Calcium catalysts

Fig. 5. Semilogarithmic plots for polymerization of formaldehyde at —30°C (1) catalyst calcium stearate, concentration 4x10" molel (2) catalyst tetrabutyl-ammonium laurate, concentration 2 x 10" mole 1" (3) catalyst triethylamine, concentration 3 x 10" mole 1". g is the degree of conversion.

As a catalyst calcium magnesium phosphate appeared to be the best. Dchydrohafogenation of halogenonitro alkanes, for example (25) ... 

Use Chemical (precipitant in the cyanide process, precipitant of iodine and lead salts from their solutions, catalyst, calcium carbide) decolorizing and filtering medium gas adsorbent component of black powder and other explosives fuel arc-light electrodes decolorizing and purifying oils solvent recovery deodorant. 

Further, the decrease in catalytic behavior of metal catalysts (calcium acetate and antimony trioxide) is attributed to the inhibiting action of carboxyl and/or hydroxyl groups present in the reaction medium. It has been observed in various reactions that carboxyl groups strongly inhibit the catalytic activity of Ti(OBu) [105,106] and acetates of Zn, Ca, and Mn [105,107,108], and hydroxyl groups decrease the catalytic activity of SbOj [105,107,108]. 

While calcium isopropoxide, Ca(0 Pr)2 has been employed successfully in the preparation of chiral catalysts, it was also found that calcium amide (e.g., Ca (HMDS)2) worked well in these reactions as a catalyst. Calcium amides have a stronger Brpnsted basicity and a higher solubility in many solvents compared with calcium alkoxides. Interestingly, it was reported that chiral calcium amide catalysts prepared from Ca(HMDS)2 could be employed successfully in [3+2] cycloaddition reactions (Scheme 4) [48]. 

The mechanism of the ethoxylation of esters with these complex catalysts is not well understood. It is thought to involve a transesterification which effectively inserts ethylene oxide into the ester linkage between the carbonyl carbon and the methoxy oxygen [9,15,18]. This mechanism is illustrated in Fig. 4. As shown, the active catalyst (calcium and aluminum alkoxyethoxy-late) first reacts with ethylene oxide to form the ethoxylated version of the metal alkoxythoxylate. This molecule then transesterifies with methyl ester to form the alkyl ester ethoxylate and a metal-coordinated methoxide ion. Addition of more ethylene oxide (step 2) produces progressively more highly ethoxylated versions of the metal-coordinated methoxide ions, which then transesterify with the ester (step 3) to form methyl ester ethoxylate, the alkyl ester ethoxylate, and the metal-coordinated methoxide. Steps 2 and 3 occur continuously with the addition of more ethylene oxide until excess methyl... 

The activity of each catalyst is dependent upon the pretreatment temperature. Table 4.33 summarizes the activities following pretreatment at optimum temperature for each catalyst. Calcium oxide shows markedly high activity. 

Fig. 7. SEM images of NiM60Cl 100 and NiCa3.70 catalysts - Calcium content effect.

Allyl Chloride. Comparatively poor yields are obtained by the zinc chloride - hydrochloric acid method, but the following procedure, which employs cuprous chloride as a catalyst, gives a yield of over 90 per cent. Place 100 ml. of allyl alcohol (Section 111,140), 150 ml. of concentrated hydrochloric acid and 2 g. of freshly prepared cuprous chloride (Section II,50,i one tenth scale) in a 750 ml. round-bottomed flask equipped with a reflux condenser. Cool the flask in ice and add 50 ml. of concen trated sulphuric acid dropwise through the condenser with frequent shaking of the flask. A little hydrogen chloride may be evolved towards the end of the reaction. Allow the turbid liquid to stand for 30 minutes in order to complete the separation of the allyl chloride. Remove the upper layer, wash it with twice its volume of water, and dry over anhydrous calcium chloride. Distil the allyl chloride passes over at 46-47°. 

Preparation of palladium - calcium carbonate catalyst. Prepare 60 g. of precipitated calcium carbonate by mixing hot solutions of the appropriate quantities of A.R. calcium chloride and A.R. sodium carbonate. Suspend the calcium carbonate in water and add a solution containing 1 g. of palladium chloride. Warm the suspension until all the palladium is precipitated as the hydroxide upon the calcium carbonate, i.e., until the supernatant liquid is colourless. Wash several times with... 

Alternatively, use the following procedure in which triethylamine replaces potassium acetate as the basic catalyst. Place 2 1 g. (2-0 ml.) of purified benzaldehyde, 2 0 ml. of anhydrous triethylamine and 5 0 ml. of A.R. acetic anhydride in a 200 ml. round-bottomed flask, equipped with a short reflux condenser and a calcium chloride drying tube. Boil the solution gently for 24 hours—heating may be interrupted. Incorporate a steam distillation apparatus in the flask and steam distil until the distillate is no longer cloudy (about 100 ml.) and then collect a further 50 ml. of the distillate di ard the steam distillate. Transfer the residue in the flask to a 400 ml. beaker, add water until the vplume is about 200 ml., then 0 2 g. of decolourising carbon, and boil for a few minutes. Filter the hot solution, and acidify the hot filtrate with 1 1 hydrochlorioiaoid... 

A cousin to this reduction is one using stannous chloride (a.k.a. SnCb, a.k.a. Tin chloride) which is done exactly as the calcium one except that about lOOg of SnCb is used in place of the Mg or Ca and the addition occurs at room temperature and the solution is stirred for one hour rather than 15 minutes. Some very good reductions that operate almost exclusively at room temperature with no pressure and give almost 100% yields are to follow. The only reason Strike did not detail these methods is that some of the chemicals involved are a little less common than Strike is used to but all are available to the public. These alternatives include acetlylacetone and triethylamine [73], propanedithlol and trieth-ylamine [74], triphenylphosphine [75], NaBH4 with phase transfer catalyst [76], H2S and pyridine [77], and palladium hydrox-ide/carbon with hydrazine [78], stannous chloride dihydrate [85]. 

Both objectives have been met by designing special hydrogenation catalysts The most frequently used one is the Lindlar catalyst, a palladium on calcium carbonate combi nation to which lead acetate and quinoline have been added Lead acetate and quinoline partially deactivate ( poison ) the catalyst making it a poor catalyst for alkene hydro genation while retaining its ability to catalyze the addition of H2 to the triple bond... 

Lindlar catalyst (Section 9 9) A catalyst for the hydrogenation of alkynes to as alkenes It is composed of palladium which has been poisoned with lead(II) acetate and quino line supported on calcium carbonate... 

Nickel halide complexes with amines give mixtures of linear polymer and cychc trimers (30). Nickel chelates give up to 40% of linear polymer (31). When heated with ammonia over cadmium calcium phosphate catalysts, propargyl alcohol gives a mixture of pyridines (32). 

Other Plastics Uses. The plasticizer range alcohols have a number of other uses in plastics hexanol and 2-ethylhexanol are used as part of the catalyst system in the polymerization of acrylates, ethylene, and propylene (55) the peroxydicarbonate of 2-ethylhexanol is utilized as a polymerization initiator for vinyl chloride various trialkyl phosphites find usage as heat and light stabHizers for plastics organotin derivatives are used as heat stabHizers for PVC octanol improves the compatibHity of calcium carbonate filler in various plastics 2-ethylhexanol is used to make expanded polystyrene beads (56) and acrylate esters serve as pressure sensitive adhesives. 

The most common catalysts are sodium hydroxide and calcium hydroxide, generally used at a modest excess over the nominal stoichiometric amount to avoid formaldehyde-only addition reactions. Calcium hydroxide is cheaper than NaOH, but the latter yields a more facile reaction and separation of the product does not require initial precipitation and filtration of the metal formate (57). 

Less activated substrates such as uorohaloben2enes also undergo nucleophilic displacement and thereby permit entry to other useful compounds. Bromine is preferentially displaced in -bromofluoroben2ene [460-00-4] by hydroxyl ion under the following conditions calcium hydroxide, water, cuprous oxide catalyst, 250°C, 3.46 MPa (500 psi), to give -fluorophenol [371-41-5] in 79% yield (162,163). This product is a key precursor to sorbinil, an en2yme inhibitor (aldose reductase). 

Ultimately, as the stabilization reactions continue, the metallic salts or soaps are depleted and the by-product metal chlorides result. These metal chlorides are potential Lewis acid catalysts and can greatiy accelerate the undesired dehydrochlorination of PVC. Both zinc chloride and cadmium chloride are particularly strong Lewis acids compared to the weakly acidic organotin chlorides and lead chlorides. This significant complication is effectively dealt with in commercial practice by the co-addition of alkaline-earth soaps or salts, such as calcium stearate or barium stearate, ie, by the use of mixed metal stabilizers. 

Hydrolysis of Peroxycarboxylic Systems. Peroxyacetic acid [79-21-0] is produced commercially by the controlled autoxidation of acetaldehyde (qv). Under hydrolytic conditions, it forms an equiHbrium mixture with acetic acid and hydrogen peroxide. The hydrogen peroxide can be recovered from the mixture by extractive distillation (89) or by precipitating as the calcium salt followed by carbonating with carbon dioxide. These methods are not practiced on a commercial scale. Alternatively, the peroxycarboxyHc acid and alcohols can be treated with an estetifying catalyst to form H2O2 and the corresponding ester (90,91) (see Peroxides and peroxy compounds). 

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). 

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