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CN114805069B - Method for synthesizing alpha difluoro ester derivative from terminal olefin - Google Patents

Method for synthesizing alpha difluoro ester derivative from terminal olefin Download PDF

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CN114805069B
CN114805069B CN202210465515.3A CN202210465515A CN114805069B CN 114805069 B CN114805069 B CN 114805069B CN 202210465515 A CN202210465515 A CN 202210465515A CN 114805069 B CN114805069 B CN 114805069B
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ethoxycarbonyl
benzene
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CN114805069A (en
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芦逵
苏俊奇
刘瑞月
张颖
周宁宁
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Tianjin University of Science and Technology
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Abstract

The application relates to the field of organic synthesis, in particular to a method for synthesizing alpha difluoro ester derivatives by using terminal olefin, which uses [ bis (2- (ethoxycarbonyl) -2, 2-difluoroacetoxyl) iodine ] benzene as a difluoro ethyl acetate radical precursor, generates difluoro ethyl acetate radical under the catalysis of visible light, and then generates radical addition reaction with the terminal olefin to obtain the alpha difluoro ester derivatives. Specifically, terminal olefin, [ bis (2- (ethoxycarbonyl) -2, 2-difluoroacetoxyl) iodo ] benzene was dissolved in THF in a reaction tube and reacted at room temperature under the illumination of a blue 12WLED lamp to synthesize a series of addition difluoroalkane products. The application adopts cheap and easily available [ bis (2- (ethoxycarbonyl) -2, 2-difluoroacetoxyl) iodo ] benzene as a difluoroalkyl source, prepares the alpha difluoro ester derivative from terminal olefin under the action of no light catalyst, and has simple, convenient and quick synthesis method and convenient operation.

Description

Method for synthesizing alpha difluoro ester derivative from terminal olefin
Technical Field
The application belongs to the field of organic synthesis, and relates to a method for preparing alpha difluoro ester derivatives from [ bis (2- (ethoxycarbonyl) -2, 2-difluoroacetoxyl) iodo ] benzene serving as a source of ethyl difluoroacetate free radicals by photocatalysis of terminal olefins.
Background
The fluorine atom or fluorine-containing group is introduced into the organic micromolecule, so that the properties of lipophilicity, fat solubility, metabolic stability, cell permeability and the like of the molecule can be remarkably improved. Fluorine, on the other hand, is widely regarded as a metabolically stable analogue and/or substitute for hydrogen atoms, and therefore, more than 20% of drugs and 30% of agrochemicals have at least one fluorine atom. Fluorine substitution has a significant impact on the physical and chemical properties of the drug molecule, and thus incorporation of difluoroalkylated groups into organic compounds is particularly advantageous.
A plurality of subject groups at home and abroad have successfully prepared ethyl difluoroacetate radical precursors to participate in the reaction. The ethyl difluoroacetate radical precursor includes ethyl difluorobromoacetate, ethyl difluoroiodoacetate, ethyl difluorocopper acetate, ethyl difluorophenylselenoacetate, zinc difluoromethylsulfinate, sodium difluoromethylsulfinate, difluoromethylphosphinate, etc. Some of these ethyl difluoroacetate reagents have been commercially available, but the reaction process requires an oxidizing agent, an expensive metal catalyst, or the synthesis of the difluoroalkylating agent itself is difficult. Burton in 1996 reported that ethyl difluoroacetate reaction of olefins was achieved using copper powder as a catalyst and ethyl difluoroiodoacetate as an esterification reagent. The subject group of Kumadaki professor, ltoh professor, fei fujingfei professor and the like optimizes and innovates the ethyl difluoroacetate reagent.
The current method for synthesizing the end difluoro ethyl acetate group addition synthesized alkane product comprises the following steps: 1) The alkene and the ethyl difluoroiodoacetate are obtained by heating the solution to 70 ℃ under the catalysis of copper. The method has the defects that a metal catalyst is needed, and the temperature is required to be increased in the reaction process; 2) Is prepared by reacting ethyl difluorobromoacetate with olefin under the catalysis of fac-Ir (ppy) 3 and the irradiation of a blue light LED lamp. The disadvantage of this process is the need to use expensive metal photocatalysts; 3) From the reaction of methyl difluorosulfonyl acetate with olefins, this process has the disadvantage of requiring the use of expensive metal photocatalysts.
Disclosure of Invention
The present application is directed to a process for reacting [ bis (2- (ethoxycarbonyl) -2, 2-difluoroacetoxy) iodo ] benzene as an ethyl difluoroacetate radical precursor with a terminal olefin to form a di-alpha difluoroester derivative.
The method comprises the following specific steps: adding olefin, [ bis (2- (ethoxycarbonyl) -2, 2-difluoroacetoxyl) iodine ] benzene and tetrahydrofuran under anhydrous and anaerobic conditions, and reacting at room temperature under the illumination of a blue 12W LED lamp. After the reaction is finished, the added difluoroalkane product is obtained through extraction, washing, drying and column chromatography separation.
The synthesis method of the alpha difluoro ester derivative has a reaction general formula shown in the specification, wherein R is selected from benzyl ester group, phenyl ether group, benzamide group, thiophene carboxamide group, furan carboxamide group and phthalimide group;
n＝2-6；
the reaction mechanism is as follows:
table 1 structures of the ethyl difluoroacetate based alkane products synthesized by the present application are shown in the following table:
compared with the prior art, the application has the advantages that:
the application uses [ bis (2- (ethoxycarbonyl) -2, 2-difluoroacetoxyl) iodine ] benzene as a difluoro ethyl acetate radical precursor, generates difluoro ethyl acetate radical under the catalysis of visible light, and then generates radical addition of olefin to obtain the alpha difluoro ester derivative. [ bis (2- (ethoxycarbonyl) -2, 2-difluoroacetoxy) iodo ] benzene can be conveniently prepared by reacting iodobenzene acetate with diethyl 2, 2-difluoromalonate. In addition, the method used in the patent does not need a photocatalyst or an oxidant, and is simple and convenient to operate and mild in reaction condition.
The reaction used in the application does not need a photocatalyst or an oxidant, and has simple and convenient operation and mild reaction conditions; the prepared [ bis (2- (ethoxycarbonyl) -2, 2-difluoroacetoxy) iodo ] benzene has stability and is easy to prepare.
Drawings
FIG. 1 is an H spectrum of the compound of example 1.
Figure 2 the H spectrum of the compound of example 2.
FIG. 3H spectrum of the compound of example 3.
FIG. 4-H spectrum of the compound of example 4.
Figure 5 the H spectrum of the compound of example 5.
FIG. 6H spectrum of the compound of example 6.
Figure 7 the H spectrum of the compound of example 7.
Figure 8 the H spectrum of the compound of example 8.
Figure 9H spectrum of the compound of example 9.
Figure 10 the H spectrum of the compound of example 10.
FIG. 11H spectrum of the compound of example 11.
Figure 12H spectrum of the compound of example 12.
FIG. 13H spectrum of the compound of example 13.
Figure 14H spectrum of the compound of example 14.
Detailed Description
The application provides a method for synthesizing alpha difluoro ester derivatives by using [ bis (2- (ethoxycarbonyl) -2, 2-difluoroacetoxyl) iodo ] benzene as a difluoro ethyl acetate radical precursor, and the reaction general formula is shown as follows:
the operation steps are as follows:
firstly, carrying out anhydrous and anaerobic treatment on a 10mL Schlenk tube, removing the wall and the tube orifice of the reaction tube and residual moisture in the tube at high temperature through a baking gun, carrying out nitrogen and air displacement in the reaction tube through double discharge tubes to create an anhydrous and anaerobic environment, after the Schlenk tube is cooled in a nitrogen atmosphere, sequentially adding olefin (0.30 mmol) and [ bis (2- (ethoxycarbonyl) -2, 2-difluoroacetoxy) iodo ] benzene (0.60 mmol) into the reaction tube, taking 2.00mL anhydrous THF under the protection of double discharge tubes nitrogen by using a long needle syringe, adding the two reactants into the reaction tube under stirring, and carrying out room temperature reaction under the illumination of a blue 12W LED lamp. After confirming completion of the reaction by TLC, a large amount of water was added for washing, extraction with ethyl acetate three times, washing with saturated sodium chloride solution, drying the organic phase with anhydrous sodium sulfate, removing the solvent by rotary evaporation, purifying the residue by silica gel column chromatography to obtain the product (petroleum ether: ethyl acetate as mobile phase system).
The following is described in detail by way of example:
example 1
To a stirred solution of toluene (4 mL) was added iodobenzene diacetic acid (4 mmol), and 2- (ethoxycarbonyl) -2, 2-difluoroacetic acid (1.00 mL,16 mmol) was added dropwise at room temperature. After stirring for 30min, the solvent was dried. To the crude mixture is addedToluene (2 mL) was added and the mixture was concentrated again to completely remove unreacted complete acid. After evaporation, the corresponding [ bis (2- (ethoxycarbonyl) -2, 2-difluoroacetoxy) iodo-is obtained without further purification]Benzene, white solid, 92% yield. 1 H NMR(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＝7.2Hz,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),161.10,160.89,160.79,137.46,135.07,134.99,133.36,131.82,131.79,130.28,129.05,128.25,127.50,125.32,123.09,122.98,104.89(t,J＝262.0Hz,2C),63.99(t,J＝12.0Hz,2C),29.68,29.35,21.41,13.70(t,J＝40.0Hz,2C). 19 F NMR(376MHz,CDCl 3 )δ-109.88(s,4F).
Example 2
Firstly, carrying out anhydrous and anaerobic treatment on a 10mL Schlenk tube, removing the wall of the reaction tube, a tube orifice and residual moisture in the tube at high temperature through a baking gun, carrying out nitrogen and air displacement in the reaction tube through double discharge tubes to create an anhydrous and anaerobic environment, cooling the Schlenk tube in a nitrogen atmosphere, and then, carrying out the reaction on 1-benzoate 5-hexene (0.30 mmol) and [ bis (2- (ethoxycarbonyl) -2, 2-difluoroacetoxy) iodine]Benzene (0.60 mmol) was added sequentially to the reaction tube, 2.00mL of anhydrous THF was injected into the reaction tube with a long needle syringe under the protection of double-row nitrogen, the two reactants were dissolved with stirring, and the reaction was carried out at room temperature under illumination of a blue 12W LED lamp. After confirming completion of the reaction by TLC, a large amount of water was added for washing, extraction with ethyl acetate three times, washing with saturated sodium chloride solution, drying the organic phase with anhydrous sodium sulfate, removing the solvent by rotary evaporation, purifying the residue by silica gel column chromatography to give the product as a colorless oil with a yield of 73%. 1 H NMR(400MHz,CDCl 3 )δ8.05(d,J＝7.24Hz,2H),7.55(t,J＝7.36Hz,1H),7.43(t,J＝7.72Hz,2H),4.34-4.29(m,4H),2.13-2.00(m,2H),1.80-174(m,2H),1.54-1.42(m,6H),1.34(t,J＝7.12Hz,3H). 13 C NMR(100MHz,CDCl 3 )δ166.6,164.3(t,J＝32.7Hz,1C),136.6,132.9,130.4,129.5,128.3,116.3(t,J＝248.5Hz,1C),64.8,64.1,62.7,34.4(t,J＝22.9Hz,1C),28.7,28.5,25.7,21.4(t,J＝4.2Hz,1C),13.9. 19 F NMR(376MHz,CDCl 3 )δ-105.91(s,2F).
Example 3
Firstly, carrying out anhydrous and anaerobic treatment on a 10mL Schlenk tube, removing the residual moisture in the wall, the tube orifice and the tube of the reaction tube at high temperature through a baking gun, carrying out nitrogen and air displacement in the reaction tube through double discharge tubes to create an anhydrous and anaerobic environment, cooling the Schlenk tube in a nitrogen atmosphere, and then adding (pent-4-ene-1-oxy) benzene (0.30 mmol) and [ bis (2- (ethoxycarbonyl) -2, 2-difluoroacetoxy) iodine]Benzene (0.60 mmol) was added sequentially to the reaction tube, 2.00mL of anhydrous THF was injected into the reaction tube with a long needle syringe under the protection of double-row nitrogen, the two reactants were dissolved with stirring, and the reaction was carried out at room temperature under illumination of a blue 12W LED lamp. After confirming completion of the reaction by TLC, a large amount of water was added for washing, extraction with ethyl acetate three times, washing with saturated sodium chloride solution, drying the organic phase with anhydrous sodium sulfate, removing the solvent by rotary evaporation, purifying the residue by silica gel column chromatography to give the product as a colorless oil, yield 65%. 1 H NMR(400MHz,CDCl 3 )δ7.27(t,J＝7.52Hz,2H),6.95(t,J＝7.36Hz,1H),6.88(d,J＝7.88Hz,2H),4.31(q,J＝7.16,2H),3.95(t,J＝6.32Hz,2H),2.15-2.03(m,2H),1.83-1.76(m,2H),1.54(t,J＝3.76Hz,2H),1.34(t,J＝7.12Hz,3H). 13 C NMR(100MHz,CDCl 3 )δ164.7(t,J＝32.77Hz,1C),160.0,133.8,129.5,120.6,116.3(t,J＝248.5Hz,1C),114.5,67.4,67.0,62.8,34.4(t,J＝23.0Hz,1C),29.0,25.7,21.3(t,J＝4.3Hz,1C),14.0. 19 FNMR(376MHz,CDCl 3 )δ-105.92(s,2F).HRMS ESI(m/z):calcd for C 15 H 20 O 3 F 2 [M+Na] + ,309.1273,found:309.1272.
Example 4
Firstly, carrying out anhydrous and anaerobic treatment on a 10mL Schlenk tube, removing the wall of the reaction tube, a tube orifice and residual moisture in the tube at high temperature through a baking gun, carrying out nitrogen and air displacement in the reaction tube through double discharge tubes to create an anhydrous and anaerobic environment, cooling the Schlenk tube in a nitrogen atmosphere, and then carrying out the steps of (1) allyl 4-cyanoaniline (0.30 mmol), [ bis (2- (ethoxycarbonyl) -2, 2-difluoroacetoxyl) iodine]Benzene (0.60 mmol) was added sequentially to the reaction tube, 2.00mL of anhydrous THF was injected into the reaction tube with a long needle syringe under the protection of double-row nitrogen, the two reactants were dissolved with stirring, and the reaction was carried out at room temperature under illumination of a blue 12W LED lamp. After confirming completion of the reaction by TLC, a large amount of water was added for washing, extraction with ethyl acetate three times, washing with saturated sodium chloride solution, drying the organic phase with anhydrous sodium sulfate, removing the solvent by rotary evaporation, purifying the residue by silica gel column chromatography to obtain a product, white solid, yield 85%. 1 H NMR(400MHz,CDCl 3 )δ7.88(d,J＝8.36Hz,2H),7.74(d,J＝8.40Hz,2H),6.58(s,1H),4.33(q,J＝7.16,2H),3.53(q,J＝6.76Hz,2H),2.23-2.11(m,2H),1.89-1.82(m,2H),1.35(t,J＝7.12Hz,3H). 13 C NMR(100MHz,CDCl 3 )δ166.0,164.1(t,J＝32.51Hz,1C),138.3,132.5,127.7,118.0,116.0(t,J＝248.9Hz,1C),115.1,63.1,54.4,39.4,31.8(t,J＝23.4Hz,1C),29.7,21.8(t,J＝3.9Hz,1C),14.0. 19 F NMR(376MHz,CDCl 3 )δ-105.72(s,2F).HRMS ESI(m/z):calcd for C 15 H 16 O 3 F 2 N 2 [M+Na] + ,333.1021,found:333.1024.
Example 5
Firstly, 10mL Schlenk tube is subjected to anhydrous and anaerobic treatment, residual moisture in the wall, the tube orifice and the tube is removed at high temperature by a baking gun, nitrogen and air displacement are carried out in the reaction tube by double discharge tubes, an anhydrous and anaerobic environment is created, after the Schlenk tube is cooled in a nitrogen atmosphere, allyl 4-bromobenzamide (0.30 mmol) is added to the reaction tubeBis (2- (ethoxycarbonyl) -2, 2-difluoroacetoxy) iodo]Benzene (0.60 mmol) was added sequentially to the reaction tube, 2.00mL of anhydrous THF was injected into the reaction tube with a long needle syringe under the protection of double-row nitrogen, the two reactants were dissolved with stirring, and the reaction was carried out at room temperature under illumination of a blue 12W LED lamp. After confirming completion of the reaction by TLC, a large amount of water was added for washing, extraction with ethyl acetate three times, washing with saturated sodium chloride solution, drying the organic phase with anhydrous sodium sulfate, removing the solvent by rotary evaporation, purifying the residue by silica gel column chromatography to give the product as a pale yellow oil in 96% yield. 1 H NMR(400MHz,CDCl 3 )δ7.63(d,J＝8.56Hz,2H),7.56(d,J＝8.60Hz,2H),6.45(s,1H),4.32(q,J＝7.12,2H),3.50(q,J＝6.36Hz,2H),2.22-2.10(m,2H),1.87-1.79(m,2H),1.35(t,J＝7.12Hz,3H). 13 C NMR(100MHz,CDCl 3 )δ166.8,164.1(t,J＝32.57Hz,1C),133.2,131.8,128.5,126.2,116.0(t,J＝248.8Hz,1C),107.6,63.1,106.4,67.7,67.4,63.0,39.2,31.9(t,J＝23.5Hz,1C),29.6,23.8,21.9(t,J＝3.8Hz,1C),14.0. 19 F NMR(376MHz,CDCl 3 )δ-105.77(s,2F).
Example 6
Firstly, carrying out anhydrous and anaerobic treatment on a 10mL Schlenk tube, removing the residual moisture in the wall, the tube orifice and the tube of the reaction tube at high temperature through a baking gun, carrying out nitrogen and air displacement in the reaction tube through double discharge tubes to create an anhydrous and anaerobic environment, cooling the Schlenk tube in a nitrogen atmosphere, and then adding (9H-fluoren-9-yl) methallyl carbamate (0.30 mmol) and [ bis (2- (ethoxycarbonyl) -2, 2-difluoroacetoxy) iodine]Benzene (0.60 mmol) was added sequentially to the reaction tube, 2.00mL of anhydrous THF was injected into the reaction tube with a long needle syringe under the protection of double-row nitrogen, the two reactants were dissolved with stirring, and the reaction was carried out at room temperature under illumination of a blue 12WLED lamp. After confirming completion of the reaction by TLC, a large amount of water was added for washing, extraction with ethyl acetate three times, washing with saturated sodium chloride solution, drying the organic phase with anhydrous sodium sulfate, removing the solvent by rotary evaporation, purifying the residue by silica gel column chromatography to give a product, white solidThe yield of the obtained product was 90%. 1 H NMR(400MHz,CDCl 3 )δ7.75(d,J＝7.52Hz,2H),7.57(d,J＝7.44Hz,2H),7.39(t,J＝7.36Hz,2H),7.30(t,J＝7.04Hz,2H),4.88(s,1H),4.41(d,J＝6.76Hz,2H),4.1(q,J＝7.16,2H),4.20(t,J＝6.64Hz,1H),3.24(q,J＝6.52Hz,2H),2.15-2.02(m,2H),1.74-1.69(m,2H),1.34(t,J＝7.16Hz,3H). 13 C NMR(100MHz,CDCl 3 )δ164.1(t,J＝32.57Hz,1C),156.4,133.9,141.3,127.7,127.1,125.0,120.0,,116.0(t,J＝249.1Hz,1C),107.7,106.4,67.7,67.4,66.6,63.0,47.3,40.2,31.7(t,J＝23.9Hz,1C),29.6,23.9,22.3,14.0. 19 F NMR(376MHz,CDCl 3 )δ-105.84(s,2F).HRMS ESI(m/z):calcd for C 22 H 23 O 4 F 2 N[M+Na] + ,404.1668,found:404.1669.
Example 7
Firstly, carrying out anhydrous and anaerobic treatment on a 10mL Schlenk tube, removing the wall of the reaction tube, a tube orifice and residual moisture in the tube at high temperature through a baking gun, carrying out nitrogen and air displacement in the reaction tube through double discharge tubes to create an anhydrous and anaerobic environment, cooling the Schlenk tube in a nitrogen atmosphere, and then carrying out treatment on allylthiophene-2-carboxamide (0.30 mmol) and [ bis (2- (ethoxycarbonyl) -2, 2-difluoroacetoxy) iodine]Benzene (0.60 mmol) was added sequentially to the reaction tube, 2.00mL of anhydrous THF was injected into the reaction tube with a long needle syringe under the protection of double-row nitrogen, the two reactants were dissolved with stirring, and the reaction was carried out at room temperature under illumination of a blue 12W LED lamp. After confirming completion of the reaction by TLC, a large amount of water was added for washing, extraction with ethyl acetate three times, washing with saturated sodium chloride solution, drying the organic phase with anhydrous sodium sulfate, removing the solvent by rotary evaporation, purifying the residue by silica gel column chromatography to give the product as a pale yellow oil in a yield of 70%. 1 H NMR(400MHz,CDCl 3 )δ7.53(dd,J＝3.68,0.96Hz,1H),7.47(dd,J＝5.00,0.96Hz,1H),7.068(dd,J＝4.92,3.80,1H),6.44(s,1H),4.32(q,J＝7.12,2H),3.49(q,J＝6.48Hz,2H),2.22-2.09(m,2H),1.86-1.78(m,2H),1.34(t,J＝7.12Hz,3H). 13 C NMR(100MHz,CDCl 3 )δ164.1(t,J＝32.57Hz,1C),162.2,138.8,130.0,128.1,127.7,116.0(t,J＝248.8Hz,1C),63.0,39.1,31.9(t,J＝23.4Hz,1C),22.0(t,J＝4.1Hz,1C),14.0. 19 F NMR(376MHz,CDCl 3 )δ-105.80(s,2F).HRMS ESI(m/z):calcd for C 12 H 15 O 3 F 2 NS[M+Na] + ,314.0633,found:314.0636.
Example 8
Firstly, carrying out anhydrous and anaerobic treatment on a 10mL Schlenk tube, removing the residual moisture in the wall, the tube orifice and the tube of the reaction tube at high temperature through a baking gun, carrying out nitrogen and air displacement in the reaction tube through double discharge tubes to create an anhydrous and anaerobic environment, cooling the Schlenk tube in a nitrogen atmosphere, and then carrying out the reaction of (pyrimidine-4-yl) hept-6-enamine (0.30 mmol) and [ bis (2- (ethoxycarbonyl) -2, 2-difluoroacetoxy) iodine]Benzene (0.60 mmol) was added sequentially to the reaction tube, 2.00mL of anhydrous THF was injected into the reaction tube with a long needle syringe under the protection of double-row nitrogen, the two reactants were dissolved with stirring, and the reaction was carried out at room temperature under illumination of a blue 12W LED lamp. After confirming completion of the reaction by TLC, a large amount of water was added for washing, extraction with ethyl acetate three times, washing with saturated sodium chloride solution, drying the organic phase with anhydrous sodium sulfate, removing the solvent by rotary evaporation, purifying the residue by silica gel column chromatography to obtain a product, a white solid, yield 60%. 1 H NMR(400MHz,CDCl 3 )δ8.86(s,1H),8.64(d,J＝4.12Hz,1H),8.18(d,J＝6.00Hz,1H),4.33(q,J＝7.12,2H),2.44(t,J＝7.40Hz,2H),2.12-1.99(m,2H),1.77-1.72(m,2H),1.51-1.46(m,2H),1.35(t,J＝7.16Hz,3H). 13 C NMR(100MHz,CDCl 3 )δ172.3,164.4,158.4,158.3,160.0,116.3(t,J＝248.6Hz,1C),110.2,62.8,37.5,34.3(t,J＝23.2Hz,1C),29.7,28.7(d,J＝2.25Hz,1C),24.7,21.3(t,J＝4.02Hz,1C),14.0. 19 F NMR(376MHz,CDCl 3 )δ-105.94(s,2F).HRMS ESI(m/z):calcd for C 15 H 21 O 3 F 2 N 3 [M+Na] + ,330.1624,found:330.1625.
Example 9
Firstly, carrying out anhydrous and anaerobic treatment on a 10mL Schlenk tube, removing residual moisture in the wall, a tube orifice and the tube at high temperature through a baking gun, carrying out nitrogen gas and air displacement in the reaction tube through double discharge tubes to create an anhydrous and anaerobic environment, cooling the Schlenk tube in a nitrogen atmosphere, and then carrying out treatment on 2- (prop-2-yn-1-yl) isoindoline-1, 3-dione (0.30 mmol), [ bis (2- (ethoxycarbonyl) -2, 2-difluoroacetoxy) iodine]Benzene (0.60 mmol) was added sequentially to the reaction tube, 2.00mL of anhydrous THF was injected into the reaction tube with a long needle syringe under the protection of double-row nitrogen, the two reactants were dissolved with stirring, and the reaction was carried out at room temperature under illumination of a blue 12WLED lamp. After confirming completion of the reaction by TLC, a large amount of water was added for washing, extraction with ethyl acetate three times, washing with saturated sodium chloride solution, drying the organic phase with anhydrous sodium sulfate, removing the solvent by rotary evaporation, purifying the residue by silica gel column chromatography to obtain a product, white solid, yield 84%. 1 H NMR(400MHz,CDCl 3 )δ7.82(dq,J＝49.28,3.04Hz,4H),6.37-6.29(m,1H),5.93-5.84(m,1H),4.40-4.38(m,2H),4.31(q,J＝7.16,2H),1.33(t,J＝7.16Hz,3H). 13 C NMR(100MHz,CDCl 3 )δ167.5,163.4(t,J＝33.89Hz,1C),134.3,132.4(t,J＝8.83Hz,1C),131.9,124.0(t,J＝25.39Hz,1C),123.5,117.72(t,J＝247.2Hz,1C),63.2,50.9,38.1,29.7,13.9. 19 FNMR(376MHz,CDCl 3 )δ-104.08(s,2F).HRMS ESI(m/z):calcd for C 15 H 13 O 4 F 2 N[M+Na] + ,332.0705,found:332.0706.
Example 10
Firstly, carrying out anhydrous and anaerobic treatment on a 10mL Schlenk tube, removing the wall and the mouth of a reaction tube and residual moisture in the tube at high temperature through a baking gun, carrying out nitrogen and air displacement in the reaction tube through double calandria, creating an anhydrous and anaerobic environment, and waiting for Schlenk after cooling in a nitrogen atmosphere, 2-allylindoline-1, 3-dione (0.30 mmol), [ bis (2- (ethoxycarbonyl) -2, 2-difluoroacetoxy) iodo ]]Benzene (0.60 mmol) was added sequentially to the reaction tube, 2.00mL of anhydrous THF was injected into the reaction tube with a long needle syringe under the protection of double-row nitrogen, the two reactants were dissolved with stirring, and the reaction was carried out at room temperature under illumination of a blue 12W LED lamp. After confirming completion of the reaction by TLC, a large amount of water was added for washing, extraction with ethyl acetate three times, washing with saturated sodium chloride solution, drying the organic phase with anhydrous sodium sulfate, removing the solvent by rotary evaporation, purifying the residue by silica gel column chromatography to give the product as a colorless oil with a yield of 92%. 1 HNMR(400MHz,CDCl 3 )δ7.79(dq,J＝47.52,3.08Hz,4H),4.32(q,J＝7.12Hz,2H),3.76(t,J＝7.00Hz,2H),2.20-2.08(m,2H),1.94-1.82(m,2H),1.34(t,J＝7.16Hz,3H). 13 C NMR(100MHz,CDCl 3 )δ202.3,168.2,163.9(t,J＝32.52Hz,1C),134.1,131.9,132.3(d,J＝7.30Hz,1C),115.7(t,J＝248.86Hz,1C),107.6,106.3,103.8,67.6,67.4,62.9,53.5,37.1,31.8,29.5(m,1C),23.8(d,J＝2.14Hz,1C),20.9(t,J＝4.24Hz,1C),13.9. 19 FNMR(376MHz,CDCl 3 )δ-106.03(s,2F).
Example 11
Firstly, carrying out anhydrous and anaerobic treatment on a 10mL Schlenk tube, removing the residual moisture in the wall, the tube orifice and the tube of the reaction tube at high temperature through a baking gun, carrying out nitrogen and air displacement in the reaction tube through double discharge tubes to create an anhydrous and anaerobic environment, cooling the Schlenk tube in a nitrogen atmosphere, and then carrying out the steps of (1) cooling the Schlenk tube in the nitrogen atmosphere, and (2) bis (ethoxycarbonyl) -2, 2-difluoroacetoxy) iodide]Benzene (0.60 mmol) was added sequentially to the reaction tube, 2.00mL of anhydrous THF was injected into the reaction tube with a long needle syringe under the protection of double-row nitrogen, the two reactants were dissolved with stirring, and the reaction was carried out at room temperature under illumination of a blue 12W LED lamp. After confirming completion of the reaction by TLC, a large amount of water was added for washing, extraction with ethyl acetate three times, washing with saturated sodium chloride solution, drying the organic phase with anhydrous sodium sulfate, and subjecting the solvent to rotary evaporationThe residue was removed and purified by silica gel column chromatography to give the product as a colorless oil in 73% yield. 1 HNMR(400MHz,CDCl 3 )δ7.73(d,J＝7.32Hz,2H),7.71(t,J＝7.40Hz,1H),7.61(t,J＝7.88Hz,2H),4.33(q,J＝7.12Hz,2H),3.33-3.28(m,2H),2.59-2.47(m,2H),1.34(t,J＝7.16Hz,3H). 13 C NMR(100MHz,CDCl 3 )δ163.0(t,J＝31.90Hz,1C),138.3,134.3,129.6,128.1,114.2(t,J＝250.84Hz,1C),63.6,49.0(t,J＝4.01Hz,1C),29.7,29.5,28.2(t,J＝24.35Hz,1C),13.9. 19 FNMR(376MHz,CDCl 3 )δ-105.99(s,2F).
Example 12
Firstly, 10mL of Schlenk tube is subjected to anhydrous and anaerobic treatment, residual moisture in the wall, a tube orifice and the tube is removed at high temperature through a baking gun, nitrogen and air displacement in the reaction tube are carried out through double discharge tubes, an anhydrous and anaerobic environment is created, after the Schlenk tube is cooled in a nitrogen atmosphere, dimethyl (phenyl) (vinyl) silane (0.30 mmol) and [ bis (2- (ethoxycarbonyl) -2, 2-difluoroacetoxy) iodine are added]Benzene (0.60 mmol) was added sequentially to the reaction tube, 2.00mL of anhydrous THF was injected into the reaction tube with a long needle syringe under the protection of double-row nitrogen, the two reactants were dissolved with stirring, and the reaction was carried out at room temperature under illumination of a blue 12W LED lamp. After confirming completion of the reaction by TLC, a large amount of water was added for washing, extraction with ethyl acetate three times, washing with saturated sodium chloride solution, drying the organic phase with anhydrous sodium sulfate, removing the solvent by rotary evaporation, purifying the residue by silica gel column chromatography to give the product as a colorless oil, yield 75%. 1 HNMR(400MHz,CDCl 3 )δ7.31(dd,J＝5.60,3.88,2.20Hz,2H),7.15(d,J＝2.08Hz,2H),7.19(d,J＝1.52Hz,1H),4.12(q,J＝7.12Hz,2H),1.90-1.77(m,2H),1.15(t,J＝7.12Hz,3H),0.71-0.67(m,2H),0.13(s,6H). 13 CNMR(100MHz,CDCl 3 )δ164.4(t,J＝32.96Hz,1C),137.9,137.6,133.9(d,J＝4.40Hz,1C),133.5,129.6,129.3,128.8,128.0,127.9,127.7,116.8(t,J＝248.76Hz,1C),63.0,62.7,29.4(t,J＝24.16Hz,1C),14.0,6.9(t,J＝2.79Hz,1C),-3.4(t,J＝-25.67Hz,1C). 19 F NMR(376MHz,CDCl 3 )δ-107.39(s,2F).HRMS ESI(m/z):calcd for C 14 H 20 O 2 F 2 Si[M+Na] + ,309.1093,found:309.1097.
Example 13
Firstly, carrying out anhydrous and anaerobic treatment on a 10mL Schlenk tube, removing the residual moisture in the wall, the tube orifice and the tube of the reaction tube at high temperature through a baking gun, carrying out nitrogen and air displacement in the reaction tube through double discharge tubes to create an anhydrous and anaerobic environment, cooling the Schlenk tube in a nitrogen atmosphere, and then adding allylbenzamide (0.30 mmol) and [ bis (2- (ethoxycarbonyl) -2, 2-difluoroacetoxy) iodine]Benzene (0.60 mmol) was added sequentially to the reaction tube, 2.00mL of anhydrous THF was injected into the reaction tube with a long needle syringe under the protection of double-row nitrogen, the two reactants were dissolved with stirring, and the reaction was carried out at room temperature under illumination of a blue 12W LED lamp. After confirming completion of the reaction by TLC, a large amount of water was added for washing, extraction with ethyl acetate three times, washing with saturated sodium chloride solution, drying the organic phase with anhydrous sodium sulfate, removing the solvent by rotary evaporation, purifying the residue by silica gel column chromatography to give the product as a colorless oil with a yield of 60%. 1 HNMR(400MHz,CDCl 3 )δ7.75(d,J＝7.44Hz,2H),7.51(t,J＝7.32Hz,1H),7.42(d,J＝7.60Hz,2H),6.61(s,1H),4.32(q,J＝7.16,2H),3.52(q,J＝6.56Hz,2H),2.22-2.10(m,2H),1.87-1.80(m,2H),1.34(t,J＝7.12Hz,3H). 13 C NMR(100MHz,CDCl 3 )δ168.5,164.1(t,J＝32.63Hz,1C),134.0,131.8,128.7,127.0,116.0(t,J＝248.8Hz,1C),63.6,63.0,39.3,31.9,31.8(t,J＝23.4Hz,1C),29.7(t,J＝3.96Hz,1C),29.4,22.7,21.9(t,J＝4.0Hz,1C),14.1,13.9,13.8. 19 FNMR(376MHz,CDCl 3 )δ-105.72(s,2F).HRMS ESI(m/z):calcd for C 14 H 17 O 3 F 2 N[M+H] + ,286.1249,found:286.1249。
Example 14
Firstly, carrying out anhydrous and anaerobic treatment on a 10mL Schlenk tube, removing the wall of the reaction tube, a tube orifice and residual moisture in the tube at high temperature through a baking gun, carrying out nitrogen and air displacement in the reaction tube through double discharge tubes to create an anhydrous and anaerobic environment, cooling the Schlenk tube in a nitrogen atmosphere, and then carrying out the reaction of allylthio-2-formamide (0.30 mmol) and [ bis (2- (ethoxycarbonyl) -2, 2-difluoroacetoxy) iodide]Benzene (0.60 mmol) was added sequentially to the reaction tube, 2.00mL of anhydrous THF was injected into the reaction tube with a long needle syringe under the protection of double-row nitrogen, the two reactants were dissolved with stirring, and the reaction was carried out at room temperature under illumination of a blue 12W LED lamp. After confirming completion of the reaction by TLC, a large amount of water was added for washing, extraction with ethyl acetate three times, washing with saturated sodium chloride solution, drying the organic phase with anhydrous sodium sulfate, removing the solvent by rotary evaporation, purifying the residue by silica gel column chromatography to give a yellow oil, yield 50%. 1 HNMR(400MHz,CDCl 3 )δ7.44(d,J＝0.92Hz,1H),7.11(dd,J＝3.44,0.48Hz,2H),6.50(q,J＝1.72Hz,1H),6.43(s,1H),4.33(q,J＝7.16Hz,2H),3.50(q,J＝6.76cHz,2H),2.23-2.10(m,2H),1.86-1.79(m,2H),1.35(t,J＝7.12Hz,3H). 13 C NMR(100MHz,CDCl 3 )δ164.1,158.5,147.8,143.9,114.3,112.2,63.0,38.2,31.7(d,J＝23.39Hz,1C),22.1(d,J＝3.91Hz,1C),14.0. 19 FNMR(376MHz,CDCl 3 )δ-105.94(s,2F).HRMS ESI(m/z):calcd for C 15 H 21 O 3 F 2 N 3 [M+H] + ,276.1042,found:276.1044。

Claims (2)

1. A method for synthesizing alpha difluoro ester derivatives from terminal olefins is characterized in that: a method for preparing alpha difluoro ester derivatives from terminal olefins by photocatalysis by using [ bis (2- (ethoxycarbonyl) -2, 2-difluoroacetoxyl) iodo ] benzene as a free radical precursor of ethyl difluoroacetate;
the method comprises the following specific steps: adding terminal olefin, [ bis (2- (ethoxycarbonyl) -2, 2-difluoroacetoxyl) iodine ] benzene and tetrahydrofuran under anhydrous and anaerobic conditions, reacting at room temperature under the illumination of a blue 12W LED lamp, extracting, washing, drying and separating by column chromatography to obtain an alpha difluoro ester derivative;
the reaction general formula is as follows:
wherein R is selected from the group consisting of a benzamide group, a phenyl ether group, a benzamide group, a thiophenecarboxamide group, a furancarboxamide group, and a phthalimide group; n=2-6.
2. The method for synthesizing an alpha difluoroester derivative from a terminal olefin according to claim 1, wherein: bis (2- (ethoxycarbonyl) -2, 2-difluoroacetoxy) iodo ] benzene is used as a difluoro reagent.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012250964A (en) * 2011-06-07 2012-12-20 Sagami Chemical Research Institute Method for producing (trifluoromethylsulfonyl)benzene derivative
CN112321553A (en) * 2020-10-30 2021-02-05 天津科技大学 Method for synthesizing 3-position difluoromethyl substituted coumarin derivative from aryl alkyne acid ester
WO2021169199A1 (en) * 2020-02-24 2021-09-02 江西师范大学 α-CARBONYL ALKENYL ESTER COMPOUND, PREPARATION METHOD THEREFOR AND APPLICATION THEREOF

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012250964A (en) * 2011-06-07 2012-12-20 Sagami Chemical Research Institute Method for producing (trifluoromethylsulfonyl)benzene derivative
WO2021169199A1 (en) * 2020-02-24 2021-09-02 江西师范大学 α-CARBONYL ALKENYL ESTER COMPOUND, PREPARATION METHOD THEREFOR AND APPLICATION THEREOF
CN112321553A (en) * 2020-10-30 2021-02-05 天津科技大学 Method for synthesizing 3-position difluoromethyl substituted coumarin derivative from aryl alkyne acid ester

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