etliaiiol, meiglicd 19ii ing. and had a n1.p. of Uti-137". Upon oxidation2* with 300 mg. of KMiiO, in 20 cc. of acetone, 5 cc. of water and 2 cc. o f glacial acetic acid there was obtained 40 ing. of benzoic acid and a benzophenone fraction which yielded 123 nig. cif %,4-dinitrriphenylhydrazone. The purified products were assayed for radioactivity: the benzoic acid (m.p. 122') contained 0.9.505 mc. per mole of carbon-14 and the benzophenone derivative (n1.p. 239-40') 0.019 + 0.002 mc./mole, corresponding t o a maximum of 1.9% renrrangenient after 24 hours.Benzhydryl phenyl ketone (502 mg.) labeled in the I-phenyl position (0.5954 mc./mole) and in the carbonylcarbon (1.137 mc./mole) was heated under reflux with 15 cc. of formic acid (98-99$0) for 18 hours. The reisolated ketone was crystallized once from ethanol to >-ield 372 mg. whose m.p. was 136". I t was ~l e a v e d~,~~ with nitric acid in acetic acid followed by chromic acid to yield benzophenone which was converted to 272 m if 2,4-dinitrophen?-lliy~razone; 1n.p. 239-40", radioact 5-assay 0.024 inc./mole. This assay corresponds to a maximum rearrangenlent of the total radioactivitl-of l.3yo.Benzhydryl-ZH, phenyl ketone (272 mg.) obtained through the rearrangement of Ie in cc~ld, ciiricentratcrl sul-furic acid was heated under reflux in 10 cc. of formic acid (98-9970) for 23 hours. The reisolated ketone was crystallized cince frum ethanvl (m.p. 136-13i0), and exhibited an infrared spectrum identical with that of authentic benzhy-dry1 phenyl ketone, hut different from that of thr origitial Icetone.( d ) In a typical cxperinient, 161 mg. of tripllcnylacetaltlehyde (crude, m.p. 98--10O0) \vas disscjlved in 108 cc. of 9.37; ethanol, and to it was added 54 cc. of 9.39 -1-H2SO;. .After 0.5 hour at room temperature and 0.5 hour a t 48-50 , the temperature u-ai: raised to 80" for one hour. The reaction was quenched, and rhe reisolated material was converted to 231 mg. of 2,4-di1iitrophenvlh~;drazoiie (86.6y0 of theory), m.p. 208-210" (crude). This is the same 1-ield ohtainec! \rlien ;t sample o f the tripheri)-lacetaldehyde directly to 2,i-dinitroplienr-ihpdrazone. Finally, the experiment 11-as repeated upon 83..i mg. of triplienylacetaldehyde, dissolved in 50 cc. of 93yo ethanol and 25 cc. of 9.39HzSOl. The solution was maintained at 46' fur 4 hours, then a t TU" for 17 hours. The reaction \vas quenched, and the reisolated aldehyde \\-as converted to 124 mg. (89.*5<;) of 2 ,~-d i n i t r f J p~i e n y~~i~ tir:tzone, 111.p. (crude) 208-210'.The solvolytic and deamination reactions of l,Z,Z-triphenylethanol and its derivatives, previously reported with respect to radiochemistry, have now been studied stereochemically. It has been found that (1) the products of hydrolysis and acetolysis of l,Z,Z-triphenylethyl tosylate and (2) the deamination product from the reaction of 1,2,2-triphenylethylamine with nitrous acid are formed with some racemization plus retention of conjguration. The products from the deamination of labeled (-)-amine at 36 9" and of labeled (,+)-amine ...
