Pyridine → HCID 11492573, compound

HRID 1663085Notes

Reaction equation

HRID 1663085 reaction equation
[C:1]12[C:7](=[CH:8][CH:9]=[CH:10][CH:11]=1)[NH:6][C:5](=[O:12])[O:4][C:2]2=[O:3].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(O[CH:43]([CH3:45])[CH3:44])=O)=NC(OC(C)C)=O.[N:46]1[CH:51]=CC=[CH:48][CH:47]=1>C1COCC1>[N:46]1[CH:51]=[CH:45][C:43]([CH2:44][N:6]2[C:7]3[CH:8]=[CH:9][CH:10]=[CH:11][C:1]=3[C:2](=[O:3])[O:4][C:5]2=[O:12])=[CH:48][CH:47]=1

Participants

6

Reactant 4

HCID 1049PyridineHCID 8359Isatoic AnhydrideHCID 11776TriphenylphosphineHCID 75555Diisopropyl diazene-1,2-dicarboxylate

Product 1

HCID 11492573HCID 11492573, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To a stirred mixture of isatoic anhydride (72.60 g/445.0 mmol) and triphenylphosphine (116.74 g/445.1 mmol) in THF (1 L) at 0° C. was added diisopropyl azodicarboxylate drop-wise over ca. 50 min. The resulting pale yellow reaction mixture was stirred for 10 min. before drop-wise addition of a solution of 4-hydroxmethyl pyridine (48.57 g, 445.1 mmol) in THF (250 ml). The reaction mixture was stirred at room temperature for 2 hours. The resulting red solution was filtrated through a pad of silica gel, and the filtrate was evaporated under reduced pressure. The residue was treated with EtOAc and the resulting precipitated material was isolated by filtration and re-crystallised from EtOAc affording the title compound as a white solid material (37.5 g). The filtrate from this crystallisation was extracted with 0.1M HCl aq. The pH of the aqueous layer was adjusted to 7-8 with saturated aqueous sodium bicarbonate. The precipitated material was isolated by filtration and washed with water to yield more of the title compound (9.8 g). The combined aqueous filtrates were extracted several times with EtOAc. The combined organic layers were evaporated under reduced pressure. The residue was re-crystallised from EtOAc affording an additional amount of the title compound (20.3 g). 13C-NMR (DMSO-d6) δ 158.7, 149.7, 148.2, 144.5, 141.1, 136.9, 129.5, 123.8, 121.5, 114.8, 112.1, 46.7.

Workup

  1. filtrationThe resulting red solution was filtrated through a pad of silica gel
  2. customthe filtrate was evaporated under reduced pressure
  3. additionThe residue was treated with EtOAc
  4. customthe resulting precipitated material
  5. customwas isolated by filtration
  6. customre-crystallised from EtOAc affording the title compound as a white solid material (37.5 g)
  7. customThe filtrate from this crystallisation
  8. extractionwas extracted with 0.1M HCl aq. The pH of the aqueous layer
  9. customThe precipitated material was isolated by filtration
  10. washwashed with water

Sources & evidence

ORD record
ord-a5a8930bcd894cfd8a773c4aca8178a8
Source dataset
uspto-grants-2011_10
Patent number
US08034811B2

Reaction notes

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