Triethylamine → HCID 15229925, compound

HRID 1721655Notes

Reaction equation

HRID 1721655 reaction equation
C([C:4]1[C:12]([CH2:13]/[CH:14]=[C:15](\[CH3:22])/[CH2:16][CH2:17][C:18]([O:20][CH3:21])=[O:19])=[C:11]([O:23][CH3:24])[C:10]([CH3:25])=[C:9]2[C:5]=1[C:6](=[O:26])[O:7][CH2:8]2)(O)=O.C([N:29]([CH2:32]C)CC)C.C1([O:40]P(Cl)(OC2C=CC=CC=2)=O)C=CC=CC=1.[N-]=[N+]=[N-].[Na+]>CN(C)C=O>[N:29]([C:4]1[C:12]([CH2:13]/[CH:14]=[C:15](\[CH3:22])/[CH2:16][CH2:17][C:18]([O:20][CH3:21])=[O:19])=[C:11]([O:23][CH3:24])[C:10]([CH3:25])=[C:9]2[C:5]=1[C:6](=[O:26])[O:7][CH2:8]2)=[C:32]=[O:40]

Participants

6

Reactant 4

HCID 8471TriethylamineHCID 33557Sodium AzideHCID 75654Diphenyl chlorophosphateHCID 15229924HCID 15229924, compound

Product 1

HCID 15229925HCID 15229925, compoundYield 97.2%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a stirred, 0° C. solution of 6.0 g (16.6 mmol) of methyl (E)-6-(4-carboxy-1,3-dihydro-6-methoxy-7-methyl-3-oxoisobenzofuran-5-yl)-4-methyl-4-hexenoate in 150 ml of dimethylformamide was added 4.62 ml (33.1 mmol) of triethylamine followed by dropwise addition of 4.5 ml (21.8 mmol) of diphenylchlorophosphate. The mixture was allowed to stir at room temperature for 1 hour and then recooled to 0° C., and treated with 10.8 g (166 mmol) of sodium azide. This mixture was stirred for 24 hours at 0° C. and then partitioned between aqueous sodium hydrogen sulfate and ethyl acetate. The organic phase was washed four times with water, dried over magnesium sulfate, and concentrated under reduced pressure. The residue was triturated with hexane to give 5.8 g of methyl (E)-6-(1,3-dihydro-4-isocyanato-6-methoxy-7-methyl-3-oxoisobenzofuran-5-yl)-4-methyl-4-hexenoate. A small sample was further purified by rapid silica gel chromatography with an eluant of 1:1 hexane:ethyl acetate followed by recrystallization from hexane-ethyl acetate to give purified methyl (E)-6-(1,3-dihydro-4-isocyanato-6-methoxy-7-methyl-3-oxoisobenzofuran-5-yl)-4-methyl-4-hexenoate, mp 95°-101° C.

Workup

  1. customrecooled to 0° C.
  2. stirringThis mixture was stirred for 24 hours at 0° C.
  3. custompartitioned between aqueous sodium hydrogen sulfate and ethyl acetate
  4. washThe organic phase was washed four times with water
  5. dry with materialdried over magnesium sulfate
  6. concentrationconcentrated under reduced pressure
  7. customThe residue was triturated with hexane

Sources & evidence

ORD record
ord-12f135ac51234f358c1293f5aa51fdd3
Source dataset
uspto-grants-1996_04
Patent number
US05512568

Reaction notes

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