From Acid Anhydrides

Geranyl chloride can be prepared from geraniol by the careful use of triphenylphosphine in carbon tetrachloride. Tris(dimethylamino)phosphine reacts with carbon tetrachloride to form the complex (42) which can be used to form the enol esters (43) from acid anhydrides. Similarly, aldehydes form the alkenes (44), and esters or amides of trichloroacetic acid are converted to glycidic esters. ... 

Other reagents used for the preparation of lactones from acid anhydrides are lithium borohydride [1019], lithium triethylborohydride (Superhydride ) [1019] and lithium tris sec-butyl)borohydride (L-Selectride ) [1019]. Of the three complex borohydrides the last one is most stereoselective in the reduction of 3-methylphthalic anhydride, 3-methoxyphthalic anhydride, and 1-methoxynaphthalene-2,3-dicarboxylic anhydride. It reduces the less sterically hindered carbonyl group with 85-90% stereoselectivity and is 83-91% yield [1019]. 

Tertiary alcohols and ketones result from acid anhydrides ... 

Of special interest are olefm epoxidation with peroxy acids at the moment of their formation from acid anhydrides and hydrogen peroxide. Among the catalysts of olefin oxide formation from olefins interacting with H202 in the presence of metal (Ti, W, V, Ta, Ge, Mo, U, Ru) oxides or acids are tungstic acid and its salts [47], Epoxidation is described by the following mechanism ... 

Amides can also be synthesised from acid anhydrides and esters but in general these reactions offer no advantage over acid chlorides because acid anhydrides and esters are less reactive. Moreover, with acid anhydrides, half of the parent carboxylic acid is lost as the leaving group. Thus, acid anhydrides are only used for the synthesis of amides if the acid anhydride is cheap and freely available (e.g. acetic anhydride). 

Amides and Imides, Orgonlc. An organic amide is a compt contg the monovalent -CO.NH, radical (eg, acetamide CHj.CO.NH], oxamide HjN.CO.CO.NH], benzamide C(H, CONH], etc). An organic imide is a compd of the general formula R NH in which R is an acyl radical such as CH,CO—. Another type of imide is a compd derived from acid anhydrides in which one oxygen is reolaced... 

Substituted-1,3-benzoxathiolium tetrafluoroborates (53 Scheme 25) can be prepared readily from acids, anhydrides, esters and trihalomethyl compounds. The thiolium salts can be reduced easily with NaBH4 in acetonitrile at 0-20 C to give aldehydes in 71-91% overall yields. 

The formation of amides from acid anhydrides has been described in Section 1C(4). 

In the case of ammonia, acetamide is formed the product with aniline is acetanilide, The second substance formed is the aniline salt of acetic acid this is soluble in water and is readily removed when the product of the reaction is crystallized. The preparation of anilides in this way from acid anhydrides is often effected in the identification of anhydrides. The anilides are solids, which can be readily purified as a consequence, an identification can be accomplished with a very small amount of a substance. 

The role of the APS sulfohydrolases in sulfate metabolism is not understood precisely. The lysosomal APS sulfohydrolase can hydrolyze bis(4-nitro-phenyl) phosphate and 4-nitrophenyl 5 -phosphothymidine (Roger et al., 1978). Thus the lysosomal APS sulfohydrolase is less specific than its cytosolic counterpart, which does not hydrolyze these nitrophenyl derivatives. The apparent role of the lysosomal enzyme is to hydrolyze the acid anhydrides of such compounds as FAD, ATP, and ADP in secondary lysosomes. Thus lysosomal APS sulfohydrolase is an acid anhydride hydrolase that helps the cell in the recovery of nucleoside monophosphates from acid anhydrides. The APS sulfohydrolase in the cytosolic fraction probably regulates the concentrations of PAPS and therefore plays an important role in the control of sulfate conjugation. 

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