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1. |
THE STRUCTURE OF RYANODINE. I |
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Canadian Journal of Chemistry,
Volume 29,
Issue 11,
1951,
Page 905-910
R. B. Kelly,
D. J. Whittingham,
K. Wiesner,
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摘要:
Ryanodine consumes one mole of periodic acid and gives oxoryanodine C25H33O9N. Splitting off water from ryanodine gives anhydroryanodine C25H33O8N. The analyses of these two derivatives are therefore in agreement with the formula for ryanodine C25H35O9N. Alkaline hydrolysis of ryanodine gives pyrrole-α-carboxylic acid and an alcohol C20H32O8. This alcohol splits off water to give a compound C20H30O7. Alkaline hydrolysis of oxoryanodine consumes three moles of alkali and gives a mixture of low molecular acidic products. Alkaline fusion of oxoryanodine gives a neutral aromatic nitrogen-free crystalline substance.
ISSN:0008-4042
DOI:10.1139/v51-105
出版商:NRC Research Press
年代:1951
数据来源: NRC
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2. |
STUDIES IN THE POLYOXYPHENOL SERIES: V. PREPARATION FROM PYROGALLOL OF THE ISOMERIC CYCLOHEXANE-1,2,3-TRIOLS AND -1,2-DIOLS, AND OF SEVERAL ISOPROPYLIDENE AND MONOMETHYL DERIVATIVES |
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Canadian Journal of Chemistry,
Volume 29,
Issue 11,
1951,
Page 911-925
W. R. Christian,
C. J. Gogek,
C. B. Purves,
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摘要:
A study of the high pressure hydrogenation of pyrogallol over nickel, copper – chromium oxide, and palladium catalysts showed that yields of 35% to about 60% ofcis-cis-cis-cyclohexane-l,2,3-triol were attainable, but that thecis-cis-transandcis-trans-cisisomers were formed only in minor amount. Partial hydrogenolysis of these primary products incidentally yielded some cis-cyclohexane-l,2-diol, a smaller amount of thetransform, but none of the 1,3-diols. The following derivatives were prepared apparently for the first time:cis-cis-isopropylidene-cis-cyclohexane-l,2,3-triol, an oil, and its monobenzoate, m.p. 103 °C.;cis-cis-isopropylidene-trans-cyclohexane-l,2,3-triol, m.p. 51°C., and its monobenzoate, m.p. 72° to 76°C.;cis-monomethyl-cis-cis-cyclohexanetriol, m.p. 71°C., and itsbis-3,5-dinitrobenzoate, m.p. 190°C.;trans-monomethyl-cis-cis-cyclohexane-l,2,3-triol, m.p. 37°C.;and isopropylidene-trans-cyclohexane-1,2-diol, an oil. Formation of the latter compound occurred whenp-toluene-sulphonic acid, and not the customary hydrogen chloride, was used as catalyst in the condensation of thetransdiol with acetone.
ISSN:0008-4042
DOI:10.1139/v51-106
出版商:NRC Research Press
年代:1951
数据来源: NRC
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3. |
RELATIVE STABILITIES OF THE ISOMERIC CYCLOHEXANE-1,2,3-TRIOL TRINITRATES AND 1,2-DIOL DINITRATES |
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Canadian Journal of Chemistry,
Volume 29,
Issue 11,
1951,
Page 926-937
W. R. Christian,
C. B. Purves,
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摘要:
Of the above trinitrates, thecis-cis-cisand thecis-trans-cisisomers melted at 70° and 88°C, respectively, but the racemiccis-cis-transform remained as a colorless viscid oil. When dissolved in excess 0.105 Naqueous–alcoholic sodium hydroxide at 20°C, thecis-cis-cisisomer hydrolyzed most rapidly but formed least nitrite, and the solution developed most color. The same isomer evolved the smallest amount of oxides of nitrogen when kept at 106°C., but was more readily detonated by shock than was thecis-trans-cis-trinitrate. The relative reactivities toward alkali and heat of the much more stablecisandtran-cyclo-hexane-1,2-diol dinitrates, which melted at 24° and 18.5°C., respectively, were as described for the trinitrates, but their relative sensitivities to shock were no less. All five compounds were new.
ISSN:0008-4042
DOI:10.1139/v51-107
出版商:NRC Research Press
年代:1951
数据来源: NRC
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4. |
AN IMPROVED SYNTHESIS OFCIS-CIS-TRANS-CYCLOHEXANE-1,2,3-TRIOL |
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Canadian Journal of Chemistry,
Volume 29,
Issue 11,
1951,
Page 938-945
C. J. Gogek,
R. Y. Moir,
J. A. McRae,
C. B. Purves,
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摘要:
Cyclohexene-3-ol acetate was readily made from cyclohexene and when oxidized, preferably with performic acid, gave 20 to 25% yields of partly acylatedcis-cis-trans-cyclohexane-1,2,3-triol, but only 1 to 2% of thecis-trans-cisisomer. The structures of the three cyclohexane-1,2,3-triols were deduced from the theory of the Walden Inversion.
ISSN:0008-4042
DOI:10.1139/v51-108
出版商:NRC Research Press
年代:1951
数据来源: NRC
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5. |
THE BENZOATE AND THE METHYL ETHER OF 4-HYDROXYCYCLOHEXENE |
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Canadian Journal of Chemistry,
Volume 29,
Issue 11,
1951,
Page 946-948
C. J. Gogek,
R. Y. Moir,
C. B. Purves,
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摘要:
Satisfactory preparations, from hydroquinone and its monomethyl ether respectively, were devised for the above compounds which were thought to be new. The methyl ether of 4-hydroxycyclohexene was an oil,boiling at 136 °C.; the uncrystallized benzoate hadnD, 1.5360 and b.p. 149 °C. at 12 mm. pressure.
ISSN:0008-4042
DOI:10.1139/v51-109
出版商:NRC Research Press
年代:1951
数据来源: NRC
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6. |
THE ROLE OF ALPHA-KETOLS IN THE LOW-SUGAR REDOX RECIPE FOR LOW TEMPERATURE EMULSION COPOLYMERIZATION |
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Canadian Journal of Chemistry,
Volume 29,
Issue 11,
1951,
Page 949-958
R. J. Orr,
H. Leverne Williams,
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摘要:
It was found that the induced decomposition of peroxy compounds could lead to faster rates of polymerization or practical rates of polymerization at lower temperatures. In Germany polymerization recipes were developed containing a peroxy compound in the oil phase, a reducer in the aqueous phase and a metal carrier. This idea was transferred to America after the war and became the basis of the present recipes used in the production of cold rubbers. As reducers the most commonly used appear to be digestedd-glucose or an excess of ferrous iron but recently the polyamines and other amine compounds have been found to be quite effective. The mixture of amine and sugar was better than either alone. It has been shown that this mixture will function in the presence of reactive monomers such as acrylonitrile. The role of such reducers is of considerable interest so that further studies were undertaken. The results obtained may be illustrated by acetoin. As the amount of acetoin is increased in the recipe the amount of ferrous iron required for maximal conversion in a given time is decreased. This is because at higher than the optimal amounts, although the reaction rate is still increasing, the catalyst system is rapidly exhausted so that the reaction dies at a lower conversion. The data can be explained by assuming formation of free radicals by the induced decomposition of the peroxide either by the acetoin, the ferrous iron, or a complex between the iron and acetoin. This free radical then initiates polymerization. The acetoin free radical residue can induce the further decomposition of the peroxide or possibly can reduce ferric iron to ferrous. Other compounds yield similar results.
ISSN:0008-4042
DOI:10.1139/v51-110
出版商:NRC Research Press
年代:1951
数据来源: NRC
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7. |
THE PAPILIONACEOUS ALKALOIDS: XIV. CONCERNING SPATHULATINE AND NONALUPINE |
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Canadian Journal of Chemistry,
Volume 29,
Issue 11,
1951,
Page 959-963
Léo Marion,
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摘要:
The two alkaloids nonalupine and spathulatine reported in the literature have been found to be identical and to consist of the monohydrochloride of pusilline, C15H28N2. On heatinginvacuothe hydrochloride undergoes disproportionation, giving rise to the free base and the dihydrochloride. The peculiar reactions of spathulatine are explained by the fact that they simply liberated the base from its salt. Pusilline forms a dipicrate containing an additional mole of picric acid, which accounts for the necessity of using a solution of that acid for its recrystallization.
ISSN:0008-4042
DOI:10.1139/v51-111
出版商:NRC Research Press
年代:1951
数据来源: NRC
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8. |
THE BIOGENESIS OF ALKALOIDS: III. A STUDY OF HYOSCYAMINE BIOSYNTHESIS USING ISOTOPIC PUTRESCINE |
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Canadian Journal of Chemistry,
Volume 29,
Issue 11,
1951,
Page 964-969
D. G. M. Diaper,
Sam Kirkwood,
Léo Marion,
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摘要:
Putrescine-1: 4-C14was fed to matureDaturastramoniumin an investigation of the biosynthesis ofl-hyoscyamine. Although C14was metabolized by the plant, no radioactivity was found in the isolated alkaloid; the mechanism of biosynthesis of the tropane nucleus is discussed in the light of published work and of this observation.
ISSN:0008-4042
DOI:10.1139/v51-112
出版商:NRC Research Press
年代:1951
数据来源: NRC
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9. |
HYDROLYSIS AND POLYMERIZATION OF CYCLIC DIMETHYLETHYLENE OXALATES |
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Canadian Journal of Chemistry,
Volume 29,
Issue 11,
1951,
Page 970-973
L. G. Ripley,
R. W. Watson,
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摘要:
Macrocrystalline cyclic oxalates (2,3-dimethyl-5-6-p-dioxanediones) were prepared by vacuum distillation of the polymeric mixture formed on heating ethyl oxalate, and 1, 2-dimethylethylene glycol with an ester-interchange catalyst. Monomeric dimethylethylene oxalate polymerizes less readily than propylene oxalate, and only at an elevated temperature in the presence of a catalyst. Dimethyl substitution therefore confers marked stability on the six-membered ring. Hydrolysis reaches 50% completion almost instantaneously, followed by a slow first order reaction resulting in complete cleavage of the monobasic acid in about one month at room temperature. Hydrolysis constants for thelevo- andmeso- oxalates are 0.069 and 0.076 days−1respectively. The crystalline monomers do not possess sharp melting points and represent stereoisomeric mixtures which display optical activity in solution.
ISSN:0008-4042
DOI:10.1139/v51-113
出版商:NRC Research Press
年代:1951
数据来源: NRC
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10. |
CUPRIETHYLENEDIAMINE AS A REAGENT FOR HEMICELLULOSE SEPARATION FROM WHEAT STRAW HOLOCELLULOSE |
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Canadian Journal of Chemistry,
Volume 29,
Issue 11,
1951,
Page 974-985
V. D. Harwood,
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摘要:
Wheat straw and wheat straw holocellulose were dispersed in aqueous cupriethylenediamine solutions and fractionated by graded precipitation with acid and alcohol. From the holocellulose a 25.4% recovery of a hemicellulose containing negligible quantities of hexoses was achieved. The corresponding product from wheat straw was contaminated with both lignin and cellulose but a comparison of the chemical compositions of the two hemicelluloses showed that the acid chlorite used for delignification had caused very little hydrolytic action. The acetate of the hemicellulose from holocellulose was fractionated from chloroform solution by the addition of petroleum ether into a series of fractions and subfractions. Analysis of representative fractions from this series led to the conclusion that the hexoses present were not chemically combined with pentosan. Molecular weights were determined by periodate oxidation, the Signer isothermal distillation method, and from the lowering of the vapor pressure of their chloroform solutions and showed that the hemicellulose molecules were relatively small (mol. wt. < 10,000). The decreasing ratio of xylose to arabinose in the fractions of lower molecular weight indicated increasing chain branching.
ISSN:0008-4042
DOI:10.1139/v51-114
出版商:NRC Research Press
年代:1951
数据来源: NRC
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