Benzyl Alcohol → 3-benzyloxycarbonylamino-6-methyl-2-pyridinone

HRID 567798Notes

Reaction equation

HRID 567798 reaction equation
[CH3:1][C:2]1[CH:3]=[CH:4][CH:5](C(O)=O)[C:6](=[O:8])[N:7]=1.C([N:14]([CH2:17]C)CC)C.C1(P(N=[N+]=[N-])(C2C=CC=CC=2)=[O:26])C=CC=CC=1.[CH2:36]([OH:43])[C:37]1[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=1>O1CCOCC1>[CH3:1][C:2]1[NH:7][C:6](=[O:8])[C:5]([NH:14][C:17](=[O:26])[O:43][CH2:36][C:37]2[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=2)=[CH:4][CH:3]=1

Participants

6

Reactant 4

HCID 244Benzyl AlcoholHCID 8471Triethylamine2×HCID 199401P,P-Diphenylphosphinic azide2×HCID 184709516-Methyl-2-oxo-2,3-dihydropyridine-3-carboxylic acid

Product 1

HCID 100838403-benzyloxycarbonylamino-6-methyl-2-pyridinoneYield 65.5%

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Procedure

A suspension of 6-methyl-2-oxo-2,3-dihydro-3-pyridinecarboxylic acid (20 g, 0.13 mol) in dioxan (400 ml) was treated with triethylamine (22 ml, 0.15 mol) followed by diphenylphosphoryl azide (30.8 ml, 0.14 mol) and heated under reflux for 2 hr. A further portion of diphenylphosphoryl azide (3 ml) and triethylamine (2 ml) were added and heated under reflux for a further 1 hr. The resultant mixture was then treated with benzyl alcohol (18.8 ml, 0.18 mol) and heated under reflux for 18 hr. The resultant mixture was cooled, evaporation of the solvent gave a crude solid which was triturated with water. The solid was collected by filtration, washed with HCl (1N, 300 ml) then water. The solid was triturated with diethyl ether, filtered, washed with diethyl ether and dried to give the desired product (22 g, 65%). 1H NMR (CDCl3) δ 1.20 (s, 1H), 2.30 (s, 3H), 5.20 (s, 2H), 6.05 (d, 1H), 7.40 (m, 5H), 7.70 (s, 1H), 8.00 (d, 1H). LRMS m/z=259.2 (M+1)+.

Workup

  1. temperatureheated
  2. temperatureunder reflux for 2 hr
  3. temperatureheated
  4. temperatureunder reflux for a further 1 hr
  5. temperatureheated
  6. temperatureunder reflux for 18 hr
  7. customevaporation of the solvent
  8. customgave a crude solid which
  9. customwas triturated with water
  10. filtrationThe solid was collected by filtration
  11. washwashed with HCl (1N, 300 ml)
  12. customThe solid was triturated with diethyl ether
  13. filtrationfiltered
  14. washwashed with diethyl ether
  15. customdried

Sources & evidence

ORD record
ord-5695b25b06f248f293be554a7b4e8636
Source dataset
uspto-grants-2001_01
Patent number
US06180627B2

Reaction notes

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