1H And 13C-Nmr Spectral Data Of Compound Sxh6 And Reference Substance

COSY and HMBC. The HMBC spectrum shows interactions between H-2 ( δ H 2.66) with C-3 ( δ C 217.3), H-29 ( δ H 1.23) with C-3 ( δ C 217.3) allowing us to confirm the position of the carbonyl group and two methyl groups, in addition to interactions between H-12 ( δ H 5.12) with C-14 ( δ C 47.7), H-24 ( δ H 6.08) with C-26 ( δ C 172.6), H-27 ( δ H 1.92) with C-26 ( δ C 172.6). More

In addition, the olefinic proton shift at δ H 6.08 (1H, td, 1.2; 7.3 Hz) and the high-field shifts of the singlet methyl group at δ H 1.93 and δ C 20.6 give a prediction of the E configuration of the double bond and the remaining carbonyl group between C-24 and C-25 based on reference data [186], [ 206]. The COSY spectrum of compound 3 indicates the main interactions between H-23 ( δ H 1.90) with H-24 ( δ H 6.08), H-12 ( δ H 5.29) with H-11 ( δ H 2.1). From the

The above analysis together with reference to literature [206] allows to conclude that the structure of compound SXH4 is 3-oxolanosta-11,24-dien-26-oic acid (heilaohuacid F) or coccinic acid ( Figure 3.11 ).

Table 3.4. 1 H and 13 C NMR spectral data of compound SXH4

C/H position

a,b δ C (ppm)	a* δ C (ppm) [206]	ac δ H (ppm, Hz)
1	36.8	36.7	2.11 (1H, m); 1.82 (1H, td, 5.4; 13.2)
2	34.9	34.8	2.74 (1H, dddd, 6.32; 13.4; 15.4) 2.38 (1H, dq, 3.16; 5.32; 15.4)
3	217.3	217.3
4	47.7	47.7
5	53.4	53.4	1.36 (1H, m)
6	27.7	25.9	1.35 (2H, m)
7	22.6	22.6	1.69 (1H, m); 1.41 (1H, m)
8	41.9	41.9	2.22 (1H, m)
9	147.1	147.1
10	39.1	39.1
11	116.3	116.2	5.28 (1H, d, 6.0)
12	37.2	37.2	2.08 (1H, m); 1.9 (1H, m)
13	44.3	44.4
14	47.0	47.0
15	33.9	33.9	1.34 (2H, m)
16	28.0	28.0	1.94 (1H, m); 1.58 (1H, m)
17	50.9	50.9	1.64 (1H, m)
18	21.8	21.8	0.68 (3H, s)
19	14.4	14.4	1.22 (3H, s)
20	36.1	36.0	1.42 (1H, m)
21	18.2	18.2	0.89 (3H, d, 6.4)
22	35.9	34.9	1.55 (1H, m); 1.15 (1H, m)

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26.9	25.9	2.56 (1H, m); 2.46 (1H, m)
24	147.1	145.7	6.08 (1H, td, 1.2; 7.3)
25	125.8	126.6
26	172.6	172.6
27	20.6	20.5	1.93 (3H, s)
28	22.1	22.1	1.07 (3H, s)
29	25.6	25.6	1.07 (3H, s)
30	18.4	18.4	0.74 (3H, s)
a CDCl 3 , b 150MHz, c 600 MHz, a* CDCl 3 , 150 MHz

Figure 3.11. Chemical structure of compound SXH4

*SXH6 compound

Compound SXH6 was obtained and recrystallized in the solvent system dichloromethane/acetone (20:1, v/v) as colorless needle-shaped crystals, which turned orange-yellow with 10% H 2 SO 4 reagent . No UV appeared at 254 nm. ESI-MS spectrum showed the appearance of a pseudomolecular ion peak m/z 457.0 [M + H] + , combined with 13 C-NMR spectrum, we saw the appearance of 30 carbon signals, showing that SXH6 is consistent with the molecular formula C 30 H 48 O 3 (M = 456.4).

s ) ; 1.03 ( 3H, s ) and 1.69 ( 3H , s ) giving us a hypothesis of a lupan - triterpenoid compound of compound SXH6 . Combined with the 13 C-NMR spectrum ( Table 3.5 ) and DEPT, it shows the presence of 30 C with two characteristic signals of carbonyl carbon at δ C 179.3, an olefinic group at δ C 109.7, a methine carbon at δ C 79.0 along with 6 signals of methyl carbon at δ C 28.0; 16.1; 16.2; 15.4; 14.7 and 19.4. In addition, the spectrum also shows

showed the presence of 10 methylene groups, 5 methine groups and 5 carbons not bonded to hydrogen. Two sp 2 hybridized carbons at δ C 150.4; 109.7 characterize the presence of a lupan triterpene. From the above analysis together with comparison with published documents [151], it is possible to confirm that compound SXH6 is 3 β -hydroxy- lup-20(29)-en-28-oic acid or betulinic acid ( Figure 3.12 ).

Table 3.5. 1 H and 13 C-NMR spectral data of compound SXH6 and reference substance

C/H position

a,b δ C (ppm)	a* δ C (ppm) [151]	a,b δ H (ppm, Hz)
1	38.7	39.3
2	27.4	28.2
3	79.0	78.1	3.19 (1H, solution; 4.8; 12.0)
4	38.9	39.5
5	55.4	55.3	0.68 (1H, d; 9.6)
6	18.3	18.8	1.48-1.50 (2H, m)
7	34.4	34.9	1.42 (1H, m); 1.46 (1H, m)
8	40.7	41.1
9	50.4	50.9	1.26 (1H, m)
10	37.3	37.5
11	20.9	21.7	1.47 (2H, m)
12	25.6	26.1	1.08 (1H, m); 1.60 (1H, m)
13	38.4	38.6	1.95 (1H, m)
14	42.5	42.9
15	29.7	30.3	1.17 (1H, m); 1.54 (1H, m)
16	32.2	32.9	1.38 (2H, m)
17	56.3	56.6
18	49.3	49.8	1.56 (1H, m)
19	46.9	47.8	3.00 (1H, ddd, 7.2; 12.6)
20	150.4	151.3
21	30.6	31.2	1.4 (2H, m)
22	37.0	37.6	1.39 (2H, m)
23	28.0	28.7	0.98 (3H, s)
24	16.1	16.3	0.97 (3H, s)
25	16.2	16.4	0.82 (3H, s)
26	15.4	16.4	0.75 (3H, s)
27	14.7	14.9	1.03 (3H, s)
28	179.3	178.8
29	109.7	109.9	4.74 (2H, d; 1.8)
30	19.4	19.5	1.69 (3H, s)
a CDCl 3 , b 125 MHz, c 600 MHz, a* CDCl 3 , 125 MHz

Figure 3.12. Chemical structure of compound SXH6

* Compound SXH7

Compound SXH7 is a white solid with a melting point of 284-286 o C. The 1 H- NMR spectrum ( Table 3.6 ) has resonance signals of 6 methyl groups, including 2 singlet signals at  H 0.70 (3H, s) and 1.08 ppm (3H, s), 3 doublet signals at  H 0.96 (3H, d, J = 6.5 Hz), δ H 0.85 (3H, d, J = 7.5 Hz), δ H 0.92 (3H, d, J = 7.5 Hz), and a triplet signal at  H 0.84 ppm (3H, t, J = 7.5 Hz). And a characteristic resonance signal of an alkene proton at  H 5.4 (1H, brs). The appearance of anomeric protons at δ H 4.40 (1H, d, J = 7.6 Hz) indicates the presence of a β sugar , in addition the appearance of oxymethin protons characteristic of a sugar molecule appears from  H 3.23-3.65.

13 C-NMR spectrum ( Table 3.6 ) and DEPT of SXH7 showed resonance signals of 7 methine carbon groups, 11 methylene carbon groups, 6 methyl carbon groups and 2 quaternary carbon groups, including a double bond at  C 122.1 and 141.7. In particular, the oxymetine carbons of the sugar molecule at  C 75.8; 79.4; 73.6; 77.3; 61.9 and the anomeric carbon at  C 101.2 allowed us to conclude the presence of β- glucose in the molecule, in addition to another oxymetine group at  C 77.5. The similarity of the spectral data of the aglycon part of SXH7 with the coincidence of Rf with the daucosterol standard. From the above results compared with published spectral data [216], the SXH7 compound was identified as: sitosterol-3- O - β -glucopyranosid or daucosterol ( Figure 3.13 ).

Table 3.6. 1 H and 13 C-NMR spectral data of compound SXH7 and reference substance

C/H position

a,b δ C (ppm)	a* δ C (ppm) [216]	b,c δ H (ppm, Hz)	b* δ H (ppm, Hz) [ 216]
1	36.8	38.0	1.12 (1H, m);1.92 (1H, m)	1.12 (1H, m);1.91 (1H, m)
2	29.3	30.2	1.62 (1H, m) 1.90 (1H, m)	1.63 (1H, m) 1.93 (1H, m)
3	77.5	79.6	3.58 (1H, m)	3.59 (1H, m)
4	38.8	39.3	2.28 (1H, m);2.41 (1H, m)	2.29 (1H, m);2.45 (1H, m)
5	141.3	141.7
6	122.0	122.1	5.40 (1H, brs)	5.39 (1H, brd; 4.5)
7	32.0	32.4	1.56 (1H, m);2.00 (1H, m)	1.56 (1H, m);2.00 (1H, m)
8	29.7	32.7	1.49 (1H, m)	1.49 (1H, m)
9	50.3	51.2	0.97 (1H, m)	0.98 (1H, m)
10	36.3	37.4
11	21.1	21.8	1.56 (2H, m)	1.56 (2H, m)
12	39.9	40.5	1.20 (1H, m) 2.03 (1H, m)	1.21 (1H, m) 2.07 (1H, m)
13	42.4	41.1
14	56.9	57.7	1.05 (1H, m)	1.05 (1H, m)
15	24.4	24.6	1.14 (1H, m) 1.62 (1H, m)	1.14 (1H, m) 1.63 (1H, m)
16	26.2	28.9	1.89 (2H, m)	1.88 (2H, m)
17	56.2	56.8	1.16 (1H, m)	1.16 (1H, m)
18	12.1	11.8	0.70 (3H, s)	0.74 (3H, s)
19	19.4	19.3	1.08 (3H, s)	1.07 (3H, s)
20	34.1	36.8	1.36 (1H, m)	1.39 (1H, m)
21	19.1	18.9	0.96 (3H, d; 6.5)	0.97 (3H, d; 6.5)
22	32.1	34.6	1.36 (2H, m)	1.39 (2H, m)
23	23.0	26.8	1.23 (2H, m)	1.23 (2H, m)
24	46.0	46.8	0.99 (1H, m)	0.98 (1H, m)
25	29.3	29.9	1.69 (1H, m)	1.72 (1H, m)
26	18.8	18.9	0.85 (3H, d; 7.5)	0.86 (3H, d; 6.7)
27	18.9	19.9	0.92 (3H, d; 7.5)	0.89 (3H, d; 6.7)
28	19.7	23.7	1.32 (2H, m)	1.32 (2H, m)
29	12.0	11.8	0.84 (3H, d; 2.0)	0.88 (3H, d; 7.4)
1'	101.2	102.1	4.40 (1H, d; 7.6)	4.39 (1H, d; 7.6)
2'	75.8	74.9	3.23 (1H, m)	3.17 (1H, m)
3'	79.4	77.7	3.26 (1H, m)	3.27 (1H, m)
4'	73.6	71.5	3.29 (1H, m)	3, 29 (1H, m)
5'	77.3	77.7	3.37 (1H, m)	3.37 (1H, m)
6'	61.9	62.1	3.60 (1H, m) 3.82 (1H, m)	3.67 (1H, solution; 11.0; 4.4) 3.85(1H, dd; 11.0; 3.3)
a CDCl 3 , b 125MHz, c 500 MHz, a* CDCl 3 , 125 MHz, b* CDCl 3 , 500 MHz

Figure 3.13. Chemical structure of compound SXH7

3.2.2.2. Substances isolated from ethyl acetate extract

*SXE8 compound

Compound SXE8 was obtained as a white powder. It showed an orange-yellow color on Dragendorff's reagent. The optical rotation [α] D 25 = + 55.8 (c = 0.50, MeOH).

The 1 H-NMR spectrum ( Table 3.7 ) of compound SXE8 showed characteristic signals of an olefinic proton at δ H 5.70 (1H, d, J = 5.2 Hz), a secondary methyl group at δ H 1.05 (3H, d, J = 7.0 Hz), a methine signal at δ H 2.72 (1H, d, J = 7.5 Hz). The signals at δ H 3.13 - 2.97 (m, 4H); 2.32 - 2.23 (m, 2H); 2.17 - 2.08 (m, 3H); 1.80 -1.33 (m, 3H);

1.27 - 1.20 (m, 2H); 1.86 - 1.75 (m, 2H) and 1.86 - 1.55 (m, 2H) represent the signals of methine and methylene groups.

Analysis of the 13 C-NMR spectrum ( Table 3.7 ) and DEPT spectrum of compound SXE8 showed the appearance of 16 carbon signals including 1 CH 3 group at δ C 21.1; 8 CH 2 groups , 5 CH groups and two carbon groups not bonded to hydrogen. In addition, the appearance of a carbonyl group at δ C 218.0 (C=O) and two olefinic carbons at δ C 145.0 and 127.1. Together with two carbon groups attached to the heteroatom shifted to low field at δ C 60.3 and δ C 56.2.

From the above data together with the appearance of orange-yellow color on Dragendoff reagent, it is possible to predict the appearance of a derivative containing heteronitrogen in the molecule. Combined with the reference documents [89], it can be confirmed that the structure of compound SXE8 is (+)-fawcettidine ( Figure 3.14 ).

Table 3.7. 1 H and 13 C-NMR spectral data of compound SXE8 and reference substance

C/H position

a,b δ C (ppm)	a* δ C (ppm) [89]	a,c δ H (ppm, Hz)	b* δ H (ppm, Hz) [ 89]
1	60.3	60.3	3.13 (1H, m) 3.04 (1H, m)	3.14 (2H, m)
2	29.1	29.1	1.35 (1H, m) 1.75 (1H, m)	1.34 (2H, m)
3	31.0	31.2	1.75 (1H, m) 2.27 (1H, m)	2.24 (2H, m)
4	56.2	56.2	2.32 (1H, m)	2.34 (1H, m)
5	218.0	218.8
6	44.1	44.0	1.89 (1H, m) 2.05 (1H, m)	1.91-1.83 (2H, m)
7	37.0	37.3	1.94-1.98 (1H, m)	1.99-1.93 (1H, m)
8	34.1	34.1	1.23-1.26 (2H, m)	1.18-1.21 (2H, m)
9	51.9	51.9	3.10 (1H, m) 2.97 (1H, m)	2.98 (2H, m)
10	24.0	23.7	1.60 (1H, m) 2.00 (1H, m)	1.79 (2H, m)
11	39.1	39.1	1.61 (1H, m) 2.10 (1H, m)	1.59 (2H, m)
12	46.1	46.1
13	145.0	145.7
14	127.1	127.3	5.70 (1H, d; 5.2)	5.71 (1H, d; 5.0)
15	27.7	27.7	2.74 (1H, solution; 16.8; 7.5)	2.72 (1H, solution; 7.5; 17)
16	21.1	20.8	1.05 (3H, d; 7.0)	1.04 (3H, d; 7.0)
a CDCl 3 , b 125MHz, c 500 MHz, a* CDCl 3 , 125 MHz, b* CDCl 3 , 500 MHz

Figure 3.14. Chemical structure of compound SXE8

* Compound SXE9

Compound SXE9 was obtained as a colorless amorphous solid. It showed an orange-yellow color on Dragendorff's reagent. The optical rotation [α] D = + 71.3 (c = 0.60, MeOH).

The HR-ESI-MS spectrum shows a pseudomolecular ion peak at m/z 306.2058 [M + H] + , so the molecular mass of SXE9 is M = 305.1991, based on the predicted mass in the structure containing the nitrogen heteroatom, from the above data combined with the 13 C -NMR spectrum, we can predict that the SXE9 compound is consistent with the molecular formula C18H27NO3 ( M = 305.1991). The 1 H-NMR spectrum ( Table 3.8 ) of the SXE9 compound shows the appearance of a methyl group signal at δ H 0.99 (3H, d, J = 6.5) and a singlet methyl signal at δ H 1.97 (3H, s) . 13 C-NMR spectrum ( Table 3.8 ) and HSQC spectrum show the presence of 2 CH 3 groups , 3 CH groups, 9 CH 2 groups , 2 carbons without hydrogen, in which one carbon signal is shifted to low field at δ C 94.7 and two carbonyl groups at δ C 216.4 and δ C 180.0. Based on the number of pi bonds in the molecule (n = 6), except for 2 double bonds in the C=O group, it can be assumed that the SXE9 molecule contains 4 rings. From the above spectral data, it can be predicted that the SXE9 compound is a derivative of fawcettimin [212], [119], [97] with the following structure ( Figure 3.15 ):

Figure 3.15. Preliminary structure prediction of compound SXE9

In addition, the HMBC spectrum shows interactions between the proton of the methyl group at H-16 ( δ H 0.99) with C-15 ( δ C 23.6), demonstrating that the methyl group is attached to the C-15 position, the methyl group at H-17 ( δ H 1.97) interacts with the carbonyl at C-17 ( δ C 180.0) and the low-field shift of C-13 ( δ C 94.7) demonstrates that the acetoxy group is attached to the C-13 position of the fawcettimin framework. In addition, the HMBC interactions between H-1 ( δ H 3.44)/H-4 ( δ H 2.04)/H-14 ( δ H 1.86) with C-13 ( δ C 94.7) demonstrate the binding positions of the fawcettimin framework. In addition, the HMBC interaction of H-4 ( δ H 2.04)/H-

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