Solid acids isopropanol reaction

A polymeric pinacol,poly[3-methyl-2-(4-vinylphenyl)-2,3-butanediol],has been prepared by radical polymerization of the styrenic diol monomer and shown to be cleanly and quantitatively converted to a non-conjugated ketone in the solid state by reaction with a photochemically-generated acid [151,348, 350]. The rearrangement reaction can be readily monitored by IR spectroscopy as the disappearance of the hydroxyl OH absorption is accompanied by appearance of a new ketone carbonyl absorption (Fig. 116). Since a polar alcohol (isopropanol) dissolves the polar diol polymer in the unexposed regions but cannot dissolve the less polar ketone polymer produced in the exposed regions, the resist functions as a negative system with alcohol as a developer. The diol polymer is stable thermally to 225 °C in the absence of acid. 

Sulfonated polysiloxanes have been tested in a variety of reactions. A typical reaction used to compare the acid strength of these catalysts with that of other solid acids is dehydration of isopropanol to yield propene [3]. The splitting of ethers, especially MTBE, at temperatures up to 200 °C has also been successfully demonstrated [14]. 

Scheme 9.19 The reaction of isopropanol is a diagnostic test for solid acid or basic sites.

After evaporation of the solvent, the solid residue consists of 5-(2-chlorobenzyl)-thieno[3,2-cl -pyridinium chloride which melts at 166°C (derivative n°30). This compound is taken up into a solution comprising ethanol (300 ml) and water (100 ml). Sodium borohydride (NaBH4) (20 g) is added portionwise to the solution maintained at room temperature. The reaction medium is maintained under constant stirring during 1 2 hours and is then evaporated. The residue is taken up into water and made acidic with concentrated hydrochloric acid to destroy the excess reducing agent. The mixture is then made alkaline with ammonia and extracted with ether. The ether solution is washed with water, dried and evaporated. The oily residue is dissolved in isopropanol (50 ml) and hydrochloric acid in ethanol solution is then added thereto. 

It is important to note that the one-step conversion of 27 to 28 (Scheme 4) not only facilitates purification, but also allows differentiation of the two carbonyl groups. After hydrogenolysis of the iV-benzyl group (see 28—>29), solvolysis of the -lactone-ring in 29 with benzyl alcohol and a catalytic amount of acetic acid at 70 °C provides a 3 1 equilibrium mixture of acyclic ester 30 and starting lactone 29. Compound 30 can be obtained in pure form simply by washing the solid mixture with isopropanol the material in the filtrate can be resubjected to the solvolysis reaction. 

Experimental Procedure19 for 4-bis(4-dimethylaminophenyl)methyl-2,6 dimethoxyphenol (55a). A mixture of syringaldehyde (5.46 g, 30 mmol, A.A-dimethylaniline (7.26 g, 60 mmol), urea (2.7 g), and concentrated sulfur ic acid (4.41 g) in isopropanol (100ml) was heated at 90°C under a nitrogen atmosphere for 24h. The reaction was cooled to room temperature and 40ml of water added followed by 50% NaOH until alkaline. The mixture was filtered and the residue washed with 200ml of cold water. The solid was recrystallized from ethanol and yielded 12.0g (97%), mp 136-138°C. 

Another case where the test reaction has been used to correlate catalytic behavior and physicochemical properties, is the interesting vanadium-containing system studied by Trikalitis and Pomonis (1995). They studied the transformation of isopropanol over Lai -xS VOb. This solid contains vanadium in at least two oxidation states, Vm and VIv. The systematic variation of the Sr content modifies the acid-base balance on the surface... 

Results from the comparisons between theoretically calculated (solid lines) and experimentally measured (individual symbols) acid numbers are shown for the esterification of methacrylic acid using n-propyl alcohol (Figures 1-3), and for the esterification of metharylic acid using isopropyl alcohol (Figures 4-6). The average error of fit of experimental results to proposed kinetic model is, respectively, 3.5% and 5.7%, for 9 sets of data concerning the reaction with n-propanol, for 9 sets for the esterification with n-isopropanol. 

Numerous types of basic heterogeneous catalysts, such as alkahne earth metal oxide, anion exchange resins and alkali metal compounds supported on alumina or zeolite can catalyze various chemical reactions such as isomerization, aldol, Michael, and Knoevenagel condensation, oxidation and transesterification [1], Today considerable attention is devoted to the production of biodiesel (FAMEs) as an alternative for petroleum-derived diesel fuel. Biodiesel is synthesized by direct transesterification of vegetable oil or animal fat with a short-chain alcohol, viz. methanol, ethanol, and isopropanol in presence of an acid, base or enzymatic catalyst [2], Considering the advantages of solid base catalysts, for easy separation and recovery, reduced corrosion and environmental acceptance [1], many studies have been conducted on basic heterogeneous catalysts development for biodiesel production [3-13],... 

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