Tin tetrachloride → HCID 21075899, compound

HRID 1373862Notes

Reaction equation

HRID 1373862 reaction equation
[S:1]1[C:5]([C:6]2[CH:7]=[C:8]3[C:13](=[CH:14][CH:15]=2)[C:12]([Br:16])=[C:11]([O:17][CH2:18][C:19]#[N:20])[CH:10]=[CH:9]3)=[CH:4][C:3]2[CH:21]=[CH:22][CH:23]=[CH:24][C:2]1=2.[C:25](Cl)(=[O:30])[CH2:26][CH2:27][CH2:28][CH3:29].[Sn](Cl)(Cl)(Cl)Cl>C(Cl)(Cl)Cl>[Br:16][C:12]1[C:13]2[C:8](=[CH:7][C:6]([C:5]3[S:1][C:2]4[CH:24]=[CH:23][CH:22]=[CH:21][C:3]=4[C:4]=3[C:25](=[O:30])[CH2:26][CH2:27][CH2:28][CH3:29])=[CH:15][CH:14]=2)[CH:9]=[CH:10][C:11]=1[O:17][CH2:18][C:19]#[N:20]

Participants

5

Reactant 3

HCID 24287Tin tetrachloride2×HCID 61186Valeryl chloride2×HCID 21075902HCID 21075902, compound

Product 1

HCID 21075899HCID 21075899, compoundYield 5.6%

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent

Procedure

To a 0° C. suspension of (6-benzo[b]thiophen-2-yl-1-bromo-naphthalen-2-yloxy)-acetonitrile (5.27 g, 13.4 mmol) in chloroform (400 mL) was added valeryl chloride (2.1 mL, 17 mmol) and tin (IV) chloride (2.3 mL, 20 mmol). The reaction mixture was refluxed for 22.5 hours. During reflux, valeryl chloride (8.5 mL, 70 mmol) in four portions and tin (IV) chloride (8.9 mL, 76 mmol) were added in four portions. After cooling to ambient temperature, the reaction mixture was poured into ice water. The phases were separated, and the organic phase was washed with water and brine. It was then dried with anhydrous magnesium sulfate, filtered and solvent evaporated. The residue was purified by flash chromatography using (1) 100% chloroform, (2) 20–60% methylene chloride in hexane and 100% methylene chloride and (3) HPLC in 86% acetonitrile (0.1% trifluoroacetic acid) in water. Evaporating the solvent and extracting with ethyl acetate, washing with water and brine, drying with anhydrous magnesium sulfate, filtering, concentrating and drying in vacuo at 60° C. for 30 minutes yielded (0.356 g, 5.23%) of the title compound as a clear brown gum: mass spectrum (+EI, [M+H]+) m/z 478/480. 1H NMR (500 MHz, DMSO-d6): δ8.24–8.28 (m, 2H), 8.20 (d, 1H, J=1.83 Hz), 8.10 (dd, 1H, J=6.49 Hz and 1.48 Hz), 7.96–7.97 (m, 1H), 7.81 (dd, 1H, J=8.71 Hz and 1.84 Hz), 7.73 (d, 1H, J=9.15 Hz), 7.46–7.52 (m, 2H), 5.47 (s, 2H), 2.42 (t, 2H, J=7.26 Hz), 1.41–1.46 (m, 2H), 0.97–1.04 (m, 2H), 0.57 ppm (t, 3H, J=7.33 Hz). Elemental Analysis for C25H20BrNO2S+0.6 mole H2O: Calcd: C, 61.38; H, 4.37; N, 2.86; Found: C, 61.07; H, 4.21; N, 2.67.

Workup

  1. temperatureThe reaction mixture was refluxed for 22.5 hours
  2. temperatureDuring reflux
  3. customThe phases were separated
  4. washthe organic phase was washed with water and brine
  5. dry with materialIt was then dried with anhydrous magnesium sulfate
  6. filtrationfiltered
  7. customsolvent evaporated
  8. customThe residue was purified by flash chromatography
  9. customEvaporating the solvent
  10. extractionextracting with ethyl acetate
  11. washwashing with water and brine
  12. dry with materialdrying with anhydrous magnesium sulfate
  13. filtrationfiltering
  14. concentrationconcentrating
  15. customdrying in vacuo at 60° C. for 30 minutes

Sources & evidence

ORD record
ord-3412c9dd6d1e41dd937023717c593303
Source dataset
uspto-grants-2007_01
Patent number
US07163954B2

Reaction notes

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