4-(Methylthio)phenol → 5-(4-(methylthio)phenoxy)-N,N-bis((2-(trimethylsilyl)ethoxy)methyl)pyrazolo[1,5-a]pyrimidin-7-amine

HRID 2047038Notes

Reaction equation

HRID 2047038 reaction equation
[CH3:1][S:2][C:3]1[CH:8]=[CH:7][C:6]([OH:9])=[CH:5][CH:4]=1.[H-].[Na+].Cl[C:13]1[CH:18]=[C:17]([N:19]([CH2:28][O:29][CH2:30][CH2:31][Si:32]([CH3:35])([CH3:34])[CH3:33])[CH2:20][O:21][CH2:22][CH2:23][Si:24]([CH3:27])([CH3:26])[CH3:25])[N:16]2[N:36]=[CH:37][CH:38]=[C:15]2[N:14]=1.[NH4+].[Cl-]>CN(C=O)C>[CH3:1][S:2][C:3]1[CH:8]=[CH:7][C:6]([O:9][C:13]2[CH:18]=[C:17]([N:19]([CH2:28][O:29][CH2:30][CH2:31][Si:32]([CH3:35])([CH3:34])[CH3:33])[CH2:20][O:21][CH2:22][CH2:23][Si:24]([CH3:27])([CH3:26])[CH3:25])[N:16]3[N:36]=[CH:37][CH:38]=[C:15]3[N:14]=2)=[CH:5][CH:4]=1

Participants

6

Reactant 4

HCID 140864-(Methylthio)phenolHCID 24758Sodium hydrideHCID 25517Ammonium ChlorideHCID 772312195-chloro-N,N-bis((2-(trimethylsilyl)ethoxy)methyl)pyrazolo[1,5-a]pyrimidin-7-amine

Product 1

HCID 667339295-(4-(methylthio)phenoxy)-N,N-bis((2-(trimethylsilyl)ethoxy)methyl)pyrazolo[1,5-a]pyrimidin-7-amineYield 919.6%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

The 4-(methylthio)phenol (280 mg, 2.0 mmol) was dissolved in dry DMF (3 mL) and NaH (88 mg, 60% in oil, 2.2 mmol) was added and the mixture was stirred at room temperature for 5 min. Then, 5-chloro-N,N-bis((2-(trimethylsilyl)ethoxy)methyl)pyrazolo[1,5-a]pyrimidin-7-amine (430 mg, 0.1 mmol) was added and the resulting mixture was heated up to 130° C. with Microwave and stirred for 30 min. After cooling to room temperature, NH4Cl (aq) was added to quench the reaction and extracted with EtOAc (50 mL×3). The combined organics were washed with water and brine and dried over Na2SO4. After concentration, the residue was purified with column (silica gel, 20% EtOAc/Hexane) gave the product 5-(4-(methylthio)phenoxy)-N,N-bis((2-(trimethylsilyl)ethoxy)methyl)pyrazolo[1,5-a]pyrimidin-7-amine (490 mg) HPLC-MS tR=2.98 min (UV254 nm); mass calculated for formula C25H40N4O3SSi2 532.2, observed LCMS m/z 533.2 (M+H).

Workup

  1. temperaturethe resulting mixture was heated up to 130° C. with Microwave
  2. stirringstirred for 30 min
  3. temperatureAfter cooling to room temperature
  4. customto quench
  5. customthe reaction
  6. extractionextracted with EtOAc (50 mL×3)
  7. washThe combined organics were washed with water and brine
  8. dry with materialdried over Na2SO4
  9. concentrationAfter concentration
  10. customthe residue was purified with column (silica gel, 20% EtOAc/Hexane)

Sources & evidence

ORD record
ord-762c50e1097d4c23b3bd3f4adfc83b15
Source dataset
uspto-grants-2013_11
Patent number
US08591943B2

Reaction notes

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