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Wandera - A Preliminary Phytochemical Investigation of Croton Macrostachyus Stem Bark
Wandera - A Preliminary Phytochemical Investigation of Croton Macrostachyus Stem Bark
BY
WANDERA,
|WAND CONSTANCE N.
degree.
N iMROBI
Pharmacy Department
Faculty of Medicine
University of Nairobi
KENYA.
JUNE 1986
AND
Mim lughu R. G.
Hamilton 0. Orata
/
Page
Abstract ................
Introduction .............
Figures ..... 42 - 47
I
References 4S
A B S T R A C T
The Maasai of Kenya mix the bark of C. elliotianus with curdled milk
and use it as a purgative. The seed oil from the kernel of the same
Chopped roots are added to soup made from goat's meat, and taken as
a tonic. [4]
along the E. African coast, for colds and stomach aches. [4]
- 3 -
Ethiopia, among other countries. The leaves are boiled and the
decoction drunk for coughs. Ash from burnt leaves is also licked
for coughs. Juice from fresh leaves is applied onto fresh wounds
or venereal diseases. The bark peeled off stems and roots is boiled
skin rashes. The seeds and resin of the plant are poisonous. [4]
The Maasai use the bark decoction mixed with blood, as a tonic. [3]
boiled and applied to the chest for colds by the people along the
asthma. Leaves and twigs are boiled and the juice drunk for
to cattle as a remedy for anthrax, while the leaves are burnt among
- 4 -
Swazi use the bark of C. sylvaticus for gall sickness in cattle, while
in Gazaland, the same is used as a fish poison. The Swazi use the
root for pleurisy and indigestion. [3] The Digo, found along the
while the leaf decoction is used as a wash for body swellings caused
as a purgative. [4]
Transvaal brush bleeding gums with the charred and powdered bark, while
patients. [3]
nausea, and slight purgation in man. The Shangana use the seed for
Croton oil from the seed of C. tiglium has been used as a very
and convulsion. The roots are used to clear the bowels of waste
matter, and seeds find medicinal use in Togo. The Maasai use the
Due to the wide use of plants in this genus, work has been (and is
\
CHAPTER I
Croton genus
alcohols from the Croton and Euphorbia genera. The method employed
and colour reactions on silica gel and alumina, with several different
3. Alumina E with S^ - S ^
Solvent Systems
Sy Chloroform
A - 60% w/w sulphuric acid. Plates were heated at 110°C for 15 minutes.
B - 5% vanillin in cone. 0 ^ 0 4
All plates were viewed in daylight and under UV light at 366 nm. The
when sprayed with the acid-based sprays indicated. The type of adsorbent
i
The diterpene acetates were found to fall into two groups:
(2 b) H 12 - deoxy-phorbol
diacetate
n >
/as found possible to not only separate ingenol and phorbol types, but
ilso, to obtain three times greater resolution within the phorbol types. *
'he main functional groups of the acetates are situated in rings A and B
/hich are similar for both phorbol and ingenol types, except that ingenol
triacetate has an acetate group at C-3 instead of keto, and lacks an c^- OH
3P at C-10, (Junction between rings A and B). This explains the difference
lave lower values because they have more OH groups that provide sites
proton kiyrrilis
C. humilis, and (5b.), was prepared in 5 steps from L -glutamic acid (6)
with NaOH and EtOH; and amidation with ph.CH^CH^NHg with dicyclohexyl
o
H o
Me
\ 1
HC --- C
Me
\ h 2 -- C — OEt
CH 2 CH2-ph
O
(^) R = Me tt>
(5b) R = Et
- 10 -
125° - 127°C;
hypotensive agent.
I
D. S. Bhakuni et at [8] give a full account of the work leading to
as -
1
(8 a) R = R Crotsparine
(8b) R = H; R 1 = Me..N-methyl
Crotsparine
(9a) R = R/ = H Crotsparinine
j jN lV L R N - ^ Pi .vU K U tth
UBKSRX
- 12 -
the most abundant alkaloid in this plant extract was identical (tic, ir
-32°
glaziovine
They concluded therefore, that crotsparine occured as (±) and (-) forms;
(13a) R = H Isocrotsparinine
(13b) R = Re N-methyl
isocrotsparinine
(9a) (6a H) were defined as (6aR 7aS) and (6aS 7aS) respectively,
Croton linearis
very small yield. They concluded that, the new compound was the 8,9
MeO
(16) Diacetylisocrotsparinine
Base E was found to be identical (except f°r its optical rotation) with
(18a) (19) (2 0 )
(18b) (21 ) (2 2 )
R = Ac for b series
HO
- 17 -
and C. trinitatus.
C - 69.61% H - 8.99%
0 - 21.40%
following properties.
species as 112 - 114°C, and from the nnp: and spectral data (JR». NMRj_CD
(24) Blumenol A
O
- 19 -
«»»
Vomifoliol had first been isolated from Rauuolfia vormotoria and was
method.
Oroion draco
Draconin (25) mp 184° - 6° was isolated from C. draco and its structure
determined by UV, IR, Mass and NMR spectra- Several derivatives were
Draconin
Croton tiglium
fje
MeHC = CCOO
in mice. The plant is widely used in folk medicine for treating cancer
>-o ton c o r ij I z f o l i u s
25 -\ EtOH
[<x] - 20° (EtOH) and X 227 nm = 23,800
' v max
methylene (900 cm 1)
(£>1.30 and 1.09) and a terminal methylene group ( S 4.50 and 4.84);
225 nm £ = 1 8 835
b (c d c l 3) 1.18 (3H, s)
1.40 (3H, s)
1.90 (3H, s)
2.05 (3H, s)
4.50 ( 1H, s)
4.87 (1H, s)
♦
H
(28)
Croton jacobensis
CHAPTER 2
-flowers and its fruits which are slightly 3-lobed, are J-inch in
diameter. [2]
Its use in folk medicine for treatment in various ailments has been
chcl3
241° - 2°C [°Gd -10°; the triacetate mp 217 - 218° and tetracetate
hd 153 - 4°C.
- 26 -
(JJ3J mp 143 - 144°C [0^ D - 46° (the structure of which was determined
by X-ray analysis); and (34) mp 145 - 6°C [o C]q 127°; the triacetate,
mp 141 - 2°C 151°; and the tetracetate, which was an oily product.
(30) R = R1 = H (33)
(32) (34)
This function has been shown to confer tumour inhibiting activity to other
3 HO -O
Epoxydone Senepoxyde
(36) '(37)
COOH
'CH2OCOph
,— OCOCH.
OCOCH_ .OH
HO
OH
Seneol Shikimic acid
(38) (39)
o Yohei et al [24] carried out a short term in-vitro assay for
c h 2o c o c 6h 5
(40) Epoxide
- 28 -
It is evident from the above report that not very much v/ork has been
CHAPTER 3
-A third component was isolated from the mother liquor of the pet-ether
extract; and several minor components were observed on tic, but these
Compound 1 (CMSB.1)
failed.
6. Cyclohexane; EtOAc
95 : 2 0.27 0.26 0.23
addition other minor purple spots and a major brick red one.
0=C stretching (1600 - 1680 cm'1), C — H bending in CH2 (1440 - 1480 cm'1)
'yC — (CH7)2 (1380 cm'1) 0 — H bending (1300 and 1360 cm'1); 1040,
an impurity, the IR spectra of CMSB 1.2 (fig. 1a) and lupeol (fig.Jb)
»- /
H
Lupeol
(41 )
The mass spectrum of lupeol (fig. 2a) showed the following prominent
diagnostic peaks.
C 14H21
- 33 -
■iterpenoids. [27]
CH
& 4.69 and 4.57 HA - 29 and He - 29 of 2
3.19 (quartet) H - 3
2.38 (sextet) H - 19
1.69 CH3 C - 30
1.03 - H - 23 0.83 H - 24
0.97 H - 28 0.79 H - 26
0.94 H - 25 0.77 H - 27
The literature m.p of lupeol is 218°C [28]. The one observed is much
brick red spot on tic. The sample could not be purified further because
Identification of betulin
v
• - 34 -
.o yield CMSB 3.2 as a white paste- like substance. CMSB 3.2; together
All three fractions contained a component that always migrated with the
TABLE 2
Authentic
Solvent Systems Fraction 1 CMSB 3.2 Fraction 3
betulin
/
1. CHC13 : Ether (1:1) 0.62 0.62 0.61 0.65
t etulin (42) has been previously isolated from the same plant, and has
Nf
Compound 3 (CHs.2)
I
This was obtained from the mother liquor of the crude petroleum ether
a terpenoid.
When the plate was sprayed with aqueous acetic acid, a white spot against
groups.
be drawn.
E X P E R I M E N T A L
The plant material was collected from Karatina, about 200 km North of
July-August 1985.
The plates were sprayed with anisaldehyde reagent, and placed in the
0.5 ml anisaldehyde
s.
- 37 -
j are uncorrected.
\
ss spectrum was run on a Finnigan 4000 and MAT 312/ss 200 instrument
70 ev e.i.
nknown).
The extract was concentrated to about 150 ml, was placed in a labelled
comcal flask and left in the fridge for 2 weeks, at the end of which
off.
The filtrate was concentrated to about 1/4 its volume, was labelled
(mother liquor 1) and was left in the fridge for about 4 months.
- 38 -
Fraction 1
off, the solution was concentrated and 'left in the fridge for several
days.
were unsuccessful.
The mother liquor from this fraction was concentrated and left in the
- 39 -
fridge for several days. 20.6 mg of CMSB 1.2 were obtained as greenish
in the discussion.
in the discussion.
Fractions 2-5
it suspected to be betulin.
- 40 -
fridge for 3 weeks, at the end of which a brownish sticky material was
deposi ted.
of CMSB 3.2 were each dissolved in chloroform, and all three fractions
Motner liquor 1
At the end of 4^months, a solid had deposited which was filtered off
and was triturated several times with acetone. The resulting white
wnite spot when the plate was sprayed with aqueous acetic acid.
- 41 -
IR ( KBr) \! max
- Z b -
------- — ^ —£ £ — fe^rvt^ nc- Lnc>r^l
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S LIST DATA: 8511256 ft 33
25/85 18: 13: 00 + BASE M/E: 20
1 :0 6 CALI: RW ft 3
PLE: C. M. P . 1 .1
R IC : 28eo
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+ -
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o I
PFRC.ENT TRANSMISSION
- 48 -
r e f e r e n c e s
Phytochemistry 15 ( 2) 332 - 3
161767e )
Pg 377 - 467
18. CHAN W.R; PRINCE E.C; MANCHAND P.S.; SPRINGER J.P; CLAPOY JC’*. t
SIM G. A. (1968)
J. Amer. Chem. Soc. 90 (11 ) 2982 - 3.
C. A. 1966 V o l . 64 12624 g ,
(Shannan Ire!) 13 (1 )
Ho Yohei et al (1981) Cancer Le tters
pg 29 - 37
( C.A. Vol 95 91755a)
per so n al c o m m u n ic a tio n
ADDAE - MENSAH IVAN
- 51 -
(1) Pg 94 - 95.