Reactions of N- and C-alkenylanilines: V. Synthesis of iodo-substituted heterocycles from o-cycloalkenylanilines and their transformations

Article abstract of DOI:10.1023/B:RUJO.0000045190.75301.70

Iodination of N-isopropyl- and N-benzyl-2-(2-cyclohexenyl)anilines gave the corresponding 1-iodo-hexahydrocarbazoles which underwent quantitative isomerization into 3-iodo-2,4-propano-1,2,3,4-tetrahydro-quinolines. Nucleophilic substitution in 1-iodohexah

Full text of DOI:10.1023/B:RUJO.0000045190.75301.70

Russian Journal of Organic Chemistry, Vol. 40, No. 7, 2004, pp. 986–991. Translated from Zhurnal Organicheskoi Khimii, Vol. 40, No. 7, 2004,
pp. 1027–1032.
Original Russian Text Copyright © 2004 by Gataullin, Minnigulov, Spirikhin, Abdrakhmanov.
Reactions of N- and C-Alkenylanilines: V.* Synthesis
of Iodo-Substituted Heterocycles from o-Cycloalkenylanilines
and Their Transformations
R. R. Gataullin1, F. F. Minnigulov2, 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.ri
2 Bashkir State Agrarian University, Bashkortostan, Russia
Received June 18, 2002
Abstract—Iodination of N-isopropyl- and N-benzyl-2-(2-cyclohexenyl)anilines gave the corresponding 1-iodo-
hexahydrocarbazoles which underwent quantitative isomerization into 3-iodo-2,4-propano-1,2,3,4-tetrahydro-
quinolines. Nucleophilic substitution in 1-iodohexahydrocarbazoles and 3-iodo-2,4-propano-1,2,3,3a,4,8b-
hexahydrocyclopenta[b]indole was studied. N-Allylation of the latter via reaction with allyl bromide is
accompanied by replacement of the iodine atom by bromine.
Interest in compounds of the cyclohexa- and cyclo-
penta[b]indole series arises primarily from the fact that
they constitute structural fragments of some alkaloids
[2] and are used in the synthesis of biologically active
substances [3]. The first synthesis of a compound of
the above series was described in [4]. In continuation
of our studies on cyclization of o-cycloalkenylanilines
[5, 6], in the present work we examined the cyclization
of N-isopropyl- and N-benzyl-2-(2-cyclohexenyl)-
anilines I and II by the action of iodine and nucleo-
philic substitution of the halogen atom in the resulting
1-iodohexahydrocarbazoles III and IV. Also, analo-
gous transformations of previously synthesized 3-iodo-
hexahydrocyclopenta[b]indole were studied [5].
by the action of iodine takes different pathways,
depending on the solvent. Analogous reaction of
N-substituted amines I and II with I2 in CCl4 in the
presence of NaHCO3 leads to hexahydrocarbazoles III
and IV (Scheme 1). The selectivity decreases in going
to other solvents, such as methylene chloride and
acetonitrile. Here, the reactions are accompanied by
endo-6-cyclization and intramolecular isomerization
of carbazoles III and IV into tetrahydroquinoline
derivatives V and VI. The latter were the only products
obtained from compounds I and II in acetonitrile.
Heterocycles III and IV in acetonitrile or chloroform
were converted into tetrahydroquinolines V and VI,
respectively, at different rates. By measuring intens-
ities of proton signals in the 1H NMR spectra in CDCl3
we found that the isomerization of N-isopropylcar-
We showed in [6] that cyclization of cyclohexenyl-
anilines having no substituent on the nitrogen group
Scheme 1.
H
I2, NaHCO3
solvent
4
+
I
2
3
H
I
N
NHR
N
R
R
I, II
III, IV
V, VI
I, III, V, R = i-Pr ; II, IV, VI, R = PhCH2.
* For communication IV, see [1].
1070-4280/04/4007-0986 © 2004 MAIK “Nauka/Interperiodica”

REACTIONS OF N- AND C-ALKENYLANILINES: V.
987
Scheme 2.
H
SCN–
H
I–
VII, VIII
N
R
A
III, IV
H
H
KSCN, MeCN
20°C
I2, KSCN
NaHCO3, MeCN
I
H
SCN
H SCN
N
N
R
Pr-i
IX
VII, VIII
VII, R = i-Pr; VIII, R = PhCH2.
bazole III into V is faster than the isomerization of its
N-benzyl analog IV.
zole IV with methylamine in methanol; Scheme 3)
indicates that the former is axial and that the latter is
equatorial. A strong effect of the N-substituent on the
conformation was observed for 1-iodohexahydrocar-
bazoles III and IV. The cyclohexane fragment in
hexahydrocarbazoles III and IV in solution has a chair
conformation (B) where the 1-H and 9a-H protons are
equatorial. This follows from the small coupling con-
stant J1,9a = 2–4 Hz. The large coupling constant
observed for 9a-H and 4a-H (J = 6.4–7.1 Hz) indicates
cis-junction of the rings [7]. Substituent on the nitro-
gen atom is likely to favor displacement of conforma-
tional equilibrium of hexahydrocarbazoles III and IV
toward the above form. Hexahydrocarbazoles having
no N-alkyl substituent [9, 10] were found to exist as
No expansion of the indole ring into quinoline
occurred when potassium thiocyanate (which is readily
soluble in acetonitrile) was added to a solution of
carbazole III and IV, and the corresponding 1-thio-
cyanato derivatives VII and VIII were obtained in
almost quantitative yield (Scheme 2). Thiocyanates
VII and VIII cannot be formed by transformation of
aziridinium salt A, for in this case orientation of the
substituent on C1 would be the opposite. The reaction
of amine I with I2 in acetonitrile in the presence of
KSCN and NaHCO3 gave compound IX which is
stereoisomeric to VII. Presumably, it was formed via
direct reaction of I with (SCN)2.
The NMR spectra of compounds VII and IX differ
only slightly. The 13C NMR spectrum of a mixture
of VII and IX contained a double set of signals. The
C9a–H and C1–S bonds in VII are arranged cis; in
keeping with the known rule for 1,2- or 1,3-syn ar-
rangement of substituents, the corresponding carbon
signals shift upfield.
1
conformers C. We recorded the H NMR spectra of
compound IV at 20 and 50°C. Raising the temperature
resulted in some increase of the fraction of conformer
C, as followed from increase in the coupling constant
J1,9a from 2.4 to 2.7 Hz and decrease in J4a,4-ax from
11.0 to 10.8 Hz.
A substituent can be introduced to the nitrogen
atom both before and after heterocyclization of
alkenylaniline. Moreover, taking into account different
properties of the nitrogen- and halogen-containing
The coupling constant between the 1-H and 9a-H
1
protons in the H NMR spectrum of hydroiodide X
(which was obtained by reaction of hexahydrocarba-
Scheme 3.
H
Heq
Hax
MeNH2, MeOH
20°C
I
4a
9a
Hax
4a
9a
4a
9a
1
4
Heq
83%
1
NHMe·HI
H
N
N
N
R
Heq
I
CH2Ph
R
Hax
C
B
X
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 7 2004

GATAULLIN et al.
988
Scheme 4.
H
H
H
CH2=CHCH2Br
MeCN
RNH2, MeOH
Br
I
NHR
H
H
H
N
N
N
H
H
Me
Me
Me
XIV
XI
XII, XIII
RNH2
MeOH
H
H
H
N
I2, CH2Cl2
NHR
N
N
H
H
H
N
N
Me
Me
Me
I
I
XV, XVI
XVII
XVIII
XII, XV, R = H; XIII, XVI, R = CH2=CHCH2.
moieties, either alkenylation of the amino group or
replacement of the halogen atom by alkenylamino
group can be effected. For example, cyclopenta[b]-
indole XI reacted with ammonia in acetonitrile at
100°C to give diamine XII [5] (Scheme 4). The
replacement of iodine by allylamino group occurs at
room temperature with formation of 3-allylamino-
indole XIII in high yield. The allylation of XI with
allyl bromide in acetonitrile was accompanied by
replacement of the iodine atom by bromine to afford
3-bromoindole XIV with a different configuration at
C3. By reaction of XIV with ammonia or allylamine
we obtained diamines XV and XVI, respectively, the
configuration at C3 remaining unchanged (Scheme 4).
Diallyl derivative XVI reacted with I2 to give hetero-
cycle XVII which underwent fast rearrangement into
seven-membered isomer XVIII.
EXPERIMENTAL
The H and 13C NMR spectra were recorded on
a Bruker AM-300 spectrometer (300.13 MHz for H
1
1
and 75.47 MHz for 13C); chloroform-d was used as
solvent, and tetramethylsilane, as internal reference.
The IR spectra were measured on a UR-20 instrument.
The purity of initial amines I and II was checked
by GLC on a Chrom-5 chromatograph equipped with
a flame-ionization detector and a 1200×3.5-mm
column (stationary phase SE-30 on Chromaton); oven
temperature programming at 12 deg/min; carrier gas
helium. The purity of the products was checked by
TLC on Silufol UV-254 plates; the chromatograms
were developed by treatment with iodine vapor.
N-Isopropyl-2-(2-cyclohexenyl)aniline (I). A high-
pressure reactor was charged with 1.7 g (10 mmol) of
2-(2-cyclohexenyl)aniline, 1.4 g (12 mmol) of iso-
propyl bromide, 10 ml of isopropyl alcohol, and 2 g of
potassium carbonate, and the mixture was heated for
16 h at 100°C. The mixture was filtered, the filtrate
was evaporated, the residue was dissolved in 20 ml of
CHCl3, the solution was washed in succession with
water, a 20% aqueous solution of Na2CO3, and water
again, dried over MgSO4, and evaporated, and the
residue was distilled under reduced pressure. Yield
95%, bp 126°C (3 mm). IR spectrum, ν, cm–1: 3400
(NH). 1H NMR spectrum, δ, ppm: 1.4 d (3H, CH3, J =
6.8 Hz), 1.5 d (3H, CH3, J = 6.8 Hz), 1.8–2.4 m (6H,
3CH2), 3.6 br.s (1H, NH), 3.9 m (2H, CH), 5.9 m (1H,
The structure of 3-bromocylopenta[b]indole XIV
was proved by elemental analysis and spectral data.
The JMOD 13C NMR spectrum of XIV contained
7 signals in the aliphatic region; among these, the
doublet at δC 58.4 ppm was assigned to the C3 atom
[7]. Compound XIV showed in the mass spectrum the
molecular ion peak with m/z 291, and strong peaks
with m/z 212 [M – Br]+ (base peak), 184 [M – Br –
C2H4]+, and 170 [M – Br – C6H6]+ were present.
Assuming that the replacement of iodine in XI follows
the SN2 mechanism, the 3-H and 3a-H protons in XIV
should be arranged cis.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 7 2004

REACTIONS OF N- AND C-ALKENYLANILINES: V.
989
C15H20IN. Calculated, %: C 52.80; H 5.91; I 37.19;
N 4.10.
2'-H), 6.2 m (1H, 3'-H), 6.9–7.4 m (4H, Harom).
13C NMR spectrum, δC, ppm: 21.2 (C5'), 22.9 and 23.2
(CH3), 25.0 (C4'), 28.0 (C6') 38.0 (C1'), 44.0 (CH),
111.2 (C6), 116.3 (C4), 127.2 (C5), 128.9 (C2'), 129.0
(C3), 130.3 (C3'), 132.5 (C2), 144.7 (C1). Found, %:
C 83.31; H 9.45; N 6.19. C15H21N. Calculated, %:
C 83.67; H 9.83; N 6.50.
Compound IV. Yield 90%. Rf 0.5 (C6H6). IR spec-
1
trum, ν, cm–1: 550 (C–I). H NMR spectrum, δ, ppm:
at 20°C: 1.0–2.4 m (6H, 3CH2), 3.3 d.t (1H, 4a-H,
J4a,4-ax = 11.0, J4a,4-eq = 6.2 Hz), 3.8 d.d [1H, 9a-H,
J9a,1 = 2.4, J9a,4a-eq = 6.4Hz), 4.2 d and 4.3 d (1H each,
PhCH2, J = 16.3 Hz), 4.8 d.d.d (1H, 1-H, J1,2-ax = 7.7,
J1,2-eq = 2.1 Hz), 6.5 d (1H, 8-H, 7.9 Hz), 6.8 t (1H,
6-H), 7.0 t (1H, 7-H), 7.1 d (1H, 5-H, J = 7.3 Hz), 7.2–
7.4 m (5H, Harom); at 50°C: 1.0–2.4 m (6H, 3CH2),
3.4 d.t (1H, 4a-H, J4a,4-ax = 10.8, J4a,4-eq = 6.9 Hz),
3.9 d.d (1H, 9a-H, J9a,1 = 2.7, J9a,4a-eq = 6.9 Hz), 4.2 d
and 4.3 d (1H each, PhCH2, J = 16.2 Hz), 4.8 d.d.d
(1H, 1-H, J1,2-ax = 7.7, J1,2-eq = 2.7 Hz), 6.5 d (1H, 8-H,
J = 7.9 Hz), 6.8 t (1H, 6-H), 7.0 t (1H, 7-H), 7.1 d (1H,
5-H, J = 7.3 Hz), 7.2–7.4 m (5H, Harom). 13C NMR
spectrum, δC, ppm: 20.9 (C5); 29.9 (C4); 31.1 (C2);
31.9 (C1); 38.3 (C4a); 52.5 (CH2); 72.2 (C9a); 118.9
(C8); 127.2 (C7); 127.3 (C5); 128.4 (C6); 134.1 (C4b);
138.9 (C8a); 126.9, 128.5, 128.6, 138.8 (Carom). Found,
%: C 58.28; H 4.87; I 32.29; N 3.19. C19H20IN. Calcu-
lated, %: C 58.62; N 5.18; I 32.60; N 3.60.
N-Benzyl-2-(2-cyclohexenyl)aniline (II). Benzyl
bromide, 1.7 g (10 mmol), was added dropwise under
continuous stirring to a mixture of 5.3 g of NaHCO3
and 6.9 g (40 mmol) of 2-(2-cyclohexenyl)aniline. The
mixture was stirred for 24 h at room temperature,
diluted with 20% aqueous sodium hydroxide, and
extracted with benzene. The organic phase was
separated, dried over MgSO4, and evaporated. Excess
initial amine was removed from the residue by vacuum
distillation, and product II was isolated from the still
residue by chromatography in a short column charged
with silica gel. Yield 70%, bp 142°C (1 mm). IR spec-
1
trum, ν, cm–1: 3400 (NH). H NMR spectrum, δ, ppm:
1.5–2.1 m (6H, 3CH2), 3.4 br.s (1H, NH), 4.0 m (1H,
1'-H), 4.3 s (2H, CH2), 5.7 m (1H, 3'-H), 5.8 m (1H,
2'-H), 6.7–7.5 m (9H, Harom). 13C NMR spectrum, δC,
ppm: 21.1 (C5'), 25.0 (C4'), 28.1 (C6'), 37.9 (C1'), 48.3
(PhCH2), 110.8 (C6), 117.1 (C4), 125.8 (C3), 127.4
(C2'), 127.9 (C5), 128.1 (C3", S5"), 128.6 (C4"), 128.7
(C2", C6"), 128.8 (C3'), 135.7 (C1"), 139.5 (C2), 145.3
(C1). Found, %: C 86.24; H 7.75; N 5.02. C19H21N.
Calculated, %: C 86.65; N 8.04; N 5.32.
(1R*,4aR*,9aS*)-N-Isopropyl-1-thiocyanato-
1,2,3,4,4a,9a-hexahydrocarbazole (VII). Potassium
thiocyanate, 1 g (10 mmol), was added to a solution of
0.34 g (1 mmol) of compound III in 10 ml of aceto-
nitrile. When the reaction was complete, the mixture
was evaporated, and 10 ml of water and 10 ml of
chloroform were added to the residue. The organic
phase was separated, dried over MgSO4, and
evaporated under reduced pressure. Yield 0.2 g (75%).
Rf 0.7 (C6H6). IR spectrum, ν, cm–1: 2380 m (C≡N).
1H NMR spectrum, δ, ppm: 1.2 d and 1.4 d (3H each,
2CH3, J = 7.0 Hz), 1.2–2.2 m (6H, 3CH2), 3.1 d.d.d
(1H, 4a-H, J1 = 4.0, J2 = 8.1, J3 = 11.5 Hz), 3.6 t (1H,
9a-H, J = 8.0 Hz), 3.7 m (1H, 1-H), 3.8 q (1H, CH, J =
7.0 Hz), 6.7 d (1H, 8-H, J = 8.3 Hz), 7.2–7.5 m
(4H, Harom). 13C NMR spectrum, δC, ppm: 20.6, 21.3
(2CH3); 20.9 (C3); 24.4 (C4); 30.5 (C2); 43.3 (C4a);
51.5 (C1); 52.6 (CH); 63.7 (C9a); 111.7 (SCN); 113.9,
121.2, 122.3, 127.4, 134.1, 150.5 (Carom). Found, %:
C 70.25; H 7.11; N 9.84; S 11.43. C16H20N2S. Calcu-
lated, %: C 70.55; H 7.40; N 10.28; S 11.77.
N-Isopropyl- and N-benzyl-1-iodo-1,2,3,4,4a,9a-
hexahydrocarbazoles III and IV (general proce-
dure). Sodium hydrogen carbonate, 10 mmol, and
iodine, 2 mmol, were added to a solution of 1 mmol of
amine I or II in 20 ml of carbon tetrachloride. When
the initial amine disappeared, the solvent was removed
by decanting, the precipitate was dissolved in 30 ml of
methylene chloride, the solution was treated with 10%
aqueous Na2S2O3 (2×20 ml), and the organic phase
was separated, washed with water (2×10 ml), dried
over MgSO4, and evaporated under reduced pressure.
Compound III. Yield 95%, Rf 0.6 (C6H6). IR spec-
1
trum, ν, cm–1: 550 (C–I). H NMR spectrum, δ, ppm:
1.1–2.3 m (6H, 3CH2), 1.3 d (3H, CH3, J = 6.7 Hz),
1.5 d (3H, CH3, J = 6.7 Hz), 3.2 d.t (1H, 4a-H,
J4a,4-ax = 10.0, J4a,4-eq = 3.8 Hz), 3.9 d.d [1H, 9a-H,
J9a,1 = 4.4, J9a,4a-eq = 7.1 Hz), 4.1 t (1H, CH, J =
N-Benzyl-1-thiocyanato-1,2,3,4,4a,9a-hexa-
hydrocarbazole (VIII). Potassium thiocyanate, 0.6 g
(6 mmol), was added to a solution of 0.2 g (0.6 mmol)
of compound IV in 5 ml of acetonitrile. When the
reaction was complete, the solution was evaporated,
and 10 ml of water and 10 ml of chloroform were
added to the residue. The organic phase was separated,
dried over MgSO4, and evaporated under reduced
6.7 Hz), 4.9 d.d.d [1H, 1-H, J1,2-ax = 8.6, J1,2-eq
=
4.4 Hz), 6.7–7.3 m (4H, Harom). 13C NMR spectrum, δC,
ppm: 16.8 (C3), 22.6, 23.1 (2CH3), 30.2 (C4), 30.5 (C2),
35.1 (C1), 39.4 (C4a), 47.5 (CH), 68.8 (C9a), 110.6 (C8),
122.5 (C7), 124.1 (C5), 127.3 (C6), 134.5 (C4b), 145.2
(C8a). Found, %: C 52.51; H 5.63; I 36.78; N 3.86.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 7 2004

GATAULLIN et al.
990
pressure. Yield 0.16 g (98%). Rf 0.4 (C6H6). IR spec-
7.1 Hz), 3.8 d.d [1H, 9a-H, J9a,1 = 3.5, J9a,4a-eq =
7.2 Hz), 4.3 d and 4.5 d (1H each, PhCH2, J =
16.3 Hz), 6.6 d (1H, 8-H, J = 7.6 Hz), 6.8 t (1H, 6-H,
1
trum, ν, cm–1: 2380 m (C≡N). H NMR spectrum, δ,
ppm: 1.5–2.2 m (6H, 3CH2), 3.4 m (1H, 4a-H), 3.6–
3.7 m (2H, 1-H, 9a-H), 4.5 s (2H, CH2), 6.5 d (1H,
8-H, J = 8.0 Hz), 6.8 t (1H, 6-H, J = 7.3 Hz), 7.0–
7.4 m (7H, Harom). 13C NMR spectrum, δC, ppm: 19.0
(C3); 27.4 (C4); 28.3 (C2); 39.9 (C4a); 48.3 (C1); 52.9
(CH2); 67.7 (C9a); 109.1 (C8); 111.4 (SCN); 119.0 (C7);
122.7 (C5); 127.2 (C6); 132.8 (C4b); 150.8 (C8a); 127.0,
127.7, 128.6, 138.4 (Carom). Found, %: C 74.55;
H 5.91; N 8.41; S 9.63. C20H20N2S. Calculated, %:
C 74.96; H 6.29; N 8.74; S 10.00.
J = 7.3 Hz), 7.0 m (1H, 7-H), 7.0–7.4 m (8H, Harom
,
NH2I). 13C NMR spectrum, δC, ppm: 19.0 (C3); 24.0
(C4); 29.0 (C2); 31.3 (NCH3); 38.6 (C4a); 53.9 (CH2);
56.4 (C1); 65.0 (C9a); 110.4 (C8); 119.9 (C7); 123.0
(C5); 127.6 (C6); 134.7 (C4b); 151.1 (C8a); 127.2, 128.4,
128.6, 138.7 (Carom). Found, %: C 56.84; H 5.65;
I 29.78; N 6.32. C20H25IN2. Calculated, %: C 57.14;
H 6.01; I 30.19; N 6.66.
3-Allylamino-5-methyl-1,2,3,3a,4,8b-hexahydro-
cyclopenta[b]indole (XIII). Allylamine, 0.14 g
(2.4 mmol), was added with stirring to a solution of
0.6 g (2 mmol) of compound XI in 10 ml of aceto-
nitrile. The mixture was left to stand for 12 h and
evaporated, 10 ml of 10% aqueous sodium hydroxide
and 10 ml of methylene chloride were added, and the
mixture was shaken. The organic phase was separated
and dried over MgSO4, the solvent was removed, and
the residue was subjected to chromatography on silica
gel using benzene–ethyl acetate (9:1) as eluent. Yield
0.4 g (70%). Rf 0.3. IR spectrum, ν, cm–1: 3328 (NH).
(1S*,4aR*,9aR*)-N-Isopropyl-1-thiocyanato-
1,2,3,4,4a,9a-hexahydrocarbazole (IX). A mixture of
0.22 g (1 mmol) of compound I, 0.84 g (10 mmol) of
NaHCO3, 0.51 g (2 mmol) of I2, and 0.19 g (2 mmol)
of KSCN in 20 ml of acetonitrile was shaken for 24–
130 h at 20°C, the progress of the reaction being
monitored by TLC using benzene as eluent. When the
reaction was complete, 50 ml of methylene chloride
was added, the mixture was filtered, and the precipitate
was washed with methylene chloride (10 ml). The
organic phase was treated with a 5% aqueous solution
of Na2S2O3 (3×10 ml) and water (20 ml) and dried 1H NMR spectrum, δ, ppm: 1.4–2.4 m (4H, 2CH2),
over Na2SO4. The solvent was removed under reduced
pressure, and the residue was subjected to column
chromatography on silica gel (0.5×30 cm) using ben-
2.1 s (3H, CH3), 3.0 d.t (1H, 3-H, J1 = 3.2, J2 =
5.3 Hz), 3.3 m (2H, CH2), 3.9 d.t (1H, 8b-H, J1 = 3.2,
J2 = 9.0 Hz), 3.5–4.3 br.s (2H, 2NH), 4.0 d.d (1H,
3a-H, J1 = 3.2, J2 = 9.0 Hz), 5.1 d.d (1H, 1'-HA, J1 =
1.4, J2 = 10.2 Hz), 5.2 d.q (1H, 1'-HB, J1 = 1.4, J2 =
17.1 Hz), 6.0 d.d.t (1H, 2-H, J1 = 4.0, J2 = 10.2, J3 =
17.1 Hz), 6.7 t (1H, 7-H, J = 7.0 Hz), 6.9 d (1H, 6-H,
J = 7.0 Hz), 7.0 d (1H, 8-H, J = 7.0 Hz). 13C NMR
spectrum, δC, ppm: 30.9 (C2), 32.0 (C1), 46.4 (C8b),
50.8 (C3'), 67.8 (C3), 69.2 (C3a), 116.1 (C1'), 118.3 (C5),
118.8 (C7), 121.8 (C8), 128.3 (C8a), 132.4 (C6), 136.8
(C3'), 149.0 (C4a). Found, %: C 78.54; H 8.66; N 11.94.
C15H20N2. Calculated, %: C 78.90; H 8.83; N 12.27.
1
zene as eluent. Yield 0.2 g (75%). H NMR spectrum,
δ, ppm: 1.2 d and 1.4 d (3H each, 2CH3, J = 7.0 Hz),
1.3–2.2 m (6H, 3CH2), 3.0 d.d.d (1H, 4a-H, J1 = 4.0,
J2 = 8.1, J3 = 11.5 Hz), 3.5 t (1H, 9a-H, J = 8.0 Hz),
3.6 m (1H, 1-H), 3.7 q (1H, CH, J = 7.0 Hz), 6.8–
7.2 m (4H, Harom). 13C NMR spectrum, δC, ppm: 20.6,
20.9 (2CH3); 21.2 (C3); 24.5 (C4); 30.1 (C2); 42.3
(C4a); 51.0 (C1); 51.8 (CH); 65.2 (C9a); 110.7 (SCN);
112.7, 127.1, 128.3, 133.2, 136.0, 152.3 (Carom).
Found, %: C 70.31; H 7.03; N 9.98; S 11.36.
C16H20N2S. Calculated, %: C 70.54; H 7.40; N 10.28;
S 11.77.
N-Allyl-3-bromo-5-methyl-1,2,3,3a,4,8b-hexa-
hydrocyclopenta[b]indole (XIV). Allyl bromide,
0.7 g (6 mmol), was added with stirring to a mixture
of 0.9 g (3 mmol) of 3-iodoindole XI and 1.1 g
(10 mmol) of NaHCO3 in 20 ml of acetonitrile, and the
mixture was kept for 24 h. When the reaction was
complete (TLC), the solvent was distilled off under
reduced pressure, and 10 ml of water and 20 ml of
chloroform were added to the residue. The organic
phase was separated and dried over MgSO4. The
solvent was removed under reduced pressure, and the
residue was subjected to chromatography on silica gel
using benzene as eluent. Yield 0.4 g (39%). Rf 0.8
1-Methylamino-1,2,3,4,4a,9a-hexahydrocarba-
zole hydroiodide (X). A 20% solution of methylamine
in THF, 1 ml (7 mmol), was added to a solution of
0.2 g (0.6 mmol) of carbazole IV in 5 ml of aceto-
nitrile. When the reaction was complete, the solution
was evaporated, and 10 ml of water and 10 ml of
chloroform were added. The organic phase was
separated and dried over MgSO4, and the solvent was
removed to obtain 0.2 g (98%) of compound X. Rf 0.2
1
(C6H6). IR spectrum, ν, cm–1: 3370 (NH). H NMR
spectrum, δ, ppm: 1.4–2.0 m (6H, 3CH2), 2.5 s
1
(3H, NCH3), 3.3 d.d.d (1H, 1-H, J1,2-ax = 3.0, J1,2-eq
3.2 Hz), 3.6 d.d.d (1H, 4a-H, J4a,4-ax = 9.0, J4a,4-eq
=
=
(C6H6). H NMR spectrum, δ, ppm: 1.61–2.5 m (4H,
2CH2), 3.7 m (2H, CH2), 3.9 t (1H, 8b-H, J = 8.7 Hz),
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 7 2004

REACTIONS OF N- AND C-ALKENYLANILINES: V.
991
4.2 d (1H, 3a-H, J = 8.9 Hz), 4.3 m (1H, 3-H), 5.0–
5.2 m (2H, CH2), 5.8 d.d.t (1H, CH, J1 = 5.8, J2 = 10.2,
J3 = 17.2 Hz), 6.6 t (1H, 7-H), 6.7 d and 6.8 d (1H
each, 6-H, 8-H). 13C NMR spectrum, δC, ppm: 19.1
(CH3), 33.1 (C1), 33.9 (C2), 44.4 (C8b), 54.5 (CH2),
58.4 (C3), 79.2 (C3a), 117.2 (CH2=), 119.6 (C7), 122.2
(C8), 130.8 (CH=S), 134.3 (C5), 134.8 (C6), 149.1 (C4a).
Mass spectrum, m/z: 291 [M]+, 212 [M – Br]+ (base
peak), 184 [M – Br – C2H4]+, 170 [M – Br – C6H6]+.
Found, %: C 61.39; H 6.07; Br 26.89; N 4.43.
C15H18BrN. Calculated, %: C 61.65; H 6.22; Br 27.34;
N 4.79.
spectrum, δC, ppm: 18.4 (CH3), 29.7 (C2), 31.7 (C1),
44.1 (C8b), 50.0 (NCH2), 53.9 (NHCH2), 65.3 (C3),
75.2 (C3a), 115.2 (CH2=), 116.0 (CH2=), 119.0 (C8),
119.4 (C8a), 121.3 (C7), 129.7 (C6), 135.0 (CH=), 135.1
(CH=), 136.3 (C5), 149.2 (C4a). Found, %: C 80.50;
H 8.97; N 10.40. C18H24H2. Calculated, %: C 80.50;
H 9.01; N 10.44.
3-Allyl-5-iodo-7-methyl-2,2a,3,4,5,6,10b,10c-
octahydro-1H-3,6a-diazabenzo[a]cyclopenta[cd]-
azulene (XVIII). Sodium hydrogen carbonate,
10 mmol, and iodine, 2 mmol, were added to a solution
of 1 mmol of compound XVI in 20 ml of methylene
chloride. When the initial amine disappeared, the
mixture was treated with a 10% aqueous solution of
Na2S2O3 (2×20 ml), and the organic phase was
separated, washed with water (2×10 ml), and dried
over MgSO4. The solvent was removed under reduced
pressure to obtain assumingly compound XVII which
was gradually converted into XVIII. Yield 0.4 g
(90%). Rf 0.8 (C6H6). 1H NMR spectrum, δ, ppm: 1.7–
2.6 m (4H, 2CH2), 2.2 s (3H, CH3), 3.6 m (1H, 2a-H),
3.8 m (2H, 6-H), 4.0 m (2H, 1'-H), 4.2 m (1H, 10b-H),
4.35 m (1H, 10c-H), 5.1–5.3 m (2H, 4-H), 5.6 m (1H,
5-H), 5.8 m (2H, 3'-H), 6.3 m (1H, 2'-H), 6.7–6.9 m
(3H, Harom). 13C NMR spectrum, δC, ppm: 13.8 (C5),
18.4 (CH3), 26.8 (C1), 31.4 (C2), 44.9 (C10b), 48.1 (C6),
54.2 (C1'), 60.0 (C4), 64.7 (C2a), 71.7 (C10s), 117.7 (C3'),
120.7 (C10), 121.1 (C10a), 124.3 (C7), 127.0 (C9), 130.2
(C8), 134.0 (C2'), 148.6 (C6b). Found, %: C 54.75;
H 5.80; I 32.15; N 7.05. C18H23IN2. Calculated, %:
C 54.83; H 5.88; I 32.18; N 7.10.
N-Allyl-3-amino-5-methyl-1,2,3,3a,4,8b-hexa-
hydrocyclopenta[b]indole (XV). Gaseous ammonia
was passed over a period of 10 min through a solution
of 0.6 g (2 mmol) of indole XIV in 10 ml of aceto-
nitrile under stirring at 0°C. The mixture was left to
stand for 0.5 h and evaporated, 10 ml of 10% aqueous
sodium hydroxide and 20 ml of methylene chloride
were added, and the mixture was shaken and washed
with 20 ml of water. The organic phase was separated
and dried over MgSO4, the solvent was removed, and
the residue was subjected to chromatography on silica
gel using benzene–ethyl acetate (9:1) as eluent. Yield
0.3 g (70%). Rf 0.3 (C6H6). IR spectrum, ν, cm–1: 3370
1
(NH). H NMR spectrum, δ, ppm: 1.4–1.8 m (4H,
2CH2), 2.3 s (3H, CH3), 3.3 m (1H, 3-H), 3.6 d.d (1H,
3a-H, J1 = 2.5, J2 = 9.3 Hz), 3.8–3.9 m (5H, NCH2,
8b-H, NH2), 5.2 m (2H, =CH2), 5.9 m (1H, CH=), 6.6–
6.9 m (3H, 6-H, 7-H, 8-H). 13C NMR spectrum, δC,
ppm: 18.7 (CH3), 31.5 (C2), 32.3 (C3), 44.0 (C8b), 54.5
(NCH2), 59.5 (C1), 78.5 (C3a), 116.2 (=CH2), 119.3 (C8),
119.8 (C8a), 121.7 (C6), 130.1 (C7), 135.3 (C5), 135.6
(CH=), 149.5 (C4a). Found, %: C 78.64; H 8.65; N 12.02.
C15H20N2. Calculated, %: C 78.90; H 8.83; N 12.27.
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Compounds, Berlin: Springer, 1983.
N-Allyl-3-allylamino-5-methyl-1,2,3,3a,4,8b-
hexahydrocyclopenta[b]indole (XVI). Allylamine,
0.14 g (2.4 mmol), was added with stirring to a solu-
tion of 0.6 g (2 mmol) of compound XIV in 10 ml of
acetonitrile. The mixture was left to stand for 12 h and
evaporated, 10 ml of 10% aqueous sodium hydroxide
and 20 ml of methylene chloride were added, the mix-
ture was shaken, and the organic phase was separated
and dried over MgSO4. The solvent was removed, and
the residue was subjected to chromatography on silica
gel using benzene–ethyl acetate (9:1) as eluent. Yield
0.3 g (60%). Rf 0.5 (C6H6). 1H NMR spectrum, δ, ppm:
1.3–2.2 m (4H, 2CH2), 2.2 s (3H, CH3), 3.0 m (1H,
3-H), 3.2 m (2H, CH2), 3.6 d.d (1H, 3a-H, J1 = 2.0,
J2 = 9.0 Hz), 3.7 m (2H, CH2), 3.8 m (1H, 8b-H),
5.2 m (5H, 2CH2=, NH), 5.9 m (2H, 2CH=), 6.6 t (1H,
7-H), 6.8 d and 6.9 d (1H each, 6-H, 8-H). 13C NMR
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 7 2004