4-(Diethoxymethyl)benzaldehyde → N-[[4-(Diethoxymethyl)phenyl]methyl]tetrahydropyran-4-amine

HRID 81379

반응식

HRID 81379 반응식
Br[C:2]1[C:3](N)=[N:4][CH:5]=[C:6](Br)N=1.[CH2:10]([O:12][CH:13]([O:22][CH2:23][CH3:24])[C:14]1[CH:21]=[CH:20]C(C=O)=[CH:16][CH:15]=1)[CH3:11].[BH4-].[Na+]>CO>[CH2:23]([O:22][CH:13]([O:12][CH2:10][CH3:11])[C:14]1[CH:15]=[CH:16][C:6]([CH2:5][NH:4][CH:3]2[CH2:2][CH2:13][O:12][CH2:10][CH2:11]2)=[CH:20][CH:21]=1)[CH3:24]

참가 물질

5

반응물 3

HCID 5959934-(Diethoxymethyl)benzaldehydeHCID 6200042-Amino-3,5-dibromopyrazineHCID 4311764Sodium borohydride

생성물 1

HCID 86680725N-[[4-(Diethoxymethyl)phenyl]methyl]tetrahydropyran-4-amine수율 183.1%

시약·촉매·용매 1

HCID 887Methanol용매

실험 절차

To a solution of tetrahydropyran-4-amine 1 (100 g, 988.7 mmol) in MeOH (3.922 L) was added 4-(diethoxymethyl)benzaldehyde (196.1 g, 941.6 mmol) over 2 min at RT. The reaction mixture was stirred at RT for 80 min, until the aldimine formation was complete (as seen by NMR). NaBH4 (44.49 g, 1.176 mol) was carefully added over 45 min, maintaining the temperature between 24° C. and 27° C. by mean of an ice bath. After 75 min at RT, the reaction has gone to completion. The reaction mixture was quenched with 1M NaOH (1 L). The reaction mixture was partitioned between brine (2.5 L) and TBDME (4 L then 2×1 L). The organic phase was washed with brine (500 mL) and concentrated in vacuo. The crude mixture was redissolved in DCM (2 L). The aqueous phase was separated, the organic phase was dried over MgSO4, filtered and concentrated in vacuo to give the title compound as a yellow oil (252.99 g, 91% Yield); 1H NMR (400 MHz, CDCl3) δ 1.26 (t, 6H), 1.43-1.52 (m, 2H), 1.85-1.89 (m, 2H), 3.40 (td, 2H), 3.53-3.66 (m, 4H), 3.85 (s, 2H), 4.00 (dt, 2H), 5.51 (s, 1H), 7.33 (d, 2H) and 7.45 d, 2H) ppm; MS (ES+) 293.9.

후처리

  1. temperaturemaintaining the temperature between 24° C. and 27° C. by mean of an ice bath
  2. customThe reaction mixture was quenched with 1M NaOH (1 L)
  3. customThe reaction mixture was partitioned between brine (2.5 L) and TBDME (4 L
  4. washThe organic phase was washed with brine (500 mL)
  5. concentrationconcentrated in vacuo
  6. dissolutionThe crude mixture was redissolved in DCM (2 L)
  7. customThe aqueous phase was separated
  8. dry with materialthe organic phase was dried over MgSO4
  9. filtrationfiltered
  10. concentrationconcentrated in vacuo

출처 및 근거

ORD 기록
ord-b73a1a86c08a4685bc4f5d7029a82bbc
출처 데이터셋
uspto-grants-2014_09
특허 번호
US08846686B2

연결된 노트

불러오는 중…