(S)-4-methylbenzenesulfinamide → (NE,S)-4-methyl-N-[(5-nitro-2-propan-2-ylsulfanylphenyl)methylidene]benzenesulfinamide

HRID 272784Notes

Reaction equation

[CH:1]([S:4][C:5]1[CH:12]=[CH:11][C:10]([N+:13]([O-:15])=[O:14])=[CH:9][C:6]=1[CH:7]=O)([CH3:3])[CH3:2].[C:16]1([CH3:25])[CH:21]=[CH:20][C:19]([S@@:22]([NH2:24])=[O:23])=[CH:18][CH:17]=1>C(Cl)Cl>[CH:1]([S:4][C:5]1[CH:12]=[CH:11][C:10]([N+:13]([O-:15])=[O:14])=[CH:9][C:6]=1/[CH:7]=[N:24]/[S@:22]([C:19]1[CH:20]=[CH:21][C:16]([CH3:25])=[CH:17][CH:18]=1)=[O:23])([CH3:3])[CH3:2]

Participants

Conditions

Temperature: 75 °C

Procedure

To 2-(isopropylthio)-5-nitrobenzaldehyde (234 mg, 1.0 mmol) and (S)-(+)-p-toluenesulfinamide (161 mg, 1.0 mmol) in CH2Cl2 (10 mL) was added Ti(OEt)4 (25% tech, 0.54 mL). The mixture was heated at 75° C. for 3.0 h. TLC indicated a clean reaction. Solvent was removed and the residue was redissolved in EtOAc, under stirring sat. Na2SO4 solution was added and the slurry was stirred at rt for 30 min before it was filtered through a pad of Celite®. The filtrate was extracted with EtOAc, washed with brine and dried over Na2SO4. After evaporation of solvent, 98A (320 mg, 88% yield) was obtained as a solid used for next step without further purification. 1H NMR (400 MHz, CDCl3) δ ppm 1.34 (d, J=6.59 Hz, 6H) 2.34 (s, 3H) 3.51-3.61 (m, 1H) 7.27 (d, J=7.91 Hz, 2H) 7.45 (d, J=8.79 Hz, 1H) 7.59 (d, J=8.35 Hz, 2H) 8.14 (dd, J=8.79, 2.64 Hz, 1H) 8.69 (d, J=2.64 Hz, 1H) 9.17 (s, 1H).

Workup

customa clean reaction
customSolvent was removed
dissolutionthe residue was redissolved in EtOAc, under stirring sat. Na2SO4 solution
additionwas added
filtrationwas filtered through a pad of Celite®
extractionThe filtrate was extracted with EtOAc
washwashed with brine
dry with materialdried over Na2SO4
customAfter evaporation of solvent

Sources & evidence

ORD record: ord-09d5f0f613394bbbab5bbdff444d2db2
Source dataset: uspto-grants-2008_11
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07456195B2

Reaction notes

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