CN112642489A - Homogeneous bimetallic complex catalyst, preparation method thereof and application thereof in preparation of aldehyde from alcohol - Google Patents

Homogeneous bimetallic complex catalyst, preparation method thereof and application thereof in preparation of aldehyde from alcohol Download PDF

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CN112642489A
CN112642489A CN202011536633.6A CN202011536633A CN112642489A CN 112642489 A CN112642489 A CN 112642489A CN 202011536633 A CN202011536633 A CN 202011536633A CN 112642489 A CN112642489 A CN 112642489A
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bis
catalyst
crown
diphenylphosphino
citral
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CN112642489B (en
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马啸
马慧娟
董凤婵
籍晓飞
钟天明
于明
秦陈陈
黄珊珊
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Shandong Nhu Pharmaceutical Co ltd
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Shandong Nhu Pharmaceutical Co ltd
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    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
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Abstract

The invention discloses a homogeneous bimetallic complex catalyst, a preparation method thereof and application thereof in preparing aldehyde from alcohol. The catalyst is used for synthesizing the citral through linalool oxidation reaction, shows higher reaction activity and selectivity, improves the yield and the product quality of citral products, reduces the occurrence of side reactions, is clean and environment-friendly, has higher economic and environment-friendly benefits, and is beneficial to industrial mass production of the citral.

Description

Homogeneous bimetallic complex catalyst, preparation method thereof and application thereof in preparation of aldehyde from alcohol
Technical Field
The invention belongs to the technical field of organic synthesis, and relates to a method for preparing aldehyde by catalytic oxidation under mild conditions by using alcohol as a raw material and a catalyst, in particular to a method for preparing citral by catalytic oxidation under mild conditions by using linalool as a raw material and a catalyst.
Background
Citral (also known as 3, 7-dimethyl-2, 6-octadiene-1-aldehyde) is a very important open-chain monoterpene spice, has strong lemon fragrance, is contained in plant essential oils such as pungent litse fruit oil, lemongrass oil, eucalyptus oil, grass oil and lemon basil oil, can be used for preparing citrus-flavor food spice, and can be directly used for beverage and food processing. In addition, citral is also a fine chemical intermediate with broad application prospects, can be used for synthesizing isopulegol, hydroxycitronellal and ionone, and can also be converted into important starting materials for producing vitamin E, vitamin A, isophytol or beta-ionone.
At present, citral is mainly obtained by chemical synthesis, and mainly comprises six methods, namely an aldol condensation method, an isoprene method, an acetone method, a nitrogen oxide method, a geraniol gas-phase oxidation method, a dehydrolinalool rearrangement method and the like.
The company of L.GIVAUDAN, CIE Societe Anyme and the like successfully synthesizes citral by adopting fixed bed gas phase oxidative dehydrogenation of a mixture of geraniol and nerol. The reaction is carried out at 300-500 ℃ and 4-300 mmHg with a gold/copper wire mesh or grid plate as a catalyst and air as an oxidant, and the yield of the citral product is about 40-50%. The disadvantages are that: the reaction conditions are harsh, high temperature and high pressure are required, and the activity and selectivity of the catalyst are low, so that the yield of the citral is low, the requirement on equipment is high, and the production cost is increased.
US 5241122A discloses a group IB metal catalyst, wherein a copper compound is impregnated on copper particles with a small specific surface area, geraniol steam is subjected to oxidative dehydrogenation by the catalyst at 200-500 ℃ to prepare citral, and the maximum molar yield of the citral is 85%. The disadvantages are that: the reaction temperature is high, the catalyst is easy to sinter and aggregate, and active ingredients are easy to lose, so that the service life of the catalyst is short and the catalyst needs to be replaced frequently.
In patent CN 1305983A, citral is synthesized by fixed bed gas phase selective oxidative dehydrogenation of geraniol, and alkali metal or alkaline earth metal or a mixture of the alkali metal and the alkaline earth metal or the mixture of the alkali metal and the alkaline earth metal is added into a silver or silver-copper catalyst as a promoter, so that byproducts are reduced, and the yield of citral products is improved. The reaction pressure is 0.01-0.2 MPa, the temperature is 230-400 ℃, geraniol steam, air and water vapor are quickly cooled to 50-80 ℃ through the backup of a catalyst bed layer, citral is obtained, the conversion rate of geraniol can reach 72%, and the selectivity of citral can reach 90%. The disadvantages are that: the conversion rate of raw materials is low, the selectivity needs to be improved, and the auxiliary agent in the catalyst is easy to lose, thereby further influencing the selectivity and yield of the reaction.
The patent CN108997096A discloses that a supported catalyst prepared by using a mixture of titanium dioxide, palladium oxide and ruthenium dioxide supported by a molecular sieve is heated in a fixed bed reactor in a salt bath manner, geraniol is gasified by a vaporizer and then is mixed with air to form a gas mixture, and then the gas mixture is introduced into the reactor, and the reaction pressure is 0.05MPa, the reaction temperature is 150-230 ℃, and the reaction space velocity is 4000-5000 h-1The reaction is carried out under the condition, the gas after the reaction is trapped by a condensation trap to obtain the citral, the conversion rate of the geraniol reaches more than 90%, and the selectivity of the citral reaches more than 98%. The disadvantages are that: the reaction temperature is higher, the production energy consumption is increased, and the industrial mass production is not facilitated.
Therefore, in the method for preparing citral by geraniol oxidation, pure metals consisting of metals such as silver and copper and corresponding supported catalysts have long been considered to be good catalysts, but these metal catalysts all have their own disadvantages. The invention aims to research and develop a method for synthesizing citral by directly oxidizing linalool, which has high activity, high selectivity, stable performance and relatively mild reaction conditions.
Disclosure of Invention
Aiming at the defects of synthesizing citral by linalool in the prior art, the invention provides a method for synthesizing citral by directly oxidizing linalool. The method uses a homogeneous bimetallic complex catalyst to catalyze the oxidative isomerization synthesis of linalool with high activity and high selectivity.
In order to solve the problems, the technical scheme of the invention is as follows:
a homogeneous bimetallic complex catalyst comprises a metal active center, a complexing agent and a modifier;
the metal active center is formed by transition metal ions; the complexing agent is crown ether; the modifier is a multidentate phosphine ligand.
The transition metal ion and the complexing agent form a complex, and the modifier modifies the complex through coordination with the transition metal ion and hydrogen bonding of the complexing agent.
The components of the homogeneous bimetallic complex catalyst provided by the invention comprise a metal active center, a complexing agent and a modifier: because the crown ether has a hydrophobic external framework and a hydrophilic inner cavity which can form a bond with metal ions, the metal ions and the crown ether form a complex through coordination, the complex not only provides an active center for oxidation reaction, but also provides a 'place' for the oxidation reaction, reduces the occurrence of side reactions and improves the selectivity of the reaction. The polydentate phosphine ligand is used as a modifier to play a role in modifying a complex through coordination bonds with metal ions and hydrogen bonds with crown ethers, has relatively large steric hindrance, can promote isomerization reaction to be efficiently carried out simultaneously through a space effect while carrying out oxidation reaction, and carries out catalytic reaction with an active metal complex together.
Preferably, the crown ether is one of 18-crown-6, 15-crown-5, dibenzo-18-crown-6, benzo-15-crown-5, dicyclohexyl-18-crown-6, dibenzo-24-crown-8, dibenzo-21-crown-7, dibenzo-27-crown-9, 1, 10-dithia-18-crown-6, diaza-18-crown-6, cryptate [2,2,2], cryptate [2,1,1], cryptate [2,2,1 ].
Preferably, the polydentate phosphine ligand is selected from the group consisting of 1, 2-bis (dimethylphosphino) ethane, bisdiphenylphosphinomethane, trans-1, 2-bis (diphenylphosphino) ethylene, 1, 2-bis (diphenylphosphino) ethane, 1, 3-bis (diphenylphosphino) propane, 1, 4-bis (diphenylphosphino) butane, 1, 5-bis (diphenylphosphino) pentane, 1, 6-bis (diphenylphosphino) hexane, 1, 2-bis (dipentafluorophenylphosphino) -ethane, 1, 2-bis (diphenylphosphino) benzene, 1, 3-bis [ (di-t-butylphosphino) oxo ] benzene, 2' -bis (diphenylphosphino) biphenyl, 1' -binaphthyl-2, 2' -bisdiphenylphosphino, 1, 8-bis (diphenylphosphino) naphthalene.
The transition metal ions comprise first metal ions and second metal ions, wherein the first metal ions are selected from non-noble metal ions, the second metal ions are selected from noble metal ions, and the bimetallic active center has a synergistic effect, so that the reaction activity of the catalyst is enhanced, and the function of adjusting the reaction selectivity is also realized. Preferably, the first metal ion is selected from any one of metal ions of soluble salts of Ni, Fe, Co, V, Cu, Zn, Mn, Cd, Sn, In, Cr, Re, Bi and Zr; the second metal ion is selected from any one of metal ions of soluble salts of Pd, Au, Ag, Ru, Rh, Pt and Ir.
Further, the molar ratio of the first metal ions to the second metal ions is: 1: 0.1-1.0.
The molar ratio of the transition metal ions to the complexing agent is as follows: 1: 1-10.
The molar ratio of the transition metal ions to the modifier is as follows: 1: 1-10.
The invention also provides a preparation method of the homogeneous bimetallic complex catalyst, which comprises the following steps:
(1) dissolving metal salt in water according to a certain proportion at a certain temperature, and dissolving a complexing agent in an organic solvent;
(2) mixing the two solutions, violently oscillating, removing the solvent, and drying to obtain a complex;
(3) adding the complex into a solvent containing a modifier at a certain temperature, mixing and stirring, removing the solvent, and drying to obtain the catalyst for later use.
The metal salt comprises a first metal salt and a second metal salt which are soluble salts containing the first metal ion and the second metal ion respectively. Still further, the first metal salt is selected from FeCl3、Cu(NO3)2、NiSO4、Co(NO3)2、NH4VO3、ZnCl2、MnSO4、Cd(Ac)2、SnCl4、InCl3、Cr2(SO3)3、Re2O7、Bi(NO3)3、Zr(NO3)4Wherein the second metal salt is selected from RhCl3、PdCl2、IrCl3、AgNO3、RuCl3、PtCl4、AuCl3One kind of (1).
The method comprises the following steps:
(1) dissolving a first metal salt and a second metal salt in purified water according to a certain proportion at 60 ℃ in a container, and dissolving crown ether in an organic solvent to obtain two solutions.
(2) The two solutions were mixed in a container at 60 ℃ and shaken vigorously until no more precipitate formed. The solvent was removed under reduced pressure to give a precipitate and dried to give the complex.
(3) Adding the complex into an organic solvent containing a polydentate phosphine ligand in a container at 60 ℃, stirring for 4 hours, removing the solvent under reduced pressure, and drying the solid matter until the solid matter is heavy, thus obtaining the catalyst.
The organic solvent in the step (1) is an organic solvent capable of dissolving crown ether, and is selected from one of methanol, toluene, n-butanol, acetonitrile and dichloromethane.
The organic solvent in the step (3) is toluene.
The invention also provides a method for synthesizing citral by directly oxidizing linalool, which comprises the following steps: under the catalysis of the homogeneous bimetallic complex catalyst, molecular oxygen is used as an oxidant, and linalool is subjected to homogeneous catalytic oxidation under mild conditions to prepare citral.
The mass ratio of the homogeneous bimetallic complex catalyst to the linalool is 2.0-9.0 wt.%: 1.
the oxidation reaction catalyzed by the homogeneous bimetallic complex catalyst can be a continuous reaction mode, and a fixed bed and a microreactor are preferred; it may be a batch reaction system, preferably an autoclave. The invention adopts an intermittent reaction mode and selects a high-pressure reaction kettle as a reaction container.
The oxidation reaction temperature is 100-180 ℃, the reaction time is 2-6 hours, and the oxygen pressure is 0.1-0.3 MPa.
The oxidant of the oxidation reaction is molecular oxygen, and the oxygen source is air or oxygen. The invention selects oxygen.
The solvent for the oxidation reaction is toluene.
The homogeneous bimetallic complex catalyst can be used for synthesizing citral through linalool oxidation reaction, and can also be used for preparing the isopropenyl aldehyde through methyl butenol and 3-methyl-3-butenol oxidation reaction.
Compared with the prior art, the invention has the following beneficial effects:
(1) the catalyst provided by the invention is used for synthesizing citral through linalool oxidation reaction, shows higher reaction activity and selectivity, and improves the yield and product quality of citral products.
(2) The catalyst of the invention is convenient to recover, can be repeatedly used for more than 10 times, and has basically unchanged activity and better stability.
(3) The method for synthesizing the citral by the linalool direct oxidation reaction has the advantages of mild reaction conditions, reduction of side reactions, cleanness, environmental protection, higher economic and environmental benefits, contribution to industrial mass production of the citral and reference for oxidation reactions of other compounds with similar structures.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The product contents in the following examples are GC contents unless otherwise specified.
Example 1
At 60 ℃, 0.1mol of anhydrous FeCl3And 0.05mol of RhCl3·3H2Dissolving O in 200mL of purified water, dispersing 0.5mol of dicyclohexyl-18-crown-6 in 200mL of methanol, uniformly mixing the two solutions, violently oscillating until the precipitate is not separated out, stopping oscillating, removing the solvent under reduced pressure to obtain a precipitate, drying the precipitate, adding 0.5mol of 1, 5-bis (diphenylphosphino) pentane into 500mL of DMF, adding the precipitate, stirring, keeping the temperature at 60 ℃ for 4 hours, cooling, removing the solvent under reduced pressure, drying the obtained solid matter in a constant-temperature drying oven at 80 ℃ to constant weight to obtain the catalyst, wherein the catalyst yield is 99.6%, and the mark is 1# catalyst.
In a 500mL stainless steel reaction kettle, replacing 3 times with nitrogen, replacing 3 times with oxygen, sequentially adding 100g of toluene and 5g of No. 1 catalyst, activating at 80 ℃ for 30min, then adding 100g of linalool, wherein the oxygen pressure is 0.2MPa (gauge pressure, the same below), heating to 120 ℃, carrying out heat preservation reaction for 3 hours, sampling after the reaction is finished, analyzing the concentration of each component of the reaction solution by using a gas chromatograph, and the conversion rate of the linalool is 99.04%.
Transferring the reaction solution into a 500mL three-neck flask, vacuumizing by using a vacuum pump, rectifying by using a glass spring packed tower, and removing a solvent; and then, controlling the reflux ratio to be 3-5 to collect the former part, finishing the rectification of the former part after the impurity content in the front of the tower kettle is less than 0.2%, and then rectifying to obtain 97.01g of citral finished product and 5.1g of kettle liquid, wherein the kettle liquid is indiscriminately used for the next batch of reaction.
And (3) calculating: the yield of citral was 98.59% with a content of 99.35%.
Note: the unconverted linalool raw material can be recycled, and the yield of the citral is calculated according to the following formula:
yield-finished citral yield/(linalool input-conversion-152.23/154.25) -100%
Example 2
0.1mol of Cu (NO) at 60 DEG C3)2·3H2O and 0.02mol of PdCl2Dissolving the mixture in 200mL of purified water, dispersing 0.5mol of 18-crown-6 in 200mL of acetonitrile, uniformly mixing the two solutions, oscillating vigorously until no precipitate is precipitated, stopping oscillation, removing the solvent under reduced pressure to obtain a precipitate, drying the precipitate, adding 0.8mol of 1, 2-bis (dimethylphosphine) ethane into 500mL of toluene, adding the precipitate, stirring, keeping the temperature at 60 ℃ for 4 hours, cooling, removing the solvent under reduced pressure, and drying the obtained solid matter in a constant-temperature drying oven at 80 ℃ until the weight is constant to obtain the catalyst of the invention, wherein the catalyst yield is 98.2% and the label is No. 2 catalyst.
In a 500mL stainless steel reaction kettle, replacing 3 times with nitrogen, replacing 3 times with oxygen, sequentially adding 100g of toluene and 7g of 2# catalyst, activating at 80 ℃ for 30min, then adding 100g of linalool, keeping the temperature, reacting for 4 hours, sampling after the reaction is finished, analyzing the concentration of each component of the reaction solution by using a gas chromatograph, wherein the conversion rate of the linalool is 98.85%.
The reaction solution was treated in the same manner as in example 1 to obtain 96.61g of citral product and 5.15g of the residue, which was used in the next batch.
And (3) calculating: the yield of citral was 98.37%, with a content of 99.34%.
Example 3
At 60 ℃, 0.1mol of NiSO4·6H2O and 0.02mol of IrCl3·3H2Dissolving O in 200mL of purified water, dispersing 0.5mol of 15-crown-5 in 200mL of n-butyl alcohol, uniformly mixing the two solutions, violently oscillating until the precipitate is not separated out, stopping oscillating, removing the solvent under reduced pressure to obtain a precipitate, drying the precipitate, adding 0.6mol of bis (diphenylphosphinomethane) into 500mL of toluene, adding the precipitate, stirring, keeping the temperature at 60 ℃ for 4 hours, cooling, removing the solvent under reduced pressure, and drying the obtained solid matter in a constant-temperature drying oven at 80 ℃ to constant weight to obtain the catalyst, wherein the catalyst yield is 99.5 percent and is marked as No. 3 catalyst.
In a 500mL stainless steel reaction kettle, replacing 3 times with nitrogen, replacing 3 times with oxygen, sequentially adding 100g of toluene and 4g of 3# catalyst, activating at 80 ℃ for 30min, then adding 100g of linalool, keeping the temperature and reacting for 5 hours, sampling after the reaction is finished, analyzing the concentration of each component of the reaction solution by using a gas chromatograph, wherein the conversion rate of the linalool is 98.52%.
The reaction solution was treated in the same manner as in example 1 to obtain 96.27g of citral product and 4.26g of the residue, which was used in the next batch.
And (3) calculating: the yield of citral was 98.35% with a content of 99.34%.
Example 4
At 60 ℃, 0.1mol of Co (NO)3)2·6H2O and 0.06mol of AgNO3Dissolving the mixture in 200mL of purified water, dispersing 0.7mol of dibenzo-18-crown-6 in 200mL of n-butanol, uniformly mixing the two solutions, violently oscillating until the precipitate is not separated out, stopping oscillating, removing the solvent under reduced pressure to obtain a precipitate, drying the precipitate, adding 0.9mol of bis (diphenylphosphinomethane) into 500mL of toluene, adding the precipitate, stirring, keeping the temperature at 60 ℃ for 4 hours, cooling, removing the solvent under reduced pressure, drying the obtained solid matter in a constant-temperature drying oven at 80 ℃ to constant weight to obtain the catalyst, wherein the catalyst yield is 99.6%, and the catalyst is marked as No. 4 catalyst.
In a 500mL stainless steel reaction kettle, replacing 3 times with nitrogen, replacing 3 times with oxygen, sequentially adding 100g of toluene and 6g of 4# catalyst, activating at 80 ℃ for 30min, then adding 100g of linalool, keeping the temperature and reacting for 4 hours, sampling after the reaction is finished, analyzing the concentration of each component of the reaction solution by using a gas chromatograph, wherein the conversion rate of the linalool is 98.75%.
The reaction solution was treated in the same manner as in example 1 to obtain 96.65g of citral product and 6.21g of the residue, which was used in the next batch.
And (3) calculating: the yield of citral was 98.55%, with a content of 99.36%.
Example 5
At 60 ℃, 0.1mol of NH4VO3And 0.07mol of RuCl3·3H2Dissolving O in 200mL of purified water, dispersing 0.7mol of dibenzo-24-crown-8 in 200mL of methanol, uniformly mixing the two solutions, violently oscillating until no precipitate is separated out, stopping oscillating, removing the solvent under reduced pressure to obtain a precipitate, drying the precipitate, adding 1.0mol of trans-1, 2-bis (diphenylphosphino) ethylene into 500mL of toluene, adding the precipitate, stirring, keeping the temperature at 60 ℃ for 4 hours, cooling, removing the solvent under reduced pressure, drying the obtained solid matter in a constant-temperature drying oven at 80 ℃ until the weight is constant, thus obtaining the catalyst of the invention, wherein the catalyst yield is 99.5%, and the mark is 5# catalyst.
In a 500mL stainless steel reaction kettle, replacing 3 times with nitrogen, replacing 3 times with oxygen, sequentially adding 100g of toluene and 4g of 5# catalyst, activating at 80 ℃ for 30min, then adding 100g of linalool, keeping the temperature and reacting for 6 hours, sampling after the reaction is finished, analyzing the concentration of each component of the reaction solution by using a gas chromatograph, wherein the conversion rate of the linalool is 98.41%.
The reaction solution was treated in the same manner as in example 1 to obtain 96.05g of citral product and 4.2g of the residue, and the residue was used in the next batch.
And (3) calculating: the citral yield was 98.24%, with a content of 99.34%.
Example 6
At 60 ℃, 0.1mol of ZnCl is added2And 0.09mol of PtCl4Dissolving the mixture in 200mL of purified water, dispersing 0.8mol of dibenzo-21-crown-7 in 200mL of methanol, uniformly mixing the two solutions, violently oscillating until no precipitate is separated out, stopping oscillating, removing the solvent under reduced pressure to obtain a precipitate, drying the precipitate, adding 0.9mol of 1, 2-bis (diphenylphosphine) ethane into 500mL of toluene, adding the precipitate, stirring, keeping the temperature at 60 ℃ for 4 hours, cooling, removing the solvent under reduced pressure, drying the obtained solid matter in a constant-temperature drying oven at 80 ℃ until the weight is constant, thus obtaining the catalyst of the invention, wherein the catalyst yield is 99.6%, and the label is No. 6 catalyst.
In a 500mL stainless steel reaction kettle, replacing 3 times with nitrogen, replacing 3 times with oxygen, sequentially adding 100g of toluene and 2.5g of 6# catalyst, activating at 80 ℃ for 30min, then adding 100g of linalool, keeping the temperature, reacting for 4 hours, sampling after the reaction is finished, analyzing the concentration of each component of the reaction solution by a gas chromatograph, wherein the conversion rate of the linalool is 98.28%.
The reaction solution was treated in the same manner as in example 1 to obtain 95.63g of citral product and 3.1g of the residue, which was used in the next batch.
And (3) calculating: : the yield of citral was 97.94% with a content of 99.34%.
Example 7
At 60 ℃, 0.1mol of MnSO4And 0.1mol of AuCl3Dissolving the mixture in 200mL of purified water, dispersing 0.8mol of dibenzo-27-crown-9 in 200mL of methanol, uniformly mixing the two solutions, violently oscillating until no precipitate is separated out, stopping oscillating, removing the solvent under reduced pressure to obtain a precipitate, drying the precipitate, adding 0.7mol of 1, 3-bis (diphenylphosphine) propane into 500mL of toluene, adding the precipitate, stirring, keeping the temperature at 60 ℃ for 4 hours, cooling, removing the solvent under reduced pressure, drying the obtained solid matter in a constant-temperature drying oven at 80 ℃ until the weight is constant, thus obtaining the catalyst of the invention, wherein the catalyst yield is 99.5%, and the label is 7# catalyst.
In a 500mL stainless steel reaction kettle, replacing 3 times with nitrogen, replacing 3 times with oxygen, sequentially adding 100g of toluene and 5g of 7# catalyst, activating at 80 ℃ for 30min, then adding 100g of linalool, keeping the temperature, reacting for 4 hours, sampling after the reaction is finished, analyzing the concentration of each component of the reaction solution by using a gas chromatograph, wherein the conversion rate of the linalool is 98.45%.
The reaction solution was treated in the same manner as in example 1 to obtain 95.38g of citral product and 5.36g of the residue, which was used in the next batch.
And (3) calculating: the yield of citral was 97.49% with a content of 99.32%.
Example 8
At 60 ℃, 0.1mol of Cd (Ac)2·2H2O and 0.06mol of PdCl2Purification in 200mLIn water, 0.8mol of 1, 10-dithia-18-crown-6 is dispersed in 200mL of dichloromethane, then the two solutions are uniformly mixed and vigorously shaken until no precipitate is separated out, shaking is stopped, the solvent is removed under reduced pressure to obtain a precipitate, the precipitate is dried, 1.0mol of 1, 6-bis (diphenylphosphino) hexane is added into 500mL of toluene, then the precipitate is added, stirring is carried out, the temperature is kept at 60 ℃ for 4 hours, the temperature is reduced, the solvent is removed under reduced pressure, the obtained solid matter is dried in a constant temperature drying oven at 80 ℃ until the weight is constant, and the catalyst of the invention is obtained, wherein the catalyst yield is 99.6%, and the mark is 8# catalyst.
In a 500mL stainless steel reaction kettle, replacing 3 times with nitrogen, replacing 3 times with oxygen, sequentially adding 100g of toluene and 9g of 8# catalyst, activating at 80 ℃ for 30min, then adding 100g of linalool, keeping the temperature and reacting for 5 hours, sampling after the reaction is finished, analyzing the concentration of each component of the reaction solution by using a gas chromatograph, wherein the conversion rate of the linalool is 98.13%.
The reaction mixture was treated in the same manner as in example 1 to obtain 94.92g of citral product and 9.87g of a pot liquid, which was used in the next batch.
And (3) calculating: the yield of citral was 97.33%, with a content of 99.32%.
Example 9
At 60 ℃, adding 0.1mol of SnCl4And 0.01mol of RuCl3·3H2Dissolving O in 200mL of purified water, dispersing 0.8mol of diaza 18-crown ether-6 in 200mL of n-butyl alcohol, uniformly mixing the two solutions, violently oscillating until no precipitate is separated out, stopping oscillating, removing the solvent under reduced pressure to obtain a precipitate, drying the precipitate, adding 1.0mol of 1, 2-bis (dipentafluorophenylphosphinyl) -ethane into 500mL of toluene, adding the precipitate, stirring, keeping the temperature at 60 ℃ for 4 hours, cooling, removing the solvent under reduced pressure, drying the obtained solid matter in a constant-temperature drying oven at 80 ℃ until the weight is constant, thus obtaining the catalyst of the invention, wherein the catalyst yield is 99.6%, and the mark is 9# catalyst.
In a 500mL stainless steel reaction kettle, replacing 3 times with nitrogen, replacing 3 times with oxygen, sequentially adding 100g of toluene and 8g of No. 9 catalyst, activating at 80 ℃ for 30min, then adding 100g of linalool, keeping the temperature and reacting for 6 hours, sampling after the reaction is finished, analyzing the concentration of each component of the reaction solution by using a gas chromatograph, wherein the conversion rate of the linalool is 98.0%.
The reaction mixture was treated in the same manner as in example 1 to obtain 94.65g of citral product and 8.6g of a pot liquid, which was used in the next batch.
And (3) calculating: the yield of citral was 97.18%, with a content of 99.32%.
Example 10
At 60 ℃, 0.1mol of InCl3And 0.09mol of RhCl3·3H2O was dissolved in 200mL of purified water and 1.0mol of cryptate [2, 2]]Dispersing the two solutions in 200mL of toluene, uniformly mixing the two solutions, violently oscillating until precipitates are not separated out, stopping oscillating, removing the solvent under reduced pressure to obtain a precipitate, drying the precipitate, adding 1.0mol of 1, 2-bis (diphenylphosphino) benzene into 500mL of toluene, adding the precipitate, stirring, keeping the temperature at 60 ℃ for 4 hours, cooling, removing the solvent under reduced pressure, drying the obtained solid substance in a constant-temperature drying box at 80 ℃ to constant weight to obtain the catalyst, wherein the catalyst yield is 99.6%, and the mark is 10# catalyst.
In a 500mL stainless steel reaction kettle, replacing 3 times with nitrogen, replacing 3 times with oxygen, sequentially adding 100g of toluene and 6g of 10# catalyst, activating at 80 ℃ for 30min, then adding 100g of linalool, wherein the oxygen pressure is 0.2MPa, heating to 120 ℃, carrying out heat preservation reaction for 3 hours, sampling after the reaction is finished, analyzing the concentration of each component of the reaction solution by using a gas chromatograph, and the conversion rate of the linalool is 98.81%.
The reaction solution was treated in the same manner as in example 1 to obtain 96.13g of citral product and 6.34g of the residue, which was used in the next batch.
And (3) calculating: the yield of citral was 97.9% with a content of 99.32%.
Example 11
At 60 ℃, 0.1mol of Cr2(SO3)3·6H2O and 0.07mol of PdCl2Dissolved in 200mL of purified water and 1.0mol of cryptate [2,1]Dispersing in 200mL of toluene, mixing the two solutions, shaking vigorously until no precipitate is formed, stopping shaking, removing solvent under reduced pressure to obtain precipitate, drying, adding 1.0mol of 1, 3-bis [ (di-tert-butylphosphino) oxy ] 1, 3-bis [ (di-tert-butylphosphino) to 500mL of toluene]And adding the precipitate into benzene, stirring, keeping the temperature at 60 ℃ for 4 hours, cooling, decompressing to remove the solvent, and drying the obtained solid substance in a constant-temperature drying oven at 80 ℃ to constant weight to obtain the catalyst, wherein the catalyst yield is 99.5 percent and is marked as No. 11 catalyst.
In a 500mL stainless steel reaction kettle, replacing 3 times with nitrogen, replacing 3 times with oxygen, sequentially adding 100g of toluene and 5g of 11# catalyst, activating at 80 ℃ for 30min, then adding 100g of linalool, wherein the oxygen pressure is 0.2MPa, heating to 100 ℃, carrying out heat preservation reaction for 5 hours, sampling after the reaction is finished, analyzing the concentration of each component of the reaction solution by using a gas chromatograph, and the conversion rate of the linalool is 98.05%.
The reaction mixture was treated in the same manner as in example 1 to obtain 94.08g of citral product and 5.78g of a pot solution, which was used in the next batch.
And (3) calculating: the yield of citral was 96.55%, with a content of 99.32%.
Example 12
At 60 ℃, 0.1mol of Re2O7And 0.08mol of AgNO3Dissolved in 200mL of purified water and 1.0mol of cryptate [2,2,1]]Dispersing the two solutions in 200mL of toluene, uniformly mixing the two solutions, violently oscillating until precipitates are not separated out, stopping oscillating, removing the solvent under reduced pressure to obtain a precipitate, drying the precipitate, adding 1.0mol of 2,2' -bis (diphenylphosphino) biphenyl into 500mL of toluene, adding the precipitate, stirring, keeping the temperature at 60 ℃ for 4 hours, cooling, removing the solvent under reduced pressure, drying the obtained solid in a constant-temperature drying box at 80 ℃ to constant weight to obtain the catalyst, wherein the catalyst yield is 99.6%, and the mark is 12# catalyst.
In a 500mL stainless steel reaction kettle, replacing 3 times with nitrogen, replacing 3 times with oxygen, sequentially adding 100g of toluene and 5g of 12# catalyst, activating at 80 ℃ for 30min, then adding 100g of linalool, wherein the oxygen pressure is 0.2MPa, heating to 100 ℃, carrying out heat preservation reaction for 3 hours, sampling after the reaction is finished, analyzing the concentration of each component of the reaction solution by using a gas chromatograph, and the conversion rate of the linalool is 98.54%.
The reaction solution was treated in the same manner as in example 1 to obtain 96.15g of citral product and 5.2g of the residue, which was used in the next batch.
And (3) calculating: the yield of citral was 98.19% with a content of 99.32%.
Example 13
At 60 ℃, 0.1mol of Bi (NO)3)3·5H2O and 0.08mol of PdCl2Dissolved in 200mL of purified water and 0.8mol of cryptate [2, 2]]Dispersing the two solutions in 200mL of toluene, uniformly mixing the two solutions, violently oscillating until precipitates are not separated out, stopping oscillating, removing the solvent under reduced pressure to obtain a precipitate, drying the precipitate, adding 1.0mol of 1,1 '-binaphthyl-2, 2' -bis-diphenylphosphine into 500mL of toluene, adding the precipitate, stirring, keeping the temperature at 60 ℃ for 4 hours, cooling, removing the solvent under reduced pressure, and drying the obtained solid substance in a constant-temperature drying oven at 80 ℃ to constant weight to obtain the catalyst, wherein the catalyst yield is 99.6%, and the mark is 13# catalyst.
In a 500mL stainless steel reaction kettle, replacing 3 times with nitrogen, replacing 3 times with oxygen, sequentially adding 100g of toluene and 5g of 13# catalyst, activating at 80 ℃ for 30min, then adding 100g of linalool, keeping the temperature, reacting for 4 hours, sampling after the reaction is finished, analyzing the concentration of each component of the reaction solution by using a gas chromatograph, wherein the conversion rate of the linalool is 98.86%.
The reaction solution was treated in the same manner as in example 1 to obtain 96.72g of citral product and 5.15g of the residue, which was used in the next batch.
And (3) calculating: the yield of citral was 98.45% with a content of 99.32%.
Example 14
0.1mol of Zr (NO) is added at 60 DEG C3)4·5H2O and 0.09mol of AgNO3Dissolved in 200mL of purified water and 0.9mol of cryptate [2, 2]]Dispersing the two solutions in 200mL of toluene, uniformly mixing the two solutions, violently oscillating until precipitates are not separated out, stopping oscillating, removing the solvent under reduced pressure to obtain a precipitate, drying the precipitate, adding 1.0mol of 1, 8-bis (diphenylphosphino) naphthalene into 500mL of toluene, adding the precipitate, stirring, keeping the temperature at 60 ℃ for 4 hours, cooling, removing the solvent under reduced pressure, drying the obtained solid in a constant-temperature drying box at 80 ℃ to constant weight to obtain the catalyst, wherein the catalyst yield is 99.6%, and the mark is 14# catalyst.
In a 500mL stainless steel reaction kettle, replacing 3 times with nitrogen, replacing 3 times with oxygen, sequentially adding 100g of toluene and 2g of 14# catalyst, activating at 80 ℃ for 30min, then adding 100g of linalool, keeping the temperature and reacting for 6 hours, sampling after the reaction is finished, analyzing the concentration of each component of the reaction solution by using a gas chromatograph, wherein the conversion rate of the linalool is 96.78%.
The reaction solution was treated in the same manner as in example 1 to obtain 92.48g of citral product and 3.4g of the residue, which was used in the next batch.
And (3) calculating: the yield of citral was 96.17% with a content of 99.34%.
Example 15
Experiment for applying catalyst
The catalyst of example 1 was subjected to a catalyst application experiment to examine the stability of the catalyst. The residue obtained in example 1 was used again, and when the conversion rate decreased by more than 1.0% and the yield decreased by more than 0.5%, the residue was washed with toluene three times at 60 ℃ and then removed under reduced pressure, and the catalyst was dried to constant weight at 80 ℃ and used again under the same reaction conditions as in example 1. The application data are shown in table 1.
Table 1 catalyst application data
Numbering Conversion ratio of raw Material (%) Yield (%) Content (%)
New throwing 99.04 99.24 99.35
Sleeve 1 99.03 99.23 99.35
Sleeve 2 99.03 99.21 99.35
Cover 3 99.01 99.18 99.35
Cover 4 99.0 99.14 99.35
Sleeve 5 99.01 99.12 99.35
Sleeve 6 98.97 99.08 99.35
Sleeve 7 98.94 99.0 99.35
Sleeve 8 98.92 98.99 99.35
Sleeve 9 98.90 98.96 99.35
Sleeve 10 98.90 98.94 99.35
After the catalyst is used for ten times, the conversion rate of the reaction is reduced by 0.14 percent, and the yield is reduced by 0.3 percent, which shows that the catalyst of the invention is very stable and can be used repeatedly.
Comparative example 1 No crown Ether addition
The preparation method comprises the following steps: at 60 ℃, 0.1mol of anhydrous FeCl3And 0.05mol of RhCl3·3H2Dissolving O in 200mL of purified water, adding 0.5mol of 1, 5-bis (diphenylphosphino) pentane into 500mL of DMF, adding the solution, stirring, keeping the temperature at 60 ℃ for 4 hours, cooling, removing the solvent under reduced pressure, drying the obtained solid substance in a constant-temperature drying oven at 80 ℃ to constant weight to obtain the catalyst, wherein the catalyst yield is 99.7%, and the label is 1' # catalyst.
In a 500mL stainless steel reaction kettle, replacing 3 times with nitrogen, replacing 3 times with oxygen, sequentially adding 100g of toluene and 5g of 1' # catalyst, activating at 80 ℃ for 30min, then adding 100g of linalool, keeping the temperature, reacting for 4 hours, sampling after the reaction is finished, analyzing the concentration of each component of the reaction solution by a gas chromatograph, wherein the conversion rate of the linalool is 70.24%.
The reaction mixture was treated in the same manner as in example 1 to obtain 41.48g of citral product and 11.89g of a reaction product residue.
And (3) calculating: the yield of citral was 54.48%, with a content of 91.05%.
Comparative example 2 No phosphine ligand was added
The preparation method comprises the following steps: at 60 ℃, 0.1mol of anhydrous FeCl3And 0.05mol of RhCl3·3H2Dissolving O in 200mL of purified water, dispersing 0.8mol of 0.5mol of dicyclohexyl-18-crown-6 in 200mL of methanol, uniformly mixing the two solutions, oscillating vigorously until no precipitate is separated out, stopping oscillation, removing the solvent under reduced pressure to obtain a precipitate, drying the obtained solid substance in a constant-temperature drying oven at 80 ℃ to constant weight to obtain the catalyst, wherein the yield of the catalyst is 99.6%, and the label is 1' # catalyst.
In a 500mL stainless steel reaction kettle, replacing 3 times with nitrogen, replacing 3 times with oxygen, sequentially adding 100g of toluene and 5g of 1' # catalyst, activating at 80 ℃ for 30min, then adding 100g of linalool, keeping the temperature, reacting for 4 hours, sampling after the reaction is finished, analyzing the concentration of each component of the reaction solution by a gas chromatograph, wherein the conversion rate of the linalool is 75.16%.
The reaction mixture was treated in the same manner as in example 1 to obtain 46.34g of citral product and 10.67g of a pot liquid.
And (3) calculating: the yield of citral was 56.99%, with a content of 91.25%.
The present invention is illustrated in detail by the examples described above, but the present invention is not limited to the details described above, i.e., it is not intended that the present invention be implemented by relying on the details described above. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (10)

1. A homogeneous bimetallic complex catalyst is characterized by comprising a metal active center, a complexing agent and a modifier;
the metal active center is formed by transition metal ions; the complexing agent is crown ether; the modifier is a multidentate phosphine ligand.
The transition metal ion and the complexing agent form a complex, and the modifier modifies the complex through coordination with the transition metal ion and hydrogen bonding of the complexing agent.
2. The homogeneous bimetallic complex catalyst of claim 1, wherein the crown ether is one of 18-crown-6, 15-crown-5, dibenzo-18-crown-6, benzo-15-crown-5, dicyclohexyl-18-crown-6, dibenzo-24-crown-8, dibenzo-21-crown-7, dibenzo-27-crown-9, 1, 10-dithia-18-crown-6, diaza 18-crown-6, cryptate [2,2,2], cryptate [2,1,1], cryptate [2,2,1 ].
3. The homogeneous, bimetallic complex catalyst of claim 1 or 2, wherein the polydentate phosphine ligand is selected from the group consisting of 1, 2-bis (dimethylphosphino) ethane, bis (diphenylphosphinomethane), trans-1, 2-bis (diphenylphosphino) ethylene, 1, 2-bis (diphenylphosphino) ethane, 1, 3-bis (diphenylphosphino) propane, 1, 4-bis (diphenylphosphino) butane, 1, 5-bis (diphenylphosphino) pentane, 1, 6-bis (diphenylphosphino) hexane, 1, 2-bis (dipentafluorophenylphosphino) -ethane, 1, 2-bis (diphenylphosphino) benzene, 1, 3-bis [ (di-tert-butylphosphino) oxo ] benzene, 2 '-bis (diphenylphosphino) biphenyl, 1' -binaphthyl-2, 2 '-bis-diphenylphosphino, 1, 3' -bis (diphenylphosphino), 1, 8-bis (diphenylphosphino) naphthalene.
4. The homogeneous bimetallic complex catalyst of claim 1, wherein the transition metal ions comprise a first metal ion and a second metal ion, the first metal ion being selected from any one of the metal ions of Ni, Fe, Co, V, Cu, Zn, Mn, Cd, Sn, In, Cr, Re, Bi, Zr soluble salts; the second metal ion is selected from any one of metal ions of soluble salts of Pd, Au, Ag, Ru, Rh, Pt and Ir.
5. The homogeneous bimetallic complex catalyst of claim 1, wherein the molar ratio of the first metal ion to the second metal ion is: 1: 0.1-1.0;
the molar ratio of the transition metal ions to the complexing agent is as follows: 1: 1-10;
the molar ratio of the transition metal ions to the modifier is as follows: 1: 1-10.
6. A method for preparing a homogeneous bimetallic complex catalyst as claimed in any one of claims 1 to 5, comprising the steps of:
(1) dissolving a metal salt in water to form a metal salt solution, and dissolving a complexing agent in an organic solvent to form a complexing agent solution;
(2) mixing the metal salt solution and the complexing agent solution, violently oscillating, removing the solvent, and drying to obtain a complex;
(3) and adding the complex into a solvent containing a modifier, mixing and stirring, removing the solvent, and drying to obtain the homogeneous bimetallic complex catalyst.
7. The method for preparing a homogeneous bimetallic complex catalyst as in claim 6, wherein the organic solvent in the step (1) is one of methanol, acetonitrile, n-butanol, dichloromethane and toluene;
the solvent in the step (3) is DMF or toluene.
8. A preparation method of aldehyde is characterized in that under the catalysis of the homogeneous bimetallic complex catalyst of any one of claims 1 to 7, molecular oxygen is used as an oxidant, alcohol is used as a raw material, and catalytic oxidation reaction is carried out to obtain the aldehyde;
the aldehyde is citral or isopentene aldehyde;
the alcohol is linalool, methyl butenol or 3-methyl-3-butenol.
9. The method for producing an aldehyde according to claim 8, wherein the alcohol is linalool, and the aldehyde is citral;
the temperature of the catalytic oxidation reaction is 100-180 ℃, and the reaction time is 2-6 hours.
10. The method for producing an aldehyde according to claim 9, wherein the solvent for the catalytic oxidation reaction is toluene.
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