Reactions of Nand C-alkenylanilines: II. Halocyclization of 2-(2-cycloalkenyl)anilines

Article abstract of DOI:10.1023/A:1013183605455

The reaction of 2-(2-cyclopentenyl)anilines with I₂ in the presence of NaHCO₃ results in formation of 3-iodocyclopenta[b]indoles in high yields. Under similar conditions 2-(2-cyclohexenyl)anilines give rise to cyclization products wh

Full text of DOI:10.1023/A:1013183605455

Russian Journal of Organic Chemistry, Vol. 37, No. 9, 2001, pp. 1289 1296. Translated from Zhurnal Organicheskoi Khimii, Vol. 37, No. 9, 2001,
pp. 1357 1363.
Original Russian Text Copyright
2001 by Gataullin, Minnigulov, Fatykhov, Spirikhin, Abdrakhmanov.
Reactions of N- and C-Alkenylanilines:
II.* Halocyclization of 2-(2-Cycloalkenyl)anilines
R. R. Gataullin1, F. F. Minnigulov2, A. A. Fatykhov1,
L. V. Spirikhin1, and I. B. Abdrakhmanov1
1
Institute of Organic Chemistry, Ufa Research Center, Russian Academy of Sciences,
pr. Oktyabrya 71, Ufa, 450054 Bashkortostan, Russia
fax: (3472)356066; e-mail: chemorg@anrb.ru
2
Bashkir State Agrarian University, Ufa, Bashkortostan, Russia
Received November 15, 2000
Abstract The reaction of 2-(2-cyclopentenyl)anilines with I2 in the presence of NaHCO3 results in formation
of 3-iodocyclopenta[b]indoles in high yields. Under similar conditions 2-(2-cyclohexenyl)anilines give rise
to cyclization products whose structure depends on the solvent and substituents in the aromatic ring and on
the nitrogen atom.
Halocyclization reactions [2] are characterized by
high stereo- and regioselectivity; these reactions also
ensure subsequent ready functionalization of inter-
mediates. Halocyclizations are widely used in the
synthesis of nitrogen-containing heterocycles from
unsaturated aliphatic amines [3, 4] and carbamates
[5, 6], but only a few examples of halocyclizations
involving ortho-alkenylanilines have been reported
[7]. In continuation of our studies [8 10] on hetero-
cyclization of ortho-alkenylanilines with the goal of
obtaining intermediate products for preparation of
potential biologically active substances [11 13], in
the present work we examined iodocyclization of
2-(2-cyclopentenyl)- and 2-(2-cyclohexenyl)anilines
and -methoxyanilines which were synthesized by con-
densation of 3-chlorocyclopentene and 3-bromocyclo-
hexene with anilines [14].
The reaction of 2-(2-cyclopentenyl)anilines I and
II with I2 in different solvents afforded 3-iodo-5-R-
1,2,3,3a,4,8b-hexahydrocyclopenta[b]indoles III and
IV in 85 88% yield (Scheme 1). By reaction of
N-acetyl-2-(2-cyclopentenyl)-6-methoxyaniline (V)
with N-bromosuccinimide in CHCl3 we obtained 91%
of 3-bromohexahydrocyclopenta[b]indole (VI)
(Table 1). The structure of the products indicates that
the process follows the 5-exo-cyclization path [15].
The reactions of 2-(2-cyclohexenyl)anilines VII
and VIII with I2, depending on the solvent, gave only
1-iodo-1,2,3,4,4a,9a-hexahydrocarbazoles IX and X or
their mixtures with 13-iodo-8-azatricyclo[7.3.1.02,7]-
trideca-2,4,6-trienes XI and XII (Scheme 2; Tables 1
and 2). When the cyclization of amines VII and VIII
was performed in acetonitrile, the major products were
azatricyclodecatrienes XI and XII, while in carbon
Scheme 1.
I IV, R = H; V, VI, R = Ac; I, III, R = Me; II, IV VI, R = OMe; III, V, Hlg = I; VI, Hlg = Br.
____________
*
For communication I, see [1].
1070-4280/01/3709-1289$25.00 2001 MAIK Nauka/Interperiodica

1290
GATAULLIN et al.
Scheme 2.
VII, IX, XI, R = H; VIII, X, XII, R = OMe.
tetrachloride hexahydrocarbazoles IX and X were
formed exclusively (Table 2). Although acetonitrile
is hardly suitable for preparation of hexahydrocarba-
zoles IX and X, conditions can be found under which
azatricyclotridecatrienes XI and XII are formed as
the sole products. We have found that compounds IX
and X in acetonitrile at room temperature undergo
a fairly fast rearrangement into isomeric azatricyclo-
tridecatrienes XI and XII in quantitative yield. The
complete conversion of IX takes 10 days, and its
methoxy analog X rearranges in 30 days. In chloro-
form, the same transformations require 90 and
240 days, respectively. The only known example of
ring expansion of (1-iodoalkyl)pyrrolidines into
3-iodopiperidine was reported in [16]. The isomeriza-
tion occurred on heating in acetonitrile under reflux,
of amines VII and VIII with I2, the carbazole struc-
ture is likely to result from the transformation of
complex B, shown in Scheme 3. The 6-endo-cycliza-
tion product, azatricyclotridecatriene, may be formed
by both intramolecular isomerization of heterocycles
IX and X and directly through further transformation
of complex B. The cyclization of amine VII by the
action of I2 in methylene chloride is complete in 12 h,
and the products are hexahydrocarbazole IX and aza-
tricyclotridecatriene XI at a ratio of 7:1 (Table 2).
This ratio almost does not change on storage of the
reaction mixture for 30 days. The large fraction of
tricyclic product XI in the reaction mixture by the
end of the process can be explained by considerable
contribution of the 6-endo-cyclization pathway.
Cyclohexenylaniline derivatives XIII XV reacted
and it was characerized by poor yield and low selec- with iodine in acetonitrile to afford exclusively hexa-
tivity. Presumably, the intramolecular isomerization of
hexahydrocarbazoles IX and X into azatricyclotrideca-
trienes XI and XII follows the same mechanism as
that proposed in [16], i.e., through intermediate forma-
tion of aziridinium salt A (Scheme 2). In the reactions
hydrocarbazoles XVI XVIII (Scheme 4). Hexahydro-
carbazole XX was obtained in 78% yield by treatment
with iodine of substituted urea XIX which was syn-
thesized by heating of amide XIV in a 16% solution
of ammonia in methanol under pressure.
Scheme 3.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 9 2001

REACTIONS OF N- AND C-ALKENYLANILINES: II.
1291
Table 1. Yields, Rf values, and IR and 13C NMR spectra of compounds IV VI and IX XXII
Comp.
no.
Yield,
%
IR spectrum,
Rfa
13C NMR spectrum (CDCl3), C, ppm
1
, cm
IV
87
0.5 (A) 3400 (N H) 33.0 (C1), 35.1 (C2), 36.9 (C3), 45.9 (C8b), 54.8 (OCH3), 73.9 (C3a), 108.8
(C6), 116.5 (C7), 132.6 (C4a), 138.3 (C8a), 143.7 (C5)
V
98
91
0.5 (A) 3280 (N H)
VI
0.7 (B) 648 (C Br) 20.9 (CH3); 30.0 (OCH3); 30.9 (C1); 34.8 (C2); 45.4 (C8b); 55.5 (C3); 74.8
(C3a); 121.1 , 125.7 , 128.3, 130.3, 136.2, 140.5 (Carom
)
IX
X
90
90
0.6 (B) 3472 (N H) 23.2 (C3), 23.5 (C4), 36.3 (C2), 39.0 (C1), 42.6 (C4a), 69.5 (C9a), 110.5
(C8), 119.2 (C6), 122.7 (C5), 127.4 (C7), 129.5 (C4b), 149.7 (C8a)
0.6 (B) 3470 (N H) 23.4 (C3), 23.9 (C4), 35.5 (C2), 38.4 (C1), 42.3 (C4a), 55.8 (OCH3), 69.2
(C9a), 109.0 (C7), 114.7 (C5), 119.3 (C6), 130.4 (C4b), 138.2 (C8a),
145.4 (C8)
XI
73
75
0.6 (B) 3475 (N H) 16.7 (C11), 30.0 (C12), 30.1 (C10), 33.2 (C13), 41.3 (C1), 51.7 (C9), 112.5
(C6), 118.1 (C4), 123.4 (C2), 127.2 (C3), 127.8 (C5), 144.3 (C7)
XII
0.5 (B) 3473 (N H) 16.9 (C11), 29.9 (C12), 30.5 (C10), 33.1 (C13), 41.3 (C1), 51.6 (C9), 55.2
(OCH3), 107.9 (C5), 115.5 (C3), 120.1 (C4), 123.7 (C7), 134.2 (C2),
145.1 (C6)
b
XIII
XIV
89
93
3290 (N H)
c
3280 (N H) 14.2 (CH3), 20.9 (C5 ), 24.5 (C6 ), 29.6 (C4 ), 39.3 (C1 ), 50.7 (OCH2),
126.5 (C6), 128.4 (C3 ), 128.7 (C5), 128.9 (C4), 129.3 (C2 ), 129.6 (C5),
131.3 (C2), 135.0 (C1), 154.0 (C O)
XV
93
86
0.4 (A) 3280 (N H) 21.4 (C5 ), 24.1 (CH3), 24.8 (C6 ), 29.8 (C4 ), 39.1 (C1 ), 121.4 (C6), 125.7
(C3 ), 127.9 (C4), 128.2 (C2 ), 129.5 (C5), 129.8 (C3), 136.4 (C2), 138.5
(C1), 168.5 (C O)
XVI
0.6 (B) 564 (C I) 22.7 (C3), 24.5 (C4), 31.0 (C1), 36.1 (C2), 38.3 (SCH3), 42.6 (C4a), 71.7
(C9a), 118.8 (C8), 123.3 (C6), 125.3 (C5), 128.1 (C7), 135.2 (C4b), 141.3
(C8a)
XVII
62
74
0.6 (B) 542 (C I)
XVIII
0.6 (B) 588 (C I) 21.2 (CH3), 22.5 (C3), 23.6 (C4), 29.8 (C1), 34.6 (C2), 38.3 (C4a), 73.7
(C9a), 115.9 (C8), 124.8 (C5), 125.4 (C6), 126.6 (C7), 135.0 (C4b), 137.5
(C8a), 168.5 (C O)
XIX
XX
89
46
0.2 (C) 3300 3450
(NH, NH2)
0.3 (B) 3400 (NH2) 22.8 (C3), 23.0 (C4), 31.2 (C1), 37.2 (C2), 43.3 (C4a), 70.2 (C9a), 118.2
(C8), 122.5 (C6), 127.4 (C5), 128.2 (C7), 133.7 (C4b), 142.1 (C8a), 147.0
(C O)
XXI
83
44
0.6 (B) 3400 (NH,
NH2)
22.4 (C3), 28.9 (C2), 29.2 (C4), 42.4 (C4a), 55.2 (OCH3), 64.2 (C1), 70.6
(C9a), 109.2 (C7), 115.7 (C5), 119.5 (C6), 136.3 (C4b), 138.4 (C8a),
145.9 (C8)
XXII
0.6 (B) 558 (C I) 16.6 (C11), 27.5 (C12), 28.3 (C13), 29.6 (C10), 39.4 (SCH3), 42.1 (C1), 56.5
(C9), 117.3 (C6), 122.9 (C4), 128.0 (C3), 128.4 (C7), 129.3 (C5), 137.1
(C2)
a
b
c
Eluent CCl4 (A), CH2Cl2 (B), C6H6 (C).
mp 115 116 C.
bp 98 C (1 mm).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 9 2001

1292
GATAULLIN et al.
Table 2. Product ratio in the reactions of compounds VII and VIII with iodine in various solvents
Reaction time, h
Initial compound
Solvent
B
Products (ratio)
108
48
12
48
72
VII
VII
VII
VIII
VIII
MeCN
CCl4
CH2Cl2
CCl4
37.4
2.23
9.08
2.23
160
0
23
0
IX, XI (1: 4)
IX
IX, XI (7: 1)
X
MeCN
37.4
160
X, XII (1: 2)
It is known [2] that kinetically controlled cycliza-
tion of unsaturated acids or amides by the action
of I2 yields mainly thermodynamically less favored
product due to different rates of formation of stereo-
or regioisomers. The above experiments were carried
out under conditions (I2/NaHCO3/solvent) correspond-
ing to kinetic control. When the reaction of XIII with
I2 was performed under conditions of thermodynamic
control (I2/MeCN), hexahydrocarbazole XVI was the
only reaction product. Presumably, compound XVI
is the only thermodynamically stable structure or
the presence of the methylsulfonyl group hampers
formation of the endo-6 isomer.
and the five-membered rings are fused cis (the 3a-H
and 3-H protons are arranged trans).
The 1-H signal in the spectra of carbazoles IX, X,
XVI XVIII, and XX is characterized by two large
coupling constants, J1, 2-ax
=
11 12 Hz and J1, 9a
8 9 Hz, indicating two axial axial interactions, i.e.,
both 1-H and 9a-H protons are axial (Table 3). The
coupling constant for the 9a-H and 4a-H protons
( 7 8 Hz) suggests their cis arrangement and hence
cis junction of the rings [18]. Irradiation at a fre-
quency corresponding to the C4H2 protons results in
transformation of the 4a-H multiplet into a doublet
with J = 7 7.5 Hz. The 1-H proton is coupled with
2-Hax and 2-Heq through constants of 12.0 (large)
and 4.0 Hz (small) [18, 19]. Analogous coupling
constants were given in [20] for structurally related
carbazole derivative.
Scheme 4.
Replacement of the iodine atom in X by NH2
group on heating in a methanolic ammonia solution
(Scheme 5) gives product XXI which exists in a chair
conformation with the axial 4a-H proton. The 9a-H
1
proton of XXI shows in the H NMR spectrum two
coupling constants, J9a, 1 = 4.6 and J9a, 4a = 6.5 Hz
which indicate equatorial orientation of 9a-H. Sup-
pression of the 9a-H signal in the double-resonance
spectrum gives rise to a doublet of doublets from the
4a-H proton, J4a, 4-eq = 6.2 and J4a, 4-ax = 11.5 Hz
[18] (Table 3).
XIII, XVI, R = MeSO2; XIV, XVII, R = CO2Et; XV,
XVIII, R = Ac; XIX, XX, R = NH2C(O).
The structure of compounds II XXI was derived
from their IR and NMR spectra and analytical data
(Tables 3, 4). The spectral parameters of dihydro-
indole III were reported in [17], and those of com-
pounds IV and VI are given in Experimental. The
position of the 8b-H and 3a-H protons in molecules
III, IV, and VI was proved by the large values of
Scheme 5.
the corresponding vicinal coupling constants (J3a, 8b
=
8 9 Hz) which were determined by the double-reson-
ance technique and by observation of intramolecular
nuclear Overhauser effect. Saturation of the 3a-H
signal induces a 8% increase of the 8b-H signal
in the spectrum of III, whereas the 3-H signal remains
unchanged. These data indicate that the 3a-H and
8b-H protons are located close to each other, which
is possible when these protons are oriented axially
The 4a-H signal appears as a doublet of doublets,
J4a, 9a = 6.5 and J4a, 9a = 11.5 Hz, on irradiation of the
equatorial 4-H proton. The 1-H proton is axial. Its
signal is a doublet of triplets with J1 = 4.6 Hz (the
coupling constants for 2-Heq 1-H and 9a-H 1-H
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 9 2001

REACTIONS OF N- AND C-ALKENYLANILINES: II.
1293
Table 3. 1H NMR spectra of compounds IV, VI, IX XIV, XVI XVIII, and XX XXII
Comp.
no.
Chemical shifts , ppm (J, Hz)
IV
VI
IX
X
1.5 2.7 m [(CH2)2], 3.9 s (OCH3), 4.1 t (8b-H, J = 8.8), 4.3 m (3-H), 4.4 s (NH), 4.8 d (9a-H, J = 8.8,),
6.7 6.9 m (3H, Ar)
1.7 2.3 m [(CH2)2], 2.2 s (CH3), 2.4 s (OCH3), 4.0 t (8b-H, J = 8.0), 4.3 m (3-H), 4.9 d.d, (9a-H, J = 8.0), 6.9
7.3 m (3H, Ar)
1.1 2.2 m [(CH2)3], 3.2 m (9a-H), 3.9 d.d (9a-H, J1 = 9.0, J2 = 7.1), 4.0 d.d.d (1-H, J1 = 3.9, J2 = 11.97, J3 =
9.0), 4.2 br. s (NH), 6.7 t (6-H), 6.8 d (8-H, 7.6), 7.1 d (5-H, 7.5), 7.2 t (7-H)
1.3 2.3 m [(CH2)3], 3.4 m (9a-H), 3.8 s (OCH3), 3.9 d.d (9a-H, J1 = 8.0, J2 = 7.0), 4.0 d.d.d (1-H, J1 = 3.9,
J2 = 12.0, J3 = 8.0), 4.5 br. s (NH), 6.7 6.9 (3H, Harom
)
XI
1.5 2.6 m [(CH2)3], 3.2 m (1-H), 3.7 d.d.d (13-H, J1 = 1.6, J2 = 1.9, J3 = 2.0), 4.2 br.s (NH), 4.9 m (9-H), 6.6 d
(J = 8.0, 6-H), 6.8 t (4-H, J = 7.3), 7.0 d (3-H, J = 7.3), 7.2 t (5-H)
XII
1.3 2.6 m [(CH2)3], 3.1 m (1-H), 3.7 m (13-H), 4.4 br.s (NH), 4.7 m (9-H), 6.5 6.7 m (3H, Harom)
XIII
XIV
1.3 2.2 m [(CH2)3], 3.0 s (CH3), 3.8 m (1 -H), 5.6 5.9 m (2 -H, 3 -H), 7.1 7.4 m (4H, Ar), 7.4 s (NH)
1.3 t (CH3), 1.5 2.1 m [(CH2)3], 3.5 m (1 -H), 5.6 d.d.d (3 -H, J1 = 2.0, J2 = 6.2, J3 = 10.0), 6.0 m (2 -H),
7.0 7.2 m (4H, Harom), 7.7 s (NH)
XVI
1.3 2.3 m [(CH2)3], 3.0 s (CH3), 3.7 m (9a-H), 4.3 d.d.d (1-H, J1 = 4.0, J2 = 11.5, J3 = 8.5), 4.7 d.d (9a-H,
J1 = 8.5, J2 = 7.5), 7.2 7.6 m (4H, Harom
XVII 1.3 2.3 m [(CH2)3], 1.4 t (CH3, 7.2), 3.6 m (9a-H), 4.1 d.d.d (1-H, J1 = 4.0, J2 = 12.1, J3 = 8.8), 4.3 q (CH2),
4.9 d.d (9a-H, J1 = 8.8, J2 = 8.0), 6.9 7.5 m (4H, Harom
XVIII 1.3 2.3 m [(CH2)3], 1.4 s (CH3), 3.7 m (9a-H), 4.1 d.d.d (1-H, J1 = 4.0, J2 = 11.2, J3 = 8.7), 4.7 d.d (9a-H, J1 =
8.7, J2 7.4), 6.9 7.5 m (4H, Harom
1.2 2.3 m [(CH2)3], 3.5 m (9a-H), 3.9 d.d.d (1-H, J1 = 4.0, J2 = 11.3, J3 = 9.0), 4.6 d.d (9a-H, J1 = 9.0, J2 =
7.0), 5.9 s (NH2), 6.9 7.5 m (4H, Harom
1.1 1.9 m [(CH2)3], 3.1 d.d.d (9a-H, J1 = 6.5, J2 = 6.2, J3 = 11.2), 3.8 s (OCH3), 3.9 d.d.d (1-H, J1 = 10.5, J2 =
4.6, J3 = 4.6), 4.5 br.s (NH, NH2), 4.6 d.d (9a-H, J1 = 4.6, J2 = 6.56), 6.6 6.8 (3H, Harom
XXII 1.1 2.5 m [(CH2)3], 3.0 s (SCH3), 3.1 m (1-H), 3.6 m (13-H), 4.2 m (9-H), 6.9 7.7 m (3H, Harom
)
)
)
XX
)
XXI
)
)
coincided with each other) and J1, 2-ax = 10.5 Hz. Had
the 1-H proton been oriented equatorially, the coupl-
ing constant J1, 2-ax would be much smaller. In the
JMOD 13C NMR spectra of carbazoles IX, X, XVI
XVIII, and XX the C2 signal is displaced downfield
[17]. Moreover, using the double resonance technique
we have found that the 13-H proton is coupled with
the two protons in the bridgehead positions (1-H and
9-H) and two equatorial protons (12-Heq and 10-Heq)
whose signals appear in the region
(W-coupling). The 12-Hax and 10-Hax signals are
observed at 1.6 1.8 ppm.
2.3 2.6 ppm
(
34 36 ppm) due to -effect of iodine [21]
(TCable 1).
Signals in the 13C NMR spectra of azatricyclotri-
In order to prove that hexahydrocarbazole IX and
methylsulfonyl derivative XVI have the same struc-
decatrienes XI and XII were assigned on the basis
of their multiplicity, taking into account increments
of 13C chemical shifts given in [18]. Also, published
data for substituted bicyclo[3.1.1]heptanes [22] and
related bridged systems [23] were used. The anti
orientation of the iodine atom with respect to the
Scheme 6.
1
phenyl group was proved by the H NMR data. The
13-H proton in the bridging group gives rise to eight
lines or four doublets with coupling constants J not
exceeding 2 Hz. Such values correspond to the syn
orientation of 13-H with respect to the phenyl group
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 9 2001

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GATAULLIN et al.
Table 4. Elemental analyses of compounds IV VI, IX XIV, and XVI XXII
Found, %
Calculated, %
Comp.
Formula
no.
C
H
Hlg
N
C
H
Hlg
N
IV
V
VI
IX
X
XI
XII
XIII
XIV
XVI
XVII
XVIII
XIX
XX
XXI
XXII
45.30
72.32
57.29
47.67
47.07
48.42
47.12
61.91
73.08
40.94
48.17
48.87
71.87
45.19
71.14
40.81
4.21
7.14
5.51
4.86
4.54
4.23
4.47
6.54
7.61
3.98
4.32
4.29
7.13
4.01
8.11
4.16
39.79
27.13
3.93
5.71
4.62
3.92
3.87
4.00
3.69
5.30
5.19
3.32
3.28
3.68
12.48
7.81
12.41
3.45
C12H14INO
C14H17NO2
C14H16BrNO2
C12H14IN
C13H16INO
C12H14IN
C13H16INO
C13H17NO2Sa
C15H19NO2
C13H16INO2Sb
C15H18INO2
C14H16INO
C13H16N2O
C13H15IN2O
C13H18N2O
C13H16INO2Sc
45.73
72.70
57.16
48.18
47.43
48.18
47.43
62.15
73.44
41.39
48.53
49.28
72.19
45.63
71.53
41.39
4.48
7.41
5.48
4.72
4.90
4.72
4.90
6.77
7.81
4.27
4.89
4.73
7.46
4.42
8.31
4.27
40.27
27.16
4.44
6.05
4.76
4.68
4.25
4.68
4.25
5.58
5.71
3.71
3.77
4.10
12.95
8.19
12.83
3.71
38.97
41.94
38.87
39.46
42.42
39.46
33.17
33.74
36.76
33.64
34.19
37.19
36.65
33.15
37.09
33.64
a
b
c
Found S: 12.29%; calculated S: 12.75%.
Found S: 8.08%; calculated S: 8.50%.
Found S: 8.19%; calculated S: 8.50%.
ture of the tricyclic fragment, amines IX and XI were
treated with methanesulfonyl chloride in pyridine.
Compounds XVI and XXII were thus obtained
(Scheme 6). Comparison of the 13C NMR spectra of
the products showed that carbazole IX obtained from
amine VII and compound XVI obtained from XIII
have similar structures. The presence of methylsul-
fonyl group on the nitrogen exerts shielding effect on
C1 in XVI and C13 in XXII, so that the corresponding
signals appear more upfield relative to those observed
for IX and X.
solution of NaHCO3 (until CO2 no longer evolved)
and with 20 ml of water, dried over MgSO4, and
evaporated under reduced pressure. Anilide XV was
described in [1].
4-Acetyl-3-bromo-5-methoxy-1,2,3,3a,4,8b-hexa-
hydrocyclopenta[b]indole (VI). A mixture of 0.5 g
of anilide V and 0.45 g of N-bromosuccinimide in
10 ml of chloroform was stirred for 48 h at 20 C. It
was then filtered, and the filtrate was washed with
20 ml of a 10% aqueous solution of NaHCO3 and
evaporated under reduced pressure. The residue was
filtered through a thin layer of silica gel (2 g; eluent
methylene chloride.
EXPERIMENTAL
1
The H and 13C NMR spectra were recorded on
N-Methylsulfonyl-2-(2-cyclohexenyl)aniline
(XIII). 2-(2-Cyclohexenyl)aniline (VII), 0.52 g, was
dissolved in 4 ml of pyridine, and 0.6 ml of methane-
sulfonyl chloride was added dropwise. The mixture
was kept for 24 h at room temperature, diluted with
20 ml of water, stirred for 30 min, and extracted with
40 ml of CHCl3. The organic phase was washed with
20 ml of a 10% aqueous solution of NaHCO3 and
20 ml of water, dried over Na2SO4, and evaporated
under reduced pressure. The residue was recrystallized
from benzene.
a Bruker AM300 instrument at 300 and 75 MHz,
respectively; CDCl3 was used as solvent, and Me4Si,
as internal reference. The IR spectra were obtained on
a UR-20 spectrometer. The progress of reactions was
monitored by TLC on Silufol UV-254 plates.
N-Acetyl-6-(2-cyclopentenyl)-2-methoxyaniline
(V) and N-acetyl-2-(2-cyclohexenyl)aniline (XV) [1].
Acetic anhydride, 2.04 g, was added to a solution of
10 mmol of amine II or VII in 10 ml of methylene
chloride, and the mixture was kept for 18 h, treated
with water, and extracted with 100 ml of methylene
chloride. The extract was washed with a 5% aqueous
2-(2-Cyclohexenyl)-N-(ethoxycarbonyl)aniline
(XIV). A solution of 20 mmol of ethyl chloroformate
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REACTIONS OF N- AND C-ALKENYLANILINES: II.
1295
in 10 ml of methylene chloride was added dropwise
with stirring to a mixture of 10 mmol of amine VII,
80 mmol of K2CO3, and 30 ml of methylene chloride.
The mixture was kept for 18 h at 20 C and treated
with water. It was then stirred for 30 min and
extracted with 100 ml of methylene chloride. The
extract was washed with 20 ml of water, dried over
MgSO4, and the solvent was evaporated under
reduced pressure. The product was isolated by vacuum
distillation.
N-[2-(2-Cyclohexenyl)phenyl]urea (XIX).
A 17-ml high-pressure reactor was charged with 2 g
of compound XIV and 15 ml of a 16% solution of
NH3 in methanol, and the mixture was heated for 24 h
at 100 C. It was then cooled to 20 C, and the precip-
itate was filtered off.
complete, the solvent was removed under reduced
pressure, and products XI and XII were purified by
chromatography on silica gel as described above.
1-Amino-8-methoxy-1,2,3,4,4a,9a-hexahydrocar-
bazole (XXII). A mixture of 1 mmol of compounds
XI and 15 ml of a 16% solution of ammonia in
methanol was heated for 24 h at 100 C in a high-
pressure reactor. The mixture was cooled, the solvent
was distilled off, the residue was dissolved in chloro-
form (30 ml), and the solution was washed with
a 5% aqueous solution of NaHCO3 (20 ml) and with
water (20 ml). The organic phase was dried over
Na2SO4 and evaporated under reduced pressure, and
the residue was subjected to chromatography on silica
gel (10 g) using CCl4 as eluent.
Hexahydrocarbazoles IX and X. A mixture of
1 mmol of substituted aniline VII or VIII, 1.5 g of
NaHCO3, and 0.51 g of I2 in 10 ml of CCl4 was
shaken for 48 h at 20 C. The progress of the reaction
was monitored by TLC using hexane methanol
(9.8:0.2) as eluent. The solvent was decanted from
the precipitate, the latter was washed with 5 ml of
CCl4 and dissolved in 40 ml of methylene chloride,
30 ml of a 5% aqueous solution of Na2S2O3 was
added, the mixture was stirred for 5 min, and the
organic phase was separated, washed with 20 ml of
water, and dried over Na2SO4. The solvent was
removed under reduced pressure to obtain pure hexa-
hydrocarbazole IX or X.
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