tra of benzophenone and benzhydrol showed that the aromatic protons of the former absorb further downfield than those of the latter, so that the presence of a small amount of benzophenone in the sample would not interfere with the deuterium analysis.Carbonation of the Remaining Grignard Reagent.-The carbonation was begun 20 min after the reaction of the Grignard reagent with 0.5 equiv of benzophenone. Crushed Dry Ice contained in a 250-ml erlenmeyer flask was slowly added through Gooch tubing to the unconsumed Grignard reagent contained in a round-bottomed flask equipped with condenser and mechanical stirrer. Once all the Dry Ice had been added, the reaction mixture was allowed to attain room temperature overnight.The mixture was then treated with 6 N hydrochloric acid until two clear layers separated. The aqueous layer was extracted several times with ether, and the extracts were combined with the organic layer. The yield of norbornyl acid was 62% of the theoretical amount as determined by titration of an aliquot of the ethereal solution in 65% methanol with standard sodium hydroxide solution to a phenolphthalein end point. The solution of norbornyl acid was then extracted with three 50-ml portions of 2 N sodium hydroxide solution and one 50-ml portion of water. The combined base extracts were held for the methylation step.Reaction of Norbornyl Acid with Diazomethane.-Diazomethane was prepared from Diaz aid (21.5 g, 0.1 mol).' 9Just prior to the reaction with diazomethane, the norbornyl acid was liberated from the sodium salt by acidification and extraction with ether. Esterification was accomplished by the dropwise addition of the dried norbornyl acid solution to diazomethane at 0°. The mixture was allowed to stand until nitrogen was no longer evolved and was then treated with 3 M sulfuric acid until the disappearance of the yellow color. The two layers were separated, and the aqueous layer was extracted several times with ether. The extracts were combined with the organic layer, washed with two 50-ml portions of 0.05 M sodium carbonate solution, and then dried (MgSCh). The ethereal solution was then filtered, combined with an ether wash of the magnesium sulfate, and concentrated by distillation at atmospheric pressure. Analysis of the residual oil by glpc gave (19) Th.

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3-Cyclohexenecarboxylic acid reacts with osmium tetraoxide in aqueous buffer solutions in the presence of a variety of pyridines to form osmate(V1) esters of the general formtda (RO)ZOSOZLZ, where L represents the monodentate ligand. The compounds appear to be octahedral osmyl complexes with a trans O=Os=O group. The general kinetic equation describing the formation of the esters is rate = ko[Os04] [SI + klPl[Os04] [SI [L] + kzpz[Os04] [SI [LIZ where S is the substrate,3-cyclohexenecarboxylic acid, and 61 and PZ are the overall stability constants for the osmium tetraoxide-ligand system.

Grignard reagent obtained from 250 mmol of allyl chloride. The crude product was purified by chromatography on a silica gel column using benzene as the eluent: nmr (CDCL) S 7.4-7.0 (m, 5), 5.9-4.7 (m, 6), 2.50 (m, 4), and 2.14 (s, 1). To 2.96 g (15.8 mmol) of this alcohol in 25 ml of acetonitrile was added 18.95 g (34.6 mmol) of CAN in 20 ml of acetonitrile and 5 ml of water at 80°. After 10 min the initially formed deep red color faded to a light yellow. The mixture was cooled and 50 ml of water and 50 ml of ether were added. The ether layer was separated, washed with saturated NaCl solution, dried (MgS04), and concentrated. Distillation gave 3.7 mmol (23% yield) of a yellowish oil: bp 59-63°( 0.04 mm) [lit.6 bp 100-102°(0.5 mm)]; nmr (CDC1,) S 8.1-7.8 (m, 2), 7.6-7.2 (m, 5), 6.4-6.9 (m, 3), and 3.60 (m, 2).Oxidation Procedure.-Typically, 0.625 mmol of the alcohol, 7.50 mmol of acetonitrile, and 1.25 ml of water were added to a flask equipped with a condenser and magnetic stirring bar. A quantity of 1.25 ml of 1.00 M CAN was added, the flask was immersed in an oil bath at 80°, and the solution was stirred.In the case of 1 and 2 an initial dark red color formed which faded to a light yellow after 4 min. In the case of 3 the initial color was bright yellow and it faded to a light yellow after 30 min. After the reaction was complete, the flask was cooled in a water bath and 8 ml of water and 8 ml of ether were added to it. The ethereal solution was washed three times with 8-ml portions of water, dried (MgS04), and concentrated. The products from 1 were determined by nmr analysis by integration of the signals for the methylene protons of 4 ( 3.55, m), the benzylic protons of 5 ( 4.15, s), and the benzylic protons of 1 ( 3.05, s). In several runs, the total recovery was determined by the use of octadecane or p-di-lert-butylbenzene as standards. The products from 2 were determined by nmr analysis by integration of the signals for the methyl protons of 2 ( 0.90, s), the methyl protons of 6 ( 1.22, s), and the methylene protons of 4 ( 3.55, m). In several cases, the total recovery was determined by the use of mesitylene as a standard. The products from 3 were determined by glpc analysis using benzophenone as a standard and correcting for thermal conductivity and extraction differences as previously described.ab Stability of Benzyl Phenyl Ketone (5) and Pivalophenone (6) to the Oxidation Conditions.-To 0.193 g (1.00 mmol) of 5 and 0.163 g (1.00 mmol) of 6 in 24 ml of acetonitrile and 7.4 ml of water at 80°was added 0.60 ml of a 1.00 M CAN solution.After 30 min at 80°, the mixture was cooled and 0.1822 g of standard (benzophenone) was added. Ether and water (20 ml of each) were added and after extraction the ether layer was separated, washed three times with water, dried (MgS04), and concentrated. Analysis by glpc (correcting for extraction and thermal conductivity differences) showed 97% recovery of 4 and quantitative recovery of 5.

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