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Photochemical formation of berberine alkaloids from protopine alkaloids
Tetmhohn ktkrr 110.26, pp. 2M-2M5,
PHOTOCHEMICAL
FORMATION
FROM X.
A.
Super&es
Department
of Chemistry,
of Chemistry,
Delgodo
Tecnologico
Monterrey,
y de
Mexico
P. Reeves
Texas P. D.
Department
lnstituto
de Monterrey, W.
Britain.
ALKALOIDS
ond Jesus Garcia
of Chemistry,
in Great
OF RERRERINE ALKALOIDS
PROTOPINE
Dominguex
Department
Prom Ltd. Printed
1967. POT-
Luthemn College,
Seguin,
Texas
Gardner
University
of Utah,
Salt lake
City,
Utah
(Received 17 April 1967) a-Allocryptopine
(I),
ing spectroscopically membered
ring.
cryptopine
(II)
A significant
family,
Irradiation forded,
after
berberinium
ground state intemction
ante
berberine
of a dilute
chromatogmphy picmte
(34%),
of the ultmviolet
with protopine authentic
epiberberine
solution
of cryptopine
on silica m.p.
between
tmnsformation
(IV),
(V) (II)
(dec)
gave identical
yield
of coptisine
ultraviolet
carbonyl
in 95%
(3).
ethanol
amine
which functions
and infrared
2493
in a ten-
has been shown to exist
under pure nitrogen satumted
was monitored
(1).
members of
and mixed m.p.
215217O
spectra and ran together
for 100 hours afwith picric
by observing
of bards at 350 and 460 9. m.p.
is interest-
(VI).
from 95% ethanol
The reaction
(VI),
of alkaloids
and tertiary
these two functions
and coptisine
gel and recrystallization
220-22Y
comprise a family
of these three substances to corresponding
maximum at 286 mu and appearance
(Ill) gave a 23%
coptisine
(III)
in that each member possesses transannulor
We report here a new type of photochemical the berberine
and proiopine
A similar
(4).
acid,
epi-
the diroppearexperiment
The product and
on three dimensional
TLC.
2494
No.24
Irradiation 255-259.
of a-allocryptopine It was identical
I
II
=
C&O,
R,
=
CHz02)
(R,
=
CH,Oz
(R,
It is interesting
=
afforded
berberine
in all respects with
(R,
Rz = III
(I)
=
which was isolated
an authentic
Cl-$0
Cl$O, R,
(Vi)
ferent
CH20z)
by simple
recrystallization
mechanism
is opemtive
in halogenated
tions of ultraviolet
irradiation.
The reaction
of protopine, starting
for example,
material
It is obvious
when monitored
and product.
m.p.
IV
(R,
and R, as in I)
V
(RI
and R,as
VI
(Rt
and R, as in Ill)
in II)
CYO)
to note that the use of chloroform
(as the nitrate)
nitmte,
sample.
in place of ethanol or methanol
gave the same products but at a more rapid rate and in higher yield. of berberine
as krberinium
solvents
At the termination
that the identification
and sequential
a-allocryptopine
of the photomixture.
very complex in alcohol
showed the presence of five of the run,
only the yellow
gave a 76%
It seems quite
which are known to be good mdical
is undoubtedly
by TLC
Thus,
as the irradiation
spot (UV)
yield
that a dif-
sources under condi-
solvents.
transient
appearance of these intermediates
possible
solvent
The irradiation
species in addition due to coptisine
must be established
to
remained before a
mechanism can be deliniated.
Acknowledgement.
This work was supported
in part by National
Institutes
of Health
Grant
GM 07861.
REFERENCES 1.
E. H. Mottus, action
N.
J.
0.
Halpern,
Leonard,
Record Chem. ---
J. Am. _-
82,
3.
W.
Perkin,
4.
We are indebted slovakia
Marion,
Can. ---
31, =
J. Cham.,
1147
(1953).
state as well
The generality
has been described
of this inter-
by Leonard and
(2).
ibid., -= H.
and L
in the ground state and in some cases in the excited
co-workers 2.
H. Schwarz
4075
Chem. -me
E,
Progr.,
Sot.,
80,
N. >. Leonard, J.
243 (1956).
4858
(1958).
N.
J.
Leomrd,
A.
T. W.
Adamcik,
Milligan
C.
and T.
Djemssi
and
L. Brown,
(1960). Jr.,
J. Chem. _--
to Professor J.
for an authentic
Sot.,
l&,
Slavic,
492
(1918)
Department
sample of coptisine.
reports m.p.
of Medicinal
222’
(dec).
Chemistry,
Purkyne
University,
Czecho-
PHOTOCHEMICAL
FORMATION
FROM X.
A.
Super&es
Department
of Chemistry,
of Chemistry,
Delgodo
Tecnologico
Monterrey,
y de
Mexico
P. Reeves
Texas P. D.
Department
lnstituto
de Monterrey, W.
Britain.
ALKALOIDS
ond Jesus Garcia
of Chemistry,
in Great
OF RERRERINE ALKALOIDS
PROTOPINE
Dominguex
Department
Prom Ltd. Printed
1967. POT-
Luthemn College,
Seguin,
Texas
Gardner
University
of Utah,
Salt lake
City,
Utah
(Received 17 April 1967) a-Allocryptopine
(I),
ing spectroscopically membered
ring.
cryptopine
(II)
A significant
family,
Irradiation forded,
after
berberinium
ground state intemction
ante
berberine
of a dilute
chromatogmphy picmte
(34%),
of the ultmviolet
with protopine authentic
epiberberine
solution
of cryptopine
on silica m.p.
between
tmnsformation
(IV),
(V) (II)
(dec)
gave identical
yield
of coptisine
ultraviolet
carbonyl
in 95%
(3).
ethanol
amine
which functions
and infrared
2493
in a ten-
has been shown to exist
under pure nitrogen satumted
was monitored
(1).
members of
and mixed m.p.
215217O
spectra and ran together
for 100 hours afwith picric
by observing
of bards at 350 and 460 9. m.p.
is interest-
(VI).
from 95% ethanol
The reaction
(VI),
of alkaloids
and tertiary
these two functions
and coptisine
gel and recrystallization
220-22Y
comprise a family
of these three substances to corresponding
maximum at 286 mu and appearance
(Ill) gave a 23%
coptisine
(III)
in that each member possesses transannulor
We report here a new type of photochemical the berberine
and proiopine
A similar
(4).
acid,
epi-
the diroppearexperiment
The product and
on three dimensional
TLC.
2494
No.24
Irradiation 255-259.
of a-allocryptopine It was identical
I
II
=
C&O,
R,
=
CHz02)
(R,
=
CH,Oz
(R,
It is interesting
=
afforded
berberine
in all respects with
(R,
Rz = III
(I)
=
which was isolated
an authentic
Cl-$0
Cl$O, R,
(Vi)
ferent
CH20z)
by simple
recrystallization
mechanism
is opemtive
in halogenated
tions of ultraviolet
irradiation.
The reaction
of protopine, starting
for example,
material
It is obvious
when monitored
and product.
m.p.
IV
(R,
and R, as in I)
V
(RI
and R,as
VI
(Rt
and R, as in Ill)
in II)
CYO)
to note that the use of chloroform
(as the nitrate)
nitmte,
sample.
in place of ethanol or methanol
gave the same products but at a more rapid rate and in higher yield. of berberine
as krberinium
solvents
At the termination
that the identification
and sequential
a-allocryptopine
of the photomixture.
very complex in alcohol
showed the presence of five of the run,
only the yellow
gave a 76%
It seems quite
which are known to be good mdical
is undoubtedly
by TLC
Thus,
as the irradiation
spot (UV)
yield
that a dif-
sources under condi-
solvents.
transient
appearance of these intermediates
possible
solvent
The irradiation
species in addition due to coptisine
must be established
to
remained before a
mechanism can be deliniated.
Acknowledgement.
This work was supported
in part by National
Institutes
of Health
Grant
GM 07861.
REFERENCES 1.
E. H. Mottus, action
N.
J.
0.
Halpern,
Leonard,
Record Chem. ---
J. Am. _-
82,
3.
W.
Perkin,
4.
We are indebted slovakia
Marion,
Can. ---
31, =
J. Cham.,
1147
(1953).
state as well
The generality
has been described
of this inter-
by Leonard and
(2).
ibid., -= H.
and L
in the ground state and in some cases in the excited
co-workers 2.
H. Schwarz
4075
Chem. -me
E,
Progr.,
Sot.,
80,
N. >. Leonard, J.
243 (1956).
4858
(1958).
N.
J.
Leomrd,
A.
T. W.
Adamcik,
Milligan
C.
and T.
Djemssi
and
L. Brown,
(1960). Jr.,
J. Chem. _--
to Professor J.
for an authentic
Sot.,
l&,
Slavic,
492
(1918)
Department
sample of coptisine.
reports m.p.
of Medicinal
222’
(dec).
Chemistry,
Purkyne
University,
Czecho-