Preparation method of 1-morpholinyl-4-(2,4,5-trifluorophenyl)butane-1,3-dione
An alkyl and methyl technology is applied in the field of preparation of 1-morpholine-4-butane-1,3-dione, which can solve the problems of using dangerous diazomethane, not using industrialized large-scale production, and complicated post-processing. , to achieve the effect of mild reaction conditions, simple post-processing and high yield
- Summary
- Abstract
- Description
- Claims
- Application Information
AI Technical Summary
Problems solved by technology
Method used
Image
Examples
Embodiment 1
[0057] Embodiment 1 prepares morpholine monopotassium malonate
[0058]
[0059] Morpholine (357g, 4.1mol) was dissolved in xylene (3.5L); while stirring, dimethyl malonate (720g, 5.45mol) was added. The temperature was raised to 130° C., and the stirring was continued for 24 h; TLC showed that the starting material disappeared. Concentrate under reduced pressure to obtain 1100 g of crude product, which is purified by column chromatography to obtain 620 g of colorless oily product 2-(4-morpholinecarbonyl) methyl acetate, with a yield of 81%. HNMR (400MHz, CDCl 3 )δ3.73(s, 3H), 3.68-3.65(m, 4H), 3.63(s, 2H), 3.62-3.42(m, 4H)
[0060]
[0061] At 20°C, methyl 2-(4-morpholinecarbonyl)acetate (20 g, 0.11 mol) was dissolved in MeOH (200 mL); KOH (1.0 eq, 6.2 g) and H 2 O (2.0eq, 4g); Stir at this temperature for 16h; Concentrate and remove the solvent under reduced pressure; Add MTBE (40mL*2) for beating twice; After drying, 20.3 g of monopotassium morpholine malonate was...
Embodiment 2
[0062] Embodiment 2 prepares 2,4,5-trifluorophenylacetyl imidazoles
[0063]
[0064] At 30°C, 2,4,5-trifluorophenylacetic acid (1g, 5.26mmol) was added to acetonitrile (10mL), and then N,N'-carbonyldiimidazole (CDI) (0.94g, 5.79mmol) was added; Stirred at 25°C for 3h, TLC showed disappearance of starting material. The obtained reaction solution was directly used in the next step without purification.
Embodiment 3
[0065] Example 3 Preparation of morphine 2,4,5-trifluorophenylacetoacetate
[0066]
[0067] Add morpholine monopotassium malonate (1.33g, 6.31mmol) in acetonitrile (6mL), nitrogen protection, then add triethylamine (1.28g, 12.62mmol) and magnesium chloride (0.6g, 6.31mmol); At ℃, stir for 2h; cool down to 0℃; slowly add dropwise the solution of 2,4,5-trifluorophenylacetylimidazole (1.26g, 5.26mmol) prepared in Example 2 in acetonitrile (10mL); at 25℃, stir for 16h ; Cool down to 5°C; add saturated brine (10mL) to quench the reaction, adjust the pH value to 3-4 with 1N HCl; extract the product with ethyl acetate (15mL×3); combine and dry the organic phase; concentrate; column Chromatography (PE:EA=1:1) gave a pale yellow solid (1.1 g, 69.4% overall yield over two steps).
[0068] HNMR (400MHz, DMSO-D6) δ7.52-7.45(m, 1H), 7.40-7.33(m, 1H), 3.91(s, 2H), 3.76(s, 2H), 3.53-3.51(m, 4H) , 3.44-3.42 (m, 2H), 3.41-3.32 (m, 2H).
PUM
Login to View More Abstract
Description
Claims
Application Information
Login to View More 


