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Supporting Information
Preparative Separation of - and -Santalenes and (Z)-- and (Z)--Santalols using Silver Nitrate-Impregnated Silica Gel Medium Pressure Liquid Chromatography and Analysis of Sandalwood Oil
Pankaj P. Daramwar a, Prabhakar Lal Srivastava a, Balaraman Priyadarshinia, Hirekodathakallu V. Thulasiram a, b*
a Chemistry-Biology Unit, Division of Organic Chemistry, National Chemical Laboratory, Council of Scientific and Industrial Research (CSIR), Pune 411008, India
b Institute of Genomics and Integrative Biology, Council of Scientific and Industrial Research (CSIR), Mall Road, New Delhi-110007, India
* Corresponding author:
Dr. Thulasiram H. V. National Chemical Laboratory, Pune 411008, India Telephone +91 20 25902478 Fax +91 20 25902629 E mail: [email protected]
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Contents Page no.
Fig S1: 1H NMR spectrum of 1 in CDCl3 at 500 MHz. 4
Fig S2: 13C NMR spectrum of 1 in CDCl3 at 125 MHz. 5
Fig S3: DEPT NMR spectrum of 1 in CDCl3 at 125 MHz. 6
Fig S4: 1H NMR spectrum of 2 & 3 in CDCl3 at 500 MHz. 7
Fig S5: 13C NMR spectrum of 2 & 3in CDCl3 at 125 MHz. 8
Fig S6: DEPT NMR spectrum of 2 & 3 in CDCl3 at 125 MHz. 9
Fig S7: 1H NMR spectrum of 4 in CDCl3 at 200 MHz. 10
Fig S8: 13C NMR spectrum of 4 in CDCl3 at 50 MHz. 11
Fig S9: DEPT NMR spectrum of 4 in CDCl3 at 50 MHz. 12
Fig S10: 1H NMR spectrum of 5 in CDCl3 at 500 MHz. 13
Fig S11: 13C NMR spectrum of 5 in CDCl3 at 125 MHz. 14
Fig S12: DEPT NMR spectrum of 5 in CDCl3 at 125 MHz. 15
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Fig S13: 1H NMR spectrum of 6 & 7 in CDCl3 at 500 MHz. 16
Fig S14: 13C NMR spectrum of 6 & 7 in CDCl3 at 125 MHz. 17
Fig S15: DEPT NMR spectrum of 6 & 7 in CDCl3 at 125 MHz. 18
Fig S16: 1H NMR spectrum of 11 in CDCl3 at 200 MHz. 19
Fig S17: 13C NMR spectrum of 11 in CDCl3 at 50 MHz. 20
Fig S18: DEPT NMR spectrum of 11 in CDCl3 at 50 MHz. 21
Fig S19: Standard graphs for purified components (1, 2 & 3, 4, 5, 6 & 7, 8, 9, 11). 22 &23
Fig S20: Co-injection of purified components (1, 2 & 3, 4, 5, 6 & 7, 8, 9, 11) with Sandalwood oil 24 & 25
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4
10 9 8 7 6 5 4 3 2 1 0
4.18 3.222.052.001.00
TMS
Chloroform-d
0.00
0.82
0.99
1.05
1.25
1.26
1.54
1.57
1.59
1.79
1.96
1.97
1.97
2.00
4.14
5.30
5.31
5.33
7.26
Fig S1: 1H NMR spectrum of 1 in CDCl3 at 500 MHz.
OH 1
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5
200 150 100 50 0
TMS
Chloroform-d
0.00
10.6
517
.5119
.45
22.9
027
.36
31.0
031
.49
34.9
838
.12
45.8
4
61.5
8
77.0
2
129.
5313
3.64
Fig S2: 13C NMR spectrum of 1 in CDCl3 at 125 MHz.
OH 1
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200 150 100 50 0
10.66
17.5321.28
22.9
231
.02
31.5
134
.99
38.12
61.5
9
129.55
Fig S3: DEPT NMR spectrum of 1 in CDCl3 at 125 MHz.
OH 1
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7
10 9 8 7 6 5 4 3 2 1 0
4.213.612.08 1.561.00 0.990.99
TMSChloroform-d
0.00
1.04
1.221.
271.
401.
431.
661.
671.
782.
012.
09
2.67
4.144.45
4.73
5.27
5.29
5.31
7.27
Fig S4: 1H NMR spectrum of 2 & 3 in CDCl3 at 500 MHz.
OH OH 2 3
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200 150 100 50 0
Chloroform-d
21.2
222.5
923
.17
23.6
529
.64
37.0
541
.48
44.5
946
.75
61.5
9
76.6
977
.00
77.3
2
99.6
8
129.
0113
3.90
166.
15
Fig S5: 13C NMR spectrum of 2 & 3in CDCl3 at 125 MHz.
OH OH 2 3
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9
200 150 100 50 0
21.2222.60
23.1
823
.66
29.6
4
37.0
541
.49
44.5946.75
61.5
9
99.6
9
129.01
Fig S6: DEPT NMR spectrum of 2 & 3 in CDCl3 at 125 MHz.
OH OH 2 3
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10 9 8 7 6 5 4 3 2 1 0
7.31 6.20 2.931.88 1.231.00
Chloroform-d
0.00
0.83
1.161.
20
1.63
1.65
1.66
1.82
2.00
2.16
2.17
2.19
2.232.
332.
36
4.17
5.205.
215.22
5.37
5.41
7.27
Fig S7: 1H NMR spectrum of 4 in CDCl3 at 200 MHz.
OH 4
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11
200 150 100 50 0
Chloroform-d
17.3
321
.14
22.8
923
.26
31.0
631
.4438
.87
41.0
345
.22
61.2
4
77.0
0
116.
39
128.
9313
3.83
144.
21
Fig S8: 13C NMR spectrum of 4 in CDCl3 at 50 MHz.
OH 4
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12
200 150 100 50 0
17.3421.1622.91
23.2
731
.0831
.45
38.81
38.8
9
45.22
61.2
5
116.40
128.94
Fig S9: DEPT NMR spectrum of 4 in CDCl3 at 50 MHz.
OH 4
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10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0
5.233.771.00
Chloroform-d
0.01
0.84
1.00
1.05
1.08
1.16
1.58
1.62
1.69
1.89
1.90
1.92
1.94
1.955.
115.
115.12
5.135.14
7.27
Fig S10: 1H NMR spectrum of 5 in CDCl3 at 500 MHz.
5
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14
200 150 100 50 0
Chloroform-d
130.
8012
5.46
77.0
0
45.8
138
.13
34.5
331
.50
30.9
827
.39
23.2
419
.50
17.5
0
10.6
7
Fig S11: 13C NMR spectrum of 5 in CDCl3 at 125 MHz.
5
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15
200 150 100 50 0
125.
47
38.1
3
34.54 31.5230.98
25.7
3
23.25
19.5
0 17.5
2
10.6
8
Fig S12: DEPT NMR spectrum of 5 in CDCl3 at 125 MHz.
5
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16
10 9 8 7 6 5 4 3 2 1 0
9.73 3.141.021.00 0.97
Chloroform-d 0.00
1.01
1.04
1.22
1.38
1.56
1.611.
671.
681.
962.
012.
022.
122.
132.
66
4.46
4.72
5.095.09
5.12
5.14
5.14
7.26
Fig S13: 1H NMR spectrum of 6 & 7 in CDCl3 at 500 MHz.
6 7
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17
200 150 100 50 0
Chloroform-d
166.
93 166.
52
131.
08
125.
01
99.4
499
.15
77.0
0
46.7
845
.16
41.1
737
.07
29.6
925
.69
23.6
923
.57
22.6
117
.56
Fig S14: 13C NMR spectrum of 6 & 7 in CDCl3 at 125 MHz.
6 7
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200 150 100 50 0
125.00
99.4
599
.15
46.78
44.51
41.1
737
.08
29.6
929
.10
25.70
23.7
023
.57
22.6217.57
Fig S15: DEPT NMR spectrum of 6 & 7 in CDCl3 at 125 MHz.
6 7
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19
10 9 8 7 6 5 4 3 2 1 0
6.97 6.20 2.931.88 1.231.00
Chloroform-d
0.00
0.83
1.161.
201.
261.
281.
631.
651.
66
1.82
2.00
2.032.
162.
172.
192.33
4.17
5.205.215.22
5.22
5.37
5.41
7.27
Fig S16: 1H NMR spectrum of 11 in CDCl3 at 200 MHz.
HO
11
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200 150 100 50 0
Chloroform-d
21.2
623
.42
26.3
428
.2730
.70
31.3
634.9
839
.75
61.5
8
77.0
0
107.
50
120.
66
128.
13
133.
7813
4.50
153.
88
Fig S17: 13C NMR spectrum of 11 in CDCl3 at 50 MHz.
HO
11
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21
200 150 100 50 0
21.2723.43
26.3
328
.2630.7
0
34.9
8
39.75
61.5
8107.
49
120.66
128.13
Fig S18: DEPT NMR spectrum of 11 in CDCl3 at 50 MHz.
HO
11
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Fig S19: Graphs from quantification studies of components of sandalwood oil:
(Z)--Santalol (1): B) (Z)-(�+ epi-)-Santalol (2 & 3): C) (Z)--trans-Bergamotol (4): D) -Santalene (5):
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E) (�+ epi-)-Santalene (6 & 7): F) (-)--Bisabolol (8):
G) (E), (E)-Farnesol (9): H) (Z)-Lanceol (11):
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Fig. S20: Co-injection of purified components with Sandalwood oil:
A) Sandalwood oil B) Co-injection of (Z)--Santalol (1) with Sandalwood oil
C) Co-injection of (Z)-(+ epi-)-Santalol (2&3) D) Co-injection of (Z)--trans-Bergamotol (4) with Sandalwood oil with Sandalwood oil
E) Co-injection of (-)--Bisabolol (8) with Sandalwood oil F) Co-injection of (E), (E)-Farnesol (9) with Sandalwood oil
45 50 55 60 65 70
9
45 50 55 60 65 70
8
45 50 55 60 65 70
4
45 50 55 60 65 70
1
45 50 55 60 65 70
3&2
45 47 49 51 53 55 57 59 61 63 65 67 69
1
2
3 4
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G) Co-injection of (Z)-Lanceol (11) with Sandalwood oil H) Santalenes mixture
H) Co-injection of -Santalene (5) with J) Co-injection of (+ epi-)-Santalene (6&7) with Sandalwood oil Sandalwood oil.
25 30 35 40 45 50
5
25 30 35 40 45 50
7&6
25 30 35 40 45 50
56
7
12
45 50 55 60 65 70
11
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