Phenol phenyl benzyl ether, effect

Furthermore, we studied the effect of phenolic compounds on the thermolysis of phenyl benzyl ether at 320°C, because even reactive phenols such as p-methoxy phenol are quite stable at this temperature. 

TABLE IV EFFECT OF PHENOLS ON THE THERMAL DECOMPOSITION OF PHENYL BENZYL ETHER AT 320°C FOR 30 MIN (Phenyl benzyl ether 27 mmole, Tetralin 220 mmole, Additive 140 mmole)... 

Previous studies of the reactions of guaiacol (orthomethoxy-phenol) (3 ), dibenzyl ether (4 ), and benzyl phenyl amine (5) in dense water elucidated parallel hydrolysis and pyrolysis pathways, the selectivity to the latter increasing with water density. Reactant decomposition kinetics were interestingly nonlinear in water density and consistent with two mechanistic interpretations. The first involved "cage" effects, as described for reactions in liquid solutions (6 ). The second led to parallel pyrolysis and solvolysis reaction pathways wherein associated rate constants were dependent upon pressure. These two schemes are probed herein through the reactions of benzyl phenyl amine (BPA) in water and methanol. 

Relatively little basic information has been published regarding the kinetics of phenol-formaldehyde intermediates, especially of phenols, methylol phenols, benzyl alcohol and benzylic ethers with isocyanates. Due to the fact that a typical resole contains both phenolic and benzylic hydroxyl groups, it was of interest to determine their reactivity toward isocyanates in the presence of various catalysts, as well as the effect of substitution on their reactivity. This investigation describes the kinetics of model phenols and model benzyl alcohols with phenyl isocyanate catalyzed with either a tertiary amine (dimethylcyclo-hexylamine, DMCHA) or an organotin catalyst, dibutyltin dilaurate (DBTDL) in either dioxane or dimethylformamide solution. 

Fission of aryl ethers can also be effected by metallic sodium or potassium. For instance, diphenyl ether, which is one of the most resistant ethers, is decomposed by liquid potassium-sodium alloy at room temperature.38 Weber and Sowa have cleaved 4,4 -disubstituted diphenyl ethers into benzene and phenol derivatives by sodium in liquid ammonia.39 Diallyl ether is converted by sodium dust at 35° into allylsodium and sodium allyl oxide, which provides a suitable method for preparation of allylsodium.3 7a Anisole, phenetole, benzyl phenyl ether, and diphenyl ether give the phenols in 90% yield, without by-products, when boiled with sodium or potassium in pyridine.40... 

The second order nature of quaternization reactions in our system was confirmed by rate studies on model compounds. Although benzyl chloride is usually selected as the model for chloro-methylated polymers , we chose to synthesize a difunctional model that would be sensitive to neighboring group effects. Condensation of 4-chlorophenyl phenyl sulfone with the disodlum salt of bis-phenol-A yielded an excellent model for the polysulfone segment, Quantitative chloromethylation of with a chloromethyl methyl ether/ methyl acetate mixture in the presence of stannic chloride afforded the corresponding bischloromethyl adduct,... 

---