Acetic anhydride aromatic ethers acylation

The lower members of the homologous series of 1. Alcohols 2. Aldehydes 3. Ketones 4. Acids 5. Esters 6. Phenols 7. Anhydrides 8. Amines 9. Nitriles 10. Polyhydroxy phenols 1. Polybasic acids and hydro-oxy acids. 2. Glycols, poly-hydric alcohols, polyhydroxy aldehydes and ketones (sugars) 3. Some amides, ammo acids, di-and polyamino compounds, amino alcohols 4. Sulphonic acids 5. Sulphinic acids 6. Salts 1. Acids 2. Phenols 3. Imides 4. Some primary and secondary nitro compounds oximes 5. Mercaptans and thiophenols 6. Sulphonic acids, sulphinic acids, sulphuric acids, and sul-phonamides 7. Some diketones and (3-keto esters 1. Primary amines 2. Secondary aliphatic and aryl-alkyl amines 3. Aliphatic and some aryl-alkyl tertiary amines 4. Hydrazines 1. Unsaturated hydrocarbons 2. Some poly-alkylated aromatic hydrocarbons 3. Alcohols 4. Aldehydes 5. Ketones 6. Esters 7. Anhydrides 8. Ethers and acetals 9. Lactones 10. Acyl halides 1. Saturated aliphatic hydrocarbons Cyclic paraffin hydrocarbons 3. Aromatic hydrocarbons 4. Halogen derivatives of 1, 2 and 3 5. Diaryl ethers 1. Nitro compounds (tertiary) 2. Amides and derivatives of aldehydes and ketones 3. Nitriles 4. Negatively substituted amines 5. Nitroso, azo, hy-drazo, and other intermediate reduction products of nitro com-pounds 6. Sulphones, sul-phonamides of secondary amines, sulphides, sulphates and other Sulphur compounds... 

The acylation of aromatic ethers by acyl chlorides is highly regioselective in the presence of 10 mol% Sml3.53 Some aromatic compounds are efficiently acylated by acid anhydrides catalysed by niobium pentachloride with silver perchlorate.54 Arenes of a range of reactivity are acylated by acetic anhydride in a fluorous biphasic system catalysed by Hfps SCLCgFn L (1 mol%)55 The catalyst is easily recoverable and can usually be used again without decrease in activity. 

Reactions of Enol Ethers and Esters.—When enol acetylation of a steroid 4-en-3-one with acetic anhydride is catalysed by perchloric acid (or boron trifluoride ), C-acetylation of the enol acetate (373) occurs on prolonged reaction. This step, probably involving acetyl perchlorate ior airs, is akin to Friedel-Crafts acylation of aromatic compounds. Both 6-acetylation and 2-acetyIation are known, although each is prevented by the presence of a methyl group at the site. The products can be of various enolic types (e.g. 374 and 375). 

Table 3.16 Aluminum-hydrogensulfate-promoted acylation of aromatic ethers with acetic and propionic anhydrides...

An efficient method for the continnons flow selective acylation of aromatics, including ethers, ovCT HBEA zeolite is reported [41, 42]. The process is performed in a fixed-bed tubnlar reactor charged with HBEA(25) zeolite deposited on a small layo- of glass pellets or directly packed without any support or mixed with alumina. The aromatic substrate and acetic anhydride are passed through the reactor heated at 90-150°C for a period of 6-7 h. Substituted acetophenones are so obtained in 63-100% yield. 

Acylation The reagent catalyses the arylation of activated aromatic compounds by reaction with carboxylic acids. Thus methyl phenyl ether can be acylated with acetic acid in presence of trifluoroacetic anhydride in good yields. 

Maleic anhydride grafting (cont.) poly(styrene-co-divinylbenzene), 694 poly(styrene-co-isobutylene), 675, 689 poly(styrene-co-nfialeic anhydride), 676, 679 poly(vinyl acetate), 676, 694 poly(vinyl acetate-co-vinyl fluoride), 678 poly(vinyl alkyl ethers), 675, 679, 692, 701 poly(vinyl chloride), 683, 692, 693, 695, 702 poly(vinylidene chloride), 691 poly(vinyl toluene-co-butadiene), 689 radical—initiated, 459-462, 464-466, 471, 475, 476 radiation—initiated, 459, 461, 466, 471, 474 redox-initiated, 476 rubber, 678, 686, 687, 691, 694 to saturated polymers, 459-466, 475, 476 solvents used 460-463, 465, 466, 469, 474-476 styrene block copolymers, 679 tall oil pitch, 678, 697 terpene polymers, 679, 700 thermally-initiated, 462, 464-467, 469, 476 to unsaturated polymers, 459, 466-474 vapor-phase techniques, 464, 474, 475 to wool fibers, 476 Maleic anhydride monomer acceptor for complex formation, 207-210 acetal copolymerization, 316 acetone CTC thermodynamic constants, 211 acetone photo-adduct pyrolysis, 195, 196 acetylacetone reaction, 235 acetylenic photochemical reactions, 193-196 acrylamide eutectic mixtures, 285 acylation of aromatic acids, 97 acylation of aromatics, 91, 92 acylation of fused aromatics, 92, 95, 97, 98 acylation of olefins, 99 acylation of phenols, 94-96 acylic diene Diels-Alder reactions, 104-111, 139 addition polymer condensations, 503-505 adduct with 2-cyclohexylimino-cyclopentanedi-thiocarboxylic acid, 51 adducts for epoxy resins curing, 507-510 adduct with 2-iminocyclopentanedithiocarboxylic acid, 51... 

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