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

HRID 1665842노트

반응식

HRID 1665842 반응식
[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]

참가 물질

5

반응물 2

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

생성물 1

HCID 59365495Methyl 2,4,5-triamino-3-fluorobenzoate수율 108.4%

시약·촉매·용매 2

HCID 23938Palladium촉매HCID 887Methanol용매

실험 절차

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.

후처리

  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

출처 및 근거

ORD 기록
ord-79137ce3d72144149806382efbace155
출처 데이터셋
uspto-grants-2011_10
특허 번호
US08039637B2

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