Pergamon

0146-6380(94)00110-3
Org. Geochem, Vol. 23, No. 1, pp. 21-27, 1995
Copyright 1995 Elsevier Science Ltd
Printed in Great Britain. All rights reserved
0146-6380/95 $9.50 + 0.00
Occurrence of 28-nor-18~-oleanane in the hydrous pyrolysate of a
lignite
CARIM ARMANIOS, l ROBERT ALEXANDER, l ROBERT I. KAGI, I
BRIAN W. SKELTON 2 and ALLAN H. WHITE 2
~Australian Petroleum CRC/Centre for Petroleum Environmental Organic Geochemistry, Curtin
University of Technology, GPO Box U 1987, Perth, Western Australia 6001 and 2Department of
Chemistry, University of Western Australia, Nedlands, Western Australia 6009
(Received 23 May 1994; returned for revision 28 July 1994; accepted 20 September 1994)
Abstraet--28-nor-18ct-Oleanane has been isolated from the hydrous pyrolysate of a Western Australian
lignite and characterised by a single crystal X-ray structure determination.
Key words--28-nor-18ct-oleanane, triterpane, lignite, X-ray crystallography, ~3C NMR spectroscopy,
molecular sieves
INTRODUCTION
Oleanane and 18ct-oleanane (I) occur in crude oils
and sediments (e.g. Ekweozor and Udo, 1988). These
compounds arise from either the defunctionalisation
of higher plant derived natural product precursors
such as the amyrins or from acid-induced conversion
of other pentacyclic triterpenoids (Ames et al., 1954;
Halsall et al., 1952; Coates, 1967; Rullk6tter et aL,
1994). In immature sediments oleanane is often the
most abundant isomer (according to IUPAC rules
"oleanane" has 18fl stereochemistry), but with in-
creasing maturation the more thermodynamically
stable 18ct-oleanane assumes greater relative abun-
dance (ten Haven and Rullk6tter, 1988; Ekweozor
and Telnaes, 1990). In addition to these two isomers,
24,28-bisnor-18a-oleanane has also been identified in
petroleum (Trendel et al., 1991). In this paper we
report the isolation and identification of 28-nor-18ct-
oleanane from the hydrous pyrolysate of a lignite.
EXPERIMENTAL
Sample
The Heartbreak lignite sample was obtained as
core material. The sample had been sealed in PVC
tubes to prevent moisture loss and exposure to air
during storage. The lignite was from a deposit of
Eocene age located in the Bremer Basin, southeastern
Western Australia.
Isolation of a C29 triterpane
The coal was dried, crushed and extracted with
dichloromethane for 48 h using a Soxhlet apparatus.
The extracted coal (4 x 250 g) was pyrolysed in the
presence of water (150 ml) in a stainless steel vessel
(1L) at 330C for 72h. The aqueous phase was
extracted with dichloromethane and the insoluble
material air dried and extracted with dichloro-
methane. The two extracts were combined and the
solvent removed by distillation. The bitumen extract
(125 g) was subjected to a series of liquid chromatog-
raphy procedures. First the extract was chromato-
graphed on alumina to collect the less polar
components eluted with n-pentane. This fraction was
chromatographed on silica gel to obtain a total
alkane fraction which was then chromatographed on
ZSM-5 molecular sieve to give a branched and cyclic
alkane fraction (4.5 g). A high molecular weight
fraction (0.7 g) enriched in the 28-nor-18ct-oleanane
was obtained by reduced pressure distillation of the
branched and cyclic alkane fraction. This was then
chromatographed on an ultrastable-Y modecular
sieve column 40 x 1 cm i.d. using n-pentane and
fractions were collected. The first eluted fraction,
containing compounds which were too large to be
sorbed by the sieves, was comprised (75% by GC) of
two pentacyclic hydrocarbons, namely a C29 (1) and
a C30 (2) triterpane (Fig. la). The C29 triterpane
(5.8 mg) was fractionally crystallised from the mix-
ture using ethylmethylketone (200 p l) as a solvent.
Recrystallisation from ethylacetate (150/~ 1) gave long
needle-like crystals suitable for a single crystal X-ray
study.
X-ray crystallography
A unique room-temperature diffractometer data
set (T ~ 295 K; Enraf-Nonius machine, monochro-
matic MoK~ radiation, 2 0.71073 ~; co scan mode,
20m~ ~ 45 ) was measured for the unknown C29 triter-
pane (Fig. l(a), peak 1), yielding 2693 independent
reflections, 877 with I >3a ( I ) being considered
o~ 23,1~" 21
22 Carim Armanios et al.
2 4 2 3
I I I
Scheme 1.
2~COOH
NO" 4~.
2 4 23
I I I
"obser ved" and used in the large bl ock least squares
refinement wi t hout absor pt i on correct i on.
NMR spectroscopy
A 13 C spect rum of the unknown C29 t ri t erpane was
obt ai ned using a Bruker ARX- 500 nucl ear magnet i c
resonance spect romet er oper at i ng at 127.77 MHz.
The ~3C chemical shift assi gnment s were recorded
in ppm relative to TMS using CDC13 as i nt ernal
reference.
Gas chromatography-mass spectrometry
The analysis of branched and cyclic al kane
fract i ons by GC- MS was carri ed out using a
Hewl et t - Packar d 5890 Series II gas chr omat ogr aph
connect ed to a HP 5971 mass selective det ect or
oper at i ng at 70eV. The gas chr omat ogr aph was
equi pped with a 4 0 m 0 . 1 8 mm i.d. fused silica
capi l l ary col umn coat ed with a DB- 1 st at i onar y phase
(J & W). Hel i um was used as the carri er gas at a linear
flow velocity of 27 cm/s. The oven was pr ogr ammed
from 70 to 280C at 4C/min.
RESULTS AND DISCUSSION
GC - MS analysis o f triterpanes
The hydr ous pyrol ysat e of a lignite from West ern
Aust r al i a was subjected to sequential t r eat ment with
al umi na, silica gel, and mol ecul ar sieves and finally to
reduced pressure di st i l l at i on to obt ai n a high mol ecu-
l ar weight branched and cyclic al kane fract i on en-
riched in t ri t erpanes. Fi gur e l (a) shows a par t i al
m/ z 191 mass chr omat ogr am of pent acycl i c t ri t erpane
component s in the hydr ous pyrol ysat e. Besides the
homol ogous series of 17g, 21~(H)-hopanes and more-
tanes, four ot her t ri t erpanes were det ect ed (peaks
1 4). An unknown C29 (1) t ri t erpane, which has a
slightly l onger ret ent i on time t han 30-nor hopane (29),
was the most abundant t ri t erpane in this sampl e and
is the subject of this paper. A C30 t ri t erpane (2), also
i sol at ed in this work, was identified by ~3C NMR
spect roscopy to be lupane. GC- MS analysis of the
compound represent ed by peak 2 using a pol ar BP-20
col umn, which enabl ed the compl et e resol ut i on of
l upane from the oleananes, confi rmed t hat it was
al most entirely compri sed of l upane with no de-
tectable cont r i but i on from either ol eanane or 18~-
ol eanane. Anot her C29 t ri t erpane (3), which elutes j ust
before hopane (30), was also observed in a Tert i ary
crude oil from Indonesi a and was previ ousl y t ent a-
tively identified as a 28-nortaraxastane ( Ar mani os
et al., 1994). Lastly, a C30 t ri t erpane (4) was tenta-
tively identified as a t ar axast ane isomer based on
mass spectral features and its report ed G. C. ret ent i on
behavi our (e.g. Rul l k6t t er et al., 1994).
X- ray structure determination o f C29 triterpane
The mol ecul ar structure and st ereochemi st ry of the
i sol at ed C29 t ri t erpane (melting poi nt of 185-186C)
was est abl i shed by a single cryst al X- r ay st udy to be
28-nor-18~-oleanane (II). The weak and limited dat a
avai l abl e from a margi nal l y small specimen woul d
not suppor t meaningful ani sot r opi c t hermal par-
amet er refinement and the i sot ropi c form was refined
t hr oughout for C,O; (x, y, z, Ui,o)n were i ncl uded
const rai ned at est i mat ed values. The assi gnment
of the met hyl subst i t uent di sposi t i on t hroughout ,
nevertheless, appears unambi guous. Convent i onal
residuals R, Rw, on IF[ at convergence were 0.074,
0.060 (statistical weights, deri vat i ve of a 2 ( i ) = a2
I di f f + 0.0004 o4(lain-). Neut r al at om compl ex scatter-
ing fact ors were used, chi ral i t y being assigned from
the expect at i ons of the associ at ed chemistry; compu-
t at i on used the XTAL 3.2 pr ogr am system (Hal l
et al., 1992). Pert i nent results are given in Fig. 2(a)
and Tabl e 1; full mol ecul ar non- hydr ogen geometries
and t hermal and hydrogen par amet er s have been
deposi t ed with the Cambr i dge Cr yst al l ogr aphi c Dat a
Centre.
Crystal data. C29H50, M 398.7. Or t hor hombi c,
space gr oup P212121 (D~, No. 19), a 43.27(3), b
15.91(1), c 7.217(5) ~. V 4970 , ~3. D,. ( Z = 8 )
1.07 g. cm- 3; F(000) 1792. ~Mo 0.6 c m- l ; specimen:
0.04 0.05 x 0.62 mm.
1~C NMR spectroscopy
The ~3C NMR spectrum of the 28-nor-18~-
ol eanane showed 29 resonances which were resolved
with the ai d of DEPT experi ment s into seven methyl,
Occurrence of 28-nor-18ct-oleanane in the hydrous pyrolysate of a lignite 23
m/ z 191
29 2!
17Ix, 2 l l ~( H) - hopanes
mor et anes
t r i t er panes 1-4
( a)
P
30
t 4 31R 31 32
S S R
e~
0
29
29,
30
30
( b )
t j j
31
R
i t s 32 R
50 55 60 65
Retention time (min)
Fig. 1. Partial m/z 191 mass chromatograms showing the presence of 28-nor-18~-oleanane in the hydrous
pyrolysate branched and cyclic alkane fraction from two Australian lignites. (a) Heartbreak lignite from
the Bremer Basin and (b) Loy Yang lignite from the Gippsland Basin.
24 C a r i m A r m a n i o s et aL
twelve methylene, five met hi ne and five quat er nar y
car bon signals. The ~3C NMR chemical shifts
(Tabl e 2) were assigned based on t hose r epor t ed for
24,28-dinor-18et-oleanane (Trendel et al., 1991) and
l upane ( Ammann et al., 1982).
Mass spectrometry
The mass spect rum of 28-nor-18~-oleanane
(Fig. 2b) shows a st rong C29 mol ecul ar i on at m/ z 398
and a base peak at m/ z 191. Fr agment i ons at m/ z 260
~ A
(a)
C19~
C20A
Cl A
C25A
CgA
C11A
C12A
C16A
C17A
CIlM
e 2~ f l . ~ e4A
o ,
Fi g. 2( a )
Oc c ur r e nc e o f 28-nor-18ct-oleanane in t he h y d r o u s pyr ol ys a t e o f a l i gni t e 25
100%
80
. ~ 60
r ~
4 0
2 0
0
55
l
I I
95
109
L L t i7 163
,L
100
191
177
260 " " "
I I " H q - - . _
245 260
, I t 2 ~ 7 " I , I .
2o0 300
" - - m/ z v
( b)
398
383
I
4 0 0
Fi g. 2( b)
Fi g. 2. Pr oj e c t i on o f mol ecul e A n o r ma l t o a nd t h r o u g h t he skel et al " p l a n e s " (a) a nd ma s s s p e c t r u m (b)
o f 28-nor-18t-oleanane i sol at ed f r o m t he h y d r o u s pyr ol ys a t e o f a l i gni t e f r o m We s t e r n Aus t r al i a.
a nd m / z 245 ar e suggest ed t o be due t o ABC- r i ng and
CDE- r i n g f r a gme nt a t i on, respect i vel y,
Ori gi n
28- nor - 18c t - Ol e anane has a likely or i gi n f r om C-28
f unct i onal i sed na t ur a l pr oduc t s such as ol ean- 12- en-
3fl -ol -28-oi c aci d ( I l l ) whi ch occur wi del y in ext ant
pl ant s ( Pant a nd Ras t ogi , 1979; Da s a nd Ma ha t o,
1983). Dur i ng diagenesis, t hese nat ur al pr oduc t pr e-
cur s or s ma y under go def unct i onal i sat i on and hydr o-
genat i on t o gi ve 28- nor - t r i t e r pe noi ds (t en Ha v e n
et al., 1992). Because aci d cat al ys ed i nt er conver si on
o f t r i t er panes o f di fferent skel et al t ypes ma y occur
(e.g. Ames e t aL, 1954; Hal sal l e t al., 1952; Coat es,
Table 1. Non-hydrogen positional and isotropic displacement parameters
At om x y z U x y z U
Molecule A Molecule B
C(I) 0.5890 (5) 0.538 (I) 0.793 (4) 0.047 (8) 0.6559 (5) 0.561 (1) 1.302 (4) 0.062 (9)
C(2) 0.5916 (6) 0.638 (I) 0.819 (4) 0.060 (9) 0.6526 (5) 0.463 (1) 1,327 (4) 0.055 (8)
C(3) 0.5907 (6) 0.679 (I) 0.632 (5) 0.065 (9) 0.6544 (5) 0.422 (1) 1.137 (4) 0.055 (9)
C(4) 0.5627 (6) 0.659 (2) 0.511 (5) 0.053 (9) 0.6836 (6) 0.438 (2) 1.014 (4) 0.050 (9)
C(5) 0.5594 (6) 0,560 (2) 0.499 (4) 0.05 (I) 0.6872 (5) 0.539 ( l ) 1.023 (4) 0.031 (8)
C(6) 0.5317 (5) 0.528 (I) 0.378 (4) 0.037 (8) 0.7119 (6) 0.563 (2) 0.896 (4) 0.051 (9)
C(7) 0.5387 (5) 0.434 (2) 0.330 (5) 0.062 (9) 0.7101 (5) 0.658 (l ) 0.834 (4) 0.044 (8)
C(8) 0.5424 (6) 0.376 (2) 0.487 (4) 0.039 (8) 0.7061 (6) 0.717 (2) 0.996 (4) 0.043 (9)
C(9) 0.5657 (5) 0.414 (1) 0.637 (4) 0.039 (8) 0.6818 (5) 0.683 (l ) 1.132 (4) 0.039 (8)
COO) 0.5608 (6) 0.513 (2) 0.676 (5) 0.054 (9) 0.6860 (5) 0.585 (I) 1.199 (4) 0.041 (8)
C01) 0.5690 (6) 0.358 (2) 0.813 (5) 0.08 (1) 0.6779 (6) 0.742 (2) 1.304 (4) 0.054 (8)
C(12) 0.5789 (5) 0.269 (I) 0.744 (4) 0.054 (9) 0.6692 (5) 0,832 (1) 1.235 (4) 0.048 (9)
C(13) 0.5590 (5) 0.230 (2) 0.606 (4) 0.032 (8) 0.6925 (6) 0.869 (2) 1.102 (4) 0.045 (9)
C(14) 0.5564 (5) 0.284 (2) 0.428 (4) 0.031 (9) 0.6944 (6) 0.809 (2) 0.935 (4) 0.046 (9)
C(15) 0.5356 (6) 0,245 (2) 0.287 (5) 0.07 (l ) 0.7185 (5) 0.845 (1) 0.786 (4) 0.048 (8)
C(16) 0.5428 (6) 0.153 (2) 0.236 (5) 0.061 (9) 0.7096 (5) 0.936 (2) 0.739 (4) 0.057 (9)
C(17) 0.5457 (5) 0.099 (2) 0.413 (4) 0.047 (9) 0.7086 (5) 0.989 (2) 0.903 (5) 0.048 (9)
C(18) 0.5690 (6) 0.137 ( l ) 0.548 (4) 0.035 (8) 0.6850 (5) 0.958 ( I ) 1,042 (4) 0.033 (9)
C(19) 0.5711 (5) 0.083 (2) 0.719 (4) 0.050 (9) 0.6835 (5) 1.017 (1) 1.218 (4) 0.052 (8)
C(20) 0.5798 ( 6) - 0. 012 (2) 0.667 (4) 0.051 (9) 0.6776 (7) 1.114 (2) 1.161 (5) 0.09 (1)
C(21) 0.5576 (6) - 0, 046 (2) 0.535 (5) 0.07 (1) 0.6988 (7) 1.138 (2) 1.013 (5) 0.08 (1)
C(22) 0.5542 (5) 0,009 (2) 0.367 (5) 0.06 (I) 0.7014 (5) 1.085 (2) 0.852 (4) 0.055 (9)
C(23) 0.5324 (6) 0.701 (2) 0.589 (5) 0.08 (l ) 0.7103 (5) 0.394 (1) 1.106 (4) 0.048 (8)
C(24) 0.5648 (6) 0.693 (2) 0.321 (5) 0.08 (I) 0.6779 (6) 0.404 (2) 0.846 (5) 0.08 (1)
C(25) 0.5328 (5) 0.523 (2) 0.817 (4) 0.059 (8) 0.7123 (5) 0.571 (2) 1.322 (4) 0.057 (8)
C(26) 0.5106 (5) 0.364 ( I ) 0.571 (4) 0.051 (8) 0.7381 (5) 0.724 (1) 1.088 (4) 0.059 (9)
C(27) 0.5875 (5) 0.298 (1) 0.338 (4) 0.048 (8) 0.6639 (5) 0.802 (1) 0.837 (4) 0.048 (8)
C(29) 0.6126 (6) - 0. 018 (2) 0.592 (5) 0.08 (I) 0.6446 (6) 1.120 (I) 1.089 (5) 0.065 (9)
C(30) 0.5789 (5) - 0. 062 (1) 0.858 (4) 0.059 (9) 0.6784 (6) 1.163 (2) 1.340 (5) 0.08 (1)
26 Carim Armanios et al.
Table 2. ~3C Chemical shift assignments (ppm relative to
TMS) for lupane (Ammann et al., 1982), 24,28-bisnor-18~-
oleanane (Trendel et al., 1991) and 28-nor-18~-oleanane
24,28-bisnor- 28-nor-
Carbon Lupane 18~-Oleanane 18~-Oleanane
1 40.36 39.81 40.37
2 18.69" 21.51 18.69~
3 42.16 36.63 42.11
4 33.20 30.58 33.26
5 56.36 54.42 56.46
6 18.72" 20.97 18.60~
7 34.42 33.06 33.88
8 41.12 40.49t 40.77
9 50.25 48.55 50.58
10 37.47 37.07 37.44
11 21.88 21.21 20.89
12 26.94 25.03 24.90
13 37.88 43.04 42.98
14 43.08 41.61t 41.50
15 27.36 31.06 31.11
16 35.61 29.66 29.57
17 43.12 43.75 43.69
18 47.69 37.88 37.82
19 44.75 43.94 43.86
20 29.36 31.09 31.05
21 21.93 39.19 39.11
22 40.43 30.41 30.33
23 33.34 20.54 33.35
24 21.57 - - 21.54
25 16.00 14.13 16.25
26 16.08 15.78 15.70
27 14.49 14.91 15.02
28 18.08 - - - -
29 15.13 25.39 25.35
30 22.93 33.74 33.69
*t:~ ~3C resonance assignments are interchangeable.
1967) and such processes have been report ed to occur
in sedi ment s (e.g. ten Haven and Rullk6tter, 1988;
Ekweozor and Telnaes, 1990), it can be inferred that,
provi ded the absence of a subst i t uent at C-28 does
not inhibit the rearrangement processes, 28- nor- 180t -
ol eanane may be derived from a range of ot her
28- nor - t r i t e r pe noi ds .
The presence of 2 8 - n o r - 1 8 ~- o l e a n a n e in the
hydr ous pyrol ysat e but not in the soluble organi c
mat t er indicates t hat it is intimately associated with
the kerogen. This associ at i on may be due to the
t ri t erpane being physically ent rapped or alternatively
being chemically bound to the kerogen.
This occurrence of 28- nor - 18c t - ol e anane in a lignite
formed in a t emperat e climate and the report ed
occurrence of 28- nor olean- 12-ene-3-one in sedi ment s
from t he Mahakam Del t a (Corbet et al . , 1980) de-
posi t ed in very different climatic condi t i ons suggests
t hat 2 8 - n o r - o l e a n a n e s mi ght be more wi despread in
sedi ment ary organi c mat t er of Tertiary age t han has
previously been recognised. A comprehensi ve study
of the occurrence of 2 8 - n o r - 1 8 ~- o l e a n a n e in sedimen-
tary organi c mat t er is beyond t he scope of this paper,
however its presence in the pyrol ysat e of anot her
lignite from a different basin (Fig. l b) suggests to us
t hat it may be common to Tertiary lignites. Dat a
present ed here confi rms doubt s expressed by ten
Haven et al. (1992) regardi ng the aut hent i ci t y of a
previ ous assi gnment of 2 8 - n o r - o l e a n a n e in a Jurassic
coal by Wang et al. (1990). Thei r compound had a
significantly lower GC ret ent i on time (relative to
3 0 - n o r h o p a n e ) compar ed with t hat for our aut hent i c
st andard. One expl anat i on for the apparent absence
of 2 8 - n o r - 1 8 ~- o l e a n a n e in sedi ment s and crude oils is
t hat it is poorl y resolved from C29Ts ( Mol dowan
et al . , 1991) and the spi rot ri t erpane (Hills et al . , 1968)
in gas chr omat ogr ams obt ai ned using common
st at i onary phases and may have gone undet ect ed (e.g.
Ekweozor and Udo, 1988).
As s oc i at e Edi t or A. G. Requejo
Acknowl edgement s - - We thank CRA exploration Pty Lim-
ited for providing the lignite sample and Dr Lindsay Byrne
for carrying out the ~3C NMR analysis. C.A. acknowledges
financial support in the form of an Australian Postgraduate
Research Award (APRA).
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