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Kundzz, Kundu, and Dutta 2749 497. Synthetical Studies on Terpenoids. Part X.l * Sterwspecific Syntheses of ( &)-Clovan-9-one and ( &)-Clovane By ANIL KUMAR KUNDU, NITYA GOPAL KUNDU, and PHANINDRA CHANDRA DUTTA Stereospecific syntheses of ( &)-clovan-9-one and (&)-dovane have been described and their structural and stereochemical identity has been established with the corresponding products from natural sources by infrared studies.CARYOPHYLLENE and isocaryophyllene, because of the presence of an interesting ringsystem in their molecular framework, undergo under acidic conditions varied types of rearrangements, characteristic of medium-sized rings. Caryophyllene under mild acid treatment affords caryolan-1-01 (I) and clovene (11), whereas under vigorous acid treatment isoclovene (111) and +clovene (IV) are formed. The tendency to undergo molecular rearrangement is not confined to hydrocarbons but is found also in their derivatives. Thus, caryophyllene monoxide, on acid treatment, affords clovan-2~,9~x-diol (V) and this has been converted into the ketone (VI) .2b On Wolff-Kishner reduction of the diketone corresponding to the diol, clovane (VII) was obtained and shown to be identical with the hydrocarbon available from catalytic reduction of clovene.2 Recently, two additional carbonyl compounds (VIII) and (IX) along with the glycol (V) have been isolated from the reaction mixture and the salient structural features of these two interesting compounds have been fully established.Synthetical studies have of late been undertaken in this field with remarkable success, resulting in the total syntheses of caryophyllenes. In addition, Raphael has disclosed the total synthesis6 of clovene. Experiments were also initiated in this laboratory for the synthesis of the ring system present in clovene and a preliminary Communication7 covering some aspects of this attempt has already appeared.

Narang a d Dutta : 574. Synthetical Studies of Terpenoids. Part V.l A New Synthesis of ( & ) -6 p -Acetox y-5,5,9 ptrimethyltrans -2 -decalone.By SARAN ADHAR NARANG and PHANINDRA CHANDRA DUTTA.A new synthesis of the compound named in the title begins with preparation of the ketone (11) and its condensation with 2-chloroethyl ethyl ketone,

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Bisher ist ein einziges Monomethyl-tocol bekannt l ) , das die Methylgruppe in Stellung 8 enthiilt. Die Schwierigkeit der Darstellung der beiden anderen Isomeren (5-sowie 7-Monomethyl-tocol) liegt darin, dass zur Zeit keine Methode existiert, zwei Stellungen im Toluhydrochinon vorubergehend so zu blockieren, dass die dritte Stelle bei der Tocolsynthese in Reaktion treten muss, und nachher die vorubergehend eingefuhrten Substituenten wieder zu entfernen. Dieses Problem bildete den Ausgangspunkt fur die folgenden Versuche.In der Einwirkung von Ramy-Nickel besitzt man heute ein einfaches Verfahren, um aus organischen Schwefelverbindungen die schwefelhaltige Gruppe reduktiv zu eliminieren. Wir versuchten daher, Methylmercaptoderivate des Toluhydrochinons herzustellen, diese mit Phytol zu den entsprechenden Methyl-methylmercaptotocolen zu kondensieren und aus letzteren nachtriiglich die Methylmercaptogruppe mittels Raney-Nickel zu entfernen, z. B.