A-Aminodiphenylmethane

Benzophenoneoxime has been prepared in quantity by treating an aqueous alcoholic mixture of benzophenone and hydroxyl-amine hydrochloride with hydrochloric acid,2 with sodium carbonate,3 with alcoholic potassium hydroxide,4 or with aqueous sodium hydroxide. It has also been obtained by treating bis-nitrosylbenzohydryl with alcoholic potassium hydroxide,6 and by the oxidation of a-aminodiphenylmethane with magnesium persulfate solution.7... 

Preparative routes to 5JT-dibenz[7>,e]azepine-6,ll-diones (morphanthridinediones) are based mainly on the cyclization of 2-aminobenzophenone-2 -carboxylic acids and their derivatives (55LA(594)89). Studies on a-aminodiphenylmethane-2 -carboxylic acid reveal that cyclization to 5,1 l-dibenz[Z>,e]azepinone (188) is much slower at room temperature than the cyclizations of the analogous 2-aminobiphenyl-2 -carboxylic acid and the 2 -aminobiphenylacetic acid (189), which at room temperature cyclize spontaneously to phenanthridone and dibenz[f>,d]azepin-6-one (190) respectively (61JOC1329). The hydrogen bromide-induced cyclization of dinitriles (Scheme 16) is adaptable to the synthesis of 2-amino-7-bromo-3iT-azepines and 5i/-dibenz[c,e]azepin-7-ones (67JOC3325). Apparently, for unsymmetrical dinitriles cyclization is such as always to give the azepine with the bromo substituent attached to the carbon of the a,j8-unsaturated nitrile as exemplified in Scheme 16. 

A flask containing 3.6 gm (0.02 mole) of o-aminodiphenylmethane in 8 ml of concentrated hydrochloric acid and 80 ml of water is cooled to 0°C to —10°C while a solution of 1.4 gm (0.02 mole) of sodium nitrite in 10 ml of water is slowly added. After 15 min, 1.5 gm (0.023 mole) of sodium azide in 10 ml of water is added dropwise. The resulting solution is extracted twice with 100 ml portions of ether, washed with 5 % sodium hydroxide, and dried over sodium sulfate. The ether is removed under reduced pressure and the residue chromatographed on alumina. The azide is eluted with petroleum ether (b.p. 60°-90°C) to afford, after concentration, 3.8 gm (92 %) of o-azidodiphenylmethane giving satisfactory C, H, and N analysis. 

The progress of polymerization of Matrimid 5292 can be monitored by Py-GC/MS [19]. The levels of methylphenol, 4-succinimido-4 -aminodiphenylmethane, and 2-(2-propenyl)-4-methylphenol are increased in the pyrolysate as the degree of curing increases. At the same time, the level of 3,3 -diallyl bisphenol A decreases with increasing cure. 

Boronic esters will also react under appropriate circumstances. Petasis used bis(isopropyl) (2B)-bromoethenylboronic ester in a reaction with glyoicyUc acid and aminodiphenylmethane [34]. Scobie and co-workers have reported the coupbng of pinacolyl aryl and alkenylboronic esters with secondary amines (38). The reaction gave good yields with alkenylboronic esters (70-82%), but worked poorly with aryl-boronic esters (0-12%). In contrast to the above results, the reaction did not proceed with primary amines under the same conditions. 

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