Dichloromethane ethylacetate → 2-Chloro-5-fluoropyridin-4-amine

HRID 1061500Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1061500
[Cl:1][C:2]1[CH:7]=[C:6]([N+:8]([O-])=O)[C:5]([F:11])=[CH:4][N+:3]=1[O-].C(Cl)Cl.CCOC(C)=O>[Ni].C(O)C>[NH2:8][C:6]1[C:5]([F:11])=[CH:4][N:3]=[C:2]([Cl:1])[CH:7]=1

Komponenten

5

Edukt 2

HCID 21226138Dichloromethane ethylacetateHCID 222840222-Chloro-5-fluoro-4-nitro-1-oxo-1lambda~5~-pyridine

Produkt 1

HCID 222840352-Chloro-5-fluoropyridin-4-amineAusbeute 91 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 935NickelKatalysatorHCID 702EthanolLösungsmittel

Versuchsvorschrift

A mixture of 2-chloro-5-fluoro-4-nitropyridine-1-oxide (11, 1.3 g, 6.8 mmol) and 1.6 g of Raney nickel in 80 mL of anhydrous ethyl alcohol was hydrogenated at 40 psi in a Parr hydrogenation apparatus for 3 h when TLC showed that the starting material had disappeared and a new spot was detected (CH2Cl2/EtOAc, 4:1, v/v, Rf0.78 and 0.71, for the starting material and the product, respectively). The catalyst was removed by filtration and washed carefully with ethyl alcohol. The filtrate and washings were combined and evaporated in vacuo to give 0.9 g (91%) of product as an off-white solid. A small analytical sample was purified by recrystallization from hot water to afford white crystals: mp 110-111° C.; 1H NMR (CDCl3) δ4.50 (br s, 2 H, NH2, D2O exchangeable), 7.15 (d, 1 H, 3-H, J=6 Hz), 7.95 (d, 1H, 6-H, J=2 Hz). Analysis calculated for C5H4ClFN2: C, 40.97; H, 2.75; N, 19.12. Found: C, 41.18; H, 2.39; N, 18.89.

Aufarbeitung

  1. customThe catalyst was removed by filtration
  2. washwashed carefully with ethyl alcohol
  3. customevaporated in vacuo

Quellen und Nachweise

ORD-Eintrag
ord-24e236fa91f74f8cb09f083efcc9a204
Quelldatensatz
uspto-grants-2005_11
Patentnummer
US06960568B2

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