Phenyl ethers, hydrogenation

In order to study the hydrogenolysis in phenyl ether and its relationship to the formation of intermediates, Fukuchi and Nishimura hydrogenated phenyl ether and related compounds over unsupported ruthenium, rhodium, osmium, iridium, and platinum metals in f-butyl alcohol at 50°C and the atmospheric hydrogen pressure.151 The results are shown in Tables 11.11 and 11.12. In general, the greater part of the initial products as determined by an extrapolation method has been found to be cyclohexyl phenyl ether, phenol, and cyclohexane (Table 11.11). Over ruthenium, however, cyclohexanol was found in a greater amount than phenol even in the initial products. Small amounts of cyclohexyl ether, 1-cyclohexenyl cyclohexyl ether, cyclohexanol, cyclohexanone, and benzene were also formed simultaneously. 

Isopropyl phenyl ether + excess hydrogen bromide + heat... 

The condenser returns to the flask a small amount of phenyl ether, which would otherwise be carried away by the hydrogen sulfide. 

R2NC1, 91, 92 phenyl acetate, Fries rearrangement of, 475 phenyacetyl halides, acylation by, 173 2-phenylbenzoic acid, cycliacylation, 185 phenyl ethers, alkylation of, 149 —, bromination of, 130 —, hydrogen exchange with, 260 —, rearrangement of, 476 phenyl ethyl mercury, mercuridemercuration of, 359, 360... 

This aldehyde synthesis is applicable to compounds of the aromatic series having a labile hydrogen atom (phenyl ethers,1 naphthols,2 dialkylanilines,3-4 naphthostyril,2 anthrones 2) and to certain hydrocarbons of requisite reactivity (anthracene,5-6 7 1,2-benzanthracene,6 3,4-benzpyrene,3 7 pyrene,8 styrene,9 and a, a-diarylethylenes 9). With polynuclear hydrocarbons the best results are secured by the use of a solvent such as o-dichloro-benzene. 9-Anthraldehyde has also been prepared by the action of hydrogen cyanide and aluminum chloride on anthracene in chlorobenzene.10... 

Neutral oils, obtained by extracting the monophenol cut with caustic, were tried as paste oil. These gave monophenols and must have contained phenyl ethers which cleaved upon hydrogenation. 

In 1863, Bechamp 2 heated aniline arsenite with an excess of aniline at 190-200° and obtained a colorless solid which he thought was an acidic anilide. However, in 1907, Ehrlich and Bertheim 67 clearly demonstrated that the reaction, now known as the Bechamp reaction, involves the replacement of a nuclear hydrogen by the arsono group and that the compound produced is 4-aminophenylarsonic acid. Since its discovery the Bechamp reaction has been extended to include many phenols, substituted phenyl ethers, amines, and their various derivatives. In all, the literature contains more than sixty articles dealing with this method. 

Benzophenone was converted in the presence of a catalytic amount of hydrogen fluoride to a,a-difluorobenzyl phenyl ether, while exclusive phenyl ring migration was observed in reaction with 4-nitrophenyl phenyl ether107. 

Equation 11.22 is an example showing poor tendency toward hydrogenolysis as well as high stereoselectivity of ruthenium catalyst in the hydrogenation of a phenol or phenyl ether derivative.106... 

Rylander and Kilroy studied the formation of cyclohexyl phenyl ether intermediate in the hydrogenation of phenyl ether over binary platinum-rhodium oxide catalysts in cyclohexane at room temperature and atmospheric hydrogen pressure. The yield of the intermediate varied greatly with the catalyst composition. The highest yield (48%) was obtained over the catalyst consisting of 30% Pt-70% Rh.149... 

TABLE 11.11 Hydrogenation of Phenyl Ether over Platinum Metals Selectivities for Formation of Products at Initial Stage ,fc... 

TABLE 11.12 Proportions of Hydrogenolysis (%) in Hydrogenation of Phenyl Ether, Cyclohexyl Phenyl Ether, and Phenol over Platinum Metals ... 

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