tert-Butylsulfinamide, (R)-(+)- → HCID 89183665, compound

HRID 1626099Notes

Reaction equation

HRID 1626099 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([N:8]2[CH:12]=[C:11]([C:13](=O)[CH3:14])[CH:10]=[N:9]2)[CH:5]=[CH:6][CH:7]=1.[CH3:16][C:17]([S@:20]([NH2:22])=[O:21])([CH3:19])[CH3:18]>O1CCCC1.[O-]CC.[Ti+4].[O-]CC.[O-]CC.[O-]CC>[Br:1][C:2]1[CH:3]=[C:4]([N:8]2[CH:12]=[C:11](/[C:13](=[N:22]/[S@@:20]([C:17]([CH3:19])([CH3:18])[CH3:16])=[O:21])/[CH3:14])[CH:10]=[N:9]2)[CH:5]=[CH:6][CH:7]=1

Participants

5

Reactant 2

HCID 10964479tert-Butylsulfinamide, (R)-(+)-HCID 71008951HCID 71008951, compound

Product 1

HCID 89183665HCID 89183665, compoundYield 60%

Reagents, catalysts & solvents 2

HCID 76524Titanium tetraethoxideCatalystHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
25 °C

Procedure

A solution of 1-[1-(3-bromo-phenyl)-1H-pyrazol-4-yl]-ethanone (1.0 g, 4.53 mmol), (R)-2-methylpropane-2-sulfinic acid amide (0.66 g, 5.43 mmol) and titanium (IV) ethoxide (2.1 ml, 9.96 mmol) in tetrahydrofuran (20 ml) was refluxed for 12 hours. The reaction mixture was cooled to 25° C., quenched with brine (20 ml), and extracted with ethyl acetate (5×20 ml). The combined organic layers were washed with brine (50 ml), dried over sodium sulphate, and evaporated at reduced pressure. The crude material thus obtained was purified by column chromatography on silica gel using a gradient of hexane/ethyl acetate=85:15 to 80:20 as the eluent to give the (R)-2-methyl-propane-2-sulfinic acid [1-[1-(3-bromo-phenyl)-1H-pyrazol-4-yl]-eth-(E)-ylidene]-amide (1.0 g, 60% yield) as a yellow solid. MS (ISP): m/z=368.0 [M+H]+.

Workup

  1. customquenched with brine (20 ml)
  2. extractionextracted with ethyl acetate (5×20 ml)
  3. washThe combined organic layers were washed with brine (50 ml)
  4. dry with materialdried over sodium sulphate
  5. customevaporated at reduced pressure
  6. customThe crude material thus obtained
  7. customwas purified by column chromatography on silica gel using a gradient of hexane/ethyl acetate=85:15 to 80:20 as the eluent

Sources & evidence

ORD record
ord-904c7943a1f64b39949873ec08818b9c
Source dataset
uspto-grants-2014_07
Patent number
US08785436B2

Reaction notes

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