Hydrochloric Acid → 3,5-Dichloro-4-(1-methyl-2,2,3,3,3-pentafluoropropoxy)aniline

HRID 1637246Notes

Reaction equation

HRID 1637246 reaction equation
C(O)C.O.[Cl:5][C:6]1[CH:7]=[C:8]([N+:23]([O-])=O)[CH:9]=[C:10]([Cl:22])[C:11]=1[O:12][CH:13]([CH3:21])[C:14]([F:20])([F:19])[C:15]([F:18])([F:17])[F:16].Cl>C(O)C.[Fe]>[Cl:5][C:6]1[CH:7]=[C:8]([CH:9]=[C:10]([Cl:22])[C:11]=1[O:12][CH:13]([CH3:21])[C:14]([F:19])([F:20])[C:15]([F:17])([F:18])[F:16])[NH2:23]

Participants

6

Reactant 3

HCID 313Hydrochloric Acid2×HCID 19096565Water ethanolHCID 193488673,5-Dichloro-4-(1-methyl-2,2,3,3,3-pentafluoropropoxy)nitrobenzene

Product 1

HCID 154518823,5-Dichloro-4-(1-methyl-2,2,3,3,3-pentafluoropropoxy)anilineYield 86.8%

Reagents, catalysts & solvents 2

HCID 23925IronCatalystHCID 702EthanolSolvent2×

Procedure

4.0 g iron filings, 240 mL of a 2/1 ethanol-water mixture, and 4.86 g 3,5-dichloro-4-(1-methyl-2,2,3,3,3-pentafluoropropoxy)nitrobenzene was stirred vigorously and heated under reflux while 1.0 mL conc. HCl in 2 mL ethanol was added dropwise. After one hour 2.0 mL conc. HCl in 2.0 mL ethanol was added and reflux was maintained overnight (about 15 hours). The mixture was filtered hot through Celite. The filtrate was concentrated under vacuum before being partitioned in saturated sodium bicarbonate and diethyl ether. The layers were separated and the aqueous layer was extracted with diethyl ether. The combined organics were washed with brine, dried (MgSO4), filtered, and concentrated to give 3.86 g of 3,5-Dichloro-4-(1-methyl-2,2,3,3,3-pentafluoropropoxy)aniline as an amber oil. 1H NMR and GC/MS confirm pure product. Anal. calcd C10H8Cl2F5NO: C, 37.06; H, 2.49; N, 4.32. Found: C, 38.71; H, 2.51; N, 4.65.

Workup

  1. temperatureheated
  2. additionwas added dropwise
  3. temperaturereflux
  4. temperaturewas maintained overnight (about 15 hours)
  5. filtrationThe mixture was filtered hot through Celite
  6. concentrationThe filtrate was concentrated under vacuum
  7. custombefore being partitioned in saturated sodium bicarbonate
  8. customThe layers were separated
  9. extractionthe aqueous layer was extracted with diethyl ether
  10. washThe combined organics were washed with brine
  11. dry with materialdried (MgSO4)
  12. filtrationfiltered
  13. concentrationconcentrated

Sources & evidence

ORD record
ord-e94ee833bdcb4f788d3a3bd545cece8b
Source dataset
uspto-grants-2000_03
Patent number
US06040345

Reaction notes

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