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Urospermal a glucoside from urospermum picroides
Short Reports
692
sot. Jpn. so, 1201. 9. Honda, S., Yamauchi, N. and Kakehi, K. (1979) J. Chromatogr. 169, 287. 10. Okamura, N., Yagi, A. and Nishioka, I. (1981) Chem. Pharm. Bull. 29, 3507.
Phytochemisrry,
Vol. 23, No. 3, pp. 692-693,
11. Colson, P., Jennings, H. J. and Smith, I. C. P. (1974) J. Am. Chem. Sot. %,8081. 12. Hakomori, S. (1964) J. Biocbem. 55, 205. 13. Jansson, P., Knee, L., Liedgren, H., Lindherg, B. and Lonngren, J. (1976) Univ. Stockholm Chem. Commun. No. 8.
1984.
003 l-9422/84
UROSPERMAL,
$3.00 + 0.00
0 1984Pergamon Press Ltd.
Printed in Great Britain.
A GLUCOSIDE
FROM UROSPERMUM
PICROZDES
MOHAMED M. A. AMER,* OSAMA M. SALAMA,* FERDINAND BoHLMANNt and J~RGEN ZlEsCHEt *Pharmacognosy
Department, Faculty of Pharmacy, Mansoura University, Mansoura, Egypt; t Institute for Organic Chemistry, Technical University of Berlin, D-1000 Berlin 12, West Germany (Received 20 May 1983)
Key Word Index-Urospermum
Abstract-The
picroides; Compositae; sesquiterpene lactones; urospermal A glucoside.
roots of Urospermum
picroides
afforded urospermal A 15-O-@glucoside.
The aerial parts of Urospermum picroides (L.) Stop. ex F. W. Schmidt contain the melampolide urospermal A and the p-hydroxyphenyl acetate of the corresponding glucoside [l]. We have now studied the polar fractions from the roots. Thin-laver chromatoaranhv afforded two compounds, the giucosides 1 a;d -2..Acetylation gave the acetates 3 and 4, the latter being identical with the acetylation product of the glucoside 2 isolated from the aerial parts [ 11.The ‘H NMR spectrum of 3 (Table 1) was close to that of 4. However, the signals of the phydroxyphenyl acetate were replaced by an additional acetate methyl signal. As observed previously [l] the hydrogen-bonded 8a-hydroxyl group was not acetylated. The ‘H NMR spectrum of the natural compound 1 could be measured only in deutero-pyridine (Table 1).All signals were assigned by spin decoupling in the usual way, starting with the H-7 signal although all signals were
“CHO
1 R=R’=H
2 R=H,R’=COCHpCsH40H(p) 3 R = R’= AC 4 R=Ac,R’=COCHzC6H40Ac(p)
Table 1. ‘H NMR spectral data of compounds 1 and 3 (400 MHz, TMS as internal standard)
1 (C,D,N)
3 (CDC&)
H-l H-2
6.67 br dd
6.81 br dd
H-2 H-3 H-3 H-4 H-6 H-7 H-8 H-9 H-9 H-13 H-13 H-14 H-15 H-15 H-l’ H-2 H-3 H-4’ H-5’ H-6; H-6; OH OAc
2.26 ddd 2.68 ddd 1.80br dd 5.15br d 4.98 dd 2.65 dddd 4.27 ddd 2.98 dd 2.44 br d 6.6Odd 6.33 dd 9.49 br s 4.77d 4.441
2.53 ddd
4.91 d 4.OOdd 4.20 m 3.95 m 4.54 dd 4.36 dd 6.06d -
2.54 m 2.6 1 ddd 2.03 m 5.15br d 4.57dd 2.45 dddd 3.90 dddd 2.70dd 2.37 br d 6.52dd 6.30dd 9.44 br s 4.4Od 4.33d 4.58d 5.04dd 5.22 dd 5.08 dd 3.73 dd 4.26dd 4.17dd 6.07 d 2.08 s 2.03 s 2.02 s 1.98s
J (Hz): 1,2 = 9; 1,2’ = 8; 1,9 _ 1; 5,6 = 6, 7 = 7, 8 = 14 7,13 = 3.5; 7, 13’ = 3; 8, OH = 11,5; 8,9 =5;8,9’=11;9,9’= 16;13,13’=2;15,15’=12; l’, 2’ = 8.5; 2, 3’= 3’, 4’ = 4;, 5’ = 9.5; 5’, 6; = 2.5; 5’, 6; = 5; 6;, 6; = 12.
692
sot. Jpn. so, 1201. 9. Honda, S., Yamauchi, N. and Kakehi, K. (1979) J. Chromatogr. 169, 287. 10. Okamura, N., Yagi, A. and Nishioka, I. (1981) Chem. Pharm. Bull. 29, 3507.
Phytochemisrry,
Vol. 23, No. 3, pp. 692-693,
11. Colson, P., Jennings, H. J. and Smith, I. C. P. (1974) J. Am. Chem. Sot. %,8081. 12. Hakomori, S. (1964) J. Biocbem. 55, 205. 13. Jansson, P., Knee, L., Liedgren, H., Lindherg, B. and Lonngren, J. (1976) Univ. Stockholm Chem. Commun. No. 8.
1984.
003 l-9422/84
UROSPERMAL,
$3.00 + 0.00
0 1984Pergamon Press Ltd.
Printed in Great Britain.
A GLUCOSIDE
FROM UROSPERMUM
PICROZDES
MOHAMED M. A. AMER,* OSAMA M. SALAMA,* FERDINAND BoHLMANNt and J~RGEN ZlEsCHEt *Pharmacognosy
Department, Faculty of Pharmacy, Mansoura University, Mansoura, Egypt; t Institute for Organic Chemistry, Technical University of Berlin, D-1000 Berlin 12, West Germany (Received 20 May 1983)
Key Word Index-Urospermum
Abstract-The
picroides; Compositae; sesquiterpene lactones; urospermal A glucoside.
roots of Urospermum
picroides
afforded urospermal A 15-O-@glucoside.
The aerial parts of Urospermum picroides (L.) Stop. ex F. W. Schmidt contain the melampolide urospermal A and the p-hydroxyphenyl acetate of the corresponding glucoside [l]. We have now studied the polar fractions from the roots. Thin-laver chromatoaranhv afforded two compounds, the giucosides 1 a;d -2..Acetylation gave the acetates 3 and 4, the latter being identical with the acetylation product of the glucoside 2 isolated from the aerial parts [ 11.The ‘H NMR spectrum of 3 (Table 1) was close to that of 4. However, the signals of the phydroxyphenyl acetate were replaced by an additional acetate methyl signal. As observed previously [l] the hydrogen-bonded 8a-hydroxyl group was not acetylated. The ‘H NMR spectrum of the natural compound 1 could be measured only in deutero-pyridine (Table 1).All signals were assigned by spin decoupling in the usual way, starting with the H-7 signal although all signals were
“CHO
1 R=R’=H
2 R=H,R’=COCHpCsH40H(p) 3 R = R’= AC 4 R=Ac,R’=COCHzC6H40Ac(p)
Table 1. ‘H NMR spectral data of compounds 1 and 3 (400 MHz, TMS as internal standard)
1 (C,D,N)
3 (CDC&)
H-l H-2
6.67 br dd
6.81 br dd
H-2 H-3 H-3 H-4 H-6 H-7 H-8 H-9 H-9 H-13 H-13 H-14 H-15 H-15 H-l’ H-2 H-3 H-4’ H-5’ H-6; H-6; OH OAc
2.26 ddd 2.68 ddd 1.80br dd 5.15br d 4.98 dd 2.65 dddd 4.27 ddd 2.98 dd 2.44 br d 6.6Odd 6.33 dd 9.49 br s 4.77d 4.441
2.53 ddd
4.91 d 4.OOdd 4.20 m 3.95 m 4.54 dd 4.36 dd 6.06d -
2.54 m 2.6 1 ddd 2.03 m 5.15br d 4.57dd 2.45 dddd 3.90 dddd 2.70dd 2.37 br d 6.52dd 6.30dd 9.44 br s 4.4Od 4.33d 4.58d 5.04dd 5.22 dd 5.08 dd 3.73 dd 4.26dd 4.17dd 6.07 d 2.08 s 2.03 s 2.02 s 1.98s
J (Hz): 1,2 = 9; 1,2’ = 8; 1,9 _ 1; 5,6 = 6, 7 = 7, 8 = 14 7,13 = 3.5; 7, 13’ = 3; 8, OH = 11,5; 8,9 =5;8,9’=11;9,9’= 16;13,13’=2;15,15’=12; l’, 2’ = 8.5; 2, 3’= 3’, 4’ = 4;, 5’ = 9.5; 5’, 6; = 2.5; 5’, 6; = 5; 6;, 6; = 12.