Methyl 3-fluoro-4-(2-(5-nitropyridin-2-ylamino)thiazol-5-ylthio)picolinate → Methyl 4-(2-(5-aminopyridin-2-ylamino)thiazol-5-ylthio)-3-fluoropicolinate

HRID 1685352ノート

反応式

HRID 1685352 の反応式
[F:1][C:2]1[C:3]([C:24]([O:26][CH3:27])=[O:25])=[N:4][CH:5]=[CH:6][C:7]=1[S:8][C:9]1[S:13][C:12]([NH:14][C:15]2[CH:20]=[CH:19][C:18]([N+:21]([O-])=O)=[CH:17][N:16]=2)=[N:11][CH:10]=1>C(O)(=O)C.C1COCC1.[Pt]>[NH2:21][C:18]1[CH:19]=[CH:20][C:15]([NH:14][C:12]2[S:13][C:9]([S:8][C:7]3[CH:6]=[CH:5][N:4]=[C:3]([C:24]([O:26][CH3:27])=[O:25])[C:2]=3[F:1])=[CH:10][N:11]=2)=[N:16][CH:17]=1

参加物

5

反応物 1

HCID 59200453Methyl 3-fluoro-4-(2-(5-nitropyridin-2-ylamino)thiazol-5-ylthio)picolinate

生成物 1

HCID 59200430Methyl 4-(2-(5-aminopyridin-2-ylamino)thiazol-5-ylthio)-3-fluoropicolinate

試薬・触媒・溶媒 3

HCID 23939Platinum触媒2 回HCID 176Acetic Acid溶媒HCID 8028Tetrahydrofuran溶媒

実験手順

A stirring solution of methyl 3-fluoro-4-(2-(5-nitropyridin-2-ylamino)thiazol-5-ylthio)picolinate (1.77 g, 4.34 mmol), 10% Pt/C (366 mg) in acetic acid (5 mL) and THF (20 mL) was purged 4× with H2, then pressurized to 140 psi in a steel bomb reactor and stirred overnight. The reaction was depressurized, and LCMS showed intermediate nitroso as predominant product. Pt/C (270 mg) was added and the reaction repressurized to 140 psi and stirred overnight. The reaction was depressurized, LCMS showed complete reaction. The reaction was filtered through Celite, washed with THF and DCM, the filtrate was concentrated. The residue was recrystallized from EtOAc and hexane, the solid was collected by filtration and washed with hexane. The product was obtained (828 mg, 51%) as a solid: 1H NMR (400 MHz, DMSO-d6) δ ppm: 11.43 (1H, s), 8.31 (1H, d, J=5.05 Hz), 7.72 (1H, s), 7.66 (1H, d, J=2.27 Hz), 7.11 (1H, t, J=5.31 Hz), 7.06 (1H, dd, J=8.59, 2.78 Hz), 6.87 (1H, d, J=8.59 Hz), 4.99 (2H, s), 3.89 (3H, s); LC/MS (M+H)+: 378. HPLC ret. time (Condition E): 1.45 min.

後処理

  1. custompressurized to 140 psi in a steel bomb reactor
  2. stirringstirred overnight
  3. customreaction
  4. filtrationThe reaction was filtered through Celite
  5. washwashed with THF and DCM
  6. concentrationthe filtrate was concentrated
  7. customThe residue was recrystallized from EtOAc and hexane
  8. filtrationthe solid was collected by filtration
  9. washwashed with hexane
  10. customThe product was obtained (828 mg, 51%) as a solid
  11. custom1.45 min.

出典と根拠

ORDレコード
ord-109eae02bf8348a99ea209ed067e15b1
出典データセット
uspto-grants-2012_04
特許番号
US08148400B2

反応ノート

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