Dimethyl acetylenedicarboxylate → Dimethyl 3-ethyl-5-methoxyphthalate
Reaction equation
[CH2:1]([C:3]1OC(=O)[CH:6]=[C:5]([O:10][CH3:11])[CH:4]=1)[CH3:2].[CH3:12][O:13][C:14]([C:16]#[C:17][C:18]([O:20][CH3:21])=[O:19])=[O:15]>ClCCl>[CH3:12][O:13][C:14](=[O:15])[C:16]1[C:17](=[C:3]([CH2:1][CH3:2])[CH:4]=[C:5]([O:10][CH3:11])[CH:6]=1)[C:18]([O:20][CH3:21])=[O:19]Participants
Reactant 2
Product 1
Reagents, catalysts & solvents 1
Procedure
The following is based on the procedure described in Tam, T. F. and Coles P., Synthesis, 383 (1988). 6-ethyl-4-methoxy-2H-pyran-2-one (40.5 g, 263 mmol) was placed in a 500 mL round bottom flask and dimethylacetylenedicarboxylate (42 mL, 342 mmol) was added. This mixture was stirred until the solid completely dissolved. The flask was fitted with a water condenser and placed in a preheated oil bath at 180° C. for 3 hours. The reaction was allowed to cool to room temperature, diluted with dichloromethane (75 mL), and was purified by silica gel chromatography using a gradient of 5-20% ethyl acetate in hexanes. The appropriate fractions were collected and concentrated by rotary evaporation to yield compound P (44.16 g, 67%) as a clear oil. 1H NMR CDCl3 δ: 7.30 (d, 1H, J=3 Hz), 6.95 (s, 1H, J=3 Hz), 3.90 (s, 3H), 3.88 (s, 3H), 3.85 (s, 3H), 2.64 (q, 2H, J=8.0 Hz), 1.21 (t, 3H, J=8.0 Hz). ESMS m/z: 221 [M−OCH3]+, 275 [M+Na+].
Workup
- custom, Synthesis, 383 (1988)
- dissolutioncompletely dissolved
- customThe flask was fitted with a water condenser
- customwas purified by silica gel chromatography
- customThe appropriate fractions were collected
- concentrationconcentrated by rotary evaporation
Sources & evidence
- ORD record
- ord-0154dbb6bce9441f94770d8f7bafef22
- Source dataset
- uspto-grants-2011_02
- Patent number
- US07879846B2
Reaction notes
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