Acetic Acid → 4-(1-Methoxycarbonyl-but-3-ynyl)

HRID 1707597Notes

Reaction equation

HRID 1707597 reaction equation
[H-].[K+].[CH3:3][O:4][C:5](=[O:17])[CH2:6][C:7]1[CH:16]=[CH:15][C:10]([C:11]([O:13][CH3:14])=[O:12])=[CH:9][CH:8]=1.[CH2:18](Br)[C:19]#[CH:20].C(O)(=O)C>O1CCCC1.O>[CH3:3][O:4][C:5](=[O:17])[CH:6]([CH2:20][C:19]#[CH:18])[C:7]1[CH:16]=[CH:15][C:10]([C:11]([O:13][CH3:14])=[O:12])=[CH:9][CH:8]=1

Participants

7

Reactant 4

HCID 176Acetic AcidHCID 7842Propargyl bromideHCID 82127Potassium hydride2×HCID 10536335Benzeneacetic acid, 4-(methoxycarbonyl)-, methyl ester

Product 1

HCID 109885784-(1-Methoxycarbonyl-but-3-ynyl)

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

A mixture of 35% potassium hydride in oil (6.04 g, 35% w/w, 53 mmols of potassium hydride) in 240 mL of sieve dried tetrahydrofuran was cooled to 0° C. The cold mixture was treated with homoterephthalic acid dimethyl ester (10.0 g, 48 mmols). The mixture was stirred at 0° C. for one hour. Propargyl bromide (53 mmols) was added and the mixture stirred at 0° C. for 30 minutes, then at room temperature for 16 hours. The resulting mixture was treated with 4.8 mL of 50% acetic acid, then poured into 480 mL of water. The mixture was extracted with ether (2×250 mL). The ether extracts were combined, dried over magnesium sulfate, and concentrated to a brown oil. Chromatography on 250 g of flash silica gel (10% ether in hexane eluent) gave the product IV-1b as a white solid mp 63°-65° C.

Workup

  1. stirringthe mixture stirred at 0° C. for 30 minutes
  2. waitat room temperature for 16 hours
  3. extractionThe mixture was extracted with ether (2×250 mL)
  4. dry with materialdried over magnesium sulfate
  5. concentrationconcentrated to a brown oil

Sources & evidence

ORD record
ord-b8f57613cf6a4fe49f286aa416ccdabe
Source dataset
uspto-grants-1994_10
Patent number
US05354751

Reaction notes

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