1,4-Dibromobenzene → N-(3-(4-bromophenyl)oxetan-3-yl)-2-methylpropane-2-sulfinamide

HRID 1047039Notes

Reaction equation

HRID 1047039 reaction equation
C([Li])CCC.Br[C:7]1[CH:12]=[CH:11][C:10]([Br:13])=[CH:9][CH:8]=1.[CH3:14][C:15]([S:18]([N:20]=[C:21]1[CH2:24][O:23][CH2:22]1)=[O:19])([CH3:17])[CH3:16]>C1COCC1>[Br:13][C:10]1[CH:11]=[CH:12][C:7]([C:21]2([NH:20][S:18]([C:15]([CH3:17])([CH3:16])[CH3:14])=[O:19])[CH2:24][O:23][CH2:22]2)=[CH:8][CH:9]=1

Participants

5

Reactant 3

HCID 78041,4-DibromobenzeneHCID 468399952-Methyl-N-(oxetan-3-ylidene)propane-2-sulfinamideHCID 178418339Butyllithium

Product 1

HCID 67067894N-(3-(4-bromophenyl)oxetan-3-yl)-2-methylpropane-2-sulfinamideYield 96%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

A solution of n-butyllithium in hexanes (1.65M, 4.92 mL) was added dropwise to a solution of 1,4-dibromobenzene (2.05 g) in THF (25 mL) dropwise over the course of 30 min at −78° C. The resulting mixture was stirred at the same temperature for 1 h. To the mixture was added a solution of 2-methyl-N-oxetan-3-ylidenepropane-2-sulfinamide (1.02 g) in THF (5 mL) dropwise over the course of 30 min at −78° C. The reaction mixture was stirred for an additional 30 min. at −78° C. then allowed to warm to room temperature. After being stirred for 1 h at room temperature, the reaction mixture was quenched by addition of saturated ammonium chloride aqueous solution. The aqueous layer was extracted with ethyl acetate. The combined organic layer was washed with saturated sodium bicarbonate solution then brine. The organics were dried over anhydrous sodium sulfate and concentrated under reduced pressure. Purification by column chromatography (50-100% ethyl acetate in hexanes then 5% methanol in ethyl acetate) gave the product (1.85 g, 96%). 1HNMR (CDCl3) 400 MHz δ: 7.55 (d, J=8.7 Hz, 2H), 7.27 (d, J=8.7 Hz, 2H), 5.16 (d, J=6.9 Hz, 1H), 5.06 (d, J=6.9 Hz, 1H), 5.02 (d, J=6.9 Hz, 1H), 4.94 (d, J=6.9 Hz, 1H), 4.05 (br s, 1H), 1.22 (s, 9H). LCMS: 332, 334 [M+H].

Workup

  1. stirringThe reaction mixture was stirred for an additional 30 min. at −78° C.
  2. stirringAfter being stirred for 1 h at room temperature
  3. customthe reaction mixture was quenched by addition of saturated ammonium chloride aqueous solution
  4. extractionThe aqueous layer was extracted with ethyl acetate
  5. washThe combined organic layer was washed with saturated sodium bicarbonate solution
  6. dry with materialThe organics were dried over anhydrous sodium sulfate
  7. concentrationconcentrated under reduced pressure
  8. customPurification by column chromatography (50-100% ethyl acetate in hexanes

Sources & evidence

ORD record
ord-4cf6a7d429ed4b12b67ae0d3a251eae1
Source dataset
uspto-grants-2013_10
Patent number
US08569331B2

Reaction notes

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