Dichloromethane → HCID 12171905, compound

HRID 2402126Notes

Reaction equation

HRID 2402126 reaction equation
[Cl:1][C:2]1[CH:9]=[CH:8][C:5]([CH:6]=O)=[CH:4][CH:3]=1.[CH3:10][C:11]([S@@:14]([NH2:16])=[O:15])([CH3:13])[CH3:12].CC([S@](N)=O)(C)C.C(Cl)Cl>O1CCCC1.CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-].[Ti+4].O>[Cl:1][C:2]1[CH:9]=[CH:8][C:5](/[CH:6]=[N:16]/[S:14]([C:11]([CH3:13])([CH3:12])[CH3:10])=[O:15])=[CH:4][CH:3]=1

Participants

8

Reactant 4

HCID 6344DichloromethaneHCID 77264-ChlorobenzaldehydeHCID 10964479tert-Butylsulfinamide, (R)-(+)-HCID 11355477tert-Butylsulfinamide, (S)-(-)-

Product 1

HCID 12171905HCID 12171905, compoundYield 139%

Reagents, catalysts & solvents 3

HCID 11026Titanium isopropoxideCatalystHCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a solution of 4-chlorobenzaldehyde (2.88 g, 20.5 mmol), (S)-(−)-2-methyl-2-propanesulfinamide (1.40 g, 11.6 mmol), and (R)-(+)-2-methyl-2-propanesulfinamide (1.40 g, 11.6 mmol) in anhydrous tetrahydrofuran (30.0 mL) under nitrogen atmosphere was added titanium tetraisopropoxide (6.00 mL, 20.3 mmol) dropwise. The clear solution was stirred at room temperature for 3 hours. Methylene chloride (200 mL) and water (2.0 mL) were added and the mixture was stirred at room temperature for 1 hour. The suspension was filtered through Celite and washed with DCM. The filtrate was concentrated in vacuo and purified by column chromatography (gradient elution: 0-20% EtOAc/hexane) to afford N-[(E)-(4-chlorophenyl)methylene]-2-methylpropane-2-sulfinamide (3.93 g, yield 78.7%). LCMS: (FA) ES+ 244; 1H NMR (400 MHz, CDCl3) δ 8.55 (s, 1H), 7.78-7.80 (d, 2H, J=8.53 Hz), 7.44-7.47 (d, 2H, J=8.53 Hz), 1.26 (s, 9H).

Workup

  1. stirringthe mixture was stirred at room temperature for 1 hour
  2. filtrationThe suspension was filtered through Celite
  3. washwashed with DCM
  4. concentrationThe filtrate was concentrated in vacuo
  5. custompurified by column chromatography (gradient elution: 0-20% EtOAc/hexane)

Sources & evidence

ORD record
ord-62ce8f45aeea4bada5b1b1bae6d1daf9
Source dataset
uspto-grants-2014_08
Patent number
US08796271B2

Reaction notes

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