( + ) - U S N I C A C I D IN F A R E A S T E R N L I C H E N S

V . N . S v i r i d o v a n d L . I . S t r i g i n a UDC 547.577+547.728+615.779.933

On invest igat ing the chemica l composi t ion of the F a r Eas te rn l ichens Dactylina a r c t i ca (Hook) Nyl and Usnea annulata (Mull. Argo) Tomin, we isola ted f rom them a compound (I) which, f rom the r e su l t s of e l emen ta ry analys is and i ts m a s s s p e c t r u m , cor responded to the empi r i ca l fo rmula C18HlsOT. The IR spec t rum showed the p resence in (I) of an a roma t i c r ing, a furan r ing, hydroxy groups , and an enol izable 1,3-dione grouping [1]. On chromatography on a thin l aye r , (I) gave a green spot with l(Fc H2SO 4 [2] and the colorat ion with the Ehrl ich reagent that is cha r ac t e r i s t i c for usnic acid [3]. The NMR and m a s s spec t r a of (I) were comple te ly identical with those desc r ibed for usnic acid by Shibata et al . , [4] and by Huneck et a l . , [5].

Thus, compound (I) is (+)-usnic acid. This conf i rms the hypothesis put fo rward by Fol lmann et al . , on the p re sence of usnic acid in the lichen Dactylina a r c t i ca which was made on the bas is of a study by TLC and micro chemical reac t ions .

The identity of the compounds isola ted f r o m the two spec ies of lichen mentioned above was shown by a compar i son of their mel t ing points and their [~]D va lues , the absence of a depress ion of the melt ing point of a mix tu re , and the identi ty of thei r IR, NMR, and m a s s spec t ra .

We have shown that usnic acid is absent f r o m the lichen Thamnol ia v e r m i c u l a r i s (Sw.) Ach. ex Schaer . The Dactylina a r c t i c a and Thamnol ia v e r m i c u l a r i s were collected in the envi rons of the vil lage of Stokovyi in the TenVki region, Magadan oblas t , in August, 1974,and the Usnea annulata in the basin of the R. Kamenushki (Mari t ime Te r r i t o ry ) in June, 1974.

The dry comminuted lichen was ex t rac ted with boiling pe t ro l eum ether (bp 70-100°C) for 3 h, and the ex t rac t was f i l tered. When it cooled, (+)-usnic acid c rys ta l l i zed out in the fo rm of yellow needles with mp 203-204°C; [~]~ +496 ° (chloroform).

L I T E R A T U R E C I T E D

1. W . R . Chan and C. H. Hassa l l , J. Chem. Soc., 3495 (1956). 2. K . H . Chance and D. L. Tibbets , Bryologis t , 76, 208 (1973). 3. N . V . Laza rev and V. N. Savich, The New Antibiotic Binan, o r the Sodium Salt of Usnic Acid [in Russian]

M o s c o w - Leningrad (1957), p. 52. 4. S. Shibata and H. Taguchi , Te t rahedron Let t . , 4867 (1967). 5. S. Huneck, C. D je ra s s i , D. Becher , M. Barbe r , M. Von Ardenne, K. Steinfelder , and R. T t immler , T e t r a -

hedron, 24, 2707 (1968). 6. G. Fol lmann, S. Huneck, and W. A. Weber , Willdenovia, 5, 7 (1968).

Pac i f ic Ocean Inst i tute of Bioorganic Chemis t ry , F a r E a s t e r n Scient i f ic Cente r of theAcademy of Sciences of the USSR, Vladivostok. T rans l a t ed f r o m Khimiya Pr i rodnykh Soedinenii, No. 1, pp. 88, J a n u a r y - F e b r u a r y , 1976. Original a r t i c le submit ted June 11, 1975.

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