The Kinetics of the Alkaline Hydrolysis of 32. The Kinetics of the Alkaline Hydrolysis of Esters ancl Amides of 1 -ancl 2-Naphihoic Acid.

SUBSTITUENT CONSTANT OF THE 3,4-BENZO GROUP 155Stirring was continued at reflux for 5 hr. and the bromide was then recovered in the usual way. The recovered bromide showed a slight increase in the amount of trans isomer, as evidenced by the diagnostic infrared bands of the latter, but was still very predominantly cis.(c) The above experiment was repeated, expect that pure as-bromide was used and the bromide was added to the silver acetate suspension one minute before bromine addition commenced. In this way, the cis-bromide was exposed to both bromine and silver bromide under the reaction conditions, rather than to silver bromide only. After 1 hr. boiling at reflux with stirring, the mixture was worked up as previously described. The product showed a marked ester band in the infrared at 5.77µ and very weak bands ascrib-able to the irons isomer, the one at 11.4µ being the most prominent (about six scale divisions). However, the recovered material was still very largely as-bromide.

In an attempt to form 2-alkylidene-1,3-oxazolidines, chiral 2-oxazolines have been N-alkylated and N-acylated. Two new Nmethyloxazolinium salts have been prepared and characterised but base treatment resulted in their decomposition. In contrast, attempts to isolate three N-benzoyloxazolinium salts gave the products of their ring hydrolysis: unsymmetrically diacylated amino alcohols whose structure was confirmed by x-ray diffraction in one case. Overall the method allows stepwise regiospecific N,O-diacylation of 1,2-amino alcohols.

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