Sodium Hydroxide → [5-tert-Butyl-2-(3-methyl-5-triisopropylsilanyloxy-phenyl)-2H-pyrazol-3-yl]-carbamic acid 2,2,2-trichloro-ethyl ester

HRID 60646Notes

Reaction equation

HRID 60646 reaction equation
[C:1]([C:5]1[CH:6]=[C:7]([NH2:28])[N:8]([C:10]2[CH:15]=[C:14]([O:16][Si:17]([CH:24]([CH3:26])[CH3:25])([CH:21]([CH3:23])[CH3:22])[CH:18]([CH3:20])[CH3:19])[CH:13]=[C:12]([CH3:27])[CH:11]=2)[N:9]=1)([CH3:4])([CH3:3])[CH3:2].[OH-].[Na+].Cl[C:32]([O:34][CH2:35][C:36]([Cl:39])([Cl:38])[Cl:37])=[O:33]>C(OCC)(=O)C>[Cl:37][C:36]([Cl:39])([Cl:38])[CH2:35][O:34][C:32](=[O:33])[NH:28][C:7]1[N:8]([C:10]2[CH:15]=[C:14]([O:16][Si:17]([CH:18]([CH3:20])[CH3:19])([CH:24]([CH3:26])[CH3:25])[CH:21]([CH3:22])[CH3:23])[CH:13]=[C:12]([CH3:27])[CH:11]=2)[N:9]=[C:5]([C:1]([CH3:2])([CH3:3])[CH3:4])[CH:6]=1

Participants

5

Reactant 3

HCID 14798Sodium HydroxideHCID 870632,2,2-Trichloroethyl chloroformateHCID 1233019165-tert-Butyl-2-(3-methyl-5-triisopropylsilanyloxy-phenyl)-2H-pyrazol-3-ylamine

Product 1

HCID 123538151[5-tert-Butyl-2-(3-methyl-5-triisopropylsilanyloxy-phenyl)-2H-pyrazol-3-yl]-carbamic acid 2,2,2-trichloro-ethyl esterYield 103%

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent2×

Procedure

To a solution of Intermediate 54b (0.73 g, assumed 1.70 mmol) in ethyl acetate (8 mL) was added 1N sodium hydroxide solution (4.5 mL, 4.50 mmol). Stirred for 5 min then 2,2,2-trichloroethyl chloroformate (275 μL, 2.00 mmol) was added and the mixture stirred vigorously at RT for 3.5 h. Diluted with EtOAc, washed with water and brine, dried, and concentrated in vacuo. The residue was purified by FCC, using 0-15% EtOAc in cyclohexane, to give the still impure title compound (1.01 g). 1H NMR (300 MHz, CDCl3): inter alia 1.02-1.15 (18H, m), 1.18-1.38 (12H, m), 2.34 (3H, s), 4.82 (2H, s), 6.43 (1H, s), 6.69-6.77 (2H, m), 6.84-6.96 (2H, m).

Workup

  1. stirringthe mixture stirred vigorously at RT for 3.5 h
  2. washwashed with water and brine
  3. customdried
  4. concentrationconcentrated in vacuo
  5. customThe residue was purified by FCC

Sources & evidence

ORD record
ord-44668bdd62b44f4caaf87c96c6429b15
Source dataset
uspto-grants-2016_09
Patent number
US09440974B2

Reaction notes

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