Diethyl Ether → N-(1-(1,5-dimethyl-1H-pyrazol-4-yl)propyl)-2-methylpropane-2-sulfinamide

HRID 2425542Notes

Reaction equation

HRID 2425542 reaction equation
[CH3:1][N:2]1[C:6]([CH3:7])=[C:5](/[CH:8]=[N:9]/[S:10]([C:12]([CH3:15])([CH3:14])[CH3:13])=[O:11])[CH:4]=[N:3]1.[CH3:16][CH2:17][Mg+].[Br-].CCOCC>C(Cl)Cl>[CH3:1][N:2]1[C:6]([CH3:7])=[C:5]([CH:8]([NH:9][S:10]([C:12]([CH3:15])([CH3:14])[CH3:13])=[O:11])[CH2:16][CH3:17])[CH:4]=[N:3]1

Participants

5

Reactant 3

HCID 3283Diethyl EtherHCID 87300965(NE)-N-[(1,5-dimethylpyrazol-4-yl)methylidene]-2-methylpropane-2-sulfinamideHCID 178461630HCID 178461630, compound

Product 1

HCID 67182419N-(1-(1,5-dimethyl-1H-pyrazol-4-yl)propyl)-2-methylpropane-2-sulfinamideYield 96%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a solution of (E)-N-((1,5-dimethyl-1H-pyrazol-4-yl)methylene)-2-methylpropane-2-sulfinamide (Step A5A) (600 mg, 2.64 mmol) in CH2Cl2 (15 ml) was added a 3.0 M solution of EtMgBr in ether (1.76 ml, 5.28 mmol) at −48° C. under nitrogen. After being stirred for 120 min, the reaction mixture was allowed to warm to rt slowly over 2 h and further stirred for 15 h at rt. The reaction was quenched by addition of sat. NH4Cl aq., diluted with water, and the aqueous layer was extracted with CH2Cl2 3 times. The combined organic extracts were dried over Na2SO4 and concentrated in vacuo. The crude product was purified by silica gel column chromatography (CH2Cl2: MeOH=50:1 to 20:1) to give the desired product as a pale yellow oil (650 mg, >96% yield). 1H NMR (270 MHz, CDCl3) δ 0.87 (3H, t, J=5.4 Hz), 1.17 (9H, s), 1.77-1.85 (2H, m), 2.25 (3H, s), 3.78 (3H, s), 3.31 (1H, brs), 4.16-4.22 (1H, m), 7.31 (1H, s).

Workup

  1. stirringfurther stirred for 15 h at rt
  2. customThe reaction was quenched by addition of sat. NH4Cl aq.
  3. additiondiluted with water
  4. extractionthe aqueous layer was extracted with CH2Cl2 3 times
  5. dry with materialThe combined organic extracts were dried over Na2SO4
  6. concentrationconcentrated in vacuo
  7. customThe crude product was purified by silica gel column chromatography (CH2Cl2: MeOH=50:1 to 20:1)

Sources & evidence

ORD record
ord-49892754f3c34f14913ed92718eb2b13
Source dataset
uspto-grants-2011_06
Patent number
US07964732B2

Reaction notes

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