Kinetics and mechanisms of oxidations with nitrous acid. Part 1. Substituted benzyl alcohols and benzyl methyl ether in aqueous sulphuric acid

Author(s):  
Roy B. Moodie ◽  
Stuart N. Richards
1999 ◽  
Vol 77 (3) ◽  
pp. 308-312 ◽  
Author(s):  
Alfons L Baumstark ◽  
Franci Kovac ◽  
Pedro C Vasquez

The oxidation of several series of secondary alcohols 2-9, ethers 10-17, and related derivatives 18 and19, by dimethyldioxirane, 1, in acetone at 25°C produced the corresponding ketones in good to excellent yields for all but two cases. (The exceptions: oxidation of 1-methoxy-2-methyl-1-phenylpropane (48%) and 1-methoxy-2,2-dimethyl-1-phenylpropane (24%).) The oxidation of the secondary alcohols was found to yield k2 values that were roughly 10-fold greater than those of the corresponding methyl ethers. The rate constant for oxidation of a silyl ether was slightly lower than that for the corresponding methyl ether while that for the ester derivative was roughly half the value. For oxidation of alcohols and methyl ethers, the k2 values became smaller as the R " series (Me, Et, nPr, iPr, and tBu) increased in steric bulk (ρ* = 1.7; r = 0.998 and ρ* = 3.2; r = 0.95, respectively). The Hammett study for the oxidation of the methyl ethers of α-methyl-p-benzyl alcohols (10, 20-25) yielded a ρ value of -0.74. The activation parameters for oxidation of the parent compound of the ether series (1-methoxy-1-phenylethane) were ΔH‡ = 14.8 ± 0.5 kcal/mol, ΔS‡ = -21.9 eu, ΔG‡ = 21.3 kcal/mol, k2 (25°C) = 1.6 × 10-3 M-1 s-1. The mechanistic aspects of the oxidation are discussed in relation to two mechanistic extremes: (a) direct insertion of the oxygen atom into the C—H bond and (b) direct abstraction of the H by dimethyldioxirane to yield a caged-radical pair, with subsequent coupling to hemi-ketal intermediates that fragment to yield acetone, alcohol or water, and ketone as the final products.Key words: dimethyldioxirane, oxidation.


1930 ◽  
Vol 2 (2) ◽  
pp. 131-143 ◽  
Author(s):  
Harold Hibbert ◽  
J. G. Morazain ◽  
A. Paquet

A discussion is given as to the nature of the factors involved in the mechanism of the formation of cyclic acetals and ketals from carbonyl and polyhydroxy derivatives. It is shown that in the two reactions involved, namely, the primary formation of a half-acetal, followed by removal of water and ring-closure, the polarity of the carbonyl derivative plays a very important rôle. Chloral combines with polyhydroxy compounds to give exceptionally stable half-acetals, which can be converted into the cyclic derivatives by the use of strong dehydrating agents.In contrast with the behavior of other aldehydes it is found that the condensation of chloral with glycerol yields only one ring compound, namely the five-membered derivative. No satisfactory explanation of this can, as yet, be given.The identity of the trichloroethylidene glycerol obtained by the condensation of glycerol and chloral under the influence of concentrated sulphuric acid has been established as a five-membered cyclic acetal by a comparison of the properties of its methyl ether with those of trichloroethylidene glycerol α-methyl ether prepared from glycerol α-methyl ether.


1883 ◽  
Vol 32 (1) ◽  
pp. 67-86 ◽  
Author(s):  
Matthew Hay

Introductory.—In the course of an inquiry into the physiological and therapeutical action of alkaline nitrites, and allied substances, I was struck with the strong resemblance which the action of nitroglycerine bears to that of the nitrites. The resemblance is, indeed, so well marked, that the action of the one may be held to be identical with that of the other, unless in respect of intensity. The suggestion, therefore, naturally occurred to me, that nitroglycerine is not a nitrate of glyceryl, as it is always represented, but a nitrite. For no ordinary nitrate, as an alkaline nitrate or nitrate of ethyl, nor any compound of glyceryl with another acid, as sulphuric acid, produces an action on the body at all resembling that of nitroglycerine. On referring to the various investigations which had been made for the purpose of ascertaining the chemical constitution of nitroglycerine, I found that none of them was sufficiently extended and exact to place beyond doubt its precise nature. The danger in manipulating so explosive a body had evidently prevented the various chemists from making a thorough examination of its composition. I at first thought that nitroglycerine might be a nitrite of glyceryl, having its nitrous acid so intimately combined with the glyceryl, that the acid did not exhibit its reactions when tested for in the usual way ; just as the acids of other ethereal compounds will not yield their usual reactions, unless special means are taken to forcibly dissociate the acid from the base ; for example, the acid of acetate of ethyl, or of chloride of ethyl. Certainly nitroglycerine gives no blue colour with a solution of starch and iodide of potassium and sulphuric acid, a very delicate test for the presence of nitrous acid. In order, however, to apply the test to the separated acid of nitroglycerine, I mixed an alcoholic solution of nitroglycerine with an alcoholic solution of pure caustic potash. The potash was ascertained to be free from nitrite, which I have frequently found present in small quantity in various specimens of ordinary potash. Decomposition of the nitroglycerine quickly occurred, and the fluid, when now tested for nitrous acid, was found to contain the acid in abundance, and so much of it, that for the moment I believed that nitroglycerine was, in reality, a nitrite of glyceryl; and hence the nature of its physiological action. Some estimations, however, of the quantity of the nitrous acid proved to me that whilst the larger portion of the nitrogen of the nitroglycerine appeared as nitrous acid in the decomposed products, yet a considerable portion was present in some other form.


1969 ◽  
Vol 22 (9) ◽  
pp. 1975 ◽  
Author(s):  
RC Cambie ◽  
DR Crump ◽  
RN Duve

Attempts have been made to effect fragmentation reactions with bromo- tetralone systems related to 6α-bromo-13-hydroxytotara-8,11,13-trien-7- one (VII), a compound which affords a secoditerpenoid (IX) when treated with DMSO-NaHCO3. On treatment with sulphuric acid in acetone, the mono- epoxide derivative (XXVIII) of the methyl ether of the secoditerpenoid undergoes a novel aromatization to a naphthalenic aldehyde (XXXI) by successive transannular cyclization and fragmentation reactions. ��� A 7β-hydroxy configuration has been confirmed for the major product from reduction of 13-acetoxytotara-8,11,13-trien-7-one (VIII) with lithium aluminium hydride. 13-Methoxytotara-8,11,13-triene (II) has been deisopropylated and then subjected to Birch reduction in an attempt to effect a high yield conversion into (+)-podocarp-8(14)-en- 13-one (XXXVII), a potentially useful intermediate for synthesis.


1968 ◽  
Vol 21 (10) ◽  
pp. 2473 ◽  
Author(s):  
CR Bennett ◽  
RC Cambie ◽  
TJ Fullerton

Methods for the conversion of 0-methylpodocarpic acid (I) into 12-methoxy-16-norpodocarpa-8,11,13-trien-4-amine (11) have been examined, a Curtius reaction on the acid chloride (IV) followed by hydrolysis of the isocyanate (111) with 85% w/w sulphuric acid affording the highest overall yield (44%). Some "simple deaminations" involving no change in oxidation state, have been investigated as possible routes to alkenes suitable for further modification of the A ring of podocarpio acid. These include nitrous acid deamination, treatment of the N-benzoate (VIII) with phosphorus pentabromide or pentachloride, and pyrolysis of the tertiary amine oxide (VII) or quaternary methylammonium iodide.


1956 ◽  
Vol 9 (3) ◽  
pp. 319 ◽  
Author(s):  
NS Bayliss ◽  
DW Watts

The ultraviolet spectrum of sodium nitrite in aqueous sulphuric acid is essentially that of nitrous acid below 40 per cent, acid, and that of nitrosonium ion above 70 per cant. acid. In the intermediate range there is evidence that the nitroacidium ion (H2NO2+) is an important constituent of the solution. Equilibria involving the three species have been calculated using activity data for water and sulphuric acid. Similar results are obtained in aqueous phosphoric acid as a solvent. In hydrochloric acid of low water activity the high chloride activity causes what appears to be almost total conversion to nitrosyl chloride. The ultraviolet spectrum of the nitrosonium ion is a structureless transition with εmax.=3850 at about 46 kK (2200 Ǻ). The nitroacidium ion does not absorb appreciably within the accessible range.


1963 ◽  
Vol 16 (6) ◽  
pp. 933 ◽  
Author(s):  
NS Bayliss ◽  
R Dingle ◽  
DW Watts ◽  
RJ Wilkie

The spectra of solutions of sodium nitrite in aqueous solutions of sulphuric and perchloric acids have been measured at a number of temperatures, and from these spectra the concentrations of the species HNO2 and NO+ have been calculated over the acid-concentration ranges 0-100% sulphuric acid (by wt.) and 0-72% perchloric acid (by wt.). The changes due to temperature were found to be less than the experimental error in the determination of the concentrations of nitrous acid and nitrosonium ion. The equilibria of importance in such systems are discussed and equilibrium constants have been calculated for the reactions H2SO4 + HNO2 <=> H2O + NO+ + HSO4- and HClO4 + HNO2 H2O + NO+ + ClO4- Attempts have been made to correlate the determined values for the concentration of nitrous acid and nitrosonium ion with the acidity functions J0, C0, and Hr for both solvent systems. The nitroacidium ion (H2NO2+) in these systems is found to be less important than previously thought.'


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