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E.-J. Vogt et al. · Chemistry of Polyhalogenated Nitrobutadienes
J = 9.2 Hz, 1 H, SCHCH2,cis), 5.98 (d,J = 16.4 Hz, 1 H, CDCl3): δ = 1.28 (t, J = 7.1 Hz, 3 H, CH3), 3.33 (bs, 4 H,
SCHCH2,trans), 6.65 (dd, J = 16.4, 9.2 Hz, 1 H, SCH), 9.97 CH2NCH2), 3.67 – 3.68 (m, 4 H, CH2NCH2), 4.17 (q, J =
(s, 1 H, CHO). – 13C NMR (50 MHz, CDCl3): δ = 23.6 (1 C, 7.1 Hz, 2 H, CH2), 5.97 (d, J = 9.1 Hz, 1 H, SCHCH2,cis),
CH2), 25.9 (2 C, CH2), 55.1 (2 C, CH2NCH2), 122.9 (1 C, 6.00 (d, J = 16.4 Hz, 1 H, SCHCH2,trans), 6.63 (dd, J =
C−CHO), 125.7 (1 C, SCH), 128.2 (1 C, SCHCH2), 136.0 16.4, 9.1 Hz, 1 H, SCH), 9.96 (s, 1 H, CHO). – 13C NMR
(1 C, C-NO2), 151.9 (1 C, C-(N(CH2)2)), 159.1 (1 C, C- (150 MHz, CDCl3): δ = 14.6 (1 C, CH3), 43.8 (2 C,
SCH), 180.1 (1 C, CHO). – IR (KBr): ν = 3088, 3002, 2952, CH2NCH2), 53.2 (2 C, CH2NCH2), 61.7 (1 C, CH2), 125.6
2939, 2921, 2846, 1617, 1531, 1486, 1462, 1443, 1423, (1 C, SCH), 125.6 (1 C, C−CHO), 128.8 (1 C, SCHCH2),
1374, 1352, 1342, 1309, 1277, 1228, 1159, 1149, 1103, 136.4 (1 C, C-NO2), 150.5 (1 C, C-(N(CH2)2)), 155.4 (1 C,
1045, 995, 966, 942, 915, 859, 813, 776, 760, 713 cm−1. – COO), 159.6 (1 C, C-SCH), 180.1 (1 C, CHO). – IR (KBr):
MS (EI, 70 eV): m/z (%) = 299 (38) [M+H]+, 281 (44), 263 ν = 2981, 2922, 2850, 1703, 1619, 1534, 1486, 1467, 1455,
(100), 250 (24), 237 (62), 224 (23), 209 (40), 199 (28), 183 1436, 1424, 1376, 1352, 1311, 1285, 1244, 1222, 1135,
(25), 164 (29), 150 (21), 136 (22), 123 (20), 112 (32), 96 1120, 1076, 1048, 1035, 999, 969, 945, 764 cm−1. – MS
(39), 84 (42), 69 (68), 55 (64). – HRMS (EI): m/z = 298.0500 (EI, 70 eV): m/z (%) = 371 (2.5) [M]+, 354 (11), 336 (15),
(calcd. 298.0446 for C12H14N2O3S2, [M]+).
227 (100), 210 (29), 197 (19), 183 (21), 168 (17), 155 (23),
144 (32), 130 (17), 116 (30), 97 (19). – HRMS ((+)-ESI):
m/z = 394.0505 (calcd. 394.0507 for C14H17N3O5S2Na,
[M+Na]+).
4-Nitro-3-(1-pyrrolidinyl)-5-(vinylsulfanyl)thiophene-2-
carbaldehyde (4c)
The product was synthesized according to the general
procedure from 4-(2-chloro-4-nitro-5-(vinylsulfanyl)-3-thi-
enyl)pyrrolidine (3c) (580 mg, 2.0 mmol), anhydrous DMF
(4 mL), and 1.2 eq. of POCl3 (0.22 mL, 2.4 mmol); r. t., 4 h,
ice water (5 mL), ethyl acetate (3 × 30 mL); column chro-
matography (petroleum ether-ethyl acetate 1 : 1). The prod-
uct was isolated as a red-brown solid; yield: 284 mg (50 %),
m. p. 161 ◦C. – 1H NMR (200 MHz, CDCl3): δ = 2.04 – 2.10
(m, 6 H, (CH2)2), 3.40 – 3.47 (m, 4 H, CH2NCH2), 5.91 (d,
J = 9.2 Hz, 1 H, SCHCH2,cis), 5.95 (d, J = 16.4 Hz, 1 H,
SCHCH2,trans), 6.65 (dd, J = 16.4, 9.2 Hz, 1 H, SCH), 9.72
(s, 1 H, CHO). – 13C NMR (50 MHz, CDCl3): δ = 26.0
(2 C, (CH2)2), 54.8 (2 C, CH2NCH2), 117.5 (1 C, C−CHO),
125.3 (1 C, SCH), 127.8 (1 C, SCHCH2), 145.5 (1 C, C-
NO2), 157.3 (1 C, C-SCH), 162.7 (1 C, C-(N(CH2)2)), 180.1
(1 C, CHO). – IR (KBr): ν = 3088, 3033, 2991, 2956, 2882,
2842, 1597, 1539, 1498, 1453, 1432, 1371, 1351, 1330,
1310, 1276, 1247, 1234, 1176, 1132, 1110, 1045, 1019, 966,
942, 874, 834, 795, 757, 741, 711 cm−1. – MS (EI, 70 eV):
m/z (%) = 285 (3) [M+H]+, 267 (16), 249 (22), 211 (12),
196 (10), 184 (20), 151 (24), 140 (18), 111 (27), 97 (48),
84 (45), 70 (100), 59 (41). – HRMS (EI): m/z = 284.0288
(calcd. 284.0289 for C11H12N2O3S2, [M]+).
2,6-Dichloro-N,N-dimethylaniline (5)
To a solution of 2,6-dichloroaniline (1.0 g, 6.2 mmol) in
toluene (10 mL) dimethyl sulfate (3.13 g, 24.5 mmol) and
anhydrous potassium carbonate (858 mg, 6.2 mmol) were
added, and the mixture was refluxed overnight. After cool-
ing to r. t. aq. ammonia solution (25 %, 20 mL) was added,
and the mixture was stirred for 5 min. Then ethyl acetate
(20 mL) was added, the fractions were separated, and the
organic fraction was washed twice with water. The product
was purified by column chromatography (petroleum ether-
ethyl acetate 10 : 1), then isolated as a colorless liquid; yield:
300 mg (25 %). – 1H NMR (400 MHz, CDCl3): δ = 2.89 (s,
6 H, Me), 6.96 (t, J = 7.8 Hz, 1 H, H-4), 7.25 (d, J = 7.8 Hz,
2 H, H-3, H-5). – 13C NMR (100 MHz, CDCl3): δ = 42.1
(2 C, Me), 125.8 (1 C, C-4), 129.1 (2 C, C-3, C-5), 135.5
(2 C, C-2, C-6), 146.4 (1 C, C-1). The NMR data were in
accordance with the literature [8].
2,4,6-Trichloro-N,N-dimethylaniline (6)
2,4,6-Trichloro-N,N-dimethylaniline (6) was prepared
according to the procedure for 5 from 2,4,6-trichloroaniline
(1.0 g, 5.1 mmol), toluene (8 mL), dimethyl sulfate (2.59 g,
20.5 mmol), and anhydrous potassium carbonate (709 mg,
5.1 mmol). The product was isolated as a colorless liquid;
Ethyl 4-(2-formyl-4-nitro-5-(vinylsulfanyl)-3-thienyl)-1-
piperazinecarboxylate (4d)
1
yield: 579 mg (51 %). – H NMR (400 MHz, CDCl3): δ =
2.86 (s, 6 H, Me), 7.27 (s, 2 H, H-3, H-5). – 13C NMR
(100 MHz, CDCl3): δ = 42.0 (2 C, Me), 128.8 (2 C, C-3, C-
5), 130.1 (1 C, C-4), 135.9 (2 C, C-2, C-6), 145.3 (1 C, C-1).
The NMR data were in accordance with the literature [8].
The product was synthesized according to the general pro-
cedure from 754 mg (2.0 mmol) ethyl 4-(2-chloro-4-nitro-5-
(vinylsulfanyl)-3-thienyl)-1-piperazinecarboxylate (3d), an-
hydrous DMF (4 mL), and 1.2 eq. of POCl3 (0.22 mL,
2.4 mmol); 50 ◦C, 5 h, ice water (5 mL), ethyl acetate
(3×30 mL); column chromatography (petroleum ether-ethyl
acetate 1 : 1). The product was isolated as an orange solid;
3-Chloro-1-methyl-1H-indole (8)
3-Chloro-1-methyl-1H-indole (8) was synthesized ac-
◦
1
yield: 534 mg (72 %), m. p. 138 C. – H NMR (600 MHz, cording to the literature for the synthesis of 3-chloro-1H-
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