Sodium hydride → HCID 67003907, compound

HRID 2095633Notes

Reaction equation

HRID 2095633 reaction equation
[CH3:1][C:2]1[C:6]([I:7])=[C:5]([CH3:8])[NH:4][N:3]=1.[H-].[Na+].CC1C=CC(S(O[CH:22]2[CH2:31][CH2:30][C:25]3([O:29][CH2:28][CH2:27][O:26]3)[CH2:24][CH2:23]2)(=O)=O)=CC=1>CN(C=O)C>[O:26]1[C:25]2([CH2:30][CH2:31][CH:22]([N:3]3[C:2]([CH3:1])=[C:6]([I:7])[C:5]([CH3:8])=[N:4]3)[CH2:23][CH2:24]2)[O:29][CH2:28][CH2:27]1

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 971153,5-Dimethyl-4-iodo-1H-pyrazoleHCID 5674891,4-Dioxaspiro[4.5]decan-8-ol, 8-(4-methylbenzenesulfonate)

Product 1

HCID 67003907HCID 67003907, compound

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Procedure

To a solution of 3,5-dimethyl-4-iodopyrazole (400.0 mg, 1.802 mmol) in DMF (7 mL, 100 mmol) was added sodium hydride (56.20 mg, 2.342 mmol), and the mixture was stirred at rt for 10 min. A solution of 1,4-dioxaspiro[4.5]dec-8-yl 4-methylbenzenesulfonate (619.1 mg, 1.982 mmol), prepared according to U.S. Pat. No. 4,360,531 example 1.B, in DMF was added, and the mixture was heated to 50° C. overnight. The material was extracted with EtOAc, and washed with water (3×). The organic layer was dry-loaded onto silica gel for column chromatography, eluting with 20-30% EtOAc/hexanes. The fractions containing the pure product were concentrated in vacuo to afford the title compound as a clear oil. 1H NMR (400 MHz, DMSO-d6): δ=1.61-1.80 (m, 6H), 1.94-2.06 (m, 2H), 2.08 (s, 3H), 2.25 (s, 3H), 3.82-3.93 (m, 4H), 4.23 (tt, J=11.5, 3.7 Hz, 1H). MS (ES+): m/z=364.07 (100) [MH+]. HPLC: tR=1.51 min (polar—3 min, UPLC-ACQUITY).

Workup

  1. temperaturethe mixture was heated to 50° C. overnight
  2. extractionThe material was extracted with EtOAc
  3. washwashed with water (3×)
  4. washeluting with 20-30% EtOAc/hexanes
  5. additionThe fractions containing the pure product
  6. concentrationwere concentrated in vacuo

Sources & evidence

ORD record
ord-7dd7d6f53a03491ba74523d3cc1f00fe
Source dataset
uspto-grants-2013_05
Patent number
US08445510B2

Reaction notes

Loading…