Decomposition acid-catalyzed

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. 

Acid-catalyzed, ionic decompositions have been reported for peroxyesters, RC(0)—OOR, in which the R group can form a particularly stable carbonium ion, eg, tropybum ion (213). 

Because monocalcium phosphate is incongmently soluble, it is typically contaminated with various amounts (6—10%) of dicalcium phosphate and free phosphoric acid resulting from in-process disproportionation of the monocalcium salt. Free phosphoric acid may render the product hygroscopic, and absorbed water plus acid catalyzes further decomposition to additional free acid and dicalcium phosphate. For this reason, industrial monocalcium phosphate may contain some dicalcium phosphate resulting from excess lime addition and then aged to ensure the removal of residual free phosphoric acid. 

Reactions of Vinyl Ethers. Vinyl ethers undergo the typical reactions of activated carbon—carbon double bonds. A key reaction of VEs is acid-catalyzed hydrolysis to the corresponding alcohol and acetaldehyde, ie, addition of water followed by decomposition of the hemiacetal. Eor example, for MVE, the reaction is... 

DAG is treated with ethanol and hydrochloric acid in the presence of inert solvent, eg, chlorinated solvents, hydrocarbons, ketones, etc. The L-ascorbic acid precipitates from the mixture as it forms, minimising its decomposition (69). Cmde L-ascorbic acid is isolated through filtration and purified by recrystallization from water. The pure L-ascorbic acid is isolated, washed with ethanol, and dried. The mother Hquor from the recrystallization step is treated in the usual manner to recover the L-ascorbic acid and ethanol contained in it. The cmde L-ascorbic acid mother Hquor contains solvents and acetone Hberated in the DAG hydrolysis. The solvents are recovered by fractional distillation and recycled. Many solvent systems have been reported for the acid-catalyzed conversion of DAG to L-ascorbic acid (46). Rearrangement solvent systems are used which contain only the necessary amount of water required to give >80% yields of high purity cmde L-ascorbic acid (70). 

Migration to the developing electron sextet at nitrogen is not restricted to hydrogen. In (79) there is methyl migration with formation of methylamine and acetone in the acid-catalyzed decomposition of (80), phenyl migration leads to aniline and acetaldehyde. 

Spectroscopic evidence indicates that protonation of 2-fluoro-and 2-chloro-quinoline is not appreciable in O.OlJf aqueous hydrochloric acid. Protonation becomes evident in more strongly acidic solution in the case of the chloro compound without any accompanying decomposition, but the fluoro compound hydrolyzes to carbostyril under the latter conditions. The hydrolysis is acid-catalyzed, but it is doubtful whether protonation on the heterocyclic nitrogen is responsible, owing to its low basicity (presumably below that for the chloro compound). An alternative explanation in this case would be hydrogen bond formation with fluorine, Ar—F. .. H-O+H2. 

Pyrrole itself is very easily converted by acid into intractable and readily autoxidized polymers. In this case and in the case of the alkyl pyrroles, it is important to distinguish between anaerobic acid-catalyzed reactions and autoxidative polymerizations the decomposition of pyrrole and its alkyl derivatives on standing in air belongs to the latter type, this review is concerned only with the former. 

DFT molecular dynamics simulations were used to investigate the kinetics of the chemical reactions that occur during the induction phase of acid-catalyzed polymerization of 205 [97JA7218]. These calculations support the experimental finding that the induction phase is characterized by the protolysis of 205 followed by a rapid decomposition into two formaldehyde molecules plus a methylenic carbocation (Scheme 135). For the second phase of the polymerization process, a reaction of the protonated 1,3,5-trioxane 208 with formaldehyde yielding 1,3,5,7-tetroxane 209 is discussed (Scheme 136). 

For the latter case an acid-catalyzed decomposition of intermediate 4 is assumed to give the carbonyl products 2 and 3, or a diketone as shown above, without going through a cyclic intermediate ... 

The acid catalyzed hydration of olefins is frequently attended by decomposition or rearrangement of the acid-sensitive substrate. A simple and mild procedure for the Markovnikov hydration of double bonds has recently been devised by Brown and co-workers 13). This reaction, which appears to be remarkably free of rearrangements, initially involves the addition of mercuric acetate to the double bond to give the 1,2-... 

In contrast to enzyme- and base-catalyzed DKRs, there are only a few reports of enzyme- and acid-catalyzed DKRs. A plausible explanation is that deactivation of the enzyme can occur under acidic conditions. Also, decomposition of the substrate has... 

The overall pathway for the conversion of the unsaturated azido ether 281 to 2,5-dihydrooxazoles 282 involves first formation of the dipolar cycloaddition product 287, which thermolyzes to oxazoline 282 or is converted by silica gel to oxazolinoaziridine 288. While thermolysis or acid-catalyzed decomposition of triazolines to a mixture of imine and aziridine is well-documented [71,73], this chemoselective decomposition, depending on whether thermolysis or exposure to silica gel is used, is unprecedented. It is postulated that acidic surface sites on silica catalyze the triazoline decomposition via an intermediate resembling 289, which prefers to close to an aziridine 288. On the other hand, thermolysis of 287 may proceed via 290 (or the corresponding diradical) in which hydrogen migration is favored over ring closure. 

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 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. 

In the context of preparing potential inhibitors of dihydrofolate reductase (DHFR), the group of Organ has developed a rapid microwave-assisted method for the preparation of biguanide libraries (Scheme 6.174) [330]. Initial optimization work was centered around the acid-catalyzed addition of amines to dicyandiamide. It was discovered that 150 °C was the optimum temperature for reaction rate and product recovery, as heating beyond this point led to decomposition. While the use of hydrochloric acid as catalyst led to varying yields of product, evaluation of trimethylsilyl chloride in acetonitrile as solvent led to improved results. As compared to the protic... 

This is an acid-catalyzed SN2 displacement from the protonated ad-nitro tautomer. The substrate is not protonated in even the strongest acids used the protonation site shown in Scheme 2 is not the most basic, but the only one that results in decomposition. Bisulfate is a poorer nucleophile than water by a factor of about 1000,119 but above 80 wt% in acidity its concentration is at least 1000 times that of water.150 Twelve compounds were studied the intercept... 

Acids catalyze the decomposition of secondary hydroperoxide with the formation of carbonyl compounds [46,83]. 

Acid catalyzes the decomposition of tertiary a-arylhydroperoxide and gives phenol and ketone [46,84]. 

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