ATHROTAXIS ALKALOIDS. PART I. ALKALOIDS OF A. CUPRESSOIDES

Article abstract of DOI:10.1016/S0040-4020(01)96885-1

Eleven homoerythrina-type alkaloids (1-9, 11, 12) have been isolated from A. cupressoides (Taxodiaceae), of which six (6-9, 11, 12) had not previously been reported.

Full text of DOI:10.1016/S0040-4020(01)96885-1

Tetrahedron Vol. 40, No. 14,
2611 to
1984
Printed in the U.S.A.
Ltd.
ALKALOI DS.
ALKALOI DS OF A.
PART I .
SI RI CHAI PANI CHANUN
AND I . RALPH C. BICK
Che mi s t r y De pa r t me nt ,
Uni ve r s i t y of Ta s ma ni a ,
Hoba r t , Ta s ma ni a , Aus t r a l i a 7005
(Received in UK 15 March 1984)
Abs t r a c t
El e ve n
a l ka l oi ds ( l - 9, 11, 12) ha ve be e n i s ol a t e d f r om
( Ta xodi a c e a e ) , of whi c h s i x
not pr e vi ous l y be e n r e por t e d.
whi c h i t i s de s i gna t e d a l ka l oi d
a nd
The ge nus
i s c onf i ne d t o Ta s ma ni a ,
a l ka l oi d
pl a nt s ,
r e s pe c t i ve l y, a nd of t hr e e f ur t he r
a nd
a nd c ompr i s e s t he onl y r e pr e s e nt a t i ve s i n t he
s out he r n he mi s phe r e of t he Ta xodi a c e a e , r a t he r
C
.
a
,
a nd
i n whi c h i t
0- me t hyl a t hr oc upr e s s i ne
a s a l ka l oi d
s ma l l f a mi l y t ha t ne ve r t he l e s s c ont a i ns s ome of
t he l a r ge s t a nd t a l l e s t t r e e s i n t he wor l d:
( Bi g Tr e e ) a nd Sequoia
oc c ur s a s a l ka l oi d
pr e s e nt i n
P.
homoe r yt hr a t i ne
f ound i n S.
a s
( Ca l i f or ni a n Re dwood) r e s pe c t -
a l ka l oi d
a nd f i na l l y homoe r yt hr a t i ne
a nd i n P. a s a l ka l oi d
The f a mi l y i s now l a r ge l y c onf i ne d t o
i ve l y.
f i r s t i s ol a t e d
The i de nt i t y of t he s e
e a s t e r n As i a a nd nor t h Ame r i c a , but wa s onc e
muc h mor e wi de l y di s t r i but e d a s s hown by f os s i l
s pe c i me ns , one of whi c h
f r om
ba s e s ha s be e n c onf i r me d by t he
a gr e e me nt of t he i r phys i c a l da t a wi t h r e por t e d
va l ue s , a nd by di r e c t c ompa r i s on wi t h
wa s f ound i n r e c e nt t i me s s t i l l
a
gr owi ng i n Chi na .
Al t hough s ome s pe c i e s ha d
no
a ut he nt i c s pe c i me ns whe r e t he s e we r e a va i l a bl e .
Of t he r e ma i ni ng a l ka l oi ds , t he s pe c t r a of
be e n f ound t o gi ve a l ka l oi d
a l ka l oi ds ha ve pr e vi ous l y be e n i s ol a t e d f r om
me mbe r s of t he
s howe d t ha t i t ha s
phe nol i c gr oup a nd t wo me t hoxyl s whi c h, a s i n
t he c a s e of t a xodi ne mus t be a t t a c he d t o
a r oma t i c a nd a l i pha t i c c a r bons r e s pe c t i ve l y
f r om t he i r nmr pr ot on r e s ona nc e s .
a
A.
Don ( Pe nc i l Pi ne ) i s
a t r e e
t ha t gr ows a bove
m i n c e nt r a l a nd we s t e r n
The pr e s e nt r e por t de s c r i be s e l e ve n
Ta s ma ni a .
Howe ve r ,
a l ka l oi ds whi c h ha ve be e n i s ol a t e d f r om i t s
ba r k a nd f ol i a ge .
2- hydr oxyt a xodi ne ha s a n e xt r a a l l yl i c a l c ohol
gr oup t ha t c a n r e a di l y be r e move d6 by
AND DI SCUSSI ON
RESULTS
i on t o t he c or r e s pondi ng c hl or i de f ol l owe d by
LAH r e duc t i on.
s i gna l a r ound 64. 3, c or r e s pondi ng i n c he mi c a l
s hi f t t o me t hi ne pr ot on i n t he c a r bi nol
gr oup of a n a l l yl i c a l c ohol , i s e l i mi na t e d
f r om t he nmr s pe c t r um of t he pr oduc t ,
whi c h pr ove d t o be i de nt i c a l wi t h t a xodi ne
In t he pr oc e s s
a mul t i pl e t
t he f r e s h pl a nt ma t e r i a l
a l ka l oi ds wa s c a r r i e d out
The e xt r a c t i on of
a nd i s ol a t i on of t he
a
by s t a nda r d me a ns a nd ha d t o be c ompl e t e d a s
s oon a s pos s i bl e t o a voi d ma r ke d di mi nut i on
i n yi e l ds : t he a l ka l oi ds be c ome unde t e c t a bl e
i n t he pl a nt ma t e r i a l a f t e r f e w da ys .
pr ove d t o ha ve s t r uc t ur e s of t he
t ype , a nd i nc l ude f i ve known ba s e s : t a xodi ne
whi c h oc c ur s i n s pp. a s
a l ka l oi d a nd i n
a s a l ka l oi d
a l s o c ons t i t ue nt of t he t wo l a t t e r pl a nt s i n
a
a
The y
t he a l c ohol gr oup i n
mus t
t hus be l oc a t e d a t C- 7 or C- 2.
A
de c i s i on i n
f a vour of t he l a t t e r a l t e r na t i ve c a n be ma de
f r om ma s s s pe c t r ome t r y: t he ms of
di ne
of
c or r e s ponds ve r y c l os e l y wi t h t hos e
2- e pi homoe r yt hr a t i ne
a
2677

2678
a nd I . R. C.
f i gur a t i on s hown i n
i s pr opos e d f or
t a xodi ne wi t h t he a l c ohol gr oup
t o t he
a nd t hi s
a c ompa r i s on of
C- 3 me t hoxyl a s i n homoe r yt hr a t i ne
s t e r e oc he mi s t r y i s s uppor t e d by
t he s pe c i f i c r ot a t i on of 2- hydr oxyt a xodi ne
wi t h t hos e of homoe r yt hr a t i ne
a nd 2- e pi homoe r yt hr a t i ne
me a s ur e d unde r c ompa r a bl e c ondi t i ons .
2- Hydr oxyi s ot a xodi ne
hydr oxyt a xodi ne
i s
wi t h
Ta xodi ne ( RI
= Me ,
a nd
a s pe c t r os c opi c c om-
3- Epi s c he l ha mme r i c i ne
0- Me t hyl a t hr oc upr e s s i ne
E- Epi homoe r yt hr a t i ne
Homoe r yt hr a t i ne
pa r i s on of t he t wo a l ka l oi ds i ndi c a t e d t ha t
t he y ha ve t he s a me f unc t i ona l gr oups a nd c l os e -
l y r e l a t e d s t r uc t ur e s a nd c onf i gur a t i ons .
The i r ms a r e a l mos t i de nt i c a l , a nd f ur t he r mor e ,
t he C- 3 me t hoxyl pr ot ons r e s ona t e a t 63. 28 i n
t he
nmr s pe c t r a of bot h ba s e s , a nd a l s o i n
t ha t of t he known a l ka l oi d
t i n e 3
Wi t h t he e pi me r i c c onf i gur a t i on of
2- Hydr oxyt a xodi ne
t he me t hoxyl ,
a
va l ue of a r ound
woul d be
e xpe c t e d f r om a na l ogy wi t h
t he C- 3 di a s t e r e ome r of
Ba r t on oxi da t i on
of
2- hydr oxyi s ot a xodi ne
ga ve
a
a
c onj uga t e d
pe a k a t
2- Epi hydr oxyi s ot a xodi ne
At hr oc upr e s s i ne
ke t one whos e
nmr s pe c t r um s hows
66. 00 c or r e s pondi ng t o a n ol e f i ni c pr ot on
t o
t he c a r bonyl gr oup; B- pr ot on woul d be e xpe c t e d
a
t o r e s oha t e di s t i nc t l y f ur t he r downf i e l d" .
c onj uga t e d ke t one wa s c l os e l y s i mi l a r t o, a l -
t hough not i de nt i c a l wi t h t ha t f or me d by
c or r e s pondi ng oxi da t i on of 2- hydr oxyt a xodi na
The a l c ohol gr oup i n mus t t hus be
The
a
l oc a t e d a t C- 2, a nd f ur t he r mor e i t mus t ha ve
t he s a me c onf i gur a t i on a s t ha t i n
Me &a t C- 3)
a nd
odi ne
f r om t he opt i c a l r ot a t i on
of
2- hydr oxyi s ot a xodi ne
a nd f r om t he c he mi c a l
a l l of whi c h
wi t h a n a l l yl i c
s hi f t ( 65. 575) of t he ol e f i ni c pr ot on i n i t s
ha ve
a s i mi l a r s t r uc t ur e t o
nmr s pe c t r um.
r e move d 6 f r om
Whe n t he a l l yl i c hydr oxyl wa s
t he pr oduc t pr ove d t o be
a nd c l os e l y s i mi l a r
t o i t s pe c t r os c opi c a l l y. The ma s s s pe c t r a of
a nd a r e vi r t ua l l y i ndi s t i ngui s ha bl e ; t he r e
a l c ohol gr oup a t C- 2 a nd
a
me t hoxyl a t C- 3. On
t he ot he r ha nd, t he r e a r e s i gni f i c a nt di f f e r -
e nc e s i n f r a gme nt a t i on pa t t e r n a s c ompa r e d wi t h
t he ms of a na l ogous ba s e s whe r e t he a l c ohol
wi t h t a xodi ne
mor e -
nmr
gr oup i s a t t a c he d
i ns t e a d of
a r e , howe ve r , s ma l l but s i gni f i c a nt di f f e r e nc e s
i n t he i r ot he r s pe c t r a , i n pa r t i c ul a r i n t he
c he mi c a l s hi f t s of t he a r oma t i c s i ngl e t s i n t he
ove r , t he C- l ol e f i ni c pr ot ons i n t he
s pe c t r a of t he l a t t e r ba s e s r e s ona t e a t
a s
t o 65. 55 f or
nmr s pe c t r a ,
a nd
a mi xe d me l t i ng poi nt
At t he s a me t i me , t hi s
t a xodi ne
s howe d t ha t t he t wo ba s e s a r e not i de nt i c a l .
The y e vi de nt l y di f f e r onl y i n t he pa t t e r n of
c he mi c a l s hi f t f or t he ol e f i ni c pr ot on i n
gi ve s e vi de nc e f or t he c onf i gur a t i on of t he
hydr oxyl gr oup a t t a c he d t o t he a dj a c e nt C- 2
pos i t i on: t he c or r e s pondi ng va l ue s f or t he
s ubs t i t ut i on i n t he i r a r oma t i c r i ngs , a nd
c or r e s pondi ng di f f e r e nc e mus t a l s o e xi s t
be t we e n t he a l ka l oi ds
a
known a l ka l oi ds homoe r yt hr a t i ne
homoe r yt hr a t i ne whi c h di f f e r onl y i n t he
or i e nt a t i on of t he i r C- 2 hydr oxyl s , a r e 65. 52
On t hi s ba s i s , t he c on-
a nd
a nd
Whe n t he H- 3
pr ot on ( c a .
of
a nd t he H- 12 pr ot ons ( c a .
we r e s e pa r a t e l y i r r a di a t e d, t he
a nd 5. 78 r e s pe c t i ve l y.

2679
alkaloids-1
s pe c t r um r e ve a l e d di s t i nc t nuc l e a r
e f f e c t s on t he t wo s i ngl e t s
whi c h mus t t hus be l oc a t e d
we r e obt a i ne d i n
ve r y s ma l l a mount s onl y, a nd c oul d not be
s a t i s f a c t or i l y s e pa r a t e d f r om one
a nd
a t C- 15 a nd C- 18 r e s pe c t i ve l y. The phe nol i c
a nd me t hoxyl gr oups of 2- hydr oxyi s ot a xodi ne a r e
i n c ons e que nc e a t t a c he d a t C- 17 a nd C- 16, i n
t he r e ve r s e a r r a nge me nt t o t ha t of
The i r s pe c t r a s how a c l os e r e s e mbl a nc e t o
t hos e of 2- hydr oxyt a xodi ne
hydr oxyi s ot a xodi ne e xc e pt t ha t a ddi t i ona l
a bs or pt i ons due t o a c e t a t e e s t e r gr oups a r e
i n pa r t i c ul a r , pe a k a t 1730
a nd
a
t a xodi ne
a nd t he s t r uc t ur e a nd s t e r e o-
pr e s e nt :
a nd
a
t hr e e - pr ot on s i ngl e t a t 62. 11 i n t he i r
nmr s pe c t r a r e s pe c t i ve l y s howe d
c he mi s t r y of 2- hydr oxyi s ot a xodi ne i s r e pr e s e nt -
e d by
i r a nd
t ha t
2- Epi hydr oxyi s ot a xodi ne
c oul d not be
a nd
a r e e s t e r s of a l c ohol s r a t he r
I nt e ns e i ons i n t he i r ms
t ha n of phe nol s .
c ompl e t e l y s e pa r a t e d f r om
whi c h ma y be f or mul a t e d a s
a nd
i ndi c a t e d
I t pr ove d t o be i s a ne r i c but not i de nt i c -
a l wi t h a nd 2- hydr oxyi s ot a xodi ne a nd on
Ba r t on oxi da t i on i t ga ve c onj uga t e d ke t one
c or r e s pondi ng t o t ha t f r om but di f f e r e nt t o
2- Epi hydr oxyi s ot a xodi ne
a nd 2- hydr oxyi s ot a xodi ne
t ha t t he a c e t oxy gr oups a r e a t t a c he d a t C- 2.
On ba s i c hydr ol ys i s , t he a l ka l oi ds ga ve pr oduc t s
a
c or r e s pondi ng t o
a nd
hydr oxyi s ot a xodi ne
t hus be r e pr e s e nt e d by
a nd t he i r s t r uc t ur e s ma y
t he ke t one f r om
a nd
r e s pe c t i ve l y.
Si nc e a c e t i c a c i d wa s us e d i n t he c our s e of
t he e xt r a c t i on a nd pur i f i c a t i on of t he a l ka -
di f f e r onl y i n t he c onf i gur a t i on of t he i r
a l l yl i c a l c ohol gr oups , a nd t hi s di f f e r e nc e i s
bor ne out by t he c he mi c a l s hi f t s of t he i r C- l
l oi ds , 2- a c e t oxyt a xodi ne
a nd
i s ot a xodi ne
c oul d c onc e i va bl y be
ol e f i ni c pr ot ons :
i ve l y ( c f . a nd
At hr oc upr e s s i ne
~5. 75 a nd
a bove ) .
r e s pe c t -
by a c yl a t i on of
a nd
a
r e s pe c t i ve l y.
r a pi d s ma l l - s c a l e
To t e s t t hi s pos s i bi l i t y,
i s
a
l owe r homol ogue of
e xt r a c t i on of t he f r e s h pl a nt ma t e r i a l wa s
c a r r i e d out , a nd t he c r ude a l ka l oi ds we r e
i s ol a t e d us i ng di l ut e s ul phur i c i ns t e a d of
a c e t i c a c i d t o s e pa r a t e t he ba s i c f r a c t i on.
t he known a l ka l oi d 0- me t hyl a t hr oc upr e s s i ne
t o whi c h i t s hows ge ne r a l s i mi l a r i t y i n
s pe c t r a . Howe ve r , i t ha s one l e s s me t hoxyl ,
but i t ha s i ns t e a d phe nol i c gr oup f r om t he
a
a
ba t hoc hr omi c s hi f t i n i t s uv s pe c t r um on
a ddi t i on of a l ka l i , a nd f r om i t s pos i t i ve
The pr e s e nc e of
a nd
t he r e i n wa s e s t a b-
l i s he d by t he ms t e c hni que of mul t i pl e
s t a bl e pe a k
Gi bbs r e a c t i on" .
i ndi c a t e s t ha t t he phe nol i c gr oup ha s
pos i t i on a nd i s t hus a t t a c he d t o C- 15 or
The s e c ond a l t e r na t i ve i s e vi de nt l y
t he c or r e c t one , s i nc e i r r a di a t i on of t he onl y
The l a t t e r obs e r va t i on
a
f r e e
t o C- 18.
a r oma t i c pr ot on i n t he
pr oduc e d a n on
nmr s pe c t r wn of
a
me t hi ne pr ot on r e s ona t i ng
a r ound 63. 3, whi c h mus t - be a t t a c he d t o t he
a l i pha t i c c a r bon ( C- 3) be a r i ng t he me t hoxyl
m/ z 236
m/ z 223
The pr ot ons of t he l a t t e r gr oup ha ve
gr oup.
t he s a me c he mi c a l s hi f t
0- me t hyl a t hr oc upr e s s i ne
a s t hos e of
EXPERI MENTAL
a nd t he s t e r e o-
c he mi s t r y a t C- 3 f or a t hr oc upr e s s i ne
Thi n- l a ye r c hr oma t ogr a phy
pr e pa r a -
a nd
mus t t hus be t he s a me a s i n
s i nc e t he
e pi me r i c c onf i gur a t i on of t he C- 3 me t hoxyl
t i ve t hi n- l a ye r c hr oma t ogr a phy
c ol umn c hr oma t ogr a phy we r e pe r f or me d wi t h
Me r c k s i l i c a ge l or CAMAG s i l i c a ge l
woul d r e s ul t i n
a va l ue a r ound 62. 75 ( c f .
The s pe c i f i c r ot a t i on a nd t he r e ma i ni ng
s pe c t r os c opi c da t a f or a t hr oc upr e s s i ne a r e i n
f ul l a c c or d wi t h t he s t r uc t ur e a nd s t e r e o-
DSF- 5, a nd t he c ompounds we r e vi s ua l i s e d by
s pr a yi ng wi t h i odopl a t i na t e r e a ge nt or by
e xa mi na t i on unde r uv l i ght . Hi gh- pe r f or ma nc e
c he mi s t r y s hown i n
i s unr e a c t i ve t o di a z ome t ha ne , a nd a n a t t e mpt
t o c onve r t t o wa s uns uc c e s s f ul .
The a l ka l oi ds
The phe nol i c gr oup i n
l i qui d c hr a na t ogr a phy
on 7. 7 25 c m c ol umn wi t h oc t a de c yl
s i l a ne a s s t a t i ona r y pha s e , a nd wi t h buf f e r e d
wa s c a r r i e d out
a
x
a nd

2680
S.
an d I. R. C.
r e duc e d pr e s s ur e a t
a que ous a c e t oni t r i l e f or e l ut i on a t
a
f l ow r a t e
a
t e mpe r a t ur e be l ow
of
2
The me l t i ng poi nt s ( mp) we r e
Ya ni gi mot o Se i s a kus ho mi c r o- me l t -
a r e unc or r e c t e d.
The r e s i due wa s di s s ol ve d i n 10 l i t r e s of
wa t e r a nd a ga i n e va por a t e d t o dr yne s s ; t he
pr oc e s s of di l ut i on a nd e va por a t i on wa s
r e pe a t e d onc e mor e t o r e move mos t of t he
r e c or de d on
i ng poi nt
a
Spe c i f i e d r ot a t i ons we r e me a s ur e d i n c hl or of or m
on
a
PEPOL 60 s pe c t r opol a r i me t e r . Ul t r a vi ol e t
a bs or pt i on s pe c t r a we r e r e c or de d on e t ha nol
a c e t i c a c i d.
s ol ve d i n 10 l i t r e s of wa t e r a nd t he s ol ut i on
wa s ba s i f i e d t o 8- 9 wi t h a mmoni a ( d 0. 88) .
Fi na l l y t he r e s i due wa s di s -
s ol ut i ons wi t h
s pe c t r ophot ome t e r , a nd t he e xt i nc t i on c oe f f i c -
i e nt s a r e gi ve n i n pa r e nt he s i s .
s pe c t r a we r e r e c or de d on c hl or of or m s ol ut i ons
a Hi t a c hi - Pe r ki n- El me r 124
The he a vy pr e c i pi t a t e t ha t f or me d wa s l e f t
ove r ni ght t o s e t t l e , t he n f i l t e r e d of f t hr ough
I nf r a r e d
Supe r c e l .
The dr i e d pr e c i pi t a t e wa s
c hl or of or m unt i l t he r e s i due
wi t h
a Be c kma n I R- 33 s pe c t r ome t e r .
Pr ot on
ga ve
a
ne ga t i ve Ma ye r ' s t e s t , a nd t he f i l t r a t e
ma gne t i c r e s ona nc e
s pe c t r a we r e r e c or d-
The
c ombi ne d c hl or of or m s ol ut i ons we r e e xt r a c t e d
wi t h 5% ( w/ v) s ul f ur i c a c i d ( 30 150 ml )
The a que ous a c i d
wa s l i ke wi s e e xt r a c t e d wi t h c hl or of or m.
e d on de ut e r oc hl or of or m s ol ut i ons wi t h
me t hyl s i l a ne a s i nt e r na l s t a nda r d, a t
x
wi t h
ot he r wi s e s pe c i f i e d; t he 270 MHz ' H- nmr s pe c t r a
we r e r e c or de d wi t h Br uke r HX- 270 s pe c t r ome t e r .
a J e ol J NM- 4H- 100 s pe c t r ome t e r unl e s s
unt i l f r e e f r om a l ka l oi ds .
s ol ut i on wa s ba s i f i e d wi t h a mmoni a ( d 0. 88)
a nd a ga i n t hor oughl y e xt r a c t e d wi t h c hl or o-
a
Che mi c a l s hi f t s a r e gi ve n i n ppm, a nd pe a ks a r e
de s c r i be d a s s i ngl e t s ( s ) , doubl e t s ( d) ,
f or m ( 20
x
150 ml ) .
The c ombi ne d c hl or of or m
a nd e va por a t e d
e xt r a c t s we r e dr i e d
t r i pl e t s ( t ) , qua r t e t s
Ma s s s pe c t r a we r e r un on
or mul t i pl e t s
Va c uum Ge ne r a l
unde r r e duc e d pr e s s ur e t o gi ve
a l ka l oi ds .
4 g of c r ude
a
Mi c r oma s s 7070
F s pe c t r ome t e r by t he di r e c t
XSOLATION, PURIFICATION,
i ns e r t i on t e c hni que a t 200" a nd 70
The c r ude a l ka l oi d mi xt ur e
( 2. 00 g) wa s s e pa r a t e d by pt l c ( 7%
i nt o f r a c t i ons :
a mount e d t o 0. 12 g, a nd c ont a i ne d
t wo c ompone nt s f r om ( 30% The
A vouc he r s pe c i me n of t he pl a nt ma t e r i a l ha s
be e n de pos i t e d i n t he c ol l e c t i on of dr i e d pl a nt
s pe c i me ns i n t he Che mi s t r y De pa r t me nt , Uni ve r s -
i t y of Ta s ma ni a .
7
Twi gs a nd l e a ve s of Pe nc i l Pi ne
we r e c ol l e c t e d a r ound t he uppe r r e a c he s of t he
Ous e Ri ve r ne a r t he Gr e a t La ke , Ta s ma ni a , i n
mi xt ur e wa s s e pa r a t e d by t r i pl e de ve l opme nt pt l c
wi t h t he s a me s ol ve nt s ys t e m. The hi ghe r
Ma y, 1980, a nd we r e
pos s i bl e a f t e r c ol l e c t i on i n 150 l i t r e s of
me t ha nol .
ma t e r i a l wa s r e move d, a i r dr i e d f or one da y,
t he n put t hr ough c ompos t s hr e dde r . The dr y
pl a nt ma t e r i a l ( 100 kg) wa s t he n pe r c ol a t e d
wi t h me t ha nol unt i l t e s t s a mpl e ga ve
a s s oon a s
c ompone nt ( 16 mg) wa s obt a i ne d a s
ye l l owi s h
oi l , a nd pr ove d t o be i de nt i c a l wi t h t he known
a l ka l oi d
Af t e r t hr e e da ys , t he pl a nt
( C = 1. 6) ;
284
a
219 nm ( 3900) ;
1210, 1120 c m- ' ;
5. 88 ( c ,
3000, 2920, 2840, 1460,
H nmr : 6. 7 ( s ,
5. 5 ( bs ,
6. 6 ( s ,
a
a
3. 21 ( s , 3H)
ne ga t i ve r e a c t i on wi t h Ma ye r ' s r e a ge nt . The
c ombi ne d e xt r a c t s we r e c onc e nt r a t e d unde r
a nd a n unr e s ol ve d numbe r of pr ot ons be t we e n
1. 5 a nd 3. 5 6; m/ z : 313
r e duc e d pr e s s ur e a t
t o t hi c k gummy da r k br own s yr up, whi c h wa s
di s s ol ve d i n 10 l i t r e s of wa r m gl a c i a l a c e t i c
a c i d.
a t e mpe r a t ur e be l ow 40° C
a
de r i va t i ve mp
unde pr e s s e d on a dmi xt ur e wi t h a n a ut he nt i c
s a mpl e .
The s ol ut i on wa s pour e d i n
a f i ne
s t r e a m i nt o 50 l i t r e s of wa t e r , whi c h wa s
s ubj e c t e d s i mul t a ne ous l y t o vi gor ous
The l owe r
c ompone nt ( 19
wa s ob-
t a i ne d a s whi t e ne e dl e s f r om he xa ne ,
i de nt i c a l wi t h t he known
a gi t a t i on wi t h
e xt r a c t wa s l e f t t o s t a nd ove r ni ght , a nd t he
pr e c i pi t a t e t ha t s e t t l e d f i l t e r e d of f ,
a vi br omi xe r .
The di l ut e a c i d
a l ka -
l oi d
mp a nd mi xe d
mp wi t h a n a ut he nt i c s a mpl e : 100- 110" ;
wa s he d wi t h wa t e r unt i l f r e e f r om a l ka l oi ds ,
t he n di s c a r de d.
+ 91"
= 1. 5) ;
228
275 nm ( 260) ;
3010, 2920, 2850, 1700,
The wa s hi ngs c ombi ne d wi t h t he a c i d a que ous
s ol ut i on we r e e va por a t e d t o dr yne s s unde r
1470, 7220 c m- ' ;
5. 58 ( bs , 3. 92 ( s ,
nmr : 6. 57
3. 22
( s ,

a l ka l oi ds - 1
2681
( s ,
numbe r of pr ot ons be t we e n 1. 5 a nd 3. 5 6;
22) ; 359. 2085,
301
3. 28 ( s ,
a nd a n unr e s ol ve d
a que ous s odi um hydr oxi de : 210, 250, 298 nm;
3380, 3000, 2920, 2840, 2500, 2450, 1210
f or
nmr : 6. 78 ( s ,
3. 87 ( s ,
6. 63
5. 52
a nd a n
m/ z 359 ( M+,
359. 2298; 328
178
( bs ,
3. 22 ( s ,
unr e s ol ve d numbe r of pr ot ons be t we e n 1. 5 a nd
254
165
146 ( 25) .
( 0. 199 g) a l s o c ont a i ne d t wo c ompon-
( 5% t he mi xt ur e wa s
3. 5
m/ z : 315
f or
256
315. 1833,
315. 1834; 284 257
178
e nt s f r om
240
137 ( 25) .
( 0. 165 g) a ppe a r e d t o be
nmr s pe c t r um, but va r i e t y of
165
s e pa r a t e d by doubl e de ve l opme nt pt l c wi t h t he
The c ompone nt of l owe r
s a me s ol ve nt s ys t e m.
146
4
a mi xt ur e
( 51. 7 mg) pr ove d t o be
a ne w
f r om
a
a l ka l oi d, a t hr oc upr e s s i ne
s ol ve nt s ys t e ms f a i l e d t o s e pa r a t e i t by pt l c .
The s e pa r a t i on wa s f i na l l y a c hi e ve d by hpl c wi t h
+
102. 23
=
xma x: 227
dr op
280 nm ( 940) ; a f t e r a ddi t i on of
a
a c e t oni t r i l e / wa t e r
a nd
buf f e r e d t o
3. 0
of 5% a que ous s odi um hydr oxi de : 237 a nd 298
3500, 3400, 3000, 2920, 2840, 1600, 1490,
f or e l ut i on. The
1310, 1120, 750
nmr ( 270
3. 94 ( s ,
a nd a n unr e s ol ve d numbe r of
6. 39
mi xt ur e of a l ka l oi ds ( 15 mg) wa s di s s ol ve d i n
ml of t he s ol ve nt s ys t e m a nd i nj e c t e d i n 200
a l i quot s ; e a c h r un r e qui r e d 32. 4 mi n. The
s e pa r a t e d f r a c t i ons we r e bul ke d a nd ba s i f i e d
5. 65
3. 28
3. 82 ( s ,
pr ot ons be t we e n 1. 5 a nd 3. 5 6. Whe n t he s i ngl e t
pr ot on a t 6. 39 wa s i r r a di a t e d, t he pr ot on
s i gna l a r ound
wi t h a que ous
( d
t he n e xt r a c t e d
3. 3 s howe d
25) ;
a
nuc l e a r Ove r ha us e r
345. 1944,
wi t h di c hl or ome t ha ne , e va por a t i on of whi c h
yi e l de d t he t wo s e pa r a t e d c ompone nt s . The mi nor
e f f e c t ; m/ z : 345
f or
c ompone nt ( 4. 9 mg) wa s i de nt i f i e d a s
345. 0378; 314
178
287
e r yt hr a t i ne
170" 1. 4) ;
mp
286
272
165
=
240
290 nm ( 5000) ;
1460, 1456,
6.58 (s,
146 ( 35) ; f ound: C 69. 19;
r e qui r e s : 69. 56;
pos i t i ve t e s t wi t h
8. 33; N 4. 05;
vma x: 3420, 3000, 2920, 2850,
1260
C
H
7. 82;
N 4. 05%.
At hr oc upr e s s i ne ga ve
Gi bbs ' r e a ge nt .
a
5.92 (s,
5. 78 ( bs ,
4. 38 ( bs ,
3. 32
a nd a n unr e s ol ve d
of
The c ompone nt of hi ghe r
( 20. 7 mg)
pr ot ons be t we e n 1. 5 a nd 3. 5 6; m/ z : 329
50) ;
c ont a i ne d t wo c ompounds pr e s e nt i n ve r y s ma l l
a mount s , i ns uf f i c i e nt f or s a t i s f a c t or y s e pa r -
329. 16407,
f or
255
329. 16778; 298
181
271
194
( 7. 8 mg)
219
a t i on.
t he mi xt ur e a ppe a r e d t o c ons i s t of t he t wo
a c e t yl de r i va t i ve s a nd xma x:
Fr om s pe c t r os c opi c a nd c he mi c a l da t a ,
162 ( 32) .
The ma j or c ompone nt of f r a c t i on
pr ove d t o be homoe r yt hr a t i ne
63. 61 ( C = 3. 63;
4
mp
270 a nd 207 nm ( no c ha nge on a ddi t i on of di l .
3400, 3000, 2920, 2840, 1730,
288 nm ( 1316) ;
3380, 2920, 2840,
nmr : 6. 82 ( s ,
5. 52 ( bs ,
1680, 1510, 1240
nmr : 6. 80 ( m,
3. 84
1490, 1470, 1240, 1040
5. 55 ( m,
3. 28 ( s ,
3. 92 ( s ,
6. 65
4. 35 ( m,
numbe r of pr ot ons be t we e n 1. 5 a nd 3. 5
5. 93
211 ( s , 3H) a nd a n unr e s ol ve d
3. 3 ( s , 3H) a nd a n unr e s ol ve d
numbe r of pr ot ons be t we e n 1. 5 a nd 3. 5 6; m/ z :
m/ z :
270
373
40) ;
373. 1912,
f or
329
50) ;
329. 16778, 298
254
329. 16407,
f or
373. 1910; 342
341
330
271
314
313
297
162
282
255
242
69. 38,
194
272
261
260
260
236
132 ( 72) .
181
162 ( 25) ; f ound:
r e qui r e s :
C
H
7. 46,
223
176
N 4. 21;
N 4. 25.
C
69. 30,
H 6. 99,
Fr a c t i on
f r om
( 0. 149 g) c ont a i ne d t wo c ompone nt s
( 8% whi c h we r e s e pa r a t e d
Fr a c t i ons
a nd
a ppe a r e d f r om
t o c ont a i n
by pt l c wi t h t he s a me s ol ve nt s ys t e m. The
c ompone nt of hi ghe r wa s non- a l ka l oi da l , a nd
t he s a me t wo c ompone nt s i n di f f e r e nt pr opor t i ons .
The c ombi ne d f r a c t i ons ( 0. 157 g) we r e s e pa r a t e d
t ha t of l owe r
wi t h t a xodi ne
( 0. 5, 6. 6 mg) pr ove d i de nt i c a l
mp 150- 152"
by pt l c ( 5%
doubl e de ve l opme nt ) , a nd
the subfraction of lower Rf (10.7 mg) yi e l de d
111.0
= 0.9);
209
230
mp
291 nm (861); a f t e r a ddi t i on of
a
dr on of 5%

2682
S.
and I., R. C.
51. 47 ( C = 1. 03) ;
212
The t hi r d s ubf r a c t i on ( 5. 7 mg) wa s obt a i ne d
i n t oo s ma l l qua nt i t y f or a de qua t e s t udy.
Fr a c t i on pr ove d t o be de voi d of a l ka l oi ds .
HYDROLYSIS OF 2-ACETOXYTAXODINE and
The mi xt ur e of a l ka -
( 10 mg) f r om f r a c t i on wa s
230
283 nm ( 750) ; a f t e r a ddi t i on of
a
a
dr op of 5% a que ous s odi um hydr oxi de : 218, 250,
7
a nd 298
1448,
3380, 3000, 2920, 2840, 1560,
1200, 1150
nmr : 6. 86
4.3 (bin,
6. 65 ( s ,
l oi ds
a nd
2
3. 85 ( s ,
3. 28 ( s , 3H) a nd a n unr e s ol ve d
di s s ol ve d i n a que ous me t ha nol
10 ml ) a nd
numbe r of pr ot ons be t we e n 1. 5 a nd 3. 5
m/ z :
di l ut e s odi um hydr oxi de
2
ml ) wa s a dde d.
60) ;
331. 1785,
273
f or
331
The s ol ut i on wa s r e f l uxe d f or
4 hour s , t he n
331.1783; 300
272
162 (30).
( 80 mg) f r om
wa s s e pa r a t e d by hpl c wi t h
s ol ve nt s ys t e m ma de up of t wo s ol ut i ons , A a nd B:
s ol ut i on c ont a i ne d a nd
buf f e r s ol ut i on
2. 5, a nd t r i e t hyl a mi ne
257
c ool e d t o r oom t e mpe r a t ur e a nd ne ut r a l i s e d
wi t h di l ut e s ul f ur i c a c i d ( 5%) . The ne ut r a l
s ol ut i on wa s e xha us t i ve l y e xt r a c t e d wi t h c hl or -
256 194
178
The c ompone nt of hi ghe r
f r a c t i ons a nd
5
6
a
of or m, a nd t he e xt r a c t on e va por a t i on l e f t
a
r e s i due ( 5 mg) whos e c ompone nt s ga ve t he s a me
a nd ms a s t hos e of a ut he nt i c s pe c i -
A
a
of
me ns of 2- hydr oxyt a xodi ne
a nd
a nd s ol ut i on
Sol ut i ons
The
ml of
i s ot a xodi ne
r e s pe c t i ve l y.
c ons i s t e d of THF/ a c e t oni t i r l e
OXIDATION OF
A
A a nd B we r e mi xe d i n t he r a t i o
mi xt ur e of a l ka l oi ds wa s di s s ol ve d i n
of
(13 mg, 0.04 m mol e ) wa s oxi di s e d
5
wi t h
( 40
bi s mut h di c hl or i de ) '
mi xe d s ol ve nt a nd i nj e c t e d on t o t he c ol umn
( ma xi mum vol ume pe r i nj e c t i on 225 The
0. 04 m mol e ) a nd pot a s s i um c a r bona t e
( 50 mg) i n c hl or of or m ( 5 ml ) a t r oom t e mpe r a -
t ur e ove r ni ght .
t he ke t one de r i va t i ve of
obt a i ne d ( 7 mg) , mg 172- 173"
230 ( 9343) 288 nm ( 1094) ; vma x: 2910, 2820,
1680, 1470, 1220, 1110, 1020 nmr :
mi xt ur e wa s s e pa r a t e d i nt o t hr e e s ubf r a c t i ons ,
whi c h we r e bul ke d a nd ba s i f i e d wi t h a que ous
Af t e r s e pa r a t i on by pt l c ( 5%
wa s
( d
t he n e xt r a c t e d wi t h
c hl or ome t ha ne .
The f i r s t s ubf r a c t i on ( 53. 6 mg)
yi e l de d 2- hydr oxyi s ot a xodi ne
not be
whi c h c oul d
60. 69 ( C = 1. 0) ;
6. 77 ( s ,
6.67 (s,
6.1 (s,
a nd a n unr e s ol ve d
6.0
3. 54
240
283 nm ( 850) ; a f t e r
dr op of 5% a que ous s odi um
3400,
3120, 2950, 2870, 1558, 1520, 1450, 1280,
numbe r of pr ot ons be t we e n 1. 5 a nd 3. 5
a ddi t i on of
a
m/ z 327
65) ;
327.14668; 284
241 240
327. 14669,
269
211
149 (25).
f or
hydr oxi de : 218, 250, a nd 298 nm;
268
192
1226, 1050
6.575, 5.575
H nmr ( 270 MHz ) : 6. 725
4.3 (bm,
179
DEHYDROXYLATION OF
A s a mpl e of ( 13. 5 mg,
s ol ve d i n ml of dr y be nz e ne a nd t r e a t e d wi t h
160
3. 85 ( s ,
3. 28 ( s , 3H) a nd a n unr e s ol ve d
mol e ) was di s -
numbe r ' of pr ot ons be t we e n 1. 5 a nd 3. 5 6; whe n
t he mul t i pl e t a t 63. 4 wa s i r r a di a t e d, t he
5
f r e s hl y di s t i l l e d t hi onyl c hl or i de ( 2 ml ) . The
r e a c t i on mi xt ur e wa s s t i r r e d a t r oom t e mpe r a t ur e
s i ngl e t a t 66. 725 s howe d a n
a nd whe n t he
mul t i pl e t a t 62. 2 wa s i r r a di a t e d, t he s i ngl e t
f or
2 hr , t he n e va por a t e d t o r e move e xc e s s of
a t 66. 575 s howe d a n
331. 1785,
m/ z : 331
f or
273
60) ;
t hi onyl c hl or i de a nd s ol ve nt . The r e s i due f r om
t he r e a c t i on mi xt ur e wa s r e di s s ol ve d i n
331.1783; 300
272
257
be nz e ne / THF ( 3 ml : 100 ml ) a nd t r e a t e d wi t h LAH
256
194
178
162 (30).
The mi xt ur e wa s r e f l uxe d ove r ni ght ,
( 100 mg) .
The s e c ond s ubf r a c t i on ( 9. 3 mg) c ons i s t e d
mi xt ur e of a nd whi c h c oul d not be
f ur t he r s e pa r a t e d.
t he n e xc e s s of LAH wa s de s t r oye d by a ddi ng wa t e r
The pr e c i pi t a t e wa s r e move d by f i l t r a t i on, a nd
wa s he d unt i l f r e e f r om a l ka l oi d. The f i l t r a t e
of
a
The ma s s s pe c t r um of t he
mi xt ur e s howe d di f f e r e nc e s i n i nt e ns i t y onl y
a s c ompa r e d wi t h t hos e of a nd nmr of
( a f t e r e l i mi na t i on of t he pr ot on s i gna l s
wa s e xt r a c t e d wi t h c hl or of or m ( 3
t he c ombi ne d e xt r a c t s we r e dr i e d
x
50 ml ) , a nd
a nd
The
e va por a t e d unde r r e duc e d pr e s s ur e .
r e s i due wa s s e pa r a t e d by pt l c ( 7%
f r om
6. 675
6.55 (s,
3. 75
5.75
4.3
3. 25
t o gi ve ' a pr oduc t ( 10
nmr , ms ) wi t h
i de nt i c a l ( i r , uv,
The mp of t he
( s ,
a nd a n unr e s ol ve d numbe r of pr ot ons
be t we e n 1. 5 a nd 3. 5

2683
alkaloids--I
de r i va t i ve wa s not de pr e s s e d on a dmi xt ur e
wi t h t he c or r e s pondi ng de r i va t i ve of
283 nm ( 4, 167) ; a f t e r a ddi t i on of
dr op of 1% a que ous s odi um hydr oxi de : 237 a nd
298 nm; 3500, 3400, 3010, 2920, 2850,
1670, 1580, 1500, 1450, 1350, 1310, 1270, 1210,
a
OXIDATTON OF HOMOERYTHRATINE
of ( 13 mg, 0. 04 m mol e ) wa s oxi di s e d wi t h
bi s mut h c hl or i de ) ' ( 40
A
1160, 1120, 1050
nmr : 6. 77 ( s ,
3. 725 ( s ,
0. 04 m mol e ) a nd pot a s s i um c a r bona t e ( 50 mg)
i n c hl or of or m ( 5 ml ) a t r oom t e mpe r a t ur e ove r -
6. 55 ( s ,
3. 425
6. 05 ( s ,
a nd a n unr e s ol ve d numbe r of
Af t e r s e pa r a t i on by pt l c ( 5%
ke t one i de nt i c a l ( i r , uv,
ni ght .
pr ot ons be t we e n 1. 5 a nd 3. 5 6; m/ z : 329
329. 1668, f or
271 243
nmr , ms )
a
30) ;
wi t h t ha t f or me d by
of
a
c or r e s pondi ng oxi da t i on
329. 1627; 286
228
242
wa s obt a i ne d ( 8 mg) .
212
192
160
DEHYDROXYLATION OF
of ( 50 mg,
A
85
83 ( 100) .
m mol e ) wa s c onve r t e d
OXIDATION OF
A
t o t he c or r e s pondi ng c hl or i de wi t h t hi onyl
c hl or i de ( 2 ml ) i n dr y be nz e ne ( 5 ml ) a s
s a mpl e of
wi t h
( 28 mg, 0. 084
mol e ) wa s
bi s mut h di c hl or -
The c r ude pr oduc t wa s
( ZOO i n ml of dr y
de s c r i be d a bove .
r e duc e d wi t h
i de ) ' 129 mg, 0. 12 m mol e ) a nd pot a s s i um c a r b-
ona t e ( 50 mg) i n c hl or of or m ( 5 ml ) a t r oom
t e mpe r a t ur e ove r ni ght . Af t e r s e pa r a t i on by
3
be nz e ne a nd 10 ml of THF. The pr oduc t ( 25
mg) wa s i de nt i c a l ( i r , uv,
nmr , ms ) wi t h
pt l c ( 5%
t he ke t one de r i va t i ve
wa s obt a i ne d ( 17 mg) a s c ol our l e s s oi l ;
230 283 ( 4, 160) ; a f t e r a ddi t i on
of
a
DEHYDROXYLATION OF
A s a mpl e of
( 28 mg, 0. 084 m mol e ) wa s c on-
of
a
dr op of 1% s odi um hydr oxi de : 237 a nd 298
3500, 3400, 3010, 2920, 2850, 1670,
ve r t e d t o t he c hl or i de de r i va t i ve wi t h t hi onyl
c hl or i de ( 1. 5 ml ) i n dr y be nz e ne ( 3 ml ) a s
nm;
1570, 1500, 1450, 1310, 1270, 1210, 1160, 1120,
The c r ude pr oduc t wa s r e duc e d
i n ml of dr y be nz e ne a nd 10
de s c r i be d a bove .
wi t h LAH
1050
nmr : 6. 675 ( s ,
3. 425 ( s ,
6. 0 ( s ,
3
3. 85 ( s ,
a nd a n unr e s ol ve d
The pr oduc t ( 4. 1 mg) wa s i de nt i c a l
nmr , ms ) wi t h t a xodi ne
ml of THF.
( i r , uv,
numbe r of pr ot ons be t we e n 1. 5 a nd 3. 5 6; m/ z :
329. 1658,
271
f or
270
70) ;
329. 1627; 286
242
329
DEHYDROXYLATION OF
A s a mpl e of
( 28 mg, 0. 084 m mol e ) wa s c on-
243
240
226
( 80) .
192
ve r t e d t o t he c or r e s pondi ng c hl or i de wi t h t hi onyl
c hl or i de ( 1. 0 ml ) i n dr y be nz e ne ( 3 ml ) a s de s -
160
OXIDATION OF
85
and
The mi xt ur e of
The c r ude pr oduc t wa s r e duc e d wi t h
ml of dr y be nz e ne a nd 10 ml of
c r i be d a bove .
a nd
LAH ( 100 mg) i n
3
( 3 mg) f r om f r a c t i ons 5- 6 wa s oxi di s e d wi t h
bi s mut h di c hl or i de ) '
The pr oduc t ( 6 mg) ha d mp
230 283 nm ( 5460) ; a f t e r
dr op of 5% a que ous s odi um hydr ox-
3400, 2920, 2840,
1855, 1500, 1450, 1270, 1210, 1100, 1080 c m- l ;
nmr : 6. 70 ( s , 5. 55 ( bs , 3. 8
3. 25 ( s , 3H) a nd a n unr e s ol ve d numbe r of
be t we e n 1. 5 a nd 3. 5 6; m/ z : 315 35) ;
THF.
219
mg) a nd
mg of pot a s s i um hydr oge n c a r bona t e
Two
a ddi t i on of
a
i n ml of c hl or of or m f or
1
2 hour s .
i de : 220, 253 a nd 295 nm;
oxi da t i on pr oduc t s we r e obt a i ne d, whi c h we r e
s e pa r a t e d by mul t i pl e de ve l opme nt pt l c ( 5%
The pr oduc t wi t h t he hi ghe r
va l ue c or r e s ponde d t o t he ke t one obt a i ne d by
oxi da t i on of
whe n t he y we r e c hr oma t ogr a phe d
315. 1833,
257
f or
256
315. 1834; 284
178 ( l oo) ,
unde r t he s a me c ondi t i ons , a nd t he pr oduc t of
240
l owe r
c or r e s ponde d t o t ha t f or me d f r om
ACKNOWLEDGEMENTS
165
146
137 ( 25) .
OXIDATION OF
A sample
0. 084 m mol e ) wa s oxi di s e d wi t h
bi s mut h di c hl or i de ) '
We t ha nk t he Uni ve r s i t y of Ta s ma ni a f or
a
Pos t gr a dua t e Re s e a r c h Sc hol a r s hi p ( t o SP) a nd
t he Aus t r a l i a n Re s e a r c h Gr a nt s Sc he me f or
f i na nc i a l a s s i s t a nc e f or t hi s wor k. We a r e
( 0. 12 g, 0. 12 m mol e ) a nd pot a s s i um c a r bona t e
( 50 mg) i n c hl or of or m ( 5 ml ) a t r oom t e mpe r a -
t ur e ove r ni ght .
t he ke t one de r i va t i ve of
obt a i ne d a s c ol our l e s s oi l ;
Af t e r s e pa r a t i on by pt l c ( 5%
gr a t e f ul
t o Or s . R. G. Powe l l a nd
( 15 mg)
230
Pot i e r f or gi f t s Of a l ka l oi d s a mpl e s , a nd t o
a

2684
S.
and I. R. C.
J.A. La mbe r t on f or a s s i s t a nc e i n c a r r yi ng
La ngl oi s , B. C. Da s , P. Pot i e r , a nd L.
La c ombe ,
(1970).
D. De bour ge s a nd N. La ngl oi s , J. Nat.
Products, 163 ( 1982) .
out t he hpl c s e pa r a t i ons . The 270 MHz
s pe c t r a we r e r e c or de d a t t he Aus t r a l i a n
nmr
France,
Na t i ona l NMR Ce nt r e i n Ca nbe r r a , a nd t he ma s s
s pe c t r a t oge t he r wi t h t he mul t i pl e me t a s t a bl e
pe a k moni t or i ng da t a by t he Ce nt r a l Sc i e nc e
La bor a t or y, Uni ve r s i t y of Ta s ma ni a .
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