Well-defined poly(ethylene oxide) (PEO) with a formyl group at one end and a hydroxyl group at the other terminus was synthesized by the anionic ring opening polymerization of ethylene oxide (EO) with a new organometallic initiator possessing an acetal moiety, potassium 3,3-diethoxypropyl alkoxide. Hydrolysis of the acetal moiety produced a formyl group-terminated heterobifunctional PEO with a hydroxyl group at the other end.

The rates of aminolyses of methyl, isopropyl, allyl and benzyl iodides have been determined in acetonitrile. Bases used were hydrazine, morpholine, imidazole and piperidine. The rates of all the aminolysis reactions can be correlated nicely with the basicities. Hydrazine also did not show any positive deviation from the Brφnsted plots. This fact suggests that the α-effect is not operative in these displacement reactions on the saturated carbon atom.

total energy changes in hydrogen peroxide due to the shifts ' p /./ of LOOH and H-0 bond length was calculated considering ,r*;peroxide was used for the calculations. According to our calculations, h.0. levels in Ha02 and observed ionization potentials for H,02 and H20 are 11-3l and 12*6eV, respectively. The results in the Table show that the lowest energy point for hydrogen changes according to its 0-H bond length, as indicated in the Figure.This mode of reaction of HOOshows the importance of the O8 oxygen atom in lowering the activation energy.For example, when the H-0 bond length is 1.5 A, H i approaches from the direction of O8 and the lowest total energy is -1047 eV which is 3 eV lower than when H+ \ '--' .' -' , I # ' 2-"8 , ap-;ba '8 Yo*, .-./ the core-core repulsion. The configuration (A) of hydrogen ' --*

SHIGERU OAE and YOSHIHITO KADOMA. Can. J. Chem. 64, 1184 (1986.The rates of aminolyses of p-toluenesulfonyl chloride with primary and tertiary amines have been determined both in acetonitrile and in ethanol. The Bronsted plots of log k, , again pKac values of amines (except hydrazine and 1,8-naphthyridine in acetonitrile) gave a good correlation when the aminolyses were carried out in acetonitrile. In ethanol, however, although Bronsted plots with all tertiary amines show a good correlation, less basic hydrazine shows a higher reactivity than n-butylamine. The abnormal rate enhancement found with hydrazine is undoubtedly due to the a-effect, while that with 1,8-naphthyridine in acetonitrile is considered to be due to the repulsion of two lone electron pairs on the two nitrogen atoms in 1,8-naphthyridine.

Die Geschwindigkeitskonstanten der durch Phenoxid‐Ionen katalysierten Eliminierungsreaktionen mit einigen p‐substituierten Phenylsulfonyläthylchloriden, ‐bromiden, ‐tosylaten und ‐dimethylsulfoniumjodiden (I) wurden in Acetonitril, Äthanol und Wasser ermittelt.