Acylation with carboxylic acids

Diaryl sulfones can be formed by treatment of aromatic compounds with aryl sulfonyl chlorides and a Friedel-Crafts catalyst. This reaction is analogous to Friedel-Crafts acylation with carboxylic acid halides (11-14). In a better procedure, the aromatic compound is treated with an aryl sulfonic acid and P2O5 in polypho-sphoric acid. Still another method uses an arylsulfonic trifluoromethanesulfonic anhydride (ArS020S02CF3) (generated in situ from ArS02Br and CF3S03Ag) without a catalyst. ... 

Acy 1-4-amino-1,5-dihydro-2-pyrrolones (6) (type Z in Scheme 1) possess the features of cyclic enaminediones. The push-pull-7r system decreases the nucleophilicity of the amino group. Therefore N-acylation with carboxylic acid chlorides requires relatively drastic conditions (dioxane, 100°C, K2C03). In particular, the reaction of the highly reactive DMF-acetal 8 to formamidine 9 succeeds only while refluxing in benzene (87TH1). (See Fig. 3.)... 

The T2 linker has recently been shown to be a versatile backbone amide anchor. Immobilized disubstituted triazenes were acylated with carboxylic acid anhydrides or chlorides to give amide derivatives. These amides were cleaved under very mild conditions using trimethyl chlorosilane. This sequence thus employs the T2 system as backbone amine linker and was demonstrated in the automated library synthesis of substituted amide derivatives.54... 

In addition, the amino group in bis[2-aminophenyl] ditellurium has been condensed with aromatic aldehydes9 and acylated with carboxylic acid chlorides10. The Schiff bases were recrystallized from ethanol/benzene (1 l)9. 

The starting materials for the preparation of 1,3-benzotellurazoles are aromatic tellurium compounds that contain an amino functionality in an orv/to-position to the tellurium atom. The reduction of 2-benzeneazophenyl tellurium trichloride with sodium borohydride in ethanol generates 2-aminobenzenetellurol. This compound is acylated with carboxylic acid anhydrides and the acylaminobenzenetellurol cyclized by treatment with concentrated... 

In contrast to the acylation with carboxylic acid chlorides, secondary 1,1-enediamines react with isocyanates and isothiocyanates to give cleanly the /7-carbon acylated products. Carbamoyl-substituted enediamines (175) have been obtained from 174 and arylsulfonyl isocyanates (equation 67)140,141. 

Oximes 659 are also acylated with carboxylic acids using DCC as condensation agent to give the O-acylated derivatives 660. ... 

IV. Acylation with Carboxylic Acid-Tripluoroacetic Anhydride Mixtures... 

In general, salt-free solutions of ylides do not react with methyl or ethyl esters of carboxylic acids. Better results can be obtained when activated esters (e.g. phenyl or pyridyl esters) are used for acyl-ation. " Acylation with carboxylic acid anhydrides also requires only one mole of starting ylide (equation 73). ... 

Acylations with carboxylic acids and anhydrides have been carried out with sulfuric acid as both solvent and catalyst, the reactive acylating agents from acyl halides probably being haloacyloxonium ions. Trifluoroacetic anhydride offers a rather milder reagent for reactions of carboxylic acids, with mixed anhydrides being likely intermediates. However, polyphosphoric acid remains the most widely used dehydrating agent for acylations by carboxylic acids. 

Anisole can be acylated with carboxylic acids over ZSM-5 catalyst. The reaction is carried out in a batch reactor under reflux for 2 d. Table 4.12 shows fhe resulfs obfained utilizing carboxylic acids with different chain length. Prom propanoic acid to stearic acid, the conversion decreases from 92% to 1%, showing a trend opposite to that observed with REY zeolites. This behavior can be ascribed to the small micropore size of ZSM-5, in which the formation of large molecules is difficulf (for penfanoic to octanoic acid) or impossible (for longer-chain carboxylic acids). The poor conversion of AAC can be affribufable to the low reflux temperature. 

Table 4.15 Ferrocene acylation with carboxylic acid-TFAA mixtures promoted by alumina...

Table 4.25 Aromatic acylation with carboxylic acids in the presence of graphite-para-toluenesulfonic acid mixture...

Chiral 2-thiazolidinethiones, e.g., 40, prepared from cysteine esters by the reaction with carbon disulfide23, are used for the enantiotopic differentiation of methylene groups (Section C.). Similarly, carbon disulfide reacts with amino alcohols such as (5)-2-amino-J-butanol or (S)-2-amino-3-methyl-1-butanol (valinol) to give the 2-thiazolidinethiones (S)-ETT 42 and (S)-IPTT 4124 which have been used as auxiliaries (after Y-acylation with carboxylic acids and dicyclo-hexylcarbodiimide) in acylimonium ion cyclizations (Section D.I.4.5.). 

The aromatic acylation with carboxylic acids (Eq. 3) instead of acid anhydrides and acyl chlorides has attracted interest, because it is an environmentally benign reaction, resulting in the formation of water as the only by-product. It has been attempted with zeolites and clays as catalysts. Heteropoly acids have proved to be more active catalysts for this... 

Selective N-acylation with carboxylic acid azides... 

Acylation with carboxylic acid esters N-Acylation of j5-ketocarboxylic acid amides C-Acylation of diacylamines... 

Features Monofunctional reactive protecting moieties by forming acetals with alcohols and acylals with carboxylic acids Properties Colorless clear liq. b.p. 147 C Rapi-Cure DDVE [ISP]... 

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