摘要:

It has been shown that deoxymercuration (conversion of an α-oxyorganomercurial to the alkene) is a second-order reaction dependent on concentration of the mercurial and of the deoxymercurating acid. Moreover the rate of deoxymercuration increases with basic strength of the alkoxy substituent in the mercurial. This tendency would indicate that the rate was dependent on the strength of the acid used for deoxymercuration. The supposition has been proved by use of trifluoroacetic acid which decomposes α-2-methoxycyclohexylmercuric trifluoroacetate more slowly than does hydrochloric acid. The trifluoroacetoxymercurial decomposes to the extent of 35% whereas its synthesis is effected in 60% maximum yield from cyclohexene and mercuric trifluoroacetate. A measurable equilibrium is thus attained in this oxymercuration, though not necessarily because of a simple reversible reaction.

ISSN:0008-4042    

DOI:10.1139/v57-182

出版商:NRC Research Press    

年代:1957

数据来源: NRC

摘要:

n-Butyl mercaptan reacts with 1-pentene when irradiated with X-rays. The dependence of reaction rate upon concentration of mercaptan and pentene has been studied as well as the dependence on dose rate. A comparison with the photoinitiated reaction is made.

ISSN:0008-4042    

DOI:10.1139/v57-183

出版商:NRC Research Press    

年代:1957

数据来源: NRC

摘要:

Butyl mercaptan reacts with 1-pentene when irradiated with X and gamma rays. Experiments on mixtures which had been rigorously degassed and dried suggest that the reaction kinetics are strongly dependent on traces of oxygen in the system. A possible mechanism for the reaction is given.

ISSN:0008-4042    

DOI:10.1139/v57-184

出版商:NRC Research Press    

年代:1957

数据来源: NRC

摘要:

The effect of energy variation on the addition ofn-butyl mercaptan to 1-pentene has been studied using radiations at 140 kvp., 1.25 Mev., and 24.5 Mevp. No appreciable energy dependence has been found over this range.

ISSN:0008-4042    

DOI:10.1139/v57-185

出版商:NRC Research Press    

年代:1957

数据来源: NRC

摘要:

The movement of the tip of a glass spoon gauge is followed by means of a linear variable differential transformer with a sensitivity of 2.2 mv. per micron. For a spoon that will stand a differential pressure of one atmosphere this amounts to 5 mv. per mm. of mercury. There is no hysteresis, the temperature coefficient is 0.1 mm. per °C, and there is a null point drift of about 0.05 mm. per hour. The over-all accuracy is 0.2 mm. in the range 0 to 760 mm.

ISSN:0008-4042    

DOI:10.1139/v57-186

出版商:NRC Research Press    

年代:1957

数据来源: NRC

摘要:

The solvolysis of 2-phenylethyl-1-C14p-toluenesulphonate in absolute ethanol, glacial acetic acid, 90% formic acid, and anhydrous formic acid gave rise to products which showed rearrangements of the C14-labeled atoms from the C-1 to the C-2 positions to the extent of 0.3%, 5.5%, 40%, and 45%, respectively. The results constitute an unequivocal proof that phenyl participation occurs in the reactions studied. The different degrees of rearrangement found for the different solvent systems are in agreement with the concept that the solvolysis process may have a range of mechanisms between the two extremes of the nucleophilic or SN2 type and the limiting or SN1 type. In the solvolysis in absolute ethanol, a small amount of "unreacted" 2-phenylethylp-toluenesulphonate recovered from the reaction mixture was found to show isotope position rearrangement of almost the same degree as the ethanolysis product. This finding is tentatively attributed to the phenomenon of internal return involving an ethyl-phenoniump-toluenesulphonate ion-pair.

ISSN:0008-4042    

DOI:10.1139/v57-187

出版商:NRC Research Press    

年代:1957

数据来源: NRC

摘要:

The properties of chlorotrihydroxydihydrophenazine were thoroughly investigated. Oxidations with sodium perborate or hydrogen peroxide in glacial acetic acid gave chloro-trihydroxyphenazine-5,10-dioxide. Methylation gave a monomethyl derivative and acetylation yielded mono-, di-, and tri-acetyl derivatives. Benzoylation gave a tetrabenzoyl compound. Bromination gave a monobromo derivative. Nitrosation produced a mononitroso and nitration a mononitro compound. Degradation by zinc dust distillation and thermal decomposition yielded phenazine. Molecular weight and absorption spectra determinations supported the chemical evidence that the compound was 1-chloro-2(or 3),6,8-trihydroxydihydrophenazine. 1,4,9-Trichloro-2(or 3),6,8-trihydroxydihydrophenazine, 1,4,9-trichloro-2(or 3, or 8),6-dihy-droxydihydrophenazine, and 1-bromo-2(or 3),6,8-trihydroxydihydrophenazine were similarly identified.

ISSN:0008-4042    

DOI:10.1139/v57-188

出版商:NRC Research Press    

年代:1957

数据来源: NRC

摘要:

A sample of body fat of the Canadian musk ox (Ovibosmoschatussubsp.) was converted to methyl esters and distilled. The fraction containing esters of C17acids was crystallized fractionally at low temperature and two straight-chain C17acids were isolated.n-Heptadecanoic acid was identified by analysis, by mixed melting point of the acid and two derivatives with authentic samples, and by its X-ray diffraction pattern. 9-Heptadecenoic acid was identified by analysis, by mixed melting point of two derivatives with authentic samples, and by oxidative cleavage. It is estimated that the fat contained 1.7% ofn-heptadecanoic acid and 0.9% ofcis-9-heptadecenoic acid, based on the total fatty acids. Although there was an appreciable content oftransacids in the fat, the heptadecenoic acid was found to contain little or none of thetransform.

ISSN:0008-4042    

DOI:10.1139/v57-189

出版商:NRC Research Press    

年代:1957

数据来源: NRC

摘要:

The preparations of Δ8-hexahydro-1,4,8-pyrimidazole, Δ9-1,5,9-triazabicyclo(4.4.0)decene, and Δ9-1,4,9-triazabicyclo(5.3.0)decene from the corresponding 2-(ω-hydroxyalkylamino)-Δ2-1,3-diazacycloalkenes by chlorination and dehydrohalogenation are described. The nitro derivatives of these bicyclic compounds are more stable towards refluxing ethanol than 1-nitro-2,3,5,6-tetrahydro-1-imidaz(1,2-a)imidazole.

ISSN:0008-4042    

DOI:10.1139/v57-190

出版商:NRC Research Press    

年代:1957

数据来源: NRC

摘要:

Dehydration, under vacuum, of magnesium sulphate heptahydrate yields a product of monohydrate composition which does not give a diffraction pattern on X-ray examination and therefore has no evident crystalline structure. The heat capacity of this product has been determined over the temperature range from 90°K. to room temperature, and has been found to be substantially higher than that of the normal crystalline monohydrate. Consideration of these differences in heat capacity in conjunction with surface area data indicates that vacuum dehydration does not result in the formation of microcrystals the surfaces of which are available for gas adsorption. It is possible that aggregates of closely packed crystallites are formed in localized regions, these being interspersed with capillaries. Alternatively, it is possible that vacuum dehydration results in an intermediate state of ionic disorder.

ISSN:0008-4042    

DOI:10.1139/v57-191

出版商:NRC Research Press    

年代:1957

数据来源: NRC