Acetic Acid → 4-(3-Bromo-5-tert-butoxy-benzenesulfonyl)-5-methylsulfanyl-thiophene-2-carboxylic acid methyl ester

HRID 723038Notes

Reaction equation

[CH3:1][S-:2].[Na+].[CH3:4][O:5][C:6]([C:8]1[S:9][C:10]([N+]([O-])=O)=[C:11]([S:13]([C:16]2[CH:21]=[C:20]([O:22][C:23]([CH3:26])([CH3:25])[CH3:24])[CH:19]=[C:18]([Br:27])[CH:17]=2)(=[O:15])=[O:14])[CH:12]=1)=[O:7].C(O)(=O)C>C1COCC1.CCOC(C)=O>[CH3:4][O:5][C:6]([C:8]1[S:9][C:10]([S:2][CH3:1])=[C:11]([S:13]([C:16]2[CH:21]=[C:20]([O:22][C:23]([CH3:26])([CH3:25])[CH3:24])[CH:19]=[C:18]([Br:27])[CH:17]=2)(=[O:15])=[O:14])[CH:12]=1)=[O:7]

Participants

Conditions

Temperature: -78 °C

Procedure

Sodium thiomethoxide (1M in EtOH, 4.4 mL, 4.4 mmol) was added dropwise to a −78° C. solution of 4-(3-bromo-5-tert-butoxy-benzenesulfonyl)-5-nitro-thiophene-2-carboxylic acid methyl ester (1.91 g, 4.0 mmol) in THF (40 mL). The solution was stirred for 30 min at −78° C. and glacial acetic acid (1 mL) was added. The solution was diluted with EtOAc (60 mL), extracted with NaHCO3 (2×30 mL), water (2×20 mL), brine (30 mL), and was dried over sodium sulfate. Concentration of the solution in vacuo followed by SiO2 flash chromatography of the residue yielded the title compound (1.48 g, 76%). 1H-NMR (CDCl3): δ 8.01 (d, 1H, J=0.5 Hz), 7.74 (m, 1H), 7.66 (m, 1H), 7.37 (m, 1H), 3.99 (s, 3H), 2.48 (s, 3H), 1.41 (s, 9H).

Workup

extractionextracted with NaHCO3 (2×30 mL), water (2×20 mL), brine (30 mL)
dry with materialwas dried over sodium sulfate

Sources & evidence

ORD record: ord-938ae9f070cf466e8595784992b13047
Source dataset: uspto-grants-2006_11
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07138530B2

Reaction notes

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