Dichloromethane → (NE,R)-2-methyl-N-[[4-[4-(trifluoromethyl)phenyl]phenyl]methylidene]propane-2-sulfinamide

HRID 2173777Notes

Reaction equation

HRID 2173777 reaction equation
[F:1][C:2]([F:18])([F:17])[C:3]1[CH:8]=[CH:7][C:6]([C:9]2[CH:14]=[CH:13][C:12]([CH:15]=O)=[CH:11][CH:10]=2)=[CH:5][CH:4]=1.[CH3:19][C:20]([S@:23]([NH2:25])=[O:24])([CH3:22])[CH3:21].ClCCl.C(=O)(O)[O-].[Na+]>[O-]CC.[Ti+4].[O-]CC.[O-]CC.[O-]CC.[Ti].CO>[CH3:19][C:20]([S@:23](/[N:25]=[CH:15]/[C:12]1[CH:13]=[CH:14][C:9]([C:6]2[CH:7]=[CH:8][C:3]([C:2]([F:18])([F:17])[F:1])=[CH:4][CH:5]=2)=[CH:10][CH:11]=1)=[O:24])([CH3:22])[CH3:21]

Participants

8

Reactant 4

HCID 6344DichloromethaneHCID 516892Sodium BicarbonateHCID 27827124'-(Trifluoromethyl)-4-biphenylcarbaldehydeHCID 10964479tert-Butylsulfinamide, (R)-(+)-

Product 1

HCID 88540239(NE,R)-2-methyl-N-[[4-[4-(trifluoromethyl)phenyl]phenyl]methylidene]propane-2-sulfinamideYield 84%

Reagents, catalysts & solvents 3

HCID 23963TitaniumCatalystHCID 76524Titanium tetraethoxideCatalystHCID 887MethanolSolvent

Procedure

A round bottom flask equipped with a condenser was charged with 4′-(trifluoromethyl)biphenyl-4-carbaldehyde (20.0 g, 79.9 mmol), (R)-(+)-2-methylpropane-2-sulfinamide (9.69 g, 79.9 mmol) and dichloromethane (400 mL). Titanium(IV) ethoxide (33.2 mL, 160 mmol) was then added, and the mixture was heated to reflux for 3 hours. Methanol (50 mL) and saturated sodium bicarbonate (10 mL) were then added to the reaction, causing the titanium salts to precipitate. This mixture was stirred for 30 minutes and then filtered, rinsing with ethyl acetate. Sodium sulfate was added to the filtrate to remove the water and then filtered a second time. The solvent was removed under reduced pressure to afford (R,E)-2-methyl-N-((4′-(trifluoromethyl)biphenyl-4-yl)methylene)propane-2-sulfinamide (23.7 g, 84%) as a white solid. 1H NMR (400 MHz, CDCl3, δ): 1.30 (s, 9H) 7.70-7.74 (m, 2H) 7.74 (s, 4H) 7.95-7.99 (m, 2H) 8.66 (s, 1H). MS (M+1): 354.1.

Workup

  1. customA round bottom flask equipped with a condenser
  2. temperaturethe mixture was heated
  3. temperatureto reflux for 3 hours
  4. customto precipitate
  5. filtrationfiltered
  6. washrinsing with ethyl acetate
  7. additionSodium sulfate was added to the filtrate
  8. customto remove the water
  9. filtrationfiltered a second time
  10. customThe solvent was removed under reduced pressure

Sources & evidence

ORD record
ord-53dbfb2869f341128625b5475b52f159
Source dataset
uspto-grants-2015_06
Patent number
US09056834B2

Reaction notes

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