Sodium hydride → tert-butyl 3-(4-iodo-1H-pyrazol-1-yl)azetidine-1-carboxylate

HRID 253996Notes

Reaction equation

HRID 253996 reaction equation
[I:1][C:2]1[CH:3]=[N:4][NH:5][CH:6]=1.[H-].[Na+].CS(O[CH:14]1[CH2:17][N:16]([C:18]([O:20][C:21]([CH3:24])([CH3:23])[CH3:22])=[O:19])[CH2:15]1)(=O)=O>CN(C=O)C>[I:1][C:2]1[CH:3]=[N:4][N:5]([CH:14]2[CH2:15][N:16]([C:18]([O:20][C:21]([CH3:24])([CH3:23])[CH3:22])=[O:19])[CH2:17]2)[CH:6]=1

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 770224-IodopyrazoleHCID 10753243Tert-butyl 3-(methanesulfonyloxy)azetidine-1-carboxylate

Product 1

HCID 58431448tert-butyl 3-(4-iodo-1H-pyrazol-1-yl)azetidine-1-carboxylateYield 62%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

At 0° C., a solution of 4-iodopyrazole (3.0 g, 15.46 mmol) in DMF (40 mL) was treated with NaH (60% mineral oil dispersion, 1.11 g, 46.39 mmol) in portions. The mixture stirred for 30 minutes, followed by the slow addition of 1-(tert-butoxycarbonyl)azetidin-3-yl methanesulfonate (5.0 g, 20.1 mmol). The reaction mixture was warmed to RT and then heated at 100° C. for 5 hours. The reaction mixture was poured into ice cold water, stirred for 30 minutes, and resulting precipitate collected by filtration and dried. The resulting residue washed with pentane and dried to obtain tert-butyl 3-(4-iodo-1H-pyrazol-1-yl)azetidine-1-carboxylate (3.3 g, 62% yield); 1H-NMR (400 MHz, CDCl3): 7.58 (s, 1H), 7.57 (s, 1H), 5.07-5.0 (m, 1H), 4.39-4.34 (m, 2H), 4.29-4.25 (dd, 2H), 1.45 (s, 9H).

Workup

  1. temperatureheated at 100° C. for 5 hours
  2. additionThe reaction mixture was poured into ice cold water
  3. stirringstirred for 30 minutes
  4. customresulting precipitate
  5. filtrationcollected by filtration
  6. customdried
  7. washThe resulting residue washed with pentane
  8. customdried

Sources & evidence

ORD record
ord-8b7511e84a8c4e1c944286f160b798bf
Source dataset
uspto-grants-2011_01
Patent number
US07872031B2

Reaction notes

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