摘要:

Fritsch's cyclization of N-(α-veratrylveratrylidene)-aminoacetal in sulphuric acid was shown to give 1.1% of papaverine and 23% of an isomer, m.p. 164.5–165.5 °C.; hydrochloride, m.p. 212 °C. decomp., which was supposed to be 4,5-bis(3,4-dimethoxyphenyl)-2H-pyrrolenine, produced by an internal condensation of the acetal or the corresponding aldehyde with the reactive methylene group. A similar structure was proposed for another unidentified isomer prepared by Schlittler and Müller. Hydrogenation of Fritsch's acetal gave N-(α-veratryl-veratryl)-aminoacetal, m.p. 69.5–70 °C., which was cyclized to a base, m.p. 155.5–156 °C.; N-acetyl derivative, m.p. 203.5–204 °C., formulated as 2,3-bis(3,4-dimethoxyphenyl)-3-pyrroline. Substances presumed to be the intermediate aldehyde and aldol were isolated as colorless oils. Condensation of the diketone veratril with aminoacetal, followed by cyclization of the crude product, constituted a new two-step synthesis of papaveraldine in 8% yield, and the reduction of the latter to papaverine was known.Other crystalline compounds prepared incidentally and thought to be new were veratril monoanil, m.p. 172–173 °C.; α,α′-biveratrylideneaminoacetal, m.p. 101–102 °C.; a compound formulated as 2,3-bis(3,4-dimethoxyphenyl)-4-ethylmer-captopyrrolidine hydrochloride, m.p. 184–185 °C; from this an unidentified mercury complex, m.p. 109 °C. decomp.; 4,4′dibenzyloxy-3,3′-dimethoxy-desoxybenzoin, m.p. 141–142 °C; and its oxime, m.p. 137.5 °C.

ISSN:0008-4042    

DOI:10.1139/v55-090

出版商:NRC Research Press    

年代:1955

数据来源: NRC

摘要:

The photolytic decomposition of hexafluoroacetone by light of wavelength 3130 Å has been used to produce trifluoromethyl radicals for a study of their reactions with methane and ethane. It has been shown that these radicals abstract hydrogen with greater facility than do methyl radicals. The activation energies for the two reactionsandare found to be 10.3 ± 0.5 kcal./mole and 7.5 ±0.5 kcal./mole respectively, if one can assume zero activation energy for the recombination of trifluoromethyl radicals.

ISSN:0008-4042    

DOI:10.1139/v55-091

出版商:NRC Research Press    

年代:1955

数据来源: NRC

摘要:

(CH3CO)2-1-C14(I) was prepared by irradiating (CH3)2CO in the presence of CH3I-C14. Acetone was then irradiated at room temperature with light of 2537 Å in the presence of (I). Radioactivity was found in all products which contained methyl groups but not in any carbon monoxide product. The amount of carbon-14 ultimately found in acetone confirms that the quantum efficiency of the primary photolytic process is nearly unity and that extensive recombination of methyl and acetyl radicals to form acetone is responsible for the low over-all quantum efficiency of decomposition.

ISSN:0008-4042    

DOI:10.1139/v55-092

出版商:NRC Research Press    

年代:1955

数据来源: NRC

摘要:

The molecular weights of organic compounds of known constitution have been determined with satisfactory accuracy, using milligram quantities of materials, by a static measurement of the vapor pressure difference between pure solvents and solutions of the compounds. The method may be used over a considerable temperature range. The suitability of solvents is governed by their chemical stability and vapor pressure. Results obtained using compounds in the molecular weight range of 600–1000 are reported.

ISSN:0008-4042    

DOI:10.1139/v55-093

出版商:NRC Research Press    

年代:1955

数据来源: NRC

摘要:

Two-body interactions between glass spheres of diametersa1anda2caused by velocity gradients vary witha1/a2. When 1 < a1/a2 < 2, well-defined collisions similar to those previously reported for spheres of equal size can be observed. Fair agreement is found between the experimentally observed and calculated collision frequencies over a range of particle concentrations and velocity gradients. Whena1/a2 > 2 the particles are separated at all times and the phenomena of interaction are more complex. Single air bubbles rotate at the same angular velocity as rigid spheres. When two air bubbles of equal size are brought into collision a doublet is formed; instead of the mirror-image separation observed with neutral rigid spheres, the doublet continues to rotate for as many as 60 rotations before coalescence occurs. Less frequently a doublet with distinct particle separation is observed. Periods of rotation of both types of doublet and certain details of the rotational orbit of a doublet of touching air bubbles have been measured and compared with values predicted from Jeffery's theoretical equations for rigid ellipsoids. Apart from their intrinsic interest, the phenomena described are of importance in theories of viscosity and coagulation of suspensions and colloidal dispersions.

ISSN:0008-4042    

DOI:10.1139/v55-094

出版商:NRC Research Press    

年代:1955

数据来源: NRC

摘要:

Solubility data have been obtained at 20 °C. and 60 °C. for the following ternary systems:No evidence of the formation of double salts or of solid solutions in the first three systems was obtained. Ammonium sulphite monohydrate does not appear to dehydrate at 60 °C. in solutions saturated with sodium sulphite or ammonium chloride. In the study of the NaCl–NH4Cl–H2O system, the data agree with average values obtained from the literature and some discrepancies in the published data have been noted. In the NaCl–Na2SO3–H2O system some anomalous results can be explained on the basis of the existence of solid solutions of the hydrated and anhydrous forms of sodium sulphite and sodium sulphate.

ISSN:0008-4042    

DOI:10.1139/v55-095

出版商:NRC Research Press    

年代:1955

数据来源: NRC

摘要:

In the above quaternary system at 60 °C., besides those representing the four salts at the corners of the Janecke diagram two other saturation areas were found. At 20 °C. there are three, and possibly more than three additional areas. In the course of the present work it was not possible to establish the nature of the solid phases in these additional areas of the quaternary system. However, the data of Lewis and Rivett suggest that at least some of these unknown areas may indicate the presence of different solid solutions of sodium sulphate in sodium sulphite. This quaternary system appears to be a rather complex one and much further work remains to be done in order to complete the knowledge of it at 60 °C. and 20 °C., particularly at the latter temperature.

ISSN:0008-4042    

DOI:10.1139/v55-096

出版商:NRC Research Press    

年代:1955

数据来源: NRC

摘要:

The nature of the intermolecular force field of the nitriles is considered on the basis of the electron orbital structure and charge distribution of the nitrile group. The directional nature of the force field is due to a well-directed lone pair orbital on the N atom, which may be expected to exhibit strong donor properties, and two π-orbitals which may exhibit weak donor properties. Accordingly with good acceptor molecules such as chloroform and hydrogen chloride, simple 1:1 molecular addition compounds should occur. The existence of molecular complexes of this type was confirmed with the aid of binary freezing-point diagrams which were determined for aceto-, propio-, butyro-, and benzo-nitrile with chloroform and hydrogen chloride. The 1:1 association complex was absent, however, in the system acetonitrile–chloroform. This is accounted for by the stronger association occurring in acetonitrile itself, the nature of which is discussed. The structure of the 1:1 molecular complexes is considered. Additional molecular complexes with lower nitrile mole ratios are indicated in the freezing-point diagrams. Of particular interest are the well-defined compounds appearing in the nitrile – hydrogen chloride systems with the composition RCN•5HCl. The possibility that the π-orbitals of the nitrile group may function as donors in these compounds is discussed, and a tentative structure is suggested.

ISSN:0008-4042    

DOI:10.1139/v55-097

出版商:NRC Research Press    

年代:1955

数据来源: NRC

摘要:

The heat of mixing of hydrogen peroxide and water and the heat of vaporization of the mixtures were measured over a wide concentration range at 0 °C. with a Bunsen ice calorimeter and at 26.9° with a diphenyl ether calorimeter. The heat capacities of the solutions were determined between these two temperatures. Similar measurements were carried out on the corresponding deuterium compounds. The heat of decomposition of hydrogen peroxide catalyzed by colloidal platinum was also measured at 26.9° as a function of concentration. Correlation of all the results leads to the following recommended values for the thermochemical properties of the pure peroxides in the liquid state at 25 °C.A number of related functions are given for convenience in recalculating these quantities to other temperatures. Apart from their practical value the new data are of interest in connection with molecular association and hydrogen bonds.

ISSN:0008-4042    

DOI:10.1139/v55-098

出版商:NRC Research Press    

年代:1955

数据来源: NRC

摘要:

The mercury (3P1) photosensitized hydrogenation of ethylene has been studied at room temperature as a function of ethylene concentration, mercury concentration, and light intensity. In addition to combination and disproportionation, ethyl radicals have been shown to take part in the reactionThe conditions favoring this reaction have been established and anomalous values previously found for the ratio of ethane to butane have been explained. The value obtained for the ratio of the rate constants for the disproportionation and combination of ethyl radicals, 0.15 ±.01, is in excellent agreement with the values obtained by other methods. Hexane formation is of some importance at low light intensities and high ethylene concentrations, and is adequately accounted for by the reactions

ISSN:0008-4042    

DOI:10.1139/v55-099

出版商:NRC Research Press    

年代:1955

数据来源: NRC