Triethylamine → (5-ethyl-2-(1-methyl-4-nitro-1H-pyrazol-5-yl)-1,3-dioxan-5-yl)methyl methanesulfonate

HRID 521874Notes

Reaction equation

HRID 521874 reaction equation
[CH2:1]([C:3]1([CH2:18][OH:19])[CH2:8][O:7][CH:6]([C:9]2[N:13]([CH3:14])[N:12]=[CH:11][C:10]=2[N+:15]([O-:17])=[O:16])[O:5][CH2:4]1)[CH3:2].CCN(CC)CC.[CH3:27][S:28](Cl)(=[O:30])=[O:29]>C(Cl)Cl.Cl>[CH3:27][S:28]([O:19][CH2:18][C:3]1([CH2:1][CH3:2])[CH2:4][O:5][CH:6]([C:9]2[N:13]([CH3:14])[N:12]=[CH:11][C:10]=2[N+:15]([O-:17])=[O:16])[O:7][CH2:8]1)(=[O:30])=[O:29]

Participants

6

Reactant 3

HCID 8471TriethylamineHCID 31297Methanesulfonyl chlorideHCID 86713820(5-ethyl-2-(1-methyl-4-nitro-1H-pyrazol-5-yl)-1,3-dioxan-5-yl)methanol2×

Product 1

HCID 86713822(5-ethyl-2-(1-methyl-4-nitro-1H-pyrazol-5-yl)-1,3-dioxan-5-yl)methyl methanesulfonate

Reagents, catalysts & solvents 2

HCID 313Hydrochloric AcidSolventHCID 6344DichloromethaneSolvent2×

Procedure

To a solution of (5-ethyl-2-(1-methyl-4-nitro-1H-pyrazol-5-yl)-1,3-dioxan-5-yl)methanol (trans isomer) (610 mg, 2.25 mmol, intermediate 66) in dry DCM (15 mL) at 0° C. was added Et3N (0.45 mL, 3.38 mmol) followed by methanesulfonyl chloride (0.21 mL, 2.70 mmol). The reaction mixture was slowly warmed to room temperature over 1.5 hr. The mixture was re-cooled to 0° C. and diluted with aqueous 1 M HCl (10 mL) and DCM (20 mL). The organic layer was washed with aqueous saturated NaHCO3 (15 mL) and water (15 mL), separated, dried over Na2SO4 and concentrated under reduced pressure to give (5-ethyl-2-(1-methyl-4-nitro-1H-pyrazol-5-yl)-1,3-dioxan-5-yl)methyl methanesulfonate as a white solid (816 mg, quantitative). 1H NMR (400 MHz, CDCl3) δ 8.01 (s, 1H), 6.38 (s, 1H), 4.14 (s, 3H), 4.05-3.88 (m, 6H), 3.22-2.92 (m, 3H), 1.96 (q, J=7.6 Hz, 2H), 1.03 (t, J=7.6 Hz, 3H).

Workup

  1. temperatureThe mixture was re-cooled to 0° C.
  2. washThe organic layer was washed with aqueous saturated NaHCO3 (15 mL) and water (15 mL)
  3. customseparated
  4. dry with materialdried over Na2SO4
  5. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-4962f91b115f424497fdcc4978a9a999
Source dataset
uspto-grants-2016_05
Patent number
US09328106B2

Reaction notes

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