Aryl- -phenyl

The reaction of 3,6-diaryl-l,2,4,5-tetrazines (aryl = phenyl, 2-furyl or 2-thienyl) with 2 equivalents of Ru(acac)2(CH3CN)2 resulted in reductive tetrazine ring opening to yield diruthenium complexes <06IC821>. 

This method has also been used for the preparation of a series of aryl phenyl cyclo-propenones,6 ... 

Phenyl aryl cyclopropenones16 were cleaved by methanolic KOH to a mixture of cis aryl cinnamic acids (318/319 R = phenyl, R = aryl), whose rates of formation gave rise to a linear Hammett-type correlation with a values in the range of -0.268 to +0.373 and p = 0.75. This also indicates that cleavage yielding the more stable carbanion is preferred. Interestingly, ortho-substituted aryl phenyl cyclopropenones gave only a-phenyl-0-aryl acrylic acids (319 R = phenyl, R = aryl), which was explained in terms of steric interactions. 

Diethyl aryl(chloro)methylenemalonates (1670) were reacted with aniline in the presence of triethylamine at 90°C for 12 hr to give aryl(phenyl-amino)methylenemalonates (1671) in 57-66% yields (90JOC2513). The thermal cyclization of compound 1671 (Ar = 3-furyl) at 250°C gave quinoli-necarboxylate (1672) in 85% yield. The cyclizations of compounds 1671 (Pr = Ph, 3-thienyl) in polyphosphoric acid at 210-230°C for 5 min afforded tetracyclic derivatives (1673) in 50-75% yields. 

E-values of similar magnitudes can also be obtained with other 3-aryl-2-methylpropan-l-ols Aryl = phenyl, Amano PS/vinyl acetate/chloroform, E = 116... 

In the atom-transfer reactions of iodine from aryl iodides to phenyl radical, intervention of [9-1-2] aryl(phenyl)-A3-iodanyl radicals is proposed [Eq. (86)] [3]. The ab initio molecular orbital study indicates that the diaryl-A3-iodanyl radicals are transition states in the atom-transfer reactions, but not intermediates [161]. Examples obtained by ab initio molecular orbital calculations with the B3LYP/6 - 31G(d) level are shown in Fig. 2. 

Aryl iodides react with benzenethiolate ions in liquid ammonia under irradiation to afford aryl phenyl sulfides in good yields [51,54—59]. 

One of the first nucleophiles recognized to react under irradiation with Arl by the S l mechanism was PhS" ion, which has led to the synthesis of many aryl phenyl sulphides in liquid ammonia. Bromoarenes also react, but much more slowly270. 

A boron-iodine exchange between vinyl- and arylboronic acids or esters and hypervalent phenyliodanes gave vinyl-aquation (117)) and aryl(phenyl)iodonium salts (Equation (118)) with complete retention of configuration.556,557... 

Sodium benzenetellurolate is arylated in liquid ammonia via photoinduced reactions with aryl halides3,4. Aryl iodides reacted with sodium benzenetellurolate in the presence of copper(I) iodide in hexamethylphosphoric triamide (but not in DMF or DMSO) to produce aryl phenyl tellurium compounds5- However, lithium benzenetellurate reacted with 1,2-bromoiodobenzene and lithium methane tellurolate with 1,2-dibromobenzene in tetrahydrofuran at 20° to yield l,2-bis[organotelluro]benzenes6. 

The reactions of aryl tellurium bromides with bromomagnesium benzeneselenolate11, sodium bcnzenethiolate, or sodium benzeneselenolate12 yield aryl phenyl tellurium chalcogen compounds (p. 208). 

Aryl tellurium trichlorides and equimolar amounts of chlorotriphenylstannane produce in refluxing toluene aryl phenyl tellurium dichlorides2 3. Tetraphenyl tin and phenyl tellurium trichloride yielded diphenyl tellurium dichloride2. 

The reaction between aryl (phenyl, substituted phenyl, naphthyl) tellurium trichlorides and aryl mercury chlorides or acetates are best carried out with dioxane as the solvent. The mercury(II) salts precipitate as their dioxane adducts. The symmetrical or unsymmetrical... 

Lithium benzetellurolate in acetonitrile at 20° in the presence of 18-crown-6 accepted the aryl groups from aryl 4-methylbcnzcnesulfonyl azo compounds forming the aryl phenyl tellurium in yields between 26 and 41 %4. 

Benzenetellurolate, generated by electrochemical reduction of diphenyl ditellurium in a solution of tetrabutylammonium hexafluorophosphate, reacted with electrochemically partly reduced chlorobenzonitriles5 and bromobenzophenones6 to produce aryl phenyl tellurium compounds in moderate yields. The following compounds were isolated from the reaction mixtures ... 

Primary and secondary alcohols may serve as the source of alkyl groups in the preparation of aryl phenyl tellurium compounds. Phenyl tellurium cyanide, conveniently obtained from diphenyl ditellurium (p. 368), reacted smoothly with alcohols in dichloromethane in the presence of tributylphosphane. The alkyl phenyl telluriums were obtained in yields ranging from 32 to 78%. Triphenylphosphane or triethyl phosphite did not catalyze these reactions2. 

The products of the reactions of 1,1-diarylethenes (aryl = phenyl, 4-methylphenyl, 2,4-dimethylphenyl) with tellurium tetrachloride that were claimed to be adducts of tellurium dichloride with two molecules of the diarylethene5 are in fact bis[diarylethenyl] tellurium dichlorides3. 

Chlorotriphenylstannane and aryl tellurium trichlorides react in refluxing toluene to form aryl phenyl tellurium dichlorides. Only one of the three phenyl groups in chlorotriphenylstannane is transferred to the tellurium atom1,2. 

Hexaphenyl dilead3, tetramethyl lead3, and triphenyl lead chloride4 donate phenyl groups to aryl tellurium trichlorides to produce aryl phenyl tellurium dichlorides in yields from 73 to 92%. The lead compounds are more reactive than the tin and silicon derivatives and even react at 20°. 

Kagan s sulfite, the method has the advantage of regioselectivity, but the limitation of producing tert-butyl or aryl phenyl sulfoxides. 

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... 

Careful tuning of conditions can also make it possible to apply this protocol to a rapid synthesis [307-309]. Such a procedure is useful for preparation of shortliving species such as that containing unstable isotopes [218]. Aryl and methyl iodides are successfully employed (Scheme 85) [310,311]. lodonium salts can be more useful if available because they usually react at rt (Scheme 86) [312]. The problem in the use of aryl(phenyl)iodonium is chemoselectivity (Scheme 87) [313]. 

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