Bromine → HCID 10297816, compound

HRID 1278823Notes

Reaction equation

HRID 1278823 reaction equation
[CH3:1][C:2]1[S:6][C:5]2[CH:7]=[C:8]3[C:13](=[C:14]([C:15]4[CH:20]=[C:19]([CH3:21])[C:18]([O:22][C:23](=[O:25])[CH3:24])=[C:17]([CH3:26])[CH:16]=4)[C:4]=2[C:3]=1[CH3:27])[CH:12]=[CH:11][CH:10]=[CH:9]3.[Br:28]Br>C(Cl)Cl>[Br:28][C:7]1[C:5]2[S:6][C:2]([CH3:1])=[C:3]([CH3:27])[C:4]=2[C:14]([C:15]2[CH:16]=[C:17]([CH3:26])[C:18]([O:22][C:23](=[O:25])[CH3:24])=[C:19]([CH3:21])[CH:20]=2)=[C:13]2[C:8]=1[CH:9]=[CH:10][CH:11]=[CH:12]2

Participants

4

Reactant 2

HCID 24408BromineHCID 10199432HCID 10199432, compound

Product 1

HCID 10297816HCID 10297816, compoundYield 55.3%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

A solution of acetic acid 4-(2,3-dimethyl-naphtho[2,3-b]thiophen-4-yl)-2,6-dimethyl-phenyl ester (10.0 g, 26.7 mmol) and ferric chloride (0.23 g, 1.4 mmol) in anhydrous methylene chloride (231 mL) was placed at −78C under nitrogen. The reaction mixture was protected from light and a solution of bromine (1.5 mL, 29.4 mmol) in anhydrous methylene chloride (38 mL) was added dropwise over a period of 50 min. After 30 min the reaction was quenched with dilute sodium bisulfite, diluted with water, and the resulting mixture was extracted with diethyl ether. The diethyl ether layer was washed twice with water, brine, and then dried (MgSO4). Concentration under reduced pressure and chromatography with petroleum ether:ethyl acetate (97:3, then 95:5) gave the title compound as a white solid (6.7 g, 55%): NMR (DMSO-d6): δ 8.27 (d, 1H), 7.60 (d, 1H), 7.56-7.52 (ddd, 1H), 7.38-7.34 (ddd, 1H), 7.06 (s, 2H), 2.43 (s, 3H), 2.41 (s, 3H), 2.22 (s, 6H), 1.64 (s, 3H); MS(EI): [M+], 1 bromine isotope pattern, 452/454; Anal. Calc. for C24H21BrO2S: C, 63.58, H, 4.67, N, 0.00. Found: C, 63.41, H, 4.45, N, 0.08.

Workup

  1. customAfter 30 min the reaction was quenched with dilute sodium bisulfite
  2. additiondiluted with water
  3. extractionthe resulting mixture was extracted with diethyl ether
  4. washThe diethyl ether layer was washed twice with water, brine
  5. dry with materialdried (MgSO4)
  6. concentrationConcentration under reduced pressure and chromatography with petroleum ether:ethyl acetate (97:3

Sources & evidence

ORD record
ord-c13dceabbba24d5c974be60ccf845780
Source dataset
uspto-grants-2002_09
Patent number
US06444670B2

Reaction notes

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