摘要:

The ring opening of γ-butyrolactone with 1 mole of potassium phthalimide and the hydrolysis of the intermediate product gave 4-aminobutyric acid with an excellent yield. The condensation of 1 mole of potassium phthalimide with 2-bromo-4-butyrolactone gave a 2-phthalimidolactone which can also be opened by treatment with a second molecule of potassium phthalimide. This diphthalimido acid when hydrolyzed gave, with an excellent yield, 2,4-diaminobutyric acid dihydrochloride.

ISSN:0008-4042    

DOI:10.1139/v58-084

出版商:NRC Research Press    

年代:1958

数据来源: NRC

摘要:

Complex oxides occurring in the systems CoO/AS2O5and NiO/As2O5have been studied using Debye–Sherrer diagrams. The compounds were prepared either by high-temperature reaction of the oxides and subsequent pyrolysis of the products or by aqueous precipitation of arsenates followed by thermal dehydration.The existence of compounds having metal oxide to arsenic pentoxide ratios of 1:1, 2:1, and 3:1 has been clearly demonstrated and the thermal stabilities of eachinvacuoand in air have been studied. Corresponding compounds in the cobalt and nickel series are isostructural and unit-cell dimensions have been determined. The compounds with a 2:1 ratio could not be isolated readily although their existence is indisputable and tentative figures for the unit-cell dimensions have been obtained.Another compound, probably with a metal oxide to arsenic pentoxide ratio of 6:1, has been observed during the pyrolysis of the 3:1 compounds. Apparently the cobalt and nickel compounds are isostructural and represent the only phase existing between the 3:1 compounds and the metal oxides.

ISSN:0008-4042    

DOI:10.1139/v58-085

出版商:NRC Research Press    

年代:1958

数据来源: NRC

摘要:

The spectral response, voltage dependence, and intensity dependence of the surface photocurrent in naphthalene, terphenyl, pyrene, stilbene, and azulene have been measured. Pyrene and naphthalene have a high sensitivity for photoconduction at the long-wavelength edge of the optical absorption spectrum. In the spectral response of pyrene three peaks appear at 4475 Å, 4275 Å, and 4100 Å. It is suggested that these peaks are due to weak optical absorptions to energy levels which are highly efficient in promoting conduction. It is possible that a similar effect occurs in naphthalene, where maximum photoconductivity coincides with a weak absorption reported by McClure and Schnepp. Azulene only shows photoconductivity at wavelengths corresponding to absorption to the second singlet state.

ISSN:0008-4042    

DOI:10.1139/v58-086

出版商:NRC Research Press    

年代:1958

数据来源: NRC

摘要:

Three new complex fluorides of trivalent titanium have been isolated from the products of electrolysis, under an inert atmosphere, of molten baths of KC1, NaCl, or mixtures of KCl and NaCl, containing either K2TiF6or Na2TiF6. Electrolytic baths containing a mixture of KCl and NaCl with either K2TiF6or Na2TiF6yielded a violet-colored, face-centered cubic compound identified as K2NaTiF6, which was virtually insoluble in water and amenable to electrostatic separation from the metallic titanium also produced in the electrolysis. Baths containing molten mixtures of K2TiF6and KCl gave a pale violet compound K3TiF6, which was slightly soluble in water. Baths containing Na2TiF6and NaCl gave a deep violet-colored compound Na3TiF6which was almost insoluble in water. The compounds K3TiF6and Na3TiF6have structures which approximate to cubic. The compounds K2NaTiF6and Na3TiF6are more stable to atmospheric oxidation than is K3TiF6. X-Ray diffraction patterns have been recorded for these compounds and some of their physical and chemical properties determined.

ISSN:0008-4042    

DOI:10.1139/v58-087

出版商:NRC Research Press    

年代:1958

数据来源: NRC

摘要:

Reactions of oxygen atoms with propylene, butene-1,iso-butene,cis-butene-2,trans-butene-2,cis-pentene-2, and tetramethyl ethylene have been studied at room temperature and at pressures between 50 and 600 mm. The following generalizations can be made. The oxygen atom adds predominantly to the "less-substituted" carbon atom of the olefinic double bond to form a short-lived biradical which rapidly rearranges into isomeric epoxy and carbonyl compounds. Rearrangements involve migration of radicals (including H atoms) from the carbon atom to which oxygen is attached to the other carbon atom of the original double bond. Partly inhibited rotation around the original double bond also takes place. Migration of H atoms is exclusively internal. Migration of larger radicals, such as CH3, is only partly internal: a large fraction of these radicals become completely detached from the rest of the molecule and the particular carbonyl compound is produced both by radical combination and by internal migration. The fragmentation resulting from the splitting off of a migrating radical is pressure independent. The final addition products formed are "hot" as a result of high heats of reaction and undergo decomposition if the excess energy is not removed by collisions. This second type of fragmentation is, therefore, pressure dependent. It is very extensive in the case of ethylene and appears to be completely suppressed in the investigated pressure range in the case of more complex olefins (possessing a greater number of degrees of freedom) such as butenes and higher homologues. Propylene exhibits an intermediate behavior. For orientation of addition of oxygen atoms a carbon atom of an olefinic double bond to which CH3is attached is "less substituted" than a corresponding carbon atom to which C2H5is attached.

ISSN:0008-4042    

DOI:10.1139/v58-088

出版商:NRC Research Press    

年代:1958

数据来源: NRC

摘要:

The formation and decomposition of the molecular complex between solid urea andn-octane vapor, in the presence and absence of initiators, has been studied by a variety of techniques. Suggestions are made for the possible mechanism of this heterophase reaction incorporating known structural and thermodynamic data.

ISSN:0008-4042    

DOI:10.1139/v58-089

出版商:NRC Research Press    

年代:1958

数据来源: NRC

摘要:

Under the influence of short ultraviolet radiation, diphenylamine and nitrate salts react to produce a yellow-colored product. The reaction appears specific and makes it possible to detect 1 μg. of nitrate ion in 0.01 ml. of solution.

ISSN:0008-4042    

DOI:10.1139/v58-090

出版商:NRC Research Press    

年代:1958

数据来源: NRC

摘要:

The dissociation constants of the cyanohydrins of a series of methylcyclohexanones have been measured. The polymethylcyclohexanone cyanohydrins show increasing instability on substitution owing to the effects of "axial crowding". The cyanohydrins of 3- and 4-methylcyclohexanone were found to be more stable than that of cyclohexanone and to explain this a new concept of "equatorial interference" is introduced.

ISSN:0008-4042    

DOI:10.1139/v58-091

出版商:NRC Research Press    

年代:1958

数据来源: NRC

摘要:

1,2-O-isopropylidene-D-glucofuranose was treated with hydrogen at 180 °C. and 2900 p.s.i. using copper chromium oxide catalyst and dioxane as solvent. The major isolated products were a hexanediol (2.4%), a mixture of hexanetriols (6.5%), a hexanetetrol (4.3%), and anisopropylidene-aldohexose (4.2%) which differed from the starting material. The latter product yieldedL-idose on hydrolysis, showing clearly that isomerization of carbon 5 of monoacetone-D-glucose occurs under the reaction conditions used.The diol and the major components of the triol mixture were found to possess a 1,2-glycol group which was derived mainly from the 5,6-glycol group of the original monoacetone-D-glucose. Thus, hydrogenolysis of 1,2-O-isopropylidene-D-glucofuranose-l-C14afforded the 1,2-hexanediol and mixed triols containing only about 30% of the total specific activity in carbon 1. The tetrol was shown to be 1,2,5,6-hexanetetrol. The results suggest that the carbon–oxygen bonds at carbons 5 and 6 ofisopropylidene-D-glucose are least prone to hydrogenolysis and that those at carbons 3 and 4 are most readily cleaved.

ISSN:0008-4042    

DOI:10.1139/v58-092

出版商:NRC Research Press    

年代:1958

数据来源: NRC

摘要:

The scope and limitations of the Étard oxidation of substituted toluenes to substituted benzaldehydes by chromyl chloride have been studied. The conditions of the reaction were investigated and an improved method of performing it was developed.

ISSN:0008-4042    

DOI:10.1139/v58-093

出版商:NRC Research Press    

年代:1958

数据来源: NRC