Tetrahydrofuran → (2,3-Dihydrothieno[3,4-b][1,4]dioxine-5,7-diyl)bis(tributylstannane)

HRID 1751319Notes

Reaction equation

HRID 1751319 reaction equation
[CH2:1]1[O:9][C:8]2[C:4](=[CH:5][S:6][CH:7]=2)[O:3][CH2:2]1.[CH2:10]1[CH2:14]O[CH2:12][CH2:11]1.[Li+].CC([N-][CH:20]([CH3:22])[CH3:21])C.[CH2:23]([Sn:27](Cl)([CH2:32][CH2:33][CH2:34][CH3:35])[CH2:28][CH2:29][CH2:30][CH3:31])[CH2:24][CH2:25][CH3:26]>C(OC(=O)C)C.O>[CH2:12]([Sn:27]([CH2:28][CH2:22][CH2:20][CH3:21])([CH2:23][CH2:24][CH2:25][CH3:26])[C:5]1[S:6][C:7]([Sn:27]([CH2:32][CH2:33][CH2:34][CH3:35])([CH2:28][CH2:29][CH2:30][CH3:31])[CH2:23][CH2:24][CH2:25][CH3:26])=[C:8]2[O:9][CH2:1][CH2:2][O:3][C:4]=12)[CH2:11][CH2:10][CH3:14]

Participants

6

Reactant 4

HCID 8028TetrahydrofuranHCID 15096Tributyltin ChlorideHCID 2724682Lithium diisopropylamideHCID 44218643,4-Ethylenedioxythiophene

Product 1

HCID 15891056(2,3-Dihydrothieno[3,4-b][1,4]dioxine-5,7-diyl)bis(tributylstannane)Yield 92%

Reagents, catalysts & solvents 1

HCID 22728543Water ethylacetateSolvent

Procedure

EDOT (5, 1.42 g, 10 mmol) was dissolved into anhydrous THF (40 ml) and cooled to 0. After stirring at 0 for 15 minutes, LDA (15 mL, 2M, THF/heptane/ethylebenzene) was added for 15 minutes, and after addition was complete, a reaction mixture was heated to room temperature for 1 hour. The reaction mixture was cooled to 0 and tributylstannyl chloride (8.1 ml, 30 mmol) was added thereto, followed by stirring at 0 for 1 hour, and water ethylacetate were added thereto. An organic layer was separated from the reactant and the separated organic layer was washed with water and lastly dried with anhydrous sodium sulfate. The solvent was evaporated under reduced pressure, and thus-obtained residues were purified by flash chromatography using hexane as eluent in silica gel pre-treated with triethylamine to obtain a colorless oil 6 (6.61 g, 92%). 1H NMR (CDCl3, 400 MHz, d/ppm): 4.03-4.02 (d, J=4 Hz, 4H2OCH2CH2O), 1.60-1.40 (m, 12, 2×Sn—(CH2—)3), 1.26-1.20 (m, 12H, 2×Sn—(CH2CH2—)3), 1.00 (m, 12H, 2×Sn—(CH2CH2CH2—)3), 0.83-0.79 (m, 18H, 2×(CH3)3). 13C NMR (CDCl3, 100 MHz, d/ppm): 148.29, 115.81, 64.62, 29.01, 27.20, 13.69, 10.48. C30H58O2SSn2 (720.27): Theoretical value C, 50.03; H, 8.12; S, 4.45; Sn, 32.96; Experimental value C, 50.18; H, 8.08; S, 4.39.

Workup

  1. temperaturecooled to 0
  2. additionafter addition
  3. additionwas added
  4. stirringby stirring at 0 for 1 hour
  5. customAn organic layer was separated from the reactant
  6. washthe separated organic layer was washed with water
  7. dry with materiallastly dried with anhydrous sodium sulfate
  8. customThe solvent was evaporated under reduced pressure
  9. customthus-obtained residues
  10. customwere purified by flash chromatography
  11. additionpre-treated with triethylamine

Sources & evidence

ORD record
ord-b4c2d29a43724a9292e3bf906cbde091
Source dataset
uspto-grants-2015_10
Patent number
US09159497B2

Reaction notes

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