摘要:

Mössbauer parameters for triphenyltin chloride and a number of its adducts with oxygen-donating Lewis bases are reported. The isomer shifts for all the compounds reported are constant within experimental error (1.29 ± 0.03 mm s−1, relative to SnO2). An approximate correlation between quadrupole splitting and the shift in element–oxygen stretching frequency between neat and complexed base is noted. This suggests that in general for these adducts, larger quadrupole splittings are associated with stronger complexes.

ISSN:0008-4042    

DOI:10.1139/v70-011

出版商:NRC Research Press    

年代:1970

数据来源: NRC

摘要:

Tetrakis(methyl cyanide) complexes of Cu(I), Cu(II), and Zn(II) fluorosulfates have been prepared by reactions of anhydrous Cu(II) and Zn(II) fluorosulfates in methyl cyanide. The infrared spectra indicate a strong interaction between the fluorosulfate anion and the complex Cu(II) and Zn(II) cations. Conductivity measurements in methyl cyanide show strong association between the fluorosulfate anion and the dipositive cations. The Cu(I) compound is completely dissociated in methyl cyanide and, according to the infrared spectrum, shows no strong interaction with fluorosulfate anion.

ISSN:0008-4042    

DOI:10.1139/v70-012

出版商:NRC Research Press    

年代:1970

数据来源: NRC

摘要:

The product of the thermal isomerization of the Diels–Alder adduct1of azodibenzoyl and cyclopentadiene has been identified by degradation and nuclear magnetic resonance analysis as thecis-bicyclic oxadiazine2a, the dihydro derivative of which has been synthesized. The isomerization is quantitative and is first order throughout in solution in a range of solvents ; kinetic and other evidence point to it being a sigmatropic rearrangement.

ISSN:0008-4042    

DOI:10.1139/v70-013

出版商:NRC Research Press    

年代:1970

数据来源: NRC

摘要:

3-Aroylaziridines and 3-acylaziridines react with diphenylcyclopropenone with the formation of novel 4-aroyl-4-oxazolines and 4-acyl-4-oxazolines respectively. The unusual physical and chemical properties of these reactive heterocycles are discussed.

ISSN:0008-4042    

DOI:10.1139/v70-014

出版商:NRC Research Press    

年代:1970

数据来源: NRC

摘要:

4-Aroyl-4-oxazolines undergo stereospecific [2 + 3] cycloaddition to olefinic dipolarophiles with the formation of 3-aroyl-4,5-dihydrofurans. The latter are also found to be reactive towards further [2 + 3] cycloaddition reactions. Possible mechanisms for these reactions are discussed and the synthesis of several new furans and dihydrofurans reported.

ISSN:0008-4042    

DOI:10.1139/v70-015

出版商:NRC Research Press    

年代:1970

数据来源: NRC

摘要:

IrCl3(PEt3)3is readily converted to IrHCl2(CO)(PEt3)2by treatment with carbon monoxide in hot acetone, ethanol, or 2-methoxyethanol. Perchlorate, tetrafluoroborate, and tetraphenylborate salts containing the [IrCl2(CO)(PEt3)3]+cation have been prepared, but attempts to obtain salts containing the [IrHCl(CO)(PEt3)3]+cation give only the neutral hydride, IrHCl2(CO)(PEt3)2. The reactions of [IrCl2(CO)(PEt3)3]+with ethanol, water, lithium aluminum hydride, aqueous potassium chloride solution, and sodium alkoxides are described.

ISSN:0008-4042    

DOI:10.1139/v70-016

出版商:NRC Research Press    

年代:1970

数据来源: NRC

摘要:

The mechanism of the elimination reaction of 2-arylethyltrimethylammonium ions with ethoxide ion in ethanol has been examined using tracer and kinetic isotope effect techniques. Absence of exchange with solvent of both 2-phenylethyltrimethylammonium-2,2-d2bromide and 2-(p-trifluoromethylphenyl)-ethyltrimethylammonium-2,2-d2bromide and the observation of nitrogen isotope effects of 1.3 and 0.9%, respectively, have eliminated a two-step process involving a freely-solvated carbanion intermediate for both salts. The observation of only a slight change in the magnitude of the nitrogen isotope effect when the solvent is changed from ethanol to water has also excluded a zwitterionic intermediate which is specifically hydrogen-bonded to the molecule of ethanol formed by removal of a β-hydrogen by ethoxide ion. Finally, tracer studies using α- and β-dideuterated substrates have eliminated the less probable reaction pathways involving ylide and carbene intermediates. It is concluded that the reaction of 2-arylethyltrimethylammonium salts with ethoxide ion is a concerted E2 process.

ISSN:0008-4042    

DOI:10.1139/v70-017

出版商:NRC Research Press    

年代:1970

数据来源: NRC

摘要:

The stereochemistry of the base-promoted elimination reactions of 2-phenylethyltrimethylammonium and 2-phenylethyldimethylanilinium ions has been investigated using both ethoxide ion in ethanol andt-butoxide int-butyl alcohol as base-solvent systems. The proton magnetic resonance spectroscopic analysis of the deuterated styrene products formed from the reactions of thethreo-2-phenylethylammonium-1,2-d2ions established that elimination proceeds more than 95% by anantiprocess.

ISSN:0008-4042    

DOI:10.1139/v70-018

出版商:NRC Research Press    

年代:1970

数据来源: NRC

摘要:

Methylpyrrole carboxylic esters generally are reductively methylated at 25–45°. Some are also reductively alkylated by aliphatic aldehydes generally to give, for example, 2,3(or 2,4)-dimethyl-4(or 3)-alkyl-5-carbethoxypyrroles, using hydriodic acid or HCl/AcOH–Zn/Hg respectively. An analogous alkylation by glyoxylic acid gave 5-carbethoxyhemopyrrole-dicarboxylic ester. Using HI, paraldehyde at 100° gave diethyl derivatives of dimethylpyrroles, and aminoacetal at 35° converted 2,4-dimethyl-3-acetylpyrrole into its 5-(2-amino-ethyl)-derivative. Reductive alkylations have been most useful with pyrroles but HI converted 2-biphenylcarbaldehyde into fluorene.

ISSN:0008-4042    

DOI:10.1139/v70-019

出版商:NRC Research Press    

年代:1970

数据来源: NRC

摘要:

not available

ISSN:0008-4042    

DOI:10.1139/v70-020

出版商:NRC Research Press    

年代:1970

数据来源: NRC