摘要:

Changes in the capacity of a test cell which contained porous Vycor glass have been measured following the adsorption of butane and ethyl chloride. The results are similar to those obtained by Snelgrove and McIntosh using silica gel and these adsorbates. That is, a sudden drop in the apparent polarization is observed at a well defined quantity of adsorbed gas. This observation thus appears characteristic of porous adsorbents. To explain the phenomenon one may postulate a low density for the material of low apparent polarizability, or its location in a different electrical field in the heterogeneous dielectric. The former is ruled out with Vycor glass because of insufficient pore volume. The latter approach has been examined using the "cluster" treatment of Channen and McIntosh with the data for silica gel systems as well as porous glass. The attempt has proved only partially successful.

ISSN:0008-4042    

DOI:10.1139/v57-028

出版商:NRC Research Press    

年代:1957

数据来源: NRC

摘要:

The infrared spectrum of S2F10has been obtained for the vapor from 5 to 35 μ and for the solid at liquid nitrogen temperatures from 10 to 24 μ. The Raman spectrum, together with depolarization ratios, was obtained for the liquid. A vibrational assignment has been made consistent with eitherD4dorD4h, symmetry and all the fundamentals identified except two low FSSF bending frequencies and the inactive torsional frequency. A normal co-ordinate calculation located the bending frequencies at 37 and 57 cm.−1while a simple potential energy calculation gave a torsional frequency of 89 cm.−1corresponding to a potential barrier of 2780 cm.−1.

ISSN:0008-4042    

DOI:10.1139/v57-029

出版商:NRC Research Press    

年代:1957

数据来源: NRC

摘要:

The entropies of oxy-anions in aqueous solution are shown to obey the empirical relationshipwith a mean deviation of 3.6 e.u. In this equationis the entropy relative to a value of −5.5 e.u. for the proton,Mis the molecular weight,zthe number of charges on the ion,nthe number of charge-bearing ligands,ris equal tor12 + 1.40, wherer12is the interatomic distance between the central atom and the surrounding oxygens, and 1.40 is the van der Waals radius of oxygen. The significance of the empirical equation is discussed.

ISSN:0008-4042    

DOI:10.1139/v57-030

出版商:NRC Research Press    

年代:1957

数据来源: NRC

摘要:

The partial molal volumes of oxy-anions, obtained from density data, have been correlated with the radius, the charge, and the number of ligands of the ions. The volumes relative to a value of −6.0 ml. for the proton are represented by the equation:whererandz_ have the same significance as in the preceding paper on entropies. The equation is compared with the one for monatomic ions, and the significance of the effective radiusris discussed.

ISSN:0008-4042    

DOI:10.1139/v57-031

出版商:NRC Research Press    

年代:1957

数据来源: NRC

摘要:

Annotinine lactam C16H19O4N has been converted by the action of dilute sulphuric acid to the lactamdiol, C16H21O5N. Oxidation studies on the lactamdiol have confirmed the presence of the epoxide ring in the alkaloid and have established the six-membered character of the lactam ring. The allylamine structure of unsaturated lactone A, C16H21O2N, has been confirmed and a number of intermediate oxidation products of this compound have been isolated and characterized. Raney nickel reduction of annotinine yielded hydroxy annotinine, C16H23O3N, and saturated lactone A, C16H23O2N. Catalytic reduction of annotinine lactam over Adams′ catalyst in acidic medium converted it partially to annotinine.

ISSN:0008-4042    

DOI:10.1139/v57-032

出版商:NRC Research Press    

年代:1957

数据来源: NRC

摘要:

The Friedel–Crafts alkylation of anisole with 2-phenylethyl-1-C14chloride and 2-phenylethanol-1-C14resulted in a product,p-methoxydibenzyl, which showed isotope position rearrangement corresponding to an essentially 50% rearrangement of the C14labeled atoms from the C-1 to the C-2 positions in the original chloride and alcohol. If one were to assume that both rearrangement and alkylation involve the same intermediate, these results may be explained on the basis of either an ionic mechanism for the Friedel–Crafts alkylation, the rearrangement being attributed to the formation of the phenylethyl cation, or a displacement mechanism in which the alkylation product is formed from a reaction between anisole and a rearranged polarized complex of aluminum chloride and alkylating agent. The possibility that rearrangement in the Friedel-Crafts alkylation may arise from a process separate from and prior to the alkylation stage itself is also discussed. On this basis, the intermediates involved in the rearrangement and alkylation stages will not necessarily have to be the same.

ISSN:0008-4042    

DOI:10.1139/v57-033

出版商:NRC Research Press    

年代:1957

数据来源: NRC

摘要:

The infrared spectra of all the deuterated methanes of high isotopic purity have been obtained with prism resolution and27of the29fundamentals were observed. The frequencies observed have been compared with the previous grating and prism data and 'best' values of the fundamentals have been suggested. The present data are considered to give more reliable frequencies for most of the fundamentals of CH3D, CH2D2, and CD3H than were previously available.

ISSN:0008-4042    

DOI:10.1139/v57-034

出版商:NRC Research Press    

年代:1957

数据来源: NRC

摘要:

The reaction of 2-chloromercurifuran witht-butyl bromide does not yield 2-t-butylfuran. Instead 2,5-di-t-butylfuran, 2,2,7,7-tetramethyloctane-3,6-dione, and 2-t-butyl-5-[2,4,4-trimethyl-2-pentyl]furan are produced. Air-oxidation of di-t-butylfuran yieldstrans-2,2,7,7-tetramethyl-4-octene-3,6-dione (converted to thecisisomer photochemically) which forms a dibromide identical with the dibromo substitution product from tetramethyloctanedione. Cold nitric acid oxidation of di-t-butylfuran or tetramethyloctanedione yields 4-hydroxy-5-isonitroso-2,2,7,7-tetramethyloctane-3,6-dione, but hot nitric acid oxidation of the tetramethyloctanedione yields the expected 2-trimethylacetyl-5-t-butylisoxazole. The corresponding oxidation product oft-butyltrimethylpentylfuran has not been identified, although it yields 2,2,4,4-tetramethylpentanoic acid, indicative of the isoöctyl substituent, upon hydrolysis. The same acid is obtained by permanganate oxidation of Friedel–Crafts-synthesized 2,5-di-[2,4,4-trimethyl-2-pentyl]furan, a compound which yieldstrans-2,2,4,4,9,9,11,11-octamethyl-6-dodecene-5,8-dione.

ISSN:0008-4042    

DOI:10.1139/v57-035

出版商:NRC Research Press    

年代:1957

数据来源: NRC

摘要:

In order to study the effect of association with π-donors, the proton resonance signal of chloroform in the aromatic solvents benzene, toluene, mesitylene, chlorobenzene,o-dichlorobenzene, bromobenzene, nitrobenzene and in the olefinic solvents 1-hexene, cyclohexene, and cyclohexadiene was measured as a function of concentration. The observed shifts of the resonance signal are indicative of specific complex formation. In the aromatic solvents benzene, toluene, and mesitylene, complex formation results in an anomalous shift of the chloroform resonance to high field, which can be attributed to a large induced diamagnetism resulting from the circulation of π-electrons in the aromatic ring. An approximate calculation indicates that the chloroform molecule in the complex is oriented with the hydrogen atom near the six-fold axis above the plane of the aromatic ring and the chlorines directed away from the ring. In nitrobenzene this type of association with chloroform gives way ton-donor association with the oxygen atom of the nitro group. This type of association also occurs to some extent in the halogenated benzenes. A small shift of the chloroform signal to low field is observed with the olefinic solvents, which is attributable to weak π-donor association. Analysis of the freezing-point diagrams of the binary systems with chloroform provide further evidence of complex formation.

ISSN:0008-4042    

DOI:10.1139/v57-036

出版商:NRC Research Press    

年代:1957

数据来源: NRC

摘要:

A trisaccharide obtained after acetolysis ofSaccharomycesrouxiimannan is shown to beO-α-D-mannopyranosyl-(1 → 2)-O-α-D-mannopyranosyl-(1 → 2)-D-mannose. Methylation and lead tetraacetate Oxidation techniques define the positions of the glycosidic linkages. The configurations of the two linkages are determined through use of two novel degradative methods which yield 2-O-α-D-mannopyranosyl-D-mannose and 2-O-α-D-mannopyranosyl-glycerol, each containing one of the glycosidic linkages of the parent trisaccharide.

ISSN:0008-4042    

DOI:10.1139/v57-037

出版商:NRC Research Press    

年代:1957

数据来源: NRC