1-Tert-butyl 3-ethyl 2-(6-chloropyridazin-3-yl)-2-fluoromalonate → Ethyl 2-(6-chloropyridazin-3-yl)-2-fluoroacetate

HRID 1925134Notes

Reaction equation

HRID 1925134 reaction equation
[Cl:1][C:2]1[N:7]=[N:6][C:5]([C:8]([F:21])(C(OCC)=O)[C:9]([O:11][C:12](C)(C)[CH3:13])=[O:10])=[CH:4][CH:3]=1>C(O)(C(F)(F)F)=O.C(Cl)Cl>[Cl:1][C:2]1[N:7]=[N:6][C:5]([CH:8]([F:21])[C:9]([O:11][CH2:12][CH3:13])=[O:10])=[CH:4][CH:3]=1

Participants

3

Reactant 1

HCID 592330691-Tert-butyl 3-ethyl 2-(6-chloropyridazin-3-yl)-2-fluoromalonate

Product 1

HCID 46941482Ethyl 2-(6-chloropyridazin-3-yl)-2-fluoroacetateYield 89%

Reagents, catalysts & solvents 1

HCID 21863450Trifluoroacetic acid methylene chlorideSolvent

Procedure

A solution of 1-tert-butyl 3-ethyl 2-(6-chloropyridazin-3-yl)-2-fluoromalonate 45B (60.2 g, 189 mmol) in 300 mL TFA/DCM (1:1) was stirred at 25° C. for 2 hrs and then concentrated to dryness via rotary evaporation. The resulting residue was dissolved in EtOAc (300 mL), washed with saturated NaHCO3 solution, dried over MgSO4, and then concentrated to dryness to give the title compound, ethyl 2-(6-chloropyridazin-3-yl)-2-fluoroacetate 45C (36.6 g, 167 mmol, 89%). The material was used immediately without further purification. 1H NMR (400 MHz, DMSO-d6) δ ppm 1.18 (t, J=7.20 Hz, 3 H) 4.23 (qd, J=7.12, 4.42 Hz, 2 H) 6.43-6.62 (m, 1 H) 8.00-8.12 (m, 2 H). ESI-MS:m/z 219.0 (M+H)+.

Workup

  1. concentrationconcentrated to dryness via rotary evaporation
  2. dissolutionThe resulting residue was dissolved in EtOAc (300 mL)
  3. washwashed with saturated NaHCO3 solution
  4. dry with materialdried over MgSO4
  5. concentrationconcentrated to dryness

Sources & evidence

ORD record
ord-c082c862e65b4b639896bc9c68d25bab
Source dataset
uspto-grants-2012_05
Patent number
US08178534B2

Reaction notes

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