Org. Geochem. Vol. 26, No. 1/2, pp.

33~12, 1997
Pergamon © 1997ElsevierScienceLid
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A study of petroleum alkylcarbazoles using 1H NMR spectroscopy

M. B. SMIRNOV and E. B. FROLOV
Institute of Petrochemical Synthesis, Russian Academy of Science, Leninski prospect 29, Moscow B-71,
Russia

Abstract--A precision method for measuring proton chemical shift calculations of methylcarbazoles has
been developed. For other abundant substituents the proton chemical shift correlation diagrams are
reported. The method makes it possible to identify a number of carbazole structures present in pet-
roleums. General structural regularities of petroleum carbazoles have been defined from 'H NMR data.
Methylcarbazole isomers with 1- and 1,8-substituents were found to be most abundant in crude oils.
Structures with three or more adjacent Me-groups and with substituents in both 4,5-positions are
absent. The distribution of methyl substituents is likely to be controlled partly by migration processes.
On the other hand the distribution of non-methyl substituents is of a different character and can vary
with chain length. © 1997 Elsevier Science Ltd

Key words--carbazoles in crude oils, IH NMR of carbazoles, chemical shift calculations for carbazoles

INTRODUCTION N M R spectra of fractions of petroleum polar com-

Carbazoles are known to be the major type of
nitrogen compounds in crude oils (Stoddart et al.,
1991). A knowledge of their structure is needed for
an understanding of the geochemistry of nitrogen.
Also, it has been found recently that the distri-
butions of N - H shielded and N - H exposed isomers
provide data on migration of petroleums (e.g. Li
and Larter, 1993; Li et al., 1994; Larter and Aplin,
1995). Petroleum carbazoles consist of a great
number of positional isomers and C2-C5 carbazole
derivatives (as believed mostly with methyl substitu-
ents) are those normally predominant in crudes
(Dorbon et al., 1984; Frolov et al., 1989; Frolov,
1995).
However, C2-C5 compounds that have been
identified constitute only a small part of the total
C2-C5 carbazole fraction. Structural investigations
are fraught with difficulties: for instance, the mass
spectra of methyl substituted carbazoles are similar
for different positional isomers; at the same time
the number of possible structures increases very
rapidly with increasing molecular weight (20 and
210 for C2 and C4 carbazoles, respectively).
1H N M R spectroscopy can be used successfully
for structural studies of substituted aromatic mol-
ecules (Chamberlain, 1977). Previously we found
that tH N M R spectra of CI-C5 petroleum carba-
zole fractions (which were mostly free of non-carba-
zole compounds) demonstrated a number of narrow
resolved signals: some of them differed by less then
0.05 ppm (Smirnov et al., 1988). The signal pos-
itions in the spectra were considerably different
when CDCI3 and CrD6 were used as solvents. It
should be noted, that such spectral resolution was
much higher than that normally observed for IH
pounds. These observations led us to believe in the
high potential of ~H N M R spectroscopy for struc-
tural investigations of petroleum carbazoles.
However, no attempts have been made to analyze
those highly resolved IH N M R spectra in order to
obtain data on structures of petroleum carbazoles.
ZH N M R spectra of 28 standard mono-, di-, tri-,
tetra- and pentamethylcarbazoles with various
arrangements and locations of methyl groups, in two
solvents (C6D6 and a mixture of CC14 + CDCI3
2:1) were measured (Smirnov et al., 1988; Smirnov
and Frolov, 1989a,c). It was shown that the chemi-
cal shift of any aromatic as well as any methyl
group proton in methyl substituted carbazole mol-
ecules can be calculated for both solutions using the
additive scheme described by Smirnov and Frolov
(1989b,c). A number of standard methyl substituted
carbazoles were also described using 1H N M R by
Kuroki and Tsunashima (1981), but 1H N M R spec-
tra of alkylcarbazoles (with substituents C2+) were
not reported.
In this paper we report for the first time the
analysis of highly resolved 1H N M R spectra of car-
bazole fractions isolated from crude oils. We
describe data on the content of Me-, Et-, n-Pr- and
n-Bu substituents and their distributions.
Preliminary data have already been published
(Smirnov and Frolov, 1995).
EXPERIMENTAL
C l - C 5 carbazole concentrates (mostly free of
non-carbazole compounds and benzocarbazoles)
were isolated from corresponding petroleum vac-
uum-distillate fractions using two-step column

33
34 M.B. Smirnov and E. B. Frolov
liquid chromatography on silica gel (Frolov et al.,
1989). The method included developing with hexane
containing Et3N (30%) as an active component.
The carbazole concentrates isolated contained 4.6-
4.8% N from elemental analyses and were free of
phenols and other types of hetero- and polycyclic
aromatic compounds as indicated by IR and low
voltage (15 eV) mass spectrometry.
The conditions for GC separation were: silica col-
umn 25 m x0.25 ram; coated with SE-30; carrier
gas H2; oven programmed at 100-280°C at 5°C/
min.
1H N M R spectra were obtained on a Bruker WM-
250 spectrometer at 250 MHz. The experimental con-
ditions were: temperature = 303°K, single channel
detection with phase alternating pulse sequence,
pulse width = 3#s (flip angle = 70), sweep
width = 3500 Hz (4500 Hz for solutions in hexam-
ethylphosphoramide (HMPA)), filter width =
10 KHz, acquisition time = 2.4 s (1.8 s for solutions
in HMPA), relaxation delay = 10s, number of
pulses = 100-200. Spectra were also obtained on a
Bruker WH-360 spectrometer at 360 MHz using
equivalent conditions (sweep width = 5040 Hz).
N-deuterated carbazole fractions were studied by
IH N M R in C6D6 and in a mixture of
CC14 + CDC13 2:1. Deuteromethanol with a trace
amount of DCI was used for H - D exchange. The
concentration of petroleum carbazoles was 9.5-
4 3
C6DsH
1
H
.d
i :11 Ar-C-C c
I [ -(1
n)
HIs I-if+
X2
• 810 ' 710
I'Ia..4
mmmm
H* H*
H H H H
Aromatic protons
Fig. i. iH NMR spectrum (250 MHz) of the N-deuterated carbazole fraction CrC5 (in C6D6) from
Samotlor crude oil.
10.5 mg/ml for solutions in CC14 + CDCI3 2:1 and
C6D6; and 5-20 mg/ml for HMPA solutions. The in-
ternal standard was TMS. The assignment of signals
in the IH N M R spectra of the standard methylcarba-
zoles, as well as chemical shifts and spin-spin coup-
ling constants, were described in Smirnov et al.
(1988), and in Smirnov and Frolov (1989a,c).
RESULTS AND DISCUSSION
G e n e r a l s t r u c t u r a l characterization
Typical IH N M R spectra of the petroleum carba-
zole fractions studied are shown in Figs 1 and 2.
As can be seen from the spectra, CI-C5 petroleum
carbazoles contain not only methyl, but also alkyl
substituents C2+ (corresponding signals are in the
field 0.7-1.8 ppm). In order to interpret correspond-
ing signals, we studied lH N M R spectra of stan-
dard alkylcarbazoles with C2+ substituents: 1-, 3-
ethyl-, 1-, 4-n-propyl-, 1-, 4-n-butyl-, 1-, 4-n-heptyl-
and 3-n-C18-carbazoles in two solvents (C6D6 and a
mixture of CC14 + CDCI3 2:1). The chemical shifts
of aromatic protons of the alkylcarbazoles exam-
ined differed from those for aromatic protons in
corresponding methyl substituted analogues by less
then 0.03ppm and were assigned using IH-{IH}
decoupling experiments and on the basis of J
values. Assignment of the proton signals of C2+
substituents was based on 3 and J values
3".0 2.0 1.0 8, ppm
i-ia.3
I.i%2 Ha- 1 H~
mmimml mm~m wy+
I.~..4 I~-2 I.~-I ~ ........
Ha.3 H~ H'v+
Protonsofalkylsubstituents I ~I l i ~".CH
I.13*2,;CH,
 A study of petroleum alkylcarbazoles 35

"r~
.~ CHCI3

e~
,.s
,=_

8~0 710
A 310
Ha-l,2,3
210
HIS H'y+
1'.0 8, ppm

I W U ~
H* H*
. . . . . .

H H Ha.,) H%1,2,3 HIS H")'+

Aromatic protons Protons of alkyl substituents

Fig. 2. IH N M R s p e c t r u m (250 M H z ) o f the N - d e u t e r a t e d c a r b a z o l e fraction C I - C 5 (CCI4 + CDCI3 2:1

solution) f r o m S a m o t l o r c r u d e oil.

(Chamberlain, 1977). Table 1 provides data on the
proton chemical shifts of the standard alkylcarba-
zoles studied in both solvents.
So as to assign signals in the spectra of petroleum
carbazole fractions, the first approximation of
chemical shift correlation diagrams (see Figs 1-4)
was obtained for both solutions taking into
account: (i) the additive scheme described for
methylcarbazoles (Smirnov and Frolov, 1989b,c);
(ii) tH N M R data on alkylcarbazoles; and (iii) stan-
dard regularities known for chemical shifts of alkyl
substituents on aromatic tings (Chamberlain, 1977).
General structural characterization of petroleum
carbazole fractions has been made in the present
paper in the following terms:
Nrt,t - - average number of aromatic H-atoms
per carbazole molecule;

Table 1. Proton chemical shifts of alkylcarbazole substituents for solutions in C6D 6 and CC14 + CDCI3 (6, ppm)
Substituent HMe. CH2-group
H~ Hg H,. Others

in C6D6
l-Et 1.117 2.464
l-n-Pr 0.860 2.478 1.546
l-n-Bu 0.865 2.537 1.536 1.278
l-n-C7 0.904 2.578 1.607 1.26
3-Et 1.279 2.736
3-n-Cis 0.916 2.811 1.764 1.338
4-n-Pr 0.956 3.121 1.821
4-n-Bu 0.867 3.179 1.800 1.408
4-n-C7 0.862 3.209 1.851 1.427 1.222
in CC14 + CDC13
l-Et 1.423 2.918
l-n-Pr 1.062 2.865 1.840
l-n-Bu 0.990 2.884 1.783 1.470
1-tI-C7 0.889 2.870 1.789 1.382 1.30
3-Et 1.335 2.808
3-n-Cis 0.884 2.751 1.684 ~333 1.250
4-n-Pr 1.103 3.174 1.878 P
4-n-Bu 1.005 3.197 1.810 1.533
4-n-C7 0.889 3.185 1.837 1.510 1.325
*Terminal Me group of a substituent.
36
i~ - protons in CH2. and CH-groups:
.t~--'q~,c";'+ ~ - ~;~..
. H
, , , , , . . . . .
3.0
Fig. 3. IH NMR spectrum (250 MHz; aliphatic region) of the N-deuterated carbazole fraction CrC5
(in C6D6) from Samotlor crude oil, and the correlation diagram for fi values.
NMe, t (NEt,t; Nn_Pr,t etc.) - - average number of
Me (Et, n-Pr etc) groups per carbazole molecule;
Ncs+,t (Nc4+,t; Nc3+,t; Nc2+t) - - average
number of C5+ (C4÷, C3÷, C2÷) substituents
per carbazole molecule;
NMe, I (NMe,2 and 3; NMe,4) - - average number
of Me groups per carbazole molecule in 1- and/
or 8-positions (2- and 3- and/or 6- and 7-; 4-
and/or 5-positions);
NEt, I (NEt.2;...; Nn-Pr,l; Nn'pr,2;...; Nn-cs+,l;
N.-c5+,2...) - - average number of Et (n-Pr . . . .
n - C 5 + , . . . ) groups per carbazole molecule in
corresponding positions.
An average number of all types of substituents
per carbazole molecule is designated as NR,t
(correspondingly NR.] - - average number of substi-
tuents per carbazole molecule in 1- and/or 8-pos-
itions and so on).
Most of the parameters listed above can be calcu-
lated from the spectral data (Figs 1-4). The average
number of a substituent can be computed as follows
(an example is given for the n-Bu group):
Nn-Bu,t = Nrl.t*(In-Bu/3Iar)c
M.B. Smirnov and E. B. Frolov
i:;:;:;:;:; " pmt°nsin CH3"groups:
.SO,
t'~- .' ~" c.;
. . . . . . . . . . . . . . . . . .
2.5 2.0 1.5 1.0 8, ppm
The index c indicates that a CC14 + CDC13 mix-
ture was used as a solvent. In-Bu is an integral inten-
sity of protons of the terminal CH3-protons of the
n-Bu group (6 0.92-1.06; see Fig. 4); Iar is an inte-
gral intensity of aromatic protons (see Fig. 2). It
should be noted that the limits of the integration
range differed slightly for various samples and were
dependent on the spectrometer frequency.
The NH,t value (which was a normalizing par-
ameter for all of those equations) can be calculated
using the data of IH N M R spectra of carbazole
fractions in HMPA. Indeed, carbazole concentrates
isolated were free of N-alkyl substituted compounds
because there were no signals in the region of 3.5-
5.0 ppm in their IH N M R spectra. So, NH,t can be
calculated as follows:
NH,t = (Iar/INH)h
where index h indicates that the spectrum in HMPA
solution was used; Iar and INn are the integral
intensities of all Har (6.5-8.5 ppm resonance region)
and of all N - H protons ( l l . l - l l . 5 p p m for com-
pounds with substituents both in the 1- and 8-pos-
itions; and l l.8-12.2ppm for the rest of the
carbazole NH protons, (Frolov et al., 1989).
 A study of petroleum alkylcarbazoles 3'7

able position of a substituent). The series of X par-

ameters were calculated as follows:

Xsbt, j = (Nsbtd/Nsbt,t)*(8/nj)
S where Sbt = R, Me, Et, n-Pr . . . . ;

j = 1; 2 and 3; 4;

nj = 2 for positions 1 and 4;

n:= 4 for positions 2 and 3.

The preferable positions for methyl groups were

observed to be 1 and 8 (XMe.1 = 1.85). The fact that
the shielded methyl carbazoles are normally predo-
minant in oils was reported early (e.g. Frolov et al.,
1989; Li and Larter, 1993; Larter and Aplin, 1995).
This has been attributed to the migrational fraction-
i . . . .
ation of petroleum carbazoles (as observed, there is
1.5 1i0 8, ppm an increase in the shielded/exposed isomer ratio
during petroleum migration). In the present work
Et, i-Pro d~ ~ : we have studied the whole C l - C 5 earbazole frac-
tion. Thus, the parameter XMe,1 ( o r XMe,I/XMe,4
which can be obtained more easily) measured by 1H
H~+ in CH, CH 2 N M R seems to be useful for migration-related
research.
Fig. 4. ~H NMR spectrum (250 MHz, 6 < 1.5 ppm) of the
N-deuterated carbazole fraction C l ~ s (in CCI4 + CDCI3 On the other hand, the positions 1 and 8 are not
2:1) from Samotlor crude oil, and the correlation diagram preferable for the non-methyl substituents
for ~ values. (XEIA = 1.15 and Xn-c3+,t <0.6). Ethyl groups can
be seen in all positions with about equal prob-
Table 2 exemplifies the results obtained. The ability. The preferable positions for the longer sub-
most abundant substituent type in the C1-C5 pet- stituents (n-C3+) seem to be 2 and/or 3. This
roleum carbazole fractions analyzed is a methyl unexpected observation may be of interest for our
group: Me > Et > n-Pr, n-Bu. However, carba- understanding of petroleum carbazole genesis.
zoles with n-C3+ substituents (n-Pr-, n-Bu- and n-
C5÷) constitute as much as ~1/8 per C r C 5 carba- Table 2. Distribution of substituents in C l - C 5 carbazole fraction
zole fraction from Samotlor oil. This estimation of Samotlor oil
was made on the assumption that carbazole mol- Substituent, position N* X**
ecules from that fraction may contain one n-C3+
R,t * 2.77
substituent. The total amount of carbazole mol- Me,t 2.15
ecules with C2 + substituents was evaluated to be as Et,t 0.48
n-Pr,t 0.032 --
much as 50% per fraction. It should be noted that n-Bu,t 0.09*
n-C3+ carbazole derivatives were not detected in n-C5+,t 0.008t
petroleums previously. R,1 1.15 1.65
R,2 and 3 1.13 0.80
Using the correlation diagrams (Figs 2 and 3) dis- R,4 0.49 0.70
tributions of different substituents on carbazole pos- Me,I 1.00 1.85
Me,2 and 3 0.82 0.75
itions can be evaluated as well; results are presented Me,4 0.33 0.60
in Table 2. Distribution of the substituents was EtA 0.14 1.15
EtA 0.13 1.10
found to be variable. So, about 50% of methyl n-C2+,l 0.15 1.00
groups were in positions 1 and 8; but only ~ 3 0 % of n-C2+,4 0.16 1.05
ethyl and less than 20% of n-C3+ alkyl groups are n-C3+,1 < 0.02t < 0.06
n-C3+ ,4 0.02 + 0.03~; 0.6 + 0.9
in the 1- and 8-positions for carbazoles of Samotlor
crude oil. *N is an average number of a substituent (Me, Et, etc.) in a pos-
ition (1, 2 and 3, 4); or in all positions totally per molecule
Deduction about the preferable positions for the (for instance, Na,t, see text).
substituents considered can be drawn from the **X is a parameter which characterizes a deviation of a substi-
tution degree from the equally probable value (see text).
values of parameter X (see Table 2), which charac- *Index t indicates that all positions are considered totally.
terize a deviation of substitution degree from the terror of N value measurements was larger than 10% re[,, for the
rest of the N values error was about 5-10% rel. (rms was
equally probable value (for instance, X = 1 in the about 2-3% tel.); the errors for the corresponding X values
case of at random distribution; X > 1 for a prefer- were about 1.5-2 times higher.
38 M . B . Smirnov and E. B. Frolov

E
-..Lz=

J
0

£gL'9 L - - - - ~ - - ' ' ' "

Z
9LL'9
0

i~L8~t9'<. ~ +

dI

E
e~

(s) L6g'L
(s) gI9"L
,M Z

(s) gg9"L "r

(s) ICL'L
(s) 6gL'L
,0
Z
~m '~ ~ ~
(P) 606"/. - - - [ 0

0
L~._J. 'x,~-= ~ F::;] [...
 A study of petroleum alkylcarbazoles 39

Table 3. CalculatedH-3 and H-5 chemicalshifts of some methylcarbazoles(solutionin CCI4+ CDCI3)

No. Carbazoles H-3 H-5
6(H-3) 6-range* 6(H-5) f-range* Multiplicity**

Ila 1,4,8-Me3- 6.869 6.844--6.894 7.942 7.917-7.967 m

llb 1,4,7-Me3- 6.845 6.820-6.870 7.963 7.938-7.988 bd
llc 1,4,6-Me3- 6.843 6.818-6.868 7.890 7.865-7.915 bs
Ilia 1,4,7,8-Me4- 6.850 6.825-6.875 7.843 7.818-7.868 bd
lllb 1,4,6,8-Me4- 6.842 6.817-6.867 7.732 7.707-7.757 bs
lllc 1,4,6,7-Me4- 6.828 6.803-6.853 7.834 7.809-7.859 bs
*The range in which a corresponding signal may be observed. Their limits have been calculated as 6(Hi) +_0.025 ppm (see Table 7,
Appendix).
**bs--broadened singlet; b d - - b r o a d e n e d doublet; m--multiplet (X-part of ABXY3 spin system with JAx = 8.1 Hz, Jxv = - 0 . 6 Hz and
I6A-6.I/JA. ~1).

Structural characterization in more detail rials corresponding to 4,5-substituted structures,

The correlation diagrams (Figs 1-3) provide some and structures with three or more adjacent substitu-
additional structural information. For instance, car- ents are not present in the spectrum of this fraction
bazoles with substituents in 1,2-positions (Fig. 3 : 6 either. Consequently, we have to consider structures
1.95-2.08 ppm) can be indicated as minor struc- (II) or (III) with one or two substituents in the sec-
tures. ond aromatic ring and with non-substituted pos-
Also we detected structures with one non-substi- ition 5 only.
tuted aromatic ring in low abundance (Fig. 1 : 6 Taking into account that Me groups are the pre-
7.3-7.4; Fig. 2:6 7.25-7.35). dominant type of substituents for carbazoles in our
Petroleum carbazole fractions have been found to fractions, we have calculated the chemical shift
be free of the structures with three or more adjacent values for H-3 and H-5 aromatic protons for all
methyl groups (Fig. 3 : 6 2.20-2.28) and of the 4,5- possible Me-carbazoles (listed in Table 3) with Type
substituted isomers (Fig. 3 : 6 2.78-2.93). Taking II or III structures. Isomer IIa must be excluded
into account the above observations, we have
obtained more precise incremental values for calcu-
lating chemical shifts of protons in ~H N M R spec-
tra of petroleum carbazoles. This made the
calculation precision abnormally high (with the rms
deviation as low as 0.01 ppm; see Appendix).
The next example demonstrates the application 11
and high potential of the additive scheme devel-
oped. We studied a CI-C6 carbazole fraction iso-
lated from the Nibel oil (Timan-Pechora basin,
upper Devonian). In the spectrum of this fraction,
dissolved in CC14 + CDCI3 2:1, the broadened
1i 8
doublet with a high intensity at 6 6.841 ppm and
with J = 7.2 Hz can be seen (Fig. 5). 7
To assign this signal the detailed correlation dia-
gram for the field 6 6.7-6.9 ppm was calculated. As
seen from the diagram (Fig. 5), this doublet must
correspond to the H-3 resonance in structure (I), G
and its J value corresponds to the above assignment
too (Smirnov and Frolov, 1989a,c).

.N ~ H
R R
[ II
R, R', R", R" = Me, Et, etc
1H N M R spectroscopy showed that the fraction
isolated from the Nibel oil is free of carbazole de-
rivatives with one non-substituted aromatic ring
(there were no signals at 6 7.3-7.4 ppm in the spec-
trum for the CC14 + CDC13 2:1 solution). The sig-
4, H
< Time
R
I[I Fig. 6. Gas chromatogram (partial) of the CrC6 carba-
zole fraction from Nibel oil. Detection: FID. Peaks co-
inciding in retention time with the standard carbazoles are
the following: C = carbazole; 1-(1), 2-(3), 3-(2), 4-(4) Me-;
1,8-(5), 1,4- +1,5-(7)Me2-; l-Et-(6), 1,3,8-(8), 1,4,8-
(9)Me3; 1,3,5,8-(10), 1,3,4,8-(11) Me4-carbazoles (figures
on GC correspond to those in bold in brackets). The peak
marked with an asterisk corresponds in retention time to
1,5,7-trimethylcarbazole (see text).
40
from consideration because the difference between
the measured and calculated 6 H-3 is larger than
3 rms (see Table 3 and Table 7 in the Appendix).
Analysis of the H-5 resonance region lets us make a
choice between the rest of the structures (IIb-IIIc).
The isomers IIc and IIIc can not be considered
because there are no singlets at 6 > 7 . 8 0 5 p p m
(Fig. 5), Structure l i b also has to be eliminated
from consideration because there is no doublet of
corresponding intensity at ~ 7.94-7.99 ppm. Also,
the doublet with J = 8.1 Hz at 6 7.818-7.868 ppm
(structure Ilia) was not seen in the spectra.
A t the same time, the singlet at 6 = 7.741 ppm
(isomer IIIb) was observed. Its integral intensity
was about two-thirds of that for the doublet at 6
6.841 ppm. Most probably, this is due to the pre-
sence of isomers with a non-methyl substituent in
position 6. Most of the well-resolved signals
observed in the spectra can be assigned in a similar
way. This allowed us to identify the abundant car-
bazole structures I V - V I I (it is not possible to say
anything about substitution in the positions with
either H or R).
iV V Vl
= Me R = Me, Et, etc
It should be noted that the structural data
obtained by IH N M R are in agreement with the
results of G C analysis of the carbazole fraction
from the Nibel oil. Some peaks of high intensity in
the G C trace were identified by co-injection of the
standard carbazoles (see Fig. 6). The most abun-
dant isomers were found to be carbazole derivatives
with Me-groups in positions 1 and 8.
H • H N
VII
1,5,7-trimethylcarbazole (VII) was detected in the
fraction analyzed by ~H N M R and in the G C trace
(VII; marked with asterisk). However, it seems to
be broadened, and may include one or more other
carbazole derivatives.
Thus ]H N M R spectroscopy seems to be a new
power tool for the investigation of petroleum carba-
zole structures.
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Sanin P. I. (1988) Use of IH NMR spectroscopy to
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spectroscopy to study petroleum alkylcarbazoles.
Dimethylcarbazoles (in Russian). Neftekhimia 29(2),
172 180.
Smirnov M. B. and Frolov E. B. (1989b) Use of ~H NMR
spectroscopy to study petroleum alkylcarbazoles.
Polymethylcarbazoles in a CC14 + CDCI3 mixture.
Petrol. Chem. USSR. 29, 220-229.
Smirnov M. B. and Frolov E. B. (1989c) Use of IH NMR
spectroscopy to study petroleum alkylcarbazoles.
Polymethylcarbazoles in hexadeuterobenzene. Petrol.
Chem. USSR. 29, 229-236.
Smirnov M. B. and Frolov E. B. (1995) A study of pet-
roleum alkylcarbazoles using IH NMR spectroscopy. In
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APPENDIX
Precise Additive Scheme For Calculating Chemical Shifts
For Petroleum Methyl Substituted Carbazoles
Calculations of the chemical shifts of aromatic (6e(Harj))
and methyl (~c(HMej)) protons were carried out using the
following equations:
 A study of petroleum alkylcarbazoles 41

which are modelling petroleum carbazoles (i.e. without

~c(HMe,j) = ~0(HMe,j) + 2Ki(HMe4)
i
(~c(Har,j) = ~o(Harj) + ~-~Ki(Har,/) + 2 K i , i + l ( H a r j ) (A2)
i i
where index j indicates the position of the Hat or Me-
group of which the chemical shift is to be calculated;
index /--the positions of other Me-groups in the isomer
under consideration; ~0 (H~j) is the H ~ 6 value in the j-
position of a non-substituted carbazole; 60(HM~j) is the 6
value of the Me-group protons in a mono-substituted j-
Me-carbazole (Table 4). K,{HaFj) and K,{HMcj) are the
effects of the substituent in position i on the ~ values of
the aromatic proton at the position j and the protons of
Me-groups in position j. These increments have been used
for Me-groups without any substituent in the adjacent
positions. Any two Me-groups in adjacent positions i,
i + 1 were regarded as one combined group with
Ki,i + I(Harj) increment. For symmetry reasons
K~{Harj) --- K9.1{Har,9.j); Ki, i + l(Hard) -----Ka_i,9.1{Har,9,j);
K,{HMcj) = K9.,{HM¢,9.j) (for instance, the effect of the
substituent in position 1 on the chemical shift of Har at
position 6 is the same as that of the substituent in position
8 on that in position 3). To calculate the increments
K,{H~rj), K i , i + l(Har4) and K,{HMej) the standard iter-
ation procedure for minimizing equations (3) and (4) was
used:
m i n ( 2 2 { S m ( H / ~ , / ) -- (~c(H~r4)}2)
i 1
m i n ( 2 E { ~ m ( H ~ e j ) - ~c(H~de4)} 2)
i I
where 6~ are the measured 6 values of aromatic (6 m (H~j)
or methyl (6m(HM~j)) protons, sum by I means summation
by protons of all our synthetic Me-substituted isomers
(AI) compounds with three or more adjacent substituents and
4,5-substituted isomers). The values of K,(H~rj),
Ki.i + l(H~j) and K,(HM=fl are given in Tables 5 and 6.
The next example illustrates the application of the additive
scheme described. Chemical shifts of Har,3 and HM~,4 in
1,2,4,8-Me-carbazole are calculated by the equations:
~c(Har.3) = 80(Hat.3) + K4(Har.3) + Kl(Har.6)
+Kt,2(Har.3) = 7 . 1 9 4 - 0.213 + 0 . 0 3 0 - 0.146
= 6.865 ppm(3m = 6.870 ppm)
t$c(HMe.4) = d0(HMe,4) + KI(HMe,4) + K2(HMe,4)
+KI(HMe,5) = 2.685 + 0.035 - 0.005 + 0.034
= 2.749 ppm(~m = 2.746 ppm).
To characterize the precision of chemical shift calculations
a number of parameters were used because the deviation
distribution may be non-random: rms deviation, bias
(Aav), maximum positive (A +) and negative (A-) devi-
ations, correlation coefficient (r) (Table 7). The calculation
by equations (A3) and (A4) with increments from
Tables 4-45 was shown to give a zero bias with an rms de-
viation of less then 0.01 ppm and a maximum deviation
(A3) <0.03 ppm for H ~ and < 0.025 ppm for HM~. It should
be noted that in the above cases the temperature and con-
centration of the solution have to be controlled carefully.
(A4) To verify the additive scheme described the calculated Me-
group proton chemical shifts for polymethyl carbazoles
were compared with the experimental ones reported by
Kuroki and Tsunashima (1981). The measured and calcu-
lated values were in very close agreement (Table 8).

Table 4. Proton chemical shifts of Har for non-substituted carbazole 60(H~r,i) and HMe for mono-substituted j-Me-carbazoles t~0(HMej)
H~,~j fio(H~r,j), ppm HMe,i 6o(Ha~,i), ppm
in C6D 6 in CCI4 + CDCI3 in C6D 6 in CC14 + CDCI~
H=~.l; Har.s 7.041 7.342 HM=a 2.101 2.555
Ha,.2; H~r.7 7.357 7.340 HMe,2 2.428 2.513
Hat.3; Hat,6 7.194 7.167 HMe,3 2.433 2.521
Har.a; Ha~.~ 7.979 8.010 HMe,4 2.685 2.864

Table 5. Increment values K,(Har,/); K i i + l(Harj); K*(HM©j)in ppm) for proton chemical shifts fi(Harj) and fi(HMe,i)of petroleum methyl-.
carbazoles in C6D6
Me-position (0 Position of the observed nucleous (j)
j= 1 j=2 j=3 j=4 j= 5 j=6 j=7 j= 8
aromatic protons (H~rj)
1- -0.230 -0.018 -0.082 0.041 0.030 0.026 0.035
2- -0.172 -0.180 -0.083 -0.009 0.008 0.001 0.011
3- -0.042 -0.177 -0.169 0.040 0.012 0.002 -0.022
4- -0.080 -0.043 -0.213 0.166 0.042 0.034 0.048
1,2- -0.146 -0.146 0.033 0.035 0.021 0.088
2,3- -0.157 -0.177 0.047 0.021 0.010 0.025
3,4- -0.126 -0.133 0.241 0.049 0.034 0.044
methyl protons (HMcd)
1- -0.104 -0.003 0.035 0.034 0.018 0.013 0.039
2- -0.123 --0.146 -0.005 0.019 -0.003 0.017 0.019
3- 0.010 --4).131 -0.076 0.040 0.013 -0.004 0.012
4- 0.017 0.007 -0.081 0.145 0.049 0.027 0.019
42 M . B . S m i r n o v a n d E. B. F r o l o v

Table 6. Increment values (K,(H~rj); Kc~ + I(Harj); K,(HM=,/) in ppm) for proton chemical shifts 6(H~r,/) and tf(HM=•) of petroleum methyl-
carbazoles in CCI4 + CDCI3
Me-position (t3 Position of the observed nucleous (/)
j= 1 j=2 j=3 j=4 j=5 j=6 j=7 j=8

aromatic protons (Hat,i)

1- -0.183 -0.083 -0.158 -0.010 0.001 -0.008 0.035
2- -0.211 -0.181 -0.137 -0.054 -0.023 -0.046 -0.036
3- --0.103 -0.162 -0.210 -0.036 -0.026 -0.022 -0.022
4- -0.149 -0.105 -0.216 0.100 0.014 0.002 0.026
1,2- -0.169 -0.257 -0.018 -0.018 -0.026 0.002
2,3- -0.247 -0.266 -0.080 -0.041 -0.053 -0.054
3,4- -0.275 -0.176 0.171 -0.006 -0.010 -0.016
methyl protons (HM=j)
1- -0.053 --0.044 -0.028 -0.009 0.012 0.006 0.030
2- --0.123 -0.116 -0.045 -0.024 -0.014 -0.014 -0.015
3- -0.042 -0.112 -0.070 -0.012 -0.011 -0.016 -0.019

Table 7. Values of parameters characterizing deviations calculated from measured chemical shifts*
Solvent Type of H-nuclei Aav rnls A+ A- r

CC14 + CDCI3 Hat 0.000 0.009 0.024 -0.028 0.9994

HMe 0.000 0.005 0.015 --0.017 0.9993
C6D6 H~r 0.000 0.008 0.026 -0.029 0.9993
HMc 0.000 0.007 0.023 -0.012 0.9996
Where Aav= (6:~m)--the average deviation between the calculated and measured 6 values;
A + = maximum positive deviation;
A- = maximum negative deviation;
r = correlation coefficient.
*For carbazoles without three or more adjacent Me-groups, and 4,5-substituted isomers.

Table 8. Comparision of the calculated chemical shifts of methyl

groups for some tetramethylcarbazoles with those measured by
Kuroki and Tsunashima (1981)
Carbazoles Me-groups 6, measured* 6, calculated

1,2,5,7-Me4- HMe.I 2.39 2.422

HMe,2 2.46 2.463
HMe,S 2.80 2.794
HMe,7 2.46 2.473
1,3,4,6-Me4- HMe, I 2.48 2.458
HMe,3 2.43 2,412
HMe.4 2.77 2,753
HMe.6 2.53 2.542
2,3,6,7-Me4- HMe.2 2.40 2.378
HMe.3 2.40 2.380
HMe,6 2.40 2.380
HMe,7 2.40 2.378
*Solution in CDCI3. HMe chemical shifts were published without
assignment.