摘要:

The infrared spectra from 4000–250 cm−1and the laser Raman spectra of NOAsF6, NO2AsF6, N2F3AsF6, F2NOAsF6, NOSbF6, NO2SbF6, N2F3Sb2F11, and F2NOSb2F11are recorded. Eight of the nine fundamentals expected for the N2F3+cation can be observed and are tentatively assigned. The vibrational spectra of the MF5adducts are in agreement with an ionic formulation; however, the mutual exclusion rule for infrared and Raman active vibrations appears to be relaxed and one of the fundamentals v5[F2g] is split into a doublet in almost all cases.

ISSN:0008-4042    

DOI:10.1139/v70-527

出版商:NRC Research Press    

年代:1970

数据来源: NRC

摘要:

CO8AS3O16, the Co analogue of the mineral aerugite, crystallizes in the rhombohedral space groupwith hexagonal unit cell parametersa = 6.046(1) andc = 28.062(8) Å, andZ = 3. The structure has been refined by a full matrix least squares technique using 613 reflections to a finalRvalue of 0.080. The cations are in tetrahedral and octahedral interstices between layers of oxygen atoms nearly showing cubic closest packing. The structure has one third of the As ions in sites of point group symmetrywith a nearly perfect octahedral environment of oxygen atoms. The remaining As ions lie in sites having the point group 3mand showing tetrahedral coordination to oxygen atoms. In the former case the mean As—O bond length is 1.84 Å while in the latter case it is 1.68 Å. The Co ions lie in positions having either2/mormsymmetry with a mean Co—O bond length of 2.13 Å in each case. All the atoms have at least mirror symmetry about them. Some deviation from stoichiometry has been found and may indicate that some of the cobalt has been oxidized.

ISSN:0008-4042    

DOI:10.1139/v70-528

出版商:NRC Research Press    

年代:1970

数据来源: NRC

摘要:

The preparation of 5-nitroacenaphthene (2) using several nitrating agents resulted in a product which was found to be contaminated with 20–30% of the 3-nitro isomeride. Separation was accomplished by t.l.c. and the n.m.r. spectra of the isomers are now reported. A new synthesis of 4,5-dinitronaphthalic anhydride (5) and an improved preparation of the dimethyl and diethyl esters of 4-nitronaphthalic anhydride and5is described. The esters were converted to the corresponding diamino derivatives by high pressure hydrogen–Pd reduction.

ISSN:0008-4042    

DOI:10.1139/v70-529

出版商:NRC Research Press    

年代:1970

数据来源: NRC

摘要:

The cyclo-γ-cyanoethylation of 3β-acetoxy-D-homo-5α-pregn-17a-en-21-al is reported. It is shown that the orientation of the cyanoethylation of 2-cycloalkyl-substituted ethenals does not significantly depend on the ring size of the cycloalkyl substituent. It is further shown that the stereochemistry of the cyclohexadienonitrile obtained by dehydration of the main reaction products seems to be, in the case of a fusion to a six-membered ring, in agreement with Moscowitz' rule relating the helicity of the chromophore to the sign of its Cotton effect, in contradistinction to the situation in the case of a system in which one of the double bonds of the chromophore is exocyclic to a five-membered ring.

ISSN:0008-4042    

DOI:10.1139/v70-530

出版商:NRC Research Press    

年代:1970

数据来源: NRC

摘要:

The structure of the tenth in the series of novel lignans from the heartwood of western red cedar(ThujaplicataDonn) has been determined as 2-(3″,4″-dihydroxy-5″-methoxybenzylidene)-3-(4′-hydroxy-3′-methoxybenzyl)-butyrolactone (γ-thujaplicatene) (1) by spectrometric methods and comparison with synthetic derivative reactions. The discovery of this lignan with a double bond conjugated with an aromatic ring confirms previously suggested biosynthetic routes to the cedar lignans.

ISSN:0008-4042    

DOI:10.1139/v70-531

出版商:NRC Research Press    

年代:1970

数据来源: NRC

摘要:

The synthesis and properties of ether derivatives6a–dof 5-hydroxymethyldeoxyuridine and their corresponding α-anomers7a–dare described. Acid-catalyzed etherification of 5-hydroxymethyluracil (1) gave the corresponding 5-alkoxymethyluracils2a–ein excellent yields. Treatment of compounds2a–ewith trimethylchlorosilane gave bis(trimethylsilyl)pyrimidines3a–ein high yields which, upon condensation with 3,5-di-(O-p-toluoyl)-2-deoxy-D-ribofuranosyl chloride, furnished an anomeric mixture of substituted nucleosides, β-anomers4a–eand a-anomers5(a–e). The nucleosides with β-configuration were the major products in each case and were recovered as crystalline solids in good yields. Deblocking of compounds4a–dby alcoholysis resulted in the corresponding ether derivatives6a–d. From mother liquors, two substituted α-anomers,5a,bwere isolated as crystalline solids in small yields. Compounds7c,dwere obtained from mother liquors after hydrolysis by using preparative t.l.c. The structures were confirmed on the basis of p.m.r. studies, u.v. and i.r. absorption spectra, and elemental analysis. The compounds2a–eand6a–ddid not inhibit thymidylate synthetase at a concentration of 2.5 mM.

ISSN:0008-4042    

DOI:10.1139/v70-532

出版商:NRC Research Press    

年代:1970

数据来源: NRC

摘要:

A relation between the diamagnetic term for a proton bonded to a carbon atom and the linear combination of atomic orbital charges on C and H is established. Proton diamagnetic terms of some vinyl ethers are calculated, and the conformation of ethoxy group in these molecules studied.

ISSN:0008-4042    

DOI:10.1139/v70-533

出版商:NRC Research Press    

年代:1970

数据来源: NRC

摘要:

A number of alloys have been examined microscopically. From these observations, from the equilibrium diagrams of the component binary systems, and from the application of the phase rule, a room temperature isothermal section has been deduced. Three vertical sections through the ternary system have been partially constructed from differential thermal analysis. These data show that invariant planes occur at 143, 148, 241, and 506 °C. From the information obtained from the vertical sections and the room temperature isothermal section, isothermal sections have also been proposed at 143 and 148°. The transformation at the 143 °C invariant plane is a ternary eutectic, at 148° a ternary peritectic, and the other transformations at 241 and 506° are also ternary peritectics.Some evidence indicates that the ξ-phase of Ag–Al system and the γ-phase of Ag–In system link up through the ternary system forming a single phase region, and that such may also be the case with the phases µ and α′ of the systems Ag–Al and Ag–In, respectively. The phases ϵ andof the system Ag–In do not appear to be capable of dissolving aluminum appreciably.

ISSN:0008-4042    

DOI:10.1139/v70-534

出版商:NRC Research Press    

年代:1970

数据来源: NRC

摘要:

The saturation vapor pressures of ten mixtures of the binary systems (1) acetone – chloroform, (2) acetone – carbon tetrachloride, and (3) benzene – carbon tetrachloride have been determined, from 100 to 230° for system1and from 100° up to the highest temperature at which liquid and vapor coexist for systems2and3. The system acetone – chloroform could not be studied at higher temperatures because of decomposition.The gas–liquid critical temperatures of the three binary systems have been determined by the disappearance of meniscus method. The orthobaric compositions of the vapour–liquid equilibria of the binary systems have been measured from 100 to 180° for system1and from 100° to the critical region for systems2and3, using a glass bomb enclosed in a steel bomb.From the vapour–liquid composition curves and the vapor pressure curves at constant temperatures (100, 150, 160, 170, and 180°), the existence of an azeotrope in the system acetone–chloroform at these temperatures, and having a composition of 36.2 mole% acetone at 100°, was confirmed. The composition of the azeotrope shifts towards lower acetone content as the temperature is raised. Azeotropes were not found in the systems acetone – carbon tetrachloride and benzene – carbon tetrachloride, over the ranges of temperature and pressure of this research.The data of the binary systems were treated thermodynamically to yield the liquid phase activity coefficients and, as suggested by Chueh and Prausnitz, the Redlick–Kwong equation was used in a modified form to obtain the fugacity coefficients of components in the vapor phase. Several liquid phase parameters, such as the binary interaction constant, Henry's constant, and dilation constant have been calculated, using the van Laar equation as modified by Chueh and Prausnitz.

ISSN:0008-4042    

DOI:10.1139/v70-535

出版商:NRC Research Press    

年代:1970

数据来源: NRC

摘要:

Tetrahedral, square, square pyramidal, and tetragonally distorted octahedral complexes of copper(II) with the title ligands are characterized by electronic and vibrational spectroscopy (at ambient and low temperature) and magnetism. The infrared spectra are utilized to infer information about the conformation of the ligands in these complexes. The variation in structural types observed is believed to be a consequence of the stereochemical adaptability of these ligands to the electronic demands of the metal ion.

ISSN:0008-4042    

DOI:10.1139/v70-536

出版商:NRC Research Press    

年代:1970

数据来源: NRC