(-)-b-D-18–Glucopiranosyl-9,15-dihydroxy Kaurenoate, a New Diterpene Glycoside from Ageratina vacciniaefolia

Pontificia Universidad Javeriana, Grupo de Investigación Fitoquímica GIFUJ, Santafé de Bogotá, Colombia.
Tel 2887740, fax 2850503, E-mail [email protected]

Received: 26 October 1998 / Published: 16 April 1999

From leaves and flowers of Ageratina vacciniaefolia we have isolated several compounds: a flavonoid, a diterpene and a new compound identified as (-)-b-D-18–glucopiranosyl-9,15-dihydroxy kaurenoate (see the formula). The structure was established by using ¹HNMR, ¹³CNMR, COSY, NOESY and HMBC spectroscopic techniques (See Table 1) [1,7].

The ethanolic extract of leaves and flowers of A. vacciniaefolia yielded white crystals after column chromatography eluted with CH₂Cl₂, EtOAc and mixtures of these solvents.

M.p. 218-220°C.

[a]²⁰_D = -100 (MeOH).

DCI-MS [isobutane] m/z: (M*+H)⁺ 497; 479 (M-18); 377; 337; 335; 317; 299; 271; 230; 187; 163; 145 (100%); 127.

¹HNMR (400 MHz, C₅D₅N): d 1.15 (dt, 1H, CH₂, J=4.3; 12.3); 1.33 (s, 3H, CH₃); 1.53 (s, 3H, CH3); 1.55 -1.70 (m, 2H, CH₂); 1.58 - 1.60 (m, 1H, CH₂); 1.66 (m, 1H, CH₂); 1.87 (ddd, 1H, CH₂; J=12.0; 3.8); 2.17 - 2.18 (m, 2H, CH₂); 2.25 (m, 1H, CH); 2.28 (m, 1H, CH₂); 2.30 (dq, 1H, CH₂; J=3.2; 12.4); 2.33 (m, 1H, CH₂); 2.44 (m, 1H, CH₂); 2.50 (dd, 1H, CH₂; J=12.0; 13.0); 2.75 (bs, 1H, CH); 4.06 (ddd, 1H, CH; J=2.4; 4.3; 9.5); 4.24 (bt, 1H, CH; J=7.8); 4.28 (t, 1H, CH; J=8.0); 4.35 (t, 1H, CH; J=8.9); 4.40 (dd, 1H, CH₂; J=4.3; 11.9); 4.46 (dd, 1H, CH₂; J=2.4; 11.9); 5.31 (bs, 1H, CH); 5.20/5.46 (bs, 2H, CH₂); 6.33 (d, 1H, CH; J=7.8, anomeric proton).

¹³C NMR (100 MHz; C₅D₅N): d 18.6 (-CH₃, C20); 20.3 (-CH₂, C1); 22.5 (-CH₂, C6); 29.4 (-CH₃, C18); 30.0 (-CH₂, C11); 31.7 (-CH₂, C7); 33.3 (CH₂, C1); 34.9 (-CH₂, C12); 37.7 (-CH₂, C14); 39.0 (-CH₂, C3); 42.4 (-CH, C13); 45.0 (-C-, C4); 45.7 (-C-, C10); 51.4 (-CH, C5); 54.3 (-C-, C8); 62.7 (-CH₂-O-, C6'); 71.6 (-CH, C4'); 74.6 (-CH, C2'); 77.4 (-C-OH, C9); 78.0 (-CH-OH, C15); 79.7 (-CH, C3'); 79.9 (-CH, C5'); 96.3 (-CH, C1'); 107.9 (=CH₂, C17); 162.3 (=C, C16); 178.0 (-COO, C19). For details, see table 1.

Table 1. Direct and long range NMR correlations and their assignments [2-6].
 

No. C	Type of C	d-ppm	C-H (JHz)	HMBC
19	COO-	178.0		6.33 2.25 1.33
16	C =	162.3		5.46 5.20 2.50 1.87
17	CH2=	107.9	5.46, 5.20 s,b
	CH - 1’	96.3	6.33 d (7.8)	4.24
	CH - 5’	79.9	4.06 ddd (2.4, 4.3, 9.5)	4.35
	CH - 3’	79.7	4.28 t (8.0)	4.35
15	CH	78.0	5.31 s,b	5.46 5.20 2.5
9	C - O	77.4		5.31 5.22 2.17 1.87, 1.6 1.53
	CH - 2’	74.6	4.24 bt (7.8)	4.28
	CH - 4’	71.6	4.35 t (8.9)	4.18 4.28
	CH2-O-6’	62.7	4.46 dd (2.4 ;11.9)	4.35
			4.40 dd (4.3 ;11.9)
8	C	54.3		5.22(OH), 2.75 2.5 2.33 2.17 1.87
5	CH	51.4	2.25 m.	2.66, 2.44, 2.17 1.66, 153, 1.33
10	C	45.7		2.25 4.66 1.53
4	C	45.0		2.44 2.25 1.33 1.15
13	CH	42.4	2.75 s.b	5.46 5.20 2.17 1.87
3	CH2	39.0	2.44 m	2.25, 1.66, 1.33
			1.15 dt (4.3 ; 12.3)
14	CH2	37.7	2.50 dd (12, 13)	531 2.17
			1.87 ddd (12, 3.8)
12	CH2	34.9	1.55 - 1.7 m (2H)	2.5 2.17
1	CH2	33.3	2.33 m	2.44 1.53
			1.66 m
7	CH2	31.7	2.18 d	2.66 2.25 1.87
11	CH2	30.0	2.17 m	5.22 (OH) 1.78
18	CH3	29.4	1.33 s	2.25 1.15
6	CH2	22.5	2.30 dq ( 3.2 ; 12.4)	2.25 2.17
			2.28 m
1	CH2	20.3	2.33 m 1.60 m	1.15 2.3
			1.58 m
20	CH3	18.6	1.53 s	2.17

References

1. Hasan, C. M., Healey, T. M. and Waterman P. T. Phytochemistry1982, 21, 1365.
2. Demetzos, C.; Harvala, C.; Phillianos, S.; Manol Skaltsounis, A. J. Nat. Prod. 1991, 53, 1365.
3. Torrenegra, R.; Pedrozo, J.; Robles, J.; Waibel, R.; Achenbach, H. Phytochemistry 1992, 31, 2415.
4. Konzi, S. A.; McChesney, J. D. J. Nat. Prod. 1991, 54, 483.
5. Aranda, G.; El Kortbi, M.S.; Lallemand, J. Y. Tetrahedron 1991, 47, 8339.
6. Konig, W.A.; Lutz, S.; Wenz, G. Angew. Chem. 1988, 100 , 989.
7. Breitmaier Eberhard, Structure Elucidation by NMR in Organic Chemistry, John Wiley & Sons, New York (1993).

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