Baeocystin in Psilocybe semilanceata

J~P HA Rt1 '. s c I .
I ~
I
it"3 - l f.41 (l C) 11)
Baeocystin in Psilocybe semilanceata
DA VID B. REPKE
*x
and DALE THOMAS
---- --------------o Ba-ocvstin and psilucvhin
LESLIE
---,_._----
.\h'l r act
were found in extracts of
.' .•ilrJ!'lv 01' Psilocvbc scmilanceuiu
Psilocybin (but not baeocystinl
wa~ also detected in extracts of a related species, Psilocybe pellicuìosa.
Traces of psilocin were present in these two species. The structures
••r I hp isolated cornpounds were corroborated using mass spectrornetry
al1(: ll\' spectroscopv.
from extracts
of Psilocvbe
identified hv rnass spectrometry and UV spectroscopy
O Psilocvbin=isolated
from extracts of Psilocvbe semilonceota
and
J' pcllicu {oso, identified by rnass spectrometry and UV spectroscopy
O I'silocvbc semi/oneeota--extracts
of carpophores. baeoeystin and
J"iloc"hin isolated. identified bv mass spectrometry
and UV spec-
h",\phrases
O Haeocvstin-c-isolated
" "lIlon(,f'Ola,
t nt~('()JlY
The genus Psilocybe contains many species with
hallucinogenic
properties (1). Their use for religious
purposes in Mexico was first recorded 4 centuries ago
(:21.However, only in the last 35 years has serious study
!wen devoted to this subject (3l. In 1959, two active
principles were isolated from several members of this
genus (4): the 4-hydroxy-3-(2-dimethylaminoethyl)indole (psilocin) and its corresponding
phosphate ester
I psilocybin).
Since then psilocin and psilocybin have
iWE'n detected in other mernbers of Psilocvbc and re!diPd genera (!)),
.
Heirn (6) sugzested that the hallucinogenic
mushr"',m described in a lfith centurv English re pori was
J'sl!ocybe semilanceaia
(Fr.I Kumrner
(Stropharia~'eae J. considered t.he tvpe species of the genus (7, 8\.
I rJ\ p,t igator~
ha\'(' verifir-d
Ihf' prp"éf)(T
psilorvhin
1';,1:,11(1\
psilocin : in ,.;n't'ra! ElIropean ('01 It".'t ion- 01 l'
, ,iunccala
(~L 1 :21.
T1Jf presence of the psilocyhin
analogs 4-phusphur-
or
t
yloxy<~-(2-methylaminoethyl)indole
and its demethyl
counterpart
(baeocystin
and norbaeocystin,
respectively) have been reported only in P. baeocystis Singer
-and Smith (13). These compounds were not found in P.
attrobrunnea (Lasch) Gillet, P. pelliculosa
(Smith)
Singer and Smith, P caerulipes
(Peck) Sa cc., or P.
«trictipes Singer and Smith (14).
During investigations
of the indole alkaloids of the
genus Psilocvbe. a compound with a mobility slightly
slower than psilocybin was consistently
detected on
thin-layer
chromatograms
of extracts
of a Pacific
Northwest varietv of P scmilonceat a This compound
was observed in ~ll collections of this species examined
over several years.
EXPERIMENTAL'
Fn-ezr--dned carpophore-, of V srrnitaucrut a C', H24 nlg. were grpund
t.u a powder and extracu-d hv shakirn; with rnet hanol 81 roorn tern
"1 TLC wa-, carried out u-",inJ! 0.2;\- and 1.(1. rum 18.\'{"r~ fOi1iCHJ!pl (; lo' on da~"
pla1t"!'. Thp solvr-nt svstr-m tI~-Ò wa- I-pr,.pantll
~.,. arnmonium
hH1ruXlft.· l:l:~1
Il:~1. Ma
sJw{'lril
'At'fI' 11lll~JilH'd wit h an Ali" .. CH--1 ~pt'CirltnU'll·~
.• " d!;~,\-'
inìr-i. Ttu- pn.h! 1t-nqwraT~:I' "'l'', :J,d~'~.HlId H," l'''' ~1I\Jrn' pnlPnTl:t! "d" ';"1' t-v
A ( . cH\ modt, j l ~, ~Hh'l n ,I) n, ", .me: t'T" V.
lI,,~'(J i, ckll'fmint·
l'\ ...: )t·(·t ~.:
- 'l'11f' ("\l!iI·ctl(\!)~
arIL tht· h-r hanun
(,j lht E~(,lIda !\IH'lon:l: d« ~'It'III'ld~
Bj,d,·,:':I("H~. I P ,.
"tlUfP
Il. t' .. "1t·):Il"t •. iillei -,, ,nlt' Ufi a 1:-., rm (h-I'(.~il ;!1 tt«
h(-rllarlllrn
01 tht ':IlI\t·r"ll\
101 Mh'ni;:ar:
Ann Arbor . ~11('h C .••rVllpÌa . .-,-.. (,j
l' ~."iilfJljc('nto
\lt,"f'rr ,-,,:Jt--cl{·n In pa:-ltJrt'~
al t t l(' lollowlI1r h)(·.·tl-,1)IJ~ v-ru vHarbor L'ount v. \'a,h, J!C:.' J!!~:, ILE:-;UE J:l;>1 alsoat
MWHI, JNi~ 'ai",
MI !\,lH'HI,:.'~:.'I;t81,.'al M!(,H, and:.'h,CI:,Jeff~NmC",m"
\'a.,h .. l!!::: I!C,
11.1':.-:1.1F l N:: ",I.,,, a: \11<'H " :.'~'''' ,al", al M !C'H l, a nd :."~·IL Ha nd;,·. \, iI,l. ,
1"7' !1.!-->~l.1F~·-:-\II!';'!'(~:--:!Xt·....()rt
l~j~·:.II.J-:"I.IF_",~!
\·,.;.,II"':t~l't,l
or
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o
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ì
i"
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w e-rr
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•..•.'!'rl~ 1.1\lll.
df'~';
T"IP, Il '11""
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l!.
i,.,.···..
!...,.n "",,toIod
;:.L~:.lt"
ì-· .'
.:il"-;~-:d;,·i~ li,.r· d"!
p; l ltt Ll:"'lw~in!'
1111"
~pt-\'dH
pi:tct'Il.'
Il:
cit,!,q ..
;11H~"'.'''''::!-
and \LI\~':\"L
.,..,..:
\I.:I"!
lo
,L', ~ h.:!I.,'·
,l'i
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:l.t-: .....:.lr-
rr: . l . P:II1"·;'''·c
•., ",;:';'/( ,'(./(; 11\;: ....
~'nlt
\l,,·d.·,
winc l. t urtlnr
....\lHl\
fllii~ \ ia nt .
t e
tu.nn-
1"1'1'
l" fid,.',
,,,,,l'''d
"onu'lil
'''r :!ii hr l'h, rr..xt ur« WH' filtered, and th« !.nhd~ were
h me-t !.ltnol Th- rorn hme-d filtrate and washings were
ra t •• d '" l'!lI'Uf, Analvt ical TLC of the extract (tw« develop
RITEHENCES
Wl'
rru-ntx) ,h"w~d psilo'ybm (RI 0.27) and the slower cornpound (RI
O.LL)
Both spol!. r-xhibited the same dark-blue coloration when
slHliV~d with 2'lo. 4·dlmethylaminobem..aldehyde in ethanol and expose-d ti, hydrogen chloride vapors. Trace amounts of psilocin were
also detected.
The concentrated residue was preparatively chromatographed on
a lumm layer of silica gel in the described solvent system. A band
rontaining the two componenti! W8& removed from the plate, and the
cornpounds were eluted with methanol containing 5% aqueous amrnonia. The eluate was concentrated under reduced pressure, and the
residue was rechromatographed on a 0.25-mm layer of silica gel to
resolve t he two cornponents. Two developmentB in the propanolamrnonia system followed by elution of the bands afforded psilocybin
Cl rng. (Ufi<Jul, mp 175-180° [lit. !l5) mp 185-195°1 and its slowermovirig counterpart (J mg. 0.12%), mp 245-248° [Iit. (14) mp 2542;)1'°1 Carpophores of P pelliculosa were extrarted in a similar
manm-r lo giv« ()'()8'\,psilocvhin Traces of psilocin were also detectf'd
RESUL TS AND DISCUSSION
The UV spectra of the two compounds were superimposable, with
290 (. 4000), 280 (sh)(5000), 268 (6300), and 222
(40,000) nm, typical ofpsilocybin (4). The mass spectra were consistent with published data for psilocybin (11) and baeocystin (13).
Psilocybin showed peaks at m/e 204 (relative abundance, 19%), 160
(4).159 (3), 146 (6),130 (3),117 (2), and 58 (100). Baeocystin showed
peaks at 190 (8),160 (4),159 (4),147 (16), 146 (14), 130 (4),117 (5),
and 44 (JOO).
Each compound exhibited typical fragrnentations of 3-indolylethylamines (16), e.g., a base peak arising from tl-bond fission of
the ethylamine side chain (psilocybin, m/e 58; and baeocystin, m/e
44 l. While neither compound showed a parent peak, both showed
sianals for the dephosphorylated species (psilocybin, m/e 204; and
baeocystin, mie 190). The concentration of psilocybin in P. semilanccato was consistent with isolated yields reported from European
collect ions (9,11).
In agreernent with Leung and Paul (14), baeocystin W8& not detected in P. pel/icu/osa. Psilocybin (but not psilocin) has been reported previously in this species (17).
Preliminary investigations suggest the presence of baeocystin in
ot her species and genera. In fact, Leung and Paul (3) and Benedict
(l H) suggested that baeocystin ma)' have been the unidentified compound observed by Stein et al. (19) in a species of Ponaeolus.
Pharmacological effects of the analogs of psilocybin have not been
studied.
À",", (methanol)
( l r R Herrr. and R G. Wassun, "Les i 'hilmpignon; Ha l lurino
g-f.nesdu Mr-xique." Museurn National D'Histoire Naturelh , l'ano,
France.1959.
(21 B. de Sahagùn, "Fiorentine Codex, Generai History of New
Spain," Books III and XI, A. J. O. Anderson and C. E. Dibble,
Translators, University of Utah Presso Salt Lake City, Utah, 1970.
(3) R. G. Wasson, Bot. Mus. Leatt. Haro. Univ., 20,25(1963).
(4) A. Hofmann, R. Heim, A. Brsck. H. Kobel, A. Frey, H. ou.
T. Petrzilka, and F. Troxler, Helv Chim. Acta, 42,1557(1959).
(5) R. E. Schultes and A. Hofrnann, "The Botany and Chemistry
of Hallucinogens," Charles C Thomas, Springfield, Ill., 1973, pp.
36-52.
- (6) R. Heim, Natur. Can., 98,415 (971).
(7) R. Singer, "The Agaricales in Modern Taxonomy," 2nd ed.,
J. Cramer, Weinheim, Germany, 1962, p. 542.
(8) P. Konrad and A. Mauhlanc, "Rèvision des Hyménomycètes
de France," Paul LeChevalier. Paris, Franee, 19~7, p. 84.
- (9) A. Hofmann, R. Heim, and H. Tscherter, C. R. Acad. Sci., 257,
10(1963).
:10) R. G. Benedict, V. E. Tyler, and R. Watling, Lloydia, 30,
150(967).
(11) P. G. Mantle and E. S. Waight, Trans. Br. Mycol. Soc .. 53,
302(1969).
(12) M. Semerdzieva and F. Nerud, Ceska Myko/., 27,42(]973).
(13) A. Y. Leung and A. G. Paul, J. Pharm. Sci., 57,1667(1968)
(l4) lbid, 56,146(1967).
(15) A. Hofmann, R. Heim, A. Brack, and H. Kobel, EIperientia,
U, 107Cl958).
(6) H. Budzikiewicz, C. Djerassi, and D. H. Williams, "Structural
Elucidation of Natural Products by Mass Spectrometry," vol. l,
Holden-Day, San Francisco, Calif., 1964, pp. 42-45.
(17) V. E. Tyler, Lloydia, 24, 7W96l).
(18) R. G. Benedict, in "Microbial Toxins," S. Kadis, A. Ciegler,
and S. J. Ajl. Eds., Academic, New York, N.Y., 1972, chap. Il.
(191 S. I. Stein, G. L. Closs, and N. W. Gabel, Mvcupathol. Myco/
App., Il, 20;,(1959).
ACKNOWLEDGMENTS
AND ADDRESSES
Received December 29, 1975, from • 148-B West Dona Street ,
Mountain View, CA 94041. and IlU4 Whitney A"enue, Los Gatos,
CA 95030
Accepted for publication Mav 28, 1976.
The authors thank Lornie Leslie and -Jean Leslie for their help with
this study and also Jerry Boydstein for assistance in collecting P
pelliculoso near Maytown. Wash.
• To whom inquiries should be directed.