Facile and efficient syntheses of carboxylic anhydrides and amides using (trimethylsilyl)ethoxyacetylene

Abstract

Trimethylsilyl)ethoxyacetylene, a stable and easy-handling reagent, serves as an excellent dehydrating agent for the synthesis of carboxylic anhydrides and amides from the corresponding carboxylic acids. By means of this reagent, various types of acid-sensitive carboxylic anhydrides and amides were obtained almost in quantitative yields. Twenty-two examples of carboxylic anhydrides and 12 examples of amides were presented.

Reversible Fluorescence Derivatization of Amino Groups Using Dansylaminomethylmaleic Acid via Its Anhydride

“…To the dried acetonitrile (25 ml) containing 0.19 g (0.48 mmol) of dansylaminomethylmaleic acid (DAM), 0.13 g (0.91 mmol) of (trimethylsilyl)ethoxyacetylene 7 was added and heated with stirring for 7 h until the solution became clear. The solution was evaporated and dried under reduced pressure.…”

“…The new reagent, DAM, has a dansyl(1-dimethylaminonaphthalene-5-sulfonyl) group as the fluorophore, which enables the sensitive determination of amines. The reagent also has a methylmaleic acid 5,6 moiety, which was easily dehydrated in the presence of (trimethylsilyl)ethoxyacetylene 7 to form dansylaminomethylmaleic anhydride (DAMA). The methylmaleic anhydride is thought to react with amines, thiols or hydroxyls, and was also known to dissociate from amino groups under mild conditions; 6 therefore, the reagent (DAM) is thought to be useful for the reversible derivatization of amino groups (Fig.…”

<b>Efficient and convenient synthesis of symmetrical carboxylic anhydrides from carboxylic acids with sulfated zirconia by phase transfer catalysis</b>

“…Generally speaking, they are prepared by dehydration of carboxylic acids with powerful acylating or dehydrating agents such as acid chlorides [4], acid anhydrides [5], thionyl chlorides [6,7], sulfonyl chlorides [8], phophoranes [9], phosgene [10], pyridazin-3(2H)-ones [11,12], ketene [13], imidazolinium chlorides [14], 1,3,5-triazines [15], DCC [16], dinitrogen tetroxide [17], chlorosulfonyl isocyanate [18], carbodiimides [19], trichloroacetonitrile/triphenylphosphine [20], and P 2 O 5 [21]. Carboxylic anhydrides can also be prepared by the reaction of acid chlorides with carboxylates [22,23] or carboxylic acids [24][25][26][27], as well as by reaction of acid chlorides under ultrasound basic media [28].…”

Synthesis of Symmetrical Carboxylic Acid Anhydrides from Acyl Chlorides in the Presence of In Metal and DMF

“…The solvent effects on the reaction were also examined. The reactions carried out in hydrocarbon or chlorinated hydrocarbon solvents afforded benzoic anhydride in good yields (entries [8][9][10][11][12]. The reactions performed in ethers such as THF, dioxane and diethyl ether gave somewhat lower yields (entries 13-15).…”

“…The reaction with heteroaromatic acyl chlorides proceeded to give high yields of the corresponding carboxylic acid anhydrides (entries 6 and 7). The reaction with aliphatic acyl chlorides required longer reaction times to be completed than the reaction with aromatic acyl chlorides (entries [8][9][10][11]. Sterically hindered acyl chloride such as pivaloyl chloride was also converted smoothly into the corresponding carboxylic acid anhydride in high yield (entry 13).…”