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Dimeric alkaloids of secodine-type from Amsonia tabernaemontana roots
Phytochemical Reports
13%
KCA. Traces of KCA were also found of L. laricina.
Freeze-dried needles of L. decidua were extracted with 707; EtOH; chlorophyll etc. was removed with Ccl,, and the extract was separated on a polyamide column and on paper. In addition to KCG, 4 new acylated glycosides were isolated and identified by standard methods as: the 3ferulylglucosides of kaempferol, quercetin, isorhamnetin and syringctin. A fifth compound could not be completely freed from KCG, but was identified as kaempferol-3-p-coumarylarabinoside- ,
AckrmwlrdgernentThe assistance Kooij and of Betty BOOnrdaiJer-WI1
in needles
of Judith KoersrlmanDijk is much :tppreciated.
REFERENCES
1. Niemann, G. J. (1974) Phfu Med. 26, 101. 2. Niemann. G. J. (1975) P/~~to,che~~ist~~~ 14, (111press). 3. Niemann. G. J. (1975) .lcr~ Uot. .V<,wl. 24. (In press). 4. Tissut. M. and Eggel-. K. ( 1077) P/I!.~oI,/I~‘J~II.\~~.I, Il.
h? I.
DIMERIC ALKALOIDS OF SECODINE-TYPE FROM AMSONIA TABERNAEMONTANA ROOTS BELA E6tviis
Lorind
(Jniversity.
ZSAIXN
and
.Jtizsr.rCentral
Research
lnstitutc
MARIA
SZILASI
Department of Chemical Technology. Xluzeum krt. 6 X. Hungary
for C‘hemistr)
H-1048
Budapest.
TAMAS
of the Hungarian
Academy
of Sciences. Budapest.
Hun@r!
and PAL KAPOSI Research
Institute
for Medicinal
Rm~//t \vo/+. Roots. Alkaloids were extracted with McOH from the air-dried ground roots (5OOg) collected in the early autumn. The crude basic material (5.2 g) was fractionated by a combination of column chromatography on alumina of activities II and III giving two dimeric alkaloids of the secodinc-type. tetrahydrosecamine (800 mg) and tctrahydroprescc~ltni~~c ( I 15 mg) in addition to eburnaminc ( 1X2 mg) and other alkaloids reported previousl\, [ I]. The secodine-type alkaloids from A//w//it/ roots proved to be identical with those isolated earlier from Rhaz~x/ species [Z ~41. Trf/.~/h!.tl/.o.sc’~~/rllj//i’.High resolution MS gave a molecular ion peak at //z;(J 680 (6X0.4305 corr. to C12H,,NIOA~ and base peak at //I,:Q 126. Amorphous: i 2X4. 291 nm; (EtOH) ‘24. rI,,~,,(CJHCI,) 3420 (NH), 1738 (s&d. ester) cm- ’ ;
Plants.
Budakahisz.
Hungarq
[xl;:’ 0’ (EtOH). 7‘c~r/.oh!,h.o/~/.~~.~(J~,~////;/~~~. C,,H,,N,O,. High resolution MS gave the molecular ion peak of the monomer i5,?0-dihydrosccodine at //zlc~340 (340214X cot-r. to C3, HzHNI02), base peak at /JI;C~136 and another characteristic peak at //?,‘o 2X1. Amorphous glass, u hich casilq transforms into tetrahqdrosecamint: on standing at room temp. in strong acid solutions for several hours. i,, (EtOH) 224, 2% . 295. 33 nm: I’ (CHCI,) 3360 (NH). 173X (satd. cstcr). 16X0 and 1610 (P-unilinoacrylic ester); [~~]“’ --- 12 (EtOH). Ehuv/w//i/w. High resolution MS gave ;I molecular ion (base) peak at //I (1 296 (296.1 WI corr. to C,,H,,N20) and other signilicant peaks at /// (1 296, 395, 27X. 267. 249. 236. 70X. 206. 193, i. (EtOH) 239.276 (. 1X2. 30 The sampI could be transformed into (+ )-cburntlmoninc hi oxidbing with CrO, or into eburnamcnine h! deh~drating in HOAc (cf. reference [!I]). A new dimeric alkaloid of the sccodine-type
Phytochemical
(11 mg) was isolated from the basic extract (1.55 g) of A tabernaemontana roots (500 g) collected late in the winter. This proved to be decarhomethoxytetrahydrosecamine. Its high resolution MS gave a molecular ion peak at m/e 622 (622.4248 corr. to C,,H,,N,OJ and base peak at m/e 126. Amorphous; b]‘” 0” (EtOH); A,, \ (EtOH) 224, 284, 292 nm; \‘,,, (CHCI,) 3360 (NH), 1738 (satd. ester) cm- ‘. (The latter is of much smaller intensity than the corr. peak of tetrahydrosecamine.)
Phytochetmsrr~,
Reports
1439 REFERENCES
B., Tam&,, J. and Szilasi, M. (1974) Acta Chim. (Budapest) 80, 359. Evans, D. A., Joule, J. A. and Smith, G. F. (1968) Phytocher,~ist~1; 7, 1429. Evans. D.A.. Smith. G. F., Smith, G. N. and Stapleford, K. S. J. (I 96X) Chrm. Comm. 859. Cordell, G. A.. Smith. G. F. and Smith, G. N. (1970) Chrm. Co,11n1ur1. I9 I. Bartlett, M. F., Sklar. R.. Smith, A. F. and Taylor, W. I. (1963) J. Or<]. Chcm. 28, 2197 and ref. therein.
I. Zsadon, 2. 3. 4. 5.
1975, Vol. 14. p. 1439. Pergamon Press. Prmted in England
ANTHOCYANIN
OF ACANTHOPANAX NARIYUKI
Department
of Biology,
Kumamoto
DIVARZCATUS
ISHIKURA University,
Kumamoto,
Japan
(Received 28 November 1974) Key Word
Index-Acanthopanax
diuaricatus; Aralidceae;
Preparative chromatography of the fruit extract of Acanthopanax divaricatus (Sieb. et Zucc.) Seeman revealed the presence of two anthocyanins, one of which was a new pigment. On complete acid hydrolysis, the new anthocyanin yielded delphinidin, xylose and galactose. The absorption spectrum (in 0.01 % MeOH-HCl) of the glycoside showed A,,, (nm) 283 and 532 and a bathochromic shift of 13 nm by the addition of AlCl, indicating the presence of a free o-dihydroxylic grouping in the B-ring. The ratios of Eu.v and E440/Evis.,,, were 58 and 22 ;~~$?~~~~~ These values suggest that the pig;ent is the 3glycoside [l]. By H,Oz oxidation the glycoside yielded the disaccharide which was identified paper chromatographically as lathyrose. On partial acid hydrolysis delphinidin 3-galactoside was detected as an intermediate. The pigment must therefore be delphinidin 3-xylosylgalactoside (3lathyroside), which has not been reported before. Recently, cyanidin 3-lathyroside has been found in the ripe berries of Aralia elata [2] and its variety canescens [3], and A. cordata [2]. Therefore, the glycosidic similarity of the anthocyanins
delphinidin
3-xylosylgalactoside.
in the plants in the family Araliaceae of systematic interest.
may be
EXPERIMENTAL
The anthocyanin extract of the ripe black fruits was separated into two components by PC in HOAc~HCl~H,O (15:3:X2). Diagnostic chromatography of the new anthocyanin, its anthocyanidin and sugars were carried out by standard procedures [4]. The quantity of the second anthocyanin was too small to examine in detail. Chromatographic identification of lathyrose followed H,Oz oxidation of the glycoside [S]. Delphinidin 3-galactoside as the partial hydrolysate was identified by direct comparison with empetrin from Empetrum nigrum L. var. japonicum K. Koch [6].
REFERENCES
1. J. B. Harborne (1967) in Compararive Biochemistry of the Flavonoids, p. 17. Academic Press, London. 2. S. Sakamura and K. Kawano (1970) Phytochemistry 9, 1147. 3. N. Ishikura, unpublished data. 4. N. Ishikura and M. Shibata (1970) Bot. Mag. Tokyo 83, 179. 5. K. Kawano and S. Sakamura (1972) Agr. Biol. Chem. 36, 27. 6. K. Hayashi, G. Suzushino and K. Ouchi (1951) Proc. Japan Acad. 27, 430.
13%
KCA. Traces of KCA were also found of L. laricina.
Freeze-dried needles of L. decidua were extracted with 707; EtOH; chlorophyll etc. was removed with Ccl,, and the extract was separated on a polyamide column and on paper. In addition to KCG, 4 new acylated glycosides were isolated and identified by standard methods as: the 3ferulylglucosides of kaempferol, quercetin, isorhamnetin and syringctin. A fifth compound could not be completely freed from KCG, but was identified as kaempferol-3-p-coumarylarabinoside- ,
AckrmwlrdgernentThe assistance Kooij and of Betty BOOnrdaiJer-WI1
in needles
of Judith KoersrlmanDijk is much :tppreciated.
REFERENCES
1. Niemann, G. J. (1974) Phfu Med. 26, 101. 2. Niemann. G. J. (1975) P/~~to,che~~ist~~~ 14, (111press). 3. Niemann. G. J. (1975) .lcr~ Uot. .V<,wl. 24. (In press). 4. Tissut. M. and Eggel-. K. ( 1077) P/I!.~oI,/I~‘J~II.\~~.I, Il.
h? I.
DIMERIC ALKALOIDS OF SECODINE-TYPE FROM AMSONIA TABERNAEMONTANA ROOTS BELA E6tviis
Lorind
(Jniversity.
ZSAIXN
and
.Jtizsr.rCentral
Research
lnstitutc
MARIA
SZILASI
Department of Chemical Technology. Xluzeum krt. 6 X. Hungary
for C‘hemistr)
H-1048
Budapest.
TAMAS
of the Hungarian
Academy
of Sciences. Budapest.
Hun@r!
and PAL KAPOSI Research
Institute
for Medicinal
Rm~//t \vo/+. Roots. Alkaloids were extracted with McOH from the air-dried ground roots (5OOg) collected in the early autumn. The crude basic material (5.2 g) was fractionated by a combination of column chromatography on alumina of activities II and III giving two dimeric alkaloids of the secodinc-type. tetrahydrosecamine (800 mg) and tctrahydroprescc~ltni~~c ( I 15 mg) in addition to eburnaminc ( 1X2 mg) and other alkaloids reported previousl\, [ I]. The secodine-type alkaloids from A//w//it/ roots proved to be identical with those isolated earlier from Rhaz~x/ species [Z ~41. Trf/.~/h!.tl/.o.sc’~~/rllj//i’.High resolution MS gave a molecular ion peak at //z;(J 680 (6X0.4305 corr. to C12H,,NIOA~ and base peak at //I,:Q 126. Amorphous: i 2X4. 291 nm; (EtOH) ‘24. rI,,~,,(CJHCI,) 3420 (NH), 1738 (s&d. ester) cm- ’ ;
Plants.
Budakahisz.
Hungarq
[xl;:’ 0’ (EtOH). 7‘c~r/.oh!,h.o/~/.~~.~(J~,~////;/~~~. C,,H,,N,O,. High resolution MS gave the molecular ion peak of the monomer i5,?0-dihydrosccodine at //zlc~340 (340214X cot-r. to C3, HzHNI02), base peak at /JI;C~136 and another characteristic peak at //?,‘o 2X1. Amorphous glass, u hich casilq transforms into tetrahqdrosecamint: on standing at room temp. in strong acid solutions for several hours. i,, (EtOH) 224, 2% . 295. 33 nm: I’ (CHCI,) 3360 (NH). 173X (satd. cstcr). 16X0 and 1610 (P-unilinoacrylic ester); [~~]“’ --- 12 (EtOH). Ehuv/w//i/w. High resolution MS gave ;I molecular ion (base) peak at //I (1 296 (296.1 WI corr. to C,,H,,N20) and other signilicant peaks at /// (1 296, 395, 27X. 267. 249. 236. 70X. 206. 193, i. (EtOH) 239.276 (. 1X2. 30 The sampI could be transformed into (+ )-cburntlmoninc hi oxidbing with CrO, or into eburnamcnine h! deh~drating in HOAc (cf. reference [!I]). A new dimeric alkaloid of the sccodine-type
Phytochemical
(11 mg) was isolated from the basic extract (1.55 g) of A tabernaemontana roots (500 g) collected late in the winter. This proved to be decarhomethoxytetrahydrosecamine. Its high resolution MS gave a molecular ion peak at m/e 622 (622.4248 corr. to C,,H,,N,OJ and base peak at m/e 126. Amorphous; b]‘” 0” (EtOH); A,, \ (EtOH) 224, 284, 292 nm; \‘,,, (CHCI,) 3360 (NH), 1738 (satd. ester) cm- ‘. (The latter is of much smaller intensity than the corr. peak of tetrahydrosecamine.)
Phytochetmsrr~,
Reports
1439 REFERENCES
B., Tam&,, J. and Szilasi, M. (1974) Acta Chim. (Budapest) 80, 359. Evans, D. A., Joule, J. A. and Smith, G. F. (1968) Phytocher,~ist~1; 7, 1429. Evans. D.A.. Smith. G. F., Smith, G. N. and Stapleford, K. S. J. (I 96X) Chrm. Comm. 859. Cordell, G. A.. Smith. G. F. and Smith, G. N. (1970) Chrm. Co,11n1ur1. I9 I. Bartlett, M. F., Sklar. R.. Smith, A. F. and Taylor, W. I. (1963) J. Or<]. Chcm. 28, 2197 and ref. therein.
I. Zsadon, 2. 3. 4. 5.
1975, Vol. 14. p. 1439. Pergamon Press. Prmted in England
ANTHOCYANIN
OF ACANTHOPANAX NARIYUKI
Department
of Biology,
Kumamoto
DIVARZCATUS
ISHIKURA University,
Kumamoto,
Japan
(Received 28 November 1974) Key Word
Index-Acanthopanax
diuaricatus; Aralidceae;
Preparative chromatography of the fruit extract of Acanthopanax divaricatus (Sieb. et Zucc.) Seeman revealed the presence of two anthocyanins, one of which was a new pigment. On complete acid hydrolysis, the new anthocyanin yielded delphinidin, xylose and galactose. The absorption spectrum (in 0.01 % MeOH-HCl) of the glycoside showed A,,, (nm) 283 and 532 and a bathochromic shift of 13 nm by the addition of AlCl, indicating the presence of a free o-dihydroxylic grouping in the B-ring. The ratios of Eu.v and E440/Evis.,,, were 58 and 22 ;~~$?~~~~~ These values suggest that the pig;ent is the 3glycoside [l]. By H,Oz oxidation the glycoside yielded the disaccharide which was identified paper chromatographically as lathyrose. On partial acid hydrolysis delphinidin 3-galactoside was detected as an intermediate. The pigment must therefore be delphinidin 3-xylosylgalactoside (3lathyroside), which has not been reported before. Recently, cyanidin 3-lathyroside has been found in the ripe berries of Aralia elata [2] and its variety canescens [3], and A. cordata [2]. Therefore, the glycosidic similarity of the anthocyanins
delphinidin
3-xylosylgalactoside.
in the plants in the family Araliaceae of systematic interest.
may be
EXPERIMENTAL
The anthocyanin extract of the ripe black fruits was separated into two components by PC in HOAc~HCl~H,O (15:3:X2). Diagnostic chromatography of the new anthocyanin, its anthocyanidin and sugars were carried out by standard procedures [4]. The quantity of the second anthocyanin was too small to examine in detail. Chromatographic identification of lathyrose followed H,Oz oxidation of the glycoside [S]. Delphinidin 3-galactoside as the partial hydrolysate was identified by direct comparison with empetrin from Empetrum nigrum L. var. japonicum K. Koch [6].
REFERENCES
1. J. B. Harborne (1967) in Compararive Biochemistry of the Flavonoids, p. 17. Academic Press, London. 2. S. Sakamura and K. Kawano (1970) Phytochemistry 9, 1147. 3. N. Ishikura, unpublished data. 4. N. Ishikura and M. Shibata (1970) Bot. Mag. Tokyo 83, 179. 5. K. Kawano and S. Sakamura (1972) Agr. Biol. Chem. 36, 27. 6. K. Hayashi, G. Suzushino and K. Ouchi (1951) Proc. Japan Acad. 27, 430.