lLIETXBOLITES O F P Y R E N O M Y C E T E S X.' ISOLATIOS OF 9-TOLUQUINOSE A N D TOLUQUIXOL FRO11 C T RI A E R LTBE S CE SS S v s i s T. CAREYand 11. S . R.?;AIR The &\-e&, York Botanical Garden, Bronx, -Yew Y o r k 10458 E-IELD.-Toluquiiione 30 mglliter: tolnquinol 5 nig liter of t h e culture liquid. inone, nip 66-67' (hexane) MW 122 had nmr signals a t 6 2.06 (3H, d J = l . 5 H z ) , 6.63 ilH, mi and 6.73 (2H, b r o a d ) . Its ir spectrum showed peaks a t 1660 ( b r o a d ) 1605. T h e nmr and i r speFtra were identical with t h a t of a recrystallized commercial saniple (H&- K Laboratories! of nieth?-l p-benzoquinone. T h e hydroquinone crj-stallized from benzene had m p 123-4" (sublimes a t 112") and X niax 291 (~3,100). On oxidation n-ith silver carbonate 'celite, it yielded toluquinone, confirming i t s identity as toluq\iinol.
K e v-ish t o report the isolation of p-toluquinone and its free reduced form, toluquinol, from the hypocrealean fungus. S e c t v i a erubesceiis (Desm.) Phill. et P l o ~ . Substituted toluquinones are present in many fungi and higher plants. Toluquinone, itself, a common metabolite of artliropods (1) occurs in plants only in its reduced form! usually as one of the glucosides, homoarbutin or isohomoarbutin. As far as we can ascertain, this is the first time that p-toluquinone and toluqinol have been isolated from a plant source.
Presence of the quinone in t h e culture liquid --as established h?- tlc. It is not unusual for a quinone-h!-droquinone pair t o occur in nature (3, 41: however, t h e culture was aerobic and, therefore, there is no w-ay t o eliminate t h e possibility t h a t t h e quinone was formed by air oxidation after t h e hydroquinone n-as released into t h e ciiltiire medium.
ESPERIlIEST-\L CULTURE.--.^ culture of -I-. eritbesceiis (73-2051, isolated and identified b>- Dr. G a r y J. Saniuels:? n-as inoculated into a dextrose yeast medium ( 2 ) in Fernbach flasks (26 x 400 m l ) . T h e still cultures were maintained a t 25" in t h e d a r k and harvested after 4s days.
ISOL.LTIOS OF
TOLUQUISOSE
.ISD
AiCHSOWLEDGIIESTS This n-ork v-as supported b y grants hI 13074, -11 13247, and -41 00228 from t h e r a t i o n a l Institutes of Health. We t h a n k A h . Francis Alanginelli and XIrs. Roxanne Beecher for technical assistance.
TOLC-
QuIsoL.--Cultiire liquid ( G liters I was extracted twice m-itli 3 liters and twice again with 2 liters of ethyl acetate. T h e conibined extrcicts were taken down t o dq-ness under vacuum (ea. 10 nim I . T h e crude extract (600 mg) v a s chromatographed over silica gel (.30 g, 2 cni x 16 e m , . T h e quinone %-aseluted n-ith ethj-1 ncetate-Skellj- B (3:l) and t h e hydroquinone with ethyl acetate.
Received 10 Jill! 1978. LITER.ITUEE CITED 1.
E..H . THOXYS,Saturally-occnrring
quinones. 2nd Edition. -Academic Press, S e n Torli, S . T. 1970, p . 93-97. 2 . D . C . . ~ L D R I D G E , -1.BORROK,R. C . FOSTER. 11. P. L.YRGE. H. PPESCER.JT. B. TCRSER, -1. Cheiii. SOC.Perkiii T h n s . I, 2136 (1972). 3. Ref. 1, p . 9s-183. 4 . XI. 5 . R . SAIR and AI. ASCHEL, Tcirnhedroii L e t t . 795 (1972).
'For P a r t I S see L . .lnanthas~thraniaiiiaii, Susan T. Carey, and XI. S . E . S a i r . T e f r o hedroii Let/. 3,527 i ~. l q T X- I ~ ? I ? eare grateful t o D r . Samuels of t h e Plant Disease Division, D . P . I . R . , .luckland. S . Z . for t h e culture of -\-. eruhesceiis.
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