Ammonium Chloride → HCID 86604507、化合物

HRID 1858829ノート

反応式

HRID 1858829 の反応式
[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

参加物

6

反応物 4

HCID 25517Ammonium ChlorideHCID 53442613Sodium hydrogen sulfide hydrateHCID 54013516HCID 54013516、化合物HCID 83670143HCID 83670143、化合物

生成物 1

HCID 86604507HCID 86604507、化合物収率 52%

試薬・触媒・溶媒 1

HCID 6228Dimethylformamide溶媒

実験手順

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.

後処理

  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

出典と根拠

ORDレコード
ord-971fbe5870e6496e9baf09d338ff9c82
出典データセット
uspto-grants-2000_11
特許番号
US06150526

反応ノート

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