Org. Geochem. Vol. 6, pp. 63-70, 1984 0146-6380/84 $[13.1~11+11.

0(I
Printed in Great Britain. All rightsrcscrved Copyright 1984 Pergamon Press Lid
Identification of some bicyclic al kanes in petrol eum
ROBERT ALEXANDER l, ROBERT IAN KAGI I, ROHINTON NOBLE l and JOHN K. VOLKMAN 2
~Pet rol eum Ge oc he mi s t r y Gr oup, School of Appl i ed Chemi s t r y, Wes t er n Aust r al i an I nst i t ut e of
Technology, Kent Street, Bentley. Western Australia 61112
2CSIRO Marine Laboratories, Division of Oceanography, GPO Box 1538, Hobart, Tasmania,
Australia 7001
Abstract--Bicyclic alkanes containing the drimane skeleton have been identified in crude oils and
sediments by synthesis of model compounds. Two other bicyclic alkanes, whose skeletons do not conform
to the isoprene rule, have also been identified from mass spectral data. A correlation between the relative
concentration of C2,~ steranes and diasteranes and drimane and two C~5 bicyclanes in an extensive sample
suite, suggests a similar mechanism is involved in the formation of diasteranes and the two C~5 bicyclanes
in the subsurface. The widespread occurrence of drimanes and drimane-related compounds in crude oils
and sediments indicates that these compounds are derived from a ubiquitous source. The presencc of
methyldrimanes in a sample rich in methylhopanes suggests that drimanes and hopanes may be derived
from similar precursors.
Key words: bicyclic alkanes, drimane, rearranged cycloalkanes, petroleum
INTRODUCTION
A wide var i et y of pol ycycl i c al kanes occur in cr ude
oils and sedi ment s, most of which have st ruct ures
der i ved from compounds of bi ol ogi cal ori gi n. Com-
mon exampl es of t hese ar e t he ubi qui t ous seri es of
hopa ne s and mor e t a ne s , whi ch ar e pent acycl i c
t r i t er panes der i ved f r om the t er penoi ds of pr ocar yo-
tic or gani sms ( Ens mi nger et al. , 1974; Van Dor s-
sel aer et aL, 1974). Ther e ar e al so several r epor t s of
t r i cycl i c and t e t r a c yc l i c t e r pa ne s in pe t r ol e um
( Ande r s an Robi ns on, 1971; Reed, 1977; Connan et
al. , 1980; Ekweozor et al . , 1981; Schmi t t er et aL,
1982). Homol ogous seri es of t hese compounds con-
t ai ni ng ext ended side chai ns, ar e now r ecogni sed as
common const i t uent s of cr ude oils and sedi ment s
( Aqui no Net o et al. , 1982; Tr endel et al. , 1982). In
this paper we r epor t on t he i dent i fi cat i on of some
bicyclic al kanes, and exami ne t he di st r i but i on of
t hese compounds in cr ude oils and anci ent sedi ment s.
The sources of bicyclic al kanes in geol ogi cal en-
vi r onment s ar e l ar gel y unknown. Ande r s and Robi n-
son (1971), in t hei r st udy of t he cycl oal kane const i -
t uent s of t he Gr e e n Ri ver Shal e, r epor t ed a seri es of
bicyclic al kanes and suggest ed t hat t hey may have
been der i ved by degr adat i on of st er oi d or t r i t er pe-
noi d pr ecur sor s. Bendor ai t i s (1974) f ound high con-
cent r at i ons of bicyclic al kanes in crude oils from
Sout h Texas. He pr opos ed t hat t hese compounds
r esul t ed f r om degr adat i on of mor e compl ex pr ecur -
sors, in par t i cul ar by t he t her mal degr adat i on of
hi gher pl ant t r i t er penes. Phi l p et al. (1981) suggest ed
t hat l and pl ant der i ved tricyclic compounds wer e a
possi bl e sour ce for bi cycl anes, wher eas Rul l k6t t er
and Wendi sch (1982) pr opos ed t hat t et r acycl i c t er -
panes of t he onocer ane t ype mi ght be t he pr ecur sor s
for t he bicyclic al kanes. In each case, occur r ences of
bi cycl anes have been r el at ed t o t er penoi d pr ecur sor s
cont ai ni ng t hr ee or mor e rings. We now pr esent
evi dence which links t he sources of t hese bicyclic
al kanes t o t hose of t he ubi qui t ous seri es of pent acy-
clic hopanes.
EXPERIMENTAL
Sampl es
Twent y- t wo cr ude oils and 26 sedi ment ext r act s
wer e anal ysed in this st udy. Tabl e 1 cont ai ns some
geol ogi cal and geochemi cal dat a for each sampl e.
The cr ude oils wer e obt ai ned f r om wi del y di st r i but ed
geogr aphi cal l ocat i ons, r epr esent i ng hydr ocar bons
f r om ei ght di f f er ent pet r ol eum- pr oduci ng nat i ons.
Sedi ment ar y r ock sampl es were obt ai ned in t he form
of side wall cores and di t ch cut t i ngs f r om oi l -dri l l i ng
oper at i ons in Wes t er n Aust r al i a.
Sedi ment extraction
Sedi ment ar y r ock sampl es were washed with wa-
t er , ai r dr i ed and crushed to pass t hr ough a 150 ~m
sieve. The cr ushed sedi ment (100 g) was ext r act ed
with di chl or omet hane (400 ml) using a Ki nemat i c
high speed bl ender (10-15 rain). The sedi ment was
r emoved by fi l t rat i on, and t he sol vent evapor at ed to
af f or d t he sol ubl e or gani c mat t er ( SOM) .
Branched/ cycl i c al kanes
Sa t ur a t e d hydr ocar bons wer e s epar at ed f r om
cr ude oils and sedi ment ext r act s ( SOM) by col umn
chr omat ogr aphy using silicic acid. El ut i on of t he
col umn with r edi st i l l ed pent ane af f or ded t he t ot al
sat ur at e al kane fract i on. An al i quot of t he sat ur at e
fract i on was t r eat ed with act i vat ed 5 ,~ mol ecul ar
si eves t o r emove n- al kanes, l eavi ng a mi xt ure of
br anched and cyclic al kanes.
63
ROBERT ALEXANDER el al.
Tabl e 1. Geol ogi cal and geochemi cal dat a for cr ude oils and s edi ment s
Sampl e St er ane pa r a me t e r s
Geol ogi cal Source+ Mat uri t y$
Numbe r Type Locat i on age* C27/ C2, , rat i o C2, 20S/20R
1 Cr ude oil Chad
2 Cr ude oil Ni geri a
3 Cr ude oil U. S. A.
4 Cr ude oil De nma r k
5 Cr ude oil U. S. A.
6 Cr ude o i l U. S. A.
7 Cr ude oil U. S. A.
8 Cr ude oil Saudi Ar abi a
9 Cr ude oil Chad
1() Cr ude oil U. S. A.
11 Cr ude oil I ndonesi a
12 Cr ude oil Chi na
13 Cr ude oil Aust r al i a
14 Cr ude oil Aust r al i a
15 Cr ude oil Aust r al i a
16 Cr ude oil Aust r al i a
17 Cr ude oil Aust r al i a
18 Cr ude oil Aust r al i a
19 Cr ude oil Aust r al i a
20 Cr ude oil Aust r al i a
21 Cr ude oil Aust r al i a
22 Cr ude oil Aust r al i a
23 Ext r act Aust r al i a
24 Ext r act Aust r al i a
25 Ext r act Aust r al i a
26 Ext r act Aust r al i a
27 Ext r act Aust r al i a
28 Ext r act Aust r al i a
29 Ext r act Aust r al i a
3(1 Ext r act Aust r al i a
31 Ext r act Aust r al i a
32 Ext r act Aust r al i a
33 Ext r act Aust r al i a
34 Ext r act Aust r al i a
35 Ext r act Aust r al i a
36 Ext r act Aust r al i a
37 Ext r act Aust r al i a
38 Ext r act Aust r al i a
39 Ext r act Aust r al i a
411 Ext r act Aust r al i a
41 Ext r act Aust r al i a
42 Ext r act Aust r al i a
43 Ext r act Aust r al i a
44 Ext r act Aust r al i a
45 Ext r act Aust r al i a
46 Ext r act Aust r al i a
47 Ext r act Aust r al i a
48 Ext r act Aust r al i a
Cr et aceous
Ter t i ar y
Ter t i ar y
Jurassi c
Pennsyl vani an
Cambr i an
Pennsyl vani an
Jurassi c
Cr et aceous
Ter t i ar y
Ter t i ar y
Cr et aceous
Cr et aceous
Cr et aceous
Cr et aceous
Cr et aceous
Jurassi c
Devoni an
Ter t i ar y
Tri assi c
Cambr i an
Devoni an
Cr et aceous
Cr et aceous
Cr et aceous
Cr et aceous
Jurassi c
Jurassi c
Tri assi c
Tri assi c
Tri assi c
Or dovi ci an
Or dovi ci an
Jurassi c
Jurassi c
Jurassi c
Jurassi c
Jurassi c
Jurassi c
Devoni an
Devoni an
Devoni an
De voma n
Devoni an
Devoni an
Devoni an
Devoni an
Devoni an
ND ND
1.1 0.8
3.8 0.7
1.5 O.7
2.5 1.1
ND ND
2. l 1.1
1.2 0.7
ND 1.0
ND ND
0.9 1.0
2.3 0.8
1.4 (I.8
0.8 0.8
1.0 O.8
0. 9 1.0
0. 9 1.1
2. 6 1.2
N D O.9
0.5 1.0
ND ND
(L9 0.7
ND ND
0. 5 0. 3
1.4 0. 2
2. 4 0. 4
1.0 0. 8
1.4 1.1
0. 5 O.7
11.3 O.4
0.8 1.2
2. l (1.7
2.3 1.0
1.3 1.1
O.8 0.2
11.6 1.1
1.0 O.9
1.6 O.8
1.8 1.0
O.3 (t.8
0.4 0.8
0.8 0,9
(1.4 0.2
0. 6 0.3
0.3 O.3
0. 4 (1.6
ND ND
(1.4 0.5
*Ref er s t o age of r eser voi r / f or mat i on.
t The t ype of source ma t t e r was est i mat ed f r om t he rat i o of C27 to C2, (2(IR)-
5u(H), 14a(H), 17~x(H) st er anes, meas ur ed by quant i t at i on of r epr es ent at i ve peaks in
t he m/ z = 217 f r agment ogr am. Val ues <1 i ndi cat ed significant t errest ri al i nput , wher eas
val ues > 1 r epr es ent ed mai nl y mar i ne der i ved organi c mat t er ( Huang and Mei nschei n,
1979).
~- The r ma l ma t u r i t y o f s a mp l e s wa s d e t e r mi n e d f r o m t h e C2 , ( 2 0 S / 2 0 R) -
5~( H) , 14ct ( H) , 17~( H) s t er ane rat i o ( meas ur ed f r om t he m/ z = 217 f r agment ogr ams ) .
Sampl es wi t h val ues <0. 4 wer e cons i der ed i mmat ur e, and not capabl e of gener at i ng
pet r ol eum ( Mackenzi e et al . , 1980).
ND- - No t de t e r mi ne d due to i mmeas ur abl e st er ane concent r at i ons .
Bicyclic alkanes in petroleum 65
Capillary gas chromatography (GC)
Sat ur at ed hydr ocar bons wer e anal ysed by capi l l ary
gas chr omat ogr aphy ( GC) using a He wl e t t - Pa c ka r d
5880 gas chr omat ogr aph fi t t ed with ei t her a 50 m x
0.3 mm i . d. WCOT fused silica OV-1 capi l l ary
col umn ( He wl e t t - Pa c ka r d) or a 50 m x 0.2 mm i. d.
WCOT fused silica cr oss- l i nked 5% phenyl met hyl
si l i cone capi l l ar y col umn ( He wl e t t - Pa c ka r d) . Hyd-
r ogen at a l i near flow vel oci t y of 28 cm s - ~ was used as
t he car r i er gas. The sampl e in pent ane was i nj ect ed in
t he spl i t l ess mode at 40C and af t er 1 rain t he oven
was heat ed t o 280C at 4C min -~. I nj ect or and FI D
t emper at ur es were set at 250 and 320C, r espect i vel y.
Gas chromatography-mass spectrometry (GC-MS)
Anal ysi s of t he br anched and cyclic al kanes by
GC- MS was car r i ed out using a He wl e t t - Pa c ka r d
5895B GC- MS equi pped with a comput er dat a
syst em. The GC- MS was fi t t ed with ei t her a 50 m
0.2 mm i . d. WCOT fused silica OV-101 col umn
( He wl e t t - Pa c ka r d) or a 50 m x 0,2 mm i . d. WCOT
cr oss- l i nked met hyl silicone col umn ( Hewl et t - Pack-
ar d) , connect ed di r ect l y to t he ion source. Each
sampl e was anal ysed in t he mul t i pl e ion det ect or
mode, with dwell t i mes of 10 ms for each of t he 20
ions moni t or ed. Sel ect ed sampl es and synt het i c com-
pounds wer e anal ysed in t he full dat a acqui si t i on
mode by scanni ng f r om 40 to 540 a. m. u, in 1.7 s
cycles. Typi cal MS oper at i ng condi t i ons were: e. m.
vol t age 2600 V; el ect r on ener gy 70 eV; source
t e mpe r a t ur e 250C.
ReJerence compounds"
813(H) Dr i mane( I ) was synt hesi zed from t he nat ur -
ally occur r i ng sesqui t er pene dr i menol by r educt i on
of t he cor r es pondi ng t osyl at e with l i t hi um al umi ni um
hydr i de, f ol l owed by hydr ogenat i on of t he doubl e
bond ( Al e xa nde r et al., 1983). 9- Deut er i omet hyl -
813(H) dr i ma ne ( l I ) was synt hesi zed by subst i t ut i ng
l i t hi um al umi ni um deut er i de in t he above synt het i c
pat hway. A smal l -scal e synt hesi s ( < 1 mg) of 813(H)
homodr i ma ne ( I I I ) was ef f ect ed by t r eat i ng dr i manyl
t osyl at e with met hyl magnes i um i odi de ( Gr i gnar d
r eagent ) in di e t hyl e t he r sol ut i on. A l arge-scal e
synt hesi s of 813(H) h o mo d r i ma n e ( I l l ) , which is
necessar y for t he full chemi cal char act er i zat i on of
this compound, has r ecent l y been compl et ed by t he
side chai n degr adat i on of a C20 l abdanoi d di t er pene,
det ai l s of which will be pr es ent ed el sewher e.
RESULTS AND DISCUSSION
Mass spectra of drimanes
The mass spect r um of 813(H) dr i mane( I ) is shown
in Fig. l ( i ) . The spect r um is char act er i sed by a base
peak at m/z = 123 and par ent ion at m/z = 208,
cor r es pondi ng to a mol ecul ar f or mul a of CI5H28. To
obt ai n f ur t her i nf or mat i on about t he f r agment at i on
R
,,,, T: R=CH 3
TI":R=CH2 D
m' : R= C2H 5
~ 3 2 E
R
C H ~ ' ~ " } / ~ ~ : R = CH 3
v i i ' R =C2H 5
of 813(H) dr i mane dur i ng MS anal ysi s, a deut er at ed
dr i mane was synt hesi zed which i ncor por at ed deut er -
ium i nt o t he met hyl gr oup at C-9. The mass spect r um
of t hi s c ompound, 9- deut er i omet hyl - 813( H) dr i -
mane( I I ) , is shown in Fig. l ( i i ) . The abundance of the
m/z = 209 i on in its mass spect r um is consi st ent with
monodeut er at i on. Fur t her , all f r agment i ons con-
t ai ni ng t he deut er at ed moi et y will show an i ncr ease
of I a. m. u, compar ed to t he cor r es pondi ng f r agment s
of t he unl abel l ed compound. A pr obabl e f r agment a-
tion pat t er n for dr i mane is out l i ned in Fig. 2.
The per cent age cont r i but i on of A- r i ng and B- r i ng
moi et i es to t he meas ur ed abundance of any f r agment
ion can be det er mi ned f r om a compar i son of ion
i nt ensi t i es in t he mass spect r a of t he l abel l ed and
unl abel l ed compounds, Thr ee st r uct ur al l y i mpor t ant
f r agment ions for 813(H) dr i mane ar e at m/z = 109,
123 and 137. Tabl e 2 shows t he r el at i ve abundance of
t hese ions, and ions with a mass i ncr ement of 1
a. m. u. , cal cul at ed f or bot h 813(H) dr i mane and
9-deut eri omet hyl -813(H) dr i mane. Since all frag-
ment s or i gi nat i ng from t he B-ri ng moi et y of dr i mane
i ncrease by 1 a. m. u, in t he deut er at ed compound, t he
di f f er ence in r el at i ve abundance of t he m/z = 110,
124 and 138 bet ween t he l abel l ed and unl abel l ed
compounds can be r el at ed to t he per cent age con-
t r i but i on of B ring f r agment s in 813(H) dr i mane. The
resul t s of t hese cal cul at i ons are given in Tabl e 2 and
Fig. 2. The base peak at m/z = 123 was f ound to resul t
pr i nci pal l y f r om' t he A ri ng f r agment , gener at ed by
cl eavage of t he 5- 6 and 9-10 bonds (82% of ion
i nt ensi t y).
Anot he r i mpor t ant aspect of t he mass spect r um of
9-deut eri omet hyl -813(H) dr i mane( I I ) is t he absence
66 ROBERT ALEXANDER et al.
100
80
60
4 0
20
0
( i 1
i,i
4O
69
, I , , , I , ,
6O
81
8O
98
,,,, 7
100 120
S t r u c t u r e
193
137 [ 208
h . . ,J,
140 160 180 2 0 0 220
( i i l
100
8 0
60
40
20
H
i,1
4 0
i
123
6 9 84 9 5
109
, . k , h , . . , , , i . , . I . . . . . . . . . . iL,
6 0 8 0 100 120 140
S t r u c t u r e TI "
194
7
160 180 200 220
100
80
60
4 0
20 $1
0 I,,.
4O
( J i l l
S t r u c t u r e 111"
81 109
69 95 207
~ 8 I ., 11. 43 7 . . . . . . . . . . . . . . . 2 2 2
2 , ..... L, , , I . . . . . . , , . . . . . . . . . . . . . . h . . . . . . , _ , L,
6 0 80 100 120 t 4 0 160 180 2 0 0 220
Fig. 1. Mass s pect r a of (i) 813(H) dr i mane; (ii) 9- deut er i omet hyl - Sl 3( H) dr i mane; (iii) 813(H) homodr i -
mane.
Tabl e 2. Mass spect ral dat a for 813(H) dr i mane and 9-deut eri omet hyl -813(H) dr i mane
Rel at i ve abundance of ions*
Di f f er ence
Fr agment 9- Deut er i omet hyl - in rel at i ve % Cont r i but i on
ion ( m/ z ) 8[3(H)dri mane 813(H) dr i mane abundance + f r om B r i ngs
1119 51.82 36.77 NA 26
110 5.76 19.20 13.44 ND
123 193.16 151.02 NA 18
124 28.60 63.37 34.77 ND
137 22.66 12.03 NA 25
138 11.89 17.58 5.69 ND
Abs ol ut e abundance of i ons
*Rel at i ve abundance of i ons in mass s pect r um = - . . . . . . . . . . 1000.
Tot al ion abundance
+The di f f er ence in rel at i ve a bunda nc e o f m/ z = 110, 124 and 138 f r agment i ons in 813(H) dr i mane and its 9- deut er i omet hyl
count er par t r epr es ent s t he amount of ion i nt ensi t y or i gi nat i ng f r om t he B-ri ng de ut e r a t e d moi et y.
:!-The % cont r i but i on f r om t he B-ri ng is cal cul at d f r om t he di f f er ence in rel at i ve abundances in l abel l ed and unl abel l cd
dr i mane, nor mal i zed agai nst t he cor r es pondi ng rel at i ve ion abundance in 8[3(H) dr i mane.
NA- - No t appl i cabl e to cal cul at i on.
ND- - No t det er mi ned.
Bicyclic alkanes in petroleum 67
m/ z 1 9 5
7 5 % 2 5 % m/ z 2 0 8 8 2 % 1 8 %
m/ z 157 m/ z 1 2 5
,l
7 7 +
7 4 % 2 6 %
m/ z 1 0 9
+.
Fig. 2. Mass spectral fragmentation pattern for drimane, showing calculated contributions of A-ring and
B-ring moieties.
of an M-16 ion (m/ z = 193). Thi s i on woul d resul t
from t he cl eavage of t he -CH2D gr oup at C-9. The
absence of this ion is cl ear evi dence t hat cl eavage of
t he met hyl gr oup at C-9 is not a f avour abl e process
under t he condi t i ons of el ect r on bombar dment .
The mass spect r um of t he Cl6 homol ogue of 813(H)
dr i mane, r ef er r ed to as 813(H) homodr i mane( I I I ) , is
shown in Fig. l ( i i i ) . This compound cont ai ns an et hyl
gr oup at C-9. Its mass spect rum displays a par ent ion at
m/ z = 222 cor r es pondi ng to a mol ecul ar f or mul a of
Ci6H3o. The base peak is at m/ z = 123, which
cor r es ponds t o t he same A- r i ng f r agment as was
obs er ved in t he mass spect r al f r agment at i on of 813(H)
dr i mane (Fig. 2). Ther e is no appr eci abl e ion abund-
ance at m/ z = 193, cor r es pondi ng to an M-29
f r agment (loss of et hyl ). The absence of t he m/ z =
193 ion in t he mass spect r um of 8~3(H) homodr i mane
is not unexpect ed, as it agai n i l l ust rat es t he unf avour -
abl e cl eavage of t he al kyl gr oup at C-9.
Assignment o f structures to petroleum bicyclanes
It is appar ent from t he mass spect r a pr es ent ed in
Fig. 1 t hat bicyclic al kanes of t he dr i mane- t ype can be
conveni ent l y det ect ed in GC- MS anal ysi s using t he
m/ z = 123 mass f r agment ogr am. The m/ z = 193
f r agment ogr am can also be used t o moni t or C~5
bi cycl anes ( Phi l p et al., 1981). Fi gur e 3 shows t hese
t wo mass f r agment ogr ams obt ai ned f r om anal ysi s of
t he br anched/ cycl i c fract i on of a cr ude oil from Saudi
Ar a bi a . The compound r epr es ent ed by peak 3 was
i dent i f i ed as 813(H) dr i mane( I ) by compar i son of its
mass spect r um with t hat of t he aut hent i c compound,
and by coel ut i on with t he s t andar d compound when
anal ysed by GC and GC- MS using t hr ee di f f er ent
capi l l ar y col umns ( OV- 1, OV-101 and 5% pheny-
l met hyl si l i cone). By an anal agous set of experi -
ment s, t he compound r epr es ent ed by peak 4 (Fig. 3)
was i dent i fi ed as 813(H) homodr i mane( I I I ) . Kovat s
i ndi ces for t e mpe r a t ur e - pr ogr a mme d GC anal ysi s
( Hayes and Pi t zer, 1982) were cal cul at ed for 8[3(H)
dr i mane and 813(H) homodr i mane on two phases,
and t hese dat a ar e pr es ent ed in Tabl e 3.
Peaks 1 and 2 (Fig. 3) r epr es ent Ct.s bi cycl anes
(M + at m/ z = 208) whose mass spect r a ar e char act e-
ri zed by base peaks at m/ z = 193, cor r es pondi ng to
loss of a met hyl gr oup from t he par ent ion. Two
bicyclic al kanes with i dent i cal mass spect r a were first
r epor t ed by Bendor ai t i s (1974) in his st udy of bi odeg-
r aded cr udes f r om Sout h Texas. Hi s anal yses est ab-
lished t hat t hese compounds wer e pent amet hyl de-
cahydr onapht hal enes . Kagr amanova et al. (1976)
i sol at ed and char act er i zed t wo bicyclic al kanes which
were pr esent in high concent r at i on in a Russi an cr ude
oil. They assi gned st ruct ures I V and V t o t hese two
bi cycl anes based upon mass spect ral and 13C NMR
dat a. The mass spect r a of t hese two compounds are
i dent i cal to t hose publ i shed by Bendor ai t i s (1974)
and t o t he mass spect r a of t he compounds r epr e-
sent ed by peaks 1 and 2 in Fig. 3. We have t her ef or e
assi gned st r uct ur es IV and V to t hese compounds
( Tabl e 3). Fi nal pr oof must , however , awai t synt hesi s
of aut hent i c st andar ds.
68 ROBERT ALEXANDER et al.
m l z 123
1
/ ., ~ , ,~ . ,
m/ z 1 9 3
i i
6 " ~ - "
. . . . . . . ~ - - . , _ . ~ o ~ . . . - - . !
2 6 ; I 3 6
R e t e n t i o n t i m e ( r a i n )
Fig. 3. Mass f r agment ogr ams of m/ z = 123 and 193 for Saudi Ar abi an cr ude oi l , showi ng bicyclic al kane
Peaks 1-4 are i dent i fi ed in Tabl e 3.
Tabl e 3. Peak i dent i fi cat i on and r et ent i on t i me dat a for bicyclic al kanes
Kovat s Indi ces
Met hod of 5% phenyl met hyl
Peak* Compound name St r uct ur e i dent i fi cat i on OV- F si l i cone:
1 C~ bieyclic al kane IV Mas s s pect r um ~ 1416 1445
2 Ct5 bicyclic al kane V Mass s pect r um ~ 1452 1482
3 813(H) dr i mane I Synt hesi s 1459 1493
4 813( H) homodr i ma ne I l l Synt hesi s 1546 1582
*Ref er s to peaks in Fig. 3.
+50 m x (1.3 mm i.d. WCOT OV-1 capi l l ary col umn ( He wl c t t - Pa c ka r d) .
:1:511 m 2(1 mm i.d. WCOT cr oss- l i nked 5% phenyl met hyl si l i cone capi l l ary col umn
(Hewl ett-Packard).
Compar i son of mass s pect r um wi t h publ i shed dat a of Kagr amanova et al. (1976).
Bicyclic alkanes in petroleum 69
Di st ri but i on o f bi cycl i c al kanes in pe t r ol e um
Twent y-t wo crude oils and 26 sediment extracts
were analysed by capillary GC- MS for the presence
of bicyclic alkanes of the dri mane type (see Table 1
for sample details). Crude oils were of widely differ-
ing geological and geographical origin, and included
samples derived from marine organic mat t er and
samples cont ai ni ng significant higher plant input.
Sedi ment samples ranged in age from Ordovician t o
Cret aceous, and spanned t hermal maturity levels
from pre-oil generat i on t o the wet gas zone. Analysis
of m/ z = 123 and 193 mass fragment ograms showed
t hat all the crude oils and sediment extracts cont ai ned
813(H) dr i mane( I ), 813(H)homodri mane(III) and the
two Ci5 bicyclanes IV and V. The presence of these
compounds in samples predat i ng the evolution of
higher plants eliminates the possibility of bicyclic
alkanes of this type being derived exclusively from
higher plant precursors, as had been previously
suggested (Bendoraitis, 1974; Philp et al . , 1981).
Rear r anged 6) 5 bi cycl i c al kanes
The structures of bicyclanes I V and V suggest that
t hey may be derived from a dri mane-rel at ed precur-
sor by a r ear r angement process involving carboni um
ion i nt er medi at es ( Ka gr a ma nova et al . , 1976;
Vor ob' eva et al . , 1978). A similar rearrangement
which occurs in subsurface sedi ment ary environ-
ments is the conversi on of sterenes to diasterenes
(Rubi nst ei n et al . , 1975; Ensmi nger et al . , 1978).
Event ual reduct i on of these diagenetic steroidal
compounds results in the steranes and diasteranes
which are present in varying proport i ons in pet-
roleums. Figure 4 shows a plot of the ratio of C29
5 a ( H) , 1 4 a ( H) , l T a ( H) s t e r a n e s a n d Cz~
1313(H), 17a(H) di ast er anes agai nst 813(H) dri-
mane( I ) and the Cl~ bicyclanes IV and V. The dat a
shown in this plot were measured from branched/
cyclic alkane fractions of crude oils and sediments, by
quant i t at i on of represent at i ve peaks in the m/ z = 217
f r agment ogr am (steranes and diasteranes) and m/ z =
123 f r agment ogr am (drimane and bicyclanes IV and
V). A positive correlation is exhibited between the
two variables in Fig. 4, showing that an increase in the
abundance of rearranged steranes relative to steranes
is also associated with an increase in rearranged
bicyclanes relative to 813(H) drimane. This correla-
tion suggests that the factors which det ermi ne the
extent of r ear r angement in sedi ment ary steroids also
affect the r ear r angement of dri mane precursors.
Ori gi n o f dr i manes
The widespread occurrence in crude oils and
sediments of bicyclic alkanes containing the dri mane
skeleton suggests t hat these compounds are derived
from a ubi qui t ous source. Al t hough some bicyclanes
could be derived from functionalized sesquiterpe-
noids of higher plant origin, such as drimenol for
example, this cannot explain their occurrence in
> .301 o
~ 2.(3
g /
i
~' O O 0 0
0 0 0 0 E x t r o c l
J / ~s o
I l I
1 0 2 0 3 0
C2 9 a Q a - s t e r a n e s / C2 9 / ~ a - d i a s t e r a n e s
Fig. 4. Pl ot o f 8 p( H) d ri mane/ Ci s bicyclanes I V and V vs
Cz,~ 5c~(H),I4a(H),17a(H) steranes/Ce,~ 1313(H),ITa(H) di-
asteranes in crude oils and sediments. Correlation coef-
ficient (r) = 0.81.
samples predat i ng the evolution of higher plants.
Moreover, the presence of a Ci6 homol ogue of
dri mane, a compound which does not obey the
i soprene rule, f ur t her belies a sesqui t erpenoi d
source. The close similarity of the bicyclane distribu-
tions found in our studies, and by Philp et al. (1981),
requires that the distribution of precursor com-
pounds must be similar in a wide range of geological
envi ronment s. This is certainly true for the pent acy-
clic hopanoi d series, which derive principally from
procaryot i c micro-organisms present in sedi ment ary
envi ronment s (Ensmi nger et al . , 1974; Van Dors-
selaer et al . , 1974). It is apparent from structures I
and I l l that 813(H) drimane and 813(H) homodr i mane
have both structural and steric similarities to the
A/ B-ri ng system of the hopanoi ds. It is t herefore our
cont ent i on that bicyclic alkanes of the dri mane-t ype
are probabl y f or med by biological alteration of
hopanoi d precursors during diagenesis.
The proposal that hopanes and drimanes have
common precursors is a logical extension of current
opinions about subsurface t ransformat i ons of higher
terpenoids. Trendel et al. (1982) recently report ed
t he i dent i f i cat i on of novel t et r acycl i c 17,21-
secohopanes, which t hey suggest may be derived
from microbial or t hermocat al yt i c degradat i on of
hopane precursors. Ekweozor et al. (1981) suggest
cleavage of terminal rings of pentacyclic triterpe-
noids t o explain the occurrence of a tetracyclic alkane
series. Our proposal essentially states that bacter-
i ohopanoi ds are extensively degraded in pet rol eum
source rocks during diagenesis, resulting in func-
tionalized bicyclic compounds of the dri mane type.
These compounds can then undergo rearrangement ,
or be reduced directly t o the hydrocarbon. We favour
70 ROBERT ALEXANDER e t al.
( i )
m/ z 191 30 H
2 7 H 29H t
l,I r ]
2 8 M H O . 3 0 M H II 3 1MH : ~ " - . . . .
=, , r - q ,'1 Ii :
J L J / p7 I , . , . , t t
6?' 7 7 8
R e t e n t i o n t i me ( r a i n )
( i i ) 1 6 D
m/ z 123
15D
16 MD
17 MD
ml z 137 5
2 9 3 3
Retention time (rain)
6
!
3 7
Fig. 5. (i) Mass fragmentograms of m/ z = 191 and 205, showing hopanes and methylhopanes. Numcrals
refer to carbon numbers. H = 17a(H) hopanes; MH = A/B methylated hopanes. ( i i ) Mass
fragmentograms of m/ z = 123 and 137, showing drimanes and methyldrimanes. Numerals refer to carbon
numbers. D = 813(H) drimanes; MD = A-ring methylated drimanes. Peaks 5 and 6 represent compounds
16 MD and 17 MD, respectively.
a di agenet i c t ransformat i on as opposed to a t hermo-
catalytic one, since dri manes are present in anci ent
sedi ment s of low mat uri t y, in which extensive car-
b o n - c a r b o n bond cr acki ng r eact i ons have not
occurred.
The proposal of a di agenet i c link bet ween hopanes
and dri manes will requi re furt her i nvest i gat i on, but
one addi t i onal piece of evidence is the occurrence of
met hyl at ed dri manes in a hydrocarbon extract from
the Canni ng Basin, West ern Aust ral i a. This sample
cont ai ns, in addi t i on to the usual series of hopanes,
an anal ogous series of met hyl hopanes. A similar
series of met hyl hopanes has been previously re-
port ed in crude oils by Seifert and Mol dowan (1978).
These compounds, like the hopanes, are most prob-
ably derived from bacterially produced precursors,
such as the 3-met hyl hopanoi ds identified in bacteria
by Rohmer and Ouri sson (1976). Figure 5 shows the
Bicyclic alkanes in petroleum 71
b
83
6 0 6 9
4O2o11] 55 lift
o ,I ,,,I , I, rl I, ,,
4 0 6 0
137
4O9
1 2 3
80 100 120 140
5 ( 1 6 MD )
2 0 7
I 222
,lh, h i , I, ,lJl ,, I,
1 6 0 1 8 0 2 0 0 2 2 0 2 4 0
100 Ci i )
8o
6 o
83
4 0 6 9
20 , o 5~ , ..I I [ I
o , ' , L I I , I I .
4 0 6 0 8 0
9 5
1.1 11 ,.
100
137
109
Ill 123
., .I . , .., .h , L, . . , b., . , .LI . . . . . , . . . . . . . . . . . . . . .
1 2 0 1 4 0 160 1 8 0 2 0 0
6 (17 MO)
221
I 2 3 6
. L
220 24 0
Fig. 6. Mass spectra of methyldrimanes. Peak numbers refer to Fig. 5.
m/ z = 191 and 205 mass f r agment ogr ams for this
sampl e. The hopane seri es is evi dent in t he m/ z = 191
f r a g me n t o g r a m, and t he A/ B- r i n g me t h y l a t e d
hopane seri es in t he m/ z = 205 f r agment ogr am
( Sei f er t and Mol dowan, 1978). Al so i l l ust r at ed in
Fig. 5 is t he m/ z = 123 f r agment ogr am, which shows
peaks due t o bicyclic al kanes of t he dr i mane t ype,
and t he rn/ z = 137 f r agment ogr am, which shows
some hi t her t o unr epor t ed bicyclic al kanes. The mass
spect r a of t he compounds r epr es ent ed by peaks 5 and
6 in t he rn/ z = 137 f r agment ogr am ar e shown in Fig.
6. Compar i s on of t hese mass spect r a with t hose of
813(H) dr i mane and 813(H) homodr i mane (Fig. l ( i )
and (i i i )), suggests t hat t hese new bi cycl anes have
st r uct ur es cont ai ni ng t he basic dr i mane skel et on,
with an addi t i onal met hyl gr oup in t he A ring. This
assumpt i on is based on t he base peaks bei ng at m/ z =
137, which ar e equi val ent to met hyl at ed A- r i ngs in
dr i manes. We t her ef or e assign st r uct ur es VI and VI I
to t he compounds r epr es ent ed by peaks 5 and 6 in
Fig. 5, r espect i vel y.
Concl usi ve pr oof of this assi gnment , det ai l i ng t he
exact posi t i on of t he A- r i ng met hyl gr oup, must awai t
synt hesi s of model compounds , which is cur r ent l y in
pr ogr ess. The pr esence of A- r i ng met hyl at ed dri -
manes in a sampl e rich in A/ B- r i ng met hyl at ed
hopanes, f ur t her suppor t s t he cont ent i on t hat t he
hopanes and dr i manes have common pr ecur sor s, and
t hat t hese pr ecur sor s ar e of bact er i al origin.
CONCLUSIONS
Bicyclic al kanes cont ai ni ng t he dr i mane skel et on
have been i dent i f i ed in cr ude oils and sedi ment s.
St r uct ur al i dent i f i cat i on of 813(H) dr i mane( I ) and
813(H) homodr i ma ne ( I I I ) has been achi eved by corn-
par i son with aut hent i c st andar ds. Two ot her Ci5
compounds whose st r uct ur es ( I V, V) have been
r epor t ed pr evi ousl y ( Kagr amanova et al . , 1976), ar e
t hought t o be r ear r angement pr oduct s of a dr i mane-
r el at ed pr ecur sor . A cor r el at i on bet ween t he r el at i ve
concent r at i on of C29 st er anes and di ast er anes, and
t hat of dr i mane and bi cycl anes I V and V was
obs er ved in an ext ensi ve sampl e sui t e, suggest i ng
t hat a si mi l ar mechani sm is i nvol ved in t he f or mat i on
of di ast er anes and r ear r anged bi cycl anes in t he
subsurface.
Dr i mane and dr i mane- r el at ed compounds have
now been r ecogni sed as wi del y occur r i ng const i t uent s
of cr ude oils and sedi ment s. Thei r wi des pr ead
occur r ence has in fact been f ound to rival t hat of t he
ubi qui t ous hopane seri es. Dr i manes ar e pr esent in all
t ypes of pet r ol eum, i ncl udi ng sampl es der i ved excl u-
sively from mar i ne organi c mat t er . Thei r occur r ence
is not dependent upon hi gher pl ant pr ecur sor s, and
we concl ude t hat t hey ar e der i ved f r om a ubi qui t ous
source. The pr esence of A- r i ng met hyl at ed dr i manes
in a sampl e rich in met hyl hopanes suggests a rel a-
t i onshi p bet ween dr i manes, hopanes and hopanoi d
pr ecur s or s . Ext ens i ve mi cr obi al de gr a da t i on of
hopanoi ds in pet r ol eum source rocks dur i ng di-
agenesi s mi ght resul t in f unct i onal i zed bicyclic com-
pounds, which coul d t hen under go r ear r angement ,
or be r educed to sat ur at ed hydr ocar bons cont ai ni ng
t he dr i mane skel et on.
Acknowl edgement s- - We thank Dr L. Slentz, Chevron.
U. S. A. , for providing us with some crude oil samples and
Professor C. J. W. Brooks for the samples of drimenol and
derivatives. This work was carried out as part of the
National Energy Research Development Demonstration
Program ofAustralia.
72 ROBERT ALEXANDER et al.
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