Tin tetrachloride → HCID 21075898, compound

HRID 1373872Notes

Reaction equation

HRID 1373872 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][CH:27]([CH3:29])[CH3:28].[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][CH:27]([CH3:29])[CH3:28])=[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 66054Isovaleryl chloride2×HCID 21075902HCID 21075902, compound

Product 1

HCID 21075898HCID 21075898, compoundYield 7.1%

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent2×

Procedure

To a 0° C. mixture of (6-benzo[b]thiophen-2-yl-1-bromo-naphthalen-2-yloxy)-acetonitrile (11.3 g, 32.4 mmol) in chloroform (560 mL) was added isovaleryl chloride (4.7 mL, 39 mmol) and tin (IV) chloride (5.8 mL, 49 mmol). The reaction mixture was then refluxed for 23 hours. During this time, isovaleryl chloride (12.7 mL, 103 mmol) in three portions and tin (IV) chloride (13.4 mL, 113 mmol) were added in three portions. After cooling to ambient temperature, the reaction mixture was poured into ice water. It was diluted with more chloroform, and the organic phase was washed with water and brine. It was dried with anhydrous magnesium sulfate, filtered and solvent evaporated. The residue was stirred in ether and filtered. The filtrate was concentrated and purified by flash chromatography using 25–50% methylene chloride in hexane and then by HPLC using 89% acetonitrile (0.1% trifluoroacetic acid) in water as the mobile phase. 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 70° C. for 50 minutes yielded {1-bromo-6-[3-(3-methyl-butyryl)-benzo[b]thiophen-2-yl]-naphthalen-2-yloxy}-acetonitrile (1.1 g, 7.10%) as a yellow semi-solid. mass spectrum (−EI, [M−H]−) m/z 476/478. 1H NMR (500 MHz, DMSO-d6): δ8.19–8.25 (m, 2H), 8.16 (d, 1H, J=1.83 Hz), 8.04–8.07 (m, 1H), 7.91–7.94 (m, 1H), 7.78 (dd, 1H, J=8.78 Hz and 1.95 Hz), 7.69 (d, 1H, J=9.15 Hz), 7.42–7.49 (m, 2H), 5.43 (s, 2H), 2.28 (d, 2H, J=6.71 Hz), 1.93–2.00 (m, 1H), 0.64 ppm (d, 6H, J=6.71 Hz). Elemental Analysis for C25H20BrNO2S: Calcd: C, 62.77; H, 4.21; N, 2.93; Found: C, 62.79; H, 4.18; N, 2.82.

Workup

  1. temperatureThe reaction mixture was then refluxed for 23 hours
  2. washthe organic phase was washed with water and brine
  3. dry with materialIt was dried with anhydrous magnesium sulfate
  4. filtrationfiltered
  5. customsolvent evaporated
  6. filtrationfiltered
  7. concentrationThe filtrate was concentrated
  8. custompurified 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 70° C. for 50 minutes

Sources & evidence

ORD record
ord-5e1f87f9f6a643b9ab2a676eea9ef9c6
Source dataset
uspto-grants-2007_01
Patent number
US07163954B2

Reaction notes

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