Yol. ¡:i 1 .(i-dibi'oinohexane in 100 ml of THF maintained tinder X2 al rtz. -0°was added dropwise over 0.7.5 hr a solution of 42..5 ml of 20') PhLi solution (70:30 C«H6-Et20). The resultant solution was allowed to mine to room temperatnre over a 2l)-br period. Hit) (.70 ml) was slowly added to destroy the unreaeted PhLi.The two phases were separated, the aqueous phase was discarded and the organic phase was washed ill.(haml dried iCaChi. The solvent, was evaporated tinder reduced pressure and the residue was distilled by means of a spinning-band column. The product, bp 79-81°(0.4.5 mm) [lit.10 bp 160-161°(17 mm ij, 27 1..52.52 1..528.5, weighed 4.13 g (34' ). Anal. (( , ) Br. Method B.-Equimolar quantities of an .V-alkylaminoethyi halide hydrohalide and Xa2S2( >:1 ,5IE() in H2() or HsO-EtOH, depending on the solubility of the former reactant, were heated on a steam hath for ra. 0..5 hr. When the reaction was complete. as indicated by failure of S to precipitate from a strongly acidified aliquot, the thiosulfuric acids crystallized from the cooled and, in some instances, concentrated reaction mixtures. The .Y-alkylaminoelhaiiethiosulfuric acids which were recrystallized until they were free of halide ion showed characteristic peaks in the ir near 8.1.5, 8.40, and 9.80 µ.2-(5-PhenylpentylaminoJethanethiosulfuric Acid. T he following exemplifies the procedure used when a carboxylic acid was the precursor of the .V-alkyl group. A mixture of 100 g (0.50 mol) of 5-phenylvaleric acid and 34.3 g (0.50 molt of 2-aminoethanol was heated gently at first, followed by a gradual inn-ease in the application of heat until the temperature was maintained 1 i .1. von Braun. Her., 44, 2877 i 19 i 1 ;, at 100 200Y The H.<) which formed in the course of the reactim. was collected in a Dean-Stark trap fitted atop a Yigreaux column The mide .Y-2-hydro.xyethyl t-5-phenylvaleramide w as used n, the next step wiihont further purification.A THK solution 20u ml i of the .Y-(2-hydroxyelhyl i-.5-plienylvaleranudc wn-added over 2.5 hr to a cooled and stirred slurry of 22.s g .0 uni of . and 500 ml of THF. After the mixture was hcined under reflux for 1 1 hr, 2.50 ml of 112() was cautiously added the moled and stirred mixture to destroy excess I.AH. The AnOHi:, which formed was filtered from the mixture and washed .Ei2()j. The aqueous phase of the filtrate was ex: meted •• F.tn ) , t lie et her anti TIIF solutions were combined, and dried -MgSI>. . and the solvents were evaporated on a rolar) evaporator. The ie-idue was distilled at reduced pressure to give 52 g .50' , of 2-• 5-phenylpentylamino iethanol. Treatment of the latter with 4s' , HBr by the method of ('órlese" gave .58 g t()9', of •>-.5-1 dieiivlpentylnmiii<>iethy 1 bromide -HBr which was converted into the thiostilfuric acid bv the reaclion with Xa-S-O 511.

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The formation of “grafted” vinyl copolymers by polymerizing one monomer in the presence of a preformed vinyl polymer has been extended to a new monomer‐polymer combination and one point of attachment of the lateral (grafted) polymer chain has been shown precisely. When ethylene was polymerized in the presence of polyvinyl acetate under a variety of conditions, modified polyvinyl acetates having lateral polyethylene chains were formed. Alkaline methanolysis of such modified polymers yielded mixtures of long‐chain fatty acids and ethylene‐modified polyvinyl alcohols (which were inseparable from any unmodified polyvinyl alcohol that may have been present). The hydrolysis to long‐chain acids shows that polyvinyl acetate acts as a chain transfer agent and that one point of lateral growth of polyethylene chains is the CH3 in the acetoxy group of polyvinyl acetate. The second hydrolysis product, the ethylene‐modified polyvinyl alcohol, shows that chain transfer, and subsequent growth of polyethylene chains, can also occur on the chain carbons of polyvinyl acetate. Oxidation of the ethylene‐modified polyvinyl alcohols yielded a mixture of oxalic acid and long‐chain fatty acids. At the low ethylene pressures studied (300 to 1200 p.s.i.) only traces to small amounts of low molecular weight polyethylene waxes were formed.