摘要:

Ebulliometric studies on the hydrolysis of tantalum pentaalkoxides Ta(OR)5, where R = Me, Prn, Bun, and Bus, have furnished important data on the polymeric nature of tantalum oxide alkoxides. It is shown from the variation of number-average degrees of polymerization as a function of degree of hydrolysis that the polymers conform to certain structural models. The structural models involve 6-co-ordinated tantalum.

ISSN:0008-4042    

DOI:10.1139/v62-011

出版商:NRC Research Press    

年代:1962

数据来源: NRC

摘要:

It is observed that ignited beryllium oxide was soluble in concentrated aqueous solutions of beryllium sulphate to the extent of 1 mole of oxide per 2 moles sulphate, saturation being virtually complete within 6 hours at 80 °C. Since the molar solubility of aluminum oxide is much lower under similar conditions, it is suggested that partial resolution of oxide mixtures might be made on this basis.

ISSN:0008-4042    

DOI:10.1139/v62-012

出版商:NRC Research Press    

年代:1962

数据来源: NRC

摘要:

It has been shown that the magnetically anisotropic double bond in bicyclic Diels–Alder adducts exerts a paramagnetic effect on protons in anexoconfiguration and a diamagnetic effect on protons in anendoconfiguration. Thus the configuration of a proton or proton-bearing substituent can be ascertained by observing the change in its chemical shift when the double bond is removed by hydrogenation. However, caution must be used in applying the method to compounds in which the double bond bears a magnetically anisotropic substituent.

ISSN:0008-4042    

DOI:10.1139/v62-013

出版商:NRC Research Press    

年代:1962

数据来源: NRC

摘要:

The infrared absorption of formaldehyde in both the polycrystalline and the monomeric form has been measured at 4 °K. In the latter case the molecules were suspended in an inert matrix of Ar or N2. The fine structure of the matrix spectra is discussed from the point of view of rotation of the monomers but this interpretation is ruled out in favor of one based on multiple trapping sites in the matrix.

ISSN:0008-4042    

DOI:10.1139/v62-014

出版商:NRC Research Press    

年代:1962

数据来源: NRC

摘要:

The complex dielectric constants of several systems comprising a gas adsorbed on Vycor glass have been measured at temperatures between 0 °C and −180 °C and frequencies between 3 kc/sec and 4 Mc/sec. The real and imaginary parts of the dielectric constant of the adsorbed phase have been computed. Loss maxima occurring at low temperatures are observed for some of the matter in the monolayer and are assumed to be due to complexes formed between the gas first admitted and hydroxyl groups which are covalently attached to the surface of the glass. The complexes may be considered either as dipoles having two equilibrium positions, or as highly damped oscillators. Ethyl chloride adsorbed in the first molecular layer and not bonded to OH behaves as an oscillatory system for which no loss is observed in the frequency and temperature ranges studied. Ethyl chloride adsorbed in the multilayers behaves similarly but shows a slightly greater temperature coefficient of ϵ′. Both these types of adsorbed ethyl chloride interact with the complexes and reduce the threshold temperature at which loss is observed in the complex. Methyl chloride interacts with OH groups in a similar fashion, butn-butane does not.

ISSN:0008-4042    

DOI:10.1139/v62-015

出版商:NRC Research Press    

年代:1962

数据来源: NRC

摘要:

Catalposide extracted from the unripe fruit ofCatalpaovataaffords bisdesoxyaucubin on reduction with lithium in liquid ammonia. The reduction is accompanied by the shift of a double bond. From this and other evidence, two possible structures are proposed for the compound.

ISSN:0008-4042    

DOI:10.1139/v62-016

出版商:NRC Research Press    

年代:1962

数据来源: NRC

摘要:

The infrared frequencies and intensities of the fundamental stretching vibration of the hydroxyl group have been measured for a number of ortho-alkyl phenols in the vapor phase over a range of temperatures. Both quantities have been shown to depend on internal steric and environmental factors. The differences in enthalpy between the cis and trans isomers of several 2-tert-alkyl phenols have been measured, and it is concluded that the latter are not significantly stabilized relative to the former by solvation in non-polar solvents.

ISSN:0008-4042    

DOI:10.1139/v62-017

出版商:NRC Research Press    

年代:1962

数据来源: NRC

摘要:

A detailed study of the nature, and the mechanism of formation, of the products of the aluminum chloride catalyzed reaction of vinyl esters and benzene has been initiated. Using vinyl acetate the formation of the previously reported acetophenone, 1,1-diphenylethane, and 9,10-dimethylanthracene has been confirmed. By means of both column chromatography and thermal distillation, a similar carbonyl-containing fraction was obtained which, as a result of a gas chromatographic study, has been shown to be a mixture of six compounds. Of these, the two major components have been identified as acetophenone andp-ethylacetophenone, the latter previously unreported as a product of this reaction.The reaction of vinyl formate and benzene has been studied for the first time. High yields of 9,10-dimethylanthracene were obtained but no carbonyl-containing compounds. A study of the effect of a variation in molar ratio of benzene to vinyl acetate indicated that a maximum yield of 9,10-dimethylanthracene was obtained using a 6:1 molar ratio.The significance of these results is discussed.A method has been devised for an improved synthesis of 9,10-dimethylanthracene. The generality of this procedure for the synthesis of other substituted polynuclear compounds is indicated.

ISSN:0008-4042    

DOI:10.1139/v62-018

出版商:NRC Research Press    

年代:1962

数据来源: NRC

摘要:

The preparation of several 3,4,5-trisubstituted-β-hydroxy-β-phenylethylamines related to mescaline, by the reduction or reductive alkylation of the corresponding nitroalcohols, is described.

ISSN:0008-4042    

DOI:10.1139/v62-019

出版商:NRC Research Press    

年代:1962

数据来源: NRC

摘要:

The preparation of 3,4-methylenedioxy-α-aminomethylbenzyl alcohol and a number of itsN-alkyl andN,N-dialkyl derivatives by the reduction or reductive alkylation of 3,4-methylenedioxy-α-nitromethylbenzyl alcohol is described.

ISSN:0008-4042    

DOI:10.1139/v62-020

出版商:NRC Research Press    

年代:1962

数据来源: NRC