摘要:

3-Phenylcholesta-3,5-diene (I) is shown to undergo electrophilic substitution reactions exclusively at the 6 position with formaldehyde – perchloric acid, acetic anhydride – aluminium chloride, and the Vilsmeier reagent.In the case of formaldehyde, the final product is "dimmer" II. The reaction is specific for formaldehyde and can be used to detect trace amounts of formaldehyde in, for example, commercial acetic acid and acetic anhydride.

ISSN:0008-4042    

DOI:10.1139/v66-338

出版商:NRC Research Press    

年代:1966

数据来源: NRC

摘要:

The free radical induced addition of acetic acid and its derivatives to olefins has been reported recently. As an extension of this reaction, the addition of acetic acid to acetylenic compounds was investigated.Adipic acid was found to be the major product of the reaction of excess acetic acid and acetylene at 110–120 °C under pressure in the presence of organic peroxides. A second oily acidic product with a molecular weight of about 300, not yet identified, was found to the extent of about 2 parts by weight to every 3 parts of adipic acid.Octen-3-oic acid and its anhydride were synthesized from hexyne-1 and excess acetic acid in the presence of organic peroxides. Acetic anhydride was substituted for acetic acid, with the net advantage that acetylene was more soluble in the solvent. The general scope of the reaction was expanded to include other transfer agents, such as acetone, formic acid, and propionic acid.

ISSN:0008-4042    

DOI:10.1139/v66-339

出版商:NRC Research Press    

年代:1966

数据来源: NRC

摘要:

The disodium adduct of benzophenone anil has been treated with a variety of reagents, and the products have been isolated and identified. With alkyl halides, ethylene oxide, and diethyl sulfate, alkylation occurs at the carbon atom. With tri- and tetra-methylene dibromide, nitrogen alkylation also occurs, thereby producing substituted pyrrolidine and piperidine derivatives. Benzaldehyde abstracts the alkali metal from the adduct whereas esters react to form theN-acyl derivatives.

ISSN:0008-4042    

DOI:10.1139/v66-340

出版商:NRC Research Press    

年代:1966

数据来源: NRC

摘要:

The glycol, C15H26O3, of m.p. 119° formed in the oxidation of caryophyllene oxide (I) has been found to have the structure and stereochemistry IVaformed by intramolecular transannular displacement at the tertiary carbon of the secondary–tertiary oxide in III. A rationalization of this mode of attack is offered. The glycol IVahas been transformed into the known keto epoxide XIIbobtained from isocaryophyllene.

ISSN:0008-4042    

DOI:10.1139/v66-341

出版商:NRC Research Press    

年代:1966

数据来源: NRC

摘要:

The extracellular fibers attached to the diatomThalassiosirafluviatilishave been shown to be pure β-(1 → 4)-linked 2-acetamido-2-deoxy-D-glucan. This polysaccharide was given the systematic trivial name chitan to distinguish it from chitin, which is not a chemically distinct species and which has a radically different X-ray diffraction pattern and infrared spectrum. Proton magnetic resonance studies on the acid hydrolysis of chitan have established that the hydrolysis occurred in three distinct steps: (a) the degradation of the polysaccharide to smaller polymeric units, (b) the production ofN-acetylglucosamine from the latter, and (c) the conversion ofN-acetylglucosamine into glucosamine and acetic acid. X-ray and infrared studies have shown that chitan has a different macrostructure from that of arthropod chitin. Chitan is completely crystalline and can be converted irreversibly into a form indistinguishable from that of chitin by treatment with hot aqueous lithium thiocyanate. Boiling chitan in water converts it into a second crystalline modification, possibly a hydrate, which can be reconverted into the starting material by dryinginvacuo. The exceptionally sharp infrared spectrum of chitan allows a more unequivocal assignment of a number of bands common to chitan and chitin, and provides information about the nature of the bands at 1 626 and 1 656 cm−1in the spectrum of chitin. The correlation of the bands in the region of 840 to 890 cm−1with the configuration at the anomeric center of glycopyranose derivatives is discussed.

ISSN:0008-4042    

DOI:10.1139/v66-342

出版商:NRC Research Press    

年代:1966

数据来源: NRC

摘要:

The nitration, halogenation, and animation reactions of benzo[b]thiophene and some of its derivatives are reported. Several new benzo[b]thiophenes have been prepared and directional influences of groups in the thiophene portion of the nucleus confirmed.

ISSN:0008-4042    

DOI:10.1139/v66-343

出版商:NRC Research Press    

年代:1966

数据来源: NRC

摘要:

Polysaccharides obtained from each of the organisms designated in the title have been resolved into three groups: galactomannans I, galactomannans II, and glucans. The five galactomannans II were homogeneous under conditions of electrophoresis, and had positive specific rotations. Methylation and hydrolysis of the five galactomannans II yielded varying amounts of the following: 2,3,5,6-tetra-O-methyl-D-galactose, 2,3,4,6-tetra-O-methyl-D-mannose, 2,3,4-tri-O-methyl-D-mannose, 3,4,6-tri-O-methyl-D-mannose, 3,5-di-O-methyl-D-mannose, and 3,4-di-O-methyl-D-mannose. The galactomannans II were therefore very similar to each other in their gross structural features. The unbranched portions of the polysaccharides were formed by 1 → 2 and 1 → 6 linked α-D-mannopyranose units, with the former predominating. Branch points were formed through substitutions at the C-2 and C-6 positions ofD-mannofuranose andD-mannopyranose, and branches were terminated byD-galactofuranose andD-mannopyranose units. The presence of 1 → 2 linked α-D-mannopyranose units in the linear portions of the galactomannans II constitutes a major structural difference between this group of polysaccharides and the galactomannans I. The two groups of galactomannans differ serologically.

ISSN:0008-4042    

DOI:10.1139/v66-344

出版商:NRC Research Press    

年代:1966

数据来源: NRC

摘要:

Polysaccharides obtained from each of the organisms designated in the title have been resolved into three groups: galactomannans I, galactomannans II, and glucans. The five glucans were homogeneous under conditions of electrophoresis, and had identical electrophoretic mobilities and infrared spectra. Methylation and hydrolysis of the glucans yielded varying amounts of the following: 2,3,4,6-tetra-O-methyl-D-glucose, 2,3,4-tri-O-methyl-D-glucose, 2,4,6-tri-O-methyl-D-glucose, and 2,4-di-O-methyl-D-glucose. The glucans were therefore branched polysaccharides, with branches formed by substitution at the C-3 and C-6 positions ofD-glucopyranose units and terminated byD-glucopyranose units. The linear portions of the glucans contained 1 → 6 and 1 → 3 linkages but in varying amounts. These differences and some variation in the degrees of branching constituted the only dissimilarities detectable in the glucans by these structural studies.

ISSN:0008-4042    

DOI:10.1139/v66-345

出版商:NRC Research Press    

年代:1966

数据来源: NRC

摘要:

not available

ISSN:0008-4042    

DOI:10.1139/v66-346

出版商:NRC Research Press    

年代:1966

数据来源: NRC

摘要:

A large number of Michael adducts have been prepared from β-morpholinoethanethiol and α,β-unsaturated compounds bearing a variety of functional groups. The extent of cleavage of 23 of these under reversal conditions has been determined quantitatively. The relation between structure and amount of cleavage has been discussed. A few heterocyclic thiols were also employed, to extend the generality of the reactions. With the latter, the thiol-cleaved product was separated and identified, to show that the cleavage was normal.

ISSN:0008-4042    

DOI:10.1139/v66-347

出版商:NRC Research Press    

年代:1966

数据来源: NRC