摘要:

In the reaction of β,β′-dichlorodiethyl sulphide with glycine and with glycylglycine in dilute aqueous base, stable complex sulphonium chlorides are formed. One of these compounds has been isolated in a pure state from the H-glycine reaction and a tentative structure has been proposed.

ISSN:0008-4042    

DOI:10.1139/v54-029

出版商:NRC Research Press    

年代:1954

数据来源: NRC

摘要:

The preparation of a number of N,N′-di-p-tolyl-O-alkyl pseudourea ethers through the alkoxide catalyzed exothermic addition of alcohols to di-p-tolyl carbodiimide is described. Triethyl amine is not effective as a catalyst for such additions. Dicyclohexylcarbodiimide has been found not to undergo such additions at all.The N,N′-diaryl-O-alkyl pseudourea ethers decompose in the presence of mono-and disubstituted hydrogen phosphates to form the diaryl urea and the neutral tertiary phosphates in excellent yield. Several mixed esters of phosphoric acid have been prepared by this method.

ISSN:0008-4042    

DOI:10.1139/v54-030

出版商:NRC Research Press    

年代:1954

数据来源: NRC

摘要:

Silver oxide has been shown to oxidize lupanine to 17-hydroxylupanine. This base gives an anhydronium perchlorate identical with the "dehydrolupanine (NBS)" perchlorate of Marion and Leonard. 17-Oxylupanine is described, and, from the observation that it can be reduced catalytically to oxysparteine, the stereochemistry of aphylline and oxysparteine is deduced. The basic strength of tertiary carbinolamines is discussed.

ISSN:0008-4042    

DOI:10.1139/v54-031

出版商:NRC Research Press    

年代:1954

数据来源: NRC

摘要:

When 1-amidino-3-nitrourea is reacted in aqueous solutions of amines, nitrous oxide and carbon dioxide are eliminated and guanylureas are formed, together with disubstituted ureas as by-products. The infrared absorption spectra of some disubstituted ureas and nitrates of guanylureas are discussed with tentative assignment of bands to some groups.

ISSN:0008-4042    

DOI:10.1139/v54-032

出版商:NRC Research Press    

年代:1954

数据来源: NRC

摘要:

The kinetics of the magnetic ortho–para conversion of hydrogen and deuterium on neodymium oxalate and hemin crystals has been determined over a wide temperature range in a static system. In these cases a similar type of rate curve is obtained: at high and at low temperatures the rate decreases with temperature, while in the intermediate region the rate increases with temperature. The behavior is explained in terms of an energetic surface heterogeneity. In case of neodymium oxalate two distinctly different groups of sites appear to be active having energy barriers to migration of the adsorbed hydrogen at considerably different height. The conversion mechanism of the "trapped" gas is assumed to be similar to the mechanism in liquids where repeated collisions are also assumed to occur.

ISSN:0008-4042    

DOI:10.1139/v54-033

出版商:NRC Research Press    

年代:1954

数据来源: NRC

摘要:

N,N′-di-p-tolyl-O-benzyl pseudourea ether has been shown to form, in the presence of acids, a mixture of the corresponding benzyl ester and unchanged acid, di-p-tolyl urea and an isomer of the urea ether which is concluded to be N-(2-benzyl-p-tolyl)-N′-p-tolyl urea. The transient coloration (to orange red) of the reaction mixture affords strong evidence for the intermediate formation of benzyl cations. The fission of N,N′-di-p-tolyl-O-allyl pseudourea ether follows an analogous course.

ISSN:0008-4042    

DOI:10.1139/v54-034

出版商:NRC Research Press    

年代:1954

数据来源: NRC

摘要:

Treatment of annotinine chlorohydrin with chromous chloride has been found to produce not only the already reported unsaturated lactone A (C16H21O2N), but also a second unsaturated lactone B (C16H21(23)O2N), and a hydroxylactone (C16H23O3N). Under the action of a concentrated solution of the same reagent the hydroxylactone is converted to the unsaturated lactone B. On hydrogenation the latter gives a dihydrolactone B which seems to contain a secondary amino group. Annotinine hydrate on treatment with thionyl chloride gives an unsaturated chlorolactone (C16H20O2NCl) which can be hydrogenated and subsequently dechlorinated to produce a third lactone C, different from either of dihydrolactones A or B, but which like the latter seems to contain an imino group. Oxidation of annotinine hydrate with chromic acid produces a hydroxyketone which can be converted into an oxime and, therefore, one of the hydroxyls of the hydrate is secondary while the other is probably tertiary. On the other hand, oxidation of annotinine with potassium permanganate gives rise to a lactam which by the Clemmensen reduction is converted to a mixture of lactam chlorohydrin and dihydrolactone A.

ISSN:0008-4042    

DOI:10.1139/v54-035

出版商:NRC Research Press    

年代:1954

数据来源: NRC

摘要:

The action of lithium aluminum hydride in dioxane solution on annotinine reduces the lactone and gives rise to a dihydroxy ether while the same reaction in tetrahydrofuran causes scission of the cyclic ether as well and produces a trihydroxy compound. The same trihydroxy compound is also obtainable by the similar reduction of annotinine chlorohydrin. Treatment of the trihydroxy compound with thionyl chloride converts it to a chlorine-containing sulphite ester which under the action of chromous chloride yields an unsaturated dihydroxy compound A, while under the conditions of the Clemmensen reaction, it yields an isomeric unsaturated dihydroxy compound B. Annotinine reacts with phenyl-lithium to give what seems to be a tetrahydroxy compound (C28H35O4N) which is oxidized by chromic acid to C28H33O4N. These reactions lead to two conclusions: (a) that hydrochloric acid and lithium aluminum hydride open the cyclic ether of annotinine in the same way, and (b) that the hydroxyl involved in the lactone is tertiary.

ISSN:0008-4042    

DOI:10.1139/v54-036

出版商:NRC Research Press    

年代:1954

数据来源: NRC

摘要:

The addition of nitrosyl chloride totrans-dibenzoylethylene produces only thesyn-benzoyl isomer of 1-chloro-2-isonitrosodibenzoylethane. This compound contains a hydrogen bond. It forms two isomeric mono-2,4-dinitro-phenylhydrazones. When boiled with hydrochloric acid it is converted into 3-benzoyl-4-chloro-5-phenylisoxazole. The reactions and derivatives of this latter compound are discussed.

ISSN:0008-4042    

DOI:10.1139/v54-037

出版商:NRC Research Press    

年代:1954

数据来源: NRC

摘要:

The pyrolysis of toluene has been studied in an attempt to verify the findings of Szwarc (2). The major products have been confirmed but styrene and isomeric dimethyl diphenyls have also been detected. First order rate constants for the decomposition have been found to depend on the condition of the surface of the reactor, the contact time, and, to a lesser degree, on the pressure. Some preliminary studies on the mechanism of the formation of the dimethyl diphenyls are also recorded.

ISSN:0008-4042    

DOI:10.1139/v54-038

出版商:NRC Research Press    

年代:1954

数据来源: NRC