Fitoterapia 70 Ž1999.

113]115

Phytochemical Communication

Complete NMR assignments of Ž q. -usnic acid

M.A. Rashid a,U , M.A. Majida , M.A. Quader b
a
Department of Pharmacy, Faculty of Pharmacy, Uni¨ ersity of Dhaka, Dhaka-1000, Bangladesh
b
Department of Chemistry, Uni¨ ersity of Dhaka, Dhaka-1000, Bangladesh

Received 25 August 1998; accepted 5 October 1998

Keywords: Parmelia kamstchandalis; Usnic acid

Plant. Parmelia kamstchandalis Ach. ŽSymbiont., locally known as Shailaja, belongs

to the Thallophyta. It was collected in September 1994 from Dhaka and authenti-
cated at Bangladesh National Herbarium, where voucher specimens are deposited.

Uses in traditional medicine. Hydrophobia, intermittent fever, jaundice, whooping

cough, heart diseases and stomach disorders w1x. The traditional healers also claim
its contraceptive activity.

Previously isolated constituents. A number of depsides, depsidones and depsones

Ž dibenzofuran derivatives . , including 2,4-dihydroxy-m ethylbenzoate,
2,6-dihydroxy-3-ethoxy-4-methylbenz-aldehyde w2x and methyl-b-orsellinate w3x.

New-isolated constituent. Žq.-Usnic acid Ž1. w4]6x, synonyms: 2,6-diacetyl-7,9-dihy-

droxy-8,9b-dimethyl-1,3Ž 2H,9bH .-dibenzofurandione, usninic acid, carbonusninic
acid. Usnic acid exists in tautomeric b-diketone form, sometimes shown as the
1-OH, 3-oxo-tautomer and the CAS name refers to the 1,3-dioxo tautomer. The

U
Corresponding author. LDDRD, NCI-FCRDC, Bldg No. 562, Room No. 201, P.O. Box B, Frederick,
MD 21702, USA. Fax: q1-301-8466157.

0367-326Xr99r$ - see front matter Q 1999 Elsevier Science B.V. All rights reserved.
PII: S 0 3 6 7 - 3 2 6 X Ž 9 8 . 0 0 0 3 3 - 1
114 M.A. Rashid et al. r Fitoterapia 70 (1999) 113]115

identity of the isolated compound was independently established by inverse-de-

tected 1 H- 13 C correlations observed in HSQC and HMBC experiments, which in
turn, allowed complete NMR assignments.

(q)-Usnic acid (1). Yellow needles ŽCHCl 3 .; m.p. 196]1988C; IR bands Žnujol.:
3280, 1730, 1680, 1525, 960, 818, 720 cmy1 ; 1 H Ž500 MHz, CDCl 3 . and 13 C Ž125
MHz, CDCl 3 . NMR: Table 1; FAB-MS m r z Žrel. int.: 345.0961 ŽwM q Hxq. Ž100.
C 18 H 17 O 7 .

Table 1
NMR assignments for Žq.-usnic acid Ž1.

13 1
Position C H mult HMBC
2 3
J J

1 198.07 s ] ] ]
2 105.10 s ] ] ]
2-OCCH3 201.77 s ] ] ]
2-OCCH3 27.88 q 2.65 s 201.77 105.10
3 191.71 s ] ] ]
3-OH ] 18.81 s 191.71 98.34, 105.10, 201.77
4 98.34 d 5.96 s 179.40 59.08, 105.10
4a 179.40 s ] ] ]
6 101.54 s ] ] ]
6-OCCH3 200.32 s ] ] ]
6-OCCH3 31.27 q 2.66 s 200.32 101.54
6a 155.21 s ] ] ]
7 163.91 s ] ] ]
7-OH ] 13.30 s 163.91 101.54, 109.36
8 109.36 s ] ] ]
8-CH3 7.54 q 2.10 s 109.36 157.52, 163.91
9 157.52 s ] ] ]
9-OH ] 11.01 s 157.52 103.96, 109.36
9a 103.96 s ] ] ]
9b 59.08 s ] ] ]
9b-CH3 32.11 q 1.75 s 59.08 103.96, 179.40, 198.07
 M.A. Rashid et al. r Fitoterapia 70 (1999) 113]115 115

Acknowledgements

We wish to thank the Natural Products Chemistry Section of the Laboratory of

Drug Discovery Research and Development, Frederick Cancer Research and
Development Centre, National Cancer Institute, Frederick, Maryland 21702, USA
for NMR studies and Dr L.K. Pannel, National Institute of Diabetic Disorders and
Kidney Diseases ŽNIDDK., Bethesda, Maryland, USA for mass spectral measure-
ment.

References
w1x Kirtikar KR, Basu BD. In: Sing MP, editor. Indian medicinal plants, vol. IV. India: Dehra Dun
1933:2760.
w2x Quader MA, Tasneem L, Ahmed M. J Bose Res Center, University of Dhaka, 1994;103.
w3x Heyland PJ, Ingolfdottir K. Phytochemistry 1985;26:127.
w4x Ingolfsdottir K, Bloomfield S, Heyland PJ. Antimicrobiol Agents Chemother 1985;28:289.
w5x Jakupovic J, Huneck SZ. Naturforsch 1989;44b:1117.
w6x Aldrich library of 13 C and 1 H FT NMR spectra, 1992;2:882C.