摘要:

At room temperature Na4P2O7crystallizes in the orthorhombic space groupP212121witha = 9.367(5),b = 5.390(2),c = 13.480(8) Å, andz = 4. The structure was refined by full-matrix least-squares using 1337 reflections measured with a Syntex Automatic diffractometer. The finalRvalue is 0.022. The anion has nearly an eclipsed configuration with a P—O—P angle of 127.5(1)°. The two bridging P—O bond lengths are 1.631(2) and 1.642(2) Å with terminal P—O bond lengths averages of 1.512 and 1.514 Å on either side of the anion. Two of the four Na+ions are coordinated to five oxygen atoms while the remainder are coordinated to six oxygen atoms. The structure contains chains of cations with four nearly collinear Na+per cell paralleling thecaxis. These are surrounded by six anions with the bridging oxygen atoms lying approximately at the corners of an octahedron with the P—P vector of the anion also paralleling thecaxis. Adjacent anions along thecaxis are separated by a pair of Na+ions.

ISSN:0008-4042    

DOI:10.1139/v72-406

出版商:NRC Research Press    

年代:1972

数据来源: NRC

摘要:

A simplified mechanism is presented for excitation of ground state CN(X2Σ+) formed from carbonaceous impurity in flowing N2subjected to a microwave discharge. Analysis of absolute intensity data from spectrometer recordings of CN(B2Σ+ → X2Σ+) violet band emission enabled order of magnitude estimates of rate constants for CN(X2Σ+) excitation by energy transfer from vibrationally excited ground state nitrogen,and formation of electronically excited NCN* in a three body reactionEnergy transfer fromis shown to be a minor source of excitation of CN to radiative levels. N2(A) is a source of vibrationally excited ground state nitrogen,which in turn excites CN. Vibrational population profiles under all conditions in this work are shown to be primarily a function ofEvidence for the participation of theA2Π state of CN is shown in the population maxima at ν = 4 and 10 of theB2Σ+state.

ISSN:0008-4042    

DOI:10.1139/v72-407

出版商:NRC Research Press    

年代:1972

数据来源: NRC

摘要:

Calorimetric heats of adsorption of sulfur dioxide at surface coverages from 0.1 to 3.5 µmol m−2have been measured on a series of γ-aluminas heat-treated at 500, 700, and 900 °C. Essential features of the structures of the adsorbents have been characterized by analysis of nitrogen adsorption/desorption isotherms and by both direct and indirect electron microscopy.Heats of adsorption of 423 °K for adsorbed amounts of 0.1 µmol m−2were 48.0, 59.0, and 85.0 kcal mol−1for the 500, 700 and 900 °C samples, respectively. The values for the 500 and 700 °C samples fell rapidly with increasing coverage to around 19.0 kcal mol−1at 3.2 to 3.3 µmol m−2, while the values for the 900 °C sample decreased slowly to 15.0 kcal mol−1at the same coverage.The pores had circular cross sections and mean diameters of 25, 35, and 40 Å were observed for the 500, 700, and 900 °C samples, respectively. Examination of carbon/platinum replicas of the surface showed the presence of agglomerates of spherical particles approximately 400 Å in diameter.It is proposed that the high initial heats on the 500 and 700 °C samples are due to the formation of a sulfate-like species on the surface and at higher coverage extensive hydrogen bonding is present. The very high heats obtained on the 900 °C sample are believed to be due to interactions with high-energy defect centers in the oxide which were created by heat treatment.

ISSN:0008-4042    

DOI:10.1139/v72-408

出版商:NRC Research Press    

年代:1972

数据来源: NRC

摘要:

The reaction of diazotized anthranilate esters with primary aliphatic amines has been reinvestigated, giving rise to a new series of comparatively unstable 1-alkyl-3-(o-carbalkoxyphenyl)-triazenes (3). The structures of the products have been confirmed by spectroscopic analysis, molecular ion mass measurements, and from the results of chemical degradation. The spectroscopic properties indicate a preference for the tautomer in which the azo-group is non-conjugated with the benzene ring, Ar•NH•N=N•R; this hypothesis is partly supported by the chemical degradation. In general, the triazenes (3) break down by fragmentation of the triazene moiety to give anthranilic acid derivatives, or undergo cyclization to 3-alkyltriazinones (1). The alkyltriazinones are also obtained directly in the coupling reaction of the diazonium salt with the amine in the presence of a sodium acetate buffer. The cyclization is quantitative when catalyzed by activity V alumina; a wide variation in the product distribution obtained by reaction with different types of alumina has been observed, and the correlation of these results with the known surface structure of alumina is discussed. Finally, an explanation is offered for the difference between the results of the present work and previous reports.

ISSN:0008-4042    

DOI:10.1139/v72-409

出版商:NRC Research Press    

年代:1972

数据来源: NRC

摘要:

The kinetic study of the reduction of styrene ozonide by various phosphites suggests the formation of an oxyphosphorane intermediate. A reevaluation of the mechanism of ozonolysis of selected oxyphosphoranes having a C—C double bond is presented.

ISSN:0008-4042    

DOI:10.1139/v72-410

出版商:NRC Research Press    

年代:1972

数据来源: NRC

摘要:

The bis(β-ketoenolates)nickel(II) adducts of piperidine, piperazine, methylpiperazine, and morpholine are isolated in the solid state and investigated by magnetic measurements and electronic and i.r. spectra. Magnetic measurements and electronic spectra give evidence oftrans-octahedral configuration while i.r. spectra show that the amines are coordinated to the nickel atom towards the nitrogen atom. The new band found in the range 385–300 cm−1for all complexes can be assigned to Ni—N vibration. In the Ni(DBM)2•4B (B = methylpiperazine and morpholine) the two additional bases are not coordinated to the metal atom.

ISSN:0008-4042    

DOI:10.1139/v72-411

出版商:NRC Research Press    

年代:1972

数据来源: NRC

摘要:

The action of a five-fold excess of potassium hydroxide in methanol on 1,1,1-trichloro-2-penten-4-one (1), 1,1,1-trichloro-6-methyl-2-hepten-4-one (5), and 1,1,1-trichloro-6,6-dimethyl-2-hepten-4-one (9) gives rise to the potassium salt of 5-chloro-2,4-pentadienoic acid (2), the potassium salt and methyl ester of 5-chloro-6-methyl-2,4-heptadienoic acid (7), and the methyl ester of 5-chloro-6,6-dimethyl-2,4-heptadienoic acid (10), respectively.When the same reaction is performed with an equimolar amount of base,1is converted into methyl 5-chloro-2,4-pentadienoate (3) as well as 1,1,1-trichloro-2-methoxy-4-pentanone (4); the latter compound (4) is shown to be a true intermediate in the formation of3.Neither 1,1,1-trichloro-5-methyl-2-hexen-4-one (11) nor 1,1,1-trichloro-5-ethyl-2-hepten-4-one (14) yields the expected dienoic acid or ester when treated with an equimolar amount of potassium hydroxide. Instead, alkaline methanolysis of11leads to the formation of a mixture of 1,1,1-trichloro-2-methoxy-5-methyl-4-hexanone (12) and 1,1-dichloro-2,5-dimethoxy-5-methyl-4-hexanone (13), whereas14gives predominantly 1,1,1-trichloro-2-methoxy-5-ethyl-4-heptanone (15) and traces of 1,1-dichloro-2,5-dimethoxy-5-ethyl-4-heptanone (16).On the basis of these observations, a mechanism is proposed for the formation of2,7, and10which requires the presence of two geminal α-hydrogen atoms in the olefinic starting material.

ISSN:0008-4042    

DOI:10.1139/v72-412

出版商:NRC Research Press    

年代:1972

数据来源: NRC

摘要:

A variety ofN-methyl andN-phenylisothiazolium salts has been synthesized and treated with sulfur in boiling pyridine. The products have been examined by chromatography and their structures determined. While 5-unsubstituted isothiazolium salts appear to give the corresponding isothiazoline-5-thiones, 3-unsubstituted salts give either the corresponding isothiazoline-3-thiones if the nitrogen is alkyl substituted, or 1,2-dithiole-3-imines if the nitrogen is aryl substituted.N-Alkyl compounds also give dealkylated products, and dithiolethiones are also found. The initial stages in the reaction appear to involve deprotonation of the isothiazolium salt.

ISSN:0008-4042    

DOI:10.1139/v72-413

出版商:NRC Research Press    

年代:1972

数据来源: NRC

摘要:

A complete analysis (8-spins) is given of the p.m.r. spectrum of aniline-15N, of the spectra of some haloanilines-15N and of 2-aminoacetophenone-15N. Intermolecular exchange of the amino protons is slow enough for observation of their spin–spin coupling to the ring protons. The magnitudes of the coupling constants between amino protons and15N or ring protons are a measure of the geometry of the amino group. This is not true of the couplings between15N and the ring protons. Long-range couplings computed in the CNDO/2 and INDO approximations of molecular orbital theory show points of agreement with experiment. For example, their signs and magnitudes are consistent with a nonplanar but not with a planar conformation of aniline. Couplings from15N to ring protons are also computed for nitrobenzene.

ISSN:0008-4042    

DOI:10.1139/v72-414

出版商:NRC Research Press    

年代:1972

数据来源: NRC

摘要:

The temperature and pressure dependence of the209Bi nuclear quadrupole coupling constant and asymmetry parameter in solid BiCl3have been measured near room temperature. It is not possible to account for the results on the basis of the conventional theory in which the field gradient parameters depend only on the crystal volume.

ISSN:0008-4042    

DOI:10.1139/v72-415

出版商:NRC Research Press    

年代:1972

数据来源: NRC