Methanol → 1,6-Dicarbomethoxy-3-hexyne
Reaction equation
[C:1]([O:7][CH3:8])(=[O:6])[CH2:2][C:3]([CH3:5])=O.[CH3:9][O-:10].[Na+].C[OH:13].Cl[CH2:15][C:16]#[C:17][CH2:18]Cl>>[C:1]([CH2:2][CH2:3][C:5]#[C:15][CH2:16][CH2:17][C:18]([O:10][CH3:9])=[O:13])([O:7][CH3:8])=[O:6]Participants
Procedure
To methyl acetoacetate (757 g, 6.52 mole) is added 28 % solution of sodium methylate in methanol (1258 g, 6.52 mole), and the mixture is cooled to room temperature. To the mixture is added 1,4-dichloro-2-butyne (200 g, 1.63 mole). The reaction temperature is raised to 60° C., and the mixture is stirred for 16 hours. After completion of the reaction, the reaction mixture is concentrated under reduced pressure, and methanol is removed therefrom. Water (2 liters) and toluene (1 liter) are added to the resulting residue, and the mixture is stirred. The aqueous layer is removed, and the toluene layer is washed with water (2 liters). The toluene layer is concentrated under reduced pressure, and further evaporated under reduced pressure to give 1,6-dicarbomethoxy-3-hexyne (96.4 g, content; 93.7 %).
Workup
- temperatureThe reaction temperature is raised to 60° C.
- customAfter completion of the reaction
- concentrationthe reaction mixture is concentrated under reduced pressure, and methanol
- customis removed
- additionWater (2 liters) and toluene (1 liter) are added to the resulting residue
- stirringthe mixture is stirred
- customThe aqueous layer is removed
- washthe toluene layer is washed with water (2 liters)
- concentrationThe toluene layer is concentrated under reduced pressure
- customfurther evaporated under reduced pressure
Sources & evidence
- ORD record
- ord-e76aa818f9674ed487cfaa57623ac1fb
- Source dataset
- uspto-grants-1993_03
- Patent number
- US05191109
Reaction notes
Loading…