Phenyl ether acylation

Table 4.9 Phenyl ether acylation with aliphatic anhydrides promoted by BEA zeolite...

R2NC1, 91, 92 phenyl acetate, Fries rearrangement of, 475 phenyacetyl halides, acylation by, 173 2-phenylbenzoic acid, cycliacylation, 185 phenyl ethers, alkylation of, 149 —, bromination of, 130 —, hydrogen exchange with, 260 —, rearrangement of, 476 phenyl ethyl mercury, mercuridemercuration of, 359, 360... 

Acylation reactions. Methoxyacetophenones and methoxypropiophenones can be obtained from acylation of methyl phenyl ether with the corresponding acid anhydrides and acid chlorides at 70 "C over Envirocat EPZG in 35 to 72 % yield. Other important reactions catalysed by this catalyst include acylation of PhNHCOCHi to acetamidoacetophenones and 1,3,5-trirnethylbenzene to 1,3,5- trimethylacetophenone. 

The synthesis of 3-aryltetrahydroisoquinolines was accomplished by electrophilic aromatic substitution of polysubstituted phenols and phenyl ethers with Lewis acid-generated tosyliminium ions of 2-tosyl-3-methoxytetrahydroisoquinoline derivatives <00SL801>. In addition isoquinoline was reported to react with N-tosylated (R)- or (S)-amino acid fluorides to afford optically active dihydroimidazoisoquinolinones. The reaction proceeds via acylation followed by attack of the tosylamino group at Cl of the intermediate 2-tosylaminoacylisoquinolinium salt <00TL5479>. 

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. 

The rate of acetylation of 0-(hydrox3Tnethyl)cellulose (and other hydroxy compounds) by mixtures of carboxylic acids and their anhydrides has been found to increase greatly in the presence of trifluoroacetic acid. The acceleration is very much less with mono- and tri-chloroacetic acids, presumably because they form unsymmetrical anhydrides which are less effective acylating agents than acyl trifluoroacetates. The exceptional acylating power of the latter anhydrides is shown by their use in the synthesis of alkyl aryl ketones from polyalkylbenzenes, phenyl ethers, furan, and thiophene under mild conditions. The principle has been extended to include acids... 

ETHYL PHENYL ETHER (103-73-1) Combustible liquid (flash point 145°F/ 63 C). Able to form unstable and explosive peroxides. Violent reaction with strong acids, strong oxidizers, ammonium persulfate, bromine dioxide, acyl halides, permanganates, peroxides. 

Beilstein Handbook Reference) AI3-00749 Benzene, 1,1 -oxybis- Benzene, phenoxy- Biphenyl oxide BRN 1364620 CCRIS 5912 Chemoryl JK-EB Diphenyl ether Diphenyl oxide EINECS 202-981-2 Ether, diphenyl- FEMA No. 3667 Geranium crystals HSDB 934 NSC 19311 Oxybisbenzene Oxydiphenyl Phenoxybenzene Phenyl ether Phenyl oxide. Used in perfumery, soaps as a heat-transfer medium and chemical intermediate for halogenation, acylation, alkylation. Solid rap a 26.8° bp = 258° d O = 1,0661 kmn 207, 217, 248, 280, 286, 295 nm (c = 39600, 39000, 19500, 1740Q, 16100, 9170, MeOH) insoluble in H2O, slightly soluble in CHCI3, soluble in EtOH, EfzO, CeHe, AcOH LD50 (rat orl) = 3370 mg/kg. Monsanto Co. Penta Mtg. 

The discovery route to ivacaftor (1) was published in 2014. The left-hand fragment as 4-0X0-l,4-dihydroquinoline-3-carboxylic acid (14) was prepared according to literature procedures. Thus, condensation of aniline with diethyl ethoxymethylenanalonate (10) afforded the Michael addition/elimination of ethanol product as anilinyl-bis-ester 11. An intramolecular Friedel-Crafts acylation of 11 was accomplished by heating 11 in phenyl ether at 228-232 °C to furnish ester 12, which was readily hydrolyzed to produce acid 13. Acid 13 is a common building block for most of the synthetic routes toward ivacaftor (1). 

Aliphatic nitriles react slowly with phenols and phenyl ethers in the presence of trifluoromethanesulphonic acid to give ketones after hydrolysis, in a variation of the Houben-Hoesch reaction. The crystalline complex of copper(i) triflate and benzene induces the acylation of aromatic substrates with selenol esters, affording a transition-metal mediated version of the Friedel-Crafts reaction. Aromatic carboxylic acids can be converted into symmetrical diaryl ketones in good yield by treatment of their 5-(2-pyridyl)thioesters with bis-(l,5-cyclo-octadiene)nickel [equation (15)]. In contrast to other methods for preparing symmetrical aromatic ketones, this method allows their preparation from a single starting material. 

Obtained by Friedel-Crafts acylation of isopropyl phenyl ether with homoveratroyl chloride in ethylene dichloride in the presence of aluminium chloride, first at 20°, then at 40° for 2-3 h and at r.t. overnight (31%) [5517]. 

In the course of this study, the authors determined /Lvalues for dibenzyl, methyl phenyl, methyl p-nitrophenyl, di-p-tolyl, di-isopropyl and tetramethylene sulphoxides and for diethyl, dipropyl and dibutyl sulphites. The /Lscales are applied to the various reactions or the spectral measurements. The /Lscales have been divided into either family-dependent (FD) types, which means two or more compounds can share the same /Lscale, family-independent (FI) types. Consequently, a variety of /Lscales are now available for various families of the bases, including 29 aldehydes and ketones, 17 carboxylic amides and ureas, 14 carboxylic acids esters, 4 acyl halides, 5 nitriles, 10 ethers, 16 phosphine oxides, 12 sulphinyl compounds, 15 pyridines and pyrimidines, 16 sp3 hybridized amines and 10 alcohols. The enthalpies of formation of the hydrogen bond of 4-fluorophenol with both sulphoxides and phosphine oxides and related derivatives fit the empirical equation 18, where the standard deviation is y = 0.983. Several averaged scales are shown in Table 1588. 

We initially tested Candida antarctica lipase using imidazolium salt as solvent because CAL was found to be the best enzyme to resolve our model substrate 5-phenyl-l-penten-3-ol (la) the acylation rate was strongly dependent on the anionic part of the solvents. The best results were recorded when [bmim][BF4] was employed as the solvent, and the reaction rate was nearly equal to that of the reference reaction in diisopropyl ether. The second choice of solvent was [bmim][PFg]. On the contrary, a significant drop in the reaction rate was obtained when the reaction was carried out in TFA salt or OTf salt. From these results, we concluded that BF4 salt and PFg salt were suitable solvents for the present lipase-catalyzed reaction. Acylation of la was accomplished by these four enzymes Candida antarctica lipase, lipase QL from Alcaligenes, Lipase PS from Burkholderia cepacia and Candida rugosa lipase. In contrast, no reaction took place when PPL or PLE was used as catalyst in this solvent system. These results were established in March 2000 but we encountered a serious problem in that the results were significantly dependent on the lot of the ILs that we prepared ourselves. The problem was very serious because sometimes the reaction did not proceed at all. So we attempted to purify the ILs and established a very successful procedure (Fig. 3) the salt was first washed with a mixed solvent of hexane and ethyl acetate (2 1 or 4 1), treated with activated charcoal and passed into activated alumina neutral type I as an acetone solution. It was evaporated and dried under reduced... 

Elimination to yield alkenes can be induced thermally or by treatment with acids or bases (for one possible mechanism, see Figure 3.39) [138,206]. Less common thermal demetallations include the thermolysis of arylmethyloxy(phenyl)carbene complexes, which can lead to the formation of aryl-substituted acetophenones [276]. Further, (difluoroboroxy)carbene complexes of molybdenum, which can be prepared by treating molybdenum hexacarbonyl with an organolithium compound and then with boron trifluoride etherate at -60 °C, decompose at room temperature to yield acyl radicals [277]. 

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