Sulfuric Acid → (2S)-5-[(benzyloxy)amino]-2-cyanopiperidine

HRID 517669

反応式

HRID 517669 の反応式
S(=O)(=O)(O)O.[CH2:6]([O:13][N:14]=[C:15]1[CH2:20][NH:19][C@H:18]([C:21]#[N:22])[CH2:17][CH2:16]1)[C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1.C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+].C(=O)([O-])O.[K+]>C(OCC)(=O)C>[CH2:6]([O:13][NH:14][CH:15]1[CH2:20][NH:19][C@H:18]([C:21]#[N:22])[CH2:17][CH2:16]1)[C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1

参加物

6

反応物 4

HCID 1118Sulfuric AcidHCID 516893Potassium BicarbonateHCID 5049666Sodium triacetoxyborohydrideHCID 90088575(2S)-5-[(benzyloxy)imino]-2-cyanopiperidine

生成物 1

HCID 117599345(2S)-5-[(benzyloxy)amino]-2-cyanopiperidine収率 88%

試薬・触媒・溶媒 1

HCID 8857Ethyl Acetate溶媒

反応条件

温度
25 °C

実験手順

Sulphuric acid (11.7 ml, 0.217 mol) was slowly added to a stirred solution of (2S)-5-[(benzyloxy)imino]-2-cyanopiperidine (IX) (10 gm, 0.0436 mol, prepared according to the procedure described in step 6) in ethyl acetate (150 ml) at −10° C. After 10 minutes of stirring, sodium triacetoxy borohydride (NaHB(OOCCH3)3) (11.7 gm, 0.0519 mol, 95% purity) was added in small portions while maintaining temperature below −5° C. After completion of the addition, stirring was further continued for 2 hour at the same temperature. The pH of the reaction mixture was adjusted to about pH 7 by using 30% aqueous potassium hydrogen carbonate solution. The mixture was allowed to warm to 25° C. and the reaction mixture was filtered under suction. The organic layer was separated and the aqueous layer extracted with fresh ethyl acetate (50 ml). The combined organic layer was washed with water (50 ml) and brine (50 ml), dried over anhydrous sodium sulphate and the solvent evaporated under reduced pressure to obtain 8.88 gm of (2S)-5-[(benzyloxy)amino]-2-cyanopiperidine (X) as an oil, in 88% yield. This was used as such for the next step without further purification.

後処理

  1. customprepared
  2. customat −10° C
  3. temperaturewhile maintaining temperature below −5° C
  4. additionAfter completion of the addition
  5. stirringstirring
  6. waitwas further continued for 2 hour at the same temperature
  7. filtrationthe reaction mixture was filtered under suction
  8. customThe organic layer was separated
  9. extractionthe aqueous layer extracted with fresh ethyl acetate (50 ml)
  10. washThe combined organic layer was washed with water (50 ml) and brine (50 ml)
  11. dry with materialdried over anhydrous sodium sulphate
  12. customthe solvent evaporated under reduced pressure

出典と根拠

ORDレコード
ord-11cd144b00c34a06b286f049aa7d3018
出典データセット
uspto-grants-2015_08
特許番号
US09115131B2

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