Ammonium Chloride → HCID 86604507, compound

HRID 1858829Notes

Reaction equation

HRID 1858829 reaction equation
[C:1]([CH:3]1[CH2:8][CH2:7][N:6]([C:9]([O:11][C:12]([CH3:15])([CH3:14])[CH3:13])=[O:10])[CH2:5][CH:4]1[OH:16])#[N:2].C(C1C(O)CCN(C(OC(C)(C)C)=O)C1)#N.O.[SH2:34].[Na].[Cl-].[NH4+]>CN(C)C=O>[OH:16][CH:4]1[CH:3]([C:1](=[S:34])[NH2:2])[CH2:8][CH2:7][N:6]([C:9]([O:11][C:12]([CH3:13])([CH3:15])[CH3:14])=[O:10])[CH2:5]1

Participants

6

Reactant 4

HCID 25517Ammonium ChlorideHCID 53442613Sodium hydrogen sulfide hydrateHCID 54013516HCID 54013516, compoundHCID 83670143HCID 83670143, compound

Product 1

HCID 86604507HCID 86604507, compoundYield 52%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

A solution of 5.8 g (25.6 mmol) of a 4:1 mixture of tert-butyl (3RS,4RS)-4-cyano-3-hydroxy-piperidine-1-carboxylate and tert-butyl (3RS,4SR)-3-cyano-4-hydroxy-piperidine-1-carboxylate in 50 ml of N,N-dimethylformamide was stirred at room temperature under argon for 4 hours with 1.8 g (38.4 mmol) of sodium hydrogen sulphide monohydrate and 2.05 g (38.4 mmol) of ammonium chloride. For the working-up, the reaction mixture was evaporated under reduced pressure and the residue was taken up in 150 ml of methylene chloride. The solution obtained was washed twice with 10 ml of water each time and the organic phase was separated, dried over sodium sulphate and then evaporated under reduced pressure. For purification and separation of the isomer mixture, the residue was chromatographed on silica gel using a 95:5:0.1 mixture of methylene chloride, methanol and ammonia as the eluent. There were obtained 3.48 g (52% of theory) of tert-butyl (3RS,4SR)-3-hydroxy-4-thiocarbamoyl-piperidine-1-carboxylate, (Rf : 0.37, silica gel; methylene chloride:methanol:ammonia=90:10:0.1 v/v/v), MS: 260 (M)+, as well as 1.2 g of a mixture of tert-butyl (3RS,4SR)-3-hydroxy-4-thiocarbamoyl-piperidine-1-carboxylate and tert-butyl (3RS,4RS)-4-hydroxy-3-thiocarbamoyl-piperidine-1-carboxylate, each as a colourless oil.

Workup

  1. customthe reaction mixture was evaporated under reduced pressure
  2. customThe solution obtained
  3. washwas washed twice with 10 ml of water each time
  4. customthe organic phase was separated
  5. dry with materialdried over sodium sulphate
  6. customevaporated under reduced pressure
  7. customFor purification and separation of the isomer mixture
  8. customthe residue was chromatographed on silica gel using
  9. additiona 95:5:0.1 mixture of methylene chloride, methanol and ammonia as the eluent

Sources & evidence

ORD record
ord-971fbe5870e6496e9baf09d338ff9c82
Source dataset
uspto-grants-2000_11
Patent number
US06150526

Reaction notes

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