摘要:

Two new compounds [NH2(C6H5)2PNP(C6H5)2NH2]2[CoCl4] and [NH2(C6H5)2PNP(C6H5)2NH2][CoCl4]CH2Cl2have been isolated, and characterized by spectrometry, as examples of the general series of quaternary amine transition metal chloride salts. Three other compounds containing the same cations, with empirical formulae, CuP2N3C25H32OCl3(1), CuP2N3C24H28Cl3(2), and Cu3P4N6C50H64O2Cl8(3) have been isolated and studied by spectrometry. The formulae [NH2(C6H5)2PNP(C6H5)2NH2]2[Cu2Cl6] and [NH2(C6H5)2PNP(C6H5)2NH2]2[Cu2Cl6]. 2CH3OH are proposed for (2) and (1) by comparison with the cobalt compounds, and interpretation of the electronic structure. These compounds were produced during attempts to synthesize mixed ring compounds of (PN) and (SN) units.

ISSN:0008-4042    

DOI:10.1139/v72-011

出版商:NRC Research Press    

年代:1972

数据来源: NRC

摘要:

Total hydrogen yields and their isotopic ratios have been measured in the single pulse, high dose rate radiolysis of H2O–D2O mixtures and acidic, basic, and nitrous oxide solutions. The yield from D2O is ~11% lower than in H2O at 7 × 1027 eV g−1s−1. In acid solutions the yields from H2O and D2O are the same within 5%. This yield,G(H2) = 1.15 ± 0.05 has been used to derive a value ofkH+OH = 2.5 ± 0.3 × 1010 M−1s−1.Using the literature values for primary yield data and for the reaction rate constants, values of α have been determined for the various hydrogen forming processes by computer calculation. We obtain values for hydrogen formation of αspur = 2.1 ± 0.1, αe+e = 6.0 ± 0.1, αH+H(effective) = 3.2 ± 0.1, and αe+H(effective) = 1.3 ± 0.2. Detailed consideration of the mechanisms involved suggest that there are little or no isotopic preferences in H + H and e + H reactions.

ISSN:0008-4042    

DOI:10.1139/v72-012

出版商:NRC Research Press    

年代:1972

数据来源: NRC

摘要:

The crystal and molecular structure of 3-chloro-3-deoxy-1,2;5,6-di-O-isopropylidene-β-D-idose has been determined from three dimensional X-ray data collected by counter methods. The structure was refined by full-matrix least-squares techniques to a conventionalRfactor of 5.7% for the 817 observed reflections. The compound crystallizes in the orthorhombic space groupP212121with four molecules in a cell of dimensionsa = 9.744(6),b = 26.76(2),c = 5.403(3) Å.The structure analysis has served to confirm the site of halogenation and that it occurs stereospecifically. The conformation of the furan ring is an envelope arrangement with C(4) displaced from the mean plane.

ISSN:0008-4042    

DOI:10.1139/v72-013

出版商:NRC Research Press    

年代:1972

数据来源: NRC

摘要:

Dielectric constants and losses of 1-propanol, 2-propen-1-ol, and 2-propyn-1-ol inp-xylene, and 1-propanol and 2-propen-1-ol in cyclohexane have been measured at up to 10 frequencies in the range 1–145 GHz at 25 °C. The low frequency dielectric constants have also been measured at 2 MHz. An analysis in terms of two relaxation times has been obtained for each system. The short relaxation times are relatively independent of the alcohol, its concentration, and the solvent. Conversely, the longer relaxation times lengthen with increased alcohol concentration, lengthen in the order 2-propyn-1-ol, 2-propen-1-ol, 1-propyn-1-ol and are considerably shorter inp-xylene than in cyclohexane.

ISSN:0008-4042    

DOI:10.1139/v72-014

出版商:NRC Research Press    

年代:1972

数据来源: NRC

摘要:

The n.m.r. spectral analysis utilising solvent- and Eu(DPM)3-induced chemical shifts demonstrates that the reaction ofN-bromosuccinimide with the methyl enol ethers of cyclohexane-1,3-dione and dimedone leads to bromine substitution at the carbon atom allylic to the olefinic bond, and not at the olefinic site or α to carbonyl, respectively, as previously claimed.

ISSN:0008-4042    

DOI:10.1139/v72-015

出版商:NRC Research Press    

年代:1972

数据来源: NRC

摘要:

Grandiflorenic acid is determined to be structure2, (−)-kaura-9(11),16-dien-19-oic acid.

ISSN:0008-4042    

DOI:10.1139/v72-016

出版商:NRC Research Press    

年代:1972

数据来源: NRC

摘要:

The aromatization of α-pinene in the vapor phase over chromia gel and chromia–alumina catalysts prepared from aluminas of different acidity has been studied. The acidity of alumina support has a remarkable influence on the composition of the aromatics resulting from the dehydrogenation of α-pinene. Over weakly acidic chromia–alumina doped with 1% sodium catalyst, α-pinene is aromatized top-cymene, 1,2,4- and 1,2,3-trimethylbenzenes with traces of toluene and xylenes, whereas over the strongly acidic chromia – pure alumina and chromia–alumina containing 5% HF catalysts it gives considerable amount ofm-cymene, toluene, and tetramethylbenzenes. A satisfactory mechanism to explain the formation of these compounds is offered.

ISSN:0008-4042    

DOI:10.1139/v72-017

出版商:NRC Research Press    

年代:1972

数据来源: NRC

摘要:

Hydrogen–deuterium exchange in tricarbonylchromium complexes of anisole, ethylbenzoate, andN,N-dimethylaniline has been studied for solutions in ethanol-O-d1, containing sodium ethoxide. The extent of deuteration has been estimated mass spectroscopically and the position of deuteration by n.m.r. spectroscopy. In this kinetically controlled reaction ortho-substitution has been found to be predominantly preferred in case of anisole complex, whereas random substitution was observed (n.m.r.) for ethylbenzoate complex. The results are interpreted in terms of chelative, inductive, mesomeric, and steric effects of the substituents.

ISSN:0008-4042    

DOI:10.1139/v72-018

出版商:NRC Research Press    

年代:1972

数据来源: NRC

摘要:

The results of a complete analysis of the proton spectra of altersolanol B acetonide indicate that this compound exists preferentially in the half-chair conformation corresponding to that favored by the parent pigment in the solid state, as shown by previous X-ray studies. In contrast, the triacetate derivative apparently adopts the alternative half-chair conformation.

ISSN:0008-4042    

DOI:10.1139/v72-019

出版商:NRC Research Press    

年代:1972

数据来源: NRC

摘要:

The piezogravimetric method has been used to study the adsorption of dimethyl and trimethylchlorosilanes on quartz crystal surfaces by varying the modes of treatment. The nature of the resulting low-energy surfaces has been discussed in the light of the extent of adsorption ofn-hexane and water, calculated at different relative pressures, from their isotherms. The results obtained permit the conclusion that after the adsorption of silanes at 240 °C, the modified surface may be described as close-packed methyl surface, impenetrable ton-alkane and water vapour.

ISSN:0008-4042    

DOI:10.1139/v72-020

出版商:NRC Research Press    

年代:1972

数据来源: NRC