摘要:

Methyl-d3bromide was easily converted by treatment with calcium iodide into methyl-d3iodide in 94% yield. The latter was reacted on the 50-millimole scale with silver acetate or silver acetate-d3to yield methyl-d3acetate or methyl-d3acetate-d3. Methyl iodide and silver acetate-d3gave methyl acetate-d3.

ISSN:0008-4042    

DOI:10.1139/v54-001

出版商:NRC Research Press    

年代:1954

数据来源: NRC

摘要:

Equilibrium constants for the isotopic exchange reaction between bisulphite ion and the addition product of eight aldehydes and ketones have been measured.At 25 °C., values ranging from 1.021 for acetone to 1.010 for anisaldehyde have been observed. Since constants of this magnitude are to be expected only if the bonding of the sulphur atom is different in the bisulphite ion and the addition product, these results are considered to confirm the carbon-sulphur bond structure of the latter. This conclusion is supported by the small constant, 1.002, obtained for the diethyl sulphate and ethyl hydrogen sulphate isotopic exchange in which the bonding of sulphur is essentially the same in the two reacting species.

ISSN:0008-4042    

DOI:10.1139/v54-002

出版商:NRC Research Press    

年代:1954

数据来源: NRC

摘要:

The reagents carbazole – sulphuric acid, cysteine hydrochloride – sulphuric acid, have been applied successfully to the quantitative colorimetric determination of sedoheptulosan in pure solution or in the presence of ribose and/or fructose. Fructose can be determined quantitatively in the presence of sedoheptulosan and/or ribose by using a combination of the two reagents. Results indicate that while sedoheptulose reacts differently to sedoheptulosan with the orcinol reagent, the reactions with carbazole and cysteine are not altered by hydration and these may form a basis for the determination of the naturally occurring seven carbon sugar sedoheptulose.

ISSN:0008-4042    

DOI:10.1139/v54-003

出版商:NRC Research Press    

年代:1954

数据来源: NRC

摘要:

The methyl glucoside tetranitrates reacted vigorously at room temperature with an excess of hydroxylamine base dissolved in anhydrous pyridine. Gas consisting of 91% nitrogen and amounting to 1.25 to 1.3 moles per mole was evolved within 20 min. and only a little more during the next 12 hr. Approximately 1.35 moles of nitrate groups in the original tetranitrate had been replaced by hydroxyl groups, for the most part at least without Walden inversions or other change, because hydrogenation of the sirupy product reduced it in more than 80% yield to crystalline methyl glucoside. The product from methyl-β-glucoside tetranitrate consisted of the 2,3,6-trinitrate (28%), the 3,6-dinitrate (17%), and an unidentified trinitrate (8%) which might have been a mixture.The structures of the first two compounds were confirmed by preparing the fully methylated derivatives, denitrating the latter, and identifying the resulting known, partly methylated methyl-β-glucosides. New syntheses of methyl-β-glucoside-3,6-dinitrate, methyl 2,4-dimethyl-β-glucoside, and methyl-4-methyl-β-glucoside were found.

ISSN:0008-4042    

DOI:10.1139/v54-004

出版商:NRC Research Press    

年代:1954

数据来源: NRC

摘要:

Une nouvelle synthèse permet d'obtenir les 2-amino alcools à partir de l'acétamidomalonate d'éthyle. La méthode consiste à condenser un dérivé halogéné approprié avec le sel de sodium de l'acétamidomalonate d'éthyle. Par monosaponification de ce di-ester suivie de décarboxylation, on obtient un ester éthyliqueN-acétamidé qu'on réduit par l'hydrure de lithium et d'aluminium en alcoolN-acétamidé. Par hydrolyse, on obtient le chlorhydrate du 2-amino alcool correspondant. LeD,L-phénylalaninol, leD,L-tyrosinol et leD,L-leucinol ont ainsi été préparés avec d'excellents rendements. La méthode semble être d'application générale et les produits intermédiaires sont faciles à isoler.

ISSN:0008-4042    

DOI:10.1139/v54-005

出版商:NRC Research Press    

年代:1954

数据来源: NRC

摘要:

Mercury dimethyl was photolyzed in the presence of 3-ethyl pentane in the temperature range from 76 °C. to 238 °C. The activation energy for the reactionwas found to be 6.8 ± 0.3 kcal. per mole.

ISSN:0008-4042    

DOI:10.1139/v54-006

出版商:NRC Research Press    

年代:1954

数据来源: NRC

摘要:

The rates of hydrolysis of sodium pyrophosphate and triphosphate in solution have been measured at 65.5 °C. over the pH range 2.0 to 12.0 and the phosphorus concentration range 0.10 to 0.25 atomic weights per liter. The reactions were found to be first order providing a constant concentration of hydrogen ion was maintained in the reaction flask. Both reactions are acid catalyzed but only the hydrolysis of triphosphate was found to be base catalyzed. Pyrophosphate and triphosphate apparently hydrolyze independently of each other.

ISSN:0008-4042    

DOI:10.1139/v54-007

出版商:NRC Research Press    

年代:1954

数据来源: NRC

摘要:

not available

ISSN:0008-4042    

DOI:10.1139/v54-008

出版商:NRC Research Press    

年代:1954

数据来源: NRC