Tert-Butanesulfinamide → N-[(3-bromophenyl)(2-cyanophenyl)methylene]-2-methylpropane-2-sulfinamide

HRID 2264720Notes

Reaction equation

HRID 2264720 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([CH:15]=[CH:16][CH:17]=1)[C:5]([C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][C:8]=1[C:13]#[N:14])=O.[CH3:18][C:19]([S:22]([NH2:24])=[O:23])([CH3:21])[CH3:20]>O1CCCC1.CO.C(=O)(O)[O-].[Na+].C(OCC)(=O)C.[O-]CC.[Ti+4].[O-]CC.[O-]CC.[O-]CC>[Br:1][C:2]1[CH:3]=[C:4]([C:5]([C:7]2[CH:12]=[CH:11][CH:10]=[CH:9][C:8]=2[C:13]#[N:14])=[N:24][S:22]([C:19]([CH3:21])([CH3:20])[CH3:18])=[O:23])[CH:15]=[CH:16][CH:17]=1

Participants

8

Reactant 2

HCID 3382465Tert-ButanesulfinamideHCID 247227443-Bromo-2'-cyanobenzophenone

Product 1

HCID 72335434N-[(3-bromophenyl)(2-cyanophenyl)methylene]-2-methylpropane-2-sulfinamideYield 66.4%

Reagents, catalysts & solvents 5

HCID 76524Titanium tetraethoxideCatalystHCID 516892Sodium BicarbonateCatalystHCID 887MethanolSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
50 °C

Procedure

To a solution of titanium (IV) ethoxide (3.48 g, 15.3 mmol) in tetrahydrofuran (14.0 mL) was added 3-bromo-2′-cyanobenzophenone (2.00, 7.0 mmol). After stirring for two minutes, 2-methyl-2-propanesulfinamide (0.93 g, 7.68 mmol) was added. The mixture was refluxed for 13 hours and heated at 50° C. for 31 hours. After cooling to ambient temperature, the mixture was diluted with methanol (15 mL) and treated with saturated aqueous sodium bicarbonate solution (15 drops) to form a gelatinous precipitate. The material was further diluted with ethyl acetate and vacuum filtered through a pad of sodium sulfate to remove the precipitate. The filtrate was concentrated to a crude oil that was purified by flash chromatography on silica gel with 10% acetonitrile/dichloromethane and triturated with hexane/ethyl acetate to give the title compound as a yellow solid (1.81 g, 66%). 1H NMR (300 MHz, DMSO-d6) δ 7.98 (d, J=7.7 Hz, 1 H), 7.87-7.79 (m, 2 H), 7.72-7.66 (m, 2 H), 7.64-7.43 (m, 3 H), 1.27 (s, 9 H).

Workup

  1. temperatureThe mixture was refluxed for 13 hours
  2. temperatureAfter cooling to ambient temperature
  3. customto form a gelatinous precipitate
  4. filtrationfiltered through a pad of sodium sulfate
  5. customto remove the precipitate
  6. concentrationThe filtrate was concentrated to a crude oil that
  7. customwas purified by flash chromatography on silica gel with 10% acetonitrile/dichloromethane
  8. customtriturated with hexane/ethyl acetate

Sources & evidence

ORD record
ord-df8fce085d324063aa3d6fa306ce48f6
Source dataset
uspto-grants-2010_12
Patent number
US07855213B2

Reaction notes

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