Organic & Biomolecular Chemistry
Paper
3
3
calcd for C21H15F3N2O2S2 (448.48): C, 56.24; H, 3.37; N, 6.25%. (1H, t, JHH = 6.9 Hz, CHpara of Ph), 7.13 (2H, d, JHH = 7.5 Hz,
1
3
Found C, 56.25; H, 3.36; N, 6.25. H NMR (300 MHz, DMSO- 2CHortho of Ph), 7.32 (2H, t, JHH = 6.9 Hz, 2CHmeta of Ph), 9.62
3
d6): 2.69 (3H, s, SMe), 3.83 (3H, s, OMe), 6.94 (2H, d, JHH
=
(1H, s, NH). 13C NMR (75.0 MHz, DMSO-d6): 17.2, 28.8, 99.8,
3
8.4 Hz, 2CHmeta of Ar), 7.05 (2H, d, JHH = 8.1 Hz, 2CHortho of 112.4, 122.2, 124.1, 124.7, 129.5, 140.5, 149.6, 161.9, 189.0. MS
Ar), 7.12 (2H, d, JHH = 8.1 Hz, 2CHmeta of Ar), 7.54 (2H, d, (EI, 70 eV): 288 (M+, 72), 258 (11), 236 (9), 215 (14), 197 (45),
3
3JHH = 8.1 Hz, 2CHortho of Ar), 9.61 (1H, s, NH). MS (EI, 70 eV): 167 (12), 149 (46), 112 (5), 82 (12), 78 (13), 71 (36), 43 (100).
447 (M+ − 1, 6), 303 (93), 261 (5), 197 (6), 135 (100), 115 (17),
4-Anilino-2-methylsulfanyl-5-(2-pyridylcarbonyl)-3-thienyl
92 (56), 77 (85).
cyanide (9m). Yellow powder, mp: 181–182 °C, 0.039 g, yield:
4-Anilino-5-(4-methylbenzoyl)-2-methylsulfanyl-3-thienyl 79%. IR (KBr)(νmax, cm−1): 3392 (NH), 2210 (CN), 1594 (CvO),
cyanide (9i). Pale yellow powder, mp: 139–140 °C, 0.042 g, 1578 and 1493 (CvC). Anal. calcd for C18H13N3OS2 (351.44): C,
yield: 82%. IR (KBr)(νmax, cm−1): 3463 (NH), 2216 (CN), 1592 61.52; H, 3.73; N, 11.96%. Found C, 61.44; H, 3.76; N, 11.88.
(CvO), 1549 (CvC). Anal. calcd for C20H16N2OS2 (364.48): C, 1H NMR (300 MHz, DMSO-d6): 2.77 (3H, s, SMe), 7.26 (1H, t,
3
65.91; H, 4.42; N, 7.69%. Found C, 65.84; H, 4.48; N, 7.63. 3JHH = 6.9 Hz, CHpara of Ph), 7.33 (2H, d, JHH = 7.2 Hz,
3
1H NMR (300 MHz, DMSO-d6): 2.38 (3H, s, Me), 2.71 (3H, s, 2CHortho of Ph), 7.40 (2H, t, JHH = 7.5 Hz, 2CHmeta of Ph),
3
SMe), 7.18 (1H, t, JHH = 7.2 Hz, CHpara of Ph), 7.24 (2H, d, 7.60–7.68 (4H, m, 4CH of pyridine), 11.01 (1H, s, NH).
3
3JHH = 7.5 Hz, 2CHortho of Ph), 7.35 (2H, t, JHH = 8.1 Hz, 13C NMR (75.0 MHz, DMSO-d6): 16.4, 95.5, 103.8, 113.2, 122.6,
3
2CHmeta of Ph), 7.36 (2H, d, JHH = 7.5 Hz, 2CH of Ar), 7.66 125.0, 127.2, 129.5, 138.5, 148.0, 153.4, 159.2, 167.1, 179.9. MS
3
(2H, d, JHH = 7.5 Hz, 2CH of Ar), 10.21 (1H, s, NH). 13C NMR (EI, 70 eV): 351 (M+, 6), 288 (53), 275 (44), 258 (32), 229 (10),
(75.0 MHz, DMSO-d6): 17.1, 21.5, 98.5, 112.4, 123.5, 125.5, 197 (87), 154 (19), 142 (27), 106 (24), 94 (26), 78 (96), 43 (100).
125.6, 128.2, 129.4, 129.6, 137.1, 139.7, 142.5, 152.1, 163.9,
Methyl
2-(3-anilino-4-cyano-5-methylsulfanyl-2-thienyl)-2-
186.2. MS (EI, 70 eV): 363 (M+ − 1, 100), 349 (13), 287 (9), 258 oxoacetate (9n). Yellow powder, mp: 164–165 °C, 0.035 g, yield:
(8), 229 (9), 198 (16), 174 (6), 145 (11), 119 (60), 91 (95), 77 (26). 76%. IR (KBr)(νmax, cm−1): 3368 (NH), 2218 (CN), 1713 (CO2Et),
4-Anilino-2-methylsulfanyl-5-(4-phenylbenzoyl)-3-thienyl 1600 (CvO), 1581 and 1539 (CvC). Anal. calcd for
cyanide (9j). Yellow powder, mp: 114–115 °C, 0.046 g, yield: C16H14N2O3S2 (346.42): C, 55.48; H, 4.07; N, 8.09%. Found C,
78%. IR (KBr)(νmax, cm−1): 3443 (NH), 2209 (CN), 1689 (CvO), 55.47; H, 4.08; N, 8.09. 1H NMR (300 MHz, DMSO-d6): 1.32
1600 and 1551 (CvC). Anal. calcd for C25H18N2OS2 (426.55): C, (3H, t, 3JHH = 6.6 Hz, OCH2CH3), 2.78 (3H, s, SMe), 4.30 (2H, q,
1
70.40; H, 4.25; N, 6.57%. Found C, 70.41; H, 4.26; N, 6.57. H 3JHH = 6.6 Hz, OCH2CH3), 7.31 (1H, t, 3JHH = 5.7 Hz, 2CHpara of
3
3
NMR (300 MHz, DMSO-d6): 2.74 (3H, s, SMe), 7.36 (1H, t, JHH Ph), 7.34 (2H, d, JHH = 6.9 Hz, 2CHortho of Ph), 7.42 (2H, t,
= 7.5 Hz, CHpara of Ph), 7.42–7.54 (5H, m, 2CHortho of Ar, 3JHH = 7.5 Hz, 2CHortho of Ph), 10.64 (1H, s, NH). 13C NMR
1CHpara and 2CHmeta of Ph), 7.75–7.88 (6H, m, 2CHortho
,
(75.0 MHz, DMSO-d6): 14.2, 16.4, 62.8, 95.3, 111.9, 112.6,
3
2CHmeta, and 2CHortho of Ph), 8.07 (2H, d, JHH = 8.1 Hz, 125.7, 125.8, 127.4, 129.5, 138.2, 156.5, 162.7. MS (EI, 70 eV):
2CHmeta of Ar), 10.26 (1H, s, NH). 13C NMR (75.0 MHz, DMSO- 346 (M+, 26), 273 (88), 258 (55), 229 (11), 197 (100), 154 (12),
d6): 17.2, 103.5, 115.6, 123.5, 127.3, 127.3, 127.4, 127.4, 128.8, 142 (16), 135 (12), 109 (18), 77 (44).
128.9, 129.5, 133.6, 138.6, 139.2, 145.6, 152.2, 163.5, 191.6. MS
(EI, 70 eV): 425 (M+ − 1, 23), 409 (31), 379 (15), 363 (4), 349 oxopropanoate (9o). Pale yellow powder, mp: 144–145 °C,
(88), 230 (6), 181 (100), 152 (62), 115 (4), 92 (9), 76 (26).
0.038 g, yield: 78%. IR (KBr)(νmax, cm−1): 3389 (NH), 2215
Methyl
3-(3-anilino-4-cyano-5-methylsulfanyl-2-thienyl)-3-
4-Anilino-5-(4-chlorobenzoyl)-2-methylsulfanyl-3-thienyl cyanide (CN), 1741 (CO2Me), 1605 (CvO), 1552 and 1502 (CvC). Anal.
(9k). Yellow powder, mp: 148–149 °C, 0.038 g, yield: 70%. IR calcd for C16H14N2O3S2 (346.42): C, 55.48; H, 4.07; N, 8.09%.
1
(KBr)(νmax, cm−1): 3443 (NH), 2211 (CN), 1605 (CvO), 1585 Found C, 55.40; H, 4.12; N, 8.08. H NMR (300 MHz, DMSO-
and 1491 (CvC). Anal. calcd for C19H13ClN2OS2 (384.90): C, d6): 2.77 (3H, s, SMe), 3.57 (3H, s, OMe), 3.72 (2H, s,
59.29; H, 3.40; N, 7.28%. Found C, 59.36; H, 3.33; N, 7.29. CH2CO2Me), 7.14 (1H, t, 3JHH = 7.2 Hz, CHpara of Ph), 7.15 (2H,
3
3
1H NMR (300 MHz, DMSO-d6): 2.72 (3H, s, SMe), 7.17 (1H, t, d, JHH = 7.5 Hz, 2CHortho of Ph), 7.34 (2H, t, JHH = 8.1 Hz,
3JHH = 7.2 Hz, CHpara of Ph), 7.22 (2H, d, JHH = 7.8 Hz, 2CHmeta of ph), 9.63 (1H, s, NH). 13C NMR (75.0 MHz, DMSO-
2CHortho of Ph), 7.34 (2H, t, JHH = 7.5 Hz, 2CHmeta of Ph), 7.57 d6): 17.2, 47.3, 52.51, 107.4, 112.2, 112.7, 122.4, 125.0, 129.5,
3
3
(2H, d, JHH = 8.1 Hz, 2CH of Ar), 7.75 (2H, d, JHH = 8.1 Hz, 140.2, 150.4, 167.8, 183.0, 183.8. MS (EI, 70 eV): 346 (M+, 12),
2CHortho of Ar), 10.14 (1H, s, NH). 13C NMR (75.0 MHz, DMSO- 313 (10), 270 (15), 238 (22), 197 (100), 169 (8), 142 (19), 94 (17),
d6): 17.1, 98.6, 112.3, 112.5, 123.4, 125.6, 129.2, 129.4, 130.0, 109 (11), 77 (28), 43 (96).
137.0, 138.3, 139.8, 152.2, 164.6, 185.0. MS (EI, 70 eV): 383
3
3
(M+ − 1, 78), 349 (6), 307 (11), 258 (11), 229 (12), 198 (32), 139
(79), 111 (100), 77 (57).
Experimental procedures and spectroscopic data for 10a–g
5-Acetyl-4-anilino-2-methylsulfanyl-3-thienyl cyanide (9l). After performing the required conditions for synthesis 9,
Orange powder, mp: 159–160 °C, 0.031 g, yield: 78%. IR (KBr) Pd(OAc)2 (0.0016 g, 0.05 mmol) and CS2CO3 (0.163 g,
(νmax, cm−1): 3411 (NH), 2212 (CN), 1612 (CvO), 1551 and 0.5 mmol) were added to the mixture. The mixture was stirred
1498 (CvC). Anal. calcd for C14H12N2OS2 (288.38): C, 58.31; H, at 80 °C for 1 h (similar to synthesis 4). Then, the mixture was
4.19; N, 9.71%. Found C, 58.30; H, 4.19; N, 9.72. 1H NMR poured into water and extracted with chloroform. The
(300 MHz, DMSO-d6): 2.38 (3H, s, Me), 2.75 (3H, s, SMe), 7.12 combined organic layer after drying over magnesium sulfate
This journal is © The Royal Society of Chemistry 2017
Org. Biomol. Chem.