Formaldehyde → (3S,4S)-4-(4-bromo-2-nitrophenylamino)-1-methylpyrrolidin-3-ol

HRID 1670622Notes

Reaction equation

HRID 1670622 reaction equation
Cl.[Br:2][C:3]1[CH:8]=[CH:7][C:6]([NH:9][C@H:10]2[CH2:14][NH:13][CH2:12][C@@H:11]2[OH:15])=[C:5]([N+:16]([O-:18])=[O:17])[CH:4]=1.[C:19](O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+].C=O.C(=O)(O)[O-].[Na+]>C(#N)C>[Br:2][C:3]1[CH:8]=[CH:7][C:6]([NH:9][C@H:10]2[CH2:14][N:13]([CH3:19])[CH2:12][C@@H:11]2[OH:15])=[C:5]([N+:16]([O-:18])=[O:17])[CH:4]=1

Participants

6

Reactant 4

HCID 712FormaldehydeHCID 516892Sodium BicarbonateHCID 5049666Sodium triacetoxyborohydrideHCID 67336101(3S,4S)-4-(4-Bromo-2-nitro-phenylamino)-pyrrolidin-3-ol hydrochloride

Product 1

HCID 57748725(3S,4S)-4-(4-bromo-2-nitrophenylamino)-1-methylpyrrolidin-3-olYield 103.4%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

To (3S,4S)-4-(4-Bromo-2-nitro-phenylamino)-pyrrolidin-3-ol hydrochloride (0.104 mol, 35.0 g) in acetonitrile add sodium triacetoxyborohydride (0.37 mol, 78.0 g) at 0° C. To this mixture, add slowly 37% aqueous formaldehyde (30 mL) over 10 min and stir at room temperature for 10 h. Add saturated aqueous sodium bicarbonate and stir for one hour. Extract with ethyl acetate, and wash with water and brine. Dry over anhydrous sodium sulfate, filter, and evaporate the solvent to obtain the title compound as a yellow solid (34.0 g, 98%). APCI MS m/z 302 [M+H]+; [α]23D +58.6° (c, 0.50, MeOH).

Workup

  1. extractionExtract with ethyl acetate
  2. washwash with water and brine
  3. dry with materialDry over anhydrous sodium sulfate
  4. filtrationfilter
  5. customevaporate the solvent

Sources & evidence

ORD record
ord-948a80ccae044e8cbfa926ea86b202b3
Source dataset
uspto-grants-2011_08
Patent number
US07994164B2

Reaction notes

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