N-Propyl orthoformate

Originally, Piacenti et al. explained the formation of isomeric products in terms of an equilibrium of alkylcobalt carbonyls with olefin-hydrocarbonyl complexes as in the Oxo reaction. More recently, however, they have noted that the conditions under which n-propyl orthoformate gave no isomeric products (below 150° C, carbon monoxide pressure 10 atm) are conditions under which isomerization occurs readily in the hydroformylation of olefins (115). Since alkylcobalt carbonyls were formed in both reactions they dismissed the possibility that this isomerization was due to alkyl- or acylcobalt carbonyls. The fact that Takegami et al. have found that branched-chain acylcobalt tetracarbonyls isomerize more readily than straight-chain acylcobalt tetracarbonyls would seem to fit in quite well with the results of Piacenti et al., however, and suggests that the two findings may not be so irreconcilable as might at first appear (see Section II, B,2). 

This reaction is similar to the Williamson synthesis of ethers (method 115). Otthofotmates in which the alkyl group is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and isoamyl have been prepared from chloroform. The yield of ethyl orthoformate is 45%. Mixed esters are obtained from a mixture of sodium alkoxides and chloroform. Benzotrichloride, C,HjCClj, is converted to methyl orthobenzoate in 86% yield by sodium methoxide in methanol, ... 

---