Diisopropylethylamine → HCID 87210018, compound

HRID 1366533Notes

Reaction equation

HRID 1366533 reaction equation
[CH3:1][N:2]([CH3:10])[CH:3]1[CH2:7][CH2:6][NH:5][C:4]1([CH3:9])[CH3:8].C(N(CC)C(C)C)(C)C.[CH3:20][C:21]([O:24][C:25]([N:27]([C:45]([O:47][C:48]([CH3:51])([CH3:50])[CH3:49])=[O:46])[N:28]([C:36]1[C:41]([F:42])=[C:40](Cl)[N:39]=[C:38]([Cl:44])[N:37]=1)[C:29]([O:31][C:32]([CH3:35])([CH3:34])[CH3:33])=[O:30])=[O:26])([CH3:23])[CH3:22]>CN(C=O)C>[CH3:23][C:21]([O:24][C:25]([N:27]([C:45]([O:47][C:48]([CH3:51])([CH3:50])[CH3:49])=[O:46])[N:28]([C:36]1[C:41]([F:42])=[C:40]([N:5]2[CH2:6][CH2:7][CH:3]([N:2]([CH3:10])[CH3:1])[C:4]2([CH3:9])[CH3:8])[N:39]=[C:38]([Cl:44])[N:37]=1)[C:29]([O:31][C:32]([CH3:33])([CH3:34])[CH3:35])=[O:30])=[O:26])([CH3:20])[CH3:22]

Participants

5

Reactant 3

HCID 81531DiisopropylethylamineHCID 23090152HCID 23090152, compoundHCID 58000755Tris(1,1-dimethylethyl) 2-(2,6-dichloro-5-fluoro-4-pyrimidinyl)-1,1,2-hydrazinetricarboxylate

Product 1

HCID 87210018HCID 87210018, compoundYield 75%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a solution of racemic N,N,2,2-tetramethyl-3-pyrrolidinamine (0.1466 g, 1.031 mmol) in DMF (6 mL) was added N,N-diisopropylethylamine (0.220 mL, 1.263 mmol) and tris(1,1-dimethylethyl)2-(2,6-dichloro-5-fluoro-4-pyrimidinyl)-1,1,2-hydrazinetricarboxylate (0.513 g, 1.031 mmol), and the solution was stirred overnight. The solution was partitioned between Et2O (100 mL) and water (20 mL), and the organic phase was washed with a fresh portion of water (20 mL). The combined aqueous phase was extracted with a fresh portion of Et2O (50 mL), and the combined organic phase was dried over anhydrous Na2SO4, filtered, and concentrated in vacuo. The residue was purified by gradient silica gel chromatography (0% to 100% EtOAc in hexanes) to give racemic tris(1,1-dimethylethyl)2-{2-chloro-6-[3-(dimethylamino)-2,2-dimethyl-1-pyrrolidinyl]-5-fluoro-4-pyrimidinyl}-1,1,2-hydrazinetricarboxylate (0.4647 g, 75% yield) as a white foam. LCMS: (M+H)+: 603.3.

Workup

  1. customThe solution was partitioned between Et2O (100 mL) and water (20 mL)
  2. washthe organic phase was washed with a fresh portion of water (20 mL)
  3. extractionThe combined aqueous phase was extracted with a fresh portion of Et2O (50 mL)
  4. dry with materialthe combined organic phase was dried over anhydrous Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customThe residue was purified by gradient silica gel chromatography (0% to 100% EtOAc in hexanes)

Sources & evidence

ORD record
ord-02d50b0aa9da415da4fe43e2fdd46070
Source dataset
uspto-grants-2011_02
Patent number
US07893056B2

Reaction notes

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