By Substituents other than Hydrogen

The hydroxyl group has been replaced by a variety of substituents in some unusual reactions. 4-Hydroxybenzophenone and benzyltriethylammonium chloride in o-xylene upon treatment under anhydrous conditions with phosgene at 95-120°C during 5.5 hours gave 4-chloroformylbenzophenone in 99% yield (ref.46). 

1-Naphthyl diethyl phosphate stirred with trimethylsilylmethyl magnesium chloride in ether containing nickel acetoacetonate at ambient temperature during 10 hours 

2-Methylphenol has been converted by way of the diethylaminothionecarbamate to thediethylaminothiol carbamate, (through the Newman-Kwart rearrangement), which in 80% acetic acid with excess chlorine gave 2-methylbenzene sulphonyi chloride in 95% yield, (characterised in 94% yield as the dimethylamide by reaction with 40% aqueous dimethyiamine) (ref.48). 

1-Naphthol with ethyl thioglycollate in benzene upon dropwise treatment with trifluoromethanesulphonic acid followed by stirring of the mixture at 50X for 3 hours gave ethyl 1-thionaphthoxyacetate in 88% yield (ref.49). 

An unusual replacement has been described in the conversion of phenol to chlorobenzene in 76% yield by addition at 70-80 C to molten tetrachlorophenylphosphorane (from chlorine and phenyldichlorophosphine at 70-80°C) and heating of the mixture to 160 C for 16 hours (ref.50). 

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