摘要:

Treatment of chlorophyllaor methyl chlorophyllideawith potassium permanganate effected oxidation of the 2-vinyl group without concomitant oxidation of the cyclopentanone ring. One of the products obtained was of especial interest because its visible absorption spectrum was identical with that of a previously known, but chemically uncharacterized, pigment—chlorophylld. The preparation and identification of this oxidation product as 2-desvinyl-2-formyl-chlorophyll-ais given and its probable identity with chlorophylldis discussed in detail.

ISSN:0008-4042    

DOI:10.1139/v59-069

出版商:NRC Research Press    

年代:1959

数据来源: NRC

摘要:

The main features of a mass spectrometer in which the ionization chamber can be cooled in a controlled way to the temperature of liquid nitrogen are given. Atoms or free radicals, formed in a heterogeneous quartz reactor that can be heated to 1000 °C, effuse through a small hole in the wall of this reactor and enter directly into the ionization chamber. With this instrument it is possible to study the various ways in which unstable particles disappear during collisions on a metallic surface maintained at low and controlled temperatures.The collision efficiency "b" of iodine atoms to form iodine molecules was found to vary between 1.7 × 10−3and 4 × 10−3on a surface at a temperature between +40 °C and −25 °C. Between−25 °C and −60 °C, the atoms are condensed at the same time as the iodine molecules; at lower temperatures, they are more "volatile" than iodine molecules, most of them colliding on the molecules of condensed iodine without reacting.

ISSN:0008-4042    

DOI:10.1139/v59-070

出版商:NRC Research Press    

年代:1959

数据来源: NRC

摘要:

The decomposition of thionyl chloride in the presence of ammonia was found to give sulphur, ammonium sulphate, and ammonium sulphamate besides ammonium chloride. Heating urea and the reaction products of thionyl chloride and ammonia under pressure yielded guanidine hydrochloride and melamine, under different conditions of temperature, time, and pressure. Under similar conditions, benzamide was transformed into benzonitrile, and phenylurea into aniline or aniline black and diphenylurea, guanidine being absent.

ISSN:0008-4042    

DOI:10.1139/v59-071

出版商:NRC Research Press    

年代:1959

数据来源: NRC

摘要:

An improved method for the preparation of dialkyl phosphoroisothiocyanatidates (II) is given. These compounds (II) are labile and decompose under the influence of heat and catalysts to the corresponding alkyl thiocyanates (III). In the presence of water they hydrolyze to dialkyl hydrogenphosphates (VI) in high yield. A series of thiourea derivatives (VII) has been prepared from II and amines.

ISSN:0008-4042    

DOI:10.1139/v59-072

出版商:NRC Research Press    

年代:1959

数据来源: NRC

摘要:

Reactions of oxygen activated by electrical discharge with butene-1 have been studied in a "spherical diffusion" reaction zone. When small concentrations of oxygen are passed through the discharge tube in helium as the carrier gas, and the concentration of butene-1 in the reaction zone is sufficiently high, the observed products are entirely explainable by an interaction of the ground-state oxygen atoms with butene-1. With large deviations from these conditions considerable complexities arise, and under some conditions α-butylene ozonide and its decomposition products become important and the products are then explainable without any significant participation of oxygen atoms in the process.

ISSN:0008-4042    

DOI:10.1139/v59-073

出版商:NRC Research Press    

年代:1959

数据来源: NRC

摘要:

The transformation of 1,5-dioxodecalin into 1,5-diphenylnaphthalene is described.

ISSN:0008-4042    

DOI:10.1139/v59-074

出版商:NRC Research Press    

年代:1959

数据来源: NRC

摘要:

The rate of adsorption of hydrogen on Ru–Al2O3has been studied at four temperatures from 100 to 257 °C at pressures from 15 to 80 cm DBP. The Elovich parameters α andafor these data have been calculated and their temperature and pressure dependencies found. It is shown that, regardless of temperature, the amount adsorbed at a given time and the parameters α and logaα show a dependence on the initial pressure which is different above and below 25 cm DBP indicating different types of adsorption. The temperature dependencies yield an energy of activation for the initial rate of the high pressure chemisorption of 17.7 kcal mole−1which is independent of the pressure. SimilarEvalues below 25 cm increase with a decrease in pressure. Four runs showed a very slow nitrogen adsorption on the same surface, raising the question of an enhancement of the adsorption of one gas by traces of another.

ISSN:0008-4042    

DOI:10.1139/v59-075

出版商:NRC Research Press    

年代:1959

数据来源: NRC

摘要:

The infrared and Raman spectra of the naphthalene-α-d4molecule have been obtained. The spectra of thed0molecule have also been repeated and for the most part previous measurements have been confirmed. Together with the literature data for the naphthalene-d8molecule, a complete assignment has been presented for all three molecules. It is recognized that the assignment is not definitive, although satisfactory agreement with the requirements of the band polarizations and contours, as well as product and sum rules, has been obtained. The calculated and observed values for the heat capacity and entropy are also in good agreement.

ISSN:0008-4042    

DOI:10.1139/v59-076

出版商:NRC Research Press    

年代:1959

数据来源: NRC

摘要:

The ultraviolet absorption spectra of 5-(substituted)amino-1,2,3,4-thiatriazoles and the corresponding isomeric 1-substituted-tetrazoline-5-thiones have been studied. The spectra and the dipole moments of the 5-(substituted)amino-1,2,3,4-thiatriazoles eliminate the possibility of meso-ionic structures for these compounds. The dipole moments of 5-amino-, 5-methylamino-, and 5-dimethylamino-1,2,3,4-thiatriazole were all high but approximately of the same value (5.77 to 5.84 D). This suggests that the amino thiatriazoles are best represented by conventional covalent structures with significant ionic resonance contributions. The thiatriazole ring system exhibits a characteristic absorption maximum at 250–255 mμ and an electron-withdrawing effect approximately equal to the tetrazolyl ring system. The tetrazolinethionolyl ring system is similarly electron-withdrawing. The relative acidities of the 1-substituted-tetrazoline-5-thiones and the 5-alkylmercaptotetrazoles have also been studied and the results support the observations made on the basis of their ultraviolet absorption spectra.

ISSN:0008-4042    

DOI:10.1139/v59-077

出版商:NRC Research Press    

年代:1959

数据来源: NRC

摘要:

Tri-O-tosyl sucrose was synthesized by the action ofp-tolylsulphonyl chloride upon sucrose in pyridine, and the tosyl groups were shown by methylation to be mainly (84%) located on the three primary hydroxyl groups.

ISSN:0008-4042    

DOI:10.1139/v59-078

出版商:NRC Research Press    

年代:1959

数据来源: NRC