3-Hydroxypyridine → HCID 67184871, compound

HRID 885963Notes

Reaction equation

HRID 885963 reaction equation
[CH3:1][C:2]1([CH3:24])[NH:7][C:6](=[O:8])[C:5]2[S:9][C:10]([N:12]3[C:17]4[CH:18]=[C:19]([CH:22]=[O:23])[CH:20]=[CH:21][C:16]=4[O:15][CH2:14][CH2:13]3)=[N:11][C:4]=2[CH2:3]1.O[C:26]1[CH:27]=[N:28][CH:29]=[CH:30][CH:31]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OCC)=O)=NC(OCC)=O>C1COCC1>[CH3:1][C:2]1([CH3:24])[NH:7][C:6](=[O:8])[C:5]2[S:9][C:10]([N:12]3[C:17]4[CH:18]=[C:19]([CH2:22][O:23][C:26]5[CH:27]=[N:28][CH:29]=[CH:30][CH:31]=5)[CH:20]=[CH:21][C:16]=4[O:15][CH2:14][CH2:13]3)=[N:11][C:4]=2[CH2:3]1

Participants

6

Reactant 4

HCID 79713-Hydroxypyridine2×HCID 11776Triphenylphosphine2×HCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 87302112HCID 87302112, compound

Product 1

HCID 67184871HCID 67184871, compoundYield 8%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

A mixture of Example 50 (0.050 g, 0.14 mmol), 3-hydroxypyridine (0.015 g, 0.14 mmol), and triphenylphosphine (0.042 g, 0.16 mmol) in THF (15 mL) was cooled to 0° C. Diethyl azodicarboxylate (0.03 mL, 0.16 mmol) was added, and the reaction mixture stirred for 30 minutes at 0° C., then at r.t. for 3 h. Further portions of 3-hydroxypyridine (0.015 g, 0.14 mmol) and triphenylphosphine (0.021 g, 0.08 mmol) were added, and stirring continued for 2 h. The mixture was concentrated in vacuo and the residue partitioned between DCM (50 mL) and water (50 mL). The organic fraction was washed with water (50 mL) and brine (50 mL), dried (MgSO4), filtered and concentrated in vacuo. The crude material was purified by preparative HPLC (Method 6) to give the title compound (0.0045 g, 8%) as a white solid. δH (CDCl3) 8.32 (2H, br. s), 8.06 (1H, d, J 1.7 Hz), 7.38-7.31 (2H, m), 7.13 (1H, dd, J 8.5 and J 1.9 Hz), 6.99 (1H, d, J 8.5 Hz), 5.07 (2H, s), 5.21 (1H, br. s), 4.38-4.32 (2H, m), 4.18-4.11 (2H, m), 2.88 (2H, s), 1.40 (6H, s). LCMS (ES+) 423.0 (M+H)+, RT 2.27 minutes (Method 1).

Workup

  1. waitat r.t. for 3 h
  2. stirringstirring
  3. waitcontinued for 2 h
  4. concentrationThe mixture was concentrated in vacuo
  5. customthe residue partitioned between DCM (50 mL) and water (50 mL)
  6. washThe organic fraction was washed with water (50 mL) and brine (50 mL)
  7. dry with materialdried (MgSO4)
  8. filtrationfiltered
  9. concentrationconcentrated in vacuo
  10. customThe crude material was purified by preparative HPLC (Method 6)

Sources & evidence

ORD record
ord-a0b3ddd36bfc4bc7b78e55b8af9d006e
Source dataset
uspto-grants-2012_08
Patent number
US08242116B2

Reaction notes

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