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Sitosterol-β-d -galactoside from Hibiscus sabdariffa
Phytochemical
Reports
829
2. Ducke, A. (1949) As Leyumi~~osus du Amuxhicc Brasileira 2nd Edn., Boletim Ticnico do lnstituto Agron8mico do Norte. No. 18, BelCm. 3. Harper. S. H., Kemp, A. D. and Underwood, W. G. E. (1965) C/lcm Commur~. 309. 4. Donnelly, D. M. X. and Fitzgerald, M. A. (1971) Phyrochemisfry 10, 3 147. 5. Adityachaudhury. N. and Gupta, P. K. (1973) Phytochrmistry 12, 425. irl Pky~ochrwistry 6. Ollis. W. D. (1968) in Rrcrnt Adwnces (Mabry, T. J.. Alston. R. E. and Runeckles. V. C.. eds.), Vol. I. p. 329. Appleton-Century-Crofts, New York. 7. Brana de Oliveira. A.. Gottlieb. 0. R. and Ollis. W. D. (19%) Phytochernisfry 10, 1863. 8. MagalhBes Alves, H., Arndt, V. H., Ollis, W. D., Eyton. W. B., Gottlieb, 0. R. and Taveira MagalhHes, M. (1966)
(source: Pari). Vatuirea mucrocarpu (Benth.) Ducke (Minas Gerais), Vutairea puraensis Ducke (Pari), Vatairea sericra Ducke (Pari), Vutaireopsis araroha (Aguiar) Ducke (Espirito Santo), Vataireopsis speciosa Ducke (Amazonas) and Vataireopsis pallidffiora Rizz. (Goias). Small, mostly heartwood, fragments were secured by courtesy of the botanist A. de Mattos. TLC (SiO*, C,H,-AcOEt-MeOH 72:25:3) examination of their C,H, extracts failed to reveal the presence of chrysophanol only in the extract from V. paf/id(flora. prepared from a softwood sample. AcknoM?ledgements-The MS were registered by Dr. C. H. Williams Jr. through the courtesy of Dr. J. de Paiva Campello, Universidade Estadual de Campinas. REFERENCES
Phytochrmisrry
1. Braz Filho,
R.. Gottlieb. Phytochernistry 14. 261.
0. R. and MourBo,
A. P. (1975)
SITOSTEROL-P-D-GALACTOSIDE HIBISCUS
A. M. OSMAN,M. Department
of Chemistry,
Key Word Index--Hibiscus
suhdar!ffh;
Malvaceae;
XIII in a series. For Part
XII see Ref. [Xl.
and
A. MOKHTAR
of Assiut, Assiut. Egypt, A.R.E.
24 JUJW 1974)
karkade:
Hibiscus sabdarifb (Malvaceae) or karkade is widely used in Egypt for curing heart and nerve diseases [1,2]. Previously [3] we reported the isolation of a steroidal compound of unknown structure from the leaves of this plant. The neutral part of the non-volatile fraction of the Et,0 extract of defatted leaves deposited colourless rosettes which were recrystallised (3 x CHCl,) to yield sitosterol-B-D-galactoside, m.p. 275-277” (decomp.), [z]~ -63’ (in pyridine), v,,,, 3450 cm- ’ (h, OH), NMR (in deuterated pyridine) showed peaks at 5 4.68 (t, one olefinic H), t at 6.29 (t, HZ- to OH). Tetraacetate (needles, MeOHCHCl,), m.p. 149-151”, [IX& -33.3’; MS; parent ion m/r 744 (agreeing with C,,H,,OIo); 331, 211, 229, 169 and 109 (characteristic for glycoside tetraacetates [4]); and at I>I/~I414 and nz/e 396 (base peak), NMR showed sharp peaks at z 7.9-8.0 (four
* Part
YOUNES
of Science, University
(Received
FROM
SABDARIFFA”
EL-GARBY
Faculty
5, 1327.
9. Braga de Oliveira, A., Fonseca c Silva, L. G. and Gottlieb, 0. R. (1972) Ph~rochrrnistry 11, 3515.
sitosterol-/I-o-galactosidc
acetate groups), z at 4.72 (t, one olefinic H). Tetrabenzoate (MeOH-CHCl,), mp 19&198”, [#x]~ + 10.5”. Acid hydrolysis [S] of the glycoside gave sitosterol (mp. mmp 132”. [xl,, -34”. TR, M’ 414) plus galactose (R,- PC 0.12; BuOH-AcOH-H20, 4: 1:2.2). Sitosterol-/?-D-galactoside was synthesized [6] from acetobromogalactose pentaacetate [7] and HBr gas in Ac,O. to obtain a green gum which was dissolved in dry dioxane and added dropwise over 1 hr to a slurry in dioxane of sitosterol, Ag,CO, and MgSO,. After 20 hr at room temp.. the product was chromatographed over alumina to give sitosterol-/?-D-galactoside tetraacetate identical in all respects (IR, mp, mmp and specific rotations) with the natural compound tetraacetate. Itisinteresting to note that whereas sitosterol+Dglucoside has been isolated from several plant sources. this is the first report of the galactoside.
830
Phytochemical
.~~~/lolt,leilye,~l~~nr.s~The authors would like to express their gratitude to Prof. .I. McLean and Dr. Bladon of the Department of Chemistry. University of Strathclydc. Gl:~spou. C. I. Scotland for the NMR :Ind MS measurements.
Reports
1.
5. 6.
REFERE\C’ES
I. Gricbel. C. (1939) %. C’~~rwwch. I,rhrww. 2. Sharaf, A. (1961) Plcrr~tcl Met/. 10, 3X. 3. Osman. A. M.. El-Garhy Youncs. M. ( 1974) /,I
77. 561. 8. and
Mokhtar,
A.
C’ORDlFOLI.4* GIIOSAL, RAMA BALI,AV P. S. CHAI~I-~ANand
SHIHNATH
RAKESH Pharmaceutical
Chemistry Banaras
MEHIA
Research Laboratory. Department of Pharmaceutics. Hindu University. Varanasi-5. India
Key Word Index--Sidu cwdijbliu; Malvaceae: [j-phenethylamines; carboxylated tryptamlnes; quinarolinr loids; /&phcnethylaminc; ephedrine; $-ephedrine: S-( +)-N,,-methyltryptophal7 methyl ester: h!p:rphorine: cmone: vasxine: vasicinol; sympathomimctic amines: hronchodilator principle.
Si& cordlftilirt L. (Malvaceae) is distributed along with other species of this genus throughout the tropical and sub-tropical plains of India. Extracts of different parts of the plant are reported to be used in the Ayurvedic system of medicine for a variety of purposes [I]. Ghosh and Dutta previously isolated [Z] ephedrine and $-ephedrine from the aerial parts of this plant, while Dutta reported [3] the presence of appreciable quantities of HzO-soluble alkaloids but could not isolate them. Reports on nitrogenous constituents of this family of over 700 species are very few. Goss~~pium is the only other genus where the presence of two biogenic amines, viz. 5hydroxytryptamine 141, and histamine [S] has been reported. No true alkaloids have been previously described in the malvaceae. From the roots of this plant, we have now isolated three fl-phenethylamines, viz. /i-phenethylamine (l), ephedrine (2), and $-ephedrine (3). 9 carboxylated tryptamines. S-(+ )-h’,-methyltrypto-
alkavasi-
phan methyl ester (4) and hypaphorine (S), and three quinazoline alkaloids. vasicinone (6). vasicine (7) and vasicinol (8). In addition, liberal amounts of choline and betaine have been obtained from the H,O-soluble alkaloid fraction.
epimeric
(2 at
and 3) the /3 -position
coz-
: ’ ii’ N+(Me)3 ::::I-i(5)
6H
* Part
I in the projected Malvaceae”.
series “Chemical
Constituents
of
(6)
bH
(7) (6)
R=H R =OH
Reports
829
2. Ducke, A. (1949) As Leyumi~~osus du Amuxhicc Brasileira 2nd Edn., Boletim Ticnico do lnstituto Agron8mico do Norte. No. 18, BelCm. 3. Harper. S. H., Kemp, A. D. and Underwood, W. G. E. (1965) C/lcm Commur~. 309. 4. Donnelly, D. M. X. and Fitzgerald, M. A. (1971) Phyrochemisfry 10, 3 147. 5. Adityachaudhury. N. and Gupta, P. K. (1973) Phytochrmistry 12, 425. irl Pky~ochrwistry 6. Ollis. W. D. (1968) in Rrcrnt Adwnces (Mabry, T. J.. Alston. R. E. and Runeckles. V. C.. eds.), Vol. I. p. 329. Appleton-Century-Crofts, New York. 7. Brana de Oliveira. A.. Gottlieb. 0. R. and Ollis. W. D. (19%) Phytochernisfry 10, 1863. 8. MagalhBes Alves, H., Arndt, V. H., Ollis, W. D., Eyton. W. B., Gottlieb, 0. R. and Taveira MagalhHes, M. (1966)
(source: Pari). Vatuirea mucrocarpu (Benth.) Ducke (Minas Gerais), Vutairea puraensis Ducke (Pari), Vatairea sericra Ducke (Pari), Vutaireopsis araroha (Aguiar) Ducke (Espirito Santo), Vataireopsis speciosa Ducke (Amazonas) and Vataireopsis pallidffiora Rizz. (Goias). Small, mostly heartwood, fragments were secured by courtesy of the botanist A. de Mattos. TLC (SiO*, C,H,-AcOEt-MeOH 72:25:3) examination of their C,H, extracts failed to reveal the presence of chrysophanol only in the extract from V. paf/id(flora. prepared from a softwood sample. AcknoM?ledgements-The MS were registered by Dr. C. H. Williams Jr. through the courtesy of Dr. J. de Paiva Campello, Universidade Estadual de Campinas. REFERENCES
Phytochrmisrry
1. Braz Filho,
R.. Gottlieb. Phytochernistry 14. 261.
0. R. and MourBo,
A. P. (1975)
SITOSTEROL-P-D-GALACTOSIDE HIBISCUS
A. M. OSMAN,M. Department
of Chemistry,
Key Word Index--Hibiscus
suhdar!ffh;
Malvaceae;
XIII in a series. For Part
XII see Ref. [Xl.
and
A. MOKHTAR
of Assiut, Assiut. Egypt, A.R.E.
24 JUJW 1974)
karkade:
Hibiscus sabdarifb (Malvaceae) or karkade is widely used in Egypt for curing heart and nerve diseases [1,2]. Previously [3] we reported the isolation of a steroidal compound of unknown structure from the leaves of this plant. The neutral part of the non-volatile fraction of the Et,0 extract of defatted leaves deposited colourless rosettes which were recrystallised (3 x CHCl,) to yield sitosterol-B-D-galactoside, m.p. 275-277” (decomp.), [z]~ -63’ (in pyridine), v,,,, 3450 cm- ’ (h, OH), NMR (in deuterated pyridine) showed peaks at 5 4.68 (t, one olefinic H), t at 6.29 (t, HZ- to OH). Tetraacetate (needles, MeOHCHCl,), m.p. 149-151”, [IX& -33.3’; MS; parent ion m/r 744 (agreeing with C,,H,,OIo); 331, 211, 229, 169 and 109 (characteristic for glycoside tetraacetates [4]); and at I>I/~I414 and nz/e 396 (base peak), NMR showed sharp peaks at z 7.9-8.0 (four
* Part
YOUNES
of Science, University
(Received
FROM
SABDARIFFA”
EL-GARBY
Faculty
5, 1327.
9. Braga de Oliveira, A., Fonseca c Silva, L. G. and Gottlieb, 0. R. (1972) Ph~rochrrnistry 11, 3515.
sitosterol-/I-o-galactosidc
acetate groups), z at 4.72 (t, one olefinic H). Tetrabenzoate (MeOH-CHCl,), mp 19&198”, [#x]~ + 10.5”. Acid hydrolysis [S] of the glycoside gave sitosterol (mp. mmp 132”. [xl,, -34”. TR, M’ 414) plus galactose (R,- PC 0.12; BuOH-AcOH-H20, 4: 1:2.2). Sitosterol-/?-D-galactoside was synthesized [6] from acetobromogalactose pentaacetate [7] and HBr gas in Ac,O. to obtain a green gum which was dissolved in dry dioxane and added dropwise over 1 hr to a slurry in dioxane of sitosterol, Ag,CO, and MgSO,. After 20 hr at room temp.. the product was chromatographed over alumina to give sitosterol-/?-D-galactoside tetraacetate identical in all respects (IR, mp, mmp and specific rotations) with the natural compound tetraacetate. Itisinteresting to note that whereas sitosterol+Dglucoside has been isolated from several plant sources. this is the first report of the galactoside.
830
Phytochemical
.~~~/lolt,leilye,~l~~nr.s~The authors would like to express their gratitude to Prof. .I. McLean and Dr. Bladon of the Department of Chemistry. University of Strathclydc. Gl:~spou. C. I. Scotland for the NMR :Ind MS measurements.
Reports
1.
5. 6.
REFERE\C’ES
I. Gricbel. C. (1939) %. C’~~rwwch. I,rhrww. 2. Sharaf, A. (1961) Plcrr~tcl Met/. 10, 3X. 3. Osman. A. M.. El-Garhy Youncs. M. ( 1974) /,I
77. 561. 8. and
Mokhtar,
A.
C’ORDlFOLI.4* GIIOSAL, RAMA BALI,AV P. S. CHAI~I-~ANand
SHIHNATH
RAKESH Pharmaceutical
Chemistry Banaras
MEHIA
Research Laboratory. Department of Pharmaceutics. Hindu University. Varanasi-5. India
Key Word Index--Sidu cwdijbliu; Malvaceae: [j-phenethylamines; carboxylated tryptamlnes; quinarolinr loids; /&phcnethylaminc; ephedrine; $-ephedrine: S-( +)-N,,-methyltryptophal7 methyl ester: h!p:rphorine: cmone: vasxine: vasicinol; sympathomimctic amines: hronchodilator principle.
Si& cordlftilirt L. (Malvaceae) is distributed along with other species of this genus throughout the tropical and sub-tropical plains of India. Extracts of different parts of the plant are reported to be used in the Ayurvedic system of medicine for a variety of purposes [I]. Ghosh and Dutta previously isolated [Z] ephedrine and $-ephedrine from the aerial parts of this plant, while Dutta reported [3] the presence of appreciable quantities of HzO-soluble alkaloids but could not isolate them. Reports on nitrogenous constituents of this family of over 700 species are very few. Goss~~pium is the only other genus where the presence of two biogenic amines, viz. 5hydroxytryptamine 141, and histamine [S] has been reported. No true alkaloids have been previously described in the malvaceae. From the roots of this plant, we have now isolated three fl-phenethylamines, viz. /i-phenethylamine (l), ephedrine (2), and $-ephedrine (3). 9 carboxylated tryptamines. S-(+ )-h’,-methyltrypto-
alkavasi-
phan methyl ester (4) and hypaphorine (S), and three quinazoline alkaloids. vasicinone (6). vasicine (7) and vasicinol (8). In addition, liberal amounts of choline and betaine have been obtained from the H,O-soluble alkaloid fraction.
epimeric
(2 at
and 3) the /3 -position
coz-
: ’ ii’ N+(Me)3 ::::I-i(5)
6H
* Part
I in the projected Malvaceae”.
series “Chemical
Constituents
of
(6)
bH
(7) (6)
R=H R =OH