摘要:

The infrared spectra of [Ru(NH3)5(CH3)2SO]X2, [Ru(ND3)5(CH3)2SO]X2, [Ru(NH3)5(CD3)2SO]X2, and [Ru(ND3)5(CD3)2SO]X2where X = PF6−have been examined in detail between 4000–200 cm−1. These data, together with the1H n.m.r. spectrum of [Ru(NH3)5(CH3)2SO](PF6)2in D2O, suggest that dimethyl sulfoxide is bonded to rutheniumviathe sulfur atom in spite of the fact that the νsofrequency is not very different from that observed for uncoordinated dimethyl sulfoxide.

ISSN:0008-4042    

DOI:10.1139/v71-599

出版商:NRC Research Press    

年代:1971

数据来源: NRC

摘要:

The crystal structure of dimethylsulfoxidepentammineruthenium(II) hexafluorophosphate ( [Ru(NH3)5DMSO]2+2PF6−) has been determined from three-dimensional X-ray data. The crystals are monoclinic, space groupP21/c, with four formula units in a unit cell of dimensionsa = 8.805(2),b = 17.335(5),c = 12.373(2) Å, β = 94.24(2)°. The structure has been refined by full matrix least-squares methods to a final residualRof 0.054 for 1987 reflections greater than 3σ. The DMSO ligand coordinates through the sulfur atom and the S—O bond distance (1.527(7) Å) is considerably longer than that found for other sulfur–donor complexes of the ligand. The Ru—S bond distance is 2.188(3) Å.

ISSN:0008-4042    

DOI:10.1139/v71-600

出版商:NRC Research Press    

年代:1971

数据来源: NRC

摘要:

Photochemical reactions of 1-o-nitrophenyl-4-phenyl-1,3-butadiene, 1,4-di-o-nitrophenyl-1,3-butadiene, 1-o-nitrophenyl-6-phenyl-1,3,5-hexatriene, and 1,6-di-o-nitrophenyl-1,3,5-hexatriene all gave the appropriate 2-substituted isatogen. The relatedm- andp-nitrophenyl polyenes were inert to the irradiation conditions. A six-membered ring isatogen-like compound, 2-phenyl-3-oxo-benzo[d,e]quinoline-N-oxide was prepared by irradiation of 1-[1′-(8′-nitronaphthyl)]-2-phenylacetylene. A seven-membered ring isatogen-like compound, 6-phenyl-7-oxo-dibenzo[b,d]azepine-N-oxide, was prepared by heating 1-[2-(2′-nitrobiphenyl)]-2-phenylacetylene.

ISSN:0008-4042    

DOI:10.1139/v71-601

出版商:NRC Research Press    

年代:1971

数据来源: NRC

摘要:

The thermal fragmentation of salicylaldehyde was studied from two aspects. Firstly, the temperature dependence of the intensity of the thermolytic fragment molecular ions was observed at 11 eV in the effluent from a helium flow thermal reactor attached through a helium separator to the ion source of a mass spectrometer. Secondly, the products of the thermolysis on a semi-preparative scale under trapping conditions were determined by coupled gas chromatographic – mass spectrometric analysis.The title compound is the major primary thermal fragment in this study and was trapped with methanol as carboxymethylcyclopentadiene.

ISSN:0008-4042    

DOI:10.1139/v71-602

出版商:NRC Research Press    

年代:1971

数据来源: NRC

摘要:

The isolation of a series of dilignol glycosides from the leaves of western red cedar trees is described. The structure of the first member of this series was determined by chemical degradation reactions and n.m.r. and mass spectra of its derivatives. It is 1-(3′-methoxy-4′-hydroxyphenyl)-2-O-1″-[2″-hydroxy-4″-(propane-3′′′-O-α-L-rhamnopyranoside)phenyl]-propane-1,3-diol (1). The novel features of this compound are discussed, together with its possible roles in the leaves.

ISSN:0008-4042    

DOI:10.1139/v71-603

出版商:NRC Research Press    

年代:1971

数据来源: NRC

摘要:

The limiting equivalent conductivities, Λ0, of the acids, HB(OOCCF3)4and HSbF5(OOCCF3), and the salt, CsB(OOCCF3)4, have been measured and found to be 22.34, 18.77, and 48.56 ohm−1cm2equiv−1, respectively. Calculation of the solvent autoprotolysis constant gives the value: 4 × 10−14 mol2l−2. The salt, CsB(OOCCF3)4is readily prepared but the parent acid, B(OOCCF3)3could not be isolated.

ISSN:0008-4042    

DOI:10.1139/v71-604

出版商:NRC Research Press    

年代:1971

数据来源: NRC

摘要:

The dielectric constants at 0.1 MHz ofn-, iso-, sec-, andt-butanol andn-decanol each at nine concentrations in the range 0.2–1.0 mole fraction in cyclohexane,p-dioxane, mesitylene, andp-xylene have been measured at 25 °C. Apparent dipole moments and Kirkwood correlation factors have been evaluated. Cyclohexane is regarded as an inert solvent in which alcohol self association alone is considered responsible for the anomalous electric polarization. The other three solvents have a disassociating effect which increasesp-xylene ≤ mesitylene < p-dioxane. At the lowest concentrations the alcohols have larger apparent dipole moments in these solvents than in cyclohexane. The opposite tends to be the case for the more concentrated alcohol solutions. The results suggest that alcohol association is initially dominated by the formation of small, weakly polar multimers, and eventually larger highly polar multimers predominate.

ISSN:0008-4042    

DOI:10.1139/v71-605

出版商:NRC Research Press    

年代:1971

数据来源: NRC

摘要:

Carboxylated polyphthalamide microcapsules were prepared by utilizing the interfacial polycondensation reaction between basic amino acids in water andp-phthaloyl dichloride in organic solvent. The yield of the microcapsules was found to be dependent on the concentration of emulsifier in the organic solvent and temperature. The microcapsules moved towards the anode in an electric field irrespective of the pHof the medium owing to the presence of carboxylic groups in the membranes. Cation binding experiments indicated an increasing order, Al3+ > Mg2+ > Cs+ > K+, NH4+, Na+ > Li+, for the binding of these cations to the microcapsules.

ISSN:0008-4042    

DOI:10.1139/v71-606

出版商:NRC Research Press    

年代:1971

数据来源: NRC

摘要:

The p.m.r. spectra of 2-chloroaniline and 2-chloroaniline-15N in benzene and toluene solutions are analyzed at 60 and 100 MHz under conditions where the amino protons are exchanging intermolecularly and also where they are not exchanging. The spectrum of 2-chloroaniline-H15ND in the absence of amino proton exchange is observed between −48 and 80 °C. In all situations fast rotation about the C—N bond evidently occurs. Long-range couplings of the amino protons to all ring protons are observed and their signs are determined. The nonplanarity of the amino group is discussed in terms of the long-range couplings, of the one-bond15N–H couplings, and of the two-bond H–H couplings in the amino group. The signs and magnitudes of the coupling constants between the ring protons and15N are also determined.

ISSN:0008-4042    

DOI:10.1139/v71-607

出版商:NRC Research Press    

年代:1971

数据来源: NRC

摘要:

The effect of 3α- and 3β-hydroxy, 3α- and 3β-acetoxy, 3-ethylene acetal, and 3α-methoxy derivatives of 5-cholestene on the addition of the Simmons–Smith reagent to the steroidal 5,6-double bond has been investigated. Reaction occurred only withepi-cholesterol to yield chiefly 3α-hydroxy-5,6α-cyclopropano-5α-cholestane. The 3α-ethyl ether, 3α-acetate, and a dialkoxymethane have been identified as byproducts. The p.m.r. and mass spectral data are given.

ISSN:0008-4042    

DOI:10.1139/v71-608

出版商:NRC Research Press    

年代:1971

数据来源: NRC