Tetrahydrofuran → Methyl 2,4,5-triamino-3-fluorobenzoate

HRID 1665842Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1665842
[NH2:1][C:2]1[C:11]([F:12])=[C:10]([NH2:13])[C:9]([N+:14]([O-])=O)=[CH:8][C:3]=1[C:4]([O:6][CH3:7])=[O:5].O1CCCC1>CO.[Pd]>[NH2:1][C:2]1[C:11]([F:12])=[C:10]([NH2:13])[C:9]([NH2:14])=[CH:8][C:3]=1[C:4]([O:6][CH3:7])=[O:5]

Komponenten

5

Edukt 2

HCID 8028TetrahydrofuranHCID 59365494Methyl 2,4-diamino-3-fluoro-5-nitrobenzoate

Produkt 1

HCID 59365495Methyl 2,4,5-triamino-3-fluorobenzoateAusbeute 108,4 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 23938PalladiumKatalysatorHCID 887MethanolLösungsmittel

Versuchsvorschrift

A mixture of methyl 2,4-diamino-3-fluoro-5-nitrobenzoate (5) (40.0 g, 173.7 mmol) and 5% Pd/C (3.0 g, Type 487; 0.4 mol % Pd relative to starting material), in methanol (300.0 mL) and tetrahydrofuran (300.0 mL) was stirred at 2000 RPM, under hydrogen (˜3.5 bar), at 50° C. in a 1.5 L hydrogenation vessel. After 6 hours the vessel was purged with nitrogen and HPLC analysis indicated that no starting material remained. The mixture was then filtered under nitrogen pressure and the filter washed through with THF (160 mL), to give a clear yellow solution. The solvent was removed by rotary evaporation, to provide methyl 2,4,5-triamino-3-fluorobenzoate (9) 37.5 g (93.3% w/w by NMR) as a solid, yield ˜100%. 1H NMR (400 MHz, d6 DMSO) δ 3.69 (3H, s, NMe), 4.20 (2H, br s, NH2), 5.24 (2H, br s, NH2), 5.70 (2H, br s, NH2), 6.83 (1H, d, J 1, Ar—H). 13C NMR (100 MHz, d6 DMSO) δ 51 (CH3), 98 (C, d, J 5), 110 (CH, d, J 2), 125 (C, d, J 6), 131 (C, d, J 12), 133 (C, d, J 12), 139 (CF, d, J 225), 166 (C═O). νmax/cm-1 3480, 3461, 3373, 3356, 3280, 3163, 1679, 1655, 1314. MS APCI (+) m/z 200 (M+1) detected.

Aufarbeitung

  1. customAfter 6 hours the vessel was purged with nitrogen and HPLC analysis
  2. filtrationThe mixture was then filtered under nitrogen pressure
  3. washthe filter washed through with THF (160 mL)
  4. customto give a clear yellow solution
  5. customThe solvent was removed by rotary evaporation

Quellen und Nachweise

ORD-Eintrag
ord-79137ce3d72144149806382efbace155
Quelldatensatz
uspto-grants-2011_10
Patentnummer
US08039637B2

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