Water → Methyl 3-amino-5-phenylthiophene-2-carboxylate

To a solution of methyl thioglycolate (1 g, 9.43 mmol) in methanol (5 mL) was added a solution of sodium methoxide (0.5 g, 9.43 mmol) in methanol (5 mL) and stirred for 0.5 h. To the above mixture, a solution of 3-chloro-3-phenylprop-2-enenitrile (1.22 g, 7.5 mmol) in DMF (3.5 mL) was added dropwise for 10 min at rt and stirred the mixture at 60° C. for 2 h. Then, a solution of sodium methoxide (1 g, 18.6 mmol) in methanol (10 mL) was added dropwise at rt and stirring was continued for 2 h at 60° C. The mixture was allowed to rt and poured into cold water and stirred for 15 min. The solution was extracted with chloroform (3×100 mL) and the combined chloroform layer was washed with water, brine and dried over sodium sulfate. The solution was filtered and evaporated the solvent. The residue was chromatographed over silica gel using hexane-ethyl acetate (92:8) as eluent to give the product as a pale yellow color solid (1.1 g, 50%), mp 130-132° C. 1H NMR (400 MHz, DMSO-d6): δ 7.62-7.65 (2H, m), 7.38-7.48 (3H, m), 7.00 (1H, s), 4.29 (2H, br s), 3.74 (3H, s); LC-MS (positive ion mode): m/z 234 (M+H)+.

1. stirringstirred the mixture at 60° C. for 2 h
2. stirringstirring
3. waitwas continued for 2 h at 60° C
4. customwas allowed to rt
5. stirringstirred for 15 min
6. extractionThe solution was extracted with chloroform (3×100 mL)
7. washthe combined chloroform layer was washed with water, brine
8. dry with materialdried over sodium sulfate
9. filtrationThe solution was filtered
10. customevaporated the solvent
11. customThe residue was chromatographed over silica gel

ORDレコード

ord-9b488cadbbca4e889ff9f28a4ab35be6

出典データセット

uspto-grants-2012_09

DOI

10.6084/m9.figshare.5104873.v1

特許番号

US08258119B2