|
1. |
ELECTROPHILIC REACTIONS OF STEROIDAL AND OTHER α-PHENYL DIENES |
|
Canadian Journal of Chemistry,
Volume 44,
Issue 19,
1966,
Page 2233-2239
Maurice Douek,
George Just,
Preview
|
PDF (360KB)
|
|
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
|
2. |
THE ADDITION OF CARBOXYLIC ACIDS TO ACETYLENIC COMPOUNDS |
|
Canadian Journal of Chemistry,
Volume 44,
Issue 19,
1966,
Page 2241-2244
J. DiPietro,
W. J. Roberts,
Preview
|
PDF (184KB)
|
|
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
|
3. |
THE REACTIONS OF THE DISODIUM ADDUCT OF BENZOPHENONE ANIL |
|
Canadian Journal of Chemistry,
Volume 44,
Issue 19,
1966,
Page 2245-2257
James G. Smith,
C. Doreen Veach,
Preview
|
PDF (629KB)
|
|
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
|
4. |
TREIBS' 119° GLYCOL; TRANSANNULAR ATTACK AT THE TERTIARY CARBON OF A SECONDARY–TERTIARY EPOXIDE |
|
Canadian Journal of Chemistry,
Volume 44,
Issue 19,
1966,
Page 2259-2267
E. W. Warnhoff,
V. Srinivasan,
Preview
|
PDF (517KB)
|
|
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
|
5. |
STUDIES ON CHITAN (β-(1 → 4)-LINKED 2-ACETAMIDO-2-DEOXY-D-GLUCAN) FIBERS OF THE DIATOM THALASSIOSIRA FLUVIATILIS HUSTEDT: II. PROTON MAGNETIC RESONANCE, INFRARED, AND X-RAY STUDIES |
|
Canadian Journal of Chemistry,
Volume 44,
Issue 19,
1966,
Page 2269-2281
Michael Falk,
D. G. Smith,
J. McLachlan,
A. G. McInnes,
Preview
|
PDF (705KB)
|
|
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
|
6. |
A STUDY OF THE SUBSTITUTION REACTIONS OF BENZO[b]THIOPHENE AND ITS DERIVATIVES |
|
Canadian Journal of Chemistry,
Volume 44,
Issue 19,
1966,
Page 2283-2289
Gerrit Van Zyl,
C. J. Bredeweg,
R. H. Rynbrandt,
D. C. Neckers,
Preview
|
PDF (345KB)
|
|
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
|
7. |
THE WATER-SOLUBLE POLYSACCHARIDES OF DERMATOPHYTES: V. GALACTOMANNANS II FROM TRICHOPHYTON GRANULOSUM, TRICHOPHYTON INTERDIGITALE, MICROSPORUM QUINCKEANUM, TRICHOPHYTON RUBRUM, AND TRICHOPHYTON SCHÖNLEINII |
|
Canadian Journal of Chemistry,
Volume 44,
Issue 19,
1966,
Page 2291-2297
C. T. Bishop,
M. B. Perry,
F. Blank,
Preview
|
PDF (390KB)
|
|
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
|
8. |
THE WATER-SOLUBLE POLYSACCHARIDES OF DERMATOPHYTES: VI. GLUCANS FROM TRICHOPHYTON GRANULOSUM, TRICHOPHYTON INTERDIGITALE, MICROSPORUM QUINCKEANUM, TRICHOPHYTON RUBRUM, AND TRICHOPHYTON SCHÖNLEINII |
|
Canadian Journal of Chemistry,
Volume 44,
Issue 19,
1966,
Page 2299-2303
C. T. Bishop,
M. B. Perry,
R. K. Hulyalkar,
F. Blank,
Preview
|
PDF (257KB)
|
|
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
|
9. |
SUBSTITUTIONS ÉLECTROPHILES EN SÉRIE NAPHTALÈNIQUE: III. SUR LE DI-t-BUTYL-2,7 NAPHTALÈNE |
|
Canadian Journal of Chemistry,
Volume 44,
Issue 19,
1966,
Page 2305-2313
Lucien Erichomovitch,
Marcel Ménard,
Francis L. Chubb,
Yvon Pépin,
Jean-Claude Richer,
Preview
|
PDF (425KB)
|
|
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
|
10. |
THE THERMAL REVERSIBILITY OF THE MICHAEL REACTION: V. THE EFFECT OF THE STRUCTURE OF CERTAIN THIOL ADDUCTS ON CLEAVAGE |
|
Canadian Journal of Chemistry,
Volume 44,
Issue 19,
1966,
Page 2315-2321
C. F. H. Allen,
W. J. Humphlett,
Preview
|
PDF (282KB)
|
|
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
|
|