Design of schiff base-like postmetallocene catalytic systems for polymerization of olefins: IV. Synthesis of 2-(aryliminomethyl)-pyrrole and 7-(aryliminomethyl)indole derivatives containing cycloalkyl substituents

Article abstract of DOI:10.1134/S1070428007040148

Reactions of 4,6-substituted 2-cycloalkylanilines with 1H-pyrrole-2- carbaldehyde and 1H-indole-7-carbaldehyde in methanol in the presence of formic acid gave the corresponding Schiff bases which can be used as ligands for titanium and zirconium complexes

Full text of DOI:10.1134/S1070428007040148

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2007, Vol. 43, No. 4, pp. 571–575. © Pleiades Publishing, Ltd., 2007.
Original Russian Text © A.I. Kochnev, I.I. Oleinik, I.V. Oleinik, S.S. Ivanchev, G.A. Tolstikov, 2007, published in Zhurnal Organicheskoi Khimii, 2007,
Vol. 43, No. 4, pp. 573–577.
Design of Schiff Base-Like Postmetallocene Catalytic Systems for
Polymerization of Olefins: IV.* Synthesis of 2-(Aryliminomethyl)-
pyrrole and 7-(Aryliminomethyl)indole Derivatives
Containing Cycloalkyl Substituents
a, b
a
a
c
a
A. I. Kochnev , I. I. Oleinik , I. V. Oleinik , S. S. Ivanchev , and G. A. Tolstikov
a
Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Division, Russian Academy of Sciences,
pr. Akademika Lavrent’eva 9, Novosibirsk, 630090 Russia
e-mail: oleynik@nioch.nsc.ru
b
Novosibirsk State University, Novosibirsk, Russia
c
St. Petersburg Branch, Boreskov Institute of Catalysis, Siberian Division, Russian Academy of Sciences,
St. Petersburg, Russia
Received June 26, 2006
Abstract—Reactions of 4,6-substituted 2-cycloalkylanilines with 1H-pyrrole-2-carbaldehyde and 1H-indole-7-
carbaldehyde in methanol in the presence of formic acid gave the corresponding Schiff bases which can be used
as ligands for titanium and zirconium complexes.
DOI: 10.1134/S1070428007040148
We previously demonstrated prospects in structural
modification of known catalysts for olefin polymeriza-
tion based on bis(aryliminopyridine)iron complexes
and bis(aryliminoacenaphthenyl)nickel complexes via
introduction of cyclic substituents into the ortho posi-
tion of the imino fragment; the modified structures
exhibited a high activity at 70–90°C [2].
2-(Aryliminomethyl)pyrrole and 7-(aryliminometh-
yl)indole ligands were synthesized by reactions of
1H-pyrrole-2-carbaldehyde (I) and 1H-indole-7-carb-
aldehyde (II) with anilines; analogous reactions with
alkylanilines and fluoroanilines were described in
[4, 6]. We used anilines having cyclopentyl and cyclo-
hexyl substituents in the ortho position to obtain new
Schiff bases III and IV and optimized the reaction
conditions. According to published data, Schiff bases
of the pyrrole series are synthesized in anhydrous etha-
nol at room temperature [4], while the corresponding
indole derivatives are obtained in boiling toluene in the
presence of p-toluenesulfonic acid [6]. However, the
conditions proposed in [4, 6] did not ensure formation
of compounds III and IV in good yields; the conver-
sion of the initial reactants was not complete even on
prolonged reaction time, while the condensations in
boiling toluene with simultaneous removal of water as
azeotrope or in benzene in the presence of molecular
sieves were accompanied by appreciable tarring.
High efficiency of titanium and zirconium com-
plexes with 2-(alkylphenyliminomethyl)pyrrole and
7
-(fluorophenyliminomethyl)indole in polymerization
and copolymerization of olefins was shown in [3–6].
The pyrrole-based ligands ensured preparation of poly-
ethylene with a very high molecular weight, while the
indole derivatives gave rise to living polymerization.
Insofar as the high catalytic activity was observed only
at moderate temperature, it was interesting and im-
portant to elucidate whether analogous complexes with
ligands modified by cycloalkyl substituents will be
active at elevated temperature. For this purpose we
synthesized new ligands, derivatives of 2-(arylimino-
methyl)pyrrole and 7-(aryliminomethyl)indole contain-
ing cyclopentyl and cyclohexyl substituents.
We succeeded in attaining almost complete conver-
sion of the reactants (according to the TLC data) by
heating aldehydes I and II with cycloalkylanilines
Va–Vh in boiling methanol for 6–12 h in the presence
*
For communication III, see [1].
571

5
72
KOCHNEV et. al.
Scheme 1.
(
)n
R
NH2
NH
MeOH, HCOOH, 65°C
N
+
CHO
N
( )
n
H
R
R'
R'
I
Va–Vh
IIIa–IIIh
NH
( )n
R
NH2
MeOH, HCOOH, 65°C
N
+
N
H
(
)n
CHO
R
R'
R'
II
Va–Vh
IVa–IVh
R = R' = H (a, e), Me (c, g); R = Me, R' = H (b, f); R = cyclopentyl, R' = H (d); R = cyclohexyl, R' = H (h); n = 1 (a–d), 2 (e–h).
of a catalytic amount of formic acid. In most cases,
the target products, Schiff bases III and IV, separated
from the reaction mixture on cooling. Readily soluble
compounds IVd and IVe were isolated by removal of
the solvent from the reaction mixture, followed by
flash chromatography on silica gel. The yields of
iminomethylpyrroles III were 48–86%, and imino-
methylindoles IV were isolated in 50–87% yield.
at δ 10.69–10.71 (IV) and 9.47–10.90 ppm (III) were
assigned to the NH protons in the indole and pyrrole
fragments, respectively. In the IR spectra of IIIa–IIIh
and IVa–IVh we observed a strong absorption band in
the region 1619–1633 cm , which belongs to stretch-
ing vibrations of the azomethine CH=N bond. The
mass spectra of all Schiff bases III and IV were char-
acterized by the presence of strong molecular ion peak.
–
1
1
H-Indole-7-carbaldehyde II was synthesized ac-
Compounds IIIa–IIIh and IVa–IVh in CDCl are
3
cording to the procedure reported in [7] by reaction of
excess vinylmagnesium bromide with o-nitrobenzalde-
hyde dibutyl acetal (VI). Compound VI was not de-
scribed previously. It was prepared in turn by heating
o-nitrobenzaldehyde with 1-butanol in boiling toluene
with simultaneous removal of water as azeotrope. In
the synthesis of aldehyde II, the rate of addition of the
Grignard compound to a solution of acetal VI was
important. If the addition was complete in 30 min, the
product was isolated in a poor yield (25–30%). The
optimal time of addition was 7 to 10 min; in this case,
aldehyde II was isolated in 50% yield.
likely to exist as a single E isomer, as follows from the
H NMR spectrum of 6-cyclohexyl-2,4-dimethyl-N-
(1H-pyrrol-2-ylmethylidene)aniline (IIIg).
1
EXPERIMENTAL
1
The H NMR spectra were recorded from solutions
in carbon tetrachloride on a Bruker WP-200SY spec-
trometer (200 MHz) using hexamethyldisiloxane as
internal reference. The IR spectra were measured in
KBr or from neat compounds on a Vector 22 spectrom-
eter. The progress of reactions and the purity of prod-
ucts were monitored by TLC on Silufol UV-254 plates
using chloroform as eluent. Flash chromatography [8]
was performed on silica gel, 5–40 μm; eluent chloro-
form–hexane, 2:1. The elemental compositions were
determined on a Carlo Erba 1106 CHN analyzer, as
well as from the high-resolution mass spectra which
were obtained on a Finnigan MAT-8200 mass spec-
trometer. The melting points were determined by
heating samples placed between glass plates at a rate
of 1 deg/min.
The structure of Schiff bases IIIa–IIIh and IVa–
IVh was confirmed by the analytical and spectral data.
1
Compounds III and IV displayed in the H NMR spec-
tra singlets from the CH=N proton at δ 7.81–8.08 and
8
.33–8.53 ppm, respectively. Methylene protons in the
cycloalkyl groups resonated as multiplets at δ 1.05–
.14 ppm, and their CH proton signals appeared at
2
δ 3.00–3.50 ppm. The spectra of Schiff bases IIIb,
IIIc, IIIf, IIIg, IVb, IVc, IVf, and IVg contained
singlets from the methyl groups at δ 2.08–2.63 ppm,
and signals from aromatic protons were located in the
region δ 6.10–7.71 ppm. Downfield broadened singlets
Substituted cycloalkylanilines Va–Vh [9], 1H-pyr-
role-2-carbaldehyde (I) [10], vinyl bromide [11],
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 4 2007

DESIGN OF SCHIFF BASE-LIKE POSTMETALLOCENE CATALYTIC SYSTEMS ... IV.
573
vinylmagnesium bromide [12], and o-nitrobenzalde-
ppm: 1.38–1.75 m (6H, CH ), 1.80–1.95 m (2H, CH ),
2
2
hyde [13] were synthesized by known methods.
2.22 s (3H, CH
J = 3 Hz), 6.38 s (1H, 5-H), 6.45 d (1H, 3'-H, J =
Hz), 6.85–7.10 m (3H, 5'-H, 3-H, 4-H), 7.88 s (1H,
3
), 3.00 m (1H, CH), 6.08 t (1H, 4'-H,
1
H-Indole-7-carbaldehyde (II) (cf. [7]). A solu-
3
tion of 15.0 g (53 mmol) of acetal VI in 150 ml of
anhydrous tetrahydrofuran was cooled to –70°C, and
a solution of 24.5 g (188 mmol) of vinylmagnesium
bromide in 150 ml of anhydrous THF was added drop-
wise with stirring under argon so that the temperature
did not exceed –40°C. The mixture was stirred for
N=CH), 10.35 br.s (1H, NH). Found, %: C 79.77;
+
H 8.04; N 11.01. [M] 252.1639. C H N . Calculated,
1
7
20
2
%: C 80.91; H 7.99; N 11.10. M 252.1626.
2-Cyclopentyl-4,6-dimethyl-N-(1H-pyrrol-2-yl-
methylidene)aniline (IIIc). Yield 79%, mp 140–
–
1
1
2
5 min at room temperature, poured into 200 ml of
142°C. IR spectrum: ν 1629 cm (N=C). H NMR
spectrum, δ, ppm: 1.40–1.75 m (6H, CH ), 1.80–
1.95 m (2H, CH ), 2.08 s (3H, CH ), 2.28 s (3H, CH ),
a saturated aqueous solution of ammonium chloride,
and treated with diethyl ether (2×50 ml). The extract
2
2
3
3
was dried over MgSO , the solvent was distilled off
3.00 m (1H, CH), 6.12 t (1H, 4'-H, J = 3 Hz), 6.45 d
(1H, 3'-H, J = 3 Hz), 6.56 s (1H, 3-H), 6.75 s (1H,
5-H), 6.83 s (1H, 5'-H), 7.86 s (1H, N=CH), 10.20 br.s
4
under reduced pressure, a mixture of 10 ml of 0.5 M
hydrochloric acid and 80 ml of THF was added to the
residue, and the mixture was stirred for 40 min under
argon, treated with 40 ml of a saturated aqueous
(1H, NH). Found, %: C 80.98; H 8.46; N 10.57.
+
[M] 266.1789. C18
H
N
. Calculated, %: C 81.16;
22
2
solution of NaHCO , and extracted with diethyl ether
H 8.32; N 10.52. M 266.1783.
3
(
5×40 ml). The extract was dried over MgSO , the sol-
4
2,6-Dicyclopentyl-N-(1H-pyrrol-2-ylmethyli-
dene)aniline (IIId). Yield 83%, mp 180°C. IR spec-
trum: ν 1629 cm (N=C). H NMR spectrum, δ, ppm:
vent was distilled off, and the oily residue was crystal-
lized from hexane. Yield 3.85 g (50%), mp 87–88°C;
published data [7]: mp 87–89°C. H NMR spectrum, δ,
ppm: 6.52 m (1H, 3-H), 7.17 t (1H, 5-H, J = 7.5 Hz),
7
(
(
–
1
1
1
1
3
6
4
.40–1.75 m (12H, CH ), 1.80–1.95 m (4H, CH ),
.01 m (2H, CH), 6.13 t (1H, 4'-H, J = 3 Hz), 6.45–
.55 m (2H, 3'-H, 5-H), 6.85–7.15 m (3H, 5'-H, 3-H,
2
2
.28 m (1H, 2-H), 7.55 d (1H, 6-H, J = 7.5 Hz), 7.83 d
1H, 4-H, J = 7.5 Hz), 10.01 s (1H, CHO), 10.20 br.s
1H, NH).
-H), 7.85 s (1H, N=CH), 10.00 br.s (1H, NH). Found,
+
%
: C 82.76; H 8.84; N 9.28. [M] 306.2091. C H N .
21
26
2
Schiff bases IIIa–IIIh and IVa–IVh (general
procedure). Two drops (10 mg) of 99% formic acid
were added to a mixture of 2 mmol of aldehyde I or II,
0 ml of methanol, and 2 mmol of cycloalkylaniline
Calculated, %: C 82.31; H 8.55; N 9.14. M 306.2096.
-Cyclohexyl-N-(1H-pyrrol-2-ylmethylidene)-
aniline (IIIe). Yield 48%, mp 71–73°C. IR spectrum:
2
–
1
1
1
ν 1623 cm (N=C). H NMR spectrum, δ, ppm: 1.10–
Va–Vh. The mixture was heated with stirring under
reflux for 6–12 h until the initial compounds disap-
peared (according to the TLC data), cooled, and the
precipitate of Schiff base IIIa–IIIh, IVa–IVc, or IVf–
IVh was filtered off and washed with 2 ml of cold
methanol. Oily Schiff bases IVd and IVe were isolated
by removal of the solvent, followed by flash chro-
matography.
1
.60 m (6H, CH ), 1.83–1.95 m (4H, CH ), 3.03 m
2
2
(
1H, CH), 6.16 t (1H, 4'-H, J = 3 Hz), 6.51 d (1H, 3'-H,
J = 3 Hz), 6.79 m (2H, 5-H, 6-H), 7.02–7.20 m
(
(
[
3H, 5'-H, 3-H, 4-H), 8.08 s (1H, N=CH), 9.47 br.s
1H, NH). Found, %: C 81.77; H 8.52; N 10.40.
M] 252.1626. C H N . Calculated, %: C 80.91;
+
1
7
20
2
H 7.99; N 11.10. M 252.1626.
-Cyclohexyl-6-methyl-N-(1H-pyrrol-2-ylmeth-
ylidene)aniline (IIIf). Yield 86%, mp 150–153°C. IR
spectrum: ν 1633 cm (N=C). H NMR spectrum, δ,
ppm: 1.38–1.75 m (6H, CH ), 1.80–1.95 m (4H, CH ),
2
2
-Cyclopentyl-N-(1H-pyrrol-2-ylmethylidene)-
–
1
1
aniline (IIIa). Yield 79%, mp 90–91°C. IR spectrum:
–1
1
ν 1619 cm (N=C). N NMR spectrum, δ, ppm: 1.38–
.80 m (6H, CH ), 1.83–2.04 m (2H, CH ), 3.48 m
2
2
1
2.30 s (3H, CH ), 2.80 m (1H, CH), 6.21 t (1H, 4'-H,
2
2
3
(
1H, CH), 6.10 t (1H, 4'-H, J = 3 Hz), 6.51–7.10 m
J = 3 Hz), 6.32 s (1H, 5-H), 6.65 d (1H, 3'-H, J =
3 Hz), 7.05–7.25 m (3H, 5'-H, 3-H, 4-H), 8.05 s (1H,
N=CH), 10.90 br.s (1H, NH). Found, %: C 81.78;
(6H, 3'-H, 5'-H, 3-H, 4-H, 5-H, 6-H), 8.08 s (1H,
N=CH), 10.00 br.s (1H, NH). Found, %: C 80.60;
H 7.69; N 11.70. [M] 238.1448. C H N . Calculated,
+
+
1
6
18
2
H 8.49; N 10.47. [M] 266.1786. C H N . Calculat-
18 22
2
%
: C 80.63; H 7.61; N 11.75. M 238.1470.
-Cyclopentyl-6-methyl-N-(1H-pyrrol-2-ylmeth-
ylidene)aniline (IIIb). Yield 79%, mp 118–120°C. IR
ed, %: C 81.16; H 8.32; N 10.52. M 266.1783.
2
2-Cyclohexyl-4,6-dimethyl-N-(1H-pyrrol-2-yl-
methylidene)aniline (IIIg). Yield 86%, mp 158–
–
1
1
–1
1
spectrum: ν 1632 cm (N=C). N NMR spectrum, δ,
160°C. IR spectrum: ν 1627 cm (N=C). H NMR
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 4 2007

5
74
KOCHNEV et. al.
–
1
1
spectrum, δ, ppm: 1.20–1.50 m (6H, CH ), 1.55–
ν 1627 cm (N=C). H NMR spectrum, δ, ppm: 1.50–
2
1
.85 m (4H, CH ), 2.03 s (3H, CH ), 2.24 s (3H, CH ),
1.75 m (12H, CH ), 1.85–2.04 m (4H, CH ), 3.00 m
2
3
3
2
2
2
.31 m (1H, CH), 6.15 t (1H, 4'-H, J = 3 Hz), 6.48 d
(2H, CH), 6.55 m (1H, 3'-H), 6.90–7.35 m (6H, 2'-H,
3-H, 4-H, 5-H, 5'-H, 6'-H), 7.72 d (1H, 4'-H, J = 8 Hz),
8.33 s (1H, N=CH), 10.69 br.s (1H, NH). Found, %:
(
3
1H, 3'-H, J = 3 Hz), 6.73 s (1H, 5-H), 6.78 s (1H,
-H), 6.83 m (1H, 5'-H), 7.84 s (1H, N=CH), 10.60 br.s
+
(
[
1H, NH). Found, %: C 81.26; H 8.77; N 10.09.
M] 280.1944. C H N . Calculated, %: C 81.38;
C 84.50; H 7.90; N 7.93. [M] 356.2245. C H N .
2
5
28
2
+
1
9
24
2
Calculated, %: C 84.23; H 7.91; N 7.86. M 356.2252.
-Cyclohexyl-N-(1H-indol-7-ylmethylidene)-
aniline (IVe). Yield 50%, oily substance. IR spectrum:
H 8.63; N 9.99. M 280.1939.
,6-Dicyclohexyl-N-(1H-pyrrol-2-ylmethylidene)-
aniline (IIIh). Yield 77%, mp 219–220°C. IR spec-
2
2
–
1
1
ν 1621 cm (N=C). H NMR spectrum, δ, ppm: 1.00–
–1
1
trum: ν 1629 cm (N=C). H NMR spectrum, δ, ppm:
1.80 m (6H, CH ), 1.80–2.35 m (4H, CH ), 3.31m (1H,
2
2
1
3
.40–1.75 m (12H, CH ), 1.80–1.95 m (8H, CH ),
.01 m (2H, CH), 6.13 t (1H, 4'-H, J = 3 Hz), 6.51 d
CH), 6.76 m (1H, 3'-H), 7.00–7.70 m (7H, 2'-H, 3-H,
4-H, 5-H, 5'-H, 6-H, 6'-H), 7.93 d (1H, 4'-H, J = 8 Hz),
8.36 s (1H, N=CH), 10.96 br.s (1H, NH). Found, %:
2
2
(1H, 3'-H, J = 3 Hz), 6.85–7.00 m (4H, 5'-H, 3-H, 4-H,
+
5-H), 8.31 s (1H, N=CH), 10.67 br.s (1H, NH). Found,
C 83.05; H 7.30; N 9.31. [M] 302.1782. C H N .
2
1
22
2
+
%
: C 82.84; H 9.25; N 8.58. [M] 334.2370. C H N .
Calculated, %: C 83.40; H 7.33; N 9.26. M 302.1783.
-Cyclohexyl-N-(1H-indol-7-ylmethylidene)-6-
methylaniline (IVf). Yield 55%, mp 65–66°C. IR
2
3
30
2
Calculated, %: C 82.59; H 9.04; N 8.37. M 334.2409.
-Cyclopentyl-N-(1H-indol-7-ylmethylidene)-
aniline (IVa). Yield 70%, mp 40–45°C. IR spectrum:
2
2
–
1
1
spectrum: ν 1627 cm (N=C). H NMR spectrum, δ,
–1
1
ν 1622 cm (N=C). H NMR spectrum, δ, ppm: 1.50–
ppm: 1.10–1.45 m (6H, CH ), 1.50–1.90 m (4H, CH ),
2
2
1
.85 m (6H, CH ), 1.90–2.14 m (2H, CH ), 3.51 m
2.14 s (3H, CH ), 2.63 m (1H, CH), 6.55 m (1H, 3'-H),
2
2
3
(
3
7
1H, CH), 6.51 m (1H, 3'-H), 6.80–7.36 m (7H, 2'-H,
-H, 4-H, 5-H, 5'-H, 6-H, 6'-H), 7.69 d (1H, 4'-H, J =
6.86–7.35 m (6H, 2'-H, 3-H, 4-H, 5-H, 5'-H, 6'-H),
7.72 d (1H, 4'-H, J = 7.5 Hz), 8.36 s (1H, N=CH),
10.70 br.s (1H, NH). Found, %: C 84.17; H 7.83;
.5 Hz), 8.53 s (1H, N=CH), 10.71 br.s (1H, NH).
+
+
Found, %: C 83.67; H 7.02; N 9.76. [M] 288.1623.
N 8.92. [M] 316.1983. C H N . Calculated, %:
2
2
24
2
C H N . Calculated, %: C 83.30; H 6.99; N 9.71.
M 288.1626.
C 83.50; H 7.65; N 8.85. M 316.1940.
-Cyclohexyl-N-(1H-indol-7-ylmethylidene)-4,6-
dimethylaniline (IVg). Yield 85%, mp 149–150°C. IR
2
0
20
2
2
2
-Cyclopentyl-N-(1H-indol-7-ylmethylidene)-6-
–
1
1
methylaniline (IVb). Yield 70%, mp 98–103°C. IR
spectrum: ν 1625 cm (N=C). H NMR spectrum, δ,
–
1
1
spectrum: ν 1625 cm (N=C). H NMR spectrum, δ,
ppm: 1.05–1.45 m (6H, CH ), 1.55–1.85 m (4H, CH ),
2
2
ppm: 1.47–1.79 m (6H, CH ), 1.82–2.00 m (2H, CH ),
2.22 s (3H, CH ), 2.28 s (3H, CH ), 2.60 m (1H, CH),
2
2
3 3
2
6
7
1
.14 s (3H, CH ), 3.05 m (1H, CH), 6.53 m (1H, 3'-H),
.86–7.28 m (6H, 2'-H, 3-H, 4-H, 5-H, 5'-H, 6'-H),
.71 d (1H, 4'-H, J = 7.5 Hz), 8.35 s (1H, N=CH),
6.53 m (1H, 3'-H), 6.77 s (1H, 5-H), 6.81 s (1H, 3-H),
7.10–7.30 m (3H, 2'-H, 5'-H, 6'-H), 7.71 d (1H, 4'-H,
J = 7.5 Hz), 8.33 s (1H, N=CH), 10.71 br.s (1H, NH).
3
+
0.70 br.s (1H, NH). Found, %: C 83.50; H 7.39;
Found, %: C 83.69; H 7.80; N 8.23. [M] 330.2101.
+
N 9.23. [M] 302.1782. C H N . Calculated, %:
C H N . Calculated, %: C 83.59; H 7.93; N 8.48.
2
1
22
2
23 26
2
C 83.40; H 7.34; N 9.26. M 302.1783.
-Cyclopentyl-N-(1H-indol-7-ylmethylidene)-4,6-
dimethylaniline (IVc). Yield 60%, mp 74–76°C. IR
M 330.2096.
2,6-Dicyclohexyl-N-(1H-indol-7-ylmethylidene)-
aniline (IVh). Yield 87%, mp 160–162°C. IR spec-
2
–
1
1
–1
1
spectrum: ν 1626 cm (N=C). H NMR spectrum, δ,
trum: ν 1626 cm (N=C). H NMR spectrum, δ, ppm:
ppm: 1.50–1.73 m (6H, 3CH ), 1.80–1.90 m (2H,
1.00–1.50 m (12H, CH ), 1.50–1.90 m (8H, CH ),
2
2
2
CH ), 2.10 s (3H, CH ), 2.28 s (3H, CH ), 3.02 m (1H,
CH), 6.53 m (1H, 3'-H), 6.76 s (1H, 5-H), 6.85 s (1H,
2.58 m (2H, CH), 6.56 m (1H, 3'-H), 6.86–7.35 m (6H,
2'-H, 3-H, 4-H, 5-H, 5'-H, 6'-H), 7.74 d (1H, 4'-H, J =
7.5 Hz), 8.36 s (1H, N=CH), 10.70 br.s (1H, NH).
2
3
3
3-H), 7.10–7.35 m (3H, 2'-H, 5'-H, 6'-H), 7.70 d (1H,
+
4
'-H, J = 7.5 Hz), 8.33 s (1H, N=CH), 10.72 br.s
Found, %: C 84.45; H 8.55; N 7.26. [M] 384.2562.
(
[
1H, NH). Found, %: C 83.95; H 7.83; N 8.97.
C H N . Calculated, %: C 84.33; H 8.39; N 7.28.
M 384.2565.
2
7
32
2
+
M] 316.1941. C H N . Calculated, %: C 83.50;
2
2
24
2
H 7.65; N 8.85. M 316.1939.
,6-Dicyclopentyl-N-(1H-indol-7-ylmethylidene)-
aniline (IVd). Yield 50%, oily substance. IR spectrum:
o-Nitrobenzaldehyde dibutyl acetal (VI). A mix-
ture of 37.8 g (0.25 mol) of o-nitrobenzaldehyde,
56.5 ml (0.62 mol) of butan-1-ol, 75 ml of freshly
2
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 4 2007

DESIGN OF SCHIFF BASE-LIKE POSTMETALLOCENE CATALYTIC SYSTEMS ... IV.
575
distilled toluene, and 0.13 g of p-toluenesulfonic acid
monohydrate was heated under reflux in a flask
equipped with a Dean–Stark trap for 12 h until 4–
chev, S.S., Tolstikov, G.A., Badaev, V.K., Ivanche-
va, N.I., Oleinik, I.I., Khaikin, S.Ya., and Oleinik, I.V.,
Vysokomol. Soedin., Ser. A, 2002, vol. 44, p. 1478; Ivan-
chev, S.S., Tolstikov, G.A., Kudryashov, V.N., Ivanche-
va, N.I., Oleinik, I.I., Gabutdinov, M.S., Badaev, V.K.,
Oleinik, I.V., Rogozin, D.G., Tikhonov, M.V., Vakh-
breit, A.Z., Khasanshin, R.A., and Balabueva, G.Ch.,
Russian Patent no. 2202559, 2003; Byull. Izobret.,
4
.5 ml of water separated. The mixture was treated
with 10 ml of a saturated aqueous solution of NaHCO3
and 60 ml of a saturated aqueous solution of sodium
chloride. The organic phase was separated and dried
over calcined potassium carbonate, the solvent was
distilled off under reduced pressure on a rotary evap-
orator, and the residue was distilled under reduced
2
003, no. 11.
. Matsuo, Y., Mashima, K., and Tani, K., Chem. Lett.,
000, p. 1114; Yoshida, Y., Matsui, S., Takagi, Y.,
3
2
pressure (oil pump), a fraction with bp 160–163°C (2–
Mitani, M., Nitabaru, M., Nakano, T., Tanaka, H., and
Fujita, T., Chem. Lett., 2000, p. 1270.
1
3
mm) being collected. Yield 63.3 g (90%). H NMR
spectrum, δ, ppm: 0.88 t (6H, CH , J = 7.5 Hz), 1.35 m
4. Yoshida, Y., Matsui, S., Kojoh, S., Takagi, Y., Mita-
ni, M., Nakano, T., Tanaka, H., Kashiwa, N., and
Fujita, T., Organometallics, 2001, vol. 20, p. 4793.
3
(
4H, CH CH ), 1.52 m (4H, OCH CH ), 3.47 m (4H,
2
3
2
2
OCH CH ), 5.93 s (1H, CH), 7.36 t.d (1H, 4-H,
2
2
J = 7.5, 1.5 Hz), 7.48 t.d (1H, 5-H, J = 7.5, 1.5 Hz),
.64 d.d (1H, 6-H, J = 7.5, 1.5 Hz), 7.72 d.d (1H, 3-H,
J = 7.5, 1.5 Hz). Found, %: C 64.14; H 8.34; N 4.92.
5. Yoshida, Y., Matsui, S., and Fujita, T., J. Organomet.
Chem., 2005, vol. 690, p. 4382; Matsugi, T., Matsui, S.,
Kojoh, S., Takagi, Y., Inoue, Y., Kashiwa, N., and
Fujita, T., Chem. Lett., 2001, p. 566.
7
+
[
M] 281.1624. C H NO . Calculated, %: C 64.03;
15 23 4
6
. Matsugi, T., Matsui, S., Kojoh, S., Takagi, Y., Inoue, Y.,
Nakano, T., Fujita, T., and Kashiwa, N., Macromole-
cules, 2002, vol. 35, p. 4880.
H 8.24; N 4.98. M 281.1627.
This study was performed under financial support
by the Siberian Division, Russian Academy of
Sciences (integration project no. 150).
7
8
9
. Dobson, D.R., Gilmore, J., and Long, D.A., Synlett,
1
992, p. 79.
. Still, W.C., Kahn, M., and Mitra, A., J. Org. Chem.,
978, vol. 43, p. 2923.
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 4 2007