Acetic Acid → 3,5-dichloro-2-fluoro-4-(1,1,2,3,3,3-hexafluoropropoxy)-N-ethyl aniline

HRID 325020Notes

Reaction equation

HRID 325020 reaction equation
[Cl:1][C:2]1[C:3]([F:20])=[C:4]([CH:6]=[C:7]([Cl:19])[C:8]=1[O:9][C:10]([F:18])([F:17])[CH:11]([F:16])[C:12]([F:15])([F:14])[F:13])[NH2:5].[BH4-].[Na+].O.C(=O)([O-])[O-].[Na+].[Na+].[C:30](O)(=O)[CH3:31]>>[Cl:1][C:2]1[C:3]([F:20])=[C:4]([CH:6]=[C:7]([Cl:19])[C:8]=1[O:9][C:10]([F:17])([F:18])[CH:11]([F:16])[C:12]([F:14])([F:15])[F:13])[NH:5][CH2:30][CH3:31]

Participants

6

Reactant 5

HCID 176Acetic AcidHCID 962WaterHCID 10340Sodium CarbonateHCID 4311764Sodium borohydrideHCID 154046083,5-Dichloro-2-fluoro-4-(1,1,2,3,3,3-hexafluoropropoxy)aniline

Product 1

HCID 155103103,5-dichloro-2-fluoro-4-(1,1,2,3,3,3-hexafluoropropoxy)-N-ethyl aniline

Procedure

To a solution of 0.28 g 3,5-dichloro-2-fluoro-4-(1,1,2,3,3,3-hexafluoropropoxy) aniline in 8 mL glacial acetic acid at room temperature under an atmosphere of nitrogen was slowly added 0.31 g sodium borohydride. The addition was carried out over a 1.5 hour period through a solid addition funnel between 25-34° C. with ice water cooling. The mixture was stirred at room temperature over night. Then the reaction mixture was added to 80 mL water and the pH was carefully adjusted to 7 by adding solid sodium carbonate. The product was extracted with 80 mL ethyl acetate. The organic layer was separated, washed with brine solution, separated, and dried over magnesium sulfate. The magnesium sulfate was removed by filtration, and the filtrate was concentrated under vacuum to give a brown oil 0.29 g. The product was chromatographed using a Michel-Miller low pressure silica gel column eluted with 9:1 heptane/ethyl acetate. Like fractions were pooled and concentrated under vacuum to give 0.19 g of a tan oil. 1H-NMR d 1.28 (t, 3H), 3.17 (q, 4H), 3.95 (bs, 1H), 4.94-5.21 (md, 1H), 6.59 (d, 1H). Anal. calcd C11H8Cl2F7N: C, 35.31; H, 2.16; N, 3.74. Found: C, 35.32; H, 2.14; N, 3.74.

Workup

  1. customat room temperature
  2. additionThe addition
  3. extractionThe product was extracted with 80 mL ethyl acetate
  4. customThe organic layer was separated
  5. washwashed with brine solution
  6. customseparated
  7. dry with materialdried over magnesium sulfate
  8. customThe magnesium sulfate was removed by filtration
  9. concentrationthe filtrate was concentrated under vacuum

Sources & evidence

ORD record
ord-b58368a96f9c4fd28f62edf0f389162b
Source dataset
uspto-grants-2001_04
Patent number
US06221912B1

Reaction notes

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