Ethyl alcohol, reactivity, with phenyl

It is also of interest to point out that DBTDL is about three times more effective a catalyst than DMCHA in the reaction of phenol with phenyl isocyanate. Baker and Gaunt [21] found that ethyl alcohol was 30 times more reactive than phenol in the uncatalyzed reaction with phenyl isocyanate. However, in the presence of a tertiary amine (triethylamine), the reactivity of phenol increased significantly and was found to be similar to that of ethyl alcohol (see Table IV). 

EFFECT OF TERTIARY AMINE CATALYST ON REACTIVITY OF PHENOL AND ETHYL ALCOHOL WITH PHENYL ISOCYANATE21... 

EFFECT OF CATALYSTS ON THE REACTIVITY OF PHENOL BENZYL ALCOHOL AND ETHYL ALCOHOL WITH PHENYL ISOCYANATE... 

Other a-halogenated compounds have been used with equal success. These include iodoacetamide (140,144,141, 34,68,32), iodo ethyl alcohol (143), a brom fatty acids, and benzyl and phenyl ethyl halides (142). All react with certain SH groups of proteins at pH 7.0-9.0 and physiological temperatures. The iodoacetamide is somewhat more reactive than iodoacetate (144). Both iodoacetate and the corresponding amide were found to react fairly rapidly with p3rridine, even at pH 6.9 and 30 C. (145). Anson and Stanley (68) have reported that after almost complete inactivation of tobacco mosaic virus with iodoacetamide they could detect little, if any, drop in the number of SH groups. This calls for further study. 

Certain classes of compounds are too reactive for the present method. Ethyl mandelate produced a racemic, protected phenyl glycine derivative. Benzylic alcohols with two methoxy groups (directly conjugating in the 2 and 4 positions) gave azide of 50% e.e. 

Ethyl mercaptan followed by a soln. of 4-chloro-5,6-dimethoxypyrimidine added to a soln. of Na in abs. alcohol, and refluxed 1 hr. after the exothermic reaction has subsided 4-ethylthio-5,6-dimethoxypyrimidine. Y 80%. — Only strong nucleophiles, such as ethyl or phenyl mercaptide ions, react smoothly with the poorly reactive chlorine substituent. F. e. s. H. Bretschneider, W. Richter, and W. Klotzer, M. 96, 1661 (1965). 

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