Bromine → Acetic acid 2-cyclopentyl-4-(9-bromo-2,3-dimethyl-naphtho[2,3-b]thiophen-4-yl)-phenyl ester

HRID 1278817Notes

Reaction equation

HRID 1278817 reaction equation
[CH:1]1([C:6]2[CH:11]=[C:10]([C:12]3[C:24]4[C:23]([CH3:25])=[C:22]([CH3:26])[S:21][C:20]=4[CH:19]=[C:18]4[C:13]=3[CH:14]=[CH:15][CH:16]=[CH:17]4)[CH:9]=[CH:8][C:7]=2[O:27][C:28](=[O:30])[CH3:29])[CH2:5][CH2:4][CH2:3][CH2:2]1.[Br:31]Br>C(Cl)Cl>[CH:1]1([C:6]2[CH:11]=[C:10]([C:12]3[C:24]4[C:23]([CH3:25])=[C:22]([CH3:26])[S:21][C:20]=4[C:19]([Br:31])=[C:18]4[C:13]=3[CH:14]=[CH:15][CH:16]=[CH:17]4)[CH:9]=[CH:8][C:7]=2[O:27][C:28](=[O:30])[CH3:29])[CH2:2][CH2:3][CH2:4][CH2:5]1

Participants

4

Reactant 2

HCID 24408BromineHCID 53716940Acetic acid 2-cyclopentyl-4-(2,3-dimethyl-naphtho[2,3-b]thiophen-4-yl)-phenyl ester

Product 1

HCID 54419856Acetic acid 2-cyclopentyl-4-(9-bromo-2,3-dimethyl-naphtho[2,3-b]thiophen-4-yl)-phenyl esterYield 79%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
-78 °C

Procedure

To acetic acid 2-cyclopentyl-4-(2,3-dimethyl-naphtho[2,3-b]thiophen-4-yl)-phenyl ester (2.9 g, 7.7 mmol) in anhydrous methylene chloride (68 mL) was added ferric chloride (66 mg, 0.41 mmol). The reaction mixture was placed under nitrogen and cooled to −78° C. The reaction mixture was protected from light and a solution of bromine (0.44 mL, 8.5 mmol) in anhydrous methylene chloride (11 mL) was added dropwise over a period of 15 min. After stirring at −78° C. for 45 min the reaction was quenched with dilute sodium bisulfite, and then poured into water (200 mL). The resulting mixture was extracted with diethyl ether (300 mL), and the diethyl ether layer was washed with water and then brine. Concentration under reduced pressure and chromatography with petroleum ether:ethyl acetate (95:5) gave the title compound as a white solid (2.7 g, 79%): (CDCl3): δ 8.28 (d, 1H), 7.58-7.52 (m, 2H), 7.39-7.34 (m, 1H), 7.29 (d, 1H), 7.18 (dd, 1H), 7.14 and 7.13 (d, 1H), 3.18 (quintet, 1H), 2.44 (s, 3H), 2.40 (s, 3H), 2.06-2.02 (m, 2H), 1.75-1.45 (in containing a singlet at δ 1.60, 9H); MS(EI): [M+], 1 bromine isotope pattern, 492/494; Anal. Calc. for C27H25BrO2S: C, 65.72, H, 5.11, N, 0.00. Found: C, 63.18, H, 4.96, N, 0.00.

Workup

  1. customwas quenched with dilute sodium bisulfite
  2. additionpoured into water (200 mL)
  3. extractionThe resulting mixture was extracted with diethyl ether (300 mL)
  4. washthe diethyl ether layer was washed with water
  5. concentrationConcentration under reduced pressure and chromatography with petroleum ether:ethyl acetate (95:5)

Sources & evidence

ORD record
ord-b54aa97f19b94c55bb1dd18b9f6e4588
Source dataset
uspto-grants-2002_09
Patent number
US06444670B2

Reaction notes

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