Chloride → tert-butyl 6-amino-3-benzyloxy-10,11-dihydropyrazino[1',2':1,2]imidazo[4,5-c]quinoline-9(8H)-carboxylate

HRID 1364063Notes

Reaction equation

HRID 1364063 reaction equation
C1C=C(Cl)C=C(C(OO)=O)C=1.[CH2:12]([O:19][C:20]1[CH:29]=[C:28]2[C:23]([C:24]3[N:32]4[CH2:33][CH2:34][N:35]([C:37]([O:39][C:40]([CH3:43])([CH3:42])[CH3:41])=[O:38])[CH2:36][C:31]4=[N:30][C:25]=3[CH:26]=[N:27]2)=[CH:22][CH:21]=1)[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1.[OH-].[NH4+:45].[Cl-]>C(Cl)(Cl)Cl>[NH2:45][C:26]1[C:25]2[N:30]=[C:31]3[CH2:36][N:35]([C:37]([O:39][C:40]([CH3:43])([CH3:42])[CH3:41])=[O:38])[CH2:34][CH2:33][N:32]3[C:24]=2[C:23]2[C:28](=[CH:29][C:20]([O:19][CH2:12][C:13]3[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=3)=[CH:21][CH:22]=2)[N:27]=1

Participants

6

Reactant 4

HCID 312ChlorideHCID 14923Ammonium HydroxideHCID 70297m-Chloroperbenzoic acidHCID 66958454tert-butyl 3-benzyloxy-10,11-dihydropyrazino[1',2':1,2]imidazo[4,5-c]quinoline-9(8H)-carboxylate

Product 1

HCID 66958130tert-butyl 6-amino-3-benzyloxy-10,11-dihydropyrazino[1',2':1,2]imidazo[4,5-c]quinoline-9(8H)-carboxylate

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent

Procedure

mCPBA (0.782 g of 77% purity, 3.49 mmol) was added to a solution of tert-butyl 3-benzyloxy-10,11-dihydropyrazino[1′,2′:1,2]imidazo[4,5-c]quinoline-9(8H)-carboxylate (1.0 g, 2.3 mmol) in chloroform (15 mL), and the reaction was stirred for 30 minutes. Ammonium hydroxide (5 mL), and the reaction was stirred for five minutes before the rapid addition of p-toluenesulfnyl chloride (0.4865 g, 2.55 mmol). The reaction was stirred overnight at ambient temperature. The organic layer was separated and concentrated under reduced pressure. The residue was purified by normal phase prep HPLC on silica gel (eluting with 2 N ammonia in methanol/chloroform in a 42-minute gradient from 0:100 to 5:95) to provide 550 mg of tert-butyl 6-amino-3-benzyloxy-10,11-dihydropyrazino[1′,2′:1,2]imidazo[4,5-c]quinoline-9(8H)-carboxylate.

Workup

  1. stirringThe reaction was stirred overnight at ambient temperature
  2. customThe organic layer was separated
  3. concentrationconcentrated under reduced pressure
  4. customThe residue was purified by normal phase prep HPLC on silica gel (
  5. washeluting with 2 N ammonia in methanol/chloroform in a 42-minute gradient from 0:100 to 5:95)

Sources & evidence

ORD record
ord-fc9d16d804a542fab3044ad163ee3195
Source dataset
uspto-grants-2011_02
Patent number
US07888349B2

Reaction notes

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