A kind of fluorine-containing carboxylic acid compound and its preparation method
A technology for fluorine-containing carboxylic acids and compounds, applied in the field of fluorine-containing carboxylic acids and their preparation, to achieve the effects of good functional group compatibility, wide substrate range, easy scale and derivatization
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Embodiment 1
[0038] Example 1 Preparation of Z-2-fluoro-3-(4-phenylphenyl)acrylic acid (hereinafter referred to as compound 2a)
[0039] Difluoroalkenes (1a, 0.4 mmol), boron reagent (0.4 mmol, 2 mL), copper catalyst (0.02 mmol), ligand (0.02 mmol), and base (1.4 mmol) were mixed, then filled with CO 2 (1 atmosphere), in CO 2 Add an organic solvent under the atmosphere, stir the reaction at 80°C for 24h, and finally cool to room temperature, quench the reaction product with ethyl acetate and hydrochloric acid, extract with ethyl acetate three times, concentrate and spin dry, and purify to obtain the final pure target product. Concrete reaction raw material sees the following table, and reaction formula is as follows:
[0040]
[0041] serial number boron reagent Ligand copper catalyst alkali solvent Yield[%] [b]
1 B 2 Pin 2
Xantphos CuTc KOAc DMF N.D. 2 B 2 Pin 2
Xantphos CuTc CsF DMF Trace 3 B 2 Pin 2
...
Embodiment 2-33
[0045] Example 2-33 Preparation of α-fluoroacrylic acid (ester) compounds (compound 2b-2ag)
[0046] The synthesis steps of this type of compound are the same as those of compound 2a, except for the raw materials. The specific reaction formula and the specific structure of the compound are as follows:
[0047]
[0048] The above [b] is CuTc (0.04 mmol), Xantphos (0.04 mmol). [c] is the separation yield after methyl iodide esterification. [d] for 19 F-NMR analysis gave the result of Z / E selectivity.
[0049] The structural formula and parameters of the obtained α-fluoroacrylic acid (ester) compound (compound 2b-2ag) are as follows:
[0050] Z-methyl 2-fluoro-3-(4-phenylphenyl)acrylate (2a')
[0051] The structural formula is:
[0052]
[0053] It is a white solid with a mass of 78mg and a yield of 76%, R f (PE / EA 10:1):0.50; 1 H NMR (400MHz, CDCl 3 )δ7.73–7.69(m,2H),7.66–7.59(m,4H),7.49–7.42(m,2H).,7.42–7.33(m,1H),6.97(d,J=35.3Hz,1H ),3.90(s,3H); 19 F NMR (376MH...
Embodiment 34-48
[0183] Example 34-48 Preparation of n-hexyl 2,2-difluoro-3-butenoate compounds (4a-4o)
[0184] The specific preparation process is:
[0185] To a dry Shrek (Schlenk) tube (25 mL) containing magnetons was added the reaction substrate (0.2 mmol), bis(2-methyl-2,4-pentanediol) borate (76.2 mg, 0.3 mmol, 1.5 equiv), then transfer the Shrek (Schlenk) tube into the glove box, and then add cuprous chloride (CuCl) (2.0 mg, 0.02 mmol, 10 mol%), 4,5-bisdiphenylphosphine- 9,9-Dimethylxanthene (Xantphos) (11.6 mg, 0.02 mmol, 10 mol%), potassium methoxide (KOMe) (42 mg, 0.6 mmol, 3.0 equiv). Remove the Schlenk tube from the glove box after sealing it and connect it to a CO 2 On the double tube of the cylinder, unscrew the cap and pump on the double tube to displace the CO 2 3 times to fill the tube with CO 2 gas, then in CO 2 Ultra-dry N-methylpyrrolidone (NMP) (2 mL) was added under atmosphere. Finally, the reaction tube was placed on a metal bath, and the reaction was stirred at ...
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