Ammonium Chloride → 2-(2,5-Dimethoxy-tetrahydrofuran-3-yl-methylidene)-1,3-dithiane

HRID 613907Notes

Reaction equation

HRID 613907 reaction equation
C[Si](C)(C)[CH:3]1[S:8][CH2:7][CH2:6][CH2:5][S:4]1.C([Li])CCC.[CH3:16][O:17][CH:18]1[CH:22]([CH:23]=O)[CH2:21][CH:20]([O:25][CH3:26])[O:19]1.[NH4+].[Cl-]>C1COCC1>[CH3:16][O:17][CH:18]1[CH:22]([CH:23]=[C:3]2[S:8][CH2:7][CH2:6][CH2:5][S:4]2)[CH2:21][CH:20]([O:25][CH3:26])[O:19]1

Participants

6

Reactant 4

HCID 25517Ammonium ChlorideHCID 834132-Trimethylsilyl-1,3-dithianeHCID 567310Tetrahydro-2,5-dimethoxyfuran-3-carbaldehydeHCID 178418339Butyllithium

Product 1

HCID 183803072-(2,5-Dimethoxy-tetrahydrofuran-3-yl-methylidene)-1,3-dithianeYield 70%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

According to a procedure described in Boger, D. L.; Brotherton, C. E. J. Org. Chem. 1984, 49, 4050-4055, to a solution of 2-trimethylsilyl-1,3-dithiane (1.2 mL, 6.3 mmol) in dry THF (40 mL) at 0° C. was added n-butyllithium (4 mL of 1.6 M in hexanes). After 15 minutes at 0°C. and 20 minutes at 4 mL of 1.6 M ambient temperature, a solution of 2,5-dimethoxytetrahydrofuran-3-carboxaldehyde (1.00 g, 6.00 mmol) in dry THF (10 mL) was added dropwise. After 17 hours at ambient temperature, the resultant mixture was treated with saturated aqueous NH4Cl (10 mL) and partitioned between EtOAc and H2O. The layers were separated and the aqueousueous phase extracted with EtOAc:hex (1:1) two times. The combined organic layers were washed with brine, dried over Na2SO4, and concentrated to afford a residue which was purified via flash column chromatography with 10% EtOAc/hex as eluant to yield 1.06 g (70%) of a mixture of diastereomeric 2-(2,5-dimethoxy-tetrahydrofuran-3-yl-methylidene)-1,3-dithiane as a yellow oil, which was used without any further purification. 1H NMR: δ 6.00 (d, 1H, J=9.6 Hz), 5.93 (d, 1H, J=9.6 Hz), 5.77 (d, 1H, J=9.6 Hz). Anal. Calculated for C11H18O3S2 : C, 50.35; H, 6.92; S, 24.44. Found: C, 50.07; H, 7.00; S, 24.33.

Workup

  1. waitAfter 17 hours at ambient temperature
  2. custompartitioned between EtOAc and H2O
  3. customThe layers were separated
  4. extractionthe aqueousueous phase extracted with EtOAc
  5. washThe combined organic layers were washed with brine
  6. dry with materialdried over Na2SO4
  7. concentrationconcentrated
  8. customto afford a residue which
  9. customwas purified via flash column chromatography with 10% EtOAc/hex as eluant

Sources & evidence

ORD record
ord-6ca3f03c4c2e456096af1ea7d1cfc8ab
Source dataset
uspto-grants-1999_12
Patent number
US06008243

Reaction notes

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