摘要:

The infrared spectra of several series of trifluoromethyl-phosphorus compounds are correlated, the compounds examined being the iodides CF3PI2and (CF3)2PI, the methyl-trifluoromethyl-phosphines of the general formula (CH3)nP(CF3)3−n, wheren = 1, 2, or 3, and the analogous phenyl-trifluoromethyl-phosphines. Satisfactory assignments are made for the majority of absorption bands in the 650–4000 cm−1region. The infrared spectra of some phosphine – boron trifluoride adducts are also examined and assignments of the principal bands are made.

ISSN:0008-4042    

DOI:10.1139/v62-063

出版商:NRC Research Press    

年代:1962

数据来源: NRC

摘要:

The ionization ratio of thioacetamide in aqueous sodium hydroxide, determined spectrophotometrically, is proportional to the concentration of hydroxide ion up to a concentration of about 1 M, and indicates a pKHAof 13.4. For more concentrated solutions the ionizing power increases more rapidly than the hydroxide ion concentration; from the experimentally determined ionization ratios the values of theh−acidity function for 1–6 Msodium hydroxide have been calculated. The relation ofh−values to the salting-out parameters and water activities of concentrated sodium hydroxide solutions is discussed.

ISSN:0008-4042    

DOI:10.1139/v62-064

出版商:NRC Research Press    

年代:1962

数据来源: NRC

摘要:

Thallium oxide, electrolytically deposited at the anode, has a defective oxide structure and the thallium (I) content is about 1% by weight. The conductivity of the oxide is (1.54 ± 0.04) × 103 ohm−1cm−1and the conductivity is of then-type. The oxide contains variable amounts of water, which it retains very tenaciously.

ISSN:0008-4042    

DOI:10.1139/v62-065

出版商:NRC Research Press    

年代:1962

数据来源: NRC

摘要:

Samples of H2O and D2O and solutions of H2O2, HClO4, HF, etc., in light and heavy water, were tritiated with T2O to activities of from 0.1 to 1 c/ml.The paramagnetic resonance spectra recorded at liquid nitrogen temperature and interpreted as representing H (D) atoms and OH (OD), HO2(DO2) free radicals were compared with those induced under analogous conditions by Co60γ-rays.The lower radical yields observed in the present work have been ascribed to the difference in linear energy transfer between Tβ-particles and more penetrating radiations.

ISSN:0008-4042    

DOI:10.1139/v62-066

出版商:NRC Research Press    

年代:1962

数据来源: NRC

摘要:

Trifluoroiodomethane reacts with triethyl- and tri-n-butylarsine, and tri-n-butylphosphine to give products of the type R2MCF3. Heptafluoroiodopropane reacts similarly with trimethylarsine. Trifluoroiodomethane also reacts with the compounds (CH3)2AsX (X = C6H5, Cl, I) and CH3AsI2to give CH3As(CF3)2; and in most of these reactions the compound CH3As(CF3)I is also formed, which is converted to the compound CH3As(CF3)Cl by reaction with silver chloride.

ISSN:0008-4042    

DOI:10.1139/v62-067

出版商:NRC Research Press    

年代:1962

数据来源: NRC

摘要:

A reliable analysis of the proton resonance spectrum of 1-fluoro-2,4-dinitrobenzene is described. Solvent effects were used to obtain this analysis and a possible source of error in a previous analysis is indicated. Spectra parameters are also derived for 1,5-difluoro-2,4-dinitrobenzene. The spectrum of the latter compound confirms the assignment of peaks in the spectrum of the former.

ISSN:0008-4042    

DOI:10.1139/v62-068

出版商:NRC Research Press    

年代:1962

数据来源: NRC

摘要:

The photolysis of nitrate esters dissolved in benzene or ethanol or absorbed on filter paper occurred readily under illumination in the 265 mμ to 334 mμ spectral region. Equimolar amounts of 1,4;3,6-dianhydro-D-glucitol-2,5-dinitrate and diphenylamine dissolved in absolute ethanol or benzene did not react in the dark at 25°. Irradiation of the nitrogen-purged solutions for 2 hours at 15° with a mercury arc followed by chromatographic separation yielded 2-nitro-, 4-nitro-, N-nitroso-, and 4-nitroso-diphenylamine together with about 4% unreacted diphenylamine and an unidentified mixture of more polar compounds. In a partial fractionation of the aromatic photoproducts approximately 80% of the original diphenylamine was recovered in the form of the monosubstituted derivatives which contained about 37% of the original ester nitrogen as C-nitro groups and 2 to 3% as C- and N-nitroso groups.Possible mechanisms of the photonitration are discussed.

ISSN:0008-4042    

DOI:10.1139/v62-069

出版商:NRC Research Press    

年代:1962

数据来源: NRC

摘要:

Optimum conditions for obtaining arylalkyl ethers from the reactions of aryl-lithium or -magnesium compounds with dialkyl peroxides have been investigated. The reactions are considered to take place by ionic or four-center mechanisms.

ISSN:0008-4042    

DOI:10.1139/v62-070

出版商:NRC Research Press    

年代:1962

数据来源: NRC

摘要:

The complex of boron trifluoride with benzoic anhydride has been prepared. One molecule of anhydride coordinates three molecules of boron trifluoride. The infrared spectrum shows that coordination takes place at the carbonyl groups, whose frequency is lowered some 200 cm−1. There is no trace of the benzoylium cation, C6H5O+. Although the spectra are complex, tentative assignments are made.

ISSN:0008-4042    

DOI:10.1139/v62-071

出版商:NRC Research Press    

年代:1962

数据来源: NRC

摘要:

Reactions involving niobium pentachloride and lithium dialkylamides (LiNR2, where R = Me, Et, Prn, Bun) led to considerable reduction of niobium to Nb(IV) as the length of the alkyl chains increased. Nb(NMe2)5was isolated by sublimation but distillation of the other products gave tetrakis-(dialkylamino)-niobium(IV) compounds. Steric factors are apparently responsible for the low stability of pentakis-(dialkylamino)-niobium(V) compounds. The smaller steric effects of —NMeBunand piperidino groups allowed the isolation of pentakis derivatives. The thermal decomposition of Nb(NMeBun)5gave mainly Nb(NMeBun)4with some BunN=Nb(NMeBun)3. Steric effects were also revealed in the replacement of —NMe2groups in Nb(NMe2)5by —NEt2groups and in replacement of —NEt2groups in Nb(NEt2)4by piperidino groups.

ISSN:0008-4042    

DOI:10.1139/v62-072

出版商:NRC Research Press    

年代:1962

数据来源: NRC