Ammonium Chloride → HCID 21189420, compound

HRID 1068552Notes

Reaction equation

HRID 1068552 reaction equation
[Cl:1][C:2]1[CH:19]=[C:18]([F:20])[C:17]([N+:21]([O-])=O)=[CH:16][C:3]=1[C:4]([O:6][CH:7]([C:13]([CH3:15])=[CH2:14])[C:8]([O:10][CH2:11][CH3:12])=[O:9])=[O:5].[NH4+].[Cl-]>O1CCCC1.[Zn]>[Cl:1][C:2]1[CH:19]=[C:18]([F:20])[C:17]([NH2:21])=[CH:16][C:3]=1[C:4]([O:6][CH:7]([C:13]([CH3:15])=[CH2:14])[C:8]([O:10][CH2:11][CH3:12])=[O:9])=[O:5]

Participants

5

Reactant 2

HCID 25517Ammonium ChlorideHCID 21189419HCID 21189419, compound

Product 1

HCID 21189420HCID 21189420, compound

Reagents, catalysts & solvents 2

HCID 23994ZincCatalystHCID 8028TetrahydrofuranSolvent

Procedure

Ethyl 2-(2-chloro-4-fluoro-5-nitrobenzoyl)oxy-3-methyl-3-butenoate (3.5 g, 10.13 mmoles) was added to a mixture of 2N NH4Cl (80 mL) in tetrahydrofuran (THF) (100 mL) at room temperature. The above mixture was cooled in an ice cold water bath and zinc dust (1.4 g, 21.4 mmoles) was added. The mixture was then stirred at room temperature for 2 hrs. The solid was removed by suction-filtration and the filtrate was concentrated under reduced pressure to give a black oily product. The crude product was subjected to a column silica gel chromatography and eluted with EtOAc/hexane (1:4) to give ethyl 2-(2-chloro-4-fluoro-5-aminobenzoyl)oxy-3-methyl-3-butenoate, 0.5 g (yield =45.6%), as an oily product. An 1H nmr (CDCl3) showed the desired product: δ 7.42 (d, 1H), 7.11 (d, 1H), 5.60 (s, 1H), 5.29 (s, 1H), 5.17 (s, 1H), 4.25 (q, 2H), 3.90 (br, 2H), 1.91 (s, 3H), 1.29 (t, 3H).

Workup

  1. temperatureThe above mixture was cooled in an ice cold water bath
  2. customThe solid was removed by suction-filtration
  3. concentrationthe filtrate was concentrated under reduced pressure
  4. customto give a black oily product
  5. washeluted with EtOAc/hexane (1:4)
  6. customto give

Sources & evidence

ORD record
ord-0355ad28a66643b38c922f05fd320649
Source dataset
uspto-grants-2001_06
Patent number
US06251829B1

Reaction notes

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