in the systems: La2Ti2O7CaTiO3, Nd2Ti2O7CaTiO3 and Ca2Nb2O7CaTiO3, have a structure derived from the structure of perovskite by periodic crystallographic shears, which delimitate n octahedra thick sheets. In the [0 1 0]1 direction, the sheets are following each other with two types of arrangement.Crystals of terms n = 4,5, 5 and 6 were investigated by X-ray diffraction. According to the type of arrangement of the sheets, the phases studied have either an orthorhombic symmetry or a monoclinic symmetry, this last one giving rise to merohedral twins. 相似文献
45.
Jean-Charles Boutonnet Francoise Rose-Munch Eric Rose Gilles Precigoux 《Journal of organometallic chemistry》1985,284(2):C25-C30
The complex CpV(CO)3THF has been prepared in THF solution (i) photochemically from CpV(CO)4, and (ii) from [CpV(H)(CO)3]?/[Ph3C]+ at low temperatures. THF is replaced by [CpV(H)(CO)3]? to form [{CpV(CO)3}2-μ-H]?, and by various ligands L with C, η2-CC, Sn, N, O, S, Se or Te functionality to yield CpV(CO)3L and cis-[CpV(CO)2LL] (LL = bipy, o-phen, tolane). The δ (51V) values range over ca. 1400 ppm and allow the assignment of distinct coordination modes for ambidentate ligands. The temperature gradient is ca. +1.2 ppm/deg. For [CpV(SnCl3)(CO)3]? (δ ?1340 ppm rel. to VOCl3), 1J(51V-117,119Sn) is 900 Hz. The isotope effect on introducing 12CO for 13CO in CpV(CO)4 is ?0.48(2) ppm; 1J(51V-13C) 107 Hz. 相似文献
46.
Dalla Serra M Coraiola M Viero G Comai M Potrich C Ferreras M Baba-Moussa L Colin DA Menestrina G Bhakdi S Prévost G 《Journal of chemical information and modeling》2005,45(6):1539-1545
Staphylococcal gamma-hemolysins are bicomponent toxins forming a protein family with leucocidins and alpha-toxin. Two active toxins (AB and CB) can be formed combining one of the class-S components, HlgA or HlgC, with the class-F component HlgB. These two gamma-hemolysins form pores with marked similarities to alpha-toxin in terms of conductance, nonlinearity of the current-voltage curve, and channel stability in the open state. AB and CB pores, however, are cation-selective, whereas alpha-toxin is anion-selective. gamma-Hemolysins' pores are hetero-oligomers formed by three or four copies of each component (indicated as 3A3B and 3C3B or 4A4B and 4C4B). Point mutants located on a beta-strand of the class-S component that forms part of the protomer-protomer contact region can prevent oligomer assembly. Interestingly, these mutants inhibit growth of pores formed not only by their natural components but also by nonstandard components. This lead to the hypothesis that mixed ABC pores could also be formed. By studying the conductance of pores, assembled in the presence of all three components (in different ratios), it was observed that the magnitudes expected for mixed pores were, indeed, present. We conclude that the gamma-hemolysin/leucocidin bicomponent toxin family may form a larger than expected number of active toxins by cross-combining various S and F components. 相似文献
47.
A
cha Ali-Bey Hasna Fatiha Loukil Gilles Gosselin Andr Mathieu Abderrezzak Mesli 《Journal of heterocyclic chemistry》1982,19(3):617-624
Hydrolysis of the imine function of a series of Schiff bases derived from pyrrole-2-carboxaldehyde and substituted anilines (X = H, p-OCH3, p-OC2H5, p-CH3, p-Cl, p-Br, m-CN, m-NO2, p-NO2) was studied in all of the pH ranges. The hydrolysis curves log kabs (mn?1) = f(pH) were established in buffered aqueous methanol by polarography or amperometry. The shapes of the curves obtained for pH > 5 indicates that N-pyrrolylmethylene-2 anilines hydrolyse according to the same mechanism as N-benzylidene anilines. The particular stability of these products for pH < 5 permits one to obtain complete hydrolysis curves in acid media. A very good Hammett correlation (kobs = + 1,73) has been established from the maxima which appear for strong acidity. This stability is interpreted as due to the specific electron-donating effect of the pyrrole nucleus. The influence of the structural parameter X on the morphology of the curves log kabs = f(pH) and on the hydrolysis mechanism of the imine function is discussed in all of the pH ranges. 相似文献
48.
A novel transesterification reaction between acetylated maritime pine sapwood (Pinus pinaster Soland) and methyl benzoate (MB), in the presence of dibutyltin oxide (DBTO) as a catalyst, was performed. Reaction was confirmed by Fourier-transform infrared spectroscopy (FTIR) and 13C nuclear magnetic resonance cross-polarisation with magic-angle spinning (NMR CP MAS) analysis: signals corresponding to benzoylated wood were identified and, when transesterification was performed with ethyl trimethylsilylacetate (ETMSA), characteristic trimethylsilyl groups were detected. The acetyl/benzoyl exchange rate was found to increase with increasing amount of DBTO, temperature and reaction time and a concurrent deterioration of the woody material was evidenced. 相似文献
49.
Krahl T Stösser R Kemnitz E Scholz G Feist M Silly G Buzaré JY 《Inorganic chemistry》2003,42(20):6474-6483
The structure of the very strong solid Lewis acid aluminum chlorofluoride (ACF, AlCl(x)F(3-x), x = 0.05-0.3) was studied by IR, ESR, Cl K XANES, (19)F MAS NMR, and (27)Al SATRAS NMR spectroscopic methods and compared with amorphous aluminum fluoride conventionally prepared by dehydration of alpha-AlF(3) x 3H(2)O. The thermal behavior of both compounds was investigated by DTA and XRD. In comparison to ACF, amorphous AlF(3) prepared in a conventional way is not catalytically active for the isomerization reaction of 1,2-dibromohexafluoropropane, which requires a very strong Lewis acid. Both compounds are mainly built up of corner-sharing AlF(6) octahedra forming a random network. The degree of disorder in ACF is higher than in amorphous AlF(3). Terminal fluorine atoms were detected in ACF by (19)F NMR. The chlorine in ACF does not exist as a separate, crystalline AlCl(3) phase. Additionally, chlorine-containing radicals, remaining from the synthesis, are trapped in cavities of ACF. These radicals are stable at room temperature but do not take part in the catalytic reaction. 相似文献
50.