CN112047839B - 1-iodine-3-perfluoroalkyl alkene compound and preparation method thereof - Google Patents

1-iodine-3-perfluoroalkyl alkene compound and preparation method thereof Download PDF

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CN112047839B
CN112047839B CN202010801423.9A CN202010801423A CN112047839B CN 112047839 B CN112047839 B CN 112047839B CN 202010801423 A CN202010801423 A CN 202010801423A CN 112047839 B CN112047839 B CN 112047839B
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周磊
李伟宇
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Sun Yat Sen University
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Abstract

The invention discloses a 1-iodine-3-perfluoroalkyl alkene compound and a preparation method thereof. The compound has a structure shown in a formula (I), and the 1-iodine-3-perfluoroalkyl alkene compound can be widely applied to coupling reaction or free-radical cycloaddition reaction due to high chemical activity and rich reactivity. The preparation method has very wide substrate adaptability, and can synthesize various 1-iodine-3-perfluoroalkyl olefin compounds; the raw materials are cheap and easy to obtain, only nitrogen is a byproduct, the green synthesis concept is met, the reaction process is simple to operate, insensitive to air and moisture, high in yield, simple in product separation and purification, high in cis-trans selectivity of alkenyl iodine, suitable for large-scale synthesis, and good in application prospect.

Description

1-iodine-3-perfluoroalkyl alkene compound and preparation method thereof
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a 1-iodo-3-perfluoroalkyl alkene compound and a preparation method thereof.
Background
Fluorine atoms have high electronegativity, and greatly influence the electron cloud distribution, the acid-base property and the dipole moment of the fluorine-containing compound, so that the physicochemical properties of the fluorine-containing compound are obviously changed. Since the beginning of the last century, many fluorine-containing organics have been increasingly used in pharmaceuticals and materials. Scientists have therefore conducted extensive research to find new ways of introducing fluorine atoms or fluorine-containing functional groups into organic molecules, where new ways of introducing perfluoroalkyl groups, particularly trifluoromethyl groups, are of particular interest. Over the past decade, significant advances have been made in the visible-light-promoted 1, 2-perfluoroalkylene iodination of perfluoroalkyl iodides with alkenes or alkynes. In addition to the conventional photosensitizer Ru, Ir complexes, the use of organic dyes, Cu (dap), has been developed in recent years2Cl, and inorganic materials and the like as photosensitizersA fluoroalkyl radical. Furthermore, RfDue to the strong electron withdrawing action of perfluoroalkyl group and the larger atomic radius and better leaving ability of iodine atom, the compound I can form electron donor-acceptor complexes (EDA complexes) with electron-rich additives such as tertiary amine compounds. The compound can generate perfluoroalkyl free radicals under the action of light or heat, thereby realizing free radical conversion without an additional photocatalyst.
Alkenyl iodide compounds have been widely used in various fields of organic synthesis, click chemistry, medicine, biology, and materials because of their high chemical activity and abundant reactivity. They can participate in various forms of coupling reactions, such as: kumada coupling reaction, Negishi coupling reaction and Sonogashira coupling reaction, and can also be used as a precursor of alkenyl free radicals to participate in a series of free ring addition reactions.
However, in the existing synthesis method of alkenyl iodide, it is usually necessary to introduce an initiator and an additive, for example, chinese patent CN106832256A discloses the use of perfluoroalkyl iodide RfThe fluorine-containing nonionic surfactant is obtained by reacting the-I with polyoxyethylene ether containing vinyl or propenyl, and the initiator is added twice in the preparation process, so that the application process has certain limitation.
Therefore, the development of a simple, high-efficiency and high-selectivity preparation method of the alkenyl iodide compound has important theoretical and practical significance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a 1-iodo-3-perfluoroalkyl alkene compound. The 1-iodine-3-perfluoroalkyl alkene compound provided by the invention contains perfluoroalkyl with important application value and alkenyl iodide with high synthesis value, has high chemical activity and rich reactivity, and can be widely applied to coupling reaction or free-radical cycloaddition reaction.
Another object of the present invention is to provide a method for preparing the 1-iodo-3-perfluoroalkylolefin compound. The preparation method has very wide substrate adaptability, and can synthesize various 1-iodine-3-perfluoroalkyl olefin compounds; the raw materials used in the method are cheap and easy to obtain, the by-product is only nitrogen, the method conforms to the green synthesis concept, the reaction process is simple to operate, insensitive to air and moisture, high in yield, simple in product separation and purification, high in cis-trans selectivity of alkenyl iodine, and suitable for large-scale synthesis.
Another object of the present invention is to provide use of the 1-iodo-3-perfluoroalkylolefin compound in a coupling reaction or a radical cycloaddition reaction.
In order to achieve the purpose, the invention adopts the following technical scheme:
a1-iodo-3-perfluoroalkyl alkene compound has a structure shown in formula (I):
Figure BDA0002627527720000021
wherein R is1、R2Independently selected from a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group, R1、R2Are independently substituents or are linked to form a cycloalkyl group; rfSelected from perfluoroalkyl, 2-difluoro-1-acyl, 2-difluoro-1-ester group; EWG is an electron withdrawing group.
The 1-iodine-3-perfluoroalkyl alkene compound provided by the invention has perfluoroalkyl with important application value and alkenyl iodide with high synthesis value, has high chemical activity and rich reactivity, and can be widely applied to coupling reaction or free-radical cycloaddition reaction.
Preferably, the alkyl group is C1～10An alkyl group. Further preferably, the alkyl group is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, sec-butyl, pentyl, neopentyl, or the like. Further preferably, the alkyl group is C1～6Alkyl groups, particularly preferably methyl, ethyl, propyl, butyl and hexyl.
Preferably, said cycloalkyl is C5～8A cycloalkyl group of (a).
Preferably, the aryl group is phenyl or substituted phenyl. The substituents may be one or more, and the positions may be ortho, para and meta. As the substituent of the phenyl group, a general substituent such as an alkyl group, an alkoxy group, a trifluoromethyl group, an alkenyl group, an aryl group, an ester group, a nitro group, a hydroxyl group, a halogen group or the like may be mentioned.
Preferably, the heterocyclic group is thienyl, furyl, pyridyl, thiazolyl, oxazolyl, piperazinyl, tetrahydrofuranyl.
Preferably, the perfluoroalkyl group is C1～10Perfluoroalkyl, 2-difluoro-1-acyl, 2-difluoro-1-ester group.
Further preferably, the 2-difluoro-1-acyl group is a 2-difluoro-1-arylformyl group, a 2-difluoro-1-arylsulfonyl group.
Further preferably, the 2-difluoro-1-acetic acid alkyl ester group, the 2-difluoro-1-acetic acid aryl ester group.
Preferably, the EWG is a formate group.
Further preferably, the EWG is an alkyl formate ester group, an aryl formate ester group.
The preparation method of the 1-iodo-3-perfluoroalkyl alkene compound comprises the following steps:
s1, carrying out ATRA reaction on an alkenyl diazo compound shown in a formula (II) and a perfluoroalkyl iodide shown in a formula (III) in an organic solvent under the condition of visible light to obtain an isomer mixture of a 1-iodo-3-perfluoroalkyl alkene compound;
s2, carrying out isomerization reaction on the 1-iodine-3-perfluoroalkyl alkene compound isomer mixture obtained in the step S1 under the condition of a manganese catalyst to obtain the cis-1-iodine-3-perfluoroalkyl alkene compound.
Figure BDA0002627527720000031
The preparation method has very wide substrate adaptability, and can synthesize various 1-iodine-3-perfluoroalkyl olefin compounds; the raw materials used in the method are cheap and easy to obtain, the by-product is only nitrogen, the method conforms to the green synthesis concept, the reaction process is simple to operate, insensitive to air and moisture, high in yield, simple in product separation and purification, high in cis-trans selectivity of alkenyl iodine, and suitable for large-scale synthesis.
Preferably, the molar ratio of the alkenyl diazo acetate to the perfluoroalkyl iodide is 1: 1-5.
Preferably, the ATRA reaction temperature is 0-80 ℃.
Preferably, the ATRA reaction time is 0.5-72 h.
Preferably, the organic solvent is one or a combination of more of dichloromethane, dichloroethane, ethyl acetate, ethanol, methanol, trifluoroisopropanol, isopropanol, acetonitrile, dimethyl sulfoxide, N-dimethylformamide, dioxane, tetrahydrofuran, toluene or chlorobenzene.
Further preferably, the organic solvent is one or a combination of several of dichloromethane, ethyl acetate, ethanol, trifluoroisopropanol, acetonitrile, tetrahydrofuran, toluene or chlorobenzene.
Preferably, the visible light is one of CFL, LED white light, LED blue light, or sunlight.
Preferably, the manganese catalyst is one or a combination of more of methylcyclopentadienyl manganese tricarbonyl, decamanganese dicarbonyl, cyclopentadienyl manganese tricarbonyl, acetyl cyclopentadienyl manganese tricarbonyl I or cyclopentadienyl manganese tricarbonyl.
Further preferably, the manganese catalyst is a decacarbonyl dimanganese catalyst.
Preferably, the manganese catalyst is added in an amount of 1:0.025 to 1.
Preferably, the isomerization reaction time is 1-20 h.
The 1-iodo-3-perfluoroalkyl alkene compound is applied to coupling reaction or free-radical cycloaddition reaction.
Compared with the prior art, the invention has the following beneficial effects:
the 1-iodine-3-perfluoroalkyl alkene compound provided by the invention has perfluoroalkyl with important application value and alkenyl iodide with high synthesis value, has high chemical activity and rich reactivity, and can be widely applied to coupling reaction or free-radical cycloaddition reaction.
The preparation method has very wide substrate adaptability, and can synthesize various 1-iodine-3-perfluoroalkyl olefin compounds; the raw materials used in the method are cheap and easy to obtain, the by-product is only nitrogen, the method conforms to the green synthesis concept, the reaction process is simple to operate, insensitive to air and moisture, high in yield, simple in product separation and purification, high in cis-trans selectivity of alkenyl iodine, and suitable for large-scale synthesis.
Detailed Description
The invention is further illustrated by the following examples. These examples are intended to illustrate the invention and are not intended to limit the scope of the invention. Experimental procedures without specific conditions noted in the examples below, generally according to conditions conventional in the art or as suggested by the manufacturer; the reactants, reagents and the like used are, unless otherwise specified, those commercially available from the conventional market and the like. Any insubstantial changes and substitutions made by those skilled in the art based on the present invention are intended to be covered by the claims.
The general formula for synthesizing the 1-iodo-3-perfluoroalkyl olefin compound in each example of the invention is as follows:
Figure BDA0002627527720000041
the method comprises the following specific steps:
s1, adding 1 part of alkenyl diazoacetate formula (II) and 1-5 parts of perfluoroalkyl iodide formula (III) into a proper amount of organic solvent, placing the mixture in a sealed reaction test tube, and carrying out ATRA reaction for 0.5-72 h under the illumination condition to generate a Z/E mixture of the 1-iodine-3-perfluoroalkyl alkene compound.
S2, carrying out reduced pressure distillation to spin off redundant perfluoroalkyl iodide, adding a proper amount of organic solvent and 0.025-1 part of manganese catalyst into the Z/E mixture, and continuously reacting for 1-20 h under the irradiation of the same light source to obtain the 1-iodine-3-perfluoroalkyl alkene compound shown in the formula (I).
The parts are molar parts.
Example 1(Z) -5,5, 5-trifluoro-2-iodopent-2-enoic acid butyl ester
Figure BDA0002627527720000051
0.4mmol of n-butyl alkenyldiazoacetate, the appropriate amount of acetonitrile and 0.8mmol of trifluoroiodomethane were added to a Schlenk flask and the reaction was stirred at room temperature for 1h under irradiation with 18W CFL light. And then concentrating the reaction liquid to remove redundant trifluoroiodomethane, adding a proper amount of acetonitrile and 0.06mmol of a decacarbonyl dimanganese catalyst into the reaction test tube, continuing to react for 9 hours under the irradiation of the same light source, concentrating the reaction liquid, and performing column chromatography purification by using a mixed solvent of petroleum ether and ethyl acetate of 50:1 as an eluent to obtain (Z) -5,5, 5-trifluoro-2-iodopent-2-enoic acid butyl ester, wherein the yield is 85%, and the Z/E is more than 30: 1. The structure is as follows:
Figure BDA0002627527720000052
compound nuclear magnetic and high resolution data are as follows:
1H NMR(400MHz,CDCl3)δ7.26(t,J＝6.4Hz,1H),4.25(t,J＝6.5Hz,2H),3.22–3.06(m,2H),1.76–1.66(m,2H),1.49–1.38(m,2H),0.96(t,J＝7.3Hz,3H)。
13C NMR(100MHz,CDCl3)δ162.2,139.9(q,J＝3.6Hz),125.2(q,J＝277.0Hz),101.1,71.02–67.3,42.1(q,J＝30.7Hz),30.6,19.24,13.79。
19F NMR(376MHz,CDCl3)δ-64.83(s,3F)。
HRMS(EI):calcd.for C9H12F3IO2[M]+:335.98286,Found:335.98290。
example 2(Z) -5,5,6,6,7, 7-heptafluoro-2-iodohept-2-enoic acid butyl ester
Figure BDA0002627527720000053
0.4mmol of n-butyl alkenyldiazoacetate, an appropriate amount of acetonitrile and 1.6mmol of perfluoroiodopropane were added to a Schlenk flask and the mixture was stirred under sunlight at room temperature for 5 hours. And then concentrating the reaction liquid to remove redundant heptafluoro iodopropane, adding a proper amount of acetonitrile and 0.01mmol of a decacarbonyl dimanganese catalyst into a reaction test tube, continuing to react for 1h under the irradiation of the same light source, concentrating the reaction liquid, and performing column chromatography purification by using a mixed solvent of petroleum ether/ethyl acetate (50: 1) as an eluent to obtain (Z) -5,5,6,6, 6,7, 7-heptafluoro-2-iodohept-2-gadoleic acid butyl ester, wherein the yield is 86%, and the Z/E is more than 30: 1. The structure is as follows:
Figure BDA0002627527720000061
compound nuclear magnetic and high resolution data are as follows:
1H NMR(400MHz,CDCl3)δ7.31(t,J＝6.6Hz,1H),4.25(t,J＝6.6Hz,2H),3.14(td,J＝17.8,6.6Hz,2H),1.75–1.66(m,2H),1.49–1.38(m,2H),0.97(t,J＝7.4Hz,3H)。
13C NMR(100MHz,CDCl3)δ162.2,139.1(t,J＝4.5Hz),119.2,118.9,116.6,116.4,116.3,116.0,113.8,101.7,67.2,39.5(t,J＝22.1Hz),30.6,19.3,13.8。
19F NMR(376MHz,CDCl3)δ-80.48(t,J＝9.5Hz,3F),-112.22–-112.31(m,2F),-127.32(d,J＝2.4Hz,2F)。
HRMS(ESI):calcd.for C11H11F7IO2[M-H]-:434.96974,Found:434.97014。
example 3(Z) -5,5,6,6,7,7,8,8, 8-nonafluoro-2-iodo-2-enoic acid butyl ester
Figure BDA0002627527720000062
0.4mmol of n-butyl alkenyldiazoacetate, an appropriate amount of dichloromethane and 2.0mmol of nonafluoro-n-butyl iodide were added to a Schlenk flask and the reaction was stirred at room temperature for 10h with 5W LED white light irradiation. And then concentrating the reaction liquid to remove redundant nonafluoro-n-butyl iodide, adding a proper amount of dichloromethane and 0.15mmol of a decacarbonyl dimanganese catalyst into a reaction test tube, continuing to react for 12 hours under the irradiation of the same light source, concentrating the reaction liquid, and purifying by column chromatography by taking a mixed solvent of petroleum ether/ethyl acetate 50:1 as an eluent to obtain (Z) -5,5,6,6,7,7,8,8, 8-nonafluoro-2-iodo-2-gadoleic acid butyl ester, wherein the yield is 85%, and the Z/E is more than 30: 1. The structure is as follows:
Figure BDA0002627527720000063
compound nuclear magnetic and high resolution data are as follows:
1H NMR(400MHz,CDCl3)δ7.31(t,J＝6.6Hz,1H),4.25(t,J＝6.6Hz,2H),3.16(td,J＝17.8,6.5Hz,2H),1.75–1.65(m,2H),1.51–1.38(m,2H),0.97(t,J＝7.4Hz,3H)。
13C NMR(100MHz,CDCl3)δ162.2,139.1(t,J＝4.5Hz),119.4,118.9,118.6,117.2,116.9,116.6,116.0,114.0,101.7,67.2,39.5(t,J＝22.2Hz),30.6,19.2,13.8。
19F NMR(376MHz,CDCl3)δ-81.04–-81.09(m,3F),-111.53(ddd,J＝13.0,5.7,2.2Hz,2F),-123.96–-124.07(m,2F),-126.03(dd,J＝14.9,10.3Hz,2F)。
HRMS(ESI):calcd.for C12H11F9IO2[M-H]-:484.96655,Found:484.96694。
example 4(Z) -4-perfluorohexyl-2-iodo-enoic acid butyl ester
Figure BDA0002627527720000071
Adding 0.4mmol of alkenyl diazoacetic acid n-butyl ester, a proper amount of tetrahydrofuran and 1.2mmol of tridecafluorohexyl n-iodide into a Schlenk bottle, irradiating and stirring the mixture by using 5W LED blue light at 40 ℃ for reaction for 3 hours, concentrating the reaction solution to remove redundant undecafluorohexyl n-iodide, adding a proper amount of dichloromethane and 0.02mmol of decacarbonyl dimanganese catalyst into a reaction test tube, continuously reacting the mixture for 20 hours under the irradiation of the same light source, concentrating the reaction solution, and purifying the mixture by using a petroleum ether/ethyl acetate 50:1 mixed solvent as eluent through column chromatography to obtain the isomerized 1-iodo-3-perfluorohexylolefin compound, wherein the yield is 85%, and the Z/E is more than 30: 1. The structure is as follows:
Figure BDA0002627527720000072
compound nuclear magnetic and high resolution data are as follows:
1H NMR(400MHz,CDCl3)δ7.31(t,J＝6.6Hz,1H),4.25(t,J＝6.6Hz,2H),3.16(td,J＝17.8,6.6Hz,2H),1.75–1.65(m,2H),1.50–1.38(m,2H),0.97(t,J＝7.4Hz,3H)。
13C NMR(100MHz,CDCl3)δ162.2,139.1,101.7,100.2,67.2,39.6(t,J＝22.4Hz),30.6,19.3,13.8。
19F NMR(376MHz,CDCl3)δ-80.83–-80.92(m,3F),-111.24–-111.31(m,2F),-121.88(s,2F),-122.70–-123.14(m,4F),-126.13–-126.20(m,2F)。
HRMS(ESI):calcd.for C14H11F13IO2[M-H]-:584.96016,Found:584.96082。
example 5(Z) -4-perfluorodecyl-2-iodo-n-butyl acrylate
Figure BDA0002627527720000081
0.4mmol of n-butyl alkenyldiazoacetate, an appropriate amount of toluene and 1.6mmol of perfluorodecyl iodide were charged into a Schlenk flask, and after stirring reaction for 2 hours at 50 ℃ under 10W of LED blue light irradiation, the excess perfluorodecyl iodide was removed. And then adding a proper amount of ethanol and 0.04mmol of decacarbonyl dimanganese catalyst into a reaction test tube, continuously reacting for 6 hours under the illumination of the same light source, concentrating the reaction solution, and performing column chromatography purification by using a mixed solvent of petroleum ether/ethyl acetate (50: 1) as an eluent to obtain the isomerized (Z) -4-perfluorodecyl-2-iodine-n-butyl acrylate, wherein the yield is 83 percent, and the Z/E is more than 30: 1. The structure is as follows:
Figure BDA0002627527720000082
compound nuclear magnetic and high resolution data are as follows:
1H NMR(400MHz,CDCl3)δ7.31(td,J＝6.6,2.2Hz,1H),4.25(td,J＝6.6,3.3Hz,2H),3.15(tdd,J＝17.8,5.5,3.7Hz,2H),1.75–1.65(m,2H),1.50–1.39(m,2H),0.96(td,J＝7.4,3.9Hz,3H)。
13C NMR(100MHz,CDCl3)δ162.0(d,J＝5.3Hz),138.9,119.7,119.4,119.1,118.8,118.5,118.2,117.2,116.9,116.5,116.0,115.6,115.3,114.6,114.3,114.0,113.8,113.5,113.2,112.9,112.6,111.1,110.8,110.5,110.2,109.8,108.9,108.5,108.3,108.2,108.0,107.8,107.7,107.5,101.4(d,J＝5.3Hz),77.3,76.9,76.6,67.2,39.4(t,J＝22.3Hz),30.4,19.0,13.6。
19F NMR(376MHz,CDCl3)δ-81.22–-81.70(m,3F),-111.69(d,J＝43.8Hz,2F),-121.93–-122.47(m,10F),-123.27(s,4F),-126.69(d,J＝54.2Hz,2F)。
HRMS(ESI):calcd.for C18H11F21IO2[M-H]-:784.94739,Found:784.94812。
example 6(Z) -5,6,6, 6-tetrafluoro-2-iodo-5- (trifluoromethyl) hexa-2-enoic acid butyl ester
Figure BDA0002627527720000083
Adding 0.4mmol of alkenyl diazoacetate, a proper amount of ethyl acetate and 1.2mmol of heptafluoro isopropyl iodide into a Schlenk bottle, irradiating and stirring the mixture by using 15W LED blue light at the temperature of 80 ℃ for 0.5h, removing redundant heptafluoro isopropyl iodide, adding a proper amount of ethanol and 0.08mmol of decacarbonyl dimanganese catalyst into a reaction test tube, continuously reacting the mixture for 10h under the irradiation of the same light source, concentrating the reaction solution, and purifying the mixture by using a petroleum ether/ethyl acetate 50:1 mixed solvent as an eluent to obtain (Z) -5,6,6, 6-tetrafluoro-2-iodine-5- (trifluoromethyl) hexa-2-butyl enoate, wherein the yield is 86 percent, and the Z/E is more than 30: 1. The structure is as follows:
Figure BDA0002627527720000091
compound nuclear magnetic and high resolution data are as follows:
1H NMR(400MHz,CDCl3)δ7.27(t,J＝6.7Hz,1H),4.25(t,J＝6.6Hz,2H),3.14(dd,J＝19.5,6.8Hz,2H),1.75–1.65(m,2H),1.49–1.37(m,2H),0.96(t,J＝7.4Hz,3H)。
13C NMR(100MHz,CDCl3)δ162.2,139.7(d,J＝6.5Hz),115.7(qd,J＝286.0,27.0Hz),100.9,91.9(dt,J＝64.8,32.3Hz),89.8(dt,J＝64.9,32.4Hz),67.2,36.7(d,J＝19.8Hz),30.6,19.2,13.8。
19F NMR(376MHz,CDCl3)δ-76.65–-76.75(m,7F)。
HRMS(APCI):calcd.for C11H13F7IO2[M+H]+:436.98430,Found:436.98438。
example 7(Z) -5, 5-difluoro-2-iodohexadi-2-enedioic acid 1-ethyl 6-butyl ester
Figure BDA0002627527720000092
Adding 0.4mmol of alkenyl diazoacetic acid n-butyl ester, a proper amount of trifluoro isopropanol and 0.4mmol of difluoro iodoacetic acid ethyl ester into a Schlenk bottle, irradiating and stirring the mixture by using 3W LED blue light at room temperature for 8 hours, removing redundant difluoro iodoacetic acid ethyl ester, then adding a proper amount of acetic ether and 0.2mmol of decacarbonyl dimanganese catalyst into a reaction test tube, continuously reacting the mixture for 10 hours under the irradiation of the same light source, concentrating the reaction solution, and purifying the mixture by using a petroleum ether/ethyl acetate (50: 1) mixed solvent as an eluent column chromatography to obtain the 5, 5-difluoro-2-iodo-hexadi-2-enedioic acid ester 1-ethyl 6-butyl ester, wherein the yield is 86% and the Z/E (19: 1). The structure is as follows:
Figure BDA0002627527720000093
compound nuclear magnetic and high resolution data are as follows:
1H NMR(400MHz,CDCl3)δ7.26(t,J＝6.7Hz,0.95×1H),6.93(t,J＝7.2Hz,0.05×1H),4.36(q,J＝7.2Hz,2H),4.23(t,J＝6.6Hz,2H),3.34(td,J＝16.7,7.1Hz,0.1×2H),3.12(td,J＝16.2,6.7Hz,1.9×2H),1.74–1.64(m,2H),1.50–1.32(m,5H),0.96(t,J＝7.4Hz,3H)。
13C NMR(100MHz,CDCl3)δ163.3(t,J＝32.1Hz),162.3,141.2(t,J＝5.4Hz),114.2(t,J＝252.9Hz),100.6,67.0,66.6,63.5,63.3,42.6(t,J＝24.3Hz),30.6,19.2,14.03,13.8。
19F NMR(376MHz,CDCl3)δ-104.00(s,0.95×2F),-105.62(s,0.05×2F)。
HRMS(ESI):calcd.for C12H18F2IO4[M+H]+:391.02123,Found:391.02140。
example 8(Z) -5, 5-difluoro-2-iodo-5- (benzenesulfonyl) pent-2-enoic acid butyl ester
Figure BDA0002627527720000101
Adding 0.4mmol of alkenyl diazoacetic acid n-butyl ester, a proper amount of chlorobenzene and 0.8mmol of difluoroiodomethyl phenyl sulfone into a Schlenk bottle, irradiating and stirring for reaction for 8 hours at room temperature by 36W CFL, removing redundant difluoroiodomethyl phenyl sulfone, then adding a proper amount of ethyl acetate and 0.4mmol of decacarbonyl dimanganese catalyst into a reaction test tube, continuously reacting for 10 hours under the irradiation of the same light source, concentrating the reaction liquid, and purifying by column chromatography by using a petroleum ether/ethyl acetate (50: 1) mixed solvent as an eluent to obtain the 5, 5-difluoro-2-iodo-5- (benzenesulfonyl) pent-2-enoic acid butyl ester, wherein the yield is 81%, and the Z/E (9: 1). The structure is as follows:
Figure BDA0002627527720000102
compound nuclear magnetic and high resolution data are as follows:
1H NMR(400MHz,CDCl3)δ8.00(t,J＝8.4Hz,2H),7.84–7.76(m,1H),7.69–7.60(m,2H),7.34(t,J＝6.7Hz,0.9×1H),6.98(t,J＝7.1Hz,0.1×1H),4.27–4.19(m,2H),3.64(td,J＝17.4,7.1Hz,0.2×1H),3.39(td,J＝17.1,6.7Hz,1.8×1H),1.73–1.64(m,2H),1.48–1.37(m,2H),0.95(t,J＝7.4Hz,3H)。
13C NMR(100MHz,CDCl3)δ162.1,139.5(t,J＝4.3Hz),135.7,131.8,130.9,129.5,122.6(t,J＝288.0Hz),67.0,38.1(t,J＝20.6Hz),30.5,19.1 13.7。
19F NMR(376MHz,CDCl3)δ-101.38(t,J＝18.1Hz,0.9×2F),-102.66(t,J＝17.9Hz,0.1×2F)。
HRMS(ESI):calcd.for C15H18F2IO4S[M+H]+458.99331,Found:458.99352。
example 9(Z) -5, 5-difluoro-2-iodo-5- (benzoyl) pent-2-enoic acid butyl ester
Figure BDA0002627527720000111
Adding 0.4mmol of alkenyl diazoacetic acid n-butyl ester, a proper amount of chlorobenzene and 1.2mmol of monoiododifluoroacetophenone into a Schlenk bottle, irradiating and stirring the mixture by using a 10W white light LED at room temperature for 20 hours, removing redundant monoiododifluoroacetophenone, then adding a proper amount of ethyl acetate and 0.06mmol of a decacarbonyl dimanganese catalyst into a reaction test tube, continuously reacting the mixture for 10 hours under the irradiation of the same light source, concentrating the reaction solution, and purifying the mixture by using a petroleum ether/ethyl acetate (50: 1) mixed solvent as an eluent column chromatography to obtain the 5, 5-difluoro-2-iodine-5- (benzoyl) pent-2-enoic acid butyl ester, wherein the yield is 89%, and the Z/E (5.4: 1). The structure is as follows:
Figure BDA0002627527720000112
compound nuclear magnetic and high resolution data are as follows:
1H NMR(400MHz,CDCl3)δ8.16–8.08(m,2H),7.69–7.62(m,1H),7.55–7.47(m,2H),7.36(t,J＝6.6Hz,0.84×1H),7.02(t,J＝7.2Hz,0.16×1H),4.27–4.17(m,2H),3.48(td,J＝17.5,7.2Hz,0.32×2H),3.24(td,J＝17.2,6.6Hz,1.68×2H),1.74–1.62(m,2H),1.49–1.37(m,2H),0.96(t,J＝7.4Hz,3H)。
13C NMR(100MHz,CDCl3)δ188.1(t,J＝30.8Hz),163.4,162.5,144.2(t,J＝5.7Hz),142.3(t,J＝5.3Hz),134.8 134.7,131.4,130.4,128.9,118.3(t,J＝256.2Hz),100.2 89.8 67.0,66.6,42.0(t,J＝23.6Hz),37.4(t,J＝23.5Hz),30.6,30.5,19.213.8(d,J＝4.6Hz)。
19F NMR(376MHz,CDCl3)δ-97.33(t,J＝18.3Hz,0.84×2F),-98.92(t,J＝18.6Hz,0.16×2F)。
HRMS(ESI):calcd.for C16H18F2IO3[M+H]+:423.02632,Found:423.02639。
example 10(Z) -6,6, 6-trifluoro-2-iodo-2-enoic acid butyl ester
Figure BDA0002627527720000113
Adding 0.4mmol of alkenyl diazoacetic acid n-butyl ester, a proper amount of chlorobenzene and 2.0mmol of 2-iodine-1, 1, 1-trifluoroethane into a Schlenk bottle, irradiating and stirring the mixture by using a 1W white light LED at 50 ℃ for reaction for 50 hours, removing redundant 2-iodine-1, 1, 1-trifluoroethane, then adding a proper amount of ethyl acetate and a 0.1mmol of a decacarbonyl dimanganese catalyst into a reaction test tube, continuing the reaction for 10 hours under the irradiation of the same light source, concentrating the reaction liquid, and purifying the mixture by using a petroleum ether/ethyl acetate 50:1 mixed solvent as an eluent column chromatography to obtain the isomerized 6,6, 6-trifluoro-2-iodo-2-gadoleic acid butyl ester with the yield of 71% and the Z/E of 13: 1. The structure is as follows:
Figure BDA0002627527720000121
compound nuclear magnetic and high resolution data are as follows:
1H NMR(400MHz,CDCl3)δ7.21(t,J＝7.0Hz,0.93×1H),6.89(t,J＝7.2Hz,0.07×1H),4.22(t,J＝6.6Hz,1.88×2H),4.14(t,J＝6.7Hz,0.12×2H),2.57(dd,J＝15.1,7.4Hz,2H),2.38–2.24(m,2H),1.73–1.61(m,2H),1.49–1.36(m,2H),0.96(t,J＝7.3Hz,3H)。
13C NMR(100MHz,CDCl3)δ166.2,162.6,148.6,144.7,126.4(q,J＝276.7Hz),124.6,123.1,121.9,119.2,100.1,97.6,66.8,64.5,31.8(q,J＝29.3Hz),30.6,29.8(q,J＝3.1Hz),19.2,13.8。
19F NMR(376MHz,CDCl3)δ-66.51(s,0.93×3F),-66.55(s,0.07×3F)。
HRMS(APCI):calcd.for C10H13F3IO2[M-H]-:348.99178,Found:348.99176。
example 11(Z) -5,5,6, 6-tetrafluoro-2, 6-diiodo-2-enoic acid butyl ester
Using n-butyl alkenyldiazoacetate and 1, 2-diiodotetrafluoroethane as raw materials, a compound having the following structure was synthesized according to the method of example 1:
Figure BDA0002627527720000122
yield: 76% and Z/E >30: 1.
Compound nuclear magnetic and high resolution data are as follows:
1H NMR(400MHz,CDCl3)δ7.36(t,J＝8.6Hz,1H),4.22(t,J＝6.6Hz,2H),4.04(d,J＝8.6Hz,2H),1.74–1.64(m,2H),1.50–1.36(m,2H),0.96(t,J＝7.4Hz,3H)。
13C NMR(100MHz,CDCl3)δ162.5,146.8,99.0,67.0,30.7,19.3,13.8,5.8.19F NMR(376MHz,CDCl3)δ-59.99(s,2F),-104.86(s,2F)。
HRMS(APCI):calcd.for C10H11F4I2O2[M-H]-:492.87900,Found:492.87911。
example 12(Z) -5,5, 5-trifluoro-2-iodopent-2-enoic acid tert-butyl ester
Taking alkenyl diazoacetic acid tert-butyl ester and trifluoroiodomethane as raw materials, synthesizing a compound with the following structure according to the method of the embodiment 2:
Figure BDA0002627527720000131
yield: 85%, Z/E >30: 1.
Compound nuclear magnetic and high resolution data are as follows:
1H NMR(400MHz,CDCl3)δ7.13(t,J＝6.6Hz,1H),3.11(qd,J＝10.5,6.8Hz,2H),1.53(s,9H)。
13C NMR(100MHz,CDCl3)δ161.0,138.8(q,J＝3.6Hz),125.3(q,J＝277.1Hz),104.0,83.9,42.2(q,J＝30.6Hz),28.0。
19F NMR(376MHz,CDCl3)δ-64.85(s,3F)。
HRMS(APCI):calcd.for C9H11F3IO2[M-H]-:334.97613,Found:334.97622。
example 13(Z) -6-Chlorohexyl 5,5, 5-trifluoro-2-iodopent-2-enoate
A compound having the following structure was synthesized from 6-chloroalkenyldiazoacetic acid hexyl ester and trifluoroiodomethane according to the method of example 3:
Figure BDA0002627527720000132
yield: 78% and Z/E >30: 1.
Compound nuclear magnetic and high resolution data are as follows:
1H NMR(400MHz,CDCl3)δ7.26(t,J＝6.6Hz,1H),4.25(t,J＝6.6Hz,2H),3.54(t,J＝6.6Hz,2H),3.14(qd,J＝10.5,6.7Hz,2H),1.85–1.69(m,4H),1.55–1.40(m,4H)。
13C NMR(100MHz,CDCl3)δ162.0,139.9(q,J＝3.7Hz),125.1(q,J＝277.1Hz),100.9,67.2,45.0,41.9(q,J＝30.7Hz),32.5,28.4,26.6,25.3。
19F NMR(376MHz,CDCl3)δ-64.79(s,3F)。
HRMS(APCI):calcd.for C11H14ClF3IO2[M-H]-:396.96846,Found:396.96896。
example 14(Z) -5,5, 5-trifluoro-2-iodopent-2-enoic acid allyl ester
Using allyl alkenyl diazoacetate and trifluoroiodomethane as raw materials, a compound having the following structure was synthesized according to the method of example 4:
Figure BDA0002627527720000141
yield: 65% and Z/E >30: 1.
Compound nuclear magnetic and high resolution data are as follows:
1H NMR(400MHz,CDCl3)δ7.30(t,J＝6.6Hz,1H),6.02–5.91(m,1H),5.40(dd,J＝17.2,1.4Hz,1H),5.31(dd,J＝10.4,1.2Hz,1H),4.74(dt,J＝5.7,1.3Hz,2H),3.14(qd,J＝10.5,6.6Hz,2H)。
13C NMR(100MHz,CDCl3)δ161.9,140.4(q,J＝3.7Hz),131.4,125.2(q,J＝277.1Hz),119.3,100.7,67.8,42.2(q,J＝30.7Hz)。
19F NMR(376MHz,CDCl3)δ-64.67(s,3F)。
HRMS(APCI):calcd.for C8H7F3IO2[M-H]-:318.94483,Found:318.94478。
example 15 propargyl (Z) -5,5, 5-trifluoro-2-iodopent-2-enoate
Using propargyl alkenyldiazoacetate and iodotrifluoromethane as raw materials, a compound having the following structure was synthesized according to the method of example 5:
Figure BDA0002627527720000142
yield: 53%, Z/E >30: 1.
Compound nuclear magnetic and high resolution data are as follows:
1H NMR(400MHz,CDCl3)δ7.33(t,J＝6.5Hz,1H),4.84(d,J＝1.1Hz,2H),3.15(qd,J＝10.4,6.6Hz,2H),2.55(t,J＝2.2Hz,1H)。
13C NMR(100MHz,CDCl3)δ161.4,141.4(q,J＝3.6Hz),125.1(q,J＝277.1Hz),99.7,76.0,54.5,42.2(q,J＝30.8Hz)。
19F NMR(376MHz,CDCl3)δ-64.72(s,3F)。
HRMS(APCI):calcd.for C8H5F3IO2[M-H]-:316.92918,Found:316.92941。
example 16(Z) - (3s,5s,7s) -adamantan-1-yl 5,5, 5-trifluoro-2-iodopent-2-enoate
Using alkenyl diazoacetic acid adamantane ester and trifluoroiodomethane as raw materials, according to the method of example 6, a compound having the following structure was synthesized:
Figure BDA0002627527720000151
1h NMR (400M yield: 85%, Z/E)>30:1。
Compound nuclear magnetic and high resolution data are as follows:
Hz,CDCl3)δ7.12(td,J＝6.6,1.0Hz,1H),3.17–3.05(m,2H),2.21(s,3H),2.17(s,6H),1.68(s,6H)。
13C NMR(100MHz,CDCl3)δ160.6,138.7(q,J＝3.6Hz),125.3(q,J＝277.1Hz),104.2,83.9,42.2(q,J＝30.5Hz),41.2,36.21,31.1。
19F NMR(376MHz,CDCl3)δ-64.83(s,3F)。
HRMS(ESI):calcd.for C15H18F3INaO2[M+Na]+:437.01958,Found:437.020039。
example 17(Z) - (R) -2,5,7, 8-tetramethyl-2- ((4R,8R) -4,8, 12-trimethyltridecyl) chromen-6-yl 5,5, 5-trifluoro-2-iodopentan-2-enoate
Using vinyl diazoacetic acid vitamin E ester and trifluoroiodomethane as raw materials, a compound having the following structure was synthesized according to the method of example 7:
Figure BDA0002627527720000152
yield: 74% and Z/E >30: 1.
Compound nuclear magnetic and high resolution data are as follows:
1H NMR(400MHz,CDCl3)δ7.43(t,J＝6.5Hz,1H),3.13(qd,J＝10.4,6.7Hz,2H),2.52(t,J＝6.6Hz,2H),2.02(s,3H),1.94(s,3H),1.90(s,3H),1.79–1.64(m,2H),1.57–1.39(m,3H),1.38–1.11(m,15H),1.10–0.93(m,6H),0.82–0.74(m,12H)。
13C NMR(100MHz,CDCl3)δ160.8,149.9,141.3(d,J＝3.6Hz),141.0,126.6,124.9,123.4,117.7,99.4,75.3,42.2(q,J＝30.8Hz),39.5,37.7,37.6,37.5,37.4,32.9,32.8,28.1,25.0,24.6,22.9,22.8,21.2,20.8,19.9,19.84,19.81,19.18,19.75,13.1,12.3,12.0。
19F NMR(376MHz,CDCl3)δ-64.69(s,3F)。
HRMS(APCI):calcd.for C34H51F3IO3[M-H]-:691.28405,Found:691.28391。
example 18(Z) - (3aS, 5S, 6R, 6aS) -5- ((S) -2, 2-dimethyl-1, 3-dioxolan-4-yl) -2, 2-dimethyltetrahydrofuran [2,3-d ] [1,3] dioxan-6-yl 5,5, 5-trifluoro-2-iodopent-2-enoate
Starting from (3aS, 5S, 6R, 6aS) -5- ((S) -2, 2-dimethyl-1, 3-dioxolan-4-yl) -2, 2-dimethyltetrahydrofuran [2,3-d ] [1,3] dioxol-6-yl 2-diazo-3-enoate and trifluoroiodomethane, a compound having the following structure was synthesized in accordance with the procedure of example 8:
Figure BDA0002627527720000161
yield: 61%, Z/E >30: 1.
Compound nuclear magnetic and high resolution data are as follows:
1H NMR(400MHz,CDCl3)δ7.31(t,J＝6.5Hz,1H),5.93(d,J＝3.5Hz,1H),5.32(d,J＝2.7Hz,1H),4.57(d,J＝3.5Hz,1H),4.37–4.27(m,1H),4.24(dd,J＝8.2,2.7Hz,1H),4.14(dd,J＝8.4,5.9Hz,1H),4.02(dd,J＝8.5,4.9Hz,1H),3.22–3.10(m,2H),1.54(s,3H),1.41(s,3H),1.31(d,J＝3.5Hz,6H)。
13C NMR(100MHz,CDCl3)δ161.0,141.3(d,J＝3.1Hz),125.1(q,J＝277.1Hz),112.6(d,J＝2.7Hz),109.6(d,J＝2.5Hz),105.2,99.0,83.1,80.1,79.0,72.5,67.7,42.0(q,J＝30.8Hz),26.9,26.8,26.3,25.2。
19F NMR(376MHz,CDCl3)δ-64.72(s,3F)。
HRMS(APCI):calcd.for C17H21F3IO7[M-H]-:521.02895,Found:521.02946。
example 19(Z) -5,5, 5-trifluoro-2-iodopent-2-enoic acid cholesterol ester
Using alkenyl diazoacetic acid cholesterol ester and trifluoroiodomethane as raw materials, a compound having the following structure was synthesized according to the method of example 9:
Figure BDA0002627527720000171
yield: 47% and Z/E >30: 1.
Compound nuclear magnetic and high resolution data are as follows:
1H NMR(400MHz,CDCl3)δ7.23(t,J＝6.6Hz,1H),5.40(d,J＝4.1Hz,1H),4.80–4.65(m,1H),3.13(qd,J＝10.5,6.8Hz,2H),2.40(d,J＝7.6Hz,2H),2.05–1.79(m,5H),1.74(s,1H),1.61–1.44(m,5H),1.40–0.95(m,18H),0.92(d,J＝6.5Hz,3H),0.87(d,J＝6.6Hz,6H),0.68(s,3H)。
13C NMR(100MHz,CDCl3)δ161.5,139.6(q,J＝3.4Hz),139.4,125.3(q,J＝277.1Hz),123.3,102.2,77.4,56.8,56.3,50.2,42.5,42.2(q,J＝30.6Hz),39.9,39.7,38.0,37.1,36.8,36.3,35.9,32.1,32.0,29.9,28.4,28.2,27.8,24.4,24.0,23.0,22.7,21.2,19.5,18.9,12.0。
19F NMR(376MHz,CDCl3)δ-64.75(s,3F)。
HRMS(APCI):calcd.for C32H47F3IO2[M-H]-:647.25783,Found:647.25838。
example 20 Ethyl (Z) -2-iodo-4- (trifluoromethyl) undecadienoate
Using (E) -2-diazo-3-enoic acid ethyl ester and trifluoroiodomethane as raw materials, according to the method of example 10, a compound having the following structure was synthesized:
Figure BDA0002627527720000172
yield: 66%, and Z/E is 12: 1.
Compound nuclear magnetic and high resolution data are as follows:
1H NMR(400MHz,CDCl3)δ7.00(d,J＝10.1Hz,0.92×1H),6.65(d,J＝10.6Hz,0.08×1H),4.36–4.26(m,2H),3.97–3.84(m,0.08×1H),3.42–3.28(m,0.92×1H),1.88–1.78(m,1H),1.69–1.56(m,1H),1.40–1.18(m,11H),0.88(t,J＝6.2Hz,3H)。
13C NMR(100MHz,,CDCl3)δ163.3,162.4,162.4,147.1(d,J＝2.4Hz),145.4(d,J＝2.3Hz),126.2(q,J＝280.4Hz),101.1,100.1,63.3,62.8,51.5(q,J＝27.0Hz),46.8(q,J＝27.0Hz),31.6,31.6,29.3,29.1,27.8,26.3,22.7。
19F NMR(376MHz,CDCl3)δ-69.23(s,0.92×3F),-70.14(s,0.08×3F)。
HRMS(APCI):calcd.for C13H19F3IO2[M-H]-:391.03873,Found:391.03852。
example 21(Z) -4- (5-butoxy-1, 1, 1-trifluoro-4-iodo-5-oxo-3-en-2-yl) piperidin-1-carboxy ester
Using (E) -4- (3-diazo-4-ethoxy-4-oxetan-1-en-1-yl) piperidine-1-carboxylic acid tert-butyl ester and trifluoroiodomethane as raw materials, a compound having the following structure was synthesized according to the method of example 1:
Figure BDA0002627527720000181
yield: 71%, and Z/E is 20: 1.
Compound nuclear magnetic and high resolution data are as follows:
1H NMR(400MHz,CDCl3)δ7.03(d,J＝10.6Hz,1H),4.31(q,J＝7.1Hz,2H),4.21–4.07(m,2H),3.35(dqd,J＝17.9,8.9,5.8Hz,1H),2.68(dd,J＝27.0,13.2Hz,2H),2.13–2.02(m,1H),1.78(dd,J＝29.5,15.8Hz,2H),1.46(s,9H),1.41–1.28(m,5H)。
13C NMR(100MHz,CDCl3)δ162.2,154.7,143.1,125.9(q,J＝281.7Hz),102.8,79.8,63.4 55.9(q,J＝26.1Hz),43.7,36.5,30.2,28.7,28.5,14.2。
19F NMR(376MHz,CDCl3)δ-65.16(s,3F)。
HRMS(ESI):calcd.for C17H25F3INO4Na[M+Na]+:514.06726,Found:514.06714。
example 22
Using trifluoroiodomethane and ethyl α -methylenyldiazoacetate as raw materials, two separable cis-trans isomers were obtained by the reaction according to the method of example 1, Z/E ═ 3:1, each having the following structure:
(Z) -5,5, 5-trifluoro-2-iodo-3-methylpent-2-enoic acid ethyl ester
Figure BDA0002627527720000182
Yield: 53 percent.
Compound nuclear magnetic and high resolution data are as follows:
1H NMR(400MHz,CDCl3)δ4.29(q,J＝7.1Hz,2H),3.25(q,J＝10.4Hz,2H),2.13(s,3H),1.34(t,J＝7.1Hz,3H).13C NMR(100MHz,CDCl3)δ165.9,140.7(d,J＝2.2Hz),125.4(q,J＝277.0Hz),90.8,62.5,47.0(q,J＝29.6Hz),21.0,14.1.19F NMR(376MHz,CDCl3)δ-62.47(s,3F).HRMS(APCI):calcd.for C8H9F3IO2[M-H]-:320.96048,Found:320.96051。
(E) -5,5, 5-trifluoro-2-iodo-3-methylpent-2-enoic acid ethyl ester
Figure BDA0002627527720000191
Yield: 18 percent.
Compound nuclear magnetic and high resolution data are as follows:
1H NMR(400MHz,CDCl3)δ4.27(q,J＝7.1Hz,2H),3.45(q,J＝10.5Hz,2H),2.19(s,3H),1.32(t,J＝7.1Hz,3H)。
13C NMR(100MHz,CDCl3)δ165.0,142.1(d,J＝2.4Hz),124.7(q,J＝278.5Hz),93.4,62.4,38.4(q,J＝29.9Hz),30.5,13.9。
19F NMR(376MHz,CDCl3)δ-63.59(s,3F)。
HRMS(APCI):calcd.for C8H9F3IO2[M-H]-:320.96048,Found:320.96053。
comparative example 23
Using 1-cyclohexenyldiazoacetic acid ethyl ester and trifluoroiodomethane as raw materials, according to the method of example 1, two cis-trans isomers which can be separated are obtained by reaction, wherein Z/E is 5:1, and each compound has the following structure:
(Z) -Ethyl-2-iodo-2- (2- (trifluoromethyl) cyclohexylidene) acetic acid ethyl ester
Figure BDA0002627527720000192
Yield: 55.8 percent.
Compound nuclear magnetic and high resolution data are as follows:
1H NMR(400MHz,CDCl3)δ4.35–4.20(m,2H),4.00(qd,J＝10.5,5.2Hz,1H),2.89(d,J＝14.6Hz,1H),2.33(td,J＝14.1,4.8Hz,1H),2.12–2.03(m,1H),1.96–1.88(m,1H),1.75–1.57(m,3H),1.48–1.35(m,1H),1.31(t,J＝7.1Hz,3H)。
13C NMR(100MHz,CDCl3)δ165.6 146.4,126.2(q,J＝282.5Hz),89.9,62.3,42.2(q,J＝27.2Hz),37.3,26.1,25.9,21.0,13.9。
19F NMR(376MHz,CDCl3)δ-64.47(s,3F)。
HRMS(ESI):calcd.for C11H15F3IO2[M+H]+:363.00633,Found:363.00652。
(E) -Ethyl 2-iodo-2- (2- (trifluoromethyl) cyclohexylidene) acetic acid ethyl ester
Figure BDA0002627527720000201
Yield: 11.2 percent.
Compound nuclear magnetic and high resolution data are as follows:
1H NMR(400MHz,CDCl3)δ4.30(q,J＝7.1Hz,2H),3.61(qd,J＝10.3,5.1Hz,1H),2.85(d,J＝14.3Hz,1H),2.33–2.14(m,2H),1.88–1.75(m,1H),1.76–1.56(m,3H),1.35(t,J＝7.1Hz,3H),1.32–1.27(m,1H)。
13C NMR(100MHz,CDCl3)δ166.3,145.6,126.92(d,J＝283.2Hz),88.6,62.5,49.6(q,J＝26.9Hz),30.7,26.7 26.0,21.0,14.1。
19F NMR(376MHz,CDCl3)δ-64.87(s,3F)。
HRMS(ESI):calcd.for C11H15F3IO2[M+H]+:363.00633,Found:363.00656。
the above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (8)

1. A method for preparing a 1-iodo-3-perfluoroalkyl alkene compound, comprising the steps of:
s1, under the condition of visible light, carrying out ATRA reaction on an alkenyl diazo compound shown in a formula (II) and a perfluoroalkyl iodide shown in a formula (III) in an organic solvent at room temperature to 80 ℃ under a closed condition to obtain an isomer mixture of a 1-iodo-3-perfluoroalkyl alkene compound;
s2, carrying out isomerization reaction on the 1-iodine-3-perfluoroalkyl alkene compound isomer mixture obtained in the step S1 under the conditions of the same light source and a manganese catalyst to obtain the 1-iodine-3-perfluoroalkyl alkene compound shown in the formula (I), wherein the manganese catalyst is decacarbonyl dimanganese;
Figure FDA0003244897090000011
in the formula (I), R1 and R2 are independently selected from hydrogen atoms and C1～10Alkyl radical, C5～8The aryl group is phenyl or phenyl containing substituent groups, and the substituent groups are selected from one or more of alkyl, alkoxy, trifluoromethyl and aryl; the heterocyclic group is selected from thienyl, furyl, pyridyl, thiazolyl, oxazolyl, piperazinyl or tetrahydrofuranyl;
r1, R2 are independently substituents or are connected to form a cycloalkyl; rf is selected from C1～10Perfluoroalkyl, 2-difluoro-1-acyl, 2-difluoro-1-ester groups; EWG is an alkyl or aryl formate ester group.
2. The method for producing a 1-iodo-3-perfluoroalkylolefin compound according to claim 1, wherein the alkenyl diazo compound is an alkenyl diazo acetate, and the molar ratio of the alkenyl diazo acetate to the perfluoroalkyl iodide is 1:1 to 5.
3. The method for producing a 1-iodo-3-perfluoroalkylolefin compound according to claim 1, wherein the ATRA reaction time is 0.5 to 72 hours.
4. The method for producing a 1-iodo-3-perfluoroalkylolefin compound according to claim 1, wherein the isomerization reaction time is 1 to 20 hours.
5. The method for producing a 1-iodo-3-perfluoroalkylolefin compound according to claim 1, wherein the organic solvent is one or a combination of dichloromethane, dichloroethane, ethyl acetate, ethanol, methanol, trifluoroisopropanol, isopropanol, acetonitrile, dimethyl sulfoxide, N-dimethylformamide, dioxane, tetrahydrofuran, toluene, or chlorobenzene.
6. The method of claim 1, wherein the visible light is one of CFL, LED white light, LED blue light, or sunlight.
7. The method for producing a 1-iodo-3-perfluoroalkylolefin compound according to claim 1, wherein the alkenyl diazo compound is an alkenyl diazo acetate, and a molar ratio of the alkenyl diazo acetate to the manganese catalyst is 1:0.025 to 1.
8. The process for producing a 1-iodo-3-perfluoroalkylolefin compound according to claim 1, wherein R1 and R2 in the formula (I) are independently selected from the group consisting of a hydrogen atom, an alkyl group; rf is selected from C1-10 perfluoroalkyl, 2-difluoro-1-acyl and 2-difluoro-1-ester group.
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