Dies in (2) eingesetzt gibt, wenn wir die Reihenfolge der Integrationen vertauschen und C ( X , 0) = 0 , C(x, 00) = c; beriicksichtigen, und hieraus folgt (6). SCHUNG danken wir fur die Unterstiitzung dieser Arbeit. Dem SCHWEIZERISCHEN NATIONALFONDS Z U R FORDERUNG DER WISSENSCHAFTLICHEN FOR-SUMMARY From sorption experiments as described by A. VAN TETS and Hs. H. GUNTHARD a time lag can be determined which is directly related to the diffusion coefficients D and 113 of the system investigated. Universitats-Augenklinik Base1 (Vorsteher : Prof. F. RINTELEN), Wissenschaftliches Laboratorium 269. uber Steroide und Sexualhormone UV.-Bestrahlung von 11-0x0-Steroiden I

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1261Cettc substance, homogene i l'examen par chromatographie gaz-liquide sur silicone, donne par micro-oz~nolyse~~) de l'aldbhyde propionique (identifi6 par la chromatographie sur papier dc sa dinitro-2,4-phBnylhydrazone) comme scule partie carbonylge volatile. SUMMARYA synthesis of racemic jasmine lactone, viz. cis-(5-pent-2-enyl)-pentanolide-(5,1), is described. FIRMENICH Sr CIE, Laboratoires de Recherches (Direction: Dr M. STOLL), Geneve 14) E. DEMOLE & H. WUEST, Chimia 15, 286 (1961). 148. uber Steroide und Sexualhormone UV.-Bestrahlung von 11-0x0-Steroiden I1 Die Darstellung von A4und A 5 -l l P , 19-Cyclo-pregnen-sowie 5/3-11/3,19-Cyclo-und 5,19-Cyclo-pregnan-Verbindungen3) von M. S . Heller4), H. Wehrlis), K. Schaffner und 0. Jeger 225. Mitteilung') 2, (13. IV. 62)Wir hatten kurzlich gezeigt 6), dass bei der UV.-Bestrahlung der 11-0x0-5apregnan-Verbindung I meitgehefid selektiv die afigdare Methylgruppe I9 angegriff en wird, wobei in ca. 38-proz. Ausbeute7) das mit I isomere Cyclobutanol-Derivat I1 entsteht. Unsere Arbeiten erstreckten sich anschliessend auch auf die d5-ungesattigten bzw. A/B-cis verknupften 11-Oxopregnane 1118) und XXI19), um den Einfluss der Konstitution und Konfiguration des Kohlenstoffatoms 5 auf das photochemische Verhalten der 11-0x0-Steroide zu untersuchen.

CH?c c , E ( e V ) < 4 b 5 4b0 E B i n d i n g E n e r g y B i n d i n g E n e r g y Flgure 4. X-ray photoelectron spectrum of I I I f : (a) N(ls) energy region, (b) C(1s) energy region. a pressure of less than lo-* torr. Samples were mounted on aluminum mesh at room temperature. ( a ) Reaction of Arylhydrazone -N -carboxylic Esters ( I ) and Hydrazlne Hydrate. A mixture of the hydrazone ester (0.01 mol) and the hydrazine hydrate (0.01 mol) in 50 mL of ethanol was refluxed on a water bath for a period of 5 h. Evaporation of the solvent left a viscous oil, which proved to be the arylhydrazone (I I). Crystallization of I I a from petroleum ether (60-80 "C) gave pale yellow crystals, mp 62 " C . The other hydrazones gave oily materials. ( b ) Reactlon of Arythydrazones ( I I a -g ) and Hydrochloric AcM. A mixture of the arylhydrazone (0.01 mol) in ethanol (20 mL) and 6 N HCI (5 mL) was warmed on a water bath for 5 min. A heavy solid was precipitated, which was filtered off and crystallized from ethanol to give azines of thiophene-2carboxaldehyde (I IIa), furan-2-carboxaldehyde (I1 Ib), pyrrole-2carboxaldehyde (I I IC), 5-methylthiophene-2-carboxaldehyde ( I 1 Id), indole-3-carboxaldehyde (I I Ie), N-methylpyrrole-2carboxaldehyde (I I If), and pyridine-4-carboxaldehyde (I I Ig).Azine I I I a was also prepared by refluxing an alcoholic solution of the arylhydrazone-N-carboxylic ester Ia and aqueous sodium hydroxide (10%) for 1 h. The alcohol was evaporated, and the product was crystallized from petroleum ether (60-80 "C) to give a product, which proved to be identical with IIa. This product was treated with hydrochloric acid, as mentioned above, to yield azine IIIa.( c ) Preparation of Authentlc Samples.(1) Hydrazone I I a was prepared by refluxing equimolecular amounts of thiophene-2-carboxaldehyde and hydrazine hydrate in ethanol for a period of 5 h and then worked up as described previously. (2) Azines IIIa-g were prepared by refluxing the corresponding heterocyclic aldehyde (2 mol) and hydrazine hydrate (1 mol) in ethanol and then worked up. The products proved to be identical with those obtained from procedure b.Elemental analyses were performed and submitted for review. Reglstry No. la,A one-step synthesis of methyl 2thiorohexane-1-and 2-chlorooctane-1-sulfonate by the novel free-radical addition of methyl chlorosulfonate to 1-hexene and 1-octene, respectively, Is reported. These products were converted by standard techniques into the corresponding sodium and benzylthiuronlum P-chiorosulfonlc acid salts and sulfonyl chlorides. Dehydrochlorination of these latter products with triethylamine afforded reglospecific formation of trans-a,p-unsaturated sulfonyl chlorides, which were transformed by conventional methods into sodium and benzylthiuronlum unsaturated and saturated sulfonlc acid salts. Eleven new compositions of matter are reported. Seven l-phenyl-2-[2-( 6-substituted qulnolyl)]ethanoneswere synthesized by the condensatlon of 2methyl-6-substkuted qulnollnes and methyl benzoate wlth sodlum hydrlde as the con...

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