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71.
Thirteen variously substituted α-ethylenic β'-allenic alcohols (1,5,6-triene-3-ols) have been synthesized by three different methods, for two of which the key step was the reaction of an organo copper reagent with a derivative of a β-hydroxy γ-ethylenic alcohol (1-ene-5-yne-3,7-diol). The[3,3]-sigmatropic rearrangement of these alcohols, following the heating of their solution in diglyme, leads to γ-dienic aldehydes and ketones. The yields are best (60–70%) for tertiary alcohols substituted on carbon 5. Comparisons of the reactivities of these 13 alcohols show that the mechanism of this rearrangement can probably vary, following the substitution from a cyclohexadiyl biradical process to a concerted pathway involving a cyclohexane transition state. 相似文献
72.
W. M. Buda K. Jaques A. Venema P. Sandra 《Analytical and bioanalytical chemistry》1995,352(7-8):679-683
The dependence of the retention on stationary phases consisting of mixtures of a cyclodextrin (perpentyl-β-cyclodextrin) and a polysiloxane (cyanopropyl-7%-, phenyl-7%-methyl-86%-or OV-1701) was investigated as function of the cyclodextrin concentration. In order to study the effect of mixing, the data on the mixed stationary phases were compared with those obtained on pure OV-1701 and perpentylated β-CD and on coupled columns, individually coated with the pure phases. The validity of the retention model proposed in the literature by Schurig and co-workers was checked. Deviation from linearity was observed for some racemates. A possible explanation of the deviation is presented and a more general retention model on mixed cyclodextrin-polysiloxane phases is proposed. 相似文献
73.
Babes L Denizot B Tanguy G Le Jeune JJ Jallet P 《Journal of colloid and interface science》1999,212(2):474-482
Colloidal iron oxides play an important role as magnetic resonance imaging (MRI) contrast agents. The superparamagnetic particles actually used are constituted by solid cores (diameter of 5-15 nm), generally coated by a thick polysaccharidic layer (hydrodynamic radii of 30-100 nm), and formulated by direct coprecipitation of iron salts in the presence of polymeric material. To better control the synthesis, we attempted to formulate new stable uncoated superparamagnetic nanoparticles. Colloids were generated by coprecipitation of an aqueous solution of iron salts and tetramethylammonium hydroxide (TMAOH) solution. The influence of parameters such as media composition, iron media, injection fluxes, Fe and TMAOH concentrations, temperature, and oxygen on size, magnetic and magnetic resonance relaxometric properties, and colloidal stability of particles were evaluated. We have determined the relative importance of these parameters as well as the optimal conditions for obtaining uncoated stable particles with an average size of 5 nm and interesting relaxivities. The interpretation of the observed limits takes into account diffusibilities of reactants and product, feeding rates of reactants, and surface properties of nanoparticles. A model of synthesis, related to spontaneous emulsification of suspensions, is proposed. Copyright 1999 Academic Press. 相似文献
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76.
Marc Lang Kapa Prasad Jaques Gosteli Robert B. Woodward 《Helvetica chimica acta》1980,63(4):1093-1097
A synthesis of 2-alkylthiopenems by an intramolecular Wittig-type reaction between a phosphorane and a trithiocarbonate ester is described. 相似文献
77.
In this paper we describe a procedure which allows to obtain estimates of the energy effects associated with the orbital interactions occurring between the component fragments of a radical species in the framework of ab initio Unrestricted Hartree-Fock computations. This procedure is used here to analyze the factors which control the conformational isomerism of the ethyl radical.On leave from C.N.R.S., GR 12, Thiais, France 相似文献
78.
79.
A synthesis of pyrrolo[3,4-c]pyridines from pyridyne intermediates is reported together with a study of the reactions of 2-methyl-2H-pyrrolo[3,4-c]pyridine (5) with oxidising and reducing agents. 相似文献
80.
van den Brink HB Blok HP Bobeldijk I Bouwhuis M Dodge GE Harakeh MN Hesselink WH Ireland DG de Jager CW Jans E de Jonge N Kalantar-Nayestanaki N Kasdorp WJ Ketel TJ Konijn J Lapikás L van Leeuwe JJ van der Meer RL Nooren GJ Norum BE Passchier E Pellegrino AR Spaltro CM van der Steenhoven G Steijger JJ Templon JA Theunissen JA van Uden MA de Vries H de Vries R de Witt Huberts PK 《Physical review letters》1995,74(18):3561-3564