Benzophenone with sulfur compounds

The halogen atoms of the geminal dihalo derivatives of diaryl diketones and of heterocyclic ketones can be replaced in reactions with sulfur compounds 0e.g., sodium hydrogen sulfide, thioacetic acid, phosphorus pentasulfide), thioketones being formed.318,319 Staudinger and Freudenberger,320 for instance, obtained thiobenzophenone in 46% yield from benzophenone dichloride (dichlorophenylmethane) and a hot alcoholic solution of sodium hydrogen sulfide ... 

Let us now discuss some of the characteristics of this quenching with mercaptans and disulfides. Interestingly, both sulfur derivatives are equally effective in inhibiting the photoreduction and are in fact interconverted during the reaction. The same equilibrium mixture of mercaptan and disulfide is obtained regardless of which was initially added to the reaction mixture. Furthermore, there appears to be no appreciable consumption of the sulfur compounds/64 When benzophenone is irradiated in the presence of isopropanol (OD) and mercaptan, isopropanol containing two deuterium atoms is isolated,... 

The reaction of the sulfur ylides with carbonyl compounds provides a valuable synthetic route to a wide range of epoxides. For instance, benzophenone (20) reacts smoothly with... 

Nitrobenzotrichloride is also obtained in high yield with no significant hydrolysis when nitration with a mixture of nitric and sulfuric acids is carried out below 30°C (31). 2,4-Dihydroxybenzophenone [131 -56-6] is formed in 90% yield by the uncatalyzed reaction of benzotrichloride with resorcinol in hydroxyHc solvents (32) or in benzene containing methanol or ethanol (33). Benzophenone derivatives are formed from a variety of aromatic compounds by reaction with benzotrichloride in aqueous or alcohoHc hydrofluoric acid (34). 

Alkyl groups are oxidized to carboxyls also in aromatic compounds containing functional groups, which may or may not be affected by the oxidant. Thus p-methylbenzophenone is transformed, on refluxing with chromium trioxide in acetic and sulfuric acid, into benzophenone-p-car-boxylic acid (yield 62-69%) [550], whereas inp-methylacetophenone, both the methyl and the acetyl groups are converted into carboxyls (equation 185) [696, 891]. 

Sulfur tetrafluoride fluorination of aryl perfluoroalkyl esters provides a route to stable aryl perfluoroalkyl ether compounds (1). By using nitrophenyl esters of perfluoroalkyl-ene and perfluoroalkylene ether dicarboxylic acids, a, w-bis (m-nitrophenoxy) perfluoroalkylene ether intermediates were prepared. The conversion of these products to the corresponding amino and isocyanatophenoxy derivatives is described. Reaction of the diamines with benzophenone-tetracarboxylic dianhydride resulted in formation of poly-imides. Cyclotrimerization of the diisocyanate intermediates formed polyisocyanurates. Both the imide and iso-cyanurate polymers have high thermal, oxidative, and hydrolytic stability. 

Dihydro-5//-l, 4-dioxepins are usually prepared by cyclization. Thus, a number of compounds of type (36), (37), and (38) (isolated as oxalates or hydrochlorides), which have found interest as sedatives, antiepileptics, and antidepressants, were prepared by cyclization of the respective carbinols (35) with concentrated sulfuric acid. The starting carbinols have been synthesized from the corresponding benzophenones (34) (Scheme 4) <79JAP(K)5307708i>. 

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