Friedel-Crafts acylation reactions synthesis from carboxylic acids

Other derivatives from carboxylic acids can be used as substrates in Friedel-Crafts acylation reactions, including anhydrides and esters. Toluene reacted with glutaric anhydride in the presence of aluminum chloride to give 197, which was used in the Vig et al. synthesis of curcumene ether.128 Lactones are also effective substrates in this cyclization, generating ketones. 129... 

Sulfonic acids and carboxylic acids can be converted into their acid chlorides by treatment with phosphorus pentachloride or phosphorus oxychloride. Thionyl chloride, SOCl is effective for the synthesis of acyl chlorides, and sulfonyl chlorides can be prepared directly from the aromatic compound by reaction with an excess of chlorosulfonic acid. The acid chlorides are efficient Friedel-Crafts acylating agents, yielding sul-... 

Three possible syntheses are presented for the given TM, each of which forms a new C-C bond as required via Grignard, Wittig, or Friedel-Crafts reactions. The acid chloride required for the Friedel-Crafts acylation can be prepared from the corresponding carboxylic acid (the synthesis of compounds containing these functional groups are discussed in Chapters 3.10 and 3.11)-... 

Numerous new examples of cyclopentenone synthesis from acetylenehexacarbonyl-dicobalt complexes and norbornene derivatives have been disclosed there is evidence of steric control, and the bulky trimethylsilyl group can be employed as a removable direction-determining group to allow synthesis of 3- instead of 2-sub-stituted cyclopentenones. Reaction of (731) with sodamide in toluene gave the new octahydro-2,5-methanoazulene system (732 R = CONHj) successive hydrolysis, reduction, and esterification converted (732 R = CONHj) into (732 R = CHjOTs) which, on solvolysis, gave the homoprotoadamantane derivative (733 X = H, R R = CH2) in high yield.The carboxylic acid (732 R = COjH) underwent spontaneous Friedel-Crafts intramolecular acylation on conversion into its acid chloride to give (733 XX = O R R = CHj) and (733 XX = O, R = Cl, R = Me). Reaction of methyl a-bromocrotonate (mixture of E- and Z-isomers) with the enolates of cyclohex-2-enone affords a mixture of stereoisomeric tricyclo-[3,2,l,0 ]octan-6-ones (734 R —R are variously H or alkyl) in moderate yield. The reaction involves double Michael addition and subsequent substitution. 

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