CN107011145B - Method for preparing 2-iodopent-2-ene-1, 4-dione derivative by visible light catalysis - Google Patents

Method for preparing 2-iodopent-2-ene-1, 4-dione derivative by visible light catalysis Download PDF

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CN107011145B
CN107011145B CN201710208064.4A CN201710208064A CN107011145B CN 107011145 B CN107011145 B CN 107011145B CN 201710208064 A CN201710208064 A CN 201710208064A CN 107011145 B CN107011145 B CN 107011145B
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allene
iodopent
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CN107011145A (en
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许孝良
叶弘强
陈军
李小年
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Zhejiang University of Technology ZJUT
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
    • C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
    • C07C45/36—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in compounds containing six-membered aromatic rings
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    • C07—ORGANIC CHEMISTRY
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    • C07B41/06—Formation or introduction of functional groups containing oxygen of carbonyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/313—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of doubly bound oxygen containing functional groups, e.g. carboxyl groups

Abstract

A method for preparing 2-iodopent-2-ene-1, 4-dione derivatives by visible light catalysis, which comprises the following steps: adding allene shown in the formula (I), perfluoroiodobutane, an additive and a photocatalyst into an organic solvent according to a molar ratio of 1: 1-2: 0.005-0.1, stirring for 10-20h under the conditions of oxygen atmosphere, visible light illumination, room temperature and normal pressure, and then carrying out aftertreatment on a reaction liquid to obtain a 2-iodopent-2-ene-1, 4-dione derivative shown in the formula (II); the additive is NaI or NH4I or KI; the organic solvent is ethanol, dichloromethane, benzene, toluene, tetrahydrofuran or acetonitrile; the photocatalyst is selected from one of the following compounds: ir (ppy)3、Eosin Y、Rose bengal、[Ir(dF‑CF3‑ppy)2(dtbbpy)]PF6、[Ir(ppy)2(dtbbpy)]PF6、Ru(bpy)3(BF4)2. The method has the advantages of mild reaction conditions, simple operation, high selectivity, good yield and expandable substituent; and the visible light catalysis is adopted, so that the method has the characteristics of no pollution, environmental friendliness and the like.

Description

Method for preparing 2-iodopent-2-ene-1, 4-dione derivative by visible light catalysis
(I) technical field
The invention relates to a method for preparing 2-iodopent-2-ene-1, 4-dione derivatives by visible light catalysis.
(II) background of the invention
2-iodopent-2-ene-1, 4-dione derivatives are important organic synthesis intermediates, have important significance in organic synthesis, can be used for synthesizing a plurality of important compounds through chemical transformation, for example, carbonyl in molecules can undergo condensation reaction, double bonds can undergo nucleophilic addition reaction, iodine atoms can undergo metallization reaction and further undergo various chemical transformations, and the like. Stoltz (j.org.chem.,2006,71,8357) et al reported the preparation of 2-iodopent-2-ene-1, 4-dione derivatives starting from 1, 4-butynedione by prolonged reflux reaction under the action of lithium iodide and acetic acid, but were often susceptible to double halogenation resulting in low product yields, poor regioselectivity, and no substituents other than furan. In other reports, the synthetic raw materials and the catalytic system of the 2-iodopent-2-ene-1, 4-dione derivative are very complex and are not beneficial to laboratory and industrial application. Kirsch (J.org.chem.,2007,72,5435) et al reported that cyclic 2-iodopent-2-ene-1, 4-dione was synthesized from alkynyl silyl ether ketone under the action of elemental iodine, the starting materials for the reaction were not readily available, and the range of the reaction substrate was narrow. Based on the analysis, research and development of a novel green method for preparing the 2-iodopent-2-ene-1, 4-dione derivative are particularly important.
Disclosure of the invention
The invention aims to provide a method for preparing a 2-iodopent-2-ene-1, 4-dione derivative by using allene as a starting material through visible light catalysis.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing 2-iodopent-2-ene-1, 4-dione derivatives by visible light catalysis, which comprises the following steps:
adding allene shown in formula (I), perfluoroiodobutane, an additive and a photocatalyst into an organic solvent according to a molar ratio of 1: 1-2: 0.005-0.1, stirring for 10-20h under the conditions of oxygen atmosphere, visible light illumination, room temperature and normal pressure, and then carrying out aftertreatment on a reaction liquid to obtain 2-iodopent-2-ene-1, 4-bis-2-ene shown in formula (II)A ketone derivative; the additive is NaI or NH4I or KI; the organic solvent is ethanol, dichloromethane, benzene, toluene, tetrahydrofuran or acetonitrile;
the photocatalyst is selected from one of the following compounds:
tris (2-phenylpyridine) iridium (III) (Ir (ppy)3) Eosin Y (eosin Y), acid Red 94(Rosebengal), Ir (dF-CF)3-ppy)2(dtbbpy)]PF6、[Ir(ppy)2(dtbbpy)]PF6、Ru(bpy)3(BF4)2；
Figure BDA0001260347820000021
Wherein R is1、R3Each independently is C1-C15 alkyl, C1-C15 alkoxy, aryl or substituted aryl; r2Is hydrogen, C1-C15 alkyl, aryl or substituted aryl; the aromatic ring of the substituted aryl can be mono-substituted or multi-substituted, and the substituents are respectively and independently selected from C1-C10 alkyl, fluorine, chlorine, bromine, iodine or cyano.
Further, the aryl is phenyl, naphthyl or furyl; the substituted aryl is substituted phenyl, substituted naphthyl or substituted furyl.
Further, the aryl group is preferably a phenyl group, and the substituted aryl group is preferably a substituted phenyl group.
Further, the alkyl group having 1 to 15 is preferably a C1 to C4 alkyl group such as methyl, ethyl, propyl, butyl or the like, more preferably methyl.
Further, the alkoxy group having 1 to 15 is preferably a C1 to C4 alkoxy group such as methoxy, ethoxy, propoxy or butoxy, etc., more preferably methoxy.
Still further, R1Preferably phenyl or C1-C4 alkyl, more preferably phenyl or methyl.
Still further, R2Preferably hydrogen or C1-C4 alkyl, more preferably hydrogen or methyl.
Still further, R3Preferably phenyl, C1-C4 alkyl or C1-C4 alkoxy, more preferablyIs selected from methyl, phenyl or methoxy.
Further, the organic solvent is preferably toluene, dichloromethane, tetrahydrofuran or acetonitrile, and most preferably toluene.
Further, the photocatalyst is most preferably Ir (ppy)3。
Further, the additive is most preferably KI.
Further, the charging molar ratio of the allene represented by the formula (I) to the perfluoroiodobutane is preferably 2: 3.
Further, the charging molar ratio of the allene represented by the formula (I) to the photocatalyst is preferably 100: 1.
Further, the feeding molar ratio of the allene shown in the formula (I) to the additive is preferably 1: 2.
Further, the volume usage amount of the organic solvent is 10 to 50mL/mmol, preferably 30mL/mmol, based on the amount of the allene substance represented by the formula (I).
In the invention, a light source of the visible light can use a 25-45W white light energy-saving lamp.
Generally, the method for post-treating the reaction solution is as follows: after the reaction is finished, washing the reaction solution, extracting the water phase by using dichloromethane, and then purifying the organic phase by using a silica gel column chromatography to obtain the target product.
The invention particularly recommends that the method for preparing the 2-iodopent-2-ene-1, 4-dione derivative by utilizing visible light catalysis is carried out according to the following steps: adding KI and Ir (ppy) in sequence into a reaction vessel3A allene of formula (I), C4F9I and toluene, in which the allene, C4F9I. KI and Ir (ppy)3The reaction solution is stirred for 10-20 hours at room temperature under the irradiation of 25-45W energy-saving lamp white light in an oxygen atmosphere, after the reaction is finished, the reaction solution is washed, the water phase is extracted by dichloromethane, and the organic phase is purified by silica gel column chromatography to obtain the 2-iodopent-2-ene-1, 4-dione derivative shown in the formula (II).
The synthesis method of part of the photocatalyst used in the preparation method of the invention is derived from the following documents:
[1]Inorg.Chem.1991,30,1685；[2]Chem.Mater.2005,17,5712；[3]J.Am.Chem.Soc.2004,126,2763；[4]Inorg.Synth.1990,338；[5]J.Am.Chem.Soc.2003,125,7377.
compared with the prior art, the invention has the beneficial effects that:
the 2-iodopent-2-ene-1, 4-dione derivative prepared by the method has the advantages of mild reaction conditions, simple operation, high selectivity, good yield and expandable substituent; and the visible light catalysis is adopted, so that the method has the characteristics of no pollution, environmental friendliness and the like, and is a promising method.
(IV) description of the drawings
FIG. 1 is a hydrogen spectrum of the product 1-phenyl-2-iodopent-2-ene-1, 4-dione
FIG. 2 is a carbon spectrum of the product 1-phenyl-2-iodopent-2-ene-1, 4-dione.
(V) detailed description of the preferred embodiments
The technical solutions of the present invention are further illustrated by the following specific examples, but the scope of the present invention is not limited thereto.
The allene structures and equations used in the following examples are as follows:
Figure BDA0001260347820000041
ir (ppy) used in the following examples3The structural formula of the catalyst is as follows:
Figure BDA0001260347820000042
example 1
To a Schlenk tube, NaI (60.0mg, 0.4mmol), Ir (ppy)3(1.3mg, 0.002mmol), 5-phenylpenta-3, 4-dien-2-one (31.6mg, 0.2mmol), C4F9I (103.8mg, 0.3mmol) and toluene (6ml) were stirred under an oxygen atmosphere at room temperature for 10h under white light irradiation from a 45W energy-saving lamp. After the reaction is finished, the reaction solution is washed for 2 times, and the water phase is reused by CH2Cl2Extracting for 2 times, mixing organic phases, spin-drying with rotary evaporator, and purifying with silica gel column chromatography to obtain light yellow target product 2-iodine-1-phenylpentaneThe yield of the (E) -2-alkene-1, 4-diketone is 48 percent, and the purity is more than or equal to 98 percent. Product characterization data were as follows: 1H NMR (500MHz, CDCl3)7.93(dt, J ═ 8.5,1.5Hz,2H), 7.63-7.58 (m,1H), 7.52-7.46 (m,2H),7.19(s,1H),2.19(s,3H).13C NMR(126MHz,CDCl3)193.74,192.64,139.95,133.98,131.96,129.19,128.90,114.24,29.79；HRMS(CI)calcd for C11H9O2I,found 299.9647.
The hydrogen spectrum and carbon spectrum of the product 1-phenyl-2-iodopent-2-ene-1, 4-dione are shown in FIGS. 1 and 2.
Example 2
In a Schlenk tube, NH was added in sequence4I(58.0mg，0.4mmol)、Ir(ppy)3(1.3mg, 0.002mmol), 5-phenylpenta-3, 4-dien-2-one (31.6mg, 0.2mmol), C4F9I (103.8mg, 0.3mmol) and toluene (6ml) were stirred under an oxygen atmosphere at room temperature for 10h under white light irradiation from a 45W energy-saving lamp. After the reaction is finished, the reaction solution is washed for 2 times, and the water phase is reused by CH2Cl2Extracting for 2 times, combining organic phases, drying by a rotary evaporator, and purifying by a silica gel column chromatography to obtain a light yellow target product (Z) -2-iodine-1-phenylpent-2-ene-1, 4-diketone with the yield of 49.6 percent and the purity of more than or equal to 98 percent.
Example 3
To a Schlenk tube, KI (66.4mg, 0.4mmol), Ir (ppy)3(1.3mg, 0.002mmol), 5-phenylpenta-3, 4-dien-2-one (31.6mg, 0.2mmol), C4F9I (103.8mg, 0.3mmol) and toluene (6ml) were stirred under an oxygen atmosphere at room temperature for 10h under white light irradiation from a 45W energy-saving lamp. After the reaction is finished, the reaction solution is washed for 2 times, and the water phase is reused by CH2Cl2Extracting for 2 times, combining organic phases, drying by a rotary evaporator, and purifying by silica gel column chromatography to obtain a light yellow target product 2-iodine-1-phenylpent-2-ene-1, 4-diketone with a yield of 63% and a purity of more than or equal to 98%.
Example 4
To a Schlenk tube, KI (66.4mg, 0.4mmol), Ir (ppy)3(1.3mg, 0.002mmol), 5-phenylpenta-3, 4-dien-2-one (31.6mg, 0.2mmol), C4F9I (103.8mg, 0.3mmol) and dichloromethane (6ml), aerobicStirring the mixture for 10 hours at room temperature under the irradiation of white light of a 45W energy-saving lamp in an air atmosphere. After the reaction is finished, the reaction solution is washed for 2 times, and the water phase is reused by CH2Cl2Extracting for 2 times, combining organic phases, drying by a rotary evaporator, and purifying by silica gel column chromatography to obtain a light yellow target product 2-iodine-1-phenylpent-2-ene-1, 4-diketone with a yield of 56% and a purity of more than or equal to 98%.
Example 5
To a Schlenk tube, KI (66.4mg, 0.4mmol), Ir (ppy)3(1.3mg, 0.002mmol), 5-phenylpenta-3, 4-dien-2-one (31.6mg, 0.2mmol), C4F9I (103.8mg, 0.3mmol) and tetrahydrofuran (6ml) were stirred at room temperature for 10h under a 45W energy-saving lamp with white light irradiation in an oxygen atmosphere. After the reaction is finished, the reaction solution is washed for 2 times, and the water phase is reused by CH2Cl2Extracting for 2 times, combining organic phases, drying by a rotary evaporator, and purifying by silica gel column chromatography to obtain a light yellow target product 2-iodine-1-phenylpent-2-ene-1, 4-diketone with a yield of 36% and a purity of more than or equal to 98%.
Example 6
To a Schlenk tube, KI (66.4mg, 0.4mmol), Ir (ppy)3(1.3mg, 0.002mmol), 5-phenylpenta-3, 4-dien-2-one (31.6mg, 0.2mmol), C4F9I (103.8mg, 0.3mmol) and acetonitrile (6ml) were stirred under an oxygen atmosphere at room temperature for 10h under white light irradiation from a 45W energy-saving lamp. After the reaction is finished, the reaction solution is washed for 2 times, and the water phase is reused by CH2Cl2Extracting for 2 times, combining organic phases, drying by a rotary evaporator, and purifying by silica gel column chromatography to obtain a light yellow target product 2-iodine-1-phenylpent-2-ene-1, 4-diketone with a yield of 31.6% and a purity of more than or equal to 98%.
Example 7
To a Schlenk tube, KI (66.4mg, 0.4mmol) and [ Ir (dF-CF) were added in this order3-ppy)2(dtbpy)]PF6(2.2mg, 0.002mmol), 5-phenylpenta-3, 4-dien-2-one (31.6mg, 0.2mmol), C4F9I (103.8mg, 0.3mmol) and dichloromethane (6ml) were stirred under an oxygen atmosphere at room temperature for 10h under white light irradiation from a 45W energy-saving lamp. After the reaction is finished, the reaction solution is washed for 2 times by water, and the water phaseReuse of CH2Cl2Extracting for 2 times, combining organic phases, drying by a rotary evaporator, and purifying by silica gel column chromatography to obtain a light yellow target product 2-iodine-1-phenylpent-2-ene-1, 4-diketone with a yield of 47.7% and a purity of more than or equal to 98%.
Example 8
To a Schlenk tube, KI (66.4mg, 0.4mmol) and [ Ir (ppy) were added in this order2(dtbpy)]PF6(1.9mg, 0.002mmol), 5-phenylpenta-3, 4-dien-2-one (31.6mg, 0.2mmol), C4F9I (103.8mg, 0.3mmol) and dichloromethane (6ml) were stirred under an oxygen atmosphere at room temperature for 10h under white light irradiation from a 45W energy-saving lamp. After the reaction is finished, the reaction solution is washed for 2 times, and the water phase is reused by CH2Cl2Extracting for 2 times, combining organic phases, drying by a rotary evaporator, and purifying by silica gel column chromatography to obtain a light yellow target product 2-iodine-1-phenylpent-2-ene-1, 4-diketone with a yield of 56.6% and a purity of more than or equal to 98%.
Example 9
To a Schlenk tube, KI (66.4mg, 0.4mmol), Ru (bpy) were added in this order3(BF4)2(1.5mg, 0.002mmol), 5-phenylpenta-3, 4-dien-2-one (31.6mg, 0.2mmol), C4F9I (103.8mg, 0.3mmol) and dichloromethane (6ml) were stirred under an oxygen atmosphere at room temperature for 10h under white light irradiation from a 45W energy-saving lamp. After the reaction is finished, the reaction solution is washed for 2 times, and the water phase is reused by CH2Cl2Extracting for 2 times, combining organic phases, drying by a rotary evaporator, and purifying by silica gel column chromatography to obtain a light yellow target product 2-iodine-1-phenylpent-2-ene-1, 4-diketone with a yield of 10% and a purity of more than or equal to 98%.
Example 10
To a Schlenk tube, KI (66.4mg, 0.4mmol), EosinY (1.4mg, 0.002mmol), 5-phenylpenta-3, 4-dien-2-one (31.6mg, 0.2mmol), and C were added in this order4F9I (103.8mg, 0.3mmol) and dichloromethane (6ml) were stirred under an oxygen atmosphere at room temperature for 10h under white light irradiation from a 45W energy-saving lamp. After the reaction is finished, the reaction solution is washed for 2 times, and the water phase is reused by CH2Cl2Extracting for 2 times, mixing organic phases, spin-drying with rotary evaporator, and separating with silica gel columnThe light yellow target product 2-iodine-1-phenylpent-2-ene-1, 4-diketone can be obtained by the analytical purification, the yield is 11.2 percent, and the purity is more than or equal to 98 percent.
Example 11
To a Schlenk tube, KI (33.2mg, 0.2mmol), Ir (ppy)3(1.3mg, 0.002mmol), 5-phenylpenta-3, 4-dien-2-one (31.6mg, 0.2mmol), C4F9I (103.8mg, 0.3mmol) and toluene (6ml) were stirred under an oxygen atmosphere at room temperature for 10h under white light irradiation from a 45W energy-saving lamp. After the reaction is finished, the reaction solution is washed for 2 times, and the water phase is reused by CH2Cl2Extracting for 2 times, combining organic phases, drying by a rotary evaporator, and purifying by silica gel column chromatography to obtain a light yellow target product 2-iodine-1-phenylpent-2-ene-1, 4-diketone with a yield of 48.2% and a purity of more than or equal to 98%.
Example 12
To a Schlenk tube, KI (99.6mg, 0.3mmol), Ir (ppy)3(1.3mg, 0.002mmol), 5-phenylpenta-3, 4-dien-2-one (31.6mg, 0.2mmol), C4F9I (103.8mg, 0.3mmol) and dichloromethane (6ml) were stirred under an oxygen atmosphere at room temperature for 10h under white light irradiation from a 45W energy-saving lamp. After the reaction is finished, the reaction solution is washed for 2 times, and the water phase is reused by CH2Cl2Extracting for 2 times, combining organic phases, drying by a rotary evaporator, and purifying by silica gel column chromatography to obtain a light yellow target product 2-iodine-1-phenylpent-2-ene-1, 4-diketone with a yield of 50% and a purity of more than or equal to 98%.
Example 13
To a Schlenk tube, KI (33.2mg, 0.2mmol), Ir (ppy)3(1.3mg, 0.002mmol), 1-phenylpenta-3, 4-dien-2-one (3) (31.6mg, 0.2mmol), C4F9I (103.8mg, 0.3mmol) and toluene (6ml) were stirred under an oxygen atmosphere at room temperature for 10h under white light irradiation from a 45W energy-saving lamp. After the reaction is finished, the reaction solution is washed for 2 times, and the water phase is reused by CH2Cl2Extracting for 2 times, combining organic phases, drying by a rotary evaporator, and purifying by silica gel column chromatography to obtain a light yellow target product 3-iodine-1-phenylpent-2-ene-1, 4-diketone (4), wherein the yield is 30.5%, and the purity is more than or equal to 98%.
Example 14
To a Schlenk tube, KI (33.2mg, 0.2mmol), Ir (ppy)3(1.3mg, 0.002mmol), methyl 1-phenyl-1, 2-dienebutyrate (5) (34.8mg, 0.2mmol), C4F9I (103.8mg, 0.3mmol) and toluene (6ml) were stirred under an oxygen atmosphere at room temperature for 10h under white light irradiation from a 45W energy-saving lamp. After the reaction is finished, the reaction solution is washed for 2 times, and the water phase is reused by CH2Cl2Extracting for 2 times, combining organic phases, drying by a rotary evaporator, and purifying by silica gel column chromatography to obtain a light yellow target product, namely 2-iodine-1-phenyl-1-oxo-2-methyl crotonate (6), wherein the yield is 30.5 percent, and the purity is more than or equal to 98 percent.
Example 15
To a Schlenk tube, KI (33.2mg, 0.2mmol), Ir (ppy)3(1.3mg, 0.002mmol), 1, 5-diphenyl-2-methylbutan-2, 3-dien-2-one (7) (46.6mg, 0.2mmol), C4F9I (103.8mg, 0.3mmol) and toluene (6ml) were stirred under an oxygen atmosphere at room temperature for 10h under white light irradiation from a 45W energy-saving lamp. After the reaction is finished, the reaction solution is washed for 2 times, and the water phase is reused by CH2Cl2Extracting for 2 times, combining organic phases, drying by a rotary evaporator, and purifying by a silica gel column chromatography to obtain a light yellow target product 2-iodine-1, 5-diphenyl-3-methyl-2-butene-1, 4-diketone (8), wherein the yield is 70 percent, and the purity is more than or equal to 98 percent.
Comparative example 1
To a Schlenk tube were added NaI (60.0mg, 0.4mmol), 5-phenylpenta-3, 4-dien-2-one (31.6mg, 0.2mmol), and C in that order4F9I (103.8mg, 0.3mmol) and toluene (6ml) were stirred under an oxygen atmosphere at room temperature for 10h under white light irradiation from a 45W energy-saving lamp. After the reaction is finished, the reaction solution is washed for 2 times, and the water phase is reused by CH2Cl2Extracting for 2 times, mixing organic phases, spin-drying with rotary evaporator, and purifying with silica gel column chromatography to obtain 0mg product with yield of 0%.
Comparative example 2
In a Schlenk tube, Ir (ppy) was added in order3(1.3mg, 0.002mmol), 5-phenylpenta-3, 4-dien-2-one (31.6mg, 0.2mmol), C4F9I (103.8mg, 0.3mmol) and toluene(6ml), the mixture was stirred in an oxygen atmosphere at room temperature for 10 hours under white light irradiation with a 45W energy-saving lamp. After the reaction is finished, the reaction solution is washed for 2 times, and the water phase is reused by CH2Cl2Extracting for 2 times, mixing organic phases, spin-drying with rotary evaporator, and purifying with silica gel column chromatography to obtain 0mg product with yield of 0%.

Claims (11)

1. A method for preparing 2-iodopent-2-ene-1, 4-dione derivatives by visible light catalysis, which comprises the following steps:
adding allene shown in the formula (I), perfluoroiodobutane, an additive and a photocatalyst into an organic solvent according to a molar ratio of 1: 1-2: 0.005-0.1, stirring for 10-20h under the conditions of oxygen atmosphere, visible light illumination, room temperature and normal pressure, and then carrying out aftertreatment on a reaction liquid to obtain a 2-iodopent-2-ene-1, 4-dione derivative shown in the formula (II); the additive is NaI or NH4I or KI; the organic solvent is ethanol, dichloromethane, benzene, toluene, tetrahydrofuran or acetonitrile;
the photocatalyst is selected from one of the following compounds:
Ir(ppy)3、EosinY、[Ir(dF-CF3-ppy)2(dtbbpy)]PF6、[Ir(ppy)2(dtbbpy)]PF6、Ru(bpy)3(BF4)2；
Figure FDA0002468762220000011
wherein R is1、R3Each independently is C1-C15 alkyl, C1-C15 alkoxy, aryl or substituted aryl; r2Is hydrogen, C1-C15 alkyl, aryl or substituted aryl; the aromatic ring of the substituted aryl can be mono-substituted or multi-substituted, and the substituents are respectively and independently selected from C1-C10 alkyl, fluorine, chlorine, bromine, iodine or cyano.
2. The method of claim 1, wherein: the aryl is phenyl, naphthyl or furyl; the substituted aryl is substituted phenyl, substituted naphthyl or substituted furyl.
3. The method of claim 1, wherein: the alkyl of C1-C15 is C1-C4 alkyl, and the alkoxy of C1-C15 is C1-C4 alkoxy.
4. The method of claim 1, wherein: r1Is phenyl or C1-C4 alkyl, R2Is hydrogen or C1-C4 alkyl, R3Is phenyl, C1-C4 alkyl or C1-C4 alkoxy.
5. The method of any of claims 1 to 4, wherein: the organic solvent is toluene, dichloromethane, tetrahydrofuran or acetonitrile.
6. The method of any of claims 1 to 4, wherein: the organic solvent is toluene, the photocatalyst is Ir (ppy)3The additive is KI.
7. The method of any of claims 1 to 4, wherein: the volume usage amount of the organic solvent is 10-50 mL/mmol based on the amount of the allene substance shown in the formula (I).
8. The method of any of claims 1 to 4, wherein: the volume usage amount of the organic solvent is 30mL/mmol based on the amount of the allene substance represented by the formula (I).
9. The method of claim 7, wherein: the feeding molar ratio of the allene shown in the formula (I) to the perfluoroiodobutane is 2:3, the feeding molar ratio of the allene shown in the formula (I) to the photocatalyst is 100:1, and the feeding molar ratio of the allene shown in the formula (I) to the additive is 1: 2.
10. The method of any of claims 1 to 4, wherein: the light source of the visible light is a 25-45W white light energy-saving lamp.
11. The method of claims 1 to 4A method as described, characterized by: the method for preparing the 2-iodopent-2-ene-1, 4-dione derivative by utilizing visible light catalysis is carried out according to the following steps: adding KI and Ir (ppy) in sequence into a reaction vessel3A allene of formula (I), C4F9I and toluene, in which the allene, C4F9I. KI and Ir (ppy)3The reaction solution is stirred for 10-20 hours at room temperature under the irradiation of 25-45W energy-saving lamp white light in an oxygen atmosphere, after the reaction is finished, the reaction solution is washed, the water phase is extracted by dichloromethane, and the organic phase is purified by silica gel column chromatography to obtain the 2-iodopent-2-ene-1, 4-dione derivative shown in the formula (II).
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