Acetals specials

A. Klausener, O/O-Acetals Special (OH/OH-Acetals, Lactols, 1,3,5-Trioxanes, OR/OEne-Acetals, OEne-Acetals etc.), in Methoden Org. Chem. (Houben-Weyl) 401 ed., 1952-, O/O- and O/S-Acetals (H. Hagemann, D. Klamann, Eds.), Vol. E14a/1, 591, Georg Thieme Verlag, Stuttgart, 1991. 

The Karl Fischer method is applied in a multitude of substances from finished products (butter, cheese, dried milk sugar, etc.) to solvents and other industrial products (paper, gas, petroleum, plastic films, etc.). Solids and not soluble samples must, prior to the measurement, either be ground into powders, extracted with anhydrous solvents, eliminated as azeotropes or heated to evaporate the water in special accessories. The only difficult cases are encountered with strongly acidic or basic media since they denature reactants as well as ketones and aldehydes which perturb the titration through formation of acetals (special reagents must be used for these instances). 

Highway Deicing Comparing Salt and Calcium Magnesium Acetate , Special Report 235, Transportation Research Board, National Research Council, Washington, DC, 1991. p.ll. 

Glacial Acetic Acid. Acetic acid is very hygroscopic, and its freezing-point is considerably affected by the water absorbed. Satisfactory results cannot be obtained with the apparatus shown in Fig. 79, p. 433, and a specially modified apparatus must be employed (see Nitrobenzene). 

Acetylating Mixture. Equal vols. of acetic anhydride and glacial acetic add (p. 107). (A special mixture is used for quantitative acetylation see p. 451.)... 

Ether - Starting fluid (works great - Quaaaaack ) 2. Home made mercuric acetate (Now this stuff can be special ordered from ones chem supplier but there s a delay, may look funny - Quaaaaack , and is more expensive. So what is the solution to this Make it yourself Its easy, quantitative, and cheaper. Strike mentions this in the book and points ducks to a reference. Follow the EXACT same procedure for Mercuric Propionate except use glacial acetic acid...quack ). You ll need to use 20 to 25% more of the home brew mercuric acetate since it is a little contaminated with acetic (ducks can t get it totally dry without a vacuum oven). 3. NaOH washed Brazillian is fine Quack No need to purify further for starting material ... 

Silyl enol ethers are other ketone or aldehyde enolate equivalents and react with allyl carbonate to give allyl ketones or aldehydes 13,300. The transme-tallation of the 7r-allylpalladium methoxide, formed from allyl alkyl carbonate, with the silyl enol ether 464 forms the palladium enolate 465, which undergoes reductive elimination to afford the allyl ketone or aldehyde 466. For this reaction, neither fluoride anion nor a Lewis acid is necessary for the activation of silyl enol ethers. The reaction also proceed.s with metallic Pd supported on silica by a special method[301j. The ketene silyl acetal 467 derived from esters or lactones also reacts with allyl carbonates, affording allylated esters or lactones by using dppe as a ligand[302]... 

One of the virtues of the Fischer indole synthesis is that it can frequently be used to prepare indoles having functionalized substituents. This versatility extends beyond the range of very stable substituents such as alkoxy and halogens and includes esters, amides and hydroxy substituents. Table 7.3 gives some examples. These include cases of introduction of 3-acetic acid, 3-acetamide, 3-(2-aminoethyl)- and 3-(2-hydroxyethyl)- side-chains, all of which are of special importance in the preparation of biologically active indole derivatives. Entry 11 is an efficient synthesis of the non-steroidal anti-inflammatory drug indomethacin. A noteworthy feature of the reaction is the... 

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... 

Section 20 5 Acid anhydrides may be prepared from acyl chlorides m the laboratory but the most commonly encountered ones (acetic anhydride phthahc anhydride and maleic anhydride) are industrial chemicals prepared by specialized methods... 

Glacial acetic acid is considered to be 99.50 wt % or higher. A different grade has a minimum concentration of 99.70 wt %. Specialty users require water solutions of 86% and 36%. Such grades are prepared on special order. Only minor quantities of these grades are marketed, and their use is vanishing. 

Acrolein is a highly toxic material with extreme lacrimatory properties. At room temperature acrolein is a Hquid with volatiUty and flammabiUty somewhat similar to acetone but unlike acetone, its solubiUty in water is limited. Commercially, acrolein is always stored with hydroquinone and acetic acid as inhibitors. Special care in handling is required because of the flammabiUty, reactivity, and toxicity of acrolein. 

Other Films. Although commercially less important than polyethylenes and polypropylenes, a number of other plastic films are in commercial use or development for special appHcations, including ethylene—vinyl acetate, ionomer, and polyacrylonitrile [25014-41-9]. 

Butane LPO conducted in the presence of very high concentrations of cobalt catalyst has been reported to have special character (2,205,217—219). It occurs under mild conditions with reportedly high efficiency to acetic acid. It is postulated to involve the direct attack of Co(III) on the substrate. Various additives, including methyl ethyl ketone, -xylene, or water, are claimed to be useful. 

Diacetone Alcohol. Diacetone alcohol (DAA) (4-hydroxy-4-methyl-2-pentanone) is a colorless, mild smelling Hquid which is completely miscible with water and most organic solvents. It is the simplest aldol condensation product of acetone, and because of its keto-alcohol functionahes it has special utility in the coatings industry where it is used to dissolve cellulose acetate to give solutions with high tolerance for water (115). 

Limonene (15) can be isomerized to terpiaolene (39) usiag Hquid SO2 and a hydroperoxide catalyst (/-butyl hydroperoxide (TBHP)) (76). Another method uses a specially prepared orthotitanic acid catalyst with a buffer such as sodium acetate (77). A selectivity of about 70% is claimed at about 50% conversion when mn at 150°C for four hours. 

Strong bases, such as potassium acetate, potassium 2-ethylhexoate, or amine—epoxide combinations are the most useful trimerization catalysts. Also, some special tertiary amines, such as 2,4,6-tns(A7,A7-dimethylarninomethyl)phenol (DMT-30) (6), l,3,5-tris(3-dimethylaminopropyl)hexahydro-j -triazine (7), and ammonium salts (Dabco TMR) (8) are good trimerization catalysts. 

Special vinyl acetate copolymer paints have been developed with gready improved resistance to blistering or peeling when immersed in water. This property allows better cleaning and use in very humid environments. These lattices exhibit the water resistance of higher priced acryUc resins (150). VAc, vinyl chloride—ethylene terpolymers have been developed which provide the exterior resistance properties of vinyl chloride with the dexibiUty of the ethylene for exterior paint vehicles (151). 

Alternatively, thermal cracking of acetals or metal-catalyzed transvinylation can be employed. Vinyl acetate or MVE can be employed for transvinylation and several references illustrate the preparation especially of higher vinyl ethers by such laboratory techniques. Special catalysts and conditions are required for the synthesis of the phenol vinyl ethers to avoid resinous condensation products (6,7). Direct reaction of ethylene with alcohols has also been investigated (8). 

In addition to the acid—base components shown in Figure 9, various organic acids are often found. Many of these acids are by-products of the atmospheric oxidation of organic matter released into the atmosphere. Of special interest are formic, acetic, oxaUc, and benzoic acids, which have been found in rainwater in concentrations occasionally exceeding a few micromoles per Hter. 

Other mixed esters, eg, cellulose acetate valerate [55962-79-3] cellulose propionate valerate [67351-41-17, and cellulose butyrate valerate [53568-56-2] have been prepared by the conventional anhydride sulfuric acid methods (25). Cellulose acetate isobutyrate [67351-38-6] (44) and cellulose propionate isobutyrate [67351-40-0] (45) have been prepared with a 2inc chloride catalyst. Large amounts of catalyst and anhydride are required to provide a soluble product, and special methods of delayed anhydride addition are necessary to produce mixed esters containing the acetate moiety. Mixtures of sulfuric acid and perchloric acid are claimed to be effective catalysts for the preparation of cellulose acetate propionate in dichi oromethane solution at relatively low temperatures (46) however, such acid mixtures are considered too corrosive for large-scale productions. 

Cellulose acetate films, specially cast to have a dense surface and a porous substmcture, are used in reverse osmosis to purify brackish water (138—141) in hollow fibers for purification of blood (artificial kidney) (142), and for purifying fmit juices (143,144) (see Membrane technology). 

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