Sodium Thiosulfate → tert-Butyl thiomorpholine-4-carboxylate

HRID 2215532

Reaction equation

HRID 2215532 reaction equation
[N:1]1([C:7]([O:9][C:10]([CH3:13])([CH3:12])[CH3:11])=[O:8])[CH2:6][CH2:5]S[CH2:3][CH2:2]1.ClC1C=CC=C(C(OO)=O)C=1.[S:25]([O-:29])([O-])(=[O:27])=S.[Na+].[Na+].C(OC([O-])=O)(OC(OC(C)(C)C)=O)=O>ClCCl>[O:27]=[S:25]1(=[O:29])[CH2:5][CH2:6][N:1]([C:7]([O:9][C:10]([CH3:12])([CH3:11])[CH3:13])=[O:8])[CH2:2][CH2:3]1

Participants

6

Reactant 4

HCID 24477Sodium ThiosulfateHCID 70297m-Chloroperbenzoic acidHCID 21949316Thiomorpholine, N-BOC protectedHCID 86600350tert-Butoxycarbonyl dicarbonate

Product 1

HCID 21949260tert-Butyl thiomorpholine-4-carboxylateYield 91.6%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

tert-Butyl thiomorpholine-4-carboxylate (1.91 g, 9.42 mol) was dissolved in dichloromethane (50 ml); m-chloroperbenzoic acid (5.0 g, 19 mmol) was gradually added while cooled with ice bath, stirred, and under nitrogen atmosphere; and the reaction mixture was stirred at room temperature for 12 hours. After addition of a saturated aqueous solution of sodium thiosulfate, the reaction mixture was kept stirred for a while; and this was subjected to extraction with ethyl acetate, washed with brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. Triethylamine (8.1 ml, 58 ml) were added to the obtained crystals; and the reaction mixture was stirred at room temperature. tert-Butoxycarbonyl dicarbonate (13.3 ml, 58 mmol) was added thereto; and the reaction mixture was stirred at room temperature for 10 hours. The reaction mixture was concentrated under reduced pressure; and the obtained crystals were suspended with a solvent mixture of diethyl ether:ethanol=10:1, filtered off, washed with diethyl ether and dried under aeration to yield the title compound as colorless crystals (2.03 g, 8.63 mmol, 91.6%).

Workup

  1. temperaturewhile cooled with ice bath
  2. stirringand the reaction mixture was stirred at room temperature for 12 hours
  3. stirringthe reaction mixture was kept stirred for a while
  4. extractionand this was subjected to extraction with ethyl acetate
  5. washwashed with brine
  6. dry with materialdried over anhydrous sodium sulfate
  7. concentrationconcentrated under reduced pressure
  8. additionTriethylamine (8.1 ml, 58 ml) were added to the obtained crystals
  9. stirringand the reaction mixture was stirred at room temperature
  10. stirringand the reaction mixture was stirred at room temperature for 10 hours
  11. concentrationThe reaction mixture was concentrated under reduced pressure
  12. additionand the obtained crystals were suspended with a solvent mixture of diethyl ether
  13. filtrationethanol=10:1, filtered off
  14. washwashed with diethyl ether
  15. customdried under aeration

Sources & evidence

ORD record
ord-78ccffa65a344032b23a9b0f65240757
Source dataset
uspto-grants-2006_09
Patent number
US07109219B2

Linked notes

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