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1,4-Bis(diphenylphosphino)butane → Ethyl 6-amino-2-chloro-5-methoxypyrimidine-4-carboxylate

HRID 1988542
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Druckvorschau

Reaktionsgleichung

Reaktionsgleichung von HRID 1988542
[Cl:1][C:2]1[N:7]=[C:6]([NH2:8])[C:5]([O:9][CH3:10])=[C:4](Cl)[N:3]=1.[C:12]([O-:15])(=[O:14])C.[Na+].[CH:17]1C=CC(P(C2C=CC=CC=2)CCCCP(C2C=CC=CC=2)C2C=CC=CC=2)=C[CH:18]=1>C(O)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[CH2:17]([O:15][C:12]([C:4]1[C:5]([O:9][CH3:10])=[C:6]([NH2:8])[N:7]=[C:2]([Cl:1])[N:3]=1)=[O:14])[CH3:18]
KomponentenReaktionsbedingungenVersuchsvorschriftAufarbeitungQuellen und NachweiseNotizen zur Reaktion

Komponenten

6

Edukt 3

HCID 821241,4-Bis(diphenylphosphino)butaneHCID 517045Sodium AcetateHCID 591269272,6-Dichloro-5-methoxypyrimidin-4-amine

Produkt 1

HCID 59126903Ethyl 6-amino-2-chloro-5-methoxypyrimidine-4-carboxylateAusbeute 232,5 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 167845palladium(II) acetateKatalysator
HCID 702EthanolLösungsmittel

Reaktionsbedingungen

Temperatur
110 °C

Versuchsvorschrift

2,6-Dichloro-5-methoxypyrimidin-4-ylamine (5.0 g, 26 mmol) was combined in 75 mL absolute ethanol with sodium acetate (2.1 g, 26 mmol), palladium acetate (280 mg, 0.91 mmol) and DPPB (1.1 g, 2.6 mmol) in a 300 mL stirred pressure reactor. The reactor was purged and pressurized to 300 psi with carbon monoxide, and heated at 110° C. for 7 h. The volatiles were removed under vacuum and the residue was taken up in ethyl acetate and water. The aqueous phase was extracted with an additional ethyl acetate; and the combined extracts were washed with brine, dried and evaporated. The residue was purified by flash chromatography on silica gel (0-30% ethyl acetate gradient in hexanes) to give the title compound (1.4 g, 23% yield): mp 118-119° C. 1H NMR (CDCl3) δ 6.18 (br s, 2H), 4.45 (q, 2H), 3.91 (s, 3H), 1.42 (t, 3H).

Aufarbeitung

  1. customThe reactor was purged
  2. customThe volatiles were removed under vacuum
  3. extractionThe aqueous phase was extracted with an additional ethyl acetate
  4. washand the combined extracts were washed with brine
  5. customdried
  6. customevaporated
  7. customThe residue was purified by flash chromatography on silica gel (0-30% ethyl acetate gradient in hexanes)

Quellen und Nachweise

ORD-Eintrag
ord-7c12127ebb5249b681922313eb88b2d3
Quelldatensatz
uspto-grants-2010_01
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US07642220B2

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