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101.
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
102.
Benz[a]azulene ( 1 ) is synthesized in five steps (cf. Scheme 2) starting from commercially available 2-iodobenzyl alcohol ( 4 ) and tropylium tetrafluoroborate in an overall yield of 44%. The key step (cf. also Scheme 1) is the intramolecular Heck reaction of the 8-phenylsulfonyl-substituted heptafulvene 7 , which leads in nearly quantitative yield directly to 10-(phenylsulfonyl)benz[a]azulene ( 8 ). The desulfonylation of 8 can be accomplished by Julia's method with Na2S2O4/NaHCO3 in DMF/H2O at 85–90°, thus leading to pure 1 in 78% yield. The phenylation of 8 with PhLi or PhCul at ?78° in THF occurs regioselectively at C(9). Dehydrogenation of the formed dihydroazulenes with o-chloroanil in toluene at room temperature gives 9-phenyl-10-(phenylsulfonyl)-benz[a]azulene ( 9 ) in 70% yield (cf. Scheme 3), which, again, can be desulfonylated with Na2S2O4/NaHCO3 in DMF/H2O in good yields. The addition of PhLi to 1 in THF occurs at temperatures ? ?25°. Ionic dehydrogenation (1. Ph3C+BF/MeCN; 2. Et3N) of the dihydro forms leads to 3 , as the main product, and its positional isomers. 相似文献
103.
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
104.
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
105.
Hans Jürgen Rosenkranz Barbara Winkler-Lardelli Hans-Jürgen Hansen Hans Schmid 《Helvetica chimica acta》1974,57(3):887-916
It is shown that treatment of indolines like 4a-methyl-1,2,3,4,4a,9a-hexahydrocarbazole ( 1 ) and even indoline-alkaloids like 5 or 6 (cf. scheme 1) with KMnO4 in boiling acetone solution leads to the indolenines 10, 29 and 33 , respectively, and, in relatively high yields, to N,N′- or C,N-coupling products (cf. schemes 2 and 5). The results of the oxidation of 6- or 8-methoxy-indolines are shown in schemes 3 and 4, respectively. Analogous ‘dimeric’ dehydrogenation products are observed when tetrahydroquinolines ( 8 and 9 , resp.) are treated with KMnO4 (cf. schemes 7 and 8, resp.). The formation of the bis-compounds is almost certainly due to the coupling of two intermediate indolenyl or tetrahydroquinolyl radicals. The cleavage of the hydrazine derivatives 11 or 17 (scheme 9) also leads to ‘dimeric’ C,N-coupling products. By heating the hydrazine derivative 17 with aqueous HCl, a complete cleavage into indoline 2 and the indolenines 16 and 20 is observed. The reaction is rationalized in scheme 10. So far no naturally occurring alkaloids related to the above mentioned C,N-coupling products have been found. 相似文献
106.
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
107.
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
108.
109.
Veith SR Hughes E Vuataz G Pratsinis SE 《Journal of colloid and interface science》2004,274(1):216-228
The restricted diffusion coefficient of water through porous silica is measured by pulsed field gradient (PFG) NMR as a function of loading in order to develop a model for self-diffusion at full pore filling in sol-gel-made porous silica particles. This model describes the pore or intraparticle diffusion coefficient as a function of particle porosity, tortuosity, and the steric hindrance applied on the molecules by the pore space. The particle morphology is characterized by nitrogen adsorption and an appropriate tortuosity model is chosen in comparison with literature data. To characterize the material, NMR relaxation and diffusion studies at different degrees of pore filling were carried out in relation to the silica/water adsorption isotherm. 相似文献
110.
Grignard reagents react with 7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride and produce in high yields the corresponding substituted bicyclo-γ-butanolides. These lactones produce the title compounds by retro Diels-Alder reaction during distillation. 相似文献