Calcium hydroxide additives, reactions with

A commercially important mixed addition involves ethanal and an excess of methanal in the presence of calcium hydroxide. Addition occurs three times and the resulting trihydroxymethylethanal (which has no a hydrogens) undergoes a crossed Cannizzaro reaction (see Exercise 16-33) with more methanal to give a tetrahydroxy alcohol known as pentaerythritol ... 

Suitable catalysts include the hydroxides of sodium (119), potassium (76,120), calcium (121—125), and barium (126—130). Many of these catalysts are susceptible to alkali dissolution by both acetone and DAA and yield a cmde product that contains acetone, DAA, and traces of catalyst. To stabilize DAA the solution is first neutralized with phosphoric acid (131) or dibasic acid (132). Recycled acetone can then be stripped overhead under vacuum conditions, and DAA further purified by vacuum topping and tailing. Commercial catalysts generally have a life of about one year and can be reactivated by washing with hot water and acetone (133). It is reported (134) that the addition of 0.2—2 wt % methanol, ethanol, or 2-propanol to a calcium hydroxide catalyst helps prevent catalyst aging. Research has reported the use of more mechanically stable anion-exchange resins as catalysts (135—137). The addition of trace methanol to the acetone feed is beneficial for the reaction over anion-exchange resins (138). 

Fully aromatic polyamides are synthesized by interfacial polycondensation of diamines and dicarboxylic acid dichlorides or by solution condensation at low temperature. For the synthesis of poly(p-benzamide)s the low-temperature polycondensation of 4-aminobenzoyl chloride hydrochloride is applicable in a mixture of N-methylpyrrolidone and calcium chloride as solvent. The rate of the reaction and molecular weight are influenced by many factors, like the purity of monomers and solvents, the mode of monomer addition, temperature, stirring velocity, and chain terminators. Also, the type and amount of the neutralization agents which react with the hydrochloric acid from the condensation reaction, play an important role. Suitable are, e.g., calcium hydroxide or calcium oxide. 

For this reaction the amine (Aldrich Chemical Company, Inc.) from a freshly opened bottle is dried by distillation from active powdered calcium hydride. Addition over 1 min or less is required to avoid excessive foaming which has been observed when slow or dropwlse addition is used. Older samples of amine which contain water should be pre-dried overnight with potassium hydroxide. 

Calcium Hydroxide and Sodium Carbonate. Disposal by slow addition to sodium carbonate and dry slaked lime resulted in a violent reaction.3 Potassium. PBr3 liquid or vapor ignites on contact with K.4... 

Several addition reactions have been or are currently used on a large scale in industrial chemical plants. For example, an older method for the preparation of ethylene oxide employed the addition of chlorine to ethylene in water to form ethylene chlorohydrin or 2-chloroethanol. (In industry, ethene is almost always called ethylene.) Treatment of the chlorohydrin with calcium hydroxide results in the formation of ethylene oxide, which is an important intermediate in the manufacture of ethylene glycol and other products (see the Focus On box on page 375). However, this method is wasteful of... 

Preparation of Fremy s salt a freshly prepared sodium bisulfite solution (100 ml) is added to a mixture of sodium nitrite (345 g) and ice (200 g) in a 1-1 beaker. On addition of 20 ml of glacial acetic acid, the reaction mixture turns black. Concentrated ammonium hydroxide (25 ml) is added and the mixture is cooled in an ice bath. A 0.2 M solution (400ml) of potassium permanganate is added dropwise over 1 h and the black precipitate which forms is immediately removed by filtration. A saturated solution of potassium chloride (250 ml) is added slowly over a 45-min period while the filtrate is gently stirred in an ice water bath. The precipitate that forms is collected by filtration and washed successively with a saturated solution of potassium chloride and methanol, each containing 5% of concentrated ammonium hydroxide and, finally, with acetone. Fremy s salt should be stored in a desiccator over calcium oxide. A small amount of ammonium carbonate in a desiccator is also very effective in protecting Fremy s salt against deeomposition. 

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