p-Toluenesulfonic acid → HCID 22341393, compound

HRID 1368362Notes

Reaction equation

HRID 1368362 reaction equation
[NH2:1][C:2]1[C:7]2[O:8][C@@H:9]([CH2:12][O:13][S:14]([C:17]3[CH:22]=[CH:21][C:20]([CH3:23])=[CH:19][CH:18]=3)(=[O:16])=[O:15])[CH2:10][O:11][C:6]=2[CH:5]=[CH:4][C:3]=1[N+:24]([O-])=O.[C:27]1(C)[CH:32]=CC(S(O)(=O)=O)=C[CH:28]=1.[H][H]>CO.[Pd]>[CH3:23][C:20]1[CH:21]=[CH:22][C:17]([S:14]([O:13][CH2:12][CH:9]2[O:8][C:7]3[C:6](=[CH:5][CH:4]=[C:3]4[NH:24][C:28]([CH2:27][CH3:32])=[N:1][C:2]4=3)[O:11][CH2:10]2)(=[O:16])=[O:15])=[CH:18][CH:19]=1

Participants

6

Reactant 3

HCID 6101p-Toluenesulfonic acidHCID 12082527HCID 12082527, compoundHCID 178418361HCID 178418361, compound

Product 1

HCID 22341393HCID 22341393, compound

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 887MethanolSolvent

Procedure

Toluene-4-sulfonic acid (2R)-8-amino-7-nitro-2,3-dihydro-benzo(1,4)dioxin-2-yl-methyl ester (1.0 g, 2.6 mmole) was dissolved in 100 mL of methanol to which 0.25 g of 10% palladium on carbon had been added. p-Toluenesulfonic acid (1.0 g, 5.2 mmole) was then added and the mixture treated with 60 psi of hydrogen on a Parr apparatus for 15 hours. The mixture was filtered through celite and concentrated in vacuum. Propionic acid (50 mL) was added and the solution refluxed under nitrogen for 4 hours. The solvent was removed in vacuum and the residue dissolved in 300 mL of methylene chloride, washed with 200 mL each of saturated aqueous sodium bicarbonate, water and saturated brine, dried over magnesium sulfate, filtered and concentrated in vacuum to give 0.84 g of the (R)-enantiomer of the title compound as a white foam. 1H-NMR (CDCl3): doublet 7.8 δ(2H); doublet 7.3 δ(2H); doublet 7.0 δ(1H); doublet 6.75 δ(1H); multiplet 4.5 δ(1H); multiplet 4.25 δ(3H); multiplet 4.05 δ(1H); quartet 2.9 δ(2H); singlet 2.45 δ(3H); triplet 1.4 δ(3H).

Workup

  1. additionhad been added
  2. filtrationThe mixture was filtered through celite and
  3. concentrationconcentrated in vacuum
  4. additionPropionic acid (50 mL) was added
  5. temperaturethe solution refluxed under nitrogen for 4 hours
  6. customThe solvent was removed in vacuum
  7. dissolutionthe residue dissolved in 300 mL of methylene chloride
  8. washwashed with 200 mL each of saturated aqueous sodium bicarbonate, water and saturated brine
  9. dry with materialdried over magnesium sulfate
  10. filtrationfiltered
  11. concentrationconcentrated in vacuum

Sources & evidence

ORD record
ord-aecf12697839454e9afa8ea2de5d6470
Source dataset
uspto-grants-2003_06
Patent number
US06573283B2

Reaction notes

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