Aryl chloroformates diaryl

Water insoluble tetrabutylammonium metaperiodate, which can be prepared from sodium metaperiodate and tetrabutylammonium hydrogen sulphate in aqueous solution, was found to be a useful reagent for the selective oxidation of sulphides in organic solvents . The reaction was generally carried out in boiling chloroform and gave dialkyl, alkyl aryl and diaryl sulphoxides in yields which are comparable with those reported for sodium metaperiodate in aqueous methanol solution (Table 4). In the case of diaryl sulphoxides, the yields decrease with prolonged reaction time. 

Spontaneous hydrolyses of carboxylic anhydrides, diaryl carbonates and aryl chloroformates are faster in cationic than in anionic micelles, regardless of the nature of the counteranion in the cetyltrimethylammonium micelle (Al-Lohedan et al., 1982b Bunton et al., 1984). This charge effect does not seem to be related to substrate hydrophobicity, although the extent of micellar inhibition (relative to reaction in water) is clearly dependent upon substrate hydrophobicity for anhydride hydrolyses. 

Examples of this behaviour are shown in Table 7 where k+ is related to reaction of substrate fully bound to a CTAX micelle and k to reaction in an anionic micelle of SDS. The ratio k+/k is consistently larger than unity for hydrolyses of open chain anhydrides, diaryl carbonates and aryl chloroformates. In addition hydrolysis of 4-nitrophenyl chloroformate is slightly faster in cationic micelles than in water. Spontaneous hydrolyses of N-acyl triazoles are also inhibited less by cationic micelles of CTABr than anionic micelles of SDS (Fadnavis and Engberts, 1982). 

From alkyl aryl or diaryl ether with bromine in glacial acetic acid or chloroform For directions and examples see Cheronis, p 545, Shriner, p 240... 

Sulphoxides and sulphoximines are reduced to thioethers by similar reaction sequences [3, 4], In most cases, the yields of the thioethers are higher (>70%) from the diaryl compounds, than from dialkyl or aryl alkyl derivatives but, when the reductions are conducted in an excess of chloroform, the yields of the thioethers are diminished [3], This observation suggests that the thioethers are reacting with dichlorocarbene and that the dialkyl and aryl alkyl compounds are more susceptible than the diaryl derivatives (Table 11.20). 

Diaryl tellurides undergo facile ligand-transfer oxidations with [bis(acyl-oxy)iodo]arenes in chloroform to give stable diaryltellurium dicarboxylates 12 (Scheme 7) [23]. Similar ligand-transfer oxidations of triarylbismuthanes and triarylstibanes with BAIB in dichloromethane leading to Bi(V) and Sb(V) diacetates 13 and 14 have also been reported [24,25]. The triarylbismuth diacetates were employed for high yield Cu(II)-catalyzed arylations of a series of aryl-amines [24]. 

Diaryl-l,2,4-selenadiazoles 79 were prepared by treatment of aryl selenoamides 274 with />-toluenesulfonyl chloride 275 in chloroform in 51-70% yield (Equation 34) <2002CCL729>. 

Diaryl ditelluriums and bis[thiocarbamoyl] disulfides reacted in hot chloroform to give aryl tellurium tris[dithiocarbamates]1. 

Alkyl aryl telluriums and diaryl telluriums react with anhydrous (V-chloro-/V-sodioarenesulfonamides in refluxing chloroform in the presence of 18-crown-6 to yield diorgano tellurium arenesulfonimides1. When the reactions are carried out with the hydrated sulfonamides in methanol, diorgano tellurium oxides are formed1. 

Diaryl telluriums and aryl methyl telluriums reacted with anhydrous chloramine-B and chloramine-T in chloroform in the presence of 18-crown-6 as the phase transfer reagent2. 

Dialkyl, diaryl, unsymmetrical dialkyl, alkyl aryl, and unsymmetrical diaryl telluriums served as the tellurium-containing starting materials (Vol. IX, p. 1075). The reactions with methyl iodide and low molecular mass organic bromides proceed at 20° in organic solvents such as chloroform and methanol or in mixtures of the neat reagents.With aryl telluriums several days are required for completion of the reaction. Diaryl telluriums with ortho-substituents react only with difficulty. Bis[2,4,6-trimethylpheny 1] tellurium did not combine with methyl iodide. The reactions with ethyl iodide and a-bromocarboxylic acids are accelerated by gentle heating. 

Diaryl-2-phenoxy-l,3,5-oxadiazinium hexachloroantimonates have been prepared in high yield (76-84%) from aryl carbonitriles (2 equivs.) and phenyl chloroformate (1 equiv.) under reflux in DCM in the presence of SbCb <93S426>. 

Several new classes of novel poly(a l ether)s have been synthesized which have very high glass transition temperatures. Most of these polymers are soluble in solvents such as dichloromethane, chloroform or chlorobenzene at room temperature and they can be cast into flexible films. Poly(aryl ether)s containing phthalocyanine moietes have also beem synthesized. Methods have been developed to introduce reactive functionality, e.g diaryl acetylene and diaryl cyclopropane moieties, into the backbone of these polymers so that they can be thermally cross-linked after fabrication. 

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