Oxidation aryl phenyl

Peroxybenzoic acid readily oxidizes aryl and alkyl sulphoxides in acetone, methylene chloride or chloroform solutions, to the sulphone in high yield . The reaction is second order and acid catalysed as is the reaction with peracetic acid . The rate of oxidation is about five times faster than when peracetic acid is used. Other work considering the oxidation of sulphoxides with peracids gathered kinetic evidence and showed that the reaction was indeed second order and that the reaction involved nucleophilic attack by the sulphoxide sulphur atom on the peracid moiety. A further study by the same authors showed that with benzyl and phenyl alkyl sulphoxides the rate of reaction was very sensitive to the inductive effect of the alkyl group. Support for the nucleophilic attack by the sulphur atom on the peracid in acidic solution was forthcoming from other sources . ... 

The corresponding hydrido/alkyl (and aryl) complexes v-[RuHR(L-L), ] (L-L = dppe, dppm, dmpe R = Me, Et, Ph) are readily prepared from m-[RuClR(L-L)2] and Li[AlH4]1659 whereas treatment of cis- or tvans-[RuCl2 (dmpe)2 ] with arene radical anions affords d.v-[RuH(f 1-aryl)(dmpe)2] (aryl = phenyl, 2-naphthyl, anthryl, phenanthryl).1389 In solution, these compounds are in tautomeric equilibria with significant concentrations of Ru° complexes (e.g. equation 148) although X-ray analysis for aryl = 2-naphthyl confirms the presence of the six-coordinate Ru" species (373) in the solid state.2459 Some reactions of (373) with various substrates to produce other hydrido complexes are shown in Scheme 74.44>24m Note that the compound of empirical formula [ Ru(dmpe)2 ] obtained by pyrolysis of [RuH(2-np)(dmpe)2] (reaction (iv) Scheme 74) is a binuclear Ru" hydrido complex, resulting from intermolecular oxidative addition of methyl groups to ruthenium.1390... 

One-electron oxidation of phenyl iron(III) tetraarylpor-phyrin complexes with bromine in chloroform at —60°C produces deep red solutions whose H and H NMR spectra indicate that they are the corresponding iron(IV) complexes. For the low-spin aryl Fe porphyrins the electron configuration is (dxyf(dxz,dyzf, with one tt-symmetry unpaired electron, and for the low-spin aryl Fe porphyrins the electron configuration is d, yf- d, zAyzf with two TT-symmetry unpaired electrons. The aryl Fe porphyrins are thermally unstable, and upon warming convert cleanly to A-phenylporphyrin complexes of Fe by reductive elimination. This process has been investigated by electrochemical techniques, by which it was shown that the reversible (at fast scan rates) one-electron oxidation of a-aryl complexes of PFe was followed by an irreversible chemical reaction that yielded the Fe complex of the A-phenylporphyrin, which could then be oxidized reversibly by one electron to yield the Fe complex of the A-phenylporphyrin. (If the Fe complex of the N-phenylporphyrin is instead reduced by one electron, the Fe complex of the A-phenylporphyrin is formed reversibly at... 

Palladium-mediated oxidative arylation of thiophene has also been reported <8SJ0CS272>. Thus, treatment of 2-formylthiophene with palladium acetate in a mixture of acetic add and benzene gave 2-formyl-4-phenylthiophene (30%), 2-formyl-5-phenylthiophene (5%) and 5,5 -diformyl-2,2 -bithienyl (16%). It has been suggested that preliminary palladation of benzene would lead to 4-phenylation of the thiophene, while palladation of the thiophene would produce the 5-phenylated product. 

Also oxidative arylation of alkenes can be carried out by the reaction of phenyl-phosphonic acid 182 with alkenes [83]. 

The oxo(salen)Mn(V) complex, (8) is the effective oxidant in the Mn(III)salen-catalysed oxidation of aryl phenyl sulfides by hypochlorite in MeCN/H20. First-order dependence on oxidant and sulfide is observed and the rate is reduced by electron-attracting substituents in the sulfides and electron-releasing substituents in salen. The Hammett p-value (-2.16.) determined for substituted sulfides indicates an electron-deficient transition state Hammett correlations for substituted salen complexes give positive /O-values for each sulfide. The substituent-, acid-, and solvent effects indicated direct transfer of the 0-atom from the oxidant to the substrate in the rate-determining step. ... 

The palladium-catalysed arylation of 2-aryl-l,2,3-triazole-A(-oxides by phenyl iodides or boronic acids occurs selectively at the 4-position. The mechanism is likely to involve oxidative addition of the arylating agent to palladium, followed by palladation of... 

The reaction of a halide with 2-butene-1,4-diol (104) affords the aldehyde 105, which is converted into the 4-substituted 2-hydroxytetrahydrofuran 106, and oxidized to the 3-aryl-7-butyrolactone 107[94], Asymmetric arylation of the cyclic acetal 108 with phenyl triflate[95] using Pd-BINAP afforded 109, which was converted into the 3-phenyllactone 110 in 72% ee[96]. Addition of a molecular sieve (MS3A) shows a favorable effect on this arylation. The reaction of the 3-siloxycyclopentene 111 with an alkenyl iodide affords the. silyl... 

Sulfation by sulfamic acid has been used ia the preparation of detergents from dodecyl, oleyl, and other higher alcohols. It is also used ia sulfating phenols and phenol—ethylene oxide condensation products. Secondary alcohols react ia the presence of an amide catalyst, eg, acetamide or urea (24). Pyridine has also been used. Tertiary alcohols do not react. Reactions with phenols yield phenyl ammonium sulfates. These reactions iaclude those of naphthols, cresol, anisole, anethole, pyrocatechol, and hydroquinone. Ammonium aryl sulfates are formed as iatermediates and sulfonates are formed by subsequent rearrangement (25,26). 

Pyrimidine, I-alkyl-2-methyltetrahydro-C-thioacylation, 4, 807 Pyrimidine, 4-alkylsulfinyl-nucleophilie displaeement reaetions, 3, 97 Pyrimidine, 6-alkylsulfinyl-nucleophilic displacement reactions, 3, 97 Pyrimidine, 2-alkylsulfonyl-nueleophilie displaeement reactions, 3, 97 Pyrimidine, 4-alkylsulfonyl-nucleophilic displacement reactions, 3, 97 Pyrimidine, 6-alkylsulfonyl-nucleophilie displaeement reactions, 3, 97 Pyrimidine, alkylthio-dealkylation, 3, 95 desulfurization, 3, 95 oxidation, 3, 96 synthesis, 3, 135, 136 Pyrimidine, 2-alkylthio-aminolysis, 3, 96 hydrolysis, 3, 95 Prineipal Synthesis, 3, 136 Pyrimidine, 4-alkylthio-aminolysis, 3, 96 hydrolysis, 3, 95 Pyrimidine, 6-alkylthio-aminolysis, 3, 96 hydrolysis, 3, 95 Pyrimidine, 4-allenyloxy-rearrangement, 3, 93 Pyrimidine, 4-allyloxy-2-phenyl-rearrangement, 3, 93 Pyrimidine, 4-allynyloxy-rearrangement, 3, 93 Pyrimidine, 4-anilino-2,5,6-trifluoro-NMR, 3, 63 Pyrimidine, 2-aryl-pyrroleaeetic aeid from, 4, 152 Pyrimidine, arylazo-synthesis, 3, 131 Pyrimidine, 4-arylazo-reduetion, 3, 88... 

Theophylline, 9-aryl-synthesis, 5, 576 Theophylline, 8-arylamino-synthesis, 5, 576 Theophylline, 9-benzyl-rearrangement, 5, 534 Theophylline, 8-chloro-reduction, 5, 541 Theophylline, 6-deoxy-reduction, 5, 541 Theophylline, 8-dimethylamino-synthesis, 5, 580 Theophylline, 8-methyl-synthesis, 5, 591 Theophylline, 8-methylthio-synthesis, 5, 578 Theophylline, 8-nitro-synthesis, 5, 538 Theophylline, 7-phenyl-synthesis, 5, 581 Theophylline, 8-phenyl-7-oxide... 

Oxidation of 5-arylazo-6-aminoquinoline 146 with copper sulfate in pyridine gave the corresponding 2-aryltriazolo[4,5-/]quinolines 147. Condensation of halo-genated nitrobenzenes with triazolo[4,5-/]quinoline 145 yielded the appropriate 2H- and 3//-aryl derivatives. The nitration of 3-phenyl-3//-triazolo[4,5-/]quino-line 147 occurred at position 4 of the phenyl ring (Scheme 46) (73T221). 

The first synthesis of a 3,5-diarylisoxazole from aryl hydroxamic acid chlorides and sodium phenyl acetylides was that effected by Weygand and Bauer in 1927. Beginning in 1946, when Quilico and Speroni showed that acid chlorides of hydroxamic acids on treatment with alkalies readily yielded nitrile oxides,numerous isoxazole and especially A -isoxazoline derivatives have been prepared. 

Poly-1,2-1//-azepines, produced by gas-phase photopolymerization of aryl azides yield, after oxidation, electrically conducting films.103 By photolyzing 4-(pcntyloxy)phenyl azide in the gas phase, a flexible polyazepine is produced which can be deposited directly as a thin polymer film onto a suitable surface. 

Oxidation of 6-aryl-5//-dibenz[c e]azepinium bromides, e.g. 8, with hydrogen peroxide results in formation of bis(6-phenyl-6,7-dihydro-5//-dibenz[c.e ]azepin-7-yl)peroxide (9).92... 

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