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1.
The mechanism and stereochemistry of δ-C atom functionalisation in the reactions of secondary straight-chain aliphatic alcohols with lead tetraacetate, ceric ammonium nitrate, and heavy metal (Pb4+, Hg2+, Ag+) salts (AcO)?1, O2?, CO32?-halogen (I2, Br2, Cl2) combinations are discussed. By demonstrating the intermediacy of 5-bromo-2-hexanol, it was confirmed that the dark silver oxidebromine induced cyclisation of 2-hexanol (and alcohols in general) involves (as the other hypohalite reactions) intramolecular 1,5-hydrogen abstraction by alkoxy radicals and formation of δ-bromohydrins. A novel and simple procedure for obtaining tetrahydrofurans from alcohols by way of the hypochlorite reaction, using silver or mercuric salts and chlorine, is described. 相似文献
2.
The stereochemistry of substituted cyclopent-2-en-1-ones was studied by NMR. The existence of non-planar rings is indicated and conformational analysis, based principally upon examination of the coupling constants enables the conformational population to be estimated; trans dihalogeno derivatives, for example, occur predominantly in the diaxial form. 相似文献
3.
A convenient, 40% overall yield synthesis of 2,3,17β-triacetoxy-1,3,5(10)-estratriene is described, which involves epoxidation of 19-nortestosterone and subsequent acetylation, lead tetra-acetate acetoxylation of the so-formed 17β-acetoxy-4β,5-epoxy-5β-estran-3-one, and aromatization of ring A, by means of acidic alumina, of the resulting 2α and 2β epimers of 2,17β-diacetoxy-4β,5-epoxy-5β-estran-3-one. 相似文献
4.
A very close triple resonance is observed in the Q-branch region of the C-H stretching fundamental transition in CF3H. The vibrational perturbations are analysed in terms of the rotational structure and of the vibrational zero-order spectrum of totally symmetric states. The relationship to time-dependent intramolecular processes is discussed. 相似文献
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6.
Di(methyl-), di(ethyl-) and di(propylcyclohexyl) esters of itaconic acid were polymerized radically in bulk. The products were characterized in solution, then fractionated and the limiting viscosity number/molecular weight relations established for toluene at 25°. From extrapolations to θ-conditions, a set of σ-values from 2.75 to about 2.90 was obtained and compared with published results for poly(dicyclohexyl itaconate) [1], the first member of this polymer homologous series. The non-uniform change of unperturbed dimensions and other thermodynamic parameters are discussed in terms of chemical composition and constitution of the monomer residues. 相似文献
7.
Ljubinka Lorenc Milan Dabović Ivan Juranić Mihailo Lj. Mihailović Günther Snatzke Gábor Tóth 《Tetrahedron》1982,38(21):3163-3168
Circular dichroism of the rearranged keto steroids 3 and 4, containing a condensed three and nine-membered ring system, shows that the conformation of the nine-membered ring is the same in solution as in the crystal; reduction of the kto group does not change this situation. CD also indicates that epimerization at C(5) in the pair and the pair leaves the cyclononanone ring conformation unchanged. 相似文献
8.
When treated with hydroxylamine or N-methylhydroxylamine, in the presence of proton donor catalysts, trans-Δ1(10)-unsaturated 5-oxo-5,10-seco-steroids, such as 3 (but not the corresponding diastereomeric cis-compounds), are converted stereospecifically and in good yield to isoxazolidine derivatives (e.g. 4 and 13), resulting from transannular 1,3-dipolar addition of the intermediately formed oximes and nitrones to the trans-double bond in the cyclodecene ring moiety of the seco-steroid system. Reactions are described and physical evidence is presented which establish the constitution and configuration of the isoxazolidine-containing cycloaddition products, and the mechanistic and steric course of this transannular ring closure process is discussed. 相似文献
9.
Solid diphenyl itaconate monomer was obtained by esterification in the presence of diphosphorus pentoxide and polymerized in bulk with AIBN as initiator. The non-film forming polymer powder was characterized by fractionation, viscosity measurements, light scattering and other techniques. The relation [n] = 3·6 × 10?30·70w, obtained for toluene at 25° was extrapolated to θ-conditions by various procedures: the σ-value of 2·60 for unperturbed dimensions indicates a less pronounced influence of phenyl compared with other C6 hydrocarbon substitutes. 相似文献
10.
An efficient procedure for the preparation of 1α-hydroxycholesterol 3-acetate 4 is described, which starts from cholesterol and involves as key steps transannular cyclization of the ten-membered ring ontaining (E)-3β-acetoxy-5,10-seco-1(10)-cholesten-5-one 1 to the oxetane derivative 1α,5-epoxy-5α-cholestan-3β-ol acetate 3, and opening of the four-membered ether ring in the latter compound. 1β-Hydroxycholesterol diacetate 9 was obtained by oxidation of 4 to the 1-oxo derivative 8, followed by metal hydride reduction and acetylation. 相似文献