Hydrochloric Acid → tert-butyl N-[(piperidin-3-yl)methyl]carbamate

HRID 2079374ノート

反応式

HRID 2079374 の反応式
Cl.[N:2]1[CH:7]=[CH:6][CH:5]=[C:4]([CH2:8][NH:9][C:10](=[O:16])[O:11][C:12]([CH3:15])([CH3:14])[CH3:13])[CH:3]=1>CO.O=[Pt]=O>[NH:2]1[CH2:7][CH2:6][CH2:5][CH:4]([CH2:8][NH:9][C:10](=[O:16])[O:11][C:12]([CH3:14])([CH3:13])[CH3:15])[CH2:3]1

参加物

5

反応物 2

HCID 313Hydrochloric AcidHCID 13948280tert-Butyl (pyridin-3-ylmethyl)carbamate

生成物 1

HCID 2756030tert-butyl N-[(piperidin-3-yl)methyl]carbamate収率 95%

試薬・触媒・溶媒 2

HCID 345198Adams' catalyst触媒HCID 887Methanol溶媒2 回

実験手順

A cold solution of HCl in MeOH (prepared by adding acetyl chloride (13.5 mL, 14.9 g, 0.19 mol) to 1 L of MeOH) was added to a cold solution of tert-butyl pyridin-3-ylmethylcarbamate (41.0 grams, 0.20 mol) in MeOH (100 mL). The solution was transferred to a Parr hydrogenation apparatus at 12° C. PtO2 (3 g) was added, and 12 bar pressure of H2 was applied. After 16 hours 1H NMR of a concentrated sample indicated the reaction to be complete. The catalyst was filtered, and conc. aq. NaOH (20 mL) was added to neutralize the HCl. The solution was concentrated to remove the bulk of the MeOH and extracted with tert-butyl methyl ether (4×200 mL). The combined organic layers were washed with saturated aqueous NaCl solution, dried over Na2SO4, and concentrated to give the product (40.16 g, 0.187 mol, 95%) as a yellow oil that crystallized upon standing. 1H NMR (300 MHz, CDCl3): δ 4.62 (bs. s, 1H), 3.06-2.94 (m, 4H), 2.52 (dt, J=12 Hz, 3 Hz, 1H), 2.28 (dd, J=12 Hz, 10 Hz, 1H), 1.82-1.72 (m, 1H), 1.70-1.51 (m, 3H), 1.49-1.34 (m, 1H), 1.42 (s, 9H), 1.06 (dq, J=12 Hz, 4 Hz, 1H) ppm.

後処理

  1. customwas transferred to a Parr hydrogenation apparatus at 12° C
  2. customthe reaction
  3. filtrationThe catalyst was filtered
  4. additionconc. aq. NaOH (20 mL) was added
  5. concentrationThe solution was concentrated
  6. customto remove the bulk of the MeOH
  7. extractionextracted with tert-butyl methyl ether (4×200 mL)
  8. washThe combined organic layers were washed with saturated aqueous NaCl solution
  9. dry with materialdried over Na2SO4
  10. concentrationconcentrated

出典と根拠

ORDレコード
ord-4c5fb3bd0df44a08a2cfe4293f77d568
出典データセット
uspto-grants-2011_04
特許番号
US07928107B2

反応ノート

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