Water → Benzenamine, 4-chloro-2-fluoro-5-(2-propynyloxy)-

HRID 1731473Notes

Reaction equation

HRID 1731473 reaction equation
[Cl:1][C:2]1[C:7]([O:8][CH2:9][C:10]#[CH:11])=[CH:6][C:5]([N+:12]([O-])=O)=[C:4]([F:15])[CH:3]=1.O>C(O)(=O)C.[Fe]>[Cl:1][C:2]1[C:7]([O:8][CH2:9][C:10]#[CH:11])=[CH:6][C:5]([NH2:12])=[C:4]([F:15])[CH:3]=1

Participants

5

Reactant 2

HCID 962WaterHCID 13281441HCID 13281441, compound

Product 1

HCID 13272927Benzenamine, 4-chloro-2-fluoro-5-(2-propynyloxy)-Yield 72.6%

Reagents, catalysts & solvents 2

HCID 23925IronCatalystHCID 176Acetic AcidSolvent2×

Conditions

Temperature
90 °C

Procedure

A suspension of electrolytic iron powder (3.5 g) in a 5% aqueous acetic acid solution (5 ml) was heated to 90° C., and a solution of 4-chloro-2-fluoro-5-(2-propynyloxy)nitrobenzene (5.7 g) in acetic acid (40 ml) was dropwise added thereto at the same temperature. The resultant mixture was stirred at 90°-105° C. for 1 hour and allowed to cool to room temperature. Water (200 ml) was added thereto. Insoluble materials were filtered off, and the filtrate was neutralized, followed by extraction with ethyl acetate. The extract was dried over anhydrous magnesium sulfate and concentrated. The residue was washed with petroleum ether and carbon tetrachloride to give 3.6 g of 4-chloro-2-fluoro-5-(2-propynyloxy)aniline. M.P. 61.0°-61.5° C. NMR (CDCl3) δ (ppm): 2.5 (1H, t, J=2 Hz), 3.4-4.2 (2H, m, J=16 Hz), 4.15 (2H, d, J=2 Hz), 6.5 (1H, d, J=8 Hz), 6.95 (1H, d, J=10 Hz).

Workup

  1. temperatureto cool to room temperature
  2. filtrationInsoluble materials were filtered off
  3. extractionfollowed by extraction with ethyl acetate
  4. dry with materialThe extract was dried over anhydrous magnesium sulfate
  5. concentrationconcentrated
  6. washThe residue was washed with petroleum ether and carbon tetrachloride

Sources & evidence

ORD record
ord-af0bef9f78964874b270f368e13a2129
Source dataset
uspto-grants-1986_11
Patent number
US04622063

Reaction notes

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