Triphenylphosphine → 5-Bromo-3-[1-(2-chloro-phenyl)-ethoxy]-thiophene-2-carboxylic acid methyl ester

HRID 533226Notes

Reaction equation

HRID 533226 reaction equation
[CH3:1][O:2][C:3]([C:5]1[S:6][C:7]([Br:11])=[CH:8][C:9]=1[OH:10])=[O:4].[Cl:12][C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][C:14]=1[CH:19](O)[CH3:20].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.CCOC(/N=N/C(OCC)=O)=O>C1COCC1>[CH3:1][O:2][C:3]([C:5]1[S:6][C:7]([Br:11])=[CH:8][C:9]=1[O:10][CH:19]([C:14]1[CH:15]=[CH:16][CH:17]=[CH:18][C:13]=1[Cl:12])[CH3:20])=[O:4]

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 260821-(2-Chlorophenyl)ethanolHCID 5462977Diethyl azodicarboxylateHCID 59857018Methyl 5-bromo-3-hydroxythiophene-2-carboxylate

Product 1

HCID 589704945-Bromo-3-[1-(2-chloro-phenyl)-ethoxy]-thiophene-2-carboxylic acid methyl esterYield 98.2%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

5-Bromo-3-hydroxy-thiophene-2-carboxylic acid methyl ester (1.67 g, 7/04 mmol, 1.0 Eq.), 1-(2-Chloro-phenyl)-ethanol (1.43 g, 9.16 mmol, 1.3 Eq.) and triphenylphosphine (2.40 g, 9.16 mmol, 1.3 Eq.) were dissolved in anhydrous THF (30 mL) under nitrogen. The resultant solution was cooled to 0° C. and DEAD (1.4 mL, 9.16 mmol, 1.3 Eq.) was added dropwise. The reaction was warmed to ambient temperature and stirred for 4.5 hours. The crude reaction was purified by column chromatography (10% EtOAc/petroleum ether) to give the sub-title compound as a yellow solid (2.60 g, 6.92 mmol, 98%); 1H NMR (400 MHz, CDCl3) δ 1.68 (3H, d), 3.88 (3H, s), 5.71 (1H, q), 6.65 (1H, s), 7.23-7.33 (2H, m), 7.37 (1H, dd), 7.66 (1H, dd).

Workup

  1. customThe crude reaction
  2. customwas purified by column chromatography (10% EtOAc/petroleum ether)

Sources & evidence

ORD record
ord-383f6b3f4ba847bfbacfbdf351a5875a
Source dataset
uspto-grants-2014_10
Patent number
US08853244B2

Reaction notes

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