Water, as catalyst

Methylacetylene and CO introduced continuously at 130°/13 atm. into a stirring autoclave containing Ni-carbonyl, methacrylic acid and a little water as catalysts, and hydroquinone methyl methacrylate. Y 80.5%. S. Kunichika, Y. Sakakibara, and T. Nakamura, Bull. Chem. Soc. Japan 41, 390 (1968). 

Synthetically, PHB is produced from racemic 3-butyrolactone and P(HB-co-HV) is made from a mixture of 3-butyrolactone and 3-valerolactone, with triethyla-luminum and water as catalyst (48). Although the stereospecificity of the resulting polymer can be controlled to a certain extent by adjusting the ratio of triethylaluminum and water, synthetic PHAs are usually optically inactive and hence only partially biodegradable. 

Heterocyclcs have also been obtained by carbonylation of o/V/70-substituted nitro compounds, by using selenium in water as catalyst. This route seems to be limited by the toxicity and volatility of compounds such as H2SC and COSe. Besides 2-benzoxazolones (37) (cq. 17) [70] ... 

Spectroscopic evidence of the seven-membered rings has been found in the preparation of polyimides from pyromellitic dianhydride and methylenediphenyl-diisocyanate (MDI) [105]. The reaction is conducted in solution of aprotic solvents, with reagents addition at low temperature and a maximum reaction temperature of about 130 °C. On the other hand, polyimides of very high molecular weight have not been reported by this method. The mechanism is different when the reaction is accelerated by the action of catalysts. Catalytic quantities of water or alcohols facilitate imide formation, and intermediate ureas and carbamates seem to be formed, which then react with anhydrides to yield polyimides [106]. Water as catalyst has been used to exemplify the mechanism of reaction of phthalic anhydride and phenyl isocyanates, with the conclusion that the addition of water, until a molecular equivalent, markedly increases the formation of phthalimide [107] (Scheme 13). The first step is actually the hydrolysis of the isocyanates, and it has been claimed that ureas are present in high concentration during the intermediate steps of the reaction [107]. Other conventional catalysts have been widely used to accelerate this reaction. Thus, tertiary amines, alkali metal alcoholates, metal lactames, and even mercury organic salts have been attempted [108]. 

Although ROP experiments were performed on all three trimers, only the 3-pyridinoxy trimer failed to polymerize at temperatures as high as 300 °C, even in the presence of hexachlorocyclotriphosphazene, AICI3 or water as catalyst. The... 

Other examples of water as an apparent catalyst are (a) carbon monoxide will not bum in oxygen unless a trace of water is present. 

Acetaldehyde, b.p. 21°, undergoes rapid pol5unerisation under the influence of a little sulphuric acid as catalyst to give the trimeride paraldehyde, a liquid b.p. 124°, which is sparingly soluble in water. The reaction is reversible, but attains equilibrium when the conversion is about 95 per cent, complete the unreacted acetaldehyde and the acid catalyst may be removed by washing with water ... 

Bromination of fatty acids in the a-position can be effected quite readily in the presence of phosphorus trichloride, red phosphorus or pyridine as catalysts or halogen carriers with acetic acid, the addition of acetic anhydride (to ensure the absence of water) improves the yield and facilitates the bromination. Examples are —... 

In general, however, the diacetyl derivatives are unstable in the presence of water, undergoing hydrolysis to the mono-acetyl compound, so that when they (or a mixture of mono- and di-acetyl derivatives) are crystallised from an aqueous solvent, e.g., dilute alcohol, only the mono-acetyl derivative is obtained. A further disadvantage of the use of acetic anhydride in the absence of a solvent is that all the impm-ities in the amine are generally present in the reaction product. Heavily substituted amines, t.g., 2 4 6-tribromoaniline, react extremely slowly with acetic anhydride, but in the presence of a few drops of concentrated sulphuric acid as catalyst acetylation occurs rapidly, for example ... 

Prepare a solution of 41 g. of anhydrous palladium chloride (1) in 10 ml. of concentrated hydrochloric acid and 25 ml. of water (as in A). Add all at once 60 ml. of 6iV-sulphuric acid to a rapidly stirred, hot (80°) solution of 63 1 g. of A.R. crystallised barium hydroxide in 600 ml. of water contained in a 2-htre beaker. Add more 6iV-sulphuric acid to render the suspension just acid to htmus (5). Introduce the palladium chloride solution and 4 ml. of 37 per cent, formaldehyde solution into the hot mechanically stirred suspension of barium sulphate. Render the suspension slightly alkaline with 30 per cent, sodium hydroxide solution, continue the stirring for 5 minutes longer, and allow the catalyst to settle. Decant the clear supernatant hquid, replace it by water and resuspend the catalyst. Wash the catalyst by decantation 8-10 times and then collect it on a medium - porosity sintered glass funnel, wash it with five 25 ml. portions of water and suck as dry as possible. Dry the funnel and contents at 80°, powder the catalyst (48 g.), and store it in a tightly stoppered bottle. 

The exchange resins 6nd application in (i) the purification of water (cation-exchange resin to remove salts, followed by anion-exchange resin to remove free mineral acids and carbonic acid), (ii) removal of inorganic impurities from organic substances, (iii) in the partial separation of amino acids, and (iv) as catalysts in organic reactions (e.g., esterification. Section 111,102, and cyanoethylation. Section VI,22). 

Prepare a saturated solution of sodium sulphide, preferably from the fused technical sodium polysulphide, and saturate it with sulphur the sulphur content should approximate to that of sodium tetrasulphide. To 50 ml. of the saturated sodium tetrasulphide solution contained in a 500 ml. round-bottomed flask provided with a reflux condenser, add 12 -5 ml. of ethylene dichloride, followed by 1 g. of magnesium oxide to act as catalyst. Heat the mixture until the ethylene dichloride commences to reflux and remove the flame. An exothermic reaction sets in and small particles of Thiokol are formed at the interface between the tetrasulphide solution and the ethylene chloride these float to the surface, agglomerate, and then sink to the bottom of the flask. Decant the hquid, and wash the sohd several times with water. Remove the Thiokol with forceps or tongs and test its rubber-like properties (stretching, etc.). 

The rate of the uncatalysed reaction in all four solvents is rather slow. (The half-life at [2.5] = 1.00 mM is at least 28 hours). However, upon complexation of Cu ion to 2.4a-g the rate of the Diels-Alder reaction between these compounds and 2.5 increases dramatically. Figure 2.2 shows the apparent rate of the Diels-Alder reaction of 2.4a with 2.5 in water as a lunction of the concentration of copper(II)nitrate. At higher catalyst concentrations the rate of the reaction clearly levels off, most likely due to complete binding of the dienophile to the catalyst. Note that in the kinetic experiments... 

Note 2. Prepared by azeotropic removal of water from the commercial, water-containing product by means of benzene. This solvent was removed in a water--pump vacuum and the remaining mass was powdered. The water-containing acid appeared to work much less efficiently as catalyst. 

Furthermore a substance such as HCl that dissociates completely when dissolved m water also dissociates completely when dissolved m an alcohol Many important reactions of alco hols involve strong acids either as reactants or as catalysts In all these reachons the first step IS formation of an alkyloxonium ion by proton transfer from the acid to the alcohol... 

Alcohols and carboxylic acids yield an ester and water in the presence of an acid catalyst The reaction is an equilibrium process that can be driven to com pletion by using either the alcohol or the acid in excess or by remov mg the water as it is formed... 

The mixture is cooled and noncondensable gases are scmbbed with water. Some of the resultant gas stream, mainly hydrogen, may be recycled to control catalyst fouhng. The Hquids are fractionally distilled, taking acetone overhead and a mixture of isopropyl alcohol and water as bottoms. A caustic treatment maybe used to remove minor aldehyde contaminants prior to this distillation (29). In another fractionating column, the aqueous isopropyl alcohol is concentrated to about 88% for recycle to the reactor. 

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). 

The esterification reaction in making ester oils is commonly carried out with a catalyst at about 210°C while removing excess water as it forms (32). Excess acid or alcohol is then stripped off, and unreacted acid is neutrali2ed with calcium carbonate or calcium hydroxide before final vacuum drying (qv) and filtration (qv). 

Desalting is a water-washing operation performed at the production field and at the refinery site for additional cmde oil cleanup. If the petroleum from the separators contains water and dirt, water washing can remove much of the water-soluble minerals and entrained soflds. If these cmde oil contaminants are not removed, they can cause operating problems duting refinery processiag, such as equipment plugging and corrosion as well as catalyst deactivation. 

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