Solvents, acidic mechanisms

Some recent general reviews deal with the mechanism of N-nitrosation in aqueous solution (345), the nitrosation of secondary amines (346). the effect of solvent acidity On diazotization (347) and the reactivity of diazonium salts (1691). Therefore, a complete rationalization of the reactivity of amino azaaromatics would be timelv. 

Polybenzaylene benzimidazoles (pyrrones) Polybenzoxazoles Thermally stable to 600°C (1112°F) insoluble in common solvents good mechanical properties. Stable in air to 500°C (932°F) insoluble in common solvents except sulfuric acid nonflammable chemical resistant film. 

The other mechanism involving acyl cleavage is the AacI mechanism. This is rare, being found only where R is very bulky, so that bimolecular attack is sterically hindered, and only in ionizing solvents. The mechanism has been demonstrated for esters of 2,4,6-trimethylbenzoic acid (mesitoic acid). This acid depresses the freezing point of sulfuric acid four times as much as would be predicted from its molecular weight, which is evidence for the equilibrium... 

The application of surface treatments to mbbers should produce improved wettability, creation of polar moieties able to react with the adhesive, cracks and heterogeneities should be formed to facilitate the mechanical interlocking with the adhesive, and an efficient removal of antiadherend moieties (zinc stearate, paraffin wax, and processing oils) have to be reached. Several types of surface preparation involving solvent wiping, mechanical and chemical treatments, and primers have been proposed to improve the adhesion of vulcanized SBR soles. However, chlorination with solutions of trichloroisocyanuric acid (TCI) in different solvents is by far the most common surface preparation for mbbers. 

The mechanism of the novel transformation of a-nitro- to a-hydroxy-ketones has been probed. The reaction, which proceeds under basic aqueous conditions, requires that the Q -nitro substrate be CH-acidic in the a -position, and that it be readily depro-tonated under the conditions employed. NO2 -OH exchange occurs with retention of configuration, with the hydroxyl oxygen being predominantly derived from the solvent. A mechanism involving neighbouring-group participation, via a Favorskii-like cyclopropanone intermediate, is proposed. 

A similar solvent trapping mechanism has been proposed to account for formation of 5-indanol from acid-catalyzed isomerization of the arene oxide tautomer of oxepin (22) (73JA60641). 

It has been known that the electrolysis in an MeCN- NaClO system generates an acid The hydrogen has to originate from the solvent. A mechanism for hydrogen abstraction from acetonitrile by the electrooxidatively generated radical 104- to produce perchloric acid has been proposed, but no evidence for the succinonitrile formation appeared (Eq. (5)). The detection of the 104- radical by the aid of HSR was tried But it was found to be difficult to differentiate between the perchlorate radical and the radical from chlorine dioxide The electrolysis in a CH Clj—... 

The mechanism of this type of esterification reaction has been much studied in recent years, using diphenyldiazomethane. In alcoholic solvents the mechanism of the reaction involves a rate-determining proton transfer from the acid to the carbon atom of the diazoalkane, to form a benzhydryldiazonium-carboxylate ion-pair135, viz. 

The following processes are used commercially for the separation of such fatty acids mechanical pressing, solvent crystallization, and hydrophilization. 

Chiral tridentate chromium(III) complexes catalyze highly enantio- and diastereo-selective hetero-Diels-Alder reaction between various aldehydes and dienes with one oxygen substituent (Sch. 60) [206]. Complex formation between catalysts and aldehydes could not be detected by IR and the successful use of acetone as a solvent casts doubt on a simple Lewis acid mechanism. 

The data for this solvent were not used to calculate the parameters in Table 54. Similarly the data for decarboxylation of oxanilic acid in anisole were not used for the AH -AS correlation. With the reported AH value of 32.6 kcal.mole , the entropy of activation is calculated to be 3.59 0.03 eu compared to the reported value of 11.1 eu. In the decarboxylation of malonic acid, the data obtained with pyridine and ) -mercaptopropionic acid solvents deviated considerably from the plots and were not included in the correlation. The data for malonic acid decarboxylation appeared to be best correlated by two lines. One line was described by the following solvents acids, phenols, nitro-aromatics, benzaldehyde, and the melt the other line involved amines, alcohols, dimethylsulfoxide and triethyl phosphate. The latter line was not as well defined as the former. However, it was our intention to correlate as many solvents as possible with a minimum number of lines. The data for decarboxylation of malonic acid in water and in benzyl alcohol fell between these two lines and were not included in either correlation. The data for decarboxylation of benzylmalonic acid also appeared to be best correlated with two lines. One line was defined by the cresols, acids and the melt, while the other line was defined by the amines. Decarboxylation of cinnamalmalonic acid was correlated by two lines as indicated in Table 54. Similarly j8-resorcylic acid was correlated by two lines. The separation of data into parallel lines is presumably due to multiple solvation mechanisms . In support of this interpretation it is seen that when two lines are observed, acids fall into one line and amines into the other. It is not unexpected that the solvation mechanisms for these two classes of solvents would differ. It is interesting to note that all of the nitrogen containing acids are correlated reasonably well with one line for both basic and acidic solvents. Also the AHq values fall in a rather narrow range for all of the acids. From the values of p in Table 54, there appears to be little correlation between this parameter and the melting point of the acids, contrary to prior reports " ... 

Clean by steam, detergents, solvents, acids, or bases. Another option to lengthen cycle time is to add solids to the feed to mechanically wear away the gel layer. The choice affects membrane life. Steam cleaning gives 50 to 150 cycles before membrane replacement nonsteam cleaning gives 200 to 500 cycles. 

Until very recently this type of conversion had not been observed for phosphine functionalised ferrocenes, although under certain conditions (solvent, acid, photochemical intiation, for example) similar conversions have been reported for related systems. [182] The bis-planar chiral ferrocenyldiphosphine bis(l-(diphenylphosphino)-T)-indenyl)iron(II) was found to undergo an isomerisation from the meso isomer to the rac isomer in tetrahydrofuran solvent at room temperature. [183] Among attempts to understand the mechanism of this... 

Iodine was reported to be a catalyst for the conversion of sucrose or d-fructose into 5-(hydroxymethyl)-2-furaldehyde in anhydrous solvents, the mechanism proposed for the reaction being based on the intermediates (56) and (59). However, the addition of a crystal of sodium acetate completely suppresses the reaction, showing the reaction to be acid-catalyzed. ... 

Many unsubstituted polymeric organic semiconductors are not easily dissolved in solvents. After mechanical processing, doping with acids, and/or processing with surfactants many of these materials can be formed into conductive dispersions and applied from solution to substrates. 

In aprotic solvents. The mechanism of protonation is basically the same as that discussed above. The second order term observed by Bronsted (1928, see above) is due to an equilibrium of the acid catalyst forming dimeric aggregates. Therefore, fastest rates are measured in dipolar aprotic solvents, e.g., dimethyl sulfoxide (Blues et al., 1974). All these kinetic measurements verify a prediction made by Staudinger and Gaule at a very early date (1916), namely, that with acetic acid or trichloroacetic acid in inert solvents the reactivity of substituted diazoalkanes and a-diazo-carbonyl and a,a -dicarbonyl diazo compounds increases as the protonation equilibrium is shifted towards the corresponding alkanediazo-nium ion. This prediction includes the compounds listed in sequence 4-23 ... 

---