Methane → Tert-butyl N-tert-butoxycarbonyl-N-[5-bromo-3-((trimethylsilyl)ethynyl)pyrazin-2-yl]carbamate

HRID 81380노트

반응식

HRID 81380 반응식
BrC1N=C(C#C[Si](C)(C)C)C(N)=NC=1.[CH3:15][C:16]1[CH:17]=CC(S(O)(=O)=O)=C[CH:21]=1.[Br:26][C:27]1[N:28]=[C:29]([C:44]#[C:45][Si:46]([CH3:49])([CH3:48])[CH3:47])[C:30]([N:33]([C:37]([O:39][C:40]([CH3:43])([CH3:42])[CH3:41])=[O:38])[C:34](=[O:36])[O-:35])=[N:31][CH:32]=1.CC(OC(OC(OC(C)(C)C)=O)=O)(C)C.C>CCOC(C)=O.CN(C1C=CN=CC=1)C>[C:40]([O:39][C:37]([N:33]([C:30]1[C:29]([C:44]#[C:45][Si:46]([CH3:47])([CH3:49])[CH3:48])=[N:28][C:27]([Br:26])=[CH:32][N:31]=1)[C:34](=[O:35])[O:36][C:16]([CH3:17])([CH3:21])[CH3:15])=[O:38])([CH3:42])([CH3:43])[CH3:41]

참가 물질

8

반응물 5

HCID 297MethaneHCID 6101p-Toluenesulfonic acidHCID 90495Di-tert-butyl dicarbonateHCID 533931895-Bromo-3-((trimethylsilyl)ethynyl)pyrazin-2-amineHCID 86680731N-[5-bromo-3-(2-trimethylsilylethynyl)pyrazin-2-yl]-N-tertbutoxycarbonyl-carbamate

생성물 1

HCID 58070279Tert-butyl N-tert-butoxycarbonyl-N-[5-bromo-3-((trimethylsilyl)ethynyl)pyrazin-2-yl]carbamate

시약·촉매·용매 2

HCID 142844-(Dimethylamino)pyridine촉매HCID 8857Ethyl Acetate용매2회

실험 절차

A solution of 5-bromo-3-((trimethylsilyl)ethynyl)pyrazin-2-amine (Compound C-2) PTSA salt 3 (2350 g, 5.31 mol) in EtOAc (11.5 L) is stirred with a 20% w/w aq. solution of KHCO3 (4.5 kg, 1.5 eq.) for at least 30 min. The layers are separated and the organic layer is concentrated then dissolved in EtOAc (7 L) and added to a reactor. DMAP (19.5 g, 0.16 mol) is added followed a solution of Boc2O (2436 g, 11.16 mol) in EtOAc (3 L) is added lowly. The reaction is stirred for at least 30 min to ensure complete reaction then activated charcoal (Darco G-60, 720 g) and Celite (720 g) are added and stirred for at least 2 h. The mixture is filtered washing the solid pad with EtOAc (2×1.8 L). The filtrate is concentrated to afford tert-butyl N-tert-butoxycarbonyl-N-[5-bromo-3-((trimethylsilyl)ethynyl)pyrazin-2-yl]carbamate (Compound C-3) that is used directly in the next step.

후처리

  1. customThe layers are separated
  2. concentrationthe organic layer is concentrated
  3. dissolutionthen dissolved in EtOAc (7 L)
  4. additionadded to a reactor
  5. additionis added lowly
  6. customreaction
  7. stirringstirred for at least 2 h
  8. filtrationThe mixture is filtered
  9. washwashing the solid pad with EtOAc (2×1.8 L)
  10. concentrationThe filtrate is concentrated

출처 및 근거

ORD 기록
ord-8e13d50c4b5f459cbacffa6ab52b8660
출처 데이터셋
uspto-grants-2014_09
특허 번호
US08846686B2

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