2.6- diphenyl-substituted anilines

Tu found that when aniline was used instead of the secondary amine under otherwise identical conditions 2,4-diphenyl-substituted quinoline was formed in 56% yield. Phenylacetylene and aniline were initially used as model substrates for exploring the aldehyde scope. With aromatic aldehydes the reactions proceeded smoothly to give the corresponding quinolines in moderate to good yields. A heteroaromatic aldehyde is also compatible with this transformation and the expected product was afforded in 83% yield. However, when ahphatic aldehydes were subjected to the reaction, the desired product was obtained in low yield (Scheme 19) [34]. 

Replacement of one of the ethereal oxygen atoms by a methylene group is compatible with anticoccidial activity. For example, condensation of substituted aniline 35 with dimethyl ethoxymethylenemalonate affords aminoacrylate 36. Thermal cyclization in diphenyl ether gives neguinate (37).11... 

Substituted anilines were reacted with EMME in diphenyl ether by heating to 185°C, with distillation of the ethanol formed. The temperature of the reaction mixture was then raised to 245°C and the reaction mixture was heated at 245°C for 1 hr to give ethyl 6-substituted quinoline-3-carboxylates in good yields (85USP4560692). 

Double cyclization in one step is also possible with the l,5-diiodo-2,4-bis(iodomethyl)-pentane precursor. Following that route, the treatment of the precursor with aniline leads to the A, A -diphenyl substituted bispidine 77 (106), whereas the reaction of the tetraiodo compound with 1-phenylethylamine yields the bispidine 78 (Scheme 7) (107). 

It was reported (94IC415) that the reactions of 2,2,3,3 tetrafluorobutyleneglycol triethylsilyl ether with 1,4-dibromotetrafluorobenzene, tetrabromoethane, and oxalyl fluoride form oxygen-containing heterocycles (Scheme 143). Adamson et al. (92JFC(58)300) showed that 1,2,3,4-tetrafluoroacridines 154 are formed in quantitative yields in reactions of pentafluorobenzaldehyde with substituted anilines at room temperature (Scheme 144). 2,3-Diphenyl-4,5,6,7-tetrafluorobenzofuran is formed in a reaction of hexafluorobenzene with phenyl benzyl ketone in the presence of sodium hydride (79BCJ2657) (Scheme 145). The reaction involves intramolecular nucleophilic cyclization of the generated O-nucleophile due to tautomerization of the intermediate ketone. 

A stepwise mechanism with a rate-limiting leaving group expulsion from the intermediate was proposed for the reactions of Z-aryl dimethyl- (43a), methylphenyl-(43b), and diphenyl-phosphinates (43c) with substituted anilines in DMSO at 333 K, based on the positive cross-interaction constants, The steric effects of the two ligands (R, R ) play a role in determining the reactivity of the phosphinates, but are relatively small compared to other phosphinate systems. A dominant frontside nucleophilic attack involving a hydrogen-bonded four-centre-type transition state (44) was proposed... 

The reaction of substituted chloronitrobenzenes with arylamines to form substituted diphenyl amines is typified by 4-rutrodiphenylamine-2-sulfoiiic acid where 4-chloronitrobenzene-3-sulfonic acid (PN salt) is condensed with aniline ia an aqueous medium at 120°C and 200 kPa (2 atm) ia the presence of alkaline buffer at low pH to avoid the competing hydrolysis of the PN salt. 

Methyl benzoate, anisole, and diphenyl ether each give sandwich compounds with chromium vapor, although in rather low yield (32, 55, 110). Chromium appears to attack alkyl ethers and this deoxygenation probably competes with complexation with the aromatic oxygen compounds. No simple product has been isolated from chromium atoms and aniline, but bis(7V,7V-dimethylaniline)chromium has been prepared (32). The behavior of molybdenum and tungsten vapors closely resembles that of chromium in reactions with oxygen- and nitrogen-substituted arenes (113). 

Photocyclization of A -methyl-(p-methoxyphenyl)anilines in the presence of aqueous hydrochloric acid gave a set of carbazolones, as illustrated by the conversion of the diarylamine 241 into the system 242 (Equation 77) <2002CC270>. In addition, it has been reported previously that photocyclization of fluorine-substituted diphenyl-amines leads to formation of carbazoles <1996J(P1)669>. 

Salts of dithiocarbamic acid can be prepared by the addition of primary or secondary amines to carbon disulfide." This reaction is similar to 16-10. Hydrogen sulfide can be eliminated from the product, directly or indirectly, to give isothiocyanates (RNCS). Isothiocyanates can be obtained directly by the reaction of primary amines and CS2 in pyridine in the presence of dicyclohexylcarbodiimide. Aniline derivatives react with CS2 and NaOH, and then ethyl chloroformate to give the aryl isothiocyanate." In the presence of diphenyl phosphite and pyridine, primary amines add to CO2 and to CS2 to give, respectively, symmetrically substituted ureas... 

This class of compounds comprises anilines containing aryloxy groups whether or not it is the ring or the nitrogen that is so substituted. The first two species are 4,4 -diamino diphenyl ether and its 3,3, 4,4 -tetraaru i no analog with their solid-phase enthalpies of formation of —17 and —116 kJ ruol 1 from References 88 and 89, respectively. For comparison, the enthalpy of formation of the parent solid diphenyl ether is —32.1 1.5 kJmol-1. 

The Wolff rearrangement of six- and five-membered a-diazocycloalkanones has been extensively applied to the synthesis of highly strained frameworks. The rearrangement of an (x-diazo-cyclobutanone was reported from 2-diazo-3,4-bis(diphenylmethylene)cyclobutanone (1). The diazo ketone (1) was prepared by treatment of the 3,4-bis(diphenylmethyl-ene)cyclobutane-l,2-dione tosylhydrazone with alumina in 95% overall yield from the corresponding cyclobutanedione. Irradiation in the presence of water, alcohols and aniline afforded 1-carboxy-, 1-alkoxycarbonyl- and 1-phenylcarbamoyl-substituted 2,3-bis(diphenyl-methylene)cyclopropanes 2, respectively, in 13-87% yields. Thermal decomposition in aqueous dioxane afforded the cyclopropanecarboxylic acid 2 (X = OH) in 52% yield. ... 

The diphenyl H-phosphonate/pyridine mixture has been found to be the most effective catalyst for this reaction. Carbamides and thiocarbamides are formed in high yields when diamines are substituted for aniline in the above scheme [131]. 

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