Stannous chloride dihydrate → HCID 18180307, compound

HRID 1359067Notes

Reaction equation

HRID 1359067 reaction equation
[N:1]#[C:2][CH:3]=[CH:4][C:5]1[C:10]2[O:11][C@@H:12]([CH2:15][O:16][S:17]([C:20]3[CH:25]=[CH:24][C:23]([CH3:26])=[CH:22][CH:21]=3)(=[O:19])=[O:18])[CH2:13][O:14][C:9]=2[CH:8]=[CH:7][C:6]=1[N+:27]([O-])=O.O.O.[Sn](Cl)Cl>C(OCC)(=O)C>[CH3:26][C:23]1[CH:24]=[CH:25][C:20]([S:17]([O:16][CH2:15][CH:12]2[O:11][C:10]3=[C:5]4[C:6](=[CH:7][CH:8]=[C:9]3[O:14][CH2:13]2)[N:27]=[C:2]([NH2:1])[CH:3]=[CH:4]4)(=[O:19])=[O:18])=[CH:21][CH:22]=1

Participants

4

Reactant 2

HCID 61436Stannous chloride dihydrateHCID 86586359HCID 86586359, compound

Product 1

HCID 18180307HCID 18180307, compound

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Procedure

To a solution of 2.5 g (6.0 mmole) of toluene-4-sulfonic acid (2R)-8-(3-nitrilo-propenyl)-7-nitro-2,3-dihydro-benzo[1,4]dioxin-2-ylmethyl ester in 200 mL of ethyl acetate was added 6.8 g (30 mmole) of tin (II) chloride dihydrate and the mixture was refluxed under nitrogen for 5 hours. The solvent was then removed in vacuum and replaced with 250 mL of methanol. Concentrated HCl (5 mL) was added and the mixture was refluxed under a nitrogen atmosphere for 15 hours. The solvent was again removed in vacuum and 500 mL of saturated aqueous sodium bicarbonate added. This was extracted twice with 250 mL portions of ethyl acetate and the combined organics washed with 400 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 5% methanol in chloroform as eluant to give 0.80 g of the (R)-enantiomer of the title compound as a yellow solid.

Workup

  1. temperaturethe mixture was refluxed under nitrogen for 5 hours
  2. customThe solvent was then removed in vacuum
  3. additionConcentrated HCl (5 mL) was added
  4. temperaturethe mixture was refluxed under a nitrogen atmosphere for 15 hours
  5. customThe solvent was again removed in vacuum and 500 mL of saturated aqueous sodium bicarbonate
  6. additionadded
  7. extractionThis was extracted twice with 250 mL portions of ethyl acetate
  8. washthe combined organics washed with 400 mL portions of water and saturated brine
  9. dry with materialdried over sodium sulfate
  10. filtrationfiltered
  11. concentrationconcentrated in vacuum
  12. customchromatographed on silica gel with 5% methanol in chloroform as eluant

Sources & evidence

ORD record
ord-a23c8edfd2964bc897bbcb68d7baf67f
Source dataset
uspto-grants-2003_07
Patent number
US06599915B2

Reaction notes

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