Vol. 71 hyde was highest the proportion of the two by-products was roughly equal, but even when the Raney nickelester ratios were varied from 5-1 to 20-1 both products were present.The identity of the alcohol was checked by preparation of 3~~,12a-diacetoxynorcholan-23-ol by direct reduction of ethyl 3cu,l2cu-diacetoxynorthiolcholanate with W-4 Raney nickel in alcohol at room temperature.* The two alcohols were identical. The compound was crystallized both from aqueous alcohol and chloroform-hexane mixture ; m. p. 148.5-151'; [ a ] 2 6~ + 110' (100.0 mg. in 10 ml. of CHC13, 11 drn.; CYD +l.lOo).Anal. Calcd. for CarHa4Os: C, 72.30; H, 9.89. Found: C, 72.49; H , 9.95. 3a,l2a-Diacetoxynorcholan-23-ol refluxed for two hours in 1-1 pyridine-acetic anhydride gave a 70% yield of 3a,-12a,23-triacetoxynorcholane, m. p. 108-110' from aqueous acetic acid.Anal. Calcd. for Cz~H4608: C, 70.98; H, 9.45. Found: C, 71.05; H , 9.38. 3~~,12a-Diacetoxynorcholan-23-ol was allowed to stand seven hours in a 5% solution of potassium hydroxide in 80% alcohol a t room temperature. The product was precipitated by the addition of water, chromatographed and crystallized from aqueous alcohol to give a 70% yield of ~a,23-dihydroxy-12-acetoxynorcholane, m. p. Hydrolysis of 3cu,l2~~-diacetoxynorcholan-23-ol in 10% alcoholic potassium hydroxide under reflux €or three hours gave 83% of 3cr,12~~,23-trihydroxynorcholane, m. p. 194-200 '. On recrystal1:zation from ethanol the compound melted at 209.5-211 . Anal. Calcd. for C23H4003: C, 75.77; H , 11.06. Found: C, 75.67; H , 10.96. The dinitrophenylhydrazones and semicarbazones reported in Table I1 were prepared as described in previous papers in this series.2 Cyanohydrins.-The preparation of the steroid aldehyde cyanohydrins listed in Table 111 is illustrated by the method used for 3~t-acetoxycholan-24-al cyanohydrin. A mixture of 0.500 g. of 3a-acetoxycholan-24-a1, 1.5 rnl. of dioxane, and 3 ml. of saturated aqueous sodium bisulfite was stirred a t room temperature for thirty minutes, then 0.5 g. of solid potassium cyanide was added and the mixture was heated for five minutes on the steam-bath, then allowed to cool to room temperature for thirty minutes, with occasional stirring. The reaction mixture was poured into 50 ml. of water giving a gummy precipitate. This was crystallized from aqueous acetic acido to give 0.476 g. (85%) of crystals melting a t 148-152 . After several crystall@tions from aqueous acetic acid the m. p. was 154.5-156 . Summary 3cr-Hydroxycholan-24-al, its 3-acetyl and 3formyl derivatives, 12aacetoxycholan -24al, 3a,-12a-diacetoxynorcholan-23-al, Sa-acetoxy-llcholen-24-a1, and 3/3-formoxy-5-cholen-24-al have been prepared by the desulfurization of the corresponding thiol esters with acetone deactivated Raney nickel catalyst.The cyanohydrins have been obtained by treating these aldehydes with sodium bisulfite and potassium cyanide in dioxane-water.Cholesterol that has been labeled with isotopic cause the elimination of the group a t the 3-posicarbon in the nucleus would be usef...

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SUMMARY Volatile components from the steam above peas in a commercial blancher were isolated by adsorption on charcoal, freeze‐drying of the charcoal, solvent extraction, and distillative concentration. The concentrate was further fractionated by distillation and gas chromatography. Ethanol and dimethyl sulfoxide were most abundant. The latter compound formed by the oxidation of dimethyl sulfide adsorbed on the charcoal. The less abundant components of the concentrate fractions were identified by capillary‐column gas‐chromatography fast‐scan mass spectrometry. The most novel group of minor components thus identified was the diethyl acetals of C1‐C6 aldehydes. It was not possible to determine from model experiments if the acetals were original components of the blancher steam or artifacts of the isolation. A control concentrate from unexposed charcoal and purified solvent differed quantitatively and qualitatively from the blancher steam concentrate.

Attempts to discover an effective antimalarial drug have been based in part on modification of the structure of quinine. Among the simplest compounds examined were ethanolamine derivatives such as quinolyl-CHOHCH2NR2 and related substances in which other aryl groups, including naphthyl, replaced quinoline (1, 2, 3, 4). A thorough investigation of such compounds was undertaken at the National Institute of Health to determine the influence of various nuclei on antimalarial action (5). It was found that, among others, compounds of this type containing the -naphthyl nucleus possessed some antimalarial activity in avian malaria (6), although King and Work (1) had not observed activity in similar substances. The corresponding /3-naphthyl derivatives were much less active. As part of a cooperative project with the National Institute of Health, we have extended the work on the -naphthyl compounds by synthesizing dialkylaminomethyl-l-naphthalenemethanols in which the naphthalene nucleus was substituted in various positions with halogen or methoxyl and in which the dialkylamino group varied from dimethylamino to di-ndecylamino.The conventional synthesis of such ethanolamine derivatives involves the reaction of an -halo ketone such as I with a dialkylamine to yield an aminó ketone II which is then reduced.