Vinylidene chloride → HCID 58966440, compound

HRID 2075113Notes

Reaction equation

HRID 2075113 reaction equation
CS(O)(=O)=O.[Br:6][C:7]1[CH:14]=[CH:13][C:12]([C:15]([F:18])([F:17])[F:16])=[CH:11][C:8]=1[CH2:9][NH2:10].[OH-].[Na+].ClC(Cl)=C.[F:25][C:26]([F:40])([F:39])[C:27]1[CH:28]=[C:29]([CH:32]=[C:33]([C:35]([F:38])([F:37])[F:36])[CH:34]=1)[CH:30]=O.C(=O)([O-])[O-].[K+].[K+]>COC(C)(C)C>[F:25][C:26]([F:39])([F:40])[C:27]1[CH:28]=[C:29]([CH:32]=[C:33]([C:35]([F:38])([F:36])[F:37])[CH:34]=1)[CH2:30][NH:10][CH2:9][C:8]1[CH:11]=[C:12]([C:15]([F:16])([F:17])[F:18])[CH:13]=[CH:14][C:7]=1[Br:6]

Participants

7

Reactant 5

HCID 6366Vinylidene chlorideHCID 11430Potassium CarbonateHCID 14798Sodium HydroxideHCID 1362473,5-Bis(trifluoromethyl)benzaldehydeHCID 86614962HCID 86614962, compound

Product 1

HCID 58966440HCID 58966440, compoundYield 95%

Reagents, catalysts & solvents 1

HCID 15413tert-Butyl methyl etherSolvent

Procedure

To the product from step A (640 g in methyl-tert-butyl-ether (4.3 L) was added 1N sodium hydroxide (3.4 L). The mixture was stirred until 2 clear layers formed. The organics were washed with brine, dried over sodium sulfate, filtered, and concentrated to the free amine (460 g). The free amine (460 g, 1.81 mol) was taken into 1,1-dichloroethene (4.3 L) and 3,5-bis(trifluoromethyl)benzaldehyde (438 g, 1.81 mol) was added. The mixture was cooled in an ice-water bath and NaBH(CH3CO2)3 (767 g, 3.62 mol) was added. The mixture was stirred for 16 hours at which point LC analysis revealed complete reaction. Saturated aq potassium carbonate was added until pH 8 was reached. Added water (1 L) and filtered undissolved salts. The layers were separated and the aqueous layer was washed with 1,1-dichloroethene (2 L). The combined organics were washed with brine, dried over sodium sulfate, filtered, and concentrated (880 g product, >95% yield). 1H-NMR of HCl salt (CD3OD) δ 8.23 (s, 2H), 8.09 (s, 1H), 7.98 (s, 1H), 7.93 (d, 8.3 Hz, 1H), 7.67 (d, 8.3 Hz, 1H) 4.61 (s, 2H), 4.56 (s, 2H). Mass Spec (ESI): M+1=480.1

Workup

  1. customformed
  2. washThe organics were washed with brine
  3. dry with materialdried over sodium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated to the free amine (460 g)
  6. additionwas added
  7. temperatureThe mixture was cooled in an ice-water bath
  8. stirringThe mixture was stirred for 16 hours at which point LC analysis
  9. customreaction
  10. filtrationAdded water (1 L) and filtered undissolved salts
  11. customThe layers were separated
  12. washthe aqueous layer was washed with 1,1-dichloroethene (2 L)
  13. washThe combined organics were washed with brine
  14. dry with materialdried over sodium sulfate
  15. filtrationfiltered
  16. concentrationconcentrated (880 g product, >95% yield)

Sources & evidence

ORD record
ord-ad5513c84bda44b6b68b0bd14fd7f12b
Source dataset
uspto-grants-2011_04
Patent number
US07919506B2

Reaction notes

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