Chemical Studies of some Fungi

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E A R

THESIS

AB9TEUCT.

74-

165

The

r a a e t i a n of a h l o r s n l l with v a r i o u s

.Ubbtitutetl phenols under bacria aandition. ha# been st-tidied. It ham been found that

t h e

yield@ of

h s n s o b i s b e n a o f ~ q u i n ~ n o i d

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d e r i v a t i v e s

a m

g r e a t e r when,rfter i n i t i a l ntreleophiXia rttaak en t h e Iceteenoid aymtem

by

t h e

oxygen atom

o f

t h e

phenoxida ion, t h o earban

aCam

artho

t o the

vinyl- - a w l e t h e r linkage is

a c t i v n t s d t o w r u d 8

farther nucloophilic a t t a c k

by the

pramanam of

a

snitably orientated s l e u t r o n relsaaing mubstituabnt. The other predueta

of the

r e a e t i o n mixture hevc been i e a l n t e d

^and

charaatarisod,

and

t h e a n e a t r a l

^{d a t m}

disaumssd f o r the derivatives of 2 , 3 4 i e t h a m i -

1 bensofttran-1,4-qninane whiah were ahtained I n

t h i s

I walC

The maas a p e a t r r of benarabisbensofuranquinones

and

the oarreaponding quinol a e s t a t e a haw. heen examincsd. Faail. l e e 8 ef methyl radiealm frera

u a m n t i a methoxy

p u p .

and ketone from

the

a a e t a t a d*rivati+oa

waa

abservod. Deo~rbanylafion

nnd

fragmentmtion irmolving the h e t e r o a y e l i c ring syetem resulted i n peake af only minor i n t s n s i e . The ready l o s e of enhetPtnsnBn as dsseribad

abava

i s explained

by

t h e remalting famuation of remanutee mtabilirsd

quheneid

ianm.

Sane eheaianl aanmtituanta of' P*nioohor%

gigmnfoa have

been

imelated and ahareaterinecl.

2 ' , 3 ' ,

6*-Trimatha~-p-$erphenyl (25)

warn ehtained

whiah

repreesnhs the first methoxylrted b-terphenyl i s o 3 n t o d

from s ftm@as. Alao obtained

warn

a mixture u o m r i s i n g

two

eompeunda,

C,gHhg and

C30R50.

^{O n}m a r 8

speetral

grotmdm

these are

propa8ad to be

t h e pentaayalia

(6)

triterpenao, laps-15,19(22)-diene (33) and

lup-

74 - [63

-19(22)-ene (34) rsmpeetively,

oxide (44) ha0 been a i a r e b l a l o ~ a a l l y hydrexylntad

by

Caloneefrla docera te form l/,

754

-d~hydroxy-l4.15-epoxy-2- -ketomanoyl oxide (45). The pouitions of the

hydroxy

rpraupo w e r a detsrained fram tha peeks

arising from fragmentatianr in ring.

A and

R in the

~ bonding obmowed i n the i.r. mpbotmam mppor$ed the equatorial canfarmatian o f the hydro- -up at C 1 whilat t h e faail. la69 a f n t s r upon elmatron impact

and

the premsnae a f

r

u i r n s l aorrssponding

t a

an equatorirl eklrb%nol proton i n the n.m.r, infers that at C 7 1 . a x i a l .

Finally, if ham been propomad that tho atrueturea

o f

the blua pigmentme aartiainr

A

and B, 1aelateQ from Cartietram .acraclnalo\rrr

by

Dean are 2,6,9-trlhydrraxy- -3,8,12-trimathaxybensa~1,2-bc4,5-~*~bhimbsn~0furur

and

2,3.8,9-tt~tramethoxyben~o[l, 2-bs4.5-b*] bimbenso-

I

f%1ran-6,12-dians r e s p e a t i w l y .

The n,m,r. spectmrft tbf

e o r t i e i n

A B H a o e t s t a and

aomprrrirran of the mare

epeatra

of

thee*

aompounds

nnd

those anthentia

aamplem

prepared

s ~ t h e t l a a l l y

irupporf

theme ~ ~ t m c t t r e n .

E r r a t w

p105 para l r

Should

read (R =

~ e ) .