Stannous chloride dihydrate → HCID 22989531, compound

HRID 1357776Notes

Reaction equation

HRID 1357776 reaction equation
[CH2:1]([C:4]1[C:9]2[O:10][C@@H:11]([CH2:14][O:15][S:16]([C:19]3[CH:24]=[CH:23][C:22]([CH3:25])=[CH:21][CH:20]=3)(=[O:18])=[O:17])[CH2:12][O:13][C:8]=2[CH:7]=[CH:6][C:5]=1[N+:26]([O-])=O)[CH:2]=[CH2:3].O.O.[Sn](Cl)Cl>C(OCC)(=O)C>[CH3:25][C:22]1[CH:23]=[CH:24][C:19]([S:16]([O:15][CH2:14][CH:11]2[O:10][C:9]3[C:4]([CH2:1][CH:2]=[CH2:3])=[C:5]([NH2:26])[CH:6]=[CH:7][C:8]=3[O:13][CH2:12]2)(=[O:18])=[O:17])=[CH:20][CH:21]=1

Participants

4

Reactant 2

HCID 61436Stannous chloride dihydrateHCID 12082206(R)-[8-allyl-7-nitro-2,3-dihydro-1,4-benzodioxin-2-yl]methyl4-methylbenzenesulfonate

Product 1

HCID 22989531HCID 22989531, compound

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Procedure

(2R)-Toluene-4-sulfonic acid 8-allyl-7-nitro-2,3-dihydro-benzo(1,4)dioxin-2-ylmethyl ester (5.3 g, 13 mmole) and tin (II) chloride dihydrate (14.7 g, 65 mmole) were combined in 500 mL of ethyl acetate and the mixture refluxed for 3 hours under nitrogen. The reaction was allowed to cool to room temperature and was quenched by the addition of 300 mL of saturated aqueous sodium bicarbonate. The biphasic mixture was filtered through celite, the phases separated and the aqueous back-extracted with 200 mL of ethyl acetate. The combined organic phases were washed with 250 mL portions of water and saturated brine, dried over sodium sulfate, filtered and concentrated in vacuum. The residue was column chromatographed on silica gel with methylene chloride as eluant to give 2.2 g of the (R)-enantiomer of the title compound as an orange oil. 1H-NMR (CDCl3): doublet 7.8 δ (2 H); doublet 7.35 δ (2 H); doublet 6.6 δ (1 H); doublet 6.25 δ (1 H); multiplet 5.8 δ (1 H); singlet 5.05 δ(1 H); doublet 5.0 δ (1 H); multiplet 4.4 δ (1 H); multiplet 4.2 δ (3 H); doublet of doublets 4.0 δ (1 H); doublet 3.25 δ (2 H); singlet 2.45 δ (3 H).

Workup

  1. temperaturethe mixture refluxed for 3 hours under nitrogen
  2. customwas quenched by the addition of 300 mL of saturated aqueous sodium bicarbonate
  3. filtrationThe biphasic mixture was filtered through celite
  4. customthe phases separated
  5. extractionthe aqueous back-extracted with 200 mL of ethyl acetate
  6. washThe combined organic phases were washed with 250 mL portions of water and saturated brine
  7. dry with materialdried over sodium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated in vacuum
  10. customchromatographed on silica gel with methylene chloride as eluant

Sources & evidence

ORD record
ord-1adbf3bcf9c64b2ab3c03888f811ebb7
Source dataset
uspto-grants-2003_07
Patent number
US06593350B2

Reaction notes

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