SUPPLEMENTARY MATERIAL
Polar compounds from Parentucellia viscosa (L.) Caruel from Sardinia.
Alessandro Venditti* ,a,b , Mauro Ballero c , Mauro Serafini b ,Armandodoriano Bianco a a) Dipartimento di Chimica, Sapienza Università di Roma, P.le A. Moro 5, 00185 Roma, Italy, b) Dipartimento di Biologia Ambientale, Sapienza Università di Roma, c) Consorzio Interuniversitario CoSMeSe, Dipartimento di Scienze Botaniche, Università di Cagliari
*E-mail: alessandro.venditti@uniroma1.it
* Corresponding author . Tel. +39 0649913229; fax: +39 0649913841; E-mail address : alessandro .venditti@uniroma1.it
(A. Venditti).
Abstract.
In this work we examined a sample of Parentucellia viscosa from Sardinia island, showing similarities and differences of the secondary metabolites content with respect to previous study conducted on an accession of continental origin, and also with Bellardia trixago , a species very close to Parentucellia . On this aspect, the proximity between these species, previously stated by a phylogenetic study, was confirmed by a phytochemical approach. Within the non iridoidic fraction a chiral polyol (mannitol) and two aromatic acids (benzoic acid and gallic acid) were evidenced.
These two acids are not common in Scropulariaceae since they have been reported only from few a species, and it is worth to note that gallic acid was never reported from the Orobanchaceae family.
Keywords.
Parentucellia viscosa (L.) Caruel, Iridoids, Gallic acid, Scrophulariaceae, Orobanchaceae.
3.4 – NMR data of isolated compounds.
Melampyroside (1) : 1
H NMR (300 MHz, CD
3
OD) δ 8.06 (2H, d J = 7.3 Hz, H2’’, H6’’), 7.54 (1H, t, J = 7.4 Hz, H4’’), 7.41 (2H, t, J = 7.6 Hz, H3’’, H5’’), 6.27 (1H, dd, J = 6.1, 1.8 Hz, H3), 5.78
(1H, s , H7), 5.08 – 5.00 (2H, m , H4, H10a), 4.93 (1H, d, J = 7.3 Hz, H10b), 4.63 (1H, d, J = 7.8 Hz,
H1’), 4.40 (1H, dd, J = 3.6, 1.7 Hz, H6), 2.93 (1H, t, J = 7.5 Hz, H9), 2.70 – 2.57 (1H, m , H5).

13 C NMR (75 MHz, CD
3
OD) δ 167.73 (ArCOO), 142.55 (C8), 141.72 (C3), 134.35 (C4’’), 132.83
(C7), 131.30 (C1’’), 130.59 (C2’’,C6’’), 129.62 (C3’’,C5’’), 105.53 (C4), 100.25 (C1’), 97.99 (C1),
82.86 (C6), 78.23 (C3’), 77.97 (C5’), 74.90 (C2’), 71.52 (C4’), 64.03 (C10), 62.80 (C6’), 46.29
(C5).
ESI-MS: m/z 473.27 [M+Na]
+
8-epiloganin (2) :
1
H NMR (400 MHz, D
2
O) δ 7.47 (1H, s , H3), 5.59 (1H, d, J = 3.0 Hz, H1), 4.82
(1H, d , J = 7.5 Hz, H1’), 3.76 (3H, s , -OC H
3
), 3.10 – 3.02 (1H, m , H5), 2.73 (1H , t, J = 8.9 Hz, H9),
2.22 (1H, dd, J = 13.7, 7.4 Hz, H8), 1.01 (3H, d , J = 7.4 Hz, H10).
13 C NMR (101 MHz, D
2
O) δ 169.87 (C11), 151.39 (C3), 113.07 (C4), 98.29 (C1’), 95.61 (C1),
78.19 (C7), 76.25 (C5’), 75.64 (C3’), 72.62 (C2’), 69.55 (C4’), 60.68 (C6’), 51.78 (O C H
3
), 42.63
(C8), 40.91 (C9), 38.69 (C6), 28.48 (C5), 13.07 (C10).
ESI-MS: m/z 413.25 [M+Na]
+
Gardoside methyl ester (3) : 1 H NMR (400 MHz, D
2
O) δ 7.50 (1H, s , H3), 5.52 (1H. d J = 4.0 Hz,
H1), 5.42 (1H, bs , H10), 4.84 (1H, overlapped with HDO, H1’), 3.95 (1H, d, J = 12.1 Hz, H6’a),
3.77 (3H, s , -OC H
3
), 3.59 (1H, d, J = 11.9 Hz, H6’b), 3.29 (1H, dd, J = 9.3, 8.1 Hz, H2’), 3.16 (2H, bs , H5; H9).
13
C NMR (101 MHz, D
2
O) δ 169.63 (C11), 152.54 (C3), 150.39 (C8), 112.86 (C4), 110.64 (C10),
98.49 (C1’), 96.04 (C1), 76.32 (C3’), 76.18 (C5’), 72.61 (C2’), 72.25 (C7), 69.51 (C4’), 62.49
(C6’), 51.83 (-O C H
3
), 43.33 (C9), 38.68 (C6), 29.93 (C5).
ESI-MS: m/z 411.25 [M+Na]
+
Shanzhiside methyl ester (4) :
1
H NMR (300 MHz, D
2
O) δ 7.44 (1H, s , H3), 5.61 (1H, bs, H1),
4.62 (1H, d, J = 8.0 Hz, H1’), 4.13 (1H, s , H6), 3.74 (3H, s , -OC H
3
), 3.00 (1H, bd, J = 11.6 Hz,
H5), 2.69 (1H, bd, J = 8.8 Hz, H9), 2.11 (1H, dd, J = 13.4, 7.0 Hz, H7a), 1.83 (1H, dd , J = 13.5, 6.4
Hz, H7b), 1.26 (3H, s , H10).
13
C NMR (75 MHz, D
2
O) δ 169.70 (C11), 151.95 (C3), 109.95 (C4), 98.36 (C1’), 93.98 (C1),
78.15 (C8), 76.41 (C6), 76.06 (C3’), 75.87 (C5’),74.25 (C2’), 71.59 (C4’), 60.86 (C6’), 52.04 (C7),
49.75 (C9), 46.81 (-O C H
3
), 38.98 (C5), 23.44 (C10).
ESI-MS: m/z 429.26 [M+Na]
+
Aucubin (5) :
1
H NMR (300 MHz, CD
3
OD) δ 6.27 (1H, dd, J = 6.1, 1.9 Hz, H3), 5.73 (1H, bs , H7),
5.05 (1H, dd, J = 6.1, 3.9 Hz, H4), 4.91 (1H, d, J = 7.1 Hz, H1), 4.64 (1H, d, J = 7.9 Hz, H1’), 4.40
(1H, m , H6), 4.30 (1H, d, J = 15.3 Hz, H10a), 4.13 (1H, d, J = 15.2 Hz, H10b), 2.86 (1h, t, J = 7.3
Hz, H9), 2.61 (1H, dddd, J = 7.5, 5.7, 3.9, 2.0 Hz, H5).
13
C NMR (75 MHz, CD
3
OD) δ 147.98 (C8), 141.52 (C3), 130.26 (C7), 105.75 (C4), 100.01 (C1),
97.82 (C1’), 82.84 (C6), 78.22 (C3’), 77.91 (C5’), 74.91 (C2’), 71.59 (C4’), 62.68(C6’), 61.38
(C10), 47.99 (C9), 46.21 (C5).
ESI-MS: m/z 369.22 [M+Na] + ; 715.48 [2M+Na] +
Mannitol (6) :
1
H NMR (400 MHz, D
2
O) δ 3.88 (2H, dd, J = 11.6, 2.6 Hz, H1a; H6a), 3.82 (2H, d, J
= 8.5 Hz, H3; H4), 3.78 (2H, dd, J = 5.9, 2.7 Hz, H2; H5), 3.69 (2H, dd, J = 11.6, 5.9 Hz, H1b;
H6b).
13 C NMR (101 MHz, D2O) δ 70.83 (C2, C5), 69.25 (C3, C4), 63.19 (C1, C6). ESI-MS: m/z
205.13 [M+Na] + ; 181.10 [M-H] -

Benzoic acid (7) :
1 H NMR (400 MHz, D2O) δ 8.00 (d, J = 8.3 Hz, 1H), 7.62 (t, J = 7.4 Hz, 1H),
7.47 (t, J = 7.9 Hz, 1H). ESI-MS: m/z 145.13 [M+Na]
+
, 120.99 [M-H]
-
Gallic acid (8) :
1
H NMR (300 MHz, CD
3
OD) δ 7.06 (2H, s, H2,H6). ESI-MS: 169.13 [M-H] -