Methyl chloroformate → methyl 4-[1-ethyl-6-(pyridin-2-ylmethoxy)-1H-pyrrolo[2,3-b]pyridin-3-yl]-3-oxopiperazine-1-carboxylate

HRID 1622900Notes

Reaction equation

HRID 1622900 reaction equation
[CH2:1]([N:3]1[C:7]2=[N:8][C:9]([O:12][CH2:13][C:14]3[CH:19]=[CH:18][CH:17]=[CH:16][N:15]=3)=[CH:10][CH:11]=[C:6]2[C:5]([N:20]2[CH2:25][CH2:24][NH:23][CH2:22][C:21]2=[O:26])=[CH:4]1)[CH3:2].C(N(CC)CC)C.Cl[C:35]([O:37][CH3:38])=[O:36]>C(Cl)Cl.CO>[CH2:1]([N:3]1[C:7]2=[N:8][C:9]([O:12][CH2:13][C:14]3[CH:19]=[CH:18][CH:17]=[CH:16][N:15]=3)=[CH:10][CH:11]=[C:6]2[C:5]([N:20]2[CH2:25][CH2:24][N:23]([C:35]([O:37][CH3:38])=[O:36])[CH2:22][C:21]2=[O:26])=[CH:4]1)[CH3:2]

Participants

6

Reactant 3

HCID 6586Methyl chloroformateHCID 8471TriethylamineHCID 678185661-[1-ethyl-6-(pyridin-2-ylmethoxy)-1H-pyrrolo[2,3-b]pyridin-3-yl]piperazin-2-one

Product 1

HCID 67816391methyl 4-[1-ethyl-6-(pyridin-2-ylmethoxy)-1H-pyrrolo[2,3-b]pyridin-3-yl]-3-oxopiperazine-1-carboxylateYield 70.5%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 6344DichloromethaneSolvent

Procedure

To a stirred solution of 1-[1-ethyl-6-(pyridin-2-ylmethoxy)-1H-pyrrolo[2,3-b]pyridin-3-yl]piperazin-2-one (0.200 g, 0.569 mmol) in DCM (10 mL) is added triethylamine (0.095 mL, 0.683 mmol), followed by methyl chloroformate (0.052 mL, 0.683 mmol). The reaction is then stirred overnight. The reaction is diluted with MeOH, and poured on to a SCX2 ion-exchange column. This is flushed with one column volume of MeOH, and then the product collected in the subsequent one column volume flush of 7 M methanolic ammonia. The solution is then concentrated in vacuo to give the title compound as an orange oil (0.1643 g, 0.401 mmol). MS (m/z): 410 (M+1). 1H-NMR (300.13 MHz, CDCl3): δ 1.37 (t, 3H). 3.79 (s, 3H), 3.74-3.82 (br, 2H), 3.83-3.90 (br, 2H), 4.15 (q, 2H), 4.27-4.39 (br, 2H), 5.58 (s, 2H), 6.71 (d, 1H), 7.04 (s, 1H), 7.19 (t, 1H), 7.45-7.50 (m, 1H), 7.64-7.70 (m, 2H), 8.60 (d, 1H).

Workup

  1. customThis is flushed with one column volume of MeOH
  2. customthe product collected in the subsequent one column volume
  3. customflush of 7 M methanolic ammonia
  4. concentrationThe solution is then concentrated in vacuo

Sources & evidence

ORD record
ord-697aae9ab520456b84b7efa32f43dd32
Source dataset
uspto-grants-2014_07
Patent number
US08778946B2

Reaction notes

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