Pergamon

Org. Geochem. Vol. 24, No. 6/7, pp. 681--690, 1996

Copyright 1996 Elsevier Science Ltd
Printed in Great Britain. All rights reserved
PII: S0146-6380(96)00059-9 0146-6380/96 $15.00 + 0.00
Ester- and ether bond cleavage in immature kerogens
ANDRE AMBLI~S, LAURENT GRASSET, GERMAI NE DUPAS and
JEAN-CLAUDE JACQUESY
Laboratoire de Chimie 12, URA-CNRS 1468, 40 Av. du Recteur-Pineau, 86022 Poitiers, France
Abstract--Quaternary ammonium salt Aliquat 336 and 18-Crown-6 enhance hydrolysis of Timahdit-M
kerogen when used as a phase transfer catalyst. The yield of hydrolysis products was higher with Aliquat
than with 18-Crown-6, but the identified products were found in lower concentration, the difference being
soluble heavy parts from kerogen which cannot be analyzed directly. Both reactions afforded series of
aliphatic mono- and dicarboxylic acids, alkylsuccinic acids and alkanols, but differences in distributions
were observed. The range of monocarboxylic acids was shorter with Aliquat than with 18-C-6, Ct4-C~
compared to C~_,-C32, but palmitic and stearic acids were dominant in the two cases. C~0 and C,2 alkyl
succinic acids were identified in Aliquat products. Aromatic acids were the major hydrolysis products
(59%) with crown ether; only one aromatic acid was found with Aliquat, Hydrocarbons and tertiary
amines were obtained from both reactions, they were obviously present in the kerogen as trapped
molecules. Many tertiary amines arising from the decomposition of the reagent were obtained with
Aliquat. The results give evidence of an important reticulation involving ester groups in the Timahdit-M
kerogen. Series of n-, iso- and anteisoalkanes were obtained through HI/LAD treatment of Irati and
Aleksinac kerogens, originating probably from glycerol-ether lipids. C27-C34 ~,/~-hopanes were also found
to be linked to kerogen (Irati) by ether bo,:ls. Reaction with CF3CO2H (Irati) afforded seven series of
branched alkenes, indicating that branched saturated alkyl chains were bound to aromatic moieties of
kerogen by ether groups. Acetates of cholesterol and 24-ethylcholesterol were identified in the
BF3-Et20/Ac20 products. Esters of fatty acids (max C~6, C~8) were also identified. Only alkanes were
produced on Alls reaction. Each reaction afforded the same series of n-alkanes. This would reflect
modifications in the kerogen matrix during these various treatments, resulting in the release of tightly
trapped molecules. Copyright 1996 Elsevier Science Ltd
Key wor ds - - k e r oge n, ether, ester, ether cleavage, phase transfer catalyst, monoacids, diacids, alkyl succinic
acids, alkanols
INTRODUCTION
One of the methods used for the structural study of
kerogens is an approach by chemical degradation.
Stepwise oxidation, for instance with sodium
dichromate (Barakat and Yen, 1987) or potassium
permanganate (Ambles e t a l . , 1994; Burke e t a l . ,
1990; Vitorovic e t a l . , 1984, 1986, 1987, 1991, 1994),
is a powerful way to access to the various kinds of
structures present in a considered kerogen, as far as
it leads to high yields of oxidation products.
However, the method informs neither about the
chemical groups still present, nor about the nature of
the oxidation sites. This information can arise only
from selective chemical reactions applied to kerogens,
for instance RuO4 oxidation (Reiss e t a l . , 1993),
boron tribromide cleavage (Chappe e t a l . , 1981;
Rullk6tter and Michaelis, 1990), and transalkylation
(Baudet e t a l . , 1994). However, structural infor-
mation is often controversial due to the heterogeneity
and the complexity of kerogens. As an example, we
reported recently that an important reticulation
involving ester groups may occur in immature
kerogens, despite total unreactivity of the kerogens in
the classical conditions used for hydrolysis. The
results were obtained using a crown ether, 18-Crown-
6 (Pedersen, 1967), as a phase transfer catalyst (PTC)
(Ambles e t a l . , 1987; Ambles e t a l . , 1993; Kribii,
1994). Ether groups were found to be unreactive
under these experimental conditions (Ambles e t a l . ,
1993).
The aim of the work was first to confirm the
increased reactivity of immature kerogens towards
hydrolysis when using PTC conditions. The imma-
ture Moroccan Timahdit (M-layer) kerogen (Ambles
e t a l . , 1988) was submitted to stepwise hydrolysis in
presence of Aliquat 336 (also named Adogen 464), a
quaternary ammonium salt (Weber and Gokel, 1977;
Loupy e t a l . , 1986). The results were compared with
those arising from 18-Crown-6/KOH hydrolysis of
the same kerogen, which were only partly published
(Ambl6s e t a l . , 1987).
The second aim of the work was to study the
products released by the reaction of kerogen with
some of the well-known "specific" reagents used
for ether cleavage in classical organic chemistry:
681
682 A. Ambles et al.
HI, FeCI3/Ac20 (Ganem and Small, 1974), boron
trifluoride (Narayanan and Iyer, 1965), trifl-
uoroacetic acid (Bhatt and Kulkarni, 1983), and
dimethylboron bromide (Guindon e t al . , 1983, 1987).
With this respect, boron tribromide or trichloride
(Chappe e t al . , 1981, 1982; Rullk6tter and Michaelis,
1990), hydrogenolysis (Mycke and Michaelis, 1986)
or HI (Vella and Holzer, 1990) were precedently used
on kerogen. Immature type I Brazilian lrati
(Vitorovic e t al . , 1987; Amblbs e t al . , 1993) and
Aleksinac (Vitorovic e t al . , 1985, 1991, 1994)
kerogens were used for this study.
EXPERIMENTAL
S a mp l e s
The sample from Moroccan Timahdit oil shale
(Upper Cretaceous; M-layer) was immature (equival-
ent vitrinite reflectance: 0.35~).45). The kerogen
concentrate contained 89.0 wt% kerogen (pyrite
correction), consisting of 64.31 wt% C, 7.40 wt% H,
4.09 wt% N, 8.84 wt% S and O: 15.36 wt% O
(by difference). The values of the atomic H/C
(1.38) and O/C (0.18) ratios corresponded to an
intermediate I-II Type kerogen (Ambl+s e t al . ,
1988).
The kerogen concentrate from Brazilian Irati oil
shale (Upper Permian; 2X sample) contained 73.1%
organic matter (C: 50.2%; H: 6.0%; N: 2.5%; O:
3.8%; S: 6.7%). The values of atomic H/C and O/C
ratios were 1.43 and 0.06, respectively, corresponding
to a Type I kerogen.
The other studied kerogen was a Type I kerogen
from Aleksinac (Serbia, Yugoslavia; Miocene). The
kerogen concentrate contained 65.57% kerogen,
consisting of 71.87 wt% C, 8.73 wt% H, 3.21 wt%
N and 16.19 wt% O + S (by difference). The atomic
H/C and O/C ratios were 1.46 and 0.17, respectively
(Type I kerogen). An equivalent vitrinite reflectance
value was estimated as 0.3% (Vitorovic e t al . , 1985).
P T C- h y d r o l y s i s
Al i quat : Aliquat 336 was purchased from Aldrich.
Aliquat is a mixture consisting mainly in tricaprylyl-
methylammonium chloride (H17C8) 3 CH 3 N CI-. In
a typical experiment, Timahdit-M kerogen concen-
trate (500 mg containing 450 mg kerogen) was added
with 960 mg Aliquat (2 mmol), 100 mmol of KOH
and a few drops of water. The mixture was heated
under stirring at 80C for 48 h under a nitrogen
atmosphere. After cooling; water was added and the
remaining kerogen was separated by centrifugation
and filtration. Neutral and basic components, named
NB, were extracted from the filtrate with diethyl
ether at basic pH. After acidification to pH 1
(HCI), high-molecular-weight components precipi-
tated. They were isolated by filtration. As in KMnO4
degradation (Ambles e t al . , 1988), they correspond to
heavy parts of kerogen and consequently they were
named PA. Soluble acids, named SA, were then
extracted from the filtrate. PA were then hydrolyzed
further (one step) in the same conditions as above,
yielding extra amounts of soluble acids, named PSA,
and neutral and basic compounds, named PNB.
The various products of the NB and PNB fractions
were separated on a SiO2 column. Chromatographic
fractions corresponding to alkanols (based on R f
values) were acetylated with acetic anhydride in
pyridine. SA and PSA fractions were methylated with
diazomethane prior to SiO2 column chromatography.
1 8 - C r o w n - 6 / K OH c o mp l e x : the crown ether used
for hydrolysis is 18-Crown-6 or 1,4,7,10,13,16-
hexaoxacyclooctadecane (Aldrich). The kerogen
concentrate (500 mg) was treated stepwise with a
toluene solution (20 ml) of KOH/18-C-6 (8 mmol)
complex at 110C for 96 h under an inert atmosphere
(Ambl6s e t al . , 1987, 1993). Five successive reactions
were applied to the kerogen concentrate. Precipitated
acids were further hydrolyzed in two steps. The
procedure for extraction and separation of hydrolysis
products was similar to that used with Aliquat. In
text, the crown ether is named 18-C-6 or 18-Crown-6.
Et h e r - b o n d cl eavage
Stepwise reactions were applied until the yield of
the individual reaction step was found to be
negligible. Consequently the number of successive
reaction steps varies according to the applied reaction
and to the studied kerogen.
HI : Irati or Aleksinac kerogen concentrate was
suspended in 20 ml of a 47% aqueous solution of HI.
The mixture was stirred for 48 h at 80C under a N2
atmosphere. After centrifugation and filtration, the
reaction products were extracted with diethyl ether.
Iodine was eliminated from Et20 layer by sodium
thiosulfate. Four successive reactions were applied on
Aleksinac kerogen concentrate (200 mg) yielding 4.5
mg of soluble products, corresponding to 3.3 wt% of
the original kerogen. Irati kerogen (288 mg
concentrate) was more reactive, eight successive
reactions yielded 12. 5 mg of soluble products,
corresponding to 6 wt% of the original kerogen.
Iodides were then reduced with LiA1D4 (LAD) in
THF.
BF3-E~O: Irati kerogen concentrate (200 rag) was
suspended in 30 ml of a mixture of benzene and acetic
anhydride (2/1; v/v). BF3-etherate (2 ml) was added
and the mixture was stirred for 1 h under a nitrogen
atmosphere, at room temperature (20C). The
mixture was then poured on cold water and
neutralized with a saturated solution of NaHCO~.
After centrifugation and filtration of the remaining
kerogen, soluble organic compounds were extracted
with diethyl ether. Three successive reactions were
applied to the kerogen, the combined extracted
organic products (16 rag) corresponded to 10.9 wt%
of the initial kerogen.
Chemical degradation of kerogens
Table I. Aliquat/KOH hydrolysis of Timahdit-M kerogen concentrate (500 mg) compared to 18-C-6 hydrolysis
683
PTC-Hydrolysis Steps NB (mg) SA (rag) PA (mg) Yield (%K)
Aliquat/KOH I 510* 20 24 I 0t
2 598* 12 192 45t
3 470* 20 98 26t
4 502* 18 40 13t
Total 4 ? 70 (16%) 354 (79%) > 94t
18-C-6/KOH (total) 5 31 (7%) 38 (8%) 313 (70%) 85
* Presence of Aliquat; + PA + SA (excluding NB).
CF~CO2H: kerogen concentrate (200 mg) was
stirred with CF3CO2H (20 ml) for 168 h at 20C under
a nitrogen atmosphere. Water was added to the
mixture. After neutralization (NaHCO3 solution) of
the mixture, the remaining kerogen was separated by
filtration and centrifugation. Reaction products were
extracted from the filtrate with chloroform. Two
successive reactions were applied on Irati kerogen
yielding 3 mg of soluble raw product (about 2 wt%
of the initial kerogen).
Al l 3: Al l 3 (0.5 g) and CH3CN (50 ml) were added
to the Irati kerogen concentrate (400 mg) and the
mixture was heated at 80C for 72 h, with stirring,
under an inert atmosphere. Water was added, the
mixture was then neutralized (NaHCO3 solution), I2
was eliminated by treatment with a Na2S203 solution.
The remaining kerogen was separated by filtration
and centrifugation. Reaction products were extracted
from the filtrate with CHCI3. Due to poor results, the
treatment was not applied to Aleksinac kerogen.
Analyses
The products were analysed by capillary GC and
GC- MS using standards (Fluka, Larodan). The GC
separations were carried out with a Packard Model
427 or 438 gas chromatograph using a CP Sil 5 CB
(Chrompack) capillary column (25 m length). The
temperature of the column was programed from
70-80'~C (5 min isothermally) to 300C (10 min
isothermally) at 2C mi n- ' . GC-MS were performed
on a Kratos MS 25 or a Finnigan Incos 500 mass
spectrometer. The GC conditions were the same as
for GC analysis.
RESULTS AND DISCUSSION
Ester bond cleavage
Despite that it was almost unreactive when it was
submitted to the classical hydrolysis conditions, the
kerogen from immature Moroccan Timahdit oil shale
(M-layer) showed a good reactivity when 18-Crown-6
was used as a phase transfer catalyst (PTC) (Table l).
The enhanced reactivity of the kerogen when using
PTC conditions was confirmed by the use of Aliquat
for hydrolysis. In the presence of Aliquat, OH - from
KOH is replaced by CI- and OH is activated
(Weber and Gokel, 1977; Loupy et al., 1986). No
solvent is needed:
Q+CI - +KOH ~Q+OH +KCI
The amounts of neutral and basic compounds (NB),
soluble acids (SA) and high-molecular-weight com-
ponents (PA) obtained in four steps from 500 mg of
kerogen concentrate (containing 450 mg of kerogen)
are given in Table 1. NB contained high amounts of
Aliquat which cannot be eliminated. Consequently,
the given total yields (wt% of the initial kerogen)
correspond only to SA and PA products. The highest
yield was obtained in step 2. As with the crown
ether/KOH system, PA were the main hydrolysis
products. As in potassium permanganate degradation
(AmbEs et al., 1988), these products can be
considered as high-molecular-weight elements of
kerogen which are soluble in an alkaline medium but
insoluble in diethyl ether. Table 1 shows that at least
94% of the initial (insoluble) kerogen was solubilized
in alkaline medium after Aliquat/KOH reaction. The
value is 85% for 18-Crown-6 reaction. The yields of
SA and PA are also higher with Aliquat. It is
obviously the opposite for NB. The final residue (50
mg) was essentially inorganic (77% ash).
PA were still reactive towards PTC hydrolysis.
Two successive reactions were applied yielding extra
amounts of neutral and basic, and acids components
(Table 2). An important loss of organic matter which
corresponded to 13 wt% of the initial PA occurred
at step 2 and the treatment was stopped. With
Aliquat, only one reaction was performed: a solid
material which was insoluble in the alkaline solution
appeared. This possibly indicated a condensation
reaction, parallel to hydrolysis. The extra amounts of
soluble acids corresponded to 7% of the initial PA
(5% of the initial kerogen) (Table 2). 83% of the
initial starting material was recovered. This yield in
soluble acids PSA was finally lower than in the
18-Crown-6 reaction of PA.
When adding the two series of Aliquat/KOH
Table 2. Further hydrolysis of precipitated acids from Timahdit-M kerogen
Steps PA (mg)(recovered) PNB (rag) PSA (rag) Total
Aliquat/KOH I 294 (83)t 730* 26 (7)t ?
18-C-6/KOH 2 161 (51)t 21 (7)t 58 (18)t 25t
*Presence of Aliquat: t % of initial PA.
684 A. Ambl6s et al.
hydrolyses of 500 mg of kerogen concentrate, the
remaining PA (294 mg) corresponded to 59% of the
initial kerogen. The yield of the summed soluble acids
SA + PSA (96 mg) was 21.3%, based on the original
kerogen. With crown ether, the total balance was,
relative to kerogen: PA: 36%; NB: 11%o; SA: 21%
(Ambl6s e t a l . , 1987).
NB and SA (after methylation) fractions arising
from the two series of hydrolyses with Aliquat were
chromatographied on a silica column. The major
products from neutral and basic fractions on the one
hand, and acid fraction on the other hand were polar
products, which were eluted from the SiO2 column
with diethyl ether. GC analyses were unsuccessful.
These polar products were found to be much more
abundant with Aliquat than with 18-Crown-6. As
an example, they corresponded to 78% of the total
methylated SA and PSA fractions. These polar
products are very probably soluble medium-molecu-
lar-weight parts of kerogen. They can be considered
as intermediate products between Et20-insoluble,
high-molecular-weight PA and less polar low-mol-
ecular-weight compounds, which can be analyzed by
GC and GC-MS. Identifiable products from SA and
PSA fractions on the one hand, from NB and PNB
fractions on the other hand, did not show significant
differences. The same was observed with 18-Crown-6.
This is an indication of a rather homogeneous
structure for the Timahdit-M kerogen. For the sake
of comparison, this was not the case for the Brazilian
Irati kerogen: some components, for instance alkane
diols, were freed only during the hydrolysis of PA
(Ambles e t a l . , 1993). n-Alkanes from Timahdit NB
and PNB fractions were identified in the range
C22-C37 with a regular distribution centered on C30.
The same hydrocarbons were found with the 18-C-6
hydrolysis or after potassium permanganate degra-
dation (Ambles e t a l . , 1988). They were obviously
present in the kerogen as strongly trapped molecules
which cannot be extracted during the preparation
of the kerogen concentrate. Many tertiary amines
were identified, but most of them arose from
Aliquat degradation (Aliquat is a mixture of
quaternary ammonium salts), they were present in the
blank experiment. Tertiary amines were also
identified in the 18-Crown-6/KOH products: N-octyl-
N-methyldecylamine, N-octyl-N-ethyldecylamine,
N-octyl-N-methyloctylamine, N-decyl-N-ethyldecyl-
amine. They were probably present in the kerogen
as trapped molecules. The primary and secondary
amines present in the 18-C-6 reaction (Ambl6s e t a l . ,
1987), which indicated the presence of amide groups
in the kerogen, were not found in the Aliquat/KOH
products. Odd-carbon-numbered C,7, C,9 and C2,
alkanols (as acetates) were found in the same
chromatographic fraction as amines. They could not
be fully identified, they are not linear components.
With 18-Crown-6, they were even-carbon-numbered
(C,2, C,4, C,6). Aliphatic monocarboxylic acids were
present in the range C,4-C,s with Aliquat, compared
to C,2-C32 with 18-C-6. C,6 and C,8 members were
highly dominant in both cases, a,o~-Dicarboxylic
acids had from 10 to 16 carbon atoms with a regular
distribution (max at C,,, C,2) in Aliquat products
(Fig. 1), compared to C,0-C20 (max C,0) in the crown
ether/KOH hydrolysis. Two C,0 and C~2 n-alkylsuc-
cinic acids were found only with Aliquat (Fig. 1).
They were identified by mass spectrometry on the
basis of a prominent m / z 146 ion arising from a
McLafferty rearrangement and a base peak at m / z
114 (loss of CH3OH from m / z 146). The mass spectra
were very similar to that reported in the literature
(Ambles e t a l . , 1991; Douglas e t a l . , 1971; Gfila~zar
e t a l . , 1989) for such components. The presence of
these acids in kerogen was scarcely reported in the
literature. The identification of C,7-C33 alkylsuccinic
acids in the Green River shale kerogen by Douglas
e t al . (1971) seems to be the unique reference, the
authors had no explanation about their origin.
Previously in soil studies, we identified a series
(C2,~234, max C30) after hydrolysis of the macromol-
ecular lipid fraction from two different acidic soils
(Ambl6s e t al . , 1991). They were not found in the
corresponding simple lipids, they originated possibly
from partly preserved biomacromolecules. The last
report on the occurrence of this type of compounds
in old organic matter concerns a 4000-year old
mummy: alkylsuccinic acids, mainly the C,7 homol-
ogue, were found only in the skull samples but the
authors had no evidence for a biochemical or a
diagenetic significance (Gfila~ar e t a l . , 1989).
The study of aromatic acids gave also evidence for
differences between Aliquat/KOH and 18-C-6/KOH
reactions. Only one aromatic acid, an alkylbenzene
dicarboxylic acid [H3C-C6H3(CO2H)2], was identified
in the products from Aliquat reaction (0.8% of the
initial kerogen) when the use of 18-Crown-6 led to the
release of various benzene and naphthalene mono-
to tricarboxylic acids as major hydrolysis products
(59% of the hydrolysis products; 11.6% of the initial
kerogen) (Ambles e t a l . , 1987).
Apparent concentrations (wt% of the initial
kerogen) were determined (Table 3), based on FID
responses in GC. Even if the values are not accurate,
the comparison of the results obtained with the
two PTC is significant. Table 3 shows that the yield
%
15
io
iI
! !
[I
! !
10"101112"12 13 1415 16
Fig. 1. Distribution of Qt,o~-dicarboxylic acids (X) and
alkylsuccinic acids (X*) obtained by Aliquat/KOH hydroly-
sis of Timahdit-M kerogen.
Chemical degradation of kerogens
Table 3. Apparent concentrations (% of initial kerogen) of identified
series of components released by PTC hydrolysis of Timahdit-M
kerogen
18-Crown-6 Aliquat
Aliphatics 12.3 2.6
monocarboxylic acids 4.2 0.4
dicarboxylic acids 5.2 0.7
alkylsuccinic acids -- 0.3
alkanols (as acetates) 1.2 1.2
amines* (as acetamides) 1.7 nd
Aromatic acids 11.6 0.4
Total 23.9 3.0
nd = not determined; * primary and secondary amines.
of identified low-molecular-weight products is eight
times lower with Aliquat than with 18-C-6. The
relative abundance of each kind of product differs
widely. The values for alkanols are comparable in the
two experiments, but it must be recalled that they are
different in distribution. Our results on Timahdit-M
(this work) and lrati (Ambles e t a l . , 1993) kerogens
indicate that the use of PTC makes kerogen
hydrolysis possible, or more generally enhances
strongly the reactivity of chemical reagents towards
hydrolyzable groups, esters and amides, when
present. Nevertheless, the selectivity of the two PTC
on these groups is not equivalent. Al i quat / KOH
treatment frees preferentially soluble high-molecular-
weight and medium-molecular-weight moieties of
kerogen. However, 18-C-6/KOH hydrolysis is more
effective for some sites, less effective for other ones,
leading to a lower yield of alkaline soluble material
(Table 1) but to a higher yield of identifiable,
low-molecular-weight elements. The same con-
clusions arose from an equivalent study of the
complex organic matter present in soil (Okom~-
Mintsa, 1991).
E t h e r b o n d c l e a v a g e
The influence of the used experimental conditions
was also studied for the cleavage of ether bonds
which are supposed to be abundant in some Type I
kerogens. The aim of the work was not an exhaustive
study of the released products but a comparison of
the reactivity on kerogen of some reagents commonly
used for this purpose in classical organic chemistry.
The reaction of trimethylsilyl iodide TMSI (Jung and
685
Kulkarni, 1983) at 80C for 48 h on Irati and
Aleksinac kerogens gave very complex mixtures. The
same result was obtained from the reaction of
synthetic phenyldecylether. Reaction of dimethyl-
boron bromi de (Guindon e t a l . , 1983, 1987) afforded
also a complex product which cannot be resolved.
The presence of amines which were not fully
identified and aromatic bromides was detected. The
reaction of HI, used in the well-known Zeisel method,
was precedently applied on kerogen (Vella and
Holzer, 1990). Four successive reactions were applied
to Aleksinac kerogen yielding 3.3% of soluble
products, based on the original kerogen. Irati
kerogen appeared to be more reactive, soluble
products corresponded to 6 wt% of the original
kerogen. After LAD reduction, the yields were 2.7
and 4.4%, respectively. In Irati products, n-alkanes
were the major components, corresponding to 67.2%
of the total resolved GC peaks. They were identified
in the C20-C~8 range (Fig. 2) with a regular
distribution centered on C27. Iso- and anteisoalkanes
were also present, corresponding to 6.1 and 4.5% of
the fraction, respectively. Their distribution is shown
in Fig. 3. Alicyclic alkanes were also present (6.2%
of the fraction) but they were not fully identified. In
Aleksinac, n-alkanes corresponded to 76.6% of
HI / LAD products, ranging from C2: to C~s with a
maximum at C28. Isoalkanes (5.3%) and anteisoalka-
nes (3.8%) were present in the same range as in Irati
but with differing distributions (Fig. 3). It must be
noted that monodeuterated hydrocarbons were
accompanied by d0-compounds in significant pro-
portions. It could indicate that the main part of the
released alkanes was initially trapped in the kerogen
matrix. If n-alkanes are commonly obtained after
chemical alteration (oxidation, transalkylation, hy-
drolysis...) of kerogens (Ambles e t a l . , 1988, 1993,
1994; Baudet e t a l . , 1994), iso- and anteisoalkanes
were never found as trapped molecules. The
hypothesis of a problem arising with LAD reduction
(excluding LAD quality) was corroborated by Ashby
e t al . (1993) who reported the occurrence of an
electronic transfer in the reduction of alkyl iodides:
the intermediate R" could fix either one deuterium
atom from LAD or one hydrogen atom from the
solvent (Et20 or THF):
R-I + Li AID 4 ~ Li AID4 +e + R- I' *
Et20
~ R* > R- D
-I- LiA1D 4
R e ) R- H
Et 20
Lister, 1977; Vickery e t a l . , 1979) and BBrs (Burwell,
1954; Chappe e t a l . , 1981; Rullk6tter and Michaelis,
1990) was not applied first, as they can react with
ester groups (Felix, 1974; Olah e t a l . , 1981; Bhatt
and Kulkarni, 1983). The reaction of FeCI3 in acet i c
anhydri de ( G anem and S mal l , 1974; Bhatt and
According to the authors, reduction of l-iodo-2,2-
dimethylhexane with LAD in THF gives only 28% of
d~-hydrocarbon. A low concentration in iodides must
favour the formation of do product.
From this result, we can assume that a part of the
n-alkanes were trapped molecules, the other part as
686 A. Amblbs et al.
13 n- al kanes
O i s o- al kanes
ant ei s o- al kanes
q hopanes 13
13
13
13
13
13
13
i
13
t ] I
t3
O
13 o
Fig. 2. Chromat ogram of hydrocarbons obtained after HI/ LAD treatment of lrati kerogen.
well as iso- and anteiso hydrocarbons were ether-
linked molecules. Their origin could be glycerol ether
lipids (Chappe e t a l . , 1981, 1982; Vella and Holzer,
1990; Pease e t a l . , 1992; Teixidor e t a l . , 1993). No
isoprenoidal alkyl groups (acyclic or cyclic) were
identified in Aleksinac and Irati kerogens indicating
that the glycerol ether lipids were not originally
produced by methanogens (Chappe e t a l . , 1981; Vella
and Holzer, 1990; Pease e t a l . , 1992; Teixidor e t al . ,
1993). Their origin could be sulfate reducing bacteria
which are known to produce glycerol ether lipids with
non-isoprenoidal alkyl side chains (Langworthy
IRATI ALEKSINAC
i s o- al kanes i s o- al kanes
~ 14 ~ 12
~2
~ 6 , ~
2
0
26 28 30 32 34 26 28 30 32 34
Carbon number Carbon number
ant ei s o- al kanes ant ei s o- al kanes
8 llli
161 16
~14
! i
12 12
IO
0 o
26 28 30 32 34 28 30 32 34
Carbon number Carbon number
Fig. 3. Distribution of iso- and anteiso-alkanes obtained from Irati and Aleksinac kerogens.
Chemical degradation of kerogens 687
C30
hopanea et~
~ hopanes [ 3 c t
hop anea (]B
SR epi rn~res 22R C29
~pim~res 22S
i i i
C30 C31
C32
O ~ C33
*' ~ S C31 ,-,-,
? ~ R 0 ~ C34
S~ l | ~ S R
I ' I ' I ' ' I
Fig. 4. Distribution of hopanes ( m/ z 191 fragmentogram) obtained after HI/LAD treatment of Irati
kerogen.
e t a l . , 1983; Vella and Holzer, 1990). C27-C34 ~,fl- and
fl,~t-hopanes (22R + 22S diastereoisomers) with ma-
jor C29 and C30 isomers were also present in the
reaction products from Irati, they represented i.7%
of the fraction, fl,fl-Hopanes were very minor
(Fig. 4). As the distribution was somewhat different
from that of hopanes identified in the extractable
lipids from the same kerogen (Kribii, 1994), it
appears that a part of the hopanes were obviously
linked to the kerogen by chemical bonds, probably by
ether linkages. It can be added that the hopanoic
acids produced by RuO4 oxidation were somewhat
different in distribution, they were C2s and C30~C34
(max C3.,) components (Kribii, 1994; Baudet e t a l . ,
1993). The presence of hopanes (as free or chemically
bound molecules) in the Irati kerogen is the signature
of a bacterial contribution in this material. Only
traces of hopanes were found in the products from
Aleksinac.
The BF3-Et20/Ac20 treatment was successfully
used for the cleavage of ether bonds or intramolecu-
lar cyclic ethers (Narayanan and lyer, 1965; Ambles
and Jacquesy, 1972). The formation of acetates and
alkenes is expected with this reagent. Three successive
reactions on Irati kerogen concentrate (200 rag)
yielded 16 mg of soluble products (10.9% wt of the
initial kerogen). Two analyzable fractions F1 and F2
were obtained after SiO2 chromatography. The F I
fraction (1 mg) contained C20-C, n-alkanes (max C2~
and C30) and C28-C3, hopanes (max C29 and C30)
identical to hopanes found in the bitumens (Kribii,
1994). No iso- and anteisoalkenes (or iso- and
anteisoalkanes as trapped molecules) were found.
The F2 fraction (2 mg) contained three main types of
components. C~4-C~9 fatty acid methyl esters with
clearly dominant C,6 and C~s members (Fig. 5a) were
identified as well as the corresponding fatty acid ethyl
esters. It must be noted that the ratio of methyl over
ethyl esters has the same value for all members. One
hypothesis could be that methyl and ethyl esters were
o Linear rnet hy l es t ers
Linear et hy l es t ers
v Acetate of c hol es t erol
Acetate of 24-ethylcholesterol
( a ) o Linear methyle.sters
Linear et hy l es t ers
v Acetate of c hol es t erol
Acetate of 24-eth,' lcholesterol v
To[
( b )
Fig. 5. Chromatogram (part) of esters and acetates obtained by reaction of BF3 on Irati kerogen (a), and
(b) co-injection with pure 24-ethylcholesterol.
688 A. Amblbs e t al ,
present as esters in the kerogen, but they were still not
identified among lipids from Irati (Kribii, 1994).
Remembering that palmitic and stearic acids were the
main fatty acids identified after KMnO4 oxidation
(Vitorovic e t a l . , 1987) or PTC-hydrolysis of the
kerogen, a second hypothesis would be that
esterification or transesterification of fatty acids
might occur with the BF3-Et20/Ac20 treatment.
Acetates of cholesterol and 24-ethylcholesterol
(fl-sitosterol or clionasterol) were also identified by
GC- MS in the F2 fraction. Mass spectra and
retention times were identical to those of standard
cholesterol and fl-sitosterol. Co-injection with pure
standards led to homogeneous peaks with unchanged
mass spectra all along the peak. A part of the
chromatogram obtained after co-injection with
24-ethylcholesterol is given as an example in Fig. 5b.
The origin of sterols in such an old sediment is very
point is not clear, the identification of the two main
sterols, each one characteristic of animal or plant
material, with total preservation of the double bond
and of the skeleton is noteworthy and surprising.
Further experiments will be conducted to expand on
this point.
The reactivity of trifluoroacetic acid was also tested
on Irati kerogen. CF3COOH is described as a specific
reagent for the cleavage of aromatic benzyl ethers
(Bhatt and Kulkarni, 1983; Marsh and Goodman,
1965). Marsh and Goodman (1965) showed that the
reaction is restricted to aromatic ethers since alkyl
benzyl ethers are not reactive. CF3COOH is supposed
to give no reaction with methyl ethers and esters
groups (Marsh and Goodman, 1965). Based on the
literature, we expected the reaction would free
alkenes or phenols if aromatic ether groups are
present in the kerogen (K: kerogen matrix):
(or plm~ls)
questionable. The reality of a sterol contamination
was not confirmed, only speculative assumptions can
be made. A first hypothesis could be that they were
present in Irati kerogen as free sterols (or acetates).
Nevertheless, contrary to hydrocarbons, they were
never identifed as trapped molecules after degra-
dation of this kerogen. A second hypothesis is that
they could be present as etherified sterols, but they
were not found in HI products. Despite that this
C14
c
C18
C2o
c22
C24 C
26
Fig. 6. Series of alkenes obtained from reaction of
trifluoroacetic acid on Irati kerogen.
The presence of seven series of isomeric branched
alkenes was detected in the reaction product, but they
could not be fully identifed. They are dominantly
even-carbon-numbered alkenes, ranging from C,4
to C26 (Fig. 6). This result seems to indicate that
aromatic ether groups are present in the kerogen. As
no phenols were found, aromatic rings are probably
inserted in the kerogen network, alkyl chains acting
as "substituents". The even carbon numbers of the
released chains clearly indicate a biological origin.
Such long chains bound to aromatic by oxygen could
be the result of O-alkylation between phenols and
aliphatic precursors, probably functionalized. The
already present kerogen could have an effect on the
formation of the anomalous alkylated species, as
reported by Williams e t a l . (1988). The alkyl chains
were possibly initially straight-chain precursors
affected by isomerization due to clay (Rigby e t a l . ,
1986). A second explanation could be a dehydration
reaction between two OH groups (etherification), the
reaction being favoured by clay (acting as acid) with
more or less pronounced isomerization. Isomeriza-
tion of the alkyl chains occurring during CF3CO2H
cleavage is also possible. The first step being
prot onat i on of the oxygen followed by O- C cleavage,
isomerization of the resulting carbocation could
occur, maybe "catalyzed" by the mineral matter
present in the kerogen concentrate. Other hypotheses
can be postulated but new investigation is needed.
The last used reagent was AiI3 which was described
to be a very powerful ether-bond cleaving reagent
(Bhatt and Kulkarni, 1983; Bhatt and Babu, 1984). In
Chemical degradation of kerogens 689
the presence of R- O- R' , 4 types of products are
expected to be formed: R-O-AII2; R' --O-AiI2; R- I
and R' - I , iodides being only present with excess of
AlL (difficult to appreciate in the case of kerogen).
Two successive reactions (72 h) gave 2% wt of soluble
products. C23-C36 n-alkanes were only present, they
were only trapped molecules on the basis of the
preceding results. This indicates that even if no
molecules chemically bound to the kerogen network
were released, bond cleavage had occurred.
As a partial conclusion, the reagents used for
ether-bond cleavage in kerogen afforded different
products, the reaction sites obviously differ widely.
The n-alkanes obtained from the reaction of
BF3/Ac20, AII3 and a part of the n-alkanes freed by
HI / LAD treatment were initially trapped molecules
in the kerogen, they were the same as n-alkanes from
the bitumens. The explanation is that with these
reagents the kerogen matrix is modified, bond
(ether?) cleavage occurs and strongly trapped
molecules can be freed. A part of the n-alkanes
produced by HI / LAD reaction on Irati and Aleksinac
kerogens arises from the cleavage of ether bonds
(partial d-labelling), as well as iso- and anteiso
alkanes and hopanes (Irati) which were not found
with the other reagents. Our results tend to indicate
that ether linkages may exist between sterols and
kerogen matrix (BF3) and between alkyl chains and
aromatic moieties of kerogen (CF3COOH). The
origin of the fatty acid methyl- and ethyl esters found
in the BF3-Et20/Ac20 reaction products is not yet
explained.
CONCLUSIONS
The results show that the use of PTC---crown ether
or Aliquat---enhances the reactivity of hydrolyzable
groups present in kerogen. The selectivity of the two
PTC is not equivalent. With Aliquat, soluble heavy
moieties from kerogen are mainly produced. Despite
that it affords lower amounts of soluble material,
18-Crown-6 can be preferred in the case of kerogen,
the yield of identifiable products being higher.
Furthermore, Aliquat-derived amines can interfere
with amide hydrolysis products.
The nature of the products released after
ether-bond cleavage on Irati kerogen differed widely
with the used experimental conditions. Series of
normal-, iso- and anteisoalkanes were obtained with
HI/LiAID4 indicating a contribution of glycerol ether
lipids. Hydroiodic degradation denoted the presence
of fl : t -hopanes linked by ether bonds. Except
n-alkanes, these products were not present in BF 3 or
CF3CO2H reaction products. The main interesting
compounds were sterols----cholesterol and 24-ethy-
cholesterol--released with BF~ and series of even
alkenes with CF3CO2H, these elements were probabl y
bound to kerogen by ether linkages. The results
suggest that natural sterols, which are relatively
unstable, could be completely preserved in immature
sediments. Reaction with CF3CO2H indicates that
saturated alkyl chains with even carbon numbers are
linked to aromatic rings by ether bonds in Irati
kerogen.
The diversity of the products freed from the same
kerogen and the unexpected low reactivity of some
reagents (All3) show that ether-bond cleavage in
kerogen is a versatile reaction. The reactive sites are
not the same from one reagent to the other, the
difference could be steric hindrance, activation or
deactivation from neighbouring groups etc. Another
point is that with such a complex material as kerogen,
the specificity of each reagent used can be
questionable. Consequently, different reagents must
be used as far as possible, before obtaining definite
conclusions. The reactions of BCI3 and BBr 3 (Chappe
et al . , 1981, 1982) on kerogen and TMSI on
hydrolysis residue from lrati kerogen are now under
investigation.
Acknowl edgement s--The authors are grateful to Prof. D.
Vitorovic (University of Belgrade) who kindly provided a
sample of Aleksinac kerogen, and to Prof. C. Costa-Neto
(University of Rio de Janeiro) who sent a substantial
amount of Irati sediment.
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