Hydrochloric Acid → 90365-74-5

HRID 1081437Notes

Reaction equation

HRID 1081437 reaction equation
S(=O)(=O)(O)O.[CH2:6]([N:13]1[C:17](=O)[C@H:16]([OH:19])[C@@H:15]([OH:20])[C:14]1=O)[C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1.B.[Na].Cl>COCCOC.O.CO>[CH2:6]([N:13]1[CH2:17][C@H:16]([OH:19])[C@@H:15]([OH:20])[CH2:14]1)[C:7]1[CH:8]=[CH:9][CH:10]=[CH:11][CH:12]=1

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 1118Sulfuric AcidHCID 7299461-Benzyl-3,4-dihydroxypyrrolidine-2,5-dioneHCID 178418435HCID 178418435, compound

Product 1

HCID 273405790365-74-5Yield 52.1%

Reagents, catalysts & solvents 3

HCID 887MethanolSolventHCID 962WaterSolventHCID 80711,2-DimethoxyethaneSolvent2×

Conditions

Temperature
75 °C

Procedure

A solution of 32.2 ml (0.6 mole) sulfuric acid in 100 ml DME was added dropwise to a suspension of 66.4 g (0.3 mole) (3R,4R)-1-benzyl-3,4-dihydroxy-2,5-pyrrolidine dione (IIb) and 45.6 g (1.2 moles) sodium boron hydride in 400 ml 1,2-dimethoxyethane (DME) within 2.5 h at room temperature. The mixture was then agitated 4 h at 75° C. After it cooled off, 75 ml MeOH were added and the mixture rotated in to dryness. The residue was taken up in 300 ml water and compounded with 50 ml conc. hydrochloric acid. The mixture was then made alkaline and extracted with 200 ml toluene twice at 65° C. The extraction residue was taken up in 100 ml each of water and toluene, adjusted to be strongly acidic with hydrochloric acid and agitated overnight at room temperature. It was then made alkaline with 30% sodium hydroxide solution. After the addition of 200 ml toluene the organic phase was separated at 65° C. The aqueous phase was extracted again with 200 ml methylene chloride. After the organic phases were rotated in, 85 g oil remained. The latter was taken up in 400 ml ethyl acetate and washed twice with 80 ml water at 65° C. The ethyl-acetate phase was rotated in after drying over sodium sulfate. 60 g residue remained which was recrystallized from 150 ml ethyl acetate. 30.2 g (52.1%) (3S,4S)-1-benzyl-3,4-dihydroxypyrrolidine (IIIb) were obtained in two fractions.

Workup

  1. temperatureAfter it cooled off
  2. extractionextracted with 200 ml toluene twice at 65° C
  3. stirringagitated overnight at room temperature
  4. additionAfter the addition of 200 ml toluene the organic phase
  5. customwas separated at 65° C
  6. extractionThe aqueous phase was extracted again with 200 ml methylene chloride
  7. washwashed twice with 80 ml water at 65° C
  8. dry with materialin after drying over sodium sulfate
  9. customwas recrystallized from 150 ml ethyl acetate

Sources & evidence

ORD record
ord-89bd1201834a435d92a61a15264fa782
Source dataset
uspto-grants-1996_12
Patent number
US05585500

Reaction notes

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