Reactions of δ-functionalized α-nitrodienes with N-mono- and N,S-binucleophiles

Full text of DOI:10.1134/S1070428010070237

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2010, Vol. 46, No. 7, pp. 1092–1094. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © T.Yu. Kretser, E.S. Lipina, 2010, published in Zhurnal Organicheskoi Khimii, 2010, Vol. 46, No. 7, pp. 1092–1093.
SHORT
COMMUNICATIONS
Reactions of δ-Functionalized α-Nitrodienes
with N-Mono- and N,S-Binucleophiles
T. Yu. Kretser and E. S. Lipina
Hertzen Russian State Pedagogical University, nab. r. Moiki 48, St. Petersburg, 191186 Russia
e-mail: kohrgpu@yandex.ru
Received July 2, 2009
DOI: 10.1134/S1070428010070237
δ-Functionalized α-nitrodienes are polyconjugated
electron-deficient systems capable of vigorously react-
ing with nucleophilic reagents. The results of reactions
of 1,4-dinitrodienes with aromatic amines and thiols
are determined by nucleophilic attack at the middle or
terminal carbon atom of the diene system [1, 2]. In the
present communication we report the results of our
study on reactions of 1-nitro-4-arylsulfonyldienes I
and II with aromatic amines and of 1,4-dinitro- and
1-nitro-4-sulfanyldienes III–V with N,S-binucleo-
philes. Products of addition of 2 equiv of aniline and
ethanethiol to 1,4-dintrodienes [1, 2], as well as prod-
ucts of substitution by aromatic thiols, were reported
previously.
reactive 1-(4-chlorophenylsulfanyl)-2,3-dimethyl-4-
nitrobuta-1,3-diene (V) failed to react with aniline
under similar conditions; however, by heating com-
pound V with toluidine hydrochloride we obtained bis-
substitution product IX which was identical to that ob-
tained in the reaction with sodium p-chlorobenzene-
thiolate. We were the first to study reactions of nitro-
dienes II–IV with N,S-binucleophiles. The latter re-
acted with participation of more nucleophilic sulfur
center, and functional group in the δ-position with
respect to the nitro group in the substrate was replaced.
The most reactive unsubstituted 1,4-dinitrobuta-1,3-
diene (III) reacted even with neutral o-aminobenzene-
thiol to give butadiene X. By contrast, 1-nitro-4-sul-
fonyl (I, II) and 1-nitro-4-sulfanyl derivatives (V)
reacted only with sodium o-aminobenzenethiolate to
form substitution products XI and XII. The structure
of the isolated compounds was proved by spectral data.
We found that, unlike dinitrodienes III and IV
which give rise to addition products [1], reactions of
1-nitro-4-sulfonyldienes I and II with aromatic amines
followed nucleophilic vinylic substitution pattern, and
the products were 1-arylamino-4-nitrodienes VI–VIII
formed via replacement of the sulfonyl group. Less
4-Nitro-N-[(1E,3E)-4-nitrobuta-1,3-dien-1-yl]-
aniline (VI). A solution of 0.13 g (0.9 mmol) of
O2N
HA
RB
ArNH2, 18°C
X = HtSO2
HD
O2N
R
O2N
HA
RB
RC
NHAr
2-H2NC6H4S(Na)H
NaSHtNH2
HD
VI–VIII
R
X
RC
X–XII
SR'
4-ClC6H4S
Me
I–V
4-ClC6H4SNa, 60°C
X = 4-ClC6H4S
Me
SC6H4Cl-4
IX
I, R = H, X = 1,3-benzothiazol-2-ylsulfonyl; II, R = H, X = 1,3-benzothiazol-2-ylsulfonyl; III, R = H, X = O2N; IV, R = Me,
X = O2N; V, R = Me, X = 4-ClC6H4S; VI, R = H, Ar = 4-O2NC6H4; VII; R = Me, Ar = Ph; VIII, R = Me, 4-O2NC6H4; X, R = H,
R′ = o-NH2C6H4; XI, R = Me, R′ = o-NH2C6H4; XII, R = Me, R′ = 6-amino-1,3-benzothiazol-2-yl; Ht = 1,3-benzothiazol-2-yl.
1092

REACTIONS OF δ-FUNCTIONALIZED α-NITRODIENES
1093
p-nitroaniline in 3 ml of acetic acid was added to
a solution of 0.2 g (0.7 mmol) nitrosulfonyldiene I in
5 ml of acetic acid. The mixture was kept for 24 h at
18°C, and the precipitate was filtered off. Yield
0.036 g (21%), mp 199–200°C (from ethanol). IR
spectrum, ν, cm–1: 3450 (NH); 1620, 1560 (C=C),
1307, 1245 (NO2). UV spectrum: λmax 400 nm
Harom). Found, %: C 53.81; H 4.97. C18H16Cl2S2·2H2O.
Calculated, %: C 53.59; H 4.96.
b. Diene IX was synthesized in 76% yield by
heating equimolar amounts of nitrodiene V and sodium
p-chlorobenzenethiolate in methanol at 60°C over
a period of 2 h.
2-[(1E,3E)-4-Nitrobuta-1,3-dien-1-ylsulfanyl]-
aniline (X). o-Aminobenzenethiol, 0.15 g (1.1 mmol),
was added at 0°C to a solution of 0.15 g (1 mmol) of
dinitrodiene III in 15 ml of methanol, the mixture was
kept for 1 h, and the precipitate was filtered off. Yield
0.074 g (32%), mp 142–143°C (from chloroform). IR
spectrum, ν, cm–1: 1640, 1590 (C=C); 1530, 1330
(NO2). UV spectrum, λmax, nm (logε): 238 (3.95), 312
1
(log ε 4.02). H NMR spectrum (CDCl3), δ, ppm:
7.89 d (1H, HD), 8.06 d (1H, HA), 8.34 d.d (1H, HC),
8.10 d and 8.41 d (4H, C6H4), 8.46 d.d (1H, HB).
Found, %: C 50.54; H 3.79; N 17.91. C10H9N3O4. Cal-
culated, %: C 51.07; H 3.83; N 17.87.
N-(2,3-Dimethyl-4-nitrobuta-1,3-dien-1-yl)ani-
line (VII). A solution of 0.09 g (1 mmol) of aniline in
5 ml of diethyl ether was added dropwise to a solution
of 0.1 g (0.3 mmol) of nitrodiene II in 10 ml of diethyl
ether, maintaining the temperature at 18°C. The mix-
ture was kept for 4 days at 18°C and subjected to
column chromatography on silica gel using Trappe’s
eluotropic series. The benzene fraction was evaporated
to isolate 0.025 g (25%) of compound VII with
mp 92–93°C. IR spectrum, ν, cm–1: 3450 (NH), 1620,
1600 (C=C), 1310, 1240, 1120 (NOO–). UV spectrum:
λmax 357 nm (logε 4.26). Found, %: C 66.10; H 6.35;
N 13.09. C12H14N2O2. Calculated, %: C 66.05; H 6.47;
N 12.84.
1
(3.60). H NMR spectrum (CDCl3), δ, ppm: 4.10 s
(NH2), 6.45 d (1H, HD), 6.62–7.20 m (4H, C6H4),
7.08 d (1H, HA), 7.15 d.d (1H, HC), 7.57 d.d (1H, HB).
Found %: C 54.23; H 4.31; N 12.36. C10H10N2O2S.
Calculated, %: C 54.04; H 4.53; N 12.60.
2-(2,3-Dimethyl-4-nitrobuta-1,3-dien-1-ylsul-
fanyl)aniline (XI). A solution of sodium o-amino-
benzenethiolate prepared from 0.125 g (1 mmol) of
o-aminobenzenethiol and 0.023 g (1 mmol) of sodium
in 10 ml of methanol was added dropwise to a solution
of 0.172 g (1 mmol) of dinitrodiene IV in 5 ml of
methanol, cooled to –5 to 0°C. The mixture was stirred
for 20 min, and the precipitate was filtered off. Yield
0.145 g (58%), mp 93–95°C. IR spectrum, ν, cm–1:
1650, 1570 (C=C); 1520, 1330 (NO2). UV spectrum,
N-(2,3-Dimethyl-4-nitrobuta-1,3-dien-1-yl)-4-
nitroaniline (VIII) was synthesized in a similar way
on heating in methanol for 3 h at 40°C. Evaporation of
the chloroform eluate gave 32% of compound VIII
with mp 137–139°C. IR spectrum, ν, cm–1: 3500 (NH),
1590 (C=C), 1380, 1150 (NOO–). UV spectrum:
λmax 351 nm (logε 4.30). Found, %: C 54.77; H 4.97;
N 16.08. C12H13N3O4. Calculated, %: C 54.75; H 4.98;
N 15.96.
1
λmax, nm (logε): 250 (4.11), 315 (3.51). H NMR spec-
trum (CDCl3), δ, ppm: 1.31 d (3H, 2-CH3), 1.52 d (3H,
3-CH3), 4.30 s (NH2), 6.09 q (1H, HA), 6.55–7.30 m
(4H, C6H4), 7.08 q (1H, HD). Found, %: C 57.28;
H 6.00; N 10.97. C12H10N2O2S. Calculated, %:
C 57.58; H 5.64; N 11.20.
The reaction of nitrodiene V with aniline oc-
curred only on heating and was accompanied by
tarring. We succeeded in isolating only a small amount
of bis-sulfanyldiene IX.
2-(2,3-Dimethyl-4-nitrobuta-1,3-dien-1-ylsul-
fanyl)-1,3-benzothiazol-6-amine (XII) was synthe-
sized in a similar way from dinitrodiene IV (yield
44%, mp 156–157°C), nitrosulfonyldiene II (yield
47%, mp 155–156°C), or nitrosulfanyldiene V (yield
23%, mp 155–157°C). IR spectrum, ν, cm–1: 1595
(C=C); 1550, 1340 (NO2). UV spectrum, λmax, nm
1,4-Bis(4-chlorophenylsulfanyl)-2,3-dimethyl-
buta-1,3-diene (IX). a. By heating a mixture of 0.27 g
(1 mmol) of nitrodiene V and 0.15 g (1 mmol) of
toluidine hydrochloride in 10 ml of boiling 10% aque-
ous methanol over a period of 3 h we obtained 0.07 g
of compound IX with mp 151°C (from ethanol). IR
spectrum, ν, cm–1: 1470 (C=Carom), 1380 (CH3). UV
1
(logε): 242 (4.22), 309 (4.27). H NMR spectrum
(CDCl3), δ, ppm: 2.02 d (3H, 2-CH3), 2.47 d (3H,
3-CH3), 3.85 s (2H, NH2), 6.82–7.73 m (3H, Ht),
7.19 q (1H, HA), 7.56 q (1H, HD). Found, %: C 50.50;
H 4.62. C13H13N3O2S. Calculated, %: C 50.79; H 4.26.
1
spectrum (CHCl3): λmax 325 nm (logε 4.38). H NMR
4
1
spectrum (CDCl3), δ, ppm: 1.96 d (6H, CH3, J =
The H NMR spectra were recorded on a Bruker
4
1.3 Hz), 6.24 q (2H, =CH, J = 1.3 Hz), 7.21 m (8H,
AC-200 spectrometer at 200 MHz). The IR spectra
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 7 2010

KRETSER, LIPINA
1094
REFERENCES
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a Shimadzu UV-2401 PC spectrophotometer. The
progress of reactions and the purity of products were
monitored by TLC on Silufol UV-254 plates using
hexane–acetone (2:1) as eluent.
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 7 2010