Allyl chloroformate → HCID 86607070, compound

HRID 2376659Notes

Reaction equation

HRID 2376659 reaction equation
[C:1]([C:4]1[CH:9]=[CH:8][C:7]([CH2:10][C:11]([O:13][CH2:14][CH3:15])=[O:12])=[C:6]([NH2:16])[CH:5]=1)(=[O:3])[CH3:2].[NH2:17][C:18]1[CH:23]=[C:22]([CH:24]([OH:26])[CH3:25])[CH:21]=[CH:20][C:19]=1[CH2:27][C:28]([O:30][CH2:31][CH3:32])=[O:29].[CH2:33]([O:36][C:37](Cl)=[O:38])[CH:34]=[CH2:35].[Cl-].[NH4+]>N1C=CC=CC=1.[Cl-].[Na+].O>[C:1]([C:4]1[CH:9]=[CH:8][C:7]([CH2:10][C:11]([O:13][CH2:14][CH3:15])=[O:12])=[C:6]([NH:16][C:37]([O:36][CH2:33][CH:34]=[CH2:35])=[O:38])[CH:5]=1)(=[O:3])[CH3:2].[CH2:33]([O:36][C:37]([NH:17][C:18]1[CH:23]=[C:22]([CH:24]([OH:26])[CH3:25])[CH:21]=[CH:20][C:19]=1[CH2:27][C:28]([O:30][CH2:31][CH3:32])=[O:29])=[O:38])[CH:34]=[CH2:35]

Participants

8

Reactant 4

HCID 18052Allyl chloroformateHCID 25517Ammonium ChlorideHCID 20154476HCID 20154476, compoundHCID 59855771HCID 59855771, compound

Product 2

HCID 86607069HCID 86607069, compoundYield 26%HCID 86607070HCID 86607070, compoundYield 50%

Reagents, catalysts & solvents 2

HCID 1049PyridineSolventHCID 57417360Sodium chloride; waterSolvent

Procedure

A mixture of ethyl (4-acetyl-2-aminophenyl)acetate and ethyl [2-amino-4-(1-hydroxyethyl)phenyl]acetate (20.4 g) prepared by step d) was dissolved in pyridine (184 mL) and thereto was dropped at room temperature allyloxycarbonyl chloride (22.2 g), followed by stirring for 30 minutes. To the reaction mixture were added a saturated ammonium chloride solution (100 mL) and saturated brine (100 mL), and then pyridine was removed in vacuo. To the aqueous layer was added 2M hydrochloric acid (200 mL) and the mixture was extracted with ethyl acetate (3×100 mL). The organic layers were combined, washed with 2M hydrochloric acid (3×50 mL) and saturated brine (50 mL), filtered and the solvent was removed in vacuo. The residue was purified with column chromatography (SiO2 500 g, hexane/ethyl acetate 3:1˜1:1) to give ethyl (4-acetyl-2-{[(allyloxy)carbonyl]amino}phenyl)acetate (7.34 g, 26%) as a gray oil, and ethyl [2-{[(allyloxy)carbonyl]amino}-4-(1-hydroxyethyl)phenyl]acetate (14.1 g, 50%) as a purple oil.

Workup

  1. custompyridine was removed in vacuo
  2. additionTo the aqueous layer was added 2M hydrochloric acid (200 mL)
  3. extractionthe mixture was extracted with ethyl acetate (3×100 mL)
  4. washwashed with 2M hydrochloric acid (3×50 mL) and saturated brine (50 mL)
  5. filtrationfiltered
  6. customthe solvent was removed in vacuo
  7. customThe residue was purified with column chromatography (SiO2 500 g, hexane/ethyl acetate 3:1˜1:1)

Sources & evidence

ORD record
ord-553c8e5297a2474ea1af854e4b23bcb2
Source dataset
uspto-grants-2008_12
Patent number
US07468364B2

Reaction notes

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