3-AMINO-4,5,6,7-TETRAHYDRO-BENZO[B]THIOPHENE-2-CARBOXYLIC ACID METHYL ESTER synthesis
- Product Name:3-AMINO-4,5,6,7-TETRAHYDRO-BENZO[B]THIOPHENE-2-CARBOXYLIC ACID METHYL ESTER
- CAS Number:119205-38-8
- Molecular formula:C10H13NO2S
- Molecular Weight:211.28
![Acetic acid, 2-[(2-cyano-1-cyclohexen-1-yl)thio]-, methyl ester](/CAS/20210305/GIF/1263199-68-3.gif)
1263199-68-3
119205-38-8
Ethyl methyl-S-(2-cyanocyclohex-1-enyl)sulfonate (9) (0.17 g, 0.78 mmol) was used as the starting material and it was mixed with freshly distilled anhydrous THF (3 mL). Potassium tert-butoxide (0.09 g, 0.78 mmol) was subsequently added and the reaction mixture was heated to reflux for 30 min. The reaction progress was monitored by thin layer chromatography (TLC) (eluent: petroleum ether/ethyl acetate, 5:1). After completion of the reaction, the mixture was concentrated under reduced pressure, dissolved by addition of dichloromethane (25 mL) and washed with distilled water (2 x 20 mL), and the organic phase was dried over anhydrous magnesium sulfate. After evaporation of the solvent, the resulting oil was dried under high vacuum (10^-1 mbar). After refrigeration overnight, the light yellow solid product methyl 3-amino-4,5,6,7-tetrahydrobenzo[b]thiophene-2-carboxylate (135 mg, 80% yield) was obtained. The product was characterized as follows: melting point 70-73 °C; 1H NMR (CDCl3) δ: 1.82 (m, 4H, H5, H6), 2.30 (m, 2H, H7), 2.67 (m, 2H, H4), 3.79 (s, 3H, COOCH3), 5.36 (br s, 2H, NH2); 13C NMR (CDCl3) δ. 21.9, 22.6 (2CH2, C5, C6), 23.1 (CH2, C4), 25.8 (CH2, C7), 51.1 (COOCH3), 97.3 (CAr), 126.2 (CAr), 143.5 (CAr), 152.6 (CAr), 165.4 (COOCH3); IR (KBr) ν: 768 , 1072, 1095, 1130, 1198, 1263, 1300, 1342, 1448, 1493, 1568, 1604, 1668, 1734 (ester), 2858, 2933, 3361 (NH2), 3464 (NH2) cm^-1 ; MS (EI, 70 eV) m/z (%): 32 ( 80), 40 (10), 45 (10), 65 (10), 77 (15), 91 (15), 118 (15), 151 (65), 179 (90), 211 (M+, 100), 212 (M+H+, 10); HRMS-FAB: m/z [M+H]+ calcd for C10H13NO2S. 211.0667; found: 211.0745.
1263199-68-3
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119205-38-8
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Yield:119205-38-8 80%
Reaction Conditions:
with potassium tert-butylate in tetrahydrofuran; for 0.5 h;Reflux;Inert atmosphere;
Steps:
Methyl-3-amino-4,5,6,7-tetrahydrobenzo[b]thiophene-2-carboxylate (1)
Methyl-S-(2-cyanocyclohex-1-enyl)sulphanylacetate (9) (0.17 g, 0.78 mmol) was mixed with freshly distilled dry THF (3 mL). Potassium t-butoxide (0.09 g, 0.78 mmol) was added and the solution was heated at reflux for 30 minutes. The reaction was monitored by TLC (eluent: PE/EtOAc 5:1). The mixture was concentrated under vacuum, CH2Cl2 (25 mL) was added and the solution was washed by distilled water (2x20 mL) and dried over MgSO4. The solvent was evaporated and the obtained oil was dried under high vacuum (10-1 mbar). The yellowish solid was obtained after refrigerating overnight (135 mg, 80 %). Mp 70-73 °C; δH (CDCl3): 1.82 (m, 4H, H5 a H6), 2.30 (m, 2H, H7), 2.67 (m, 2H, H4), 3.79 (s, 3H, COOCH3), 5.36 (brs, 2H, NH2); δC (CDCl3): 21.9 and 22.6 (2CH2 - C5 and C6), 23.1 (CH2 - C4), 25.8 (CH2 - C7), 51.1 (COOCH3), 97.3 (CAr), 126.2 (CAr), 143.5 (CAr), 152.6 (CAr), 165.4 (COOCH3); IR (KBr): 768, 1072, 1095, 1130, 1198, 1263, 1300, 1342, 1448, 1493, 1568, 1604, 1668, 1734 (ester), 2858, 2933, 3361 (NH2), 3464 (NH2); MS (EI, 70 eV): m/z (%) = 32 (80), 40 (10), 45 (10), 65 (10), 77 (15), 91 (15), 118 (15), 151 (65), 179 (90), 211 (M+, 100), 212 (M+H+, 10); HRMS-FAB: m/z [M+H]+ calcd for C10H13NO2S: 211.0667; found: 211.0745.
References:
Tenora, Luká?;Buchlovi?, Marian;Man, Stanislav;Potá?ek, Milan [Tetrahedron Letters,2011,vol. 52,# 3,p. 401 - 403] Location in patent:supporting information; experimental part