The structure of the spermine alkaloid aphelandrine from Aphelandra sguarrosa NEES SummaryThe new spermine alkaloid aphelandrine (2) has been isolated from Aphelandra squarrosa NEES. By oxidation of 2 with KMn04 followed by methylation (CH2N2) 12 and 14 could be prepared (Scheme 2). Fusion of 2 with KOH yielded spermine (1) whereas hydrolysis of 2 in hot hydrochloric acid results in lacton 17, the structure of which could be elucidated by comparison with a synthetically prepared model compound (Scheme 3). The benzylic bonds N (lo), C (1 1) as well as 0 (16), C (17) of 2 could be cleaved by hydrogenolysis (compare 23 and 26; Scheme 4). The elucidation of the correct linkage of the spermine moiety with the aromatic dicarboxylic acid is based mainly on chemical and spectroscopic evidence of the tetrahydro derivative 26, the Hofmann-degradation products 28,30 and 31 (Scheme 6) as well as the ester 35, prepared by partial hydrolysis of 2 (Scheme 7).

To 2.98 g (0.01 rnol) of crystalline X I in 50 ml Et,O is added 11.6 g of Et,NH with ice cooling. A white precipitate forms immediately. After 2 h at reflux, Et,NH.HCl is filtered and the filtrate evaporated and kept under high vacuum to remove all volatilc material. d s a residue is obtained in low yield XII1, a brownish oil. lH-NMR. (in CDCI,): CH, 1.20 (t, 36.9H); C-CH, 2.25 ( t , J p p c~~ 21, 3.6H;i ; and CH, 3.15 (wz, 22.4H).Summary. Structure 1 has been elucidatcd for chaenorbine, an alkaloid isolated from Chaeizorhinum origanzjolium (Scrophulariaceae). The key derivative for the structural elucidation is 13,14,21,22-tetrahydro-21,22-seco-chaenorhitic (21). 21 gavc upon hydrolysis sperminc and 4hydroxydihydrocinnamic acid charactcrizcd as the tctraacetyl derivative 18 and as thc dimethyl derivative respectively.Auszugsweise vorgetragen an der Sommerversammlung cler Schweizerischen Chemischen Gcsellschaft am 17. 10. 1970 in Basel 111. , )148. Mitt., vgl. [2]. Partial hydrolysis of 13,14,21,22-tetrahydro-21,22-seco-chaenorhine (21) gave the spermine derivative 29. Hofmann degradation of 21 lead to the Hofmunn-base 31 (Scheme 1) from which upon hydrolysis 4-methoxycinnamic acid (characterized as the methylester) was obtained. FurtherHofmann degradation converted 31 into the spermidine derivative 32 (Scheme 1). lntensive mass spectrometric investigation of the acetyl derivatives 1, 23 and espccially of 29 and 32 allowed to propose structure 1 for chaenorhine. Formula 1 represents the absolut configuration ((S)-chirality of center 1) of the spermine alkaloid chaenorhine.Chaenorkinum origanijolium (L.) WILLK. et LGE. ist eine ausdauernde Art der Untergattung von Linaria aus der Familie der Scrophulariaceen. Die krautartige Pflanze kommt in Tunesien, Algerien, Marokko, Spanien, Portugal, den Balearen und Sudfrankreich, selten in Italien und Griechenland vor. Unseres Wissens wurde sie bisher nicht untersucht. Fur unsere Arbeiten stand Pflanzenmaterial zur Verfugung, das wahrend der Jahre 1967-1970 voni Institut fur Biochemie der Pflanzen in Halle aufgezogen worden war. Die getrockneten oberirdischen Teile wurden mit Ammoniak angefeuchtet und anschliessend mit Chloroform extrahiert. Aus dem erlialtenen Basengemisch liess sich als Hauptalkaloid Chaenorhin in einer Ausbeute von 0,1-0,15% (bezogen auf das Trockengewicht der Droge) isolieren.Aufgrund der nachfolgenden Ausfiihrungen wird fur Chaenorhin die Struktur 1 3, abgeleitet .Chaenorhin (1, C,,H,,N,O,, M = 548, Smp. 263-268" (Zers.), [. ID = +46,7" (Chloroform/Methano19: 1, pK& = 6,O; Aqu.-Gew. Gef. 530) enthalt eine (C)-CH,-Gruppe (Kuhn-Roth-Oxydation). Im 1R.-Spektrum (KBr) erkennt man Banden fur Amidgruppen (1640, 1612 cm-l) und aromatisclie Ringe (1562, 1510 cm-I). Das UV.-Spektrum (95proz. Athanol) mit Amax 264 nm (logs = 4,00), Amin 247 (3,93) und einer Inflexion bei 280 (3,48) (Fig. 8) kann keinem bekannten Chromophor zugeordnet werden (siehe Abschnitt 7.1).HELVETICA CHIMICA ACTA -Vol. 56, Fasc. 4 (1973) -Nr. 128 strukturierte Signale fur 8 Protonen. Bei 6,...

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Isolation of 1‐Allyl‐2,3‐dimethoxy‐4,5‐methylenedioxybenzene from Heckeria umbellata (L.) KUNTH (Piperaceae) From the leaves of Heckeria umbellata (L.) KUNTH an oily substance was isolated and its structure deduced. It is 1‐allyl‐2, 3‐dimethoxy‐4, 5‐methylenedioxybenzene (= Dill‐Apiol; 2) and not as previously published 1‐allyl‐2, 5‐dimethoxy‐3, 4‐methylenedioxybenzene (= Apiol; 1) [2].

N -b e nzoyl-~-(4,5-dimethoxy-2-hydroxy)phenethylamine, 61177-94-4.