Alcohols from anhydrides

In general, the reactions of the perfluoro acids are similar to those of the hydrocarbon acids. Salts are formed with the ease expected of strong acids. The metal salts are all water soluble and much more soluble in organic solvents than the salts of the corresponding hydrocarbon acids. Esterification takes place readily with primary and secondary alcohols. Acid anhydrides can be prepared by distillation of the acids from phosphoms pentoxide. The amides are readily prepared by the ammonolysis of the acid haUdes, anhydrides, or esters and can be dehydrated to the corresponding nitriles (31). 

The o-nitrobenzyl and p-nitrobenzyl ethers can b prepared and cleaved by many of the methods described for benzyl ethers. The p-nitrobenzyl ether is also prepared from an alcohol and p-nitrobenzyl alcohol (trifluoroacetic anhydride, 2,6-lutidine, CH2CI2, 67% yield). In addition, the o-nitrobenzyl ether can be cleaved by irradiation (320 nm, 10 min, quant, yield of carbohydrate " 280 nm, 95% yield of nucleotide ). The p-nitrobenzyl ether has been cleaved by electrolytic reduction (—1.1 V, DMF, R4N X, 60% yield) and by reduction with Na2S204 (pH 8-9, 80-95% yield). These ethers can also be cleaved oxidatively (DDQ or electrolysis) after reduction to the aniline derivative. ... 

Deng also showed that (DHQD)2AQN could catalyze the parallel KR (PKR) of a variety of monosubstituted succinic anhydrides via asymmetric alcoholysis [215]. The nature of the solvent was found to have a significant influence on the selectivity. Hence, increasing the size of the alcohol from methanol to ethanol resulted in increased levels of enantioselectivity, albeit with reduced reaction rates. In this context, 2,2,2-trifluoroethanol appeared to be the alcohol of choice as it allowed the ASD of 2-methyl succinic anhydride (58a) with a remarkable level of selectivity. Indeed, the use of (DHQD)2AQN (15 mol%) provided a mixture of two regioiso-meric hemiesters 59a and 60a in a 1 1 ratio with 93 and 80% ee respectively. 

Mannitol hexanitrate is obtained by nitration of mannitol with mixed nitric and sulfuric acids. Similarly, nitration of sorbitol using mixed acid produces the hexanitrate when the reaction is conducted at 0—3°C and at —10 to —75°C, the main product is sorbitol pentanitrate (117). Xylitol, ribitol, and L-arabinitol are converted to the pentanitrates by fuming nitric acid and acetic anhydride (118). Phosphate esters of sugar alcohols are obtained by the action of phosphorus oxychloride (119) and by alcoholysis of organic phosphates (120). The 1,6-dibenzene sulfonate of D-mannitol is obtained by the action of benzene sulfonyl chloride in pyridine at 0°C (121). To obtain 1,6-dimethanesulfonyl-D-mannitol free from anhydrides and other by-products, after similar sulfonation with methane sulfonyl chloride and pyridine the remaining hydroxyl groups are acetylated with acetic anhydride and the insoluble acetyl derivative is separated, followed by deacetylation with hydrogen chloride in methanol (122). Alkyl sulfate esters of polyhydric alcohols result from the action of sulfur trioxide—trialkyl phosphates as in the reaction of sorbitol at 34—40°C with sulfur trioxide—triethyl phosphate to form sorbitol hexa(ethylsulfate) (123). 

From anhydrides and alcohols H (RC0)20 + R OH ——> RC02R T RC02H -53i. RC02R + H20 H Widely applicable acid-catalyzed. 

Fig. 8. Effect of molding pressure P on the stress in compression (crc) for a carbonized foamed plastic made from a compound binder (wood resin, furfuryl alcohol, maleic anhydride) and phenolic microspheres 381...

Oxidation of alcohols. The anhydride oxidizes benzylic alcohols to aldehydes rapidly and in high yield. Allylic and saturated alcohols are oxidized more slowly. 3-Hydroxy steroids can be oxidized to A -3-ketones by use of 4 equiv. of the reagent (60% yield). A -3-Ketones can be obtained from 3-hydroxy-4,4-dimethyl steroids in similar yields. ... 

Acyclic acid anhydrides are reduced to produce primary alcohols using NaBH4 and its many deriva-tives.2 - In most cases, the reaction gives both the primary alcohol and the carboxylate salt (1 1). Whilst such monoreduction may be desirable in cyclic anhydride chemistry (vide infra), it is inefficient when acyclic anhydrides are reduced. Thus, B2H6 or LAH reductions are the preferred synthetic methods. The reductions of mixed anhydrides, for example carboxylic/diphenylphosphoric or carboxylic/car-bonic anhydrides, produce the primary alcohol from the acyl component. ... 

Anal3Ttical and Synthetical Study of Proteins.—Fischer attacked the problem of the constitution of proteins from the synthetic side. Assuming that proteins consist of units of amino acids, as indicated by the analytical study of their hydrolytic products, he attempted to synthesize, from amino acids, compounds of similar complexity to the proteins. As already stated (p. 386), he found that the double anhydrides, resulting from the esters of amino acids by the loss of two molecules of alcohol from two molecules of the ester, took up one molecule of water when treated with dilute alkali and a single anhydride was obtained. The reactions may be represented as follows ... 

Improvement in the particle board properties made by the process based on HNO3 surface activation and ammonium lignosul-fonate-furfuryl alcohol-maleic anhydride binder was reported to result from drying of the HNO3 treated chips (J90). 

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