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Method for synthesizing alpha-difluoro ester derivative from terminal olefin
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A terminal olefin and difluorinated technology, which is applied in the field of organic synthesis, can solve the problems of cost and temperature rise, and achieve the effects of simple operation, easy preparation, and mild reaction conditions
Active Publication Date: 2022-07-29
TIANJIN UNIV OF SCI & TECH
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The shortcoming of this method is to need to use metal catalyst, and needs to heat up in the reaction process; 3 Under the catalysis of the blue lightLED lamp, it reacts with olefins to prepare
The shortcoming of this method is to need to use expensive metal photocatalyst;
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Embodiment 1
[0041]
[0042] Iodobenzenediacetic acid (4 mmol) was added to a stirred solution of toluene (4 mL), and 2-(ethoxycarbonyl)-2,2-difluoroacetic acid (1.00 mL, 16 mmol) was added dropwise at room temperature. After stirring for 30 min, the solvent was spun dry. Toluene (2 mL) was added to the crude mixture, and the mixture was concentrated again to completely remove unreacted acid. After evaporation, the corresponding [bis(2-(ethoxycarbonyl)-2,2-difluoroacetoxy)iodo]benzene was obtained without further purification as a white solid in 92% yield. 1 HNMR (400MHz, CDCl 3 )δ8.32(s, 1H), 8.17-8.15(d, 2H), 7.69(t, J=7.6Hz, 1H), 7.55(t, J=6.0Hz, 2H), 4.27(q, J=7.2 Hz,4H),1.24(t, J=7.2Hz,6H). 13 C NMR (100MHz, CDCl 3 )δ164.41(t,J=30.0Hz,2C),162.58,161.40,161.20(t,J=20.0Hz,2C),161.10,160.89,160.79,137.46,135.07,134.99,133.36,131.82,131.789,130. ,129.05,128.25,127.50, 125.32,123.09,122.98,104.89(t,J=262.0Hz,2C),63.99(t,J=12.0Hz,2C),29.68,29.35,21.41,13.70(t,J=40.0 Hz, 2C). 19 FN...
Embodiment 2
[0044]
[0045] First, the 10mL Schlenk tube was treated with water and oxygen, and the residual moisture in the reaction tube wall, the nozzle and the tube was removed by the high temperature of the drying gun, and the nitrogen and the air in the reaction tube were replaced by the double-row tube to create an anhydrous and oxygen-free environment. , after the Schlenk tube was cooled under nitrogenatmosphere, 1-benzoate 5-hexene (0.30 mmol), [bis(2-(ethoxycarbonyl)-2,2-difluoroacetoxy)iodine] Benzene (0.60 mmol) was added to the reaction tube in turn, 2.00 mL of anhydrous THF was injected into the reaction tube with a long needle syringe under the protection of nitrogen in a double row tube, and the two reactants were dissolved under stirring, and the room temperature was under the blue 12W LED light. reaction. After confirming the completion of the reaction by TLC, add a large amount of water to wash, extract three times with ethyl acetate, wash with saturated sodium chlo...
Embodiment 3
[0047]
[0048] First, the 10mL Schlenk tube was treated with water and oxygen, and the residual moisture in the reaction tube wall, the nozzle and the tube was removed by the high temperature of the drying gun, and the nitrogen and the air in the reaction tube were replaced by the double-row tube to create an anhydrous and oxygen-free environment. , after the Schlenk tube was cooled under nitrogen atmosphere, (pent-4-en-1-oxy)benzene (0.30 mmol), [bis(2-(ethoxycarbonyl)-2,2-difluoroacetoxy) ) iodine]benzene (0.60 mmol) was added to the reaction tube in turn, and 2.00 mL of anhydrous THF was injected into the reaction tube with a long needle syringe under the protection of nitrogen in the double row tube, and the two reactants were dissolved under stirring. According to the room temperature reaction. After confirming the completion of the reaction by TLC, add a large amount of water to wash, extract three times with ethyl acetate, and wash with saturated sodiumchloridesol...
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Abstract
The invention relates to the field of organic synthesis, in particular to a method for synthesizing an alpha-difluoro ester derivative from terminal olefin, which comprises the following steps: by using [bis (2-(ethoxycarbonyl)-2, 2-difluoroacetoxy) iodine] benzene as a precursor of difluoroethyl acetate free radical, generating difluoroethyl acetate free radical under the catalysis of visible light, and synthesizing the alpha-difluoro ester derivative from terminal olefin. And then carrying out free radical addition reaction with terminal olefin to obtain the alpha-difluoro ester derivative. Terminal olefin and [bis (2-(ethoxycarbonyl)-2, 2-difluoroacetoxy) iodine] benzene are dissolved with THF in a reaction tube, a reaction is carried out at room temperature under the illumination of a blue 12W LED lamp, and a series of added difluoroalkane products are synthesized. The [bis (2-(ethoxycarbonyl)-2, 2-difluoroacetoxy) iodine] benzene which is cheap and easy to obtain is used as a difluoroalkyl group source, the alpha-difluoroester derivative is prepared from terminal olefin under the action of a non-photocatalyst, and the synthesis method is simple, convenient, rapid and very convenient to operate.
Description
technical field [0001] The invention belongs to the field of organic synthesis, and relates to a method that uses [bis(2-(ethoxycarbonyl)-2,2-difluoroacetoxy)iodo]benzene as a source of ethyl difluoroacetate free radicals, in photocatalysis by the terminal A method for obtaining alpha difluoroester derivatives from olefins. Background technique [0002] The introduction of fluorine atoms or fluorine-containing groups into small organic molecules can significantly improve the lipophilicity, lipid solubility, metabolic stability, cell permeability and other properties of the molecules. Fluorine, on the other hand, is widely considered to be a metabolically stable analog and / or substitute for the hydrogen atom, and thus, more than 20% of pharmaceuticals and 30% of agrochemicals have at least one fluorine atom. Fluorine substitution has a significant effect on the physical and chemical properties of drug molecules, and thus the incorporation of difluoroalkylated groups into org...
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