(S)-4-methylbenzenesulfinamide → 4-Methyl-benzenesulfinic Acid ((2R,3R)-2,3-dimethyl-hexylidene)-amide

HRID 132621Notes

Reaction equation

HRID 132621 reaction equation
[C:1]1([CH3:10])[CH:6]=[CH:5][C:4]([S@@:7]([NH2:9])=[O:8])=[CH:3][CH:2]=1.[CH3:11][C@H:12]([C@H:15]([CH3:19])[CH2:16][CH2:17][CH3:18])[CH:13]=O>C1COCC1.[Cl-].[Na+].O.[O-]CC.[Ti+4].[O-]CC.[O-]CC.[O-]CC>[CH3:11][C@H:12]([C@H:15]([CH3:19])[CH2:16][CH2:17][CH3:18])[CH:13]=[N:9][S:7]([C:4]1[CH:5]=[CH:6][C:1]([CH3:10])=[CH:2][CH:3]=1)=[O:8]

Participants

6

Reactant 2

HCID 11116285(S)-4-methylbenzenesulfinamideHCID 57444839(2R,3R)-2,3-Dimethyl-hexanal

Product 1

HCID 865979554-Methyl-benzenesulfinic Acid ((2R,3R)-2,3-dimethyl-hexylidene)-amideYield 51.7%

Reagents, catalysts & solvents 3

HCID 76524Titanium tetraethoxideCatalystHCID 8028TetrahydrofuranSolventHCID 57417360Sodium chloride; waterSolvent

Procedure

Titanium(IV) ethoxide (5.16 g, 22.6 mmol) and (S)-(+)-p-toluenesulfinamide (7.02 g, 45.2 mmol) were added to (2R,3R)-2,3-dimethyl-hexanal (2.9 g, 22.6 mmol) in dry THF (30 mL). The resulting mixture was stirred at room temperature for 18 hours and poured into a brine solution (40 mL). The slurry was rapidly stirred for 10 minutes and filtered. The filtrate was extracted into ethyl acetate, washed with brine and dried over MgSO4. The solvent was evaporated and the residue was filtered through a silica plug, eluting with 50/50 solution of hexane/ethyl acetate to afford the titled compound (3.1 g, 51.6% yield) as an oil: 1H NMR (400 MHz, CDCl3) δ ppm 0.8 (m, 6H) 1.1 (m, 4H) 1.3 (m, 3H) 1.7 (m, 1H) 2.4 (s, 3H) 2.5 (m, 1H) 7.3 (d, J=8.3 Hz, 2H) 7.5 (d, J=8.1 Hz, 2H) 8.1 (d, J=5.4 Hz, 1H). MS, m/z (relative intensity): 266 [M+1H, 100%].

Workup

  1. stirringThe slurry was rapidly stirred for 10 minutes
  2. filtrationfiltered
  3. extractionThe filtrate was extracted into ethyl acetate
  4. washwashed with brine
  5. dry with materialdried over MgSO4
  6. customThe solvent was evaporated
  7. filtrationthe residue was filtered through a silica plug
  8. washeluting with 50/50 solution of hexane/ethyl acetate

Sources & evidence

ORD record
ord-4e901b5c056e4996a8548ae3e5c5700d
Source dataset
uspto-grants-2008_06
Patent number
US07388023B2

Reaction notes

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