ELECTROPHILIC CATALYSIS IN SOLVOLYTIC REACTIONS: IX. INDUCTOMERIC EFFECT

1966 ◽  
Vol 44 (20) ◽  
pp. 2415-2419 ◽  
Author(s):  
R. Anantaraman ◽  
M. R. Nair

The rates of solvolysis of 1-(p-alkylphenyl)ethyl chlorides (Alk = Me, Et, i-Pr, and t-Bu) in the presence and absence of mercuric chloride have been measured in aqueous acetone and ethanol solvents. In all cases, the Baker–Nathan order is followed. For all normal reactions and for the catalyzed reactions in 90% aqueous acetone and 90% aqueous ethanol there is an increase in the heats and entropies of activation as the series is ascended, while for the catalyzed reaction in 75% and 80% aqueous acetone, there is a decrease. It is suggested that in the more aqueous acetone solvents the catalyst calls into play an inductomeric effect. The effect of added chloride ions on the rate of hydrolysis has been studied and the results are discussed.

1965 ◽  
Vol 43 (6) ◽  
pp. 1770-1777 ◽  
Author(s):  
R. Anantaraman ◽  
K. Saramma

The rates of mercuric chloride catalyzed solvolysis of some alkyl chlorides in aqueous acetone and ethanol solvents have been compared. It is found that the increase in rate on changing from the acetone to the ethanol solvent is less in the catalyzed than in the normal reaction. On the basis that the electrophilic activity of the catalyst is less in aqueous ethanol than in aqueous acetone an explanation for the anomaly has been suggested. The effect, on the rates of solvolysis, of added chloride ions is in accord with the suggested explanation.


1981 ◽  
Vol 34 (11) ◽  
pp. 2385 ◽  
Author(s):  
JA Rideout ◽  
MD Sutherland

The polyhydroxyanthraquinones known from the crinoid Comatula pectinata are shown to be present largely as (fish repellent) sulfate monoesters. The sodium salt of the 3-O-sulfate of 4-butyryl-1,3-dihydroxy-6,8-dimethoxy-9,10-anthraquinone was isolated by its chromatographic mobility on alumina in aqueous acetone or on sodium bicarbonate in aqueous ethanol. The sulfate hydrolyses readily to the free phenol and is methylated (Me2SO4/K2CO3 in refluxing acetone) to 4-butyryl-1,3,6,8-tetramethoxyanthraquinone. Methylated in the presence of tertiary alcohols however, the sulfate ester resists cleavage, yielding the 1,6,8-trimethyl ether, hydrolysable to 4-butyryl-3-hydroxy-1,6,8-trimethoxyanthraquinone.


1954 ◽  
Vol 44 (01) ◽  
pp. 7-44 ◽  
Author(s):  
W.E. Boyd

Summary1. A method is described for investigating the possible action of microdoses of mercuric chloride on the hydrolysis of soluble starch with malt diastase.2. The microdoses of the mercuric chloride used in the latest crucial series carried out in1946, 1948, and 1952, were what are termed “high potencies” made in accordance with the pharmaceutical method of preparation of drugs ordinarily used in the practice of homœotherapy.3. These microdoses were prepared by separate stages of dilution, the solution at each stage being subjected to mechanical shock. The solutions were, theoretically, “dilutions” of the order of 1 in 10−61 and on present physical theory would not contain any molecules of the original mercuric chloride.4. The difference in rate of hydrolysis between flasks containing starch, diastase, and distilledwater (controls) and flasks containing starch, diastase and microdoses of mercuric chloride (tests) were compared colorimetrically by the Spekker absorptiometer, and the frequencies of the differences statistically analysed, as the results obtained showed biological scatter. More than 500 such comparisons were carried out. The differences of means were examined by the Fisher “t” test, the variances tested and Cochrane and Cox's test applied where indicated. All the series gave a highly significant difference in the rate of hydrolysis between controls and tests, the microdoses stimulating the process. Statistically the significance is shown by the fact that a probability of <0·001 was obtained independently in each of the three years 1946, 1948 and 1952. The control results gave an approximately normal distribution.5. The distribution, control methods, and accessory control procedures were considered toexclude, as a cause of the effects, adsorption of the original drug and the presence of extraneous contaminants by chance solely in test flasks. The only difference between control and microdose flasks was the addition of microdose, the distilled water being common to both controls and tests.6. It was concluded that a factor, unidentified, derived from the mercuric chloride used, waspresent in solutions prepared by serial dilution with mechanical shock which could affect the distilled water diluent, that this change was transferable to subsequent “ultramolecular” stages of “dilution”, and that this factor was the source of the activity in the microdose solutions producing the acceleration of the rate of hydrolysis.7. In an addendum there is described recent biological work which is also providing evidence of the presence of an active selective factor in “high potencies” derived from Strophanthus sarmentosus by the same methods of dilution with mechanical shock.


1965 ◽  
Vol 43 (8) ◽  
pp. 2345-2356 ◽  
Author(s):  
W. A. Szarek ◽  
J. K. N. Jones

Lead tetraacetate oxidation of 6-acetamido-6-deoxy-D-galactose (IX) yielded a syrup which was converted to a compound formulated as 4-acetamido-4-deoxy-1,2-O-isopropylidene-D-threofuranose (XII). The same syrup was obtained by alkaline degradation of the product of oxidation of 5-acetamido-5-deoxy-D-xylose diethyl dithioacetal (XVII) with peroxypropionic acid. Treatment of compound XII with p-toluenesulfonyl chloride yielded crystalline 4-acetamido-4-deoxy-1,2-O-isopropylidene-3-O-p-tolylsufonyl-D-threofuranose (XIII).Demercaptalation of 6-acetamido-2,3,4,5-tetra-O-acetyl-6-deoxy-D-galactose diethyl dithioacetal (XX) with mercuric chloride and cadmium carbonate in aqueous acetone did not yield a nitrogen-containing septanose ring but an acyclic derivative.


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