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A terpene-coumarin derivative from Ethulia conyzoides
Phyrochemisrry, 1981,
Vol.20, p. 177. mc Pergamon Press Ltd. Printed in England.
A TERPENE-COUMARIN FERDINAND *Institute
of Organic
BOHLMANN,*
DERIVATIVE SHAFIK
conq’soidrs;
Compositae;
data for 1 (270MHz, internal standard)
CDCI,,
Protons
6
J (Hz)
6-H 7-H 8-H 9-H
7.17 d (hr) 7.37 dd 7.04 d (hr) 2.76 s 5.25 d 5.30 d 6.23 dd
6,1=
new terpene-coumarin
2.57 d
4;,4; = 15
TMS
as
8
7,8 = 8 l’t, 2’ = 17.5 l’c, 2’ = 10.5
derivative.
lactone 2 previously obtained after similar treatment [l, 21.
from two of the isomers
EXPERIMENTAL The reported extraction and purification procedure [l] was repeated on another batch of plant material, 250g. The ether extract was subjected to column chromatographic analysis using SiO, and ether-petrol (= E-P) in increasing order to successively elute the isomeric compounds [l] and lastly with E-P, 1 :l, to get 1. The latter was further purified by preparative TLC on SiO, to yield 56mg, colourless crystals, mp. 128%129”, IR v”,‘,‘;crn-‘: 3450 (OH), 1695, 1600 (coumarin); MS (70eV, direct inlet): M’ m/r 360.157 (2”“) (C 20H 240 6,)’ 342 (3) (M-H,O); 327 (2) (342-‘Me); 302 (4) (MmMe,CO); 271 (25) (M-HOeHC(OH)Me,); 229 (65) (271-C,H,O):
m 1 ;
ohH
135 (100).
To 5mg 1 in 0.5ml MeOH 1Omg NalO, in 0.1 ml H,O was added. After 30min the reaction product was extracted with ether and the residue was crystallized from E-P as coloutless crystals, mp. 148” (3 mg), identical with an authentic sample (mp, ‘H NMR).
2.26 d 3.42 s 1.44 s 1.42 s 1.62 s
REFERENCES 1. Balbaa, S., Halim, A.. Halaweish,
a:
1 - L
F. and Bohlmann,
F. (1979)
F. and Zdero, C. (1977) Photochemistry
16, 1092.
Phyrochemistry18, 912.
2. Bohlmann,
PHYTO
and FATHI HALAWElsHt
5 Ma); 1980)
We have very recently characterized four isomeric terpene-coumarin derivatives with the formula C,,H,,0, from the aerial parts of Ethulia conyzoides L. [ 11. This report deals with the isolation and structural elucidation of another major compound, C,,H,,O,, representing a hydrated derivative of the above isomers. Its ‘H NMR (see Table 1) and MS data clearly establish structure 1. The stereochemistry at C-5’ and C-6’, however, has not been determined. The proposed structure was also confirmed through treatment with periodate to afford the
l’t-H l’c-H 2’-H 4;-H 4;-H 6’-H 8’-H 9’-H lO’-H
HAL~M?
Chemistry, Technical University Berlin, Strasse des 17. Juni 135, D-1000 Berlin 12, W. Germany: tFaculty of Pharmacy, Mansoura University, Mansoura, Egypt
Key Word Index--Erhu/iu
1. ‘H NMR
FROM ETH ULIA CONYZOIDES
BALE(AA,? AHMED
(Receicrd
Table
0031-9422,‘81/‘0101-0177 $02.OOiO
Vol.20, p. 177. mc Pergamon Press Ltd. Printed in England.
A TERPENE-COUMARIN FERDINAND *Institute
of Organic
BOHLMANN,*
DERIVATIVE SHAFIK
conq’soidrs;
Compositae;
data for 1 (270MHz, internal standard)
CDCI,,
Protons
6
J (Hz)
6-H 7-H 8-H 9-H
7.17 d (hr) 7.37 dd 7.04 d (hr) 2.76 s 5.25 d 5.30 d 6.23 dd
6,1=
new terpene-coumarin
2.57 d
4;,4; = 15
TMS
as
8
7,8 = 8 l’t, 2’ = 17.5 l’c, 2’ = 10.5
derivative.
lactone 2 previously obtained after similar treatment [l, 21.
from two of the isomers
EXPERIMENTAL The reported extraction and purification procedure [l] was repeated on another batch of plant material, 250g. The ether extract was subjected to column chromatographic analysis using SiO, and ether-petrol (= E-P) in increasing order to successively elute the isomeric compounds [l] and lastly with E-P, 1 :l, to get 1. The latter was further purified by preparative TLC on SiO, to yield 56mg, colourless crystals, mp. 128%129”, IR v”,‘,‘;crn-‘: 3450 (OH), 1695, 1600 (coumarin); MS (70eV, direct inlet): M’ m/r 360.157 (2”“) (C 20H 240 6,)’ 342 (3) (M-H,O); 327 (2) (342-‘Me); 302 (4) (MmMe,CO); 271 (25) (M-HOeHC(OH)Me,); 229 (65) (271-C,H,O):
m 1 ;
ohH
135 (100).
To 5mg 1 in 0.5ml MeOH 1Omg NalO, in 0.1 ml H,O was added. After 30min the reaction product was extracted with ether and the residue was crystallized from E-P as coloutless crystals, mp. 148” (3 mg), identical with an authentic sample (mp, ‘H NMR).
2.26 d 3.42 s 1.44 s 1.42 s 1.62 s
REFERENCES 1. Balbaa, S., Halim, A.. Halaweish,
a:
1 - L
F. and Bohlmann,
F. (1979)
F. and Zdero, C. (1977) Photochemistry
16, 1092.
Phyrochemistry18, 912.
2. Bohlmann,
PHYTO
and FATHI HALAWElsHt
5 Ma); 1980)
We have very recently characterized four isomeric terpene-coumarin derivatives with the formula C,,H,,0, from the aerial parts of Ethulia conyzoides L. [ 11. This report deals with the isolation and structural elucidation of another major compound, C,,H,,O,, representing a hydrated derivative of the above isomers. Its ‘H NMR (see Table 1) and MS data clearly establish structure 1. The stereochemistry at C-5’ and C-6’, however, has not been determined. The proposed structure was also confirmed through treatment with periodate to afford the
l’t-H l’c-H 2’-H 4;-H 4;-H 6’-H 8’-H 9’-H lO’-H
HAL~M?
Chemistry, Technical University Berlin, Strasse des 17. Juni 135, D-1000 Berlin 12, W. Germany: tFaculty of Pharmacy, Mansoura University, Mansoura, Egypt
Key Word Index--Erhu/iu
1. ‘H NMR
FROM ETH ULIA CONYZOIDES
BALE(AA,? AHMED
(Receicrd
Table
0031-9422,‘81/‘0101-0177 $02.OOiO