摘要:

The complex mixture of terpenes obtained on dehydrating α-terpineol with aqueous oxalic acid was almost completely separated by gas–liquid chromatography (GLC), using rapeseed oil as a new liquid phase. Terpinolene, dipentene, α- and γ-terpinene, Δ2,4(8)-p-menthadiene, and 1,8-cineole were identified as the major reaction products; three minor and seven trace constituents were also detected. One of the minor components wasp-cymene, one an oxide, and the third an unidentified hydrocarbon. The yield of these components after different reaction times was determined by GLC. The initial dehydration gives terpinolene and dipentene in the ratio of approximately 2:1. Terpinolene is isomerized to α- and γ-terpinene, Δ2,4,(8)-p-menthadiene, and the unidentified hydrocarbon, but not to dipentene. 1,8-Cineole and the other oxide are formed in a reversible reaction. Dehydration of α-terpineol with several other acidic reagents yielded mixtures of products similar to that obtained with aqueous oxalic acid. With acetic acid or acetic anhydride, however, dipentene was formed preferentially and this reaction appears to proceed via the derived acetate.

ISSN:0008-4042    

DOI:10.1139/v61-001

出版商:NRC Research Press    

年代:1961

数据来源: NRC

摘要:

Further experiments are reported on the hydrogen atom abstraction reactions of deuterated ethyl radicals produced by the photolysis of 3-pentanone-d10.

ISSN:0008-4042    

DOI:10.1139/v61-002

出版商:NRC Research Press    

年代:1961

数据来源: NRC

摘要:

The deamination of certain aromatic amines in deuterohypophosphorous acid with sodium or isoamyl nitrite has been used to label aromatic compounds in a specific position with deuterium. Aniline 2,3-d2was synthesized by this method.

ISSN:0008-4042    

DOI:10.1139/v61-003

出版商:NRC Research Press    

年代:1961

数据来源: NRC

摘要:

The effect of variations in the angle X—C—X′ (in a typical carbonyl compound XX′C=O) on the carbonyl stretching frequency (νc=o) is examined in the light of recently published empirical relations between νc=oand the ionization potential.

ISSN:0008-4042    

DOI:10.1139/v61-004

出版商:NRC Research Press    

年代:1961

数据来源: NRC

摘要:

The doublet separation in the proton resonance spectrum of the liquid was measured from −53 to 100 °C. From the variation of the separation with temperature approximate values of the trans and gauche HF coupling constants were obtained. The values of ΔH ≈ 400 cal/mole and ΔS ≈ 0 are also consistent with the d

ISSN:0008-4042    

DOI:10.1139/v61-005

出版商:NRC Research Press    

年代:1961

数据来源: NRC

摘要:

The adsorption and reactions of the four butenes on porous Vycor glass at room temperature have been studied by infrared spectroscopy. Initial adsorption was rapid and was found to perturb the surface hydroxyl groups of the glass. In the case of then-butenes rapid isomerization took place at room temperature. In addition to this the adsorbate spectra showed the occurrence of a slower reaction which led to an increase in saturated C—H groupings. C8and higher compounds were shown to have formed; on outgassing at room temperature small amounts of cracking products were collected. The polymerization of isobutene was particularly rapid. Experiments at low coverage (θ ∼ 0.001–0.002) gave identical initial spectra for then-butenes. These were discussed in terms of possible models for butene adsorption. A reduction in the alumina and zirconia content of the glass by acid leaching resulted in decreased rates of isomerization and polymerization, suggesting that one or both of these oxides are at least partially responsible for the activity of the glass. A pure silica aerogel was almost completely inactive. Quantitative measurements of the spectra of several monoolefins in solution were made for comparison with the surface species, in particular with respect to their molar intensities of absorption.

ISSN:0008-4042    

DOI:10.1139/v61-006

出版商:NRC Research Press    

年代:1961

数据来源: NRC

摘要:

The starch was oxidized with 5.5 base molar equivalents of 0.43 Mcalcium hypochlorite kept near pH 12 and 20°. The rate of oxidation was consistent with the occurrence of two first-order reactions differing in rate by a factor of 10, the more rapid of which consumed about 4 moles of hypochlorite for each C6H10O5unit actually oxidized. Oxalic acid (0.2 mole) and perhaps carbonic acidwere formed directly, but it was necessary to hydrolyze the product in order to liberateD-glucose (0.4 mole), glyoxylic acid (0.03 mole),D-erythronic acid (0.11 mole), mesotartaric acid (0.02 mole),D-tartaric acid (0.02 mole),L-tartaric acid (0.01 mole),D-glucuronic acid (0.004 mole), and probably tartronic acid.

ISSN:0008-4042    

DOI:10.1139/v61-007

出版商:NRC Research Press    

年代:1961

数据来源: NRC

摘要:

The photooxidation of azomethane has been reinvestigated over a range of conversion extending to at least 7% at relatively high oxygen pressure and at 162 °C. Kinetic and tracer (added C13H2O) studies support the view that the formaldehyde formed in the reaction can act as a source of the oxides of carbon. These were found to be enriched in C13in the tracer work.

ISSN:0008-4042    

DOI:10.1139/v61-008

出版商:NRC Research Press    

年代:1961

数据来源: NRC

摘要:

Germanium difluoride can be prepared by the reduction of germanium tetrafluoride with germanium metal. It is a white solid, m.p. 110°, and is orthorhombic,a = 8.30,b = 5.17,c = 4.67 Å. It possesses strong reducing properties.

ISSN:0008-4042    

DOI:10.1139/v61-009

出版商:NRC Research Press    

年代:1961

数据来源: NRC

摘要:

The decomposition of methane was studied in the negative glow of a d-c. discharge at pressures of 0.30 and 0.050 mm. The discharge tube was cooled by liquid or solid nitrogen.The main products were ethane, ethylene, and acetylene in addition to hydrogen and a nonvolatile product which appeared mainly on the cathode as a solid having the formula (CH)n. Smaller amounts of propane, propene, propyne, butane, butene, butadiene, and pentene were also found. Lowering the temperature of the discharge tube from −196° to −210 °C greatly increased the amount of ethylene recovered.The solid product is apparently transported to the cathode in the form of ions and may result from ionic polymerization of the acetylene. Acetylene is the volatile product formed closest to the cathode which suggests that it may also be formed by ionic processes. The formation of the remaining products is consistent with an excitation mechanism in which the C2products are formed first and the higher hydrocarbons are formed from them.

ISSN:0008-4042    

DOI:10.1139/v61-010

出版商:NRC Research Press    

年代:1961

数据来源: NRC