Reactions of N-and C-alkenylanilines: VII. Synthesis of indole heterocycles from products of reaction between N-mesyl-2-(1-alken-1-yl)anilines and halogens

Article abstract of DOI:10.1007/s11178-005-0231-x

N-Mesyl-2-(1-methyl-1-butenyl)-6-methylaniline reacted with Br₂ to afford N-mesyl-2-(3-bromo-1-penten-2-yl)aniline that under treatment with NH₃ or amines underwent cyclization into N-mesyl-7-methyl-3- methylene-2-ethylindoline. The reaction of N-mesyl-2-(1-methyl-1-buten-1-yl)-4- methyl- and 2-(1-methyl-1-buten-1-yl)aniline with Br₂ gave rise to the corresponding N-mesyl-2-(2-bromo-1-methyl-1-buten-1-yl)anilines. Under the similar conditions N-tosyl-2-(1-cyclohexen-1-yl)aniline was converted into N-tosyl-2-(6-bromo-1-cyclohexen-1-yl)aniline that under treatment with NH ₃ furnished N-tosyl-1,2,3,9a-tetrahydrocarbazole. The reaction of N-mesyl-1,2,3,9a-tetrahydrocarbazole with CuBr₂ in MeOH afforded N-mesyl-4-methoxy-1,2,3,4-tetrahydrocarbazole. N-Mesyl-6-methyl-2-(1- cyclopenten-1-yl)aniline in reaction with Br₂ in the presence of NaHCO₃ was oxidized into the corresponding cyclopentenone, and with NBS it gave N-mesyl-2-(2-bromo-1-cyclopenten-1-yl)aniline. 2005 Pleiades Publishing, Inc.

Full text of DOI:10.1007/s11178-005-0231-x

Russian Journal of Organic Chemistry, Vol. 41, No. 5, 2005, pp. 715-722. Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 5, 2005,
pp. 730-737.
Original Russian Text Copyright Ó 2005 by Gataullin, Sotnikov, Spirikhin, Abdrakhmanov.
Reactions of N-and C-Alkenylanilines:
VII.* Synthesis of Indole Heterocycles from Products of Reaction
between N-Mesyl-2-(1-alken-1-yl)anilines and Halogens
R.R. Gataullin,A.M. Sotnikov, L.V. Spirikhin, and I.B.Abdrakhmanov
Institute of Organic Chemistry, Ufa Scientific Center, Russian Academy of Sciences,
Ufa, 450054 Russia; (3472) 35-60-66
e-mail: chemorg@anrb.ru
Received January 27, 2004
Abstract—N-Mesyl-2-(1-methyl-1-butenyl)-6-methylaniline reacted with Br2 to afford N-mesyl-2-(3-bromo-1-
penten-2-yl)aniline that under treatment with NH3 or amines underwent cyclization into N-mesyl-7-methyl-3-
methylene-2-ethylindoline. The reaction of N-mesyl-2-(1-methyl-1-buten-1-yl)-4-methyl- and 2-(1-methyl-1-buten-
1-yl)aniline with Br2 gave rise to the corresponding N-mesyl-2-(2-bromo-1-methyl-1-buten-1-yl)anilines. Under
the similar conditions N-tosyl-2-(1-cyclohexen-1-yl)aniline was converted into N-tosyl-2-(6-bromo-1-cyclohexen-
1-yl)aniline that under treatment with NH3 furnished N-tosyl-1,2,3,9a-tetrahydrocarbazole. The reaction of N-
mesyl-1,2,3,9a-tetrahydrocarbazole with CuBr2 in MeOH afforded N-mesyl-4-methoxy-1,2,3,4-tetrahydrocarbazole.
N-Mesyl-6-methyl-2-(1-cyclopenten-1-yl)aniline in reaction with Br2 in the presence of NaHCO3 was oxidized into
the corresponding cyclopentenone, and with NBS it gave N-mesyl-2-(2-bromo-1-cyclopenten-1-yl)aniline.
With the goal of synthesizing 3-methyleneindoles we
studied the halogenation of N-methylsulfonylanilines that
were obtained in high yield from the ortho-(1-alken-1-
yl)anilines. By bromination of compound I we prepared
a relatively stable allyl halide II that in the presence of
a base (Et2NH or NH3) readily afforded indoline III with
an exo-methylene group. In the absence of amines
compound II slowly underwent cyclization into indole IV
in a virtually quantitative yield (Scheme 1).
Compounds of 3-methyleneindole structure are used
in the synthesis of biologically active substances. How-
ever save 2-oxoderivatives [2–5] and a limited number
of compounds lacking the 2-oxo group [6–8] these
systems are of low stability and suffer isomerization into
indole in the course of their preparation due to the influence
of various factors. Therefore the development of efficient
methods for preparation of indolines with and exo-C=C
bond is a pressing problem nowadays.
Scheme 1.
0V1+ 0H
0V1+
(W 1+ꢁRUꢁ1+
ꢁꢁꢁꢁꢁꢁꢁꢁꢂꢃ &
0H
0H
%U
%U
1D+&2
1
0V
,
,,
0H
,,,
0V&Oꢀꢁ3\ꢀꢁꢂꢃ &
+%U
1+ 0H
1+ 0H
0H
0H
,
1D+&2
1
0V
0H
,
9,
9
,9
* For communication VI, see [1].
1070-4280/05/4105-0715Ó2005 Pleiades Publishing, Inc.

GATAULLIN et al.
716
Scheme 2.
The double bond in compounds IX and X is deactivated,
and at the attack of the next Br2 molecule on bromide IX
an electrophilic substitution occurs into the position 5 of
the aromatic ring. Apparently the inductive effect of the
bromovinyl moiety is stronger than the analogous effect
of the methanesulfonyl group, and this governs the
substitution direction.
0V1+ 0H
0V1
+
0H
%U
%U
1D+&2
5
5
,;ꢀꢁ;
9,,ꢀꢁ9,,,
This difference in structure of the reaction products
formed from fairly similar alkenylanilines I, VII, and VIII
we understand as follows. Pimarily arising bromonium
cations coordinated or noncoordinated through the
sulonamide group A or B suffer a trans-attack by an
0V1+ 0H
%U
%U
1D+&2
,;
–
%U
anion Br and give rise to trans-dibromides C or D. In
event of compound I presumably due to steric hindrances
the elimination is directed to formation of bromoalkene
II having a terminal double bond. With no methyl
substituents in the position 2 of the aromatic ring the
methanesulfonyl group does not suffer repulsion in the
direction of the alkenyl moiety and does not sterically
hamper the free rotation around the C1' –C2' bond, and
thus dqbromide C takes a conformation favorable for the
trans-elimination of proton H2' and halogen Br1'.
Therefore in the case of amides VII and VIII formed
bromides IX and X (Scheme 3).
;,
R = H (VII, IX), Me (VIII, X).
Scheme 3.
0H62
+1
%U
0V1+
0H
0H
0H
RU
%U
5
5
In the presence of a cyclic fragment the cis-elimination
is impossible. Thus in reaction with Br2 mesylate XII [9]
and tosylate XIII of the cyclohexenylaniline also afford
relatively stable allyl bromides XIV [9] and XV. It was
demonstrated that bromide XIV condensated
spontaneously into tetrahydrocarbazole XVI [9]. In the
presence of a methyl substituent in the position 6 from
mesylate XVII formed less stable allyl bromide XVIII,
and in this case the final reaction mixture consisted of
XVIII and tetrahydrocarbazolea XIX. In 24 h bromide
XVIII disappeared from the mixture, and it contained
only XIX.
$
%
%U
%U
%U
+
0H
%U
0V1+
0V1+
0H
0H
%U
%U
+
5
&
'
+%U
,;ꢀꢁ;
+%U
The treatment of allyl bromides XIV and XV with
aqueous ammonia afforded tetrahydrocarbazoles XX [9]
and XXI, valuable intermediates for the synthesis of 4-
substituted tetrahydrocarbazoles. For instance,
tetrahydrocarbazole XX reacted with CuBr2 in MeOH
[10] gave 4-methoxycarbazole XXII in a high yield. This
compound can be also prepared as follows: The reaction
of amide XII or allyl bromide XIV with CuBr2 in MeOH
affords methoxyderivative XXIII. The latter brought into
reaction with Pd(OAc)2 in DMSO also affords heterocycle
XXII in a 44% yield (Scheme 4).
,,
R = H (IX), Me (X).
The attempt to prepare indoline with an exo-methylene
group and a free nitrogen atom by treating with Br2 amine
V resulted in tarring of the reaction mixture due to a
vigorous reaction. The reaction of I2 with amine V in the
presence of NaHCO3 gave rise to iododerivative VI.
N-mesyl derivatives VII and VIII in reaction with
Br2 provided as the principal products exclusively vinyl
bromides IX or X (Scheme 2).
The attempts to use bromine in preparation of a homo-
log of carbazoles XX and XXI, tetrahydrocyclopent-
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 41 No. 5 2005

REACTIONS OF N-AND C-ALKENYLANILINES: VII.
717
Scheme 4.
+
5ꢀ1
5ꢀ1+
5
5
%U
+%U
1D+&2 ꢁ0H&1ꢁRU
ꢁꢁꢁꢁꢁꢁꢁꢁꢁꢁ&+ &O
%U
1
5
5ꢀ
;,9ꢀꢁ;9ꢀꢁ;9,,,
;,,ꢀꢁ;,,,ꢀꢁ;9,,
;9,ꢀꢁ;,;
&X%U
&X%U
0H2+ꢂ
ꢃꢄ &ꢂꢁꢅꢁK
0H2+ꢂ ꢃꢄ &ꢂꢁꢇꢁK
1+ ꢆ+ 2
20H
&X%U
+
0V1
0H2+ꢂ
ꢈꢄ &
1
1
5ꢀ
0V
20H
;;ꢀꢁ;;,
;;,,,
;;,,
3Gꢉ2$Fꢊ
'06ꢂꢁꢃꢄ &
R = H, R'= Ms (XII, XIV, XVI, XX), Ts (XIII, XV, XXI); R = Me, R'= Ms (XVII, XVIII, XIX).
Scheme 5.
0V1+
0V1+
0V1+
1%6ꢁ
1D+&2
%U
&+ &O
ꢂꢃ &
%U
1D+&2
0H&1ꢀ
&+ &O
2
;;9,
%U
;;9
;;,9
3LSHULGLQH
ꢄꢄꢃ &
1D+&2
0H&1
0V1+
1
1
%U
0V
;;9,,,
0V
*
%U
;;9,,
bromine underwent halogenation into the aromatic ring
providing dibromide XXVII. On heating vinyl bromide
XXVI with piperidine cyclization into indole XXVIII
occurred in 95% yield.
[b]indole G starting with N-mesylate XXIV were
unsuccessful (Scheme 5). It was found that in reaction
with Br2 compound XXIV [11] furnished as the main
reaction product ketone XXV. Therewith at the equimolar
amount of the halogen initial compound XXIV was not
completely consumed, and additional bromine amount was
required. The analog of compound XXIV with a methyl
group in the ring under these conditions furnished a similar
ketone [12]. The mechanism of these ketones formation
is not elucidated. In reaction of amide XXIV with NBS
vinyl bromide XXVI was obtained that treated with
The composition and structure of compounds syn-
thesized was established by elemental analysis and
1
13
spectral methods. The signals in the H and C NMR
spectra were assigned using CH- and HH-correlation
methods, double resonance , and JMOD.
Hence the structure of reaction products formed from
N-mesyl and N-tosyl-2-(1-alken-1-yl)anilines depended
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 41 No. 5 2005

GATAULLIN et al.
718
on the structure of the alkenyl moiety and on the character
of the ortho-substituent in the aromatic ring.
S 13.04. C12H17NO2S. Calculated, %: C 60.22; H 7.16;
N 5.85; S 13.40.
N-Mesyl-2-[(E)-1-methyl-1-buten-1-yl]-4-methyl-
aniline (VIII).Amorphous substance. Yield 84%, Rf 0.4.
1H NMR spectrum, d, ppm: 0.95 t (3H, CH3, J 7.0 Hz),
1.72–1.86 m (2H, CH2), 1.97 s (3H, CH3), 2.10 s (3H,
CH3), 2.98 s (3H, CH3), 5.68 d.t (1H, H2', J1 1.2,
J2 7.3 Hz), 6.51 s (1H, NH), 6.89 s (1H, H3), 7.10 d.d
(1H, H5, J1 1.6, J2 8.4 Hz), 7.49 d (1H, H6, J 8.4 Hz). 13C
NMR spectrum, d, ppm: 13.7, 20.5, 22.4, 39.1 (4CH3),
25.0 (CH2), 118.3 (C6), 128.5 (C2'), 129.2 (C5), 130.8 (C4),
131.0 (C2), 131.8 (C1), 133.2 (C3), 133.7 (C1'). Found, %:
C 61.44; H 7.22; N 5.19; S 12.22. C13H19NO2S.
Calculated, %: C 61.63; H 7.56; N 5.53; S 12.65.
EXPERIMENTAL
IR spectra were recorded on a spectrophotometer
1
13
UR-20. H and C NMR spectra were registered on a
spectrometer BrukerAM 300 at operating frequency 300
and 75 MHz respectively from solutions in CDCl3, internal
reference TMS. The purity of products was checked by
GLC on a chromatograph Chrom-5, carrier gas helium
(flow rate 50 ml/min), flame-ionization detector, columns
1200´3 mm, stationary phase silicon fluid SE-30 (5%)
on Chromaton N-AW DMCS carrier, oven temperature
50–300°C. The column chromatography was carried out
on silica gel 0.063 pm (Lancaster). The qualitative TLC
was performed on Sorbfil UV-254 plates (ZAO
Sorbpolymer, Krasnodar) (eluent C6H6–EtOAc, 9:1),
spots visualized by UV irradiation (l 254 nm) and by
iodine vapor. Elemental analysis was carried out on
C–H–NAnalyzer M-185B.
N-Mesyl-6-methyl-2-(1-cyclohexen-1-yl)aniline
1
(XVII). Yield 88%, mp 116°C. H NMR spectrum, d,
ppm: 1.64–1.80 m (4H, 2CH2), 2.12–2.20 m (2H, CH2),
2.31 m (2H, CH2), 2.44 s (3H, CH3), 3.05 s (3H, CH3),
5.71 m (1H, H2'), 6.54 br.s (1H, NH), 7.03 t (1H, Ar-H,
J 5.55 Hz), 7.14–7.16 m (2H,Ar-H). 13C NMR spectrum,
d, ppm: 21.8, 22.9, 25.4, 29.9 (4CH2), 19.7, 41.9 (2CH3),
127.1 (C4), 127.6 (C3), 128.1 (C2'), 129.7 (C5), 131.3 (C6),
137.3 (C2), 138.0 (C1), 143.2 (C1'). Found, %: C 63.49;
H 7.08; N 5.30; S 11.98. C14H19NO2S. Calculated, %:
C 63.36; H 7.22; N 5.28; S 12.08.
To a solution of 5.2 mmol of amine in 10 ml of pyridine
was added dropwise at stirring 0.86g (7.5 mmol) of MsCl.
After 7 h 1 ml of water was added, the mixture was
stirred for 1 h, and the solvent was evaporated in
a vacuum. To the residue 50 ml of CHCl3 was added,
the solution was washed with a saturated water solution
of NaHCO3 (20 ml), with water (20 ml), and dried over
Na2SO4. After evaporating the solvent the reaction
products I and XVII were recrystallized from EtOH.
To a reaction mixture containing 2 mmol of
sulfonamide and 1.68 g (20 mmol) of NaHCO3 in 15 ml
of CH3CN or CHCl3 was added dropwise 0.32 g
(2 mmol) of Br2 in 5 ml of the same solvent. The solution
immediately lost color, On completion of the reaction the
solvent was evaporated in a vacuum, the residue was
diluted with 50 ml of CH2Cl2 and washed with water
(2´50 ml). The organic layer was dried over Na2SO4.
The solvent was removed in a vacuum.
N-Mesyl-2-[(E)-1-methyl-1-buten-1-yl]-6-
methyl-aniline (I). Yield 87%, mp 72–74°C. 1H NMR
spectrum, d, ppm: 1.10 t (3H, CH3, J 7.3 Hz), 2.01 s (3H,
3CH3), 2.51 s (3H, 3CH3), 3.05 s (3H, 3CH3), 2.22 q
(2H, CH2, J 7.3 Hz), 5.50 d.t (1H, H2', J1 1.2, J2 7.3 Hz),
6.33 br.s (1H, NH), 7.01–7.24 m (3H, Ar-H). 13C NMR
spectrum, d, ppm: 13.5, 19.3, 21.5, 41.6 (4CH3), 17.7
(CH2), 127.1 (C4), 127.5 (C2'), 129.4 (C5), 131.0 (C2),
133.3 (C3), 133.6 (C6), 138.0 (C1'), 144.5 (C1). Found,
%: C 61.36; H 7.18; N 5.20; S 12.22. C13H19NO2S.
Calculated, %: C 61.63; H 7.56; N 5.53; S 12.65.
N-Mesyl-2-(3-bromo-1-penten-2-yl)-6-methyl-
aniline (II). Yield of crude allyl bromide II was 97%, Rf
0.4. 1H NMR spectrum, d, ppm: 1.11 t (3H, CH3, J 7.4
Hz), 2.02 m (2H, CH2), 2.51 s ( 3H, 2CH3), 3.20 s ( 3H,
2CH3), 4.71 d.d (1H, H3', J1 4.7, J2 8.8 Hz), 5.41 s (1H,
H1'a, H1'a), 5.83 s (1H, H1'a, H1'a), 6.32 s (1H, NH), 7.00–
13
7.32 m (3H, Ar-H). C NMR spectrum, d, ppm: 12.1,
N-Mesyl-2-[1-methyl-1-(E)-buten-1-yl]aniline
(VII).Amorphous substance. Yield 82%, Rf 0.4. 1H NMR
spectrum, d, ppm: 1.05 t (3H, CH3, J 7.5 Hz), 1.95–
2.25 m (2H, CH2), 2.15 s (3H, CH3), 3.10 s (3H, CH3),
5.55 d.t (1H, H2', J1 1.2, J2 7.3 Hz), 6.75 s (1H, NH),
6.90–7.55 m (4H, Ar-H). 13C NMR spectrum, d, ppm:
13.6, 24.8, 39.2 (3CH3), 22.2 (CH2), 117.2 (C6), 123.8
(C4), 127.9 (C2'), 128.7 (C3), 130.8 (C2), 133.4 (C5), 133.6
(C1), 136.3 (C1'). Found, %: C 59.92; H 6.98; N 5.61;
19.1, 43.5 (3CH3), 29.7 (CH2), 59.6 (C3'), 119.3 (C1'),
127.5 (C4), 128.6 (C3), 130.4 (C5), 133.5 (C6), 138. (C2),
139.7 (C1), 147.7 (C2'). Found, %: C 46.59; H 5.23;
Br 23.69; N 4.01; S 9.29. C13H18BrNO2S. Calculated,
%: C 46.99: H 5.46; Br 24.05; N 4.22; S 9.65.
N-Mesyl-2-[(E)-2-bromo-1-methyl-1-buten-1-
yl]-aniline (IX). Yield 81%, mp 103–104°C (EtOH).
1H NMR spectrum, d, ppm: 1.04 t (3H, CH3, J 7,2 Hz),
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 41 No. 5 2005

REACTIONS OF N-AND C-ALKENYLANILINES: VII.
719
2.11 s (3H, CH3), 2.23 q (2H, CH2, J 7.2 Hz), 3.08 s (3H,
CH3), 6.44 s (1H, NH), 7.07 d.d (1H, H6, J1 1.6, J2
7.5 Hz), 7.15 d.t (1H, H5, J1 0.9, J2 7.2 Hz), 7.31 d.d.d
(1H, H4, J1 0.9, J2 1.6, J3 7.2 Hz), 7.60 d (1H, H3,
J 8.3 Hz). 13C NMR spectrum, d, ppm: 13.4, 24.8,
40.0 (3CH3), 31.7 (CH2), 118.3 (C6), 124.3 (C4), 128.7
(C3), 128.8 (C5), 130.5 (C2'), 131.2 (C2), 131.5 (C1), 133.4
(C1'). Found, %: C 45.12; H 4.89; Br 25.80; N 4.23;
S 10.44. C12H16BrNO2S. Calculated, %: C 45.29; H 5.07;
Br 25.11; N 4.40; S 10.07.
7-Methyl-3-methylene-1-mesyl-2-ethylindoline
(III). To a solution of 0.166 g (0.5 mmol) of bromide II
in 3 ml of MeOH was added 0.2 ml of Et2NH or 1 ml of
10% solution of NH3 in MeOH at 20°C. The reaction
mixture was left standing for 10 h, MeOH was evaporat-
ed in a vacuum, the residue was diluted with 30 ml of
CH2Cl2, washed with 10% water solution of NaHCO3
and with water. The organic phase was separated and
dried with MgSO4. On removing the solvent in a vacuum
compound III was isolated by column chromatography
on silica gel (1 g) (eluent C6H6). We obtained 0.11 g (88%)
of amorphous compound III, Rf 0.6. 1H NMR spectrum,
d, ppm: 1.01 t (3H, CH3, J 7.3 Hz), 1.31–1.92 m (2H,
CH2), 2.40 s (3H, 2CH3), 2.50 s (3H, 2CH3), 4.52 d.d
(1H, H2, J1 4.6, J2 12.4 Hz), 5.11 d (1H, H1a', J 1.5 Hz),
5.63 d (1H, H1b', J 1.5 Hz), 7.10–7.31 m (3H, Ar-H).
13C NMR spectrum, d, ppm: 9.4, 19.3, 34.2 (3CH3), 30.0
(CH2), 69.9 (C2), 104.5 (=CH2), 118.8 (C5), 126.7 (C4),
126.9 (C3a), 132.6 (C6), 133.6 (C7), 134.4 (C7a), 146.4
(C3). Mass spectrum, m/z: 251 M+. Found, %: C 61.80;
H 6.56; N 5.24; S 12.37. C13H17NO2S. Calculated, %:
C 62.12; H 6.83; N 5.57; S 12.76.
N-Mesyl-2-[(E)-2-bromo-1-methyl-1-buten-1-yl]-
4-methylaniline (X). Amorphous substance separated
from EtOH as oily compound. Yield 95%, Rf 0.6. 1H NMR
spectrum, d, ppm: 1.05 t (3H, CH3, J 7.2 Hz), 2.12 s (3H,
CH3), 2.25 q (2H, CH2, J 7.2 Hz), 2.35 s (3H, CH3),
3.08 s (3H, CH3), 6.32 s (1H, NH), 6.90 s (1H, H3),
7.12 d (1H, H5, J 8.3 Hz), 7.48 d (1H, H6, J 8.3 Hz).
13C NMR spectrum, d, ppm: 13.3, 20.5, 24.9, 39.8 (4CH3),
31.6 (CH2), 118.9 (C6), 129.2 (C3), 129.4 (C5), 130.6 (C2'),
131.9 (C4), 133.2 (C2), 133.8 (C1), 134.3 (C1'). Found, %:
C 46.72; H 5.21; Br 23.80; N 4.05; S 9.34.
C13H18BrNO2S. Calculated, %: C 47.00; H 5.46;
Br 24.05; N 4.22; S 9.65.
N-Mesyl-3,7-dimethyl-2-ethylindole (IV). After
keeping 0.21 g (0.65 mmol) of compound II for 100 h at
room temperature the substance formed was dissolved
in 10 ml of CH2Cl2, washed with a saturated water solution
of NaHCO3 (10 ml) and water (10 ml). The organic phase
was dried over Na2SO4. On removing the solvent we
N-Mesyl-5-bromo-2-[(E)-2-bromo-1-methyl-1-
buten-1-yl]aniline (XI). Yield 50%, mp 133–134°C
(EtOH). 1H NMR spectrum, d, ppm: 1.06 t (3H, CH3,
J 7.3 Hz), 2.11 s (3H, CH3), 2.24 q (2H, CH2, J 7.3 Hz),
3.06 s (3H, CH3), 6.40 s (1H, NH), 7.23 d (1H, H6,
J2.2 Hz), 7.43 d.d (1H, H3, J1 2.2, J2 8.8 Hz), 7.50 d (1H,
H8, J 8.8 Hz). 13C NMR spectrum, d, ppm: 13.4, 24.7,
40.1 (3CH3), 31.8 (CH2), 117.1 (C2'), 119.9 (C4), 129.2
(C5), 131.4 (C6), 131.6 (C3), 132.2 (C2), 132.6 (C1), 133.4
(C1'). Found, %: C 36.32; H 3.54; Br 40.40; N 3.34;
S 7.87. C12H15Br2NO2S. Calculated, %: C 36.29; H 3.81;
Br 40.24; N 3.53; S 8.07.
1
obtained 0.16 g (97%) of indole IV, Rf 0.7. H NMR
spectrum, d, ppm: 1.00 t (3H, CH3, J 7.0 Hz), 2.61 s (3H,
CH3), 2.75 s (3H, CH3), 2.85 q (2H, CH2, J 7.0 Hz),
3.50 s (3H, CH3), 7.30–8.20 m (3H, Ar-H). 13C NMR
spectrum, d, ppm: 9.2, 14.3, 21.7, 36.4 (4CH3), 20.4 (CH2),
116.1 (C3), 120.8 (C5), 125.0 (C7), 128.3 (C4), 129.1 (C6),
135.3 (C3a), 138.7 (C2), 141.9 (C7a). Found, %: C 61.86;
H 6.52; N 5.40; S 12.42. C13H17NO2S. Calculated, %:
C 62.12; H 6.82; N 5.57; S 12.76.
N-Mesyl-5-bromo-2-(2-bromo-1-cyclopenten-1-
yl)aniline (XXVII). On recrystallization from EtOH
0.6 g (51%) of dibromide XXVII was obtained, mp 172–
6-Methyl-2-[(E)-1-methyl-1-buten-1-yl]aniline
(V). In the presence of 10 g of KOH 10 g of 2-(1-methyl-
buten-2-yl-1)-6-methylaniline was heated for 1 h at 300°C,
then the reaction mixture was cooled, the products were
decanted and distilled in a vacuum. Cis- and trans-
isomers were separated by fractional distillation in a
vacuum. The main product, amine V, was the first
fraction. Yield 5.5 g (55%), bp 116°C (3 mm Hg). IR
–1
174°C. IR spectrum, n, cm : 493, 525, 535 (C–Br), 3265
(NH). 1H NMR spectrum, d, ppm: 2.18 quint (2H, CH2,
J 7.4 Hz), 2.60–2.70 m (2H, CH2), 2.85–2.95 m (2H,
CH2), 3.10 s (3H, CH3), 6.50 s (1H, NH), 7.29 d (1H,
H6, J 2.2 Hz), 7.45 d.d (1H, H4, J1 2.2, J2 7.7 Hz), 7.50 d
(1H, H3, J 7.7 Hz). 13C NMR spectrum, d, ppm: 22.1
(C4'), 37.5 (C5'), 39.6 (C3'), 40.9 (SCH3), 117.5 (C6),
121.3 (C4), 123.2 (C2'), 130.0 (C2), 131.6 (C3), 131.8 (C5),
133.9 (C1), 136.3 (C1'). Found, %: C 36.05; H 3.01;
Br 40.06; N 3.17; S 7.82. C12H13Br2NO2S. Calculated,
%: C 36.48; H 3.32; Br 40.45; N 3.55; S 8.11.
–1
spectrum, n, cm :3380, 3460 (NH2). 1H NMR spectrum,
d, ppm: 1.00 t (3H, CH3, J 7.4 Hz), 2.00 s (3H, 2CH3),
2.32 s (3H, 2CH3), 2.31–2.53 m (2H, CH2), 3.80 s (2H,
NH2), 5.82 t (1H, H2', J 7.4 Hz), 6.81–7.31 m (3H, Ar-
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 41 No. 5 2005

GATAULLIN et al.
720
H). 13C NMR spectrum, d, ppm: 14.0, 17.1, 21.5 (3CH3),
17.6 (CH2), 117.6 (C4), 122.0 (C6), 126.4 (C2'), 128.5 (C3),
131.1 (C5), 132.1 (C2), 133.1 (C1'), 141.0 (C1). Found, %:
C 82.33; H 9.50; N 7.63. C12H17N. Calculated, %:
C 82.23; H 9.78; N 7.99.
added dropwise at vigorous stirring 0.32 g (2 mmol) of
a solution of Br2 in 5 ml of the same solvent. On stirring
for 3 h the precipitate was filtered off, and the solvent
was evaporated in a vacuum. The residue was dissolved
in 30 ml of CH2Cl2, and washed with 20 ml of 5% solution
of NaHCO3. The organic phase was dried over Na2SO4.
On evaporating the solvent in a vacuum the residue was
subjected to a chromatography on a short column packed
with silica gel (1og) to obtain 0.47 g (90%) of amorphous
substance XIX, Rf 0.75. 1H NMR spectrum, d, ppm: 1.90–
2.00 m (4H, 2CH2), 2.55 m (2H, CH2), 2.60 s (3H, CH3),
2.75 s (3H, CH3), 2.90 m (2H, CH2), 7.05–7.30 m (3H,
Ar-H). 13C NMR spectrum, d, ppm: 21.2 (CH3), 22.0,
23.2, 23.4, 25.8 (4CH2), 38.0 (CH3), 115.7 (C6), 122.4
(C4a), 124.6 (C7), 127.8 (C4b), 128.4 (C5), 133.7 (C9a),
137.8 (C8), 138.5 (C8a). Found, %: C 63.49; H 6.20;
N 5.01; S 11.88. C14H17NO2S. Calculated, %: C 63.85;
H 6.51; N 5.32; S 12.17. Mass spectrum, m/z (Irel, %):
263 (16), M+, 184 (100) [M – SO2CH3]+, 168 (9),
167 (10) [M –Ms – NH3]+, 157 (12) [M – Ms – HCN]+,
156 (8) [157 –H]+), 154 (6) [157 – H – H2]+, 141 (5)
[167 – C2H2]+, 128 (7) [154 – C2H2]+, 115 (9) [167 –
2C2H2]+, 91 (2), 89 (3) [167 – 3C2H2]+, 79 (7)
[SO2CH3]+, 77 (4), 65 (3), 64 (7) [SO2]+, 63 (2), 51 (2),
48 (5) [SO]+, 41 (3), 39 (5).
4-Iodo-6-methyl-2-[1-methylbut-2(Z)-en-1-
yl]aniline (VI). To a solution of 0.7 g (4 mmol) of amine
V in 20 ml of CCl4 was added 3.4 g (40 mmol) of
NaHCO3, and 2 g (8 mmol) of I2. On consumption of the
initial amine (~6–7 h) the precipitate was filtered off, the
reaction mixyure was washed with 10% water solution
of Na2S2O3 (2´50 ml) and with water (10 ml), then the
organic phase was dried over MgSO4. On removing the
solvent in a vacuum the product was isolated by column
chromatography on silica gel. Yield 0.65 g (54%), Rf 0.4.
–1
1
IR spectrum, n, cm : 3378, 3465 (NH2). H NMR
spectrum, d, ppm: 0.91 t (3H, CH3, J 7.4 Hz), 1.82 m
(2H, CH2), 1.90 s (3H, 2CH3), 2.20 s (3H, 2CH3), 3.82 s
(2H, NH2), 5.63 t (1H, H2', J 6.9 Hz), 7.11 s (1H, H3),
7.33 s (1H, H5). 13C NMR spectrum, d, ppm: 14.3, 17.6,
24.5 (3CH3), 22.7 (CH2), 79.2 (C4), 124.7 (C1),
130.0 (C2), 132.1 (C6), 132.2 (C5), 134.8 (C3'), 137.1 (C2),
140.9 (C2'). Found, %: C 47.39; H 5.23; I 41.69; N 4.17.
C12H16IN. Calculated, %: C 47.86; H 5.35; I 42.14;
N 4.65.
9-Tosyl-1,2,3,9a-tetrahydrocarbazole (XXI). To
a solution of 0.61 g (1.86 mmol) of amide XIII and 1 g of
NaHCO3 in 20 ml of CH2Cl2 was added dropwise at
stirring 0.3 g (1.86 mmol) of Br2 in 5 ml of CH2Cl2. In
2 h the reaction mixture was washed with 50 ml of H2O
and extracted into 50 ml of CH2Cl2. The solvent was
evaporated in a vacuum to a minimal volume, and 10 ml
of 25% aqueous NH3 was added thereto. The residue
was dissolved in 100 ml of CH2Cl2 and washed with
50 ml of H2O. The organic phase was dried over Na2SO4.
On evaporating the solvent in a vacuum the yield was
N-Tosyl-2-(1-cyclohexen-1-yl)aniline (XIII). To
a solution of 0.86 g (5 mmol) of 2-(1-cyclohexenyl)-aniline
in 10 ml of pyridine was added 1.4 g (7.3 mmol) of
p-toluenesulfonyl chloride [13]. The reaction mixture was
left standing for 24 h at room temperature, then it was
diluted with 0.5 ml of H2O, stirred for 30 min, the solvent
was evaporated in a vacuum. The residue was diluted
with 30 ml of H2O and 50 ml of CH2Cl2. The organic
phase was separated, washed with 30 ml of 5% HCl
solution, then with water (2´10 ml), and dried over
MgSO4. The solvent was evaporated in a vacuum, the
residue was recrystallized from EtOH. Yield 1.42 g
(87%), mp 120–122°C. 1H NMR spectrum, d, ppm: 1.53–
1.75 m (8H, 4CH2), 2.38 s (3H, CH3), 5.36 d.t (1H, H2',
J1 1.9, J2 3.5 Hz), 6.92–7.69 m (8H, Ar-H). 13C NMR
spectrum, d, ppm: 21.3 (CH3), 21.5, 22.6, 25.0, 29.8
(4CH2), 120.9, 124.4, 126.9, 127.4, 128.3, 128.5, 129.4
(C2', C3, C4, C5, C6, C2''6'', C3''5''), 132.9, 134.9, 135.8, 136.2,
143.7 (C1, C2, C1', C1'', C4''). Found, %: C 69.58; H 6.27;
N 4.09; S 9.64. C19H21NO2S. Calculated, %: C 69.70;
H 6.46; N 4.28; S 9.79.
1
0.6 g (99%). H NMR spectrum, d, ppm: 1.45–2.90 m
(6H, 3CH2), 2.38 s (3H, CH3), 4.20 d.d (1H, H9a, J1 3.5,
J2 10.1 Hz), 5.85 q (1H, H4, J 3.6 Hz), 6.90–7.80 m
(8H,Ar-H). 13C NMR spectrum, d, ppm: 20.0, 24.3, 28.9
(3CH2), 21.3 (CH3), 63.9 (C9a); 115.2, 117.9, 119.9, 123.8,
126.3, 127.5, 129.3 (C4, C5, C6, C7, C8, C2'6', C3'5'), 128.7,
133.1, 135.4, 143.2, 144.1 (C4a, C8a, C1', C4b, C4'). Found,
%: C 70.02; H 5.79; N 4.22; S 9.77. C19H19NO2S.
Calculated, %: C 70.13; H 5.88; N 4.30; S 9.85.
4-Methoxy-9-mesyl-1,2,3,4-tetrahydrocarbazole
(XXII). a. The reaction mixture containing 0.74 g
(3.3 mmol) of CuBr2 and 0.41 g (1.65 mmol) of tetra-
hydrocarbazole XX in 20 ml of MeOH was stirred at
N-Mesyl-8-methyl-1,2,3,4-tetrahydrocarbazole
(XIX). To a solution containing 0.53 g (2 mmol) of amide
XVII and 15 mmol of NaHCO3 in 20 ml of MeCN was
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 41 No. 5 2005

REACTIONS OF N-AND C-ALKENYLANILINES: VII.
721
H2', J1 3.0, J2 4.4 Hz), 6.80–7.10 m (2H, H5, H6), 7.15–
7.25 m (1H, H4), 7.57 d.d (1H, H3, J1 1.1, J2 7.8 Hz).
13C NMR spectrum, d, ppm: 15.8 (C4'), 25.4 (C3'), 25.5
(C5'), 38.9 (CH3), 56.1 (OCH3), 76.9 (C6'), 121.1 (C6),
124.6 (C4), 128.1 (C2'), 130.4 (C3), 134.2 (C5), 135.1 (C2),
135.6 (C1'), 135.9 (C1). Found, %: C 59.33; H 6.55;
N 4.62; S 11.01. C14H19NO3S. Calculated, %: C 59.76;
H 6.81; N 4.98; S 11.39.
20°C for 24 h. On completion of the reaction the mixture
was worked up as described for compound XXIII. After
column chromatograpy on silica gel to remove tar we
obtained 0.44 g (96%) of ester XXII as a transparent
viscous substance, Rf 0.3.
b. The reaction mixture containing 0.23 g (0.82 mmol)
of ester XXIII, 0.18 g (0.82 mmol) of Pd(OAc)2, and
0.13 g (1.64 mmol) of NaOAc in 9 ml of DMSO was
stirred at 50°C for 72 h. Then the reaction mixture was
diluted with 50 ml of CH2Cl2 and washed with H2O (2´50
ml). The organic phase was dried over Na2SO4. On
removing the solvent in a vacuum the residue was
subjected to chromatography on a column packed with
silica gel (2 g). Yield of compound XXII was 0.1 g (44%),
N-Mesyl-2-(5-oxo-1-cyclopenten-1-yl)aniline
(XXV). To a solution containing 0.47 g (2 mmol) of
mesylate XXIV, 10 ml of MeCN or CH2Cl2, and 1.7 g
(20 mmol) of NaHCO3 at vigorous stirring was slowly
added dropwise a solution of 0.64 g (4 mmol) of Br2 in
5 ml of MeCN or CH2Cl2. Then the reaction mixture
was stirred for 3 h more, the precipitate was filtered off,
the solvent was evaporated in a vacuum. The product
was isolated by chromatography on silica gel (column
1´30 cm, eluent benzene). Yield 0.186 g (37%), Rf 0.42.
1H NMR spectrum, d, ppm: 2.55–2.85 m (4H, 2CH2),
2.90 s (3H, CH3), 7.11–7.70 m (4H, Ar-H), 7.85 t (1H,
H2', J 2.0 Hz). 13C NMR spectrum, d, ppm: 27.6 (C3'),
35.3 (C4'), 39.8 (CH3), 123.8 (C6), 125.7 (C4), 126.1 (C2),
129.7 (C3), 130.3 (C5), 134.4 (C1), 144.2 (C1'), 165.9 (C2'),
209.4 (C5'). Found, %: C 57.04; H 4.98; N 5.13; S 12.28.
C12H13NO3S. Calculated, %: C 57.35; H 5.21; N 5.57;
S 12.76.
1
Rf 0.3. H NMR spectrum, d, ppm: 1.70–2.20 m (4H,
2CH2), 2.80–3.00 m (2H, CH2), 3.05 s (3H, CH3), 3.55 s
(3H, CH3), 4.60 d.t (1H, H4, J1 1.5, J2 3.4 Hz), 7.27–7.32
m (2H, Ar-H), 7.60–7.65 m (1H, Ar-H), 7.95–7.99 m
(1H, Ar-H). 13C NMR spectrum, d, ppm: 18.5 (C2), 24.1
(C1), 26.3 (C3), 40.5 (SCH3), 56.1 (OCH3), 71.2 (C4),
113.2 (C8), 117.9 (C4a), 118.9 (C5), 123.3 (C6), 124.0 (C7),
128.9 (C4b), 135.6 (C9a), 137.5 (C8a). Found, %: C 59.86;
H 5.88; N 4.64; S 11.07. C14H17NO3S. Calculated, %:
C 60.19; H 6.13; N 5.01; S 11.48.
N-Mesyl-2-(6-methoxy-1-cyclohexen-1-
yl)aniline (XXIII). a. The reaction mixture containing
0.45 g (2 mmol) of CuBr2 and 0.25 g (1 mmol) of
mesylate XII in 20 ml of MeOH was heated at 50–55°
C for 7 h. On cooling the mixture to room temperature
25 ml of H2O was added, the reaction product was
extracted into 30 ml of CH2Cl2. The organic phase was
dried over Na2SO4. On removing the solvent in a vacuum
the residue was subjected to chromatography on a column
(2´40 cm) packed with silica gel (5 g, eluent C6H6). We
obtained 18 g (65%) of ester XXIII as a viscous
substance, Rf 0.35.
N-Mesyl-2-(2-bromo-1-cyclopenten-1-yl)aniline
(XXVI).Amixture of 0.71 g (3 mmol) of mesylate XXIV,
0.53 g (3 mmol) of NBS, 1 g of NaHCO3, and 20 ml of
CH2Cl2 was stirred for 4 h. Then to the reaction mixture
10 ml of 12% Na2SO3 solution was added, the mixture
was stirred for 10 min and extracted with 50 ml of CH2Cl2.
The organic phase was dried over Na2SO4. The solvent
was removed in a vacuum, the product was recrystallized
from EtOH. Yield of bromide XXVI 0.8 g (84%),
–1
mp 135–137°C. IR spectrum, n, cm : 490, 526 (C–Br),
3262 (NH). 1H NMR spectrum, d, ppm: 2.15 quint (2H,
CH2, J 7.4 Hz), 2.65 t.t (2H, CH2, J1 2.4, J2 7.4 Hz),
2.89 t.t (2H, CH2, J1 2.4, J2 7.4 Hz), 3.05 s (3H, CH3),
6.47 s (1H, NH), 7.15 d.d (1H, H6, J1 2.4, J2 8.4 Hz),
7.18 t.d (1H, H5, J1 1.0, J2 8.4 Hz), 7.35 t.d (1H, H4,
J1 2.4, J2 8.4 Hz), 7.62 d.d (1H, H3, J1 1.0, J 8.4 Hz).
13C NMR spectrum, d, ppm: 22.2 (C4'), 37.6 (C5'), 39.5
(C3'), 40.85 (SCH3), 119.7 (C6), 122.1 (C2'), 124.6 (C4),
126.1 (C2), 128.9 (C3), 129.0 (C5), 133.6 (C1), 137.6 (C1').
Found, %: C 45.24; H 4.09; Br 24.81; N 3.97; S 9.79.
C12H14BrNO2S. Calculated, %: C 45.58; H 4.46; Br
25.27; N 4.43; S 10.14.
b. To a solution of 0.45 g (2 mmol) of CuBr2 in 15 ml
of MeOH was added dropwise at stirring 0.33 g (1 mmol)
of mesylate XIV bromide in 5 ml of MeOH.After heating
for 6 h at 50–55°C the reaction mixture was cooled to
room temperature, and 25 ml of H2O was added thereto.
The reaction product was extracted into 30 ml of CH2Cl2.
The organic phase was dried over Na2SO4. On removing
the solvent in a vacuum the residue was subjected to
chromatography on a column (2´20 cm) packed with silica
gel (0.5 g, eluent C6H6). We obtained 0.27 g (96%) of
ester XXIII as a viscous substance, Rf 0.35. 1H, d, ppm:
1.45–2.20 m (6H, 3CH2), 2.77 s (3H, CH3), 3.26 s (3H,
CH3), 3.75 d.t (1H, H6', J1 0.8, J2 3.7 Hz), 5.80 d.d (1H,
N-Mesyl-1,2,3,4-tetrahydrocyclopent-[b]indole
(XXVIII). The reaction mixture containing 0.083 g
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 41 No. 5 2005

GATAULLIN et al.
722
(0.26 mmol) of bromide XXVI and 3 ml of piperidine
was heated at reflux. After 4 h the piperidine was
evaporated in a vacuum, the residue was dissolved in
15 ml of CH2Cl2 and washed with 20 ml of water. The
organic phase was dried over Na2SO4. The solvent was
evaporated in a vacuum. Yield 0.059 g (95%). 1H NMR
spectrum, d, ppm: 2.10–2.80 m (6H, 3CH2), 3.00 s (3H,
SCH3), 7.10–7.90 m (4H, Ar-H). 13C NMR spectrum, d,
ppm: 24.0 (C1), 27.4 (C2), 27.6 (C3), 40.3 (CH3),
113.8 (C5), 119.2 (C8), 123.4 (C7), 123.5 (C6), 126.3 (C8b),
127.1 (C8a), 140.2 (C4a), 143.7 (C3a). Found, %: C 61.04;
H 5.42; N 5.81; S 13.32. C12H13NO2S. Calculated, %:
C 61.25; H 5.57; N 5.95; S 13.63.
4. Mori, M. and Ban, Y., Tetrahedron Lett., 1979, p. 1133.
5. Grigg, R., Millington, E.L. and Thornton-Pett, M.,
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6. Gataullin, R.R., Afon'kin, I.S., Fatykhov, A.A., Spiri-khin,
L.V., andAbdrakhmanov, I.B., Mendeleev Commun., 2001,
p. 201.
7. Tidwell, J.H., Peat,A.J., and Buchwald, S.L., J. Org. Chem.,
1994, p. 7164.
8. Larock, R.C., Hightower, T.R., Hasvold, L.A., and Peter-
son, K.P., J. Org. Chem., 1996, p. 3584.
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Tolstikov, G.A., Mendeleev Commun., 2003, p. 235.
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Akad. Nauk, Ser. Khim., 2002, p. 572.
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