摘要:

Alkylaluminum hydride trimethylamine complexes have been obtained by several different methods: (a) reduction of an alkylaluminum halide trimethylamine complex with lithium hydride, (b) alkylation of aluminum hydride trimethylamine with dialkylmercury, (c) reaction of trialkylaluminum trimethylamine and aluminum hydride trimethylamine, and (d) reaction of dialkylaluminum chloride with lithium aluminum hydride and trimethylamine. Some physical properties of the compounds are reported, including the infrared and proton magnetic resonance spectra. Cryoscopic molecular weight determinations indicate that the compounds are associated in cyclohexane. Their possible structures are discussed.

ISSN:0008-4042    

DOI:10.1139/v63-150

出版商:NRC Research Press    

年代:1963

数据来源: NRC

摘要:

Chromyl chloride in carbon tetrachloride solution reacts in the cold with cyclohexene, cyclopentene, and 1-hexene to give the various isomeric chlorohydrins as the major products. The major product from 2-methyl-1-pentene was 2-methylpentanal. Significant amounts of α-chloro carbonyl compounds and some α,β-unsaturated carbonyl compounds were also produced. The significance of these results is discussed.

ISSN:0008-4042    

DOI:10.1139/v63-151

出版商:NRC Research Press    

年代:1963

数据来源: NRC

摘要:

The basicities of 14 diaryl ketones have been determined. Except for 4,4′-bis(dimethyl-amino)benzophenone, which protonates on nitrogen, the pKBH+values range from −4.19 for 4,4′-dihydroxybenzophenone to −10.12 for 4,4′-dinitrobenzophenone. The basicities are not correlated well by either σ or σ+substituent constants and it is believed that this is due either to a variation in the degree of rotation (and hence conjugation) of the two aryl rings or to a departure of carbonyl basicities from the conventional acidity scale based on ammonia bases. The effect on the basicity of joining the ortho positions by bridges of various sizes has also been determined and the results are discussed in terms of steric and electronic effects.

ISSN:0008-4042    

DOI:10.1139/v63-152

出版商:NRC Research Press    

年代:1963

数据来源: NRC

摘要:

The products of the condensation of 5-methoxy-3-methylbenzoic acid with aqueous formaldehyde and hydrochloric acid in the presence of glacial acetic acid are dependent on the length of the heating period. A very short period of heating (2 minutes) yields 6-methoxy-4-methylphthalide and the two chloromethylphthalides of m.p. 135° and 154 °C, related to the unisolated 4-methoxy-6-methylphthalide. If the period of heating is 20 minutes or longer, the above chloromethylphthalide melting at 135° is formed and in addition some of the 6-methoxy-4-methylphthalide is chloromethylated to 6-methoxy-7-chloromethyl-4-methylphthalide, melting at 179°. The orientation of all three chloromethylphthalides has been established.

ISSN:0008-4042    

DOI:10.1139/v63-153

出版商:NRC Research Press    

年代:1963

数据来源: NRC

摘要:

By measuring the initial rates of production of hydrodisulphide during reductions by sodium hydrosulphide in aqueous ethanol, it has been shown that the relative rates of reduction of a number of para-alkylated nitrobenzenes are in the orderp-H- > p-t-butyl- > p-isopropyl- = p-cyclohexyl- > p-ethyl- > p-methyl-nitrobenzene. This is in accord with the "hyperconjugative" order of electron release by these alkyl groups.

ISSN:0008-4042    

DOI:10.1139/v63-154

出版商:NRC Research Press    

年代:1963

数据来源: NRC

摘要:

A series of substituted phenylacetylenes has been prepared and their infrared spectra recorded. The C≡C and ≡C—H stretching frequencies are only slightly affected by substituents in the phenyl ring. Substituents in the 4-position cause a splitting of the ≡C—H band into two clearly resolved bands of similar intensity, about 10 cm−1apart.

ISSN:0008-4042    

DOI:10.1139/v63-155

出版商:NRC Research Press    

年代:1963

数据来源: NRC

摘要:

This paper is an experimental study of (a) the solid–liquid equilibria at low temperatures; (b) equilibrium compositions at temperatures other than 25 °C; (c) the critical phenomena, L1–L2, L1–V, and L2–V, in the acetic acid – chloroform – water system. No previous study has been made of critical phenomena in a system exhibiting partial liquid miscibility.

ISSN:0008-4042    

DOI:10.1139/v63-156

出版商:NRC Research Press    

年代:1963

数据来源: NRC

摘要:

The reaction of active nitrogen with methanol has been investigated at several temperatures in the range 30 to 480 °C using a fast-flow system. The only condensable products found in appreciable amounts were water and hydrogen cyanide. The overall activation energy is 3.0 and 3.2 kcal/mole and the steric factors 1.3 × 10−3and 2.1 × 10−3for streamline and turbulent flow respectively.It is postulated that the mechanism consists of the initial formation of a collision complex, [NCH3OH], which breaks down to two fragments, NCH3and OH, from which the two condensable products are formed,Attack of the methanol molecules by hydrogen atoms resulting from the main reaction occurs to a lesser extent and is responsible for the production of small quantities of methane, carbon monoxide, and additional water.

ISSN:0008-4042    

DOI:10.1139/v63-157

出版商:NRC Research Press    

年代:1963

数据来源: NRC

摘要:

Bromine was the only halogen formed in irradiated mixtures of HCl and HBr. A study of its effect on the hydrogen yield from HCl showed that it reacted with the first hydrogen-forming species (or its precursor), and indicated the same yield for this species as did the earlier experiments with chlorine. The results were consistent with thermal hydrogen atoms, formed in the reactionas the first hydrogen-forming species, and hot hydrogen atoms, resulting from the dissociation of excited HCl molecules, as the second species.The hydrogen yield from liquid HBr at −79°C was a factor of two larger than that from liquid HCl at the same temperature, and in mixtures of the two the hydrogen yield increased gradually from a value characteristic of pure HClto one characteristic of pure HBrThe smaller yield from HCl cannot be explained by radical combinations:in the radiation tracks and must be attributed either to differences in the ion-combination reactions in the two liquids or to a genuinely greater yield of ions and/or dissociative excited molecules in HBr. The hydrogen yield from solid HBr at −196 °C was.

ISSN:0008-4042    

DOI:10.1139/v63-158

出版商:NRC Research Press    

年代:1963

数据来源: NRC

摘要:

Nuclear magnetic resonance studies of methyl maleopimarate and closely related derivatives clearly establish the stereochemistry of methyl maleopimarate and, consequently, levopimaric acid. An extension of this study to other related compounds, 22 in all, provides evidence, on the basis of an intercomparison of the chemical shifts for the angular methyl protons, to support the original suggestion by Jackman (Applications of NMR in organic chemistry. Pergamon, New York. 1959. Chap. 7) that the long range shielding effect of the olefinic linkage is analogous to that of the carbonyl double bond. Coupling constants and chemical shifts for some of the protons of the bicyclo[2.2.2]octene system present in these compounds are also discussed.

ISSN:0008-4042    

DOI:10.1139/v63-159

出版商:NRC Research Press    

年代:1963

数据来源: NRC