Acid-catalyzed thermal decomposition

The acceleration of dehydrochlorination in the crosslinked insoluble fraction is probably attributable to oxidation at the tertiary carbon formed by crosslinking, and to the subsequent ease of acid-catalyzed thermal decomposition to yield olefinic structures. The oxidation and the subsequent propagation of polyene structures are free radical in nature and are therefore inhibited to some extent by antioxidants. 

The reaction of 2-bromomagnesiumthiophene with rer/-butyl peroxy-benzoate gives 2-tert-butoxythiophene, which, on acid-catalyzed thermal decomposition, yields 2-hydroxy thiophene (equation 610) [255]. 

The thermal decompositions are catalyzed by Bronsted and Lewis acids [68]. In general, when M is electron poor and Lewis acidic, the thermal decompositions occur efficiently and at low temperatures (typically between 100 and 200 °C, but sometimes at lower temperature). The addition of a catalytic amount of a Lewis or Bronsted acid (i.e., AICI3 or HCl) has been observed to accelerate the ehmination of isobutylene and the formation of three-dimensional network structures [64,124-126]. Pioneering studies on pyrolyses of various metal alkoxides by Bradley and others have also shown that alkene eliminations represent a primary decomposition pathway [104]. 

The hydrazide of 2,2-diphenyl-3-hydroxypropanoic acid was reduced with lithium aluminum hydride in 7V-ethylmorpholine at 100° to 3-amino-2,2-di-phenylpropanol in 72.5% yield [1145], Much more useful is reduction of N-arenesulfonylhydrazides of acids to aldehydes McFadyen-Stevens reduction) [284, 285] based on an alkali-catalyzed thermal decomposition according to Scheme 174. 

This reagent is used as a Lewis acid catalyst for the intramolecular addition of diazo ketones to alkenes [130], The direct synthesis of bicyclo[3.2.1]octenones from the appropriate diazoketones using BF3 Et20 (Eq. 76) is superior to the copper-catalyzed thermal decomposition of the diazo ketone to a cyclopropyl ketone and subsequent acid-catalyzed cleavage [131]. 

The nature of uncatalyzed, acid-catalyzed, and alkali-catalyzed thermal decomposition of levoglucosan was studied (54-56). The data in Table III demonstrate that the same products are obtained from uncatalyzed and acid- or alkali-catalyzed reactions, although the quantities produced vary. The acid-catalyzed reaction produced the greatest amount of char. This agrees with the findings of Fung et al. (53). 

For the modeling of the decomposition of glycerol in near- and supercritical water on the basis of elementary reactions, we assumed a combination of a free-radical thermal decomposition model and an acid-catalyzed ionic decomposition model [128]. This is supported by some studies in the hterature, which also include the... 

Some unsaturated ketones derived from acetone can undergo base- or acid-catalyzed exothermic thermal decomposition at temperatures under 200°C. Experiments conducted under adiabatic conditions (2) indicate that mesityl oxide decomposes at 96°C in the presence of 5 wt % of aqueous sodium hydroxide (20%), and that phorone undergoes decomposition at 180°C in the presence of 1000 ppm iron. The decomposition products from these reactions are endothermic hydrolysis and cleavage back to acetone, and exothermic aldol reactions to heavy residues. 

The nitrites aie most conveniently prepared from the corresponding alcohols by treatment with nitrosyl chloride in pyridine. The crude nitrites can be precipitated by addition of water and recrystallized from appropriate solvents. However nitrites prepared from carbinols in which the adjacent carbon is substituted by halogen, free or esterified hydroxyl or a carbonyl function are very readily hydrolyzed and must be recrystallized with great care. In general the photolysis gives higher yields if purified and dried nitrites are used which do not contain acids or pyridine, although occasionally the addition of small amounts of pyridine is recommended in order to prevent hydrolysis of the nitrite. Traces of acids do in fact catalyze the thermal decomposition of secondary nitrites to equimolar amounts of alcohol and ketone. ... 

Ferrous chloride-hydrochloric acid mixtures catalyzed the thermal decomposition of sulphonyl azides in isopropyl alcohol to give occasionally almost quantitative yields of sulphonamide and acetone, and the molar ratio of azide consumed to ferric chloride formed was typically of the order of 20 to 1 21>. 

The Nazarov cyclization of vinyl aryl ketones involves a disruption of the aromaticity, and therefore, the activation barrier is significantly higher than that of the divinyl ketones. Not surprisingly, the Lewis acid-catalyzed protocols [30] resulted only in decomposition to the enone derived from 46,47, and CO. Pleasingly, however, photolysis [31] readily delivered the desired annulation product 48 in 60 % yield. The photo-Nazarov cyclization reaction of aryl vinyl ketones was first reported by Smith and Agosta. Subsequent mechanistic studies by Leitich and Schaffner revealed the reaction mechanism to be a thermal electrocyclization induced by photolytic enone isomerization. The mildness of these reaction conditions and the selective activation of the enone functional group were key to the success of this reaction. 

Complex 24 was used in thermal and Lewis acid-catalyzed decomposition experiments. Intramolecular C—H reductive elimination from 24 to form exo-2-phenyl-aminonorbornane was demonstrated with labeling experiments [7]. 

The thermal decomposition of MCPBA is slow and unselective. When cobalt catalyzed, the initial reaction is very fast and selective but the reaction is Wdered by the re-arrangement of Co(in)a to Co(III)s and by the slow reaction with m-chlorotoluene. These reactions are also characterized by a high steady state concentration of Co(III). High concentrations of Co(III) are not desirable because Co(III) is known to react with the acetic acid solvent and also decarboxylate aromatic acids (2). 

In oxidation studies it has usually been assumed that thermal decomposition of alkyl hydroperoxides leads to the formation of alcohols. However, carbonyl-forming eliminations of hydroperoxides, usually under the influence of base, are well known. Of more interest, nucleophlic rearrangements, generally acid-catalyzed, have been shown to produce a mixture of carbonyl and alcohol products by fission of the molecule (6). For l-butene-3-hydroperoxide it might have been expected that a rearrangement (Reaction 1) similar to that which occurs with cumene hydroperoxide could produce two molecules of acetaldehyde. 

The carbon-carbon double bond can be reduced by diimide prepared in solution in a number of ways.34 183,184 Oxidation of hydrazine with oxygen (air) or H202 in the presence of a catalytic amount of Cu(II) ion was the first method to generate and use diimide in hydrogenation.183-185 Acid-catalyzed decomposition of alkali azido-dicarboxylates,185,186 as well as thermal or base-catalyzed decomposition of aromatic sulfonyl hydrazides,183,184 are also useful methods for preparing the diimide reducing agent. 

The ability of ethylene oxide to undergo rearrangement to acetaldehyde was mentioned (see section. L2.) in connexion with the thermal decomposition and photolysis of ethylene oxide, and also (see section m.l.C.) in connexion with catalytic ethylene oxidation at elevated temperatures. This characteristic property is discussed, again below with regard, to reactions of epoxides with Qrignard reagents (see section IV.4.F,). For the purposes of this section the subject of epoxide isomerization can be divided into two parts. The first, and most extensive, is concerned with thermal and acid-catalyzed ethylene oxide isomerisation the second involves base-catalyzed rearrangement. 

Substituent effects on aziridine formation from N-(2-halogenoethy 1) arylsulphonamides by cyclization in basic media have been studied,425 and Hammett equation studies have also been of utility in determination of mechanisms of thermal decomposition of 3-chloro-3-aryldiazirines,426 427 the acid-catalyzed methanolysis of arylepoxides,428 and the ring expansion reactions of 2-aryl-l,l-dimethylaziridinium salts with benzaldehyde to form 5-aryl-3,3-dimethyl-2-phenyloxazolidinium salts.429... 

In Section III, A the catalytic action of A1C13 and BBr3 on the thermal decomposition of thiatriazoles was mentioned. This effect is evidently connected with complex formation between a thiatriazole and a Lewis acid since the catalytic activity is lost on addition of compounds that complex more effectively with the Lewis acid.19 It is remarkable that titanium tetrachloride, in contrast to this, does not catalyze decomposition, but instead forms a thermally stable, orange 1 1 complex with 5-phenylthiatriazole.19 The complex is sensitive to atmospheric moisture and is hydrolyzed in high yield to the starting thiatriazole on addition of water. 

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