摘要:

In thioanilides,cis-transisomerism has been clearly differentiated from thioamide – thiolimidic acid tautomerism. The isomer ratio has been related to structural and environmental influences on the thioamide group by means of infrared and proton magnetic resonance spectroscopy. In the thioanilides, the thioamide group does not lie in the ring plane unless constrained to do so by hydrogen bonding between the thioamide proton and a suitable ortho substituent.

ISSN:0008-4042    

DOI:10.1139/v67-001

出版商:NRC Research Press    

年代:1967

数据来源: NRC

摘要:

A new synthesis of 3-acetamido-3-deoxy-d-glucose (kanosamine) has been devised, involving the replacement by azide ion, with inversion, of the sulfonate group in 1,2;5,6-di-O-isopropylidene-3-O-p-tolylsulfonyl-d-allofuranose.

ISSN:0008-4042    

DOI:10.1139/v67-002

出版商:NRC Research Press    

年代:1967

数据来源: NRC

摘要:

Isobutene reacts readily with excess trifluoroacetic acid in ethylene dichloride solution at ordinary temperatures to givet-butyl trifluoroacetate. The rate of the reaction is given, within the range of the experiments, by the expression d[ester]/dt=k[acid]2[olefin], and the apparent activation energy is about 6 kcal/mole. The rate of addition is markedly dependent on the strength of the reacting acid and is drastically reduced in the presence of mildly basic materials, such as dioxane. The boron fluoride catalyzed addition of acetic acid to 2-butene can be considered to follow a similar rate law, i.e. d[ester]/dt=k[acid·BF3]2[olefin], but only if some assumptions are made about the position of the equilibriumsince only the 1:1 complex is reactive.

ISSN:0008-4042    

DOI:10.1139/v67-003

出版商:NRC Research Press    

年代:1967

数据来源: NRC

摘要:

Triphenylmethyl derivatives, Ph3CX, where X = F, Cl, OH, or OCH3, react with 2 or more moles of boron fluoride to form Ph3CB2F7. Reactions take place rapidly and completely at low temperatures, except in the case of X = OCH3, where cleavage of the ether requires about 1 h at −30 °C. When X = Cl the other product is; for OH and OCH3the products are B(OH)3and B(OCH3)3·2BF3. Theion appears to be more stable than theorions.

ISSN:0008-4042    

DOI:10.1139/v67-004

出版商:NRC Research Press    

年代:1967

数据来源: NRC

摘要:

The nuclear magnetic resonance spectra ofN1,N1-diethyl-2,2-dimethylpropane-1,3-diamine (I), bis-(3-diethylamino-2,2-dimethylpropyl) amine (II) andN1-(3-diethylamino-2,2-dimethyl) propylidene-N3,N3-diethyl-2,2-dimethyl-1,3-propanediamine (III) are examined. In the spectrum of I, separate single peaks are observed for the methylene groups adjacent to the primary and tertiary nitrogen atoms. In the spectrum of II, the symmetrical secondary amine, the pair of methylene groups adjacent to the secondary nitrogen atom appears as a singlet separate from the methylene protons between the tertiary carbon and nitrogen atoms. Acetylation of I and II makes it possible to identify the methylene signals of each compound. In the spectrum of III, dissymmetry because of unsaturationis responsible for the differences in the peak positions of the signals of seemingly similar groups. This difference extends to the signals for the terminal methyl protons, which are six and seven bonds from the double bond.

ISSN:0008-4042    

DOI:10.1139/v67-005

出版商:NRC Research Press    

年代:1967

数据来源: NRC

摘要:

The ozonization of 1,4-diphenyl-2-butene in CCl4between 0 and 40° yields (on the average) 41.2% of ozonide, while 44% of the zwitterion not giving the ozonide is reduced.

ISSN:0008-4042    

DOI:10.1139/v67-006

出版商:NRC Research Press    

年代:1967

数据来源: NRC

摘要:

Borane–amine and tetrahydrofuran–borane adducts reduce 10-undecenoic acid ozonide and derivatives to 1,10-decanediol. Insufficient reagent allows selective reduction at the ozonide function, giving 10-hydroxydecanoic acid and derivatives through aldehyde intermediates. The reagents are not as selective as sodium borohydride. Thermochemical study shows an initial reaction step involving one molecule each of substrate and borane.

ISSN:0008-4042    

DOI:10.1139/v67-007

出版商:NRC Research Press    

年代:1967

数据来源: NRC

摘要:

Lobinaline, its derivatives, and its Hofmann degradation products have been examined by mass spectrometry and other spectral and chemical techniques. The results provide independent evidence for the structure of the alkaloid, but indicate that the free base may exist as a mixture of two or three tautomers.

ISSN:0008-4042    

DOI:10.1139/v67-008

出版商:NRC Research Press    

年代:1967

数据来源: NRC

摘要:

Reduction with sodium in liquid ammonia ofl-thiazolidine-4-carboxylic acid (II) leads, depending on the reaction procedure followed, toN-methyl-l-cysteine (I) or a mixture ofN-methyl-l-cysteine (I) (30%) and a dimer (50%), the structure of which is shown to be VI. Contrary to what has been expressed in the literature, the reaction of 1,2-dichloroethane with cysteine (III) at a pH of 8–10 does not lead to compound VI but to compound VIII.

ISSN:0008-4042    

DOI:10.1139/v67-009

出版商:NRC Research Press    

年代:1967

数据来源: NRC

摘要:

N-Nitrosodialkylamines underwent photolysis in the presence of an acid. From the analysis of the end products, the primary photolysis products were shown to be [NOH] and the corresponding alkylideneimine, which underwent further reaction, e.g. (i) recombination of the two species to give amidoximes, (ii) hyponitrous acid formation, and (iii) hydrolysis or polymerization. A pathway is proposed for the reaction. Evidence is presented to show that the formation of the parent amines was not the result of hydrolysis of nitrosamines.

ISSN:0008-4042    

DOI:10.1139/v67-010

出版商:NRC Research Press    

年代:1967

数据来源: NRC