摘要:

A strong correlation is found between the electronegativity,Ex, and the three proton coupling constant of the vinyl group in over a hundred compounds of the type CH2 = CHX. This correlation extends over the rangeEx = 4 to 1 and over the rangeJgem + Jcis + Jtrans = 14 to 50 c.p.s. Simple implications and some useful applications of this correlation are discussed.

ISSN:0008-4042    

DOI:10.1139/v62-001

出版商:NRC Research Press    

年代:1962

数据来源: NRC

摘要:

The rate constants for the reactions of C2H4and NH3are determined by termination of the reactions in the gas phase after different times of reaction. The average value for the rate constant of the N atom–C2H4reaction at 150 °C is 1.8 × 1010 cc mole−1sec−1, when the initial N-atom concentration is determined from the maximum production of HCN. The average value for the rate constant for the over-all reaction of NH3with excited nitrogen molecules, at 104 °C in the "poisoned" system, and 83 °C in the "unpoisoned" system, for low initial flow rates of NH3, or short reaction time, is 2.2 × 1010 cc mole−1sec−1. The decrease in value of this rate constant at higher initial flow rates of NH3and longer reaction times in the "poisoned" system indicates that the species responsible for NH3decomposition is generated during the decay of N atoms in the presence of NH3. The value for the NH3reaction is discussed in terms of energy transfer.

ISSN:0008-4042    

DOI:10.1139/v62-002

出版商:NRC Research Press    

年代:1962

数据来源: NRC

摘要:

The hydrolysis of zirconium alkoxides with secondary or tertiary alkoxide groups Zr(OR)4, where R = Pri, Bus, Bul, and Amt, has been studied. The relatively low polymers formed by the metal oxide alkoxides have been interpreted on the basis of structural models involving octahedrally 6-co-ordinated zirconium.

ISSN:0008-4042    

DOI:10.1139/v62-003

出版商:NRC Research Press    

年代:1962

数据来源: NRC

摘要:

An aldotetraouronic acid has been isolated by enzymic hydrolysis of a 4-O-methylglucuronoxylan from the wood of white birch. It has been shown to beO-4-O-methyl-α-D-glucosyluronic acid-(1 → 2)-O-β-D-xylopyranosyl-(1 → 4)-O-β-D-xylosyl-(1 → 4)D-xylose.

ISSN:0008-4042    

DOI:10.1139/v62-004

出版商:NRC Research Press    

年代:1962

数据来源: NRC

摘要:

The heats of reaction of normal-, iso-, and secondary-butyl alcohols reacting with phenyl isocyanate, the three tolyl isocyanates, and 2,4-tolylene diisocyanate were measured at 25 °C, using a differential calorimeter of the Tian–Calvet type. The results are interpreted in terms of substituent effects.From bond energy considerations the heats of formation of phenyl isocyanate and tolyl isocyanate have been estimated.

ISSN:0008-4042    

DOI:10.1139/v62-005

出版商:NRC Research Press    

年代:1962

数据来源: NRC

摘要:

The kinetics of 12 alcohol–isocyanate reactions have been studied at a series of temperatures. The reactions were studied by a calorimetric technique, as well as the usual analytical method. The results are shown to be in agreement with a mechanism previously proposed by Baker. Certain objections to Baker's mechanism are discussed.

ISSN:0008-4042    

DOI:10.1139/v62-006

出版商:NRC Research Press    

年代:1962

数据来源: NRC

摘要:

The system silver–indium–gallium has been investigated by the standard techniques of thermal analysis, photomicrography, X-ray photography, and hardness testing. The smallness of the heat effects made the determination of the liquid surface indefinite, at least in the low-temperature region where the pronounced tendency for metastable liquid phase to persist rendered all measurements indefinite, but the room-temperature isotherm was determined with more certainty. Owing to the complexity of the diagram there is still some uncertainty about some areas.A one-phase area (α phase) exists in the silver-rich region of the ternary isotherm, representing the solid solubility of indium and gallium in silver. The silver-rich intermediate phase in the system silver–indium, δ, is shown to have a close-packed hexagonal structure and its lattice constants have been determined. The structure of γ, the corresponding phase in the system silver–gallium is more complex and was not determined. δ and γ phases do not form a continuous one-phase region.Ternary peritectics exist at 623 °C and 600 °C (approximately). It is possible that two peritectics exist at the latter temperature, in close proximity.The ternary eutectic lies at 14.5 °C and has an approximate composition of 2% silver, 24% indium, and 74% gallium.

ISSN:0008-4042    

DOI:10.1139/v62-007

出版商:NRC Research Press    

年代:1962

数据来源: NRC

摘要:

The reaction of 1:1 tertiary arsine mercuric iodide complexes with iodomethane gives arsonium derivatives of triiodomercury (II).

ISSN:0008-4042    

DOI:10.1139/v62-008

出版商:NRC Research Press    

年代:1962

数据来源: NRC

摘要:

Lichenin, the poly-β-D-glucan ofCetrariaislandica(Iceland moss), is found by enzymic degradation to differ in fine structure from the poly-β-D-glucans of cereal grains. Enzymolysis has been carried out with a cellulase and a laminarinase preparation, the former yielding mainlyO-β-D-glucopyranosyl-(1 → 3)-O-β-D-glucopyranosyl-(1 → 4)-α-D-glucose, and the latter mainlyO-β-D-glucopyranosyl-(1 → 4)-O-β-D-glucopyranosyl-(1 → 3)-α-D-glucose. Di-and tetra-saccharides are produced in small proportions. Steric aspects of these enzymic degradations are discussed. The basis constitution of lichenin is represented by a tetrameric unit in which two adjacent (1 → 4) linkages alternate with an isolated (1 → 3) linkage; occasionally four consecutive monomers are linked by (1 → 4) bonds. The glucans of cereal origin differ mainly in possessing a higher proportion of the latter structural sequence. Despite their close chemical similarity to cellulose, all of these glucans are soluble, a property that appears to be related to the even distribution of β-(1 → 3) bonds along the chains, with a resulting disruption of linear orientation effects.

ISSN:0008-4042    

DOI:10.1139/v62-009

出版商:NRC Research Press    

年代:1962

数据来源: NRC

摘要:

The irradiation product of acenaphthene and benzil described by Oliveri-Mandalà, Giacalone, and Deleo has been shown to have the structure (III) and not that of the cyclobutane derivative (II, R = H) originally proposed. The main product obtained by the action of acetic anhydride and sulphuric acid on (III) is not the result of an acetylation process, but is the sultone (IV).

ISSN:0008-4042    

DOI:10.1139/v62-010

出版商:NRC Research Press    

年代:1962

数据来源: NRC