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

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. 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 2.52.33 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	25. 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

) [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]20D = -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.