Potassium Phosphate, Tribasic → Methyl 3-fluoro-4-(2-(5-nitropyridin-2-ylamino)thiazol-5-ylthio)picolinate

HRID 1685351Notes

Reaction equation

HRID 1685351 reaction equation
[N+:1]([C:4]1[CH:5]=[CH:6][C:7]([NH:10][C:11]2[S:12][C:13]([S:16][C:17]#N)=[CH:14][N:15]=2)=[N:8][CH:9]=1)([O-:3])=[O:2].SC[C@H]([C@@H](CS)O)O.ClC1[CH:33]=[CH:32][N:31]=[C:30]([C:34]([O:36][CH3:37])=[O:35])[C:29]=1[F:38].[O-]P([O-])([O-])=O.[K+].[K+].[K+]>CO.O.CN(C=O)C>[F:38][C:29]1[C:30]([C:34]([O:36][CH3:37])=[O:35])=[N:31][CH:32]=[CH:33][C:17]=1[S:16][C:13]1[S:12][C:11]([NH:10][C:7]2[CH:6]=[CH:5][C:4]([N+:1]([O-:3])=[O:2])=[CH:9][N:8]=2)=[N:15][CH:14]=1

Participants

8

Reactant 4

HCID 62657Potassium Phosphate, TribasicHCID 446094D-1,4-DithiothreitolHCID 59200355Methyl 4-chloro-3-fluoropicolinateHCID 59200372N-(5-nitropyridin-2-yl)-5-thiocyanatothiazol-2-amine

Product 1

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

Reagents, catalysts & solvents 3

HCID 887MethanolSolventHCID 962WaterSolventHCID 6228DimethylformamideSolvent

Procedure

To a stirring suspension of N-(5-nitropyridin-2-yl)-5-thiocyanatothiazol-2-amine (2.00 g, 7.16 mmol) in MeOH (72 mL) was added dithiothreitol (2.22 g, 14.39 mmol). After 5 minutes, methyl 4-chloro-3-fluoropicolinate (1.51 g, 7.97 mmol), K3PO4 (1.98 g, 9.33 mmol) and DMF (72 mL) were sequentially added. After 2 hours, the reaction was poured into an ice/water (˜1.4 L) mixture with stirring for 90 minutes, diluted to ˜3.5 L with water, allowed to sit overnight. The solid was collected by filtration, washed with water and allowed to air dry overnight. The product was obtained (2.384 g, 82%) as a solid: 1H NMR (400 MHz, DMSO-d6) δ ppm: 12.68 (1H, s), 9.19 (1H, d, J=2.78 Hz), 8.53 (1H, dd, J=9.35, 2.78 Hz), 8.32 (1H, d, J=5.05 Hz), 7.96 (1H, s), 7.23 (1H, d, J=9.35 Hz), 7.15 (1H, t, J=5.43 Hz), 3.89 (3H, s); LC/MS (M+H)+: 408. HPLC ret. time (Condition B): 1.78 min.

Workup

  1. waitAfter 2 hours
  2. waitto sit overnight
  3. filtrationThe solid was collected by filtration
  4. washwashed with water
  5. customto air dry overnight
  6. customThe product was obtained (2.384 g, 82%) as a solid
  7. custom1.78 min.

Sources & evidence

ORD record
ord-5d8317d19b6a49d38eee9cbaec09526d
Source dataset
uspto-grants-2012_04
Patent number
US08148400B2

Reaction notes

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