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Synthesis of New S-, S,S- and N,S-Substituted Nitrodienes by Reaction of
Halo-2-nitrodienes with Thiols and Amines
F. Serpil Göksel*, Elif Aydin and Cemil Ibiş
Istanbul University, Faculty of Engineering, Department of Chemistry
34320 Avcilar-Istanbul, Turkey
Email: segoksel@istanbul.edu.tr
Supplemental Materials
Spectroscopic data of the new compounds:
4-Bromo-1,3,4-trichloro-1-(2-isopropylphenylthio)-2-nitro-1,3-butadiene (3a): Compound
3a was synthesized from 1a (1.0 g, 3.17 mmol) and 2-isopropylbenzenethiol 2a (0.482 g, 3.17
mmol) according to this general procedure 1a.
Yield: 0.391 g (29%); Oil; Rf (Petroleum ether:CHCl3, 3:1): 0.81; IR (KBr): υ (cm-1) 3062 (CHaromatic), 2965, 2870 (C-Haliphatic), 1596 (C=C), 1305, 1537 (NO2); UV-Vis (CHCl3): max 349,
246 nm; 1H-NMR (500 MHz, CDCl3): δ 1.15-1.17 (m, 5H, CH3), 1.53 (s, 1H, CH3), 3.28-3.35
(m, 1H, (CH3)2CH-), 7.18-7.21 (m, 1H, CHarom.), 7.36-7.38 (d, J= 7.81 Hz, 1H, CHarom.) 7.427.47 (m, 2H, CHarom.); 13C-NMR (125 MHz, CDCl3): δ 30.35 (CH3), 22.62 (CH), 125.97, 125.99,
136.23, 136.24, 113.95, 115.11, 121.77, 123.76, 152.27, 157.23 (Carom.,Cbutad.); MS (+ESI): m/z
859.4 [2M]+; C13H11BrCl3NO2S (M, 431.566) Calcd. C: 36.18, H: 2.57, N: 3.24; Found C:
36.73, H: 2.71, N: 3.24.
1,3,4,4-Tetrachloro-1-(2-isopropylphenylthio)-2-nitro-1,3-butadiene (3b): Compound 3b was
synthesized from 1b (1.0 g, 3.69 mmol) and 2-isopropylbenzenethiol 2b (0.561 g, 3.69 mmol)
according to the general procedure 1a.
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Yield: 0.253 g (18%); Oil; Rf (Petroleum ether): 0.90; FTIR (KBr): υ (cm-1) 3062 (C-Haromatic),
2965, 2869 (C-Haliphatic), 1602 (C=C), 1294, 1537 (NO2); UV-Vis (CHCl3): max 346, 248 nm;
1
H-NMR (500 MHz, CDCl3): δ 1.18 (d, J= 6.83 Hz, 6H, CH3), 3.30-3.34 (m, 1H, (CH3)2CH-),
7.18-7.22 (m, 1H, CHarom.), 7.37-7.39 (m, 1H, CHarom.), 7.42-7.48 (m, 2H, CHarom.);
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C-NMR
(125 MHz, CDCl3): δ 28.67, 30.36 (CH3), 22.63 (CH), 120.34, 126.00, 131.42, 136.25, 152.31,
120.34, 125.96, 126.09, 127.68, 157.30 (Carom.,Cbutad.); MS (-ESI): m/z 354.21 [M-Cl]- ;
C13H11Cl4NO2S (M, 387.11) Calcd. C: 40.33, H: 2.86, N: 3.62; Found C: 40.45, H: 2.71, N:
3.80.
4-Bromo-1,3,4-trichloro-1-(4-methoxyphenylthio)-2-nitro-1,3-butadiene (3c), 4-bromo-3,4dichloro-1,1-bis(4-methoxyphenylthio)-2-nitro-1,3-butadiene (4c): Compounds 3c and 4c
were synthesized from 1a (1.0 g, 3.17 mmol) and 4-methoxybenzenethiol 2c (0.444 g, 3.17
mmol) according to the general procedure 1a.
(3c): Yield: 0.528g (40%); Oil; Rf (Petroleum ether:CHCl3, 1:1): 0.63; IR (KBr): υ (cm-1) 3003
(C-Haromatic), 2958, 2835 (C-Haliphatic), 1590 (C=C), 1289, 1533 (NO2); UV-Vis (CHCl3): max
334, 250 nm; 1H-NMR (500 MHz, CDCl3): δ 3.71-3.78 (m, 3H, O-CH3), 6.90 (d, J= 8.79 Hz,
1H, CHarom ), 6.73-6.76 (m, 1H, CHarom.), 7.37 (d, J= 8.78 Hz, 1H, CHarom ), 7.30-7.33 (m, 1H,
CHarom.);
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C-NMR (125 MHz, CDCl3): δ 54.33 (O-CH3), 113.59, 131.63, 114.19, 118.22,
127.41, 136.64, 158.89, 161.14 (Carom.,Cbutad.); MS (+ESI): m/z 417.2 [M-H]-; C11H7BrCl3NO3S
(M, 419.51) Calcd. C: 31.49, H: 1.68, N: 3.34; Found C: 31.61, H: 1.10, N: 3.04.
(4c): Yield: 0.185g (12%); Oil; Rf (petroleum ether:CHCl3, 1:1): 0.29; IR (KBr): υ (cm-1) 3002
(C-Haromatik), 2926, 2837 (C-Halifatik), 1590 (C=C), 1291, 1510 (NO2); UV-Vis (CHCl3): max 390,
254 nm; 1H-NMR (500 MHz, CDCl3): δ 3.72 (s, 3H, O-CH3), 3.74 (s, 3H, O-CH3), 6.63-6.70 (m,
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4H, CHarom.), 6.84-6.86 (m, 2H, CHarom.), 6.99-7.03 (m, 2H, CHarom.);
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C-NMR (125 MHz,
CDCl3): δ 54.44, 54.48 (O-CH3), 113.49, 113.82, 132.71, 135.28, 113.45, 113.76, 120.55,
124.95, 132.73, 135.21, 159.48, 160.05 (Carom.,Cbutad.); MS (+ESI): m/z 523.7 [M+H]+;
C18H14BrCl2NO4S2 (M, 523.25) Calcd. C: 41.32, H: 2.70, N: 2.68; Found C: 41.45, H: 2.82, N:
2.14.
1,3,4,4-Tetrachloro-1-(4-methoxyphenylthio)-2-nitro-1,3-butadiene (3d), 3,4,4-trichloro-1,1bis(4-methoxyphenylthio)-2-nitro-1,3-butadiene
(4d):
Compounds
3d
and
4d
were
synthesized from 1b (1.0 g, 3.69 mmol) and 4-methoxybenzenethiol 2d (0.517 g, 3.69 mmol)
according to the general procedure 1a.
(3d): Yield: 0.473g (34%); Oil; Rf (Petroleum ether/CHCl3, 1/1): 0.43; IR (KBr): υ (cm-1) 3008
(C-Haromatic), 2964, 2839 (C-Haliphatic), 1591 (C=C), 1293, 1537 (NO2); UV-Vis (CHCl3): max
346, 248 nm; 1H-NMR (500 MHz, CDCl3): δ 3.78-3.79 (m, 3H, O-CH3), 6.89-6.91 (m, 2H,
CHarom.), 7.37-7.39 (m, 2H, CHarom.);
C-NMR (125 MHz, CDCl3): δ 54.52 (O-CH3), 114.21,
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136.62 (CHarom.), 118.13, 120.36, 127.63, 136.96 , 158.40, 161.17 (Carom.+Cbutad.); MS (+ESI):
m/z 375.6 [M]+; C11H7Cl4NO3S (M, 375.06) Calcd. C: 35.23, H: 1.88, N: 3.73; Found C: 35.45,
H: 1.97, N: 3.87.
(4d): Yield: 0.179g (10%); Oil; Rf (petroleum ether/CHCl3, 1/1): 0.33; FTIR (KBr): υ (cm-1)
3000 (C-Haromatic), 2964, 2838 (C-Haliphatic), 1592 (C=C), 1290, 1510 (NO2); UV-Vis (CHCl3):
max 400, 250 nm; 1H-NMR (500 MHz, CDCl3): δ 3.69-3.79 (m, 6H, O-CH3), 6.64-6.77 (m, 3H,
CHarom.), 6.84-7.04 (m, 3H, CHarom.), 7.28-7.39 (m, 2H, CHarom.); 13C-NMR (125 MHz, CDCl3): δ
54.35, 54.44 (O-CH3), 113.49, 113.78, 113.79, 113.81, 132.38, 132.69, 133.06, 135.29, 113.63,
114.78, 119.92, 120.55, 121.56, 127.06, 134.30, 159.49, 160.06 (Carom.,Cbutad.); MS (+ESI): m/z
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479.4 [M]+; C18H14Cl3NO4S2 (M, 478.80) Calcd. C: 45.15, H: 2.95, N: 2.93; Found C: 45.42, H:
3.38, N: 2.04.
4-Bromo-3,4-dichloro-1,1-bis(2-isopropylphenylthio)-2-nitro-1,3-butadiene (5a): Compound
5a was synthesized from 1a (1.0 g, 3.17 mmol) and 2-isopropylbenzenethiol 2a (0.482 g, 3.17
mmol) according to the general procedure 1b.
Yield: 0.248 g (14%); Oil; Rf (Petroleum ether:CHCl3, 3:1): 0.68; IR (KBr): υ (cm-1) 3056 (CHaromatic), 2962, 2872 (C-Haliphatic), 1595 (C=C), 1261, 1523 (NO2); UV-Vis (CHCl3): max 366,
251 nm; 1H-NMR (500 MHz, CDCl3): δ 0.76-1.22 (m, 10H, CH3), 1.52 (s, 2H, CH3), 2.72-2.77
(m, 1H, (CH3)2CH-), 2.89-2.95 (m, 1H, (CH3)2CH-), 6.96-7.02 (m, 3H, CHarom.), 7.07-7.10 (m,
1H, CHarom.), 7.13-7.14 (m, 1H, CHarom.), 7.16-7.20 (m, 2H, CHarom.), 7.21-7.25 (m, 1H,
CHarom.);
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C-NMR (125 MHz, CDCl3): δ 29.92, 29.40, 28.67 (CH3), 22.63 (CH), 124.66,
125.08, 125.67, 129.84, 134.93, 113.62, 124.72, 125.71, 128.11, 129.88, 131.46, 148.24, 151.11
(Carom.,Cbutad.); MS (+ESI): m/z 547.7 [M]+; C22H22BrCl2NO2S2 (M, 547.364), Calcd. C: 48.27,
H: 4.05, N: 2.56; Found C: 48.43, H: 4.70, N: 3.19.
4-Bromo-3,4-dichloro-1-[4-(diphenylmethyl)piperazine-1-yl]-1-(2-isopropylphenylthio)-2nitro-1,3-butadiene (7b): Compound 7b was synthesized from 3a (0.1 g, 0.23 mmol) and N(diphenylmethyl)piperazine (6b) (0.059 g, 0.23 mmol) according to the general procedure 2.
Yield: 0.102 g (68%); Oil; Rf (CH2Cl2): 0.84; IR (KBr): υ (cm-1) 3060, (C-Haromatic), 2962, 2854
(C-Haliphatic), 1589 (C=C), 1268, 1540 (NO2); UV-Vis (CHCl3): max 390, 250 nm; 1H-NMR (500
MHz, CDCl3): δ 1.10-1.27 (m, 4H, CH3), 1.50 (s, 2H, CH3), 3.18-3.23 (m, 1H, (CH3)2CH-),
2.02-2.28 (m, 4H, N-CH2), 3.36 (s, 2H, N-CH2), 3.71-3.49 (m, 2H, N-CH2), 4.09 (s, 1H,
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(C6H5)2CH-), 7.06-7.14 (m, 3H, CHarom.), 7.19-7.21 (m, 5H, CHarom.), 7.21-7.33 (m, 6H, CHarom.);
C-NMR (125 MHz, CDCl3): δ 30.28 (CH3), 22.24, 23.26 (CH), 47.43, 51.86 (N-CH2), 74.24
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(C6H5)2CH-, 126.36, 126.76, 127.67, 125.52, 125.59, 127.48, 128.29, 129.06, 133.16, 140.27,
148.96 (Carom.,Cbutad.); MS (+ESI): m/z 670.1 [M+Na]+; C30H30BrCl2N3O2S (M, 647.466); Calcd.
C: 55.65, H: 4.67, N: 6.48; Found C: 56.02, H: 4.35, N: 6.14.
3,4,4-Trichloro-1-(2-isopropylphenylthio)-2-nitro-1-(4-phenylpiperazine-1-yl)-1,3butadiene (7c): Compound 7c was synthesized from 3b (0.2 g, 0.52 mmol) and Nphenylpiperazine (6a) (0.084 g, 0.52 mmol) according to the general procedure 2.
Yield: 0.137 g (52%); Oil; Rf (CH2Cl2): 0.58; IR (KBr): υ (cm-1) 3000 (C-Haromatic), 2922, 2851
(C-Haliphatic), 1599 (C=C), 1540, 1263 (NO2); UV-Vis (CHCl3): max 389, 252 nm; 1H-NMR (500
MHz, CDCl3): δ 1.11-1.23 (m, 6H, CH3), 3.30-3.43 (m, 1H, (CH3)2CH-), 2.94 (s, 4H, N-CH2),
3.55 (s, 2H, N-CH2), 3.73 (s, 2H, N-CH2), 6.85 (d, J= 6.83 Hz, 1H, CHarom.), 6.89-6.82 (t, J=
7.32 Hz, 1H, CHarom.), 7.13-7.23 (m, 4H, CHarom.), 7.25-7.32 (m, 3H, CHarom.);
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C-NMR (125
MHz, CDCl3): δ 28.68, 30.29 (CH3), 22.36 (CH), 47.96, 51.53 (N-CH2), 125.85, 126.59, 128.46,
129.36, 116.17, 124.50, 125.50, 128.18, 132.91, 149.11 (Carom., Cbutad.); MS (+ESI): m/z 514.12
[M+H]+; C23H24Cl3N3O2S (M, 512.889) Calcd. C: 53.86, H: 4.72, N: 8.19; Found C: 53.10, H:
4.95, N: 7.82.
3,4,4-Trichloro-1-[4-(diphenylmethyl)piperazine-1-yl]-1-(2-isopropylphenylthio)-2-nitro1,3-butadiene (7d): Compound 7d was synthesized from 3b (0.15 g, 0.39 mmol) and N(diphenylmethyl)piperazine (6b) (0.10 g, 0.39 mmol) according to the general procedure 2.
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Yield: 0.118 g (51%); Oil; Rf (CH2Cl2): 0.75; IR (KBr): υ (cm-1) 3021 (C-Haromatic), 2965, 2803
(C-Haliphatic), 1594 (C=C), 1543, 1268 (NO2); UV-Vis (CHCl3): max 389, 252 nm; 1H-NMR (500
MHz, CDCl3): δ 1.11-1.18 (m, 5H, CH3), 1.54 (s, 1H, CH3), 3.16-3.24 (m, 1H, (CH3)2CH-),
2.08-2.26 (m, 4H, N-CH2), 3.34 (s, 2H, N-CH2), 3.62 (s, 2H, N-CH2), 4.09 (s, 1H, (C6H5)2CH-),
7.04-7.12 (m, 3H, CHarom.), 7.17-7.30 (m, 11H, CHarom.); 13C-NMR (125 MHz, CDCl3): δ 30.18
(CH3), 23.12 (CH), 49.29, 52.42 (N-CH2), 74.18 (C6H5)2CH-, 125.59, 126.35, 126.75, 127.65,
129.09, 133.04, 140.25, 148.95, 118.15, 124.01, 125.51, 125.74, 127.45, 128.25, 142.84, 165.64
(Carom.,Cbutad.); MS (+ESI): m/z 626.1 [M+Na]+; C30H30Cl3N3O2S (M, 603.00) Calcd. C: 59.75,
H: 5.01, N: 6.97; Found C: 59.38, H: 5.15, N: 6.74.
3,4,4-Trichloro-1-[4-(4-fluorophenyl)piperazine-1-yl]-1-(2-isopropylphenylthio)-2-nitro-1,3butadiene (7e): Compound 7e was synthesized from 3b (0.15 g, 0.39 mmol) and N-(4fluorophenyl)piperazine (6c) (0.07 g, 0.39 mmol) according to the general procedure 2.
Yield: 0.043 g (20%); Oil; Rf (CH2Cl2): 0.57; IR (KBr): υ (cm-1) 3060 (C-Haromatic), 2963, 2926
(C-Haliphatic), 1600 (C=C), 1540, 1263 (NO2); UV-Vis (CHCl3): max 389, 250 nm; 1H-NMR (500
MHz, CDCl3): δ 1.11-1.24 (m, 5H, CH3), 1.51 (s, 1H, CH3), 3.28-3.34 (m, 1H, (CH3)2CH-), 2.77
(s, 4H, N-CH2), 3.46 (s, 2H, N-CH2), 3.68 (s, 2H, N-CH2), 6.67-6.71 (m, 1H, CHarom.), 6.85-6.97
(m, 2H, CHarom.), 7.12-7.22 (m, 3H, CHarom.), 7.28-7.32 (m, 2H, CHarom.);
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C-NMR (125 MHz,
CDCl3): δ 30.27 (CH3), 22.73 (CH), 48.47, 51.87 (N-CH2), 125.81, 126.51, 129.31, 133.09,
149.19, 114.74, 114.92, 117.75, 117.81, 128.27, 129.86, 157.87, 166.74 (Carom.,Cbutad.); MS
(+ESI): m/z 553.9 [M+Na]+; C23H23Cl3FN3O2S (M, 530.87) Calcd. C: 52.04, H: 4.37, N: 7.92;
Found C: 52.24, H: 4.38, N: 7.88.
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4-Bromo-3,4-dichloro-1-(4-methoxyphenylthio)-2-nitro-1-(4-phenylpiperazine-1-yl)-1,3butadiene (7f): Compound 7f was synthesized from 3c (0.2 g, 0.48 mmol) and Nphenylpiperazine (6a) (0.077 g, 0.48 mmol) according to the general procedure 2.
Yield: 0.096 g (37%); m.p.: 173-174°C; Rf (CH2Cl2): 0.48; IR (KBr): υ (cm-1) 3000 (C-Haromatic),
2923, 2837 (C-Haliphatic), 1597 (C=C), 1503, 1266 (NO2); UV-Vis (CHCl3): max 389, 252 nm;
1
H-NMR (500 MHz, CDCl3): δ 3.70-3.74 (m, 3H, O-CH3), 2.92 (s, 4H, N-CH2), 3.56 (bs, 4H, N-
CH2), 6.75-6.92 (m, 4H, CHarom.), 7.16-7.25 (m, 3H, CHarom.), 7.31-7.39 (m, 2H, CHarom.);
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C-
NMR (125 MHz, CDCl3): δ 55.79 (O-CH3), 49.17, 52.81 (N-CH2), 116.16, 129.71, 134.99,
112.88, 114.86, 117.28, 121.01, 128.50, 132.91, 161.33 (Carom.,Cbutad.); MS (+ESI): m/z 568.09
[M+Na]+; C21H20BrCl2N3O3S (M, 545.285) Calcd. C: 46.26, H: 3.70, N: 7.71; Found C: 46.73,
H: 3.69, N: 7.16.
4-Bromo-3,4-dichloro-1-[4-(diphenylmethyl)piperazine-1-yl]-1-(4-methoxyphenylthio)-2nitro-1,3-butadiene (7g): Compound 7g was synthesized from 3c (0.1 g, 0.24 mmol) and N(diphenylmethyl)piperazine (6b) (0.060 g, 0.24 mmol) according to the general procedure 2.
Yield: 0.099 g (67%); Oil; Rf (CHCl3): 0.24; IR (KBr): υ (cm-1) 3022 (C-Haromatic), 2920, 2810
(C-Haliphatic), 1592 (C=C), 1272, 1540 (NO2); UV-Vis (CHCl3): max 390, 252 nm; 1H-NMR (500
MHz, CDCl3): δ 3.79 (s, 3H, O-CH3), 2.16-2.28 (bs, 4H, N-CH2), 3.39-3.72 (bs, 4H, N-CH2),
4.02 (d, J= 6.34 Hz, 1H, (C6H5)2CH-), 6.84 (d, J= 8.29 Hz, 2H, CHarom.), 7.10-7.13 (t, 2H,
CHarom.), 7.17-7.20 (t, 4H, CHarom.), 7.23-7.34 (m, 6H, CHarom.); 13C-NMR (125 MHz, CDCl3): δ
49.39, 52.31 (N-CH2), 54.55 (O-CH3), 74.43 (C6H5)2CH-, 126.71, 127.65, 114.71, 120.08,
126.35, 133.87, 133.95, 140.39, 159.93 (Carom.,Cbutad.); MS (+ESI): m/z 658.0 [M+Na]+;
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C28H26BrCl2N3O3S (M, 635.40); Calcd. C: 52.93, H: 4.12, N: 6.61; Found C: 52.46, H: 4.01, N:
6.33.
3,4,4-Trichloro-1-(4-methoxyphenylthio)-2-nitro-1-(4-phenylpiperazine-1-yl)-1,3-butadiene
(7h): Compound 7h was synthesized from 3d (0.1 g, 0.27 mmol) and N-phenylpiperazine (6a)
(0.043 g, 0.27 mmol) according to the general procedure 2.
Yield: 0.112 g (83%); m.p.: 175-176°C, Rf (CH2Cl2): 0.43; IR (KBr): υ (cm-1) 3000 (C-Haromatic),
2926, 2834 (C-Haliphatic), 1597 (C=C), 1276, 1510 (NO2); UV-Vis (CHCl3): max 389, 252 nm;
1
H-NMR (500 MHz, CDCl3): δ 3.74 (d, J= 6.84 Hz, 3H, O-CH3), 2.88 (s, 4H, N-CH2), 3.59 (bs,
4H, N-CH2), 6.75-6.77 (m, 1H, CHarom.), 6.85-6.88 (m, 3H, CHarom.), 7.18-7.21 (m, 3H, CHarom.),
7.32-7.34 (m, 2H, CHarom.);
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C-NMR (125 MHz, CDCl3): δ 54.52 (O-CH3), 47.58, 51.73 (N-
CH2), 114.86, 128.36, 133.76, 113.60, 119.85, 125.83, 127.78, 129.86, 131.65, 160.06
(Carom.,Cbutad.); MS (+ESI): m/z 502.2 [M+H]+; C21H20Cl3N3O3S (M, 500.83) Calcd. C: 50.36, H:
4.03, N: 8.39; Found C: 50.15, H: 4.36, N: 7.95.
3,4,4-Trichloro-1-[4-(diphenylmethyl)piperazine-1-yl]-1-(4-methoxyphenylthio)-2-nitro-1,3butadiene (7i): Compound 7i was synthesized from 3d ( 0.1 g, 0.27 mmol) and N(diphenylmethyl) piperazine (6b) (0.067 g, 0.27 mmol) according to the general procedure 2.
Yield:0.107 g (67%); Oil; Rf (CH2Cl2): 0.76; IR (KBr): υ (cm-1) 3024 (C-Haromatic), 2958, 2838
(C-Haliphatic), 1592 (C=C), 1272, 1541 (NO2); UV-Vis (CHCl3): max 390, 254 nm; 1H-NMR (500
MHz, CDCl3): δ 3.78 (s, 3H, O-CH3), 1.96 (bs, 4H, N-CH2), 3.45 (bs, 4H, N-CH2), 4.02 (d, J=
4.88 Hz, 1H, (C6H5)2CH-), 6.84 (d, J= 8.30 Hz, 2H, CHarom.), 7.10-7.32 (m, 12H, CHarom.); 13CNMR (125 MHz, CDCl3): δ 49.37, 52.42 (N-CH2), 54.56 (O-CH3), 74.39 (C6H5)2CH-, 126.72,
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127.66, 114.73, 120.05, 126.35, 127.78, 131.64, 133.83, 140.37, 159.94 (Carom.,Cbutad.); MS
(+ESI): m/z 614.0 [M+Na]+; C28H26Cl3N3O3S (M, 590.95); Calcd. C: 56.91, H: 4.43, N: 7.11;
Found C: 56.83, H: 4.50, N: 7.78.
3,4,4-Trichloro-1-[4-(4-fluorophenyl)piperazine-1-yl]-1-(4-methoxyphenylthio)-2-nitro-1,3butadiene (7j): Compound 7j was synthesized from 3d (0.1 g, 0.27 mmol) and N-(4fluorophenyl)piperazine (6c) (0.048 g, 0.27 mmol) according to the general procedure 2.
Yield: 0.093 g (66%); m.p.: 158-159°C, Rf (CH2Cl2): 0.48; IR (KBr): υ (cm-1) 3000 (CHaromatick), 2955, 2838 (C-Haliphatic), 1594 (C=C), 1270, 1513 (NO2); UV-Vis (CHCl3): max 389,
251 nm; 1H-NMR (500 MHz, CDCl3): δ 3.74 (s, 3H, O-CH3), 2.78 (s, 4H, N-CH2), 3.49-3.62 (m,
4H, N-CH2), 6.69-6.72 (m, 2H, CHarom.), 6.86-6.90 (m, 4H, CHarom.), 6.91-7.34(m, 2H, CHarom.);
C-NMR (125 MHz, CDCl3): δ 48.55, 51.81 (N-CH2), 54.55 (O-CH3), 114.77, 114.85, 114.94,
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133.80, 115.01, 117.78, 118.35, 119.87, 124.14, 125.79, 145.47, 160.07 (Carom.,Cbutad.); MS
(+ESI): m/z 541.9 [M+Na]+; C21H19Cl3FN3O3S (M, 518.82); Calcd. C: 48.62, H: 3.69, N: 8.10;
Found C: 48.76, H: 3.87, N: 8.13.
3,4,4-Trichloro-1-dihexylamino-1-(4-methoxyphenylthio)-2-nitro-1,3-butadiene
(9b):
Compound 9b was synthesized from 3d ( 0.2 g, 0.54 mmol) and dihexylamine 8 (0.099 g, 0.54
mmol) according to the general procedure 2.
Yield: 0.225 g (80%); Oil; Rf (CH2Cl2): 0.63; IR (KBr): υ (cm-1) 3003 (C-Haromatic), 2955, 2858
(C-Haliphatic), 1592 (C=C), 1251, 1529 (NO2); UV-Vis (CHCl3): max 393, 252 nm; 1H-NMR (500
MHz, CDCl3): δ 0.79-0.82 (m, 6H, CH3), 1.18-1.23 (m, 12H, CH2), 1.50-1.59 (m, 4H, CH2), 3.30
(s, 4H, N-CH2), 3.75 (s, 3H, O-CH3), 6.83-6.85 (d, J= 8.79 Hz, 2H, CHarom.), 7.27-7.29 (d, J=
S 10
8.78 Hz, 2H, CHarom.) ; 13C-NMR (125 MHz, CDCl3): δ 12.93 (CH3), 21.44, 21.47, 25.46, 26.62,
30.32 (CH2), 53.02 (N-CH2), 54.45 (O-CH3), 114.55, 133.49, 117.53, 120.13, 123.27, 126.41,
159.82, 167.58 (Carom.,Cbutad.); MS (+ESI): m/z 547.1 [M+Na]+; C23H33Cl3N2O3S (M, 523.94)
Calcd. C: 52.72, H: 6.35, N: 5.35; Found C: 52.93, H: 6.56, N: 5.36.
4-Bromo-3,4-dichloro-1-(4-methoxyphenylthio)-1-(N-methyl-N-cyclohexylamino)-2-nitro1,3-butadiene (11a): Compound 11a was synthesized from 3c (0.15 g, 0.36 mmol) and Nmethyl-N-cyclohexylamine 10 (0.04 g, 0.36 mmol) according to the general procedure 2.
Yield: 0.124 g (69%); m.p.: 147-148°C; Rf (CH2Cl2): 0.44; IR (KBr): υ (cm-1) 3000 (C-Haromatic),
2938, 2854 (C-Haliphatic), 1592 (C=C), 1255, 1528 (NO2); UV-Vis (CHCl3): max 393, 309, 250
nm; 1H-NMR (500 MHz, CDCl3): δ 0.81-1.07 (m, 3H, CH3), 1.18-1.36 (m, 3H, CH2(cyclohex.)),
1.46-1.77 (m, 7H, CH2(cyclohex.)), 2.94 (s, 1H, N-CH), 3.74 (s, 3H, O-CH3), 6.82-6.85 (m, 2H,
CHarom.), 7.24-7.28 (m, 2H, CHarom.) ; 13C-NMR (125 MHz, CDCl3): δ 21.96, 24.09, 24.41, 29.79
(CH2(cyclohex.)), 37.31 (N-CH), 54.50 (O-CH3), 64.42 (N-CH3), 114.57, 133.69, 133.71, 119.90,
119.96, 127.78, 129.86, 133.64, 159.95 (Carom.,Cbutad.); MS (+ESI): m/z 518.9 [M+Na]+;
C18H21BrCl2N2O3S (M, 496.25) Calcd. C: 43.57, H: 4.27, N: 5.65; Found C: 43.44, H: 4.98, N:
4.55.
3,4,4-Trichloro-1-(4-methoxyphenylthio)-1-(N-methyl-N-cyclohexylamino)-2-nitro-1,3butadiene (11b): Compound 11b was synthesized from 3d ( 0.2 g, 0.54 mmol) and N-methyl-Ncyclohexylamine 10 (0.06 g, 0.54 mmol) according to the general procedure 2.
Yield: 0.220 g (89%); m.p.: 146-147°C; Rf (CH2Cl2): 0.32; IR (KBr): υ (cm-1) 3000 (C-Haromatic),
2939, 2847 (C-Haliphatic), 1591 (C=C), 1254, 1527 (NO2); UV-Vis (CHCl3): max 393, 309, 251
S 11
nm; 1H-NMR (500 MHz, CDCl3): δ 0.99-1.08 (m, 3H, N-CH3), 1.18-1.27 (m, 3H, CH2(cyclohex.)),
1.45-1.77 (m, 7H, CH2(cyclohex.)), 2.93 (s, 1H, N-CH), 3.74 (s, 3H, O-CH3), 6.82-6.85 (m, 2H,
CHarom.), 7.24-7.27 (m, 2H, CHarom.) ;
13
C-NMR (125 MHz, CDCl3): δ24.08, 24.42, 29.76
(CH2(cyclohex.)), 37.22 (N-CH), 54.50 (O-CH3), 64.45 (N-CH3), 114.58, 133.65, 117.10, 119.92,
122.67, 126.64, 159.96, 160.03 (Carom.,Cbutad.); MS (+ESI): m/z 475.0 [M+Na]+; C18H21Cl3N2O3S
(M, 451.79) Calcd. C: 47.85, H: 4.69, N: 6.20; Found C: 48.36, H: 4.82, N: 5.80.