Method for generating ester compound by catalytic oxidation of ether compound with visible light excited silver iodide and bismuth vanadate composite material
阅读说明：本技术 一种可见光激发碘化银钒酸铋复合材料催化氧化醚类化合物生成酯类化合物的方法 (Method for generating ester compound by catalytic oxidation of ether compound with visible light excited silver iodide and bismuth vanadate composite material ) 是由 任兰会 于 2019-10-26 设计创作，主要内容包括：本发明公开一种可见光激发碘化银钒酸铋复合材料催化氧化醚类化合物生成酯类化合物的方法,所述方法,采用的催化剂为AgI/BiVO<Sub>4</Sub>复合材料,AgI的摩尔占比为10-80 mol%；所述可见光的光源为商品化的16 W白色LED灯；采用的溶剂为水、乙醇或1,2-二氯乙烷。本发明的制备方法首次在室温下使用可见光激发AgI/BiVO<Sub>4</Sub>催化氧气或空气氧化醚类化合物生成酯类化合物的方法；本发明采用的催化剂为AgI/BiVO<Sub>4</Sub>复合材料,不需要使用染料；AgI/BiVO<Sub>4</Sub>复合材料制备简单,成本低,容易分离回收；采用的可见光LED灯的功率为16 W,耗能低,光源易得、价格低廉。(The invention discloses visible light excited silver iodide bismuth vanadate composite material for catalyzing oxygenThe method for preparing the ester compound by using the ether compound adopts AgI/BiVO as the catalyst 4 The composite material comprises AgI, wherein the molar ratio of AgI is 10-80 mol%; the light source of the visible light is a commercial 16W white LED lamp; the solvent used is water, ethanol or 1, 2-dichloroethane. The preparation method of the invention uses visible light to excite AgI/BiVO for the first time at room temperature 4 A method for generating ester compounds by oxidizing ether compounds with oxygen or air; the catalyst adopted by the invention is AgI/BiVO 4 Composite materials, which do not require the use of dyes; AgI/BiVO 4 The composite material is simple to prepare, low in cost and easy to separate and recycle; the power of the adopted visible light LED lamp is 16W, the energy consumption is low, the light source is easy to obtain, and the price is low.)
1. A method for catalyzing and oxidizing ether compounds to generate ester compounds by a visible light excited silver iodide bismuth vanadate composite material is characterized in that: in the method, the adopted catalyst is AgI/BiVO4The composite material comprises AgI, wherein the molar ratio of AgI is 10-80 mol%; the light source of the visible light is a commercial 16W white LED lamp; the solvent used is water, ethanol or 1, 2-dichloroethane.
2. The method of claim 1, wherein the method comprises the step of catalytically oxidizing an ether compound to an ester compound with a visible light-excited silver vanadate bismuth vanadate composite material, wherein the method comprises the following steps: the concentration of the ether compound in the solvent is 0.5-1 mol/L.
3. The method of claim 1, wherein the method comprises the step of catalytically oxidizing an ether compound to an ester compound with a visible light-excited silver vanadate bismuth vanadate composite material, wherein the method comprises the following steps: the dosage of the ether compound catalyst is 5-20 mg per mM.
4. The method of claim 1, wherein the method comprises the step of catalytically oxidizing an ether compound to an ester compound with a visible light-excited silver vanadate bismuth vanadate composite material, wherein the method comprises the following steps: the catalytic oxidation adopts oxygen or air as an oxidant; the ether compound is a benzyl ether compound or an allyl ether compound.
5. The method of claim 1, wherein the method comprises the step of catalytically oxidizing an ether compound to an ester compound with a visible light-excited silver vanadate bismuth vanadate composite material, wherein the method comprises the following steps: the AgI/BiVO4The composite material is prepared by hydrothermal synthesis.
6. The method of claim 1, wherein the method comprises the step of catalytically oxidizing an ether compound to an ester compound with a visible light-excited silver vanadate bismuth vanadate composite material, wherein the method comprises the following steps: the AgI/BiVO4The content of AgI in the composite material is one of 10mol%, 20mol%, 30 mol%, 40mol%, 60 mol% and 80 mol%.
7. The method of claim 1, wherein the method comprises the step of catalytically oxidizing an ether compound to an ester compound with a visible light-excited silver vanadate bismuth vanadate composite material, wherein the method comprises the following steps: the chemical formula of the ether compound is as follows:
。
8. the method of claim 7, wherein the method comprises the step of catalytically oxidizing an ether compound to an ester compound with a visible light-excited silver vanadate bismuth vanadate composite material, wherein the method comprises the following steps: said R1The substituent is one of phenyl, 2-chlorphenyl, 3-chlorphenyl, 4-chlorphenyl, 2-bromophenyl, 4-methylphenyl, 4-methoxyphenyl, 4-trifluoromethylphenyl, 2, 4-dichlorophenyl, 2, 6-dichlorophenyl, phenyl vinyl and 4-nitrophenylvinyl; the R is2The substituent is one of methyl, ethyl and benzyl.
9. The method of claim 1, wherein the method comprises the step of catalytically oxidizing an ether compound to an ester compound with a visible light-excited silver vanadate bismuth vanadate composite material, wherein the method comprises the following steps: the reaction time is 4-24 hours.
10. The method of claim 4, wherein the method comprises the step of catalytically oxidizing an ether compound to an ester compound with the visible light-excited silver vanadate bismuth vanadate composite material, wherein the method comprises the following steps: the oxygen and air are used in the form of oxygen balloons or air balloons, and each mM ether compound is used in the form of oxygen balloons or air balloons with a diameter of 28cm (1 per mM); the light source is positioned at the position of 10cm on one side of the reaction device.
Technical Field
The invention relates to a reaction for generating C = O bonds by visible light catalysis and selective oxidation of C-H bonds.
Background
The C-H bond is one of the most basic chemical bonds in the organic compound, other chemical bonds are directly constructed through the C-H bond, the reactant can be prevented from being pre-functionalized, the reaction steps are shortened, and the method has the advantages of simplicity, high efficiency, high atom economy and the like. The preparation of carbonyl compounds such as ketone, aldehyde and ester by selective oxidation of C-H bonds is one of important research directions for direct functionalization of C-H bonds, has the advantages of multiple raw material types, wide sources, low price and the like, and the corresponding oxidation products are widely used for production of dyes, preservatives, flame retardants and medicinal compounds, and have very important significance in research on the generation of the carbonyl compounds by oxidation of the C-H bonds.
Because the activation energy of the C-H bond is high, and the intermediate is easy to be oxidized, the selective oxidation of the C-H bond under mild conditions is a challenging research field. The traditional C-H bond oxidation method needs to use equivalent or excessive inorganic oxidants, such as chromium reagent, manganese reagent, high-valence iodide and the like, generates a large amount of harmful byproducts in the reaction process, has troublesome post-treatment and pollutes the environment. From the standpoint of both atom economy and environmental protection and sustainable development, there is an urgent need to develop a new environmentally friendly oxidation process to replace the conventional stoichiometric process. In the past decades, peroxides (hydrogen peroxide, t-butyl hydroperoxide, peracetic acid, and m-chloroperoxybenzoic acid) were developed for C — H bond selective oxidation, but the peroxides have poor stability and are easily exploded, and byproducts (t-butanol, acetic acid, and m-chloroperbenzoic acid) need to be further separated, increasing energy consumption.
Molecular oxygen is of interest as the most abundant, inexpensive and environmentally friendly oxidant available (water as a byproduct). In recent years, studies on the oxidation of C-H bonds to carbonyl compounds by catalytic molecular oxygen have been actively conducted. However, molecular oxygen is generally stable, according to the principle of spin conservation, molecular oxygen is in a triplet state, reaction is difficult to perform due to spin inhibition of singlet reaction substrates and triplet molecular oxygen, and development of a catalytic system capable of catalyzing molecular oxygen to oxidize C-H bonds to generate carbonyl compounds is one of the hot spots of research in the field. In the 80's of the 20 th century, scientists Gifsur-Yvette proposed a Gif catalytic system, Barton used the Gif catalytic system in the oxidation of saturated hydrocarbons to ketones under mild conditions, and found that the selectivity of the oxidation reaction of different C-H bonds in linear alkanes was 3o>2o>1o. After that, various catalytic systems using oxygen as oxygen source have been developed, such as CoPc @ Cell/KOH/NHPI/O2, Co(OAc)2•4H2O/NHPI/O2/BuOAc, CuI/AcOH/O2,CuCl2•H2O/O2/ethyl chloroacetate, Cu-CuFe2O4@HKUST-1/NHPI/O2, DDQ/TBN/O2,TEMPO-SO3Na/HCl/NaNO2/O2， H4NI/AcOH/O2。
The C = O bond synthesized by selective oxidation of the C-H bond has the advantages of wide raw material source, low price and the like, and is one of the strategies which are concerned in the field of C = O bond formation. Based on the modern catalytic chemistry and the concept of synthetic chemistry, the development of a catalytic system for catalyzing air to oxidize C-H bonds under mild conditions with green synthesis and clean conversion as a guide is one of the hot spots of research in the field.
Visible light is increasingly receiving attention from the chemical community as a clean, inexpensive, and "near-infinite" source of energy. Since 2008, the visible light catalytic oxidation-reduction reaction has attracted extensive research interest, and molecular oxygen is reported to be used for the visible light catalytic C — H bond selective oxidation reaction. In 2014, Oisaki et al reported Ru (bpy)3 2+Cu (I) catalyzes oxygen or air to oxidize fluorene compounds into ketone under the irradiation of visible light, and the yield is 41-95%. In 2015, 9-phenyl-10-methylpyridine salt was reported by leishmania to catalyze oxygen to oxidize diphenylmethane compounds to generate ketone under the irradiation of visible light, and the yield is 28-77%.
In 2017, a visible light catalytic system of tetrabromofluorescein sensitized titanium dioxide is reported by the albizzia clan, and the system can catalyze ambient air to oxidize benzyl ether to generate benzoate, wherein the yield is 54-92%.
The method has the following defects:
(1) the adopted titanium dioxide catalyst needs to be sensitized by dye, and the added dye is difficult to post-treat and is not easy to separate from the system;
(2) 160W blue LED lamps are needed to catalyze and oxidize benzyl ether to generate benzoate, and energy consumption is large.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for generating ester compounds by catalyzing and oxidizing ether compounds with a visible light excited silver iodide and bismuth vanadate composite material, which realizes the following purposes:
(1) the adopted catalyst is AgI/BiVO4Composite materials, which do not require the use of dyes;
(2) and reducing the power of the visible light LED lamp.
In order to solve the technical problems, the invention adopts the following technical scheme:
the invention discloses a method for generating an ester compound by catalyzing and oxidizing an ether compound by a visible light excited silver vanadate bismuth vanadate composite material. Uses benzyl ether compound and allyl ether compound as reaction substrate, AgI/BiVO4The composite material is a catalyst, a commercial 16W white LED lamp is a light source, oxygen or air is an oxidant, water or ethanol or 1, 2-dichloroethane is a solvent, 25oAnd reacting under C to obtain the ester compound.
The structural general formulas of the benzyl ether and allyl ether compounds are as follows:
said R1The substituent is phenyl, 2-chlorphenyl, 3-chlorphenyl, 4-chlorphenyl, 2-bromophenyl, 4-methylphenyl, 4-methoxyphenyl, 4-trifluoromethylphenyl, 2, 4-dichlorophenyl, 2, 6-dichlorophenyl, phenyl vinyl and 4-nitrophenylvinyl; r2The substituent is methyl, ethyl and benzyl.
The reaction chemical formula of the invention is as follows:
in the technical scheme, the concentration of the ether compound in the solvent is 0.5-1 mol/L,
in the technical scheme, the reaction time is 4-24 hours.
In the above technical scheme, the reaction temperature required by the reaction is 25 DEGoC。
In the technical scheme, AgI/BiVO4The dosage of the composite material is 5-20 mg/mM ether compound, AgI/BiVO4The mass ratio of the composite material to the ether compound is 1:10-1: 17;
AgI/BiVO4the molar ratio of AgI in the composite material is 10-80 mol%;
in the technical scheme, the oxygen and the air are used in the form of oxygen balloons or air balloons.
AgI/BiVO4For composite materials prepared by hydrothermal synthesis, not AgI and BiVO4Simple mixtures, AgI/BiVO4The typical hydrothermal synthesis process of the composite material is as follows: 0.001 mol of KI (0.166 g) and 0.009 mol of Bi (NO) were added to a 50 mL beaker3)3·5H2O (4.37 g), followed by addition of 40m L water, stirred vigorously to give solution A; at the same time, 0.001 mol AgNO3(0.17 g) and 0.009 mol NH4VO3(1.05 g) was added to another 50 mL beaker containing 30 mL of water and stirred vigorously to give solution B. Solution a was then added dropwise to solution B at room temperature with constant stirring. Stirring the reaction solution for 30 min, transferring the obtained suspension to a 100 mL hydrothermal kettle in an oven, and placing the kettle in the oven for 180 minoAnd C, preserving the heat for 24 hours. And after the hydrothermal process is finished, naturally cooling the reaction kettle. The synthesized sample was subjected to suction filtration, washed with ultrapure water and ethanol, and then 60oAnd C, drying for 2 h. Grinding the obtained sample and collecting to obtain the 10mol% AgI/BiVO4A composite material. By changing KI and Bi (NO)3)3·5H2O、AgNO3And NH4VO3The pure-phase AgI and BiVO can be obtained by the synthesis method4AgI/BiVO with different AgI contents4Composite material (20 mol%, 30 mol%, 40mol%, 60 mol%, 80 mol%).
The yield of the ester compound prepared by the scheme is 49-91%;
preferred technical solution a:
the reaction raw material ether compound is: benzyl methyl ether, 1-chloro-2- (methoxymethyl) benzene, 1-chloro-3- (methoxymethyl) benzene, 1-chloro-4- (methoxymethyl) benzene, 1-bromo-2- (methoxymethyl) benzene, 1-bromo-4- (methoxymethyl) benzene, 1- (methoxymethyl) -4-methylbenzene, 1-methoxy-4- (methoxymethyl) benzene, 2, 4-dichloro-1- (methoxymethyl) benzene, 2, 6-dichloro-1- (methoxymethyl) benzene, p,
Benzyl ethyl ether, 1-chloro-4- (ethoxymethyl) benzene, benzyl ether, 1-phenyl-3-methoxy-1-phenylalene;
the prepared ester compound is as follows: methyl benzoate, methyl 2-chlorobenzoate, methyl 3-chlorobenzoate, methyl 4-chlorobenzoate, methyl 2-bromobenzoate, methyl 4-methylbenzoate, methyl 4-methoxybenzoate, methyl 2, 4-dichlorobenzoate, methyl 2, 6-dichlorobenzoate, ethyl benzoate, ethyl 4-chlorobenzoate, benzyl benzoate, methyl cinnamate;
the concentration of the ether compound in the solvent is 0.5 mol/L,
the solvent is one of water, ethanol and 1, 2-dichloroethane;
the reaction time is 8-24 hours;
the reaction temperature was 25 deg.CoC；
AgI/BiVO4The dosage of the composite material is 10-20 mg per mM ether compound;
AgI/BiVO4the molar ratio of AgI in the composite material is 20-40 mol%;
the oxidant is oxygen or air, the oxygen or air is used in the form of oxygen balloon or air balloon, and 1 oxygen balloon is used per mM ether compound;
the diameter of the oxygen balloon or air balloon is 28cm,
the reaction takes a commercial 16W white LED lamp as a light source and is positioned at a position of 10cm on one side of the reaction device;
the yield of the ester compound prepared by the scheme A is 70-91%;
preferred technical solution B:
the reaction raw material ether compound is: benzyl methyl ether, 1-bromo-2- (methoxymethyl) benzene, 1-bromo-4- (methoxymethyl) benzene, 1- (methoxymethyl) -4-methylbenzene, 1-methoxy-4- (methoxymethyl) benzene, benzyl ethyl ether, 1-chloro-4- (ethoxymethyl) benzene;
the prepared ester compound is as follows: methyl benzoate, methyl 2-bromobenzoate, methyl 4-methylbenzoate, methyl 4-methoxybenzoate, ethyl benzoate, ethyl 4-chlorobenzoate;
the concentration of the ether compound in the solvent is 0.5 mol/L,
the solvent is water;
the reaction time is 9-15 hours;
the reaction temperature was 25 deg.CoC；
AgI/BiVO4The dosage of the composite material is 15-20 mg per mM ether compound;
AgI/BiVO4the molar ratio of AgI in the composite material is 20 mol%;
the oxidant is oxygen or air, and the oxygen or air is used in the form of oxygen balloon or air balloon; 1 balloon per mM ether compound;
the diameter of the oxygen balloon or air balloon is 28cm,
the reaction takes a commercial 16W white LED lamp as a light source and is positioned at a position of 10cm on one side of the reaction device;
the yield of the ester compound prepared by the scheme B is 80-91%;
further preferred technical solution C:
the reaction raw material ether compound is: benzyl methyl ether, 1-bromo-4- (methoxymethyl) benzene, 1- (methoxymethyl) -4-methylbenzene, 1-methoxy-4- (methoxymethyl) benzene;
the prepared ester compound is as follows: methyl benzoate, methyl 4-bromobenzoate, methyl 4-methylbenzoate, methyl 4-methoxybenzoate;
the concentration of the ether compound in the solvent is 0.5 mol/L;
the solvent is water;
the reaction time is 9-15 hours;
the reaction temperature was 25 deg.CoC；
AgI/BiVO4The dosage of the composite material is 15mg per mM ether compound;
AgI/BiVO4the molar ratio of AgI in the composite material is 20 mol%;
the oxidant is oxygen, the oxygen is used in the mode of oxygen spheres, and 1 oxygen sphere is used for each mM of ether compounds;
the diameter of the oxygen balloon is 28cm,
the reaction takes a commercial 16W white LED lamp as a light source and is positioned at a position of 10cm on one side of the reaction device;
the ester compound prepared in scheme C above, the yield is 87-91%.
Compared with the prior art, the invention has the following beneficial effects:
(1) the catalyst adopted by the invention is AgI/BiVO4Composite materials, which do not require the use of dyes; AgI/BiVO4The composite material is simple to prepare, low in cost and easy to separate and recover, and the yield of the ester compound prepared by the method is 49-91%;
(2) the power of the visible light LED lamp adopted by the invention is 16W, the energy consumption is low, the light source is easy to obtain, and the price is low;
(3) the AgI/BiVO of the invention4After the composite material is recycled and reused for 6 times, the catalytic activity is not reduced, and the reaction yield is only reduced by 1-1.5 percent.
Detailed Description
The present invention will be described in detail with reference to examples, but the scope of the present invention is not limited to the examples.
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