CN111978142B - Method for isomerizing cis-olefin into trans-olefin - Google Patents

Method for isomerizing cis-olefin into trans-olefin Download PDF

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CN111978142B
CN111978142B CN202010792703.8A CN202010792703A CN111978142B CN 111978142 B CN111978142 B CN 111978142B CN 202010792703 A CN202010792703 A CN 202010792703A CN 111978142 B CN111978142 B CN 111978142B
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olefin
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palladium
copper compound
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CN111978142A (en
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郑南峰
李凯佳
刘锟隆
刘圣杰
陈洁
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Xiamen University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
    • C07C5/2206—Catalytic processes not covered by C07C5/23 - C07C5/31
    • C07C5/226—Catalytic processes not covered by C07C5/23 - C07C5/31 with metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8926—Copper and noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/56—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by isomerisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/09—Geometrical isomers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with noble metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/24—Nitrogen compounds

Abstract

The invention provides a method for isomerizing cis-olefin into trans-olefin, which comprises the steps of adding a palladium/copper compound catalyst and cis-olefin into a reaction container, adding an organic solvent, uniformly mixing, and reacting in a hydrogen atmosphere to obtain the trans-olefin. In the palladium/copper compound catalyst used in the invention, palladium is dispersed on the surface of copper compound in atomic scale, and H is induced by utilizing a special interface formed between Pd and a carrier2The C ═ C double bond is reversed by means of heterolytic cleavage, so that cis-olefin is converted into trans-olefin, and the cis-olefin is not further hydrogenated into alkane, and the high selectivity to the trans-olefin is realized. Meanwhile, the method has simple operation process, can be prepared in large quantity, does not need to add various auxiliary agents in the catalysis process, reduces the complexity of a reaction system, is beneficial to the separation and purification of products, saves the cost, and has extremely high industrial application value.

Description

Method for isomerizing cis-olefin into trans-olefin
The technical field is as follows:
the invention relates to the field of olefin compound synthesis, in particular to a method for isomerizing cis-olefin into trans-olefin.
Background art:
the olefin compound is a very important fine chemical product and plays a very important role in the industries of medicines, pesticides, spices and the like. Olefin is used as an organic synthesis reagent in the chemical field, can participate in catalytic hydrogenation reaction, electrophilic addition reaction, free radical addition reaction, polymerization reaction and the like, and can produce fluorescent whitening agent, liquid crystal, light-emitting diode and the like; the trans-stilbene compound is a very important drug intermediate in the field of medicine, an olefin group is a common pharmacophore and is used for synthesizing drugs with physiological activity or forming fragments of various functional materials, and particularly, the application of the trans-olefin is the most extensive, for example, the trans-stilbene compound has remarkable pharmacological properties such as anti-tumor, anti-cardiovascular and anti-oxidation and is also applied to the preparation of chemical products such as luminescent materials, dyes and the like.
The traditional synthesis of trans olefins is numerous: (1) classical human name reactions, such as: witting, Horner-Wadsworth-Emmons, Peterson inection reaction, and the like; (2) catalyzing Heck reaction; (3) carrying out Suzuki coupling reaction; (4) olefin metathesis. These methods can obtain high yield, but a large amount of phosphine reagent, metal reagent or aldehyde and other various additives are required to be added in the reaction process, so that the purification of the product is limited, and a large amount of waste can pollute the environment.
In recent years there have also been some other processes for the synthesis of olefinic compounds: (1) the catalytic reduction method takes ammonia borane as a hydrogen source, although the method has mild reaction conditions and low requirements on equipment, the ammonia borane is expensive, and a complex of metal and a ligand needs to be prepared in advance, so that the production cost is increased, and the method is not beneficial to large-scale industrial application; (2) the catalytic reduction method using acid as hydrogen source has reduced cost compared with the former method, but the use of acid increases the loss of equipment, requires more severe conditions, and has limited industrial application, and the method has difficulty in selectively synthesizing trans-olefin. (3) The catalytic reduction method using alcohol as hydrogen source, for example, the reaction of alcohol and methyl heterocyclic compound to produce olefin, although the method can obtain higher trans-olefin yield, the preparation cost of the catalyst is high, the reaction temperature needs to be about 140 ℃, the reaction condition is harsh, and the method is not suitable for industrial application.
In conclusion, the trans-olefin compound has high application value in the pharmaceutical and chemical fields, but most of the existing synthetic methods have high cost and strict requirements on reaction conditions, and wastes generated by post-treatment can increase the burden on the environment, so that the industrial application is more or less limited.
The invention content is as follows:
an object of the present invention is to solve the existing problems and to provide a process for isomerizing cis-olefins to trans-olefins.
The invention adopts the following technical scheme:
a process for the isomerization of cis-olefins to trans-olefins comprising the steps of:
adding a palladium/copper compound catalyst and cis-olefin into a reaction container, adding an organic solvent, uniformly mixing, and reacting in a hydrogen atmosphere to obtain trans-olefin; the palladium in the palladium/copper compound catalyst is dispersed on the surface of the copper compound in an atomic scale.
Preferably, the valence of copper in the copper compound is + 1.
Further preferably, the copper compound is selected from Cu2O、Cu3And N.
Preferably, the molar ratio of Pd to cis-olefin in the palladium/copper compound catalyst is (1-10) to 1000.
Preferably, the organic solvent is selected from alcoholic solvents.
Further preferably, the alcoholic solvent is at least one selected from the group consisting of ethanol, methanol, propylene glycol, ethylene glycol, n-butanol and isobutanol.
Preferably, the reaction conditions under the hydrogen atmosphere are as follows: the time is 2-10 h; the temperature is 10-60 ℃; the hydrogen pressure is 1 to 1.5 atm.
Preferably, the cis-olefin is selected from at least one of cis-4-octene, cis-diphenylethylene, cis-1-methyl-1-styrene, cis-1-phenyl-1-butene, cis-1-phenyl-1-pentene, cis-3-phenyl-2-propen-1-ol.
Preferably, the preparation method of the palladium/copper compound catalyst comprises the following steps:
a. dispersing a palladium precursor in acetonitrile in advance, and stirring at 10-60 ℃ to obtain a palladium precursor acetonitrile solution, wherein the mass percentage concentration of the palladium precursor in the palladium precursor acetonitrile solution is 0.001% -1%;
b. dispersing a copper compound in acetonitrile, stirring in an inert gas atmosphere, adding a palladium precursor acetonitrile solution, stirring for 3-7 h at 40-70 ℃, centrifuging, washing, and vacuum drying to obtain a palladium/copper compound catalyst; the palladium in the palladium/copper compound catalyst is dispersed on the surface of the copper compound in an atomic scale.
Preferably, the palladium precursor is selected from (Ph)4P)2[Pd2(μ-CO)2Cl4]And at least one of diacetonitrile palladium chloride.
Has the advantages that:
(1) the method can catalyze cis-olefin to trans-olefin under mild conditions, the conversion rate of the cis-olefin is up to 100%, the catalyst activity is high, the selectivity is over 96%, and can be up to 98.7%, and the high-purity trans-olefin is obtained.
(2) The catalyst is applied to the technical field of isomerization of cis-olefin into trans-olefin, is pioneering and breakthrough, can still achieve 97% of selectivity of isomerization of cis-olefin into trans-olefin after 6 times of recycling, cannot be lost in the catalysis process, and greatly reduces the production process cost.
(3) The method has simple operation process, can be used for mass preparation, does not need to add various auxiliary agents in the catalysis process, reduces the complexity of a reaction system, is beneficial to the separation and purification of products, and is suitable for industrial application.
(4) The palladium/copper compound catalyst used in the method for isomerizing cis-olefin into trans-olefin induces H due to the special interface formed between Pd and the carrier2By means of heterolytic dissociation, only C ═ C double bonds can be inverted, cis-olefins are converted into trans-olefins, and the cis-olefins are not further hydrogenated into alkanes, so that the selectivity of the trans-olefins is improved.
(5) The catalytic system of the invention has strong universality to substrates, cis-olefins containing various functional groups can be isomerized into trans-olefins in high selectivity, and the catalytic system has extremely high application value.
Description of the drawings:
FIG. 1 is an electron micrograph of a palladium/copper compound catalyst according to the present invention obtained by electron microscopy.
FIG. 2 shows 0.1% Pd according to the invention1/Cu2Synchrotron radiation pattern of O catalysts.
FIG. 3 shows 0.5% Pd according to the invention1/Cu3In situ CO infrared absorption profile of N catalyst.
FIG. 4 shows 0.1% Pd in example 31/Cu2And 6 times of cycle stability experiment results of the O catalyst catalyzing the isomerization of cis-4-octene into tran-4-octene are shown in the figure.
FIG. 5 is 0.1% Pd in example 31/Cu2In-situ CO infrared absorption plots before O catalyst reaction and after 6 cycles.
The specific implementation mode is as follows:
the technical solutions of the present invention will be described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The invention provides a method for isomerizing cis-olefin into trans-olefin, which comprises the following steps:
adding a palladium/copper compound catalyst and cis-olefin into a reaction container, adding an organic solvent, uniformly mixing, and reacting in a hydrogen atmosphere to obtain trans-olefin; the palladium in the palladium/copper compound catalyst is dispersed on the surface of the copper compound in an atomic scale.
The invention selects the palladium/copper catalyst because the Pd and the copper carrier can form a special interface to induce H2By means of heterolytic dissociation, only C ═ C double bonds can be reversed, cis-olefins are converted into trans-olefins, and cis-olefins are not further hydrogenated into alkanes, so that the selectivity of trans-olefins is improved. FIG. 1 is an electron micrograph of a Pd/Cupite catalyst of the present invention obtained by electron microscopy, which shows that Pd is dispersed on the surface of the Cupite in the form of a single atom.
In the present invention, the valence of copper in the copper compound is +1, and Cu is preferable2O、Cu3And N is added. This is achieved byThe Cu/Pd interface constructed by Pd and + 1-valent Cu is favorable for inducing H2Heterolytic cleavage of (a) thereby reversing the C ═ C double bond, which is detrimental to the hydrogenation of olefins to paraffins. FIG. 2 shows 0.1% Pd according to the invention1/Cu2Synchrotron radiation pattern of O catalyst, upper 0.1Pd can be seen1/Cu2No obvious Pd-Pd bond signal appears in the O catalyst, which indicates that Pd is dispersed in Cu in a monoatomic form2On the surface of O. FIG. 3 is 0.5% Pd1/Cu3In situ CO infrared absorption of the N catalyst, 0.5% Pd1/Cu3The N catalyst has only one CO infrared absorption peak, and the Pd is also shown in the Cu3N is also dispersed in the form of monoatomic atoms in Cu3N surface.
In the invention, the molar ratio of Pd to cis-olefin in the palladium/copper compound catalyst is (1-10) to 1000, and in the selected value range, a small amount of Pd can be used for realizing isomerization of cis-olefin into trans-olefin, so that the use of Pd is greatly reduced, the atom utilization rate is improved, and the process cost is reduced.
In the invention, the solvent used in the catalytic reaction process is an organic solvent; preferably, the organic solvent may be an alcohol solvent; further preferably, the alcohol solvent may be at least one selected from the group consisting of ethanol, methanol, propylene glycol, ethylene glycol, n-butanol and isobutanol. The alcohol solvent has high universality, easy acquisition and lower cost, and the use of the alcohol solvent can save the cost and is beneficial to industrial application.
In the present invention, the conditions of the reaction under the hydrogen atmosphere are: the time is 2-10 h; the temperature is 10-60 ℃; the hydrogen pressure is 1 to 1.5 atm. The pressure of the hydrogen gas for reaction only needs to be normal pressure or slightly higher than normal pressure, the temperature only needs to be room temperature or slightly higher than room temperature, and the reaction can be completed without harsh reaction conditions of temperature and pressure.
In the present invention, the cis-olefin may be at least one selected from the group consisting of cis-4-octene, cis-diphenylethylene, cis-1-methyl-1-styrene, cis-1-phenyl-1-butene, cis-1-phenyl-1-pentene, and cis-3-phenyl-2-propen-1-ol. The method can be applied to isomerizing various cis-olefins into trans-olefins, has various choices of the cis-olefins, and is favorable for the utilization in industrial production.
In the present invention, the preparation method of the palladium/copper compound catalyst may employ the following steps:
a. dispersing a palladium precursor in acetonitrile in advance, and stirring at 10-60 ℃ to obtain a palladium precursor acetonitrile solution, wherein the mass percentage concentration of the palladium precursor in the palladium precursor acetonitrile solution is 0.001% -1%;
b. dispersing a copper compound in acetonitrile, stirring in an inert gas atmosphere, adding a palladium precursor acetonitrile solution, stirring for 3-7 h at 40-70 ℃, centrifuging, washing, and vacuum drying to obtain a palladium/copper compound catalyst; the palladium in the palladium/copper compound catalyst is dispersed on the surface of the copper compound in an atomic scale.
In the present invention, the palladium precursor may be selected from (Ph)4P)2[Pd2(μ-CO)2Cl4]And at least one of diacetonitrile palladium chloride.
Example 1: catalytic use of palladium/copper compound catalyst
1-1：0.1％Pd1/Cu2Preparation of O catalyst
Pd (CH) is preliminarily prepared3CN)2Cl2Dispersing in acetonitrile, and stirring at 10-60 ℃ for 10h to obtain Pd (CH)3CN)2Cl2Acetonitrile solution of Pd (CH)3CN)2Cl2The mass percentage concentration is 0.5%.
500mg of Cu are taken2Dispersing O in 100mL of acetonitrile, ultrasonically dispersing the O uniformly, and then dispersing the O in 50sccm N2Stirring for 15min under atmosphere, and mixing according to Pd and Cu2Pd (CH) was added dropwise at a mass ratio of O of 0.1: 1003CN)2Cl2Stirring the acetonitrile solution for 3-7 h at 40-70 ℃, cooling to room temperature, performing centrifugal separation, washing with ethanol for several times, and placing in a vacuum drying oven for vacuum drying to obtain 0.1% Pd1/Cu2And (3) an O catalyst.
1-2：0.5％Pd1/Cu2Preparation of O catalyst
Pd (CH) is preliminarily prepared3CN)2Cl2Dispersing in acetonitrile, and stirring at 10-60 ℃ for 10h to obtainPd(CH3CN)2Cl2Acetonitrile solution of Pd (CH)3CN)2Cl2The mass percentage concentration is 0.5%.
500mg of Cu are taken2Dispersing O in 100mL of acetonitrile, ultrasonically dispersing the O uniformly, and then dispersing the O in 50sccm N2Stirring for 15min under atmosphere, and mixing according to Pd and Cu2Pd (CH) was added dropwise at a mass ratio of O of 0.5: 1003CN)2Cl2Stirring the acetonitrile solution for 3-7 h at 40-70 ℃, cooling to room temperature, performing centrifugal separation, washing with ethanol for several times, and placing in a vacuum drying oven for vacuum drying to obtain 0.5% Pd1/Cu2And (3) an O catalyst.
1-3：1％Pd1/Cu2Preparation of O catalyst
Pd (CH) is preliminarily prepared3CN)2Cl2Dispersing in acetonitrile, and stirring at 10-60 ℃ for 10h to obtain Pd (CH)3CN)2Cl2Acetonitrile solution of Pd (CH)3CN)2Cl2The mass percentage concentration is 0.5%.
500mg of Cu are taken2Dispersing O in 100mL of acetonitrile, ultrasonically dispersing the O uniformly, and then dispersing the O in 50sccm N2Stirring for 15min under atmosphere, and mixing according to Pd and Cu2Pd (CH) is added dropwise with the mass ratio of O being 1: 1003CN)2Cl2Stirring the acetonitrile solution for 3-7 h at 40-70 ℃, cooling to room temperature, performing centrifugal separation, washing with ethanol for several times, and placing in a vacuum drying oven for vacuum drying to obtain 1% Pd1/Cu2And (3) an O catalyst.
1-4：0.5％Pd1/Cu3N catalyst preparation
Pd (CH) is preliminarily prepared3CN)2Cl2Dispersing in acetonitrile, and stirring at 10-60 ℃ for 10h to obtain Pd (CH)3CN)2Cl2Acetonitrile solution of Pd (CH)3CN)2Cl2The mass percentage concentration is 0.5%.
500mg of Cu are taken3Dispersing N in 100mL of acetonitrile, and after uniform ultrasonic dispersion, dispersing the mixture in 50sccm N2Stirring for 15min under atmosphere, and mixing according to Pd and Cu3The mass ratio of N is 0.5: 100Adding Pd (CH)3CN)2Cl2Stirring the acetonitrile solution for 3-7 h at 40-70 ℃, cooling to room temperature, performing centrifugal separation, washing with ethanol for several times, placing in a vacuum drying oven, and performing vacuum drying to obtain 0.5% Pd1/Cu3And (3) N catalyst.
1-5：1.5％Pd1/Cu3N catalyst preparation
Pd (CH) is preliminarily prepared3CN)2Cl2Dispersing in acetonitrile, and stirring at 10-60 ℃ for 10h to obtain Pd (CH)3CN)2Cl2Acetonitrile solution of Pd (CH)3CN)2Cl2The mass percentage concentration is 0.5%.
500mg of Cu are taken3Dispersing N in 100mL of acetonitrile, and after uniform ultrasonic dispersion, dispersing the mixture in 50sccm N2Stirring for 15min under atmosphere, and mixing according to Pd and Cu3Pd (CH) was added dropwise at a mass ratio of N of 1.5: 1003CN)2Cl2Stirring the acetonitrile solution for 3-7 h at 40-70 ℃, cooling to room temperature, performing centrifugal separation, washing with ethanol for several times, placing in a vacuum drying oven, and performing vacuum drying to obtain 1.5% Pd1/Cu3And (3) N catalyst.
1-6: catalytic isomerization application of palladium/copper compound catalyst
The prepared 0.1% Pd was weighed in an amount of 5. mu. mol Pd1/Cu2O、0.5％Pd1/Cu2O、1％Pd1/Cu2O、0.5％Pd1/Cu3N、1.5％Pd1/Cu3Respectively naming N catalysts as test groups 1, 2, 3, 4 and 5, adding the test groups into a 50mL high-pressure reaction bottle, respectively adding 1mmol of cis-4-octene, adding 10mL of ethanol as a solvent, uniformly mixing, and carrying out H reaction at 1-1.5 bar2And (3) reacting for 2-10 hours at the temperature of 10-60 ℃ in the atmosphere, sampling, and measuring the performance of different catalysts for catalyzing the isomerization of cis-4-octene into tran-4-octene by adopting an internal standard method and using gas chromatography for analysis. Table 1 shows the results of the isomerization of cis-4-octene to tran-4-octene in the presence of different catalyst groups. Can obtain that the catalysts loaded with different amounts of Pd monoatomic atoms on different copper compound carriers catalyze the isomerization of cis-4-octene into tran-4-octene through hydrogen inductionThe alkene has good activity and selectivity, the conversion rate reaches 100%, and the selectivity exceeds 97%.
TABLE 1 results of different experimental groups of catalysts for the isomerization of cis-4-octene to tran-4-octene
Figure BDA0002623238910000071
Example 2: 0.1% Pd1/Cu2Catalytic isomerization application of O catalyst
Five groups of 0.1% Pd prepared in example 1 were weighed1/Cu2O catalysts, each group containing 5 mu mol Pd, are respectively named test groups 6, 7, 8, 9 and 10, added into a 50mL high-pressure reaction bottle, then respectively added with 1mmol cis-diphenylethylene, cis-1-methyl-1-styrene, cis-1-phenyl-1-butene, cis-1-phenyl-1-pentene and cis-3-phenyl-2-propylene-1-ol, added with 10mL ethanol as a solvent, uniformly mixed, and subjected to 1bar H2And (3) reacting for 2-10 hours at the temperature of 30 ℃ in the atmosphere, sampling, and determining the performance of the catalyst for catalyzing the isomerization of cis-olefin into trans-olefin by adopting an internal standard method and using gas chromatography for analysis. Table 2 is 0.1% Pd1/Cu2The O catalyst catalyzes the isomerization of different cis-olefins into trans-olefins. The catalyst prepared by the method can be used for catalyzing cis-olefin containing different groups to be isomerized into corresponding trans-olefin, has good selectivity which can reach over 96.5 percent, and shows that the catalyst has good universality in the application of isomerizing the cis-olefin into the trans-olefin.
In this embodiment, the solvent used for the isomerization of cis-olefins to trans-olefins may be ethanol, and may be selected from methanol, propylene glycol, ethylene glycol, n-butanol, and isobutanol.
TABLE 2.0.1% Pd1/Cu2Reaction result of O catalyst catalyzing isomerization of different cis-olefins into trans-olefins
Figure BDA0002623238910000072
Figure BDA0002623238910000081
Example 3: testing the stability of the sleeves of the invention
0.1% Pd containing 5. mu. mol Pd prepared in example 1 was weighed1/Cu2Placing an O catalyst and 1mmol of cis-4-octene in a 50mL high-pressure reaction bottle, taking 10mL of ethanol as a solvent, uniformly mixing, and then adding the mixture at 1bar H2Reacting for 2-10 hours at 30 ℃ in the atmosphere, then sampling, recovering the catalyst, washing for 5 times by using ethanol, vacuum-drying at 60 ℃, applying for 6 times under the same conditions, and respectively sampling. And (3) measuring the performance of the catalyst for catalyzing the isomerization of cis-4-octene into tran-4-octene by adopting an internal standard method and gas chromatography analysis.
FIG. 4 is 0.1% Pd1/Cu2And 6 times of cycle stability experiment results of the O catalyst catalyzing the isomerization of cis-4-octene into tran-4-octene are shown in the figure. It can be seen that the selectivity of the catalyst of the method of the invention to the tran-4-octene is not obviously reduced after the catalyst is mechanically used for 6 times, and can still reach more than 97 percent, and the stability is good. FIG. 5 is 0.1% Pd1/Cu2The infrared absorption patterns of in-situ CO before O catalyst reaction and after 6 times of circulation show that 0.1% Pd1/Cu2The infrared adsorption of CO of Pd on the O catalyst before reaction has only one peak, which shows that Pd is dispersed in Cu in a monoatomic form2On the surface of O, 0.1% Pd after 6 times of cyclic application1/Cu2The infrared absorption peak of CO of the O catalyst is consistent with that before reaction, which shows that the catalyst is not lost in the catalysis process, and also shows that the catalyst of the invention has good stability.
Example 4: catalytic isomerization application of Pd and cis-olefin in different molar ratios in palladium/copper compound catalyst
A certain amount of 0.5% Pd prepared in example 1 was weighed1/Cu3N catalyst and cis-4-octene in an amount such that 0.5% Pd1/Cu3The molar ratio of Pd to cis-4-octene in the N catalyst is (1-10) to 1000, and the N catalyst is placed in a 50mL high-pressure reaction bottleIn the preparation, 10mL of ethanol is used as a solvent, and after being uniformly mixed, the mixture is subjected to 1bar H2And (3) reacting for 2-10 hours at the temperature of 30 ℃ in the atmosphere, sampling, and determining the performance of the catalyst for catalyzing the isomerization of cis-4-octene into tran-4-octene by adopting an internal standard method and using gas chromatography for analysis. Table 3 is 0.5% Pd1/Cu3The Pd in the N catalyst and cis-olefin have different molar ratios, and the N catalyst is used for isomerizing cis-olefin into trans-olefin.
TABLE 3.0.5% Pd1/Cu3Experimental result of application of Pd and cis-olefin in different molar ratios in N catalyst in isomerization of cis-olefin into trans-olefin
Figure BDA0002623238910000091
Example 5
In advance (Ph)4P)2[Pd2(μ-CO)2Cl4]Dispersing in acetonitrile, and stirring at 10-60 ℃ for 10h to obtain Pd (CH)3CN)2Cl2Acetonitrile solution of Pd (CH)3CN)2Cl2The mass percentage concentration is 0.001-1%.
500mg of Cu are taken2Dispersing O in 100mL of acetonitrile, ultrasonically dispersing the O uniformly, and then dispersing the O in 50sccm N2Stirring for 15min under atmosphere, and mixing according to Pd and Cu2O was added dropwise at a mass ratio of 0.1: 100 (Ph)4P)2[Pd2(μ-CO)2Cl4]Stirring acetonitrile solution at 60 deg.C for 5 hr, cooling to room temperature, centrifuging, washing with ethanol for several times, and vacuum drying in vacuum drying oven to obtain 0.1% Pd1/Cu2And (3) an O catalyst.
0.1% Pd prepared by weighing 5 μmol Pd1/Cu2Adding an O catalyst into a 50mL high-pressure reaction bottle, adding 1mmol of cis-4-octene, adding 10mL of ethanol as a solvent, uniformly mixing, and adding 1-1.5 bar H2Reacting for 2-10 hours at the temperature of 10-60 ℃ in the atmosphere, sampling, analyzing by gas chromatography by adopting an internal standard method, and determining the performance of the catalyst for catalyzing the isomerization of cis-4-octene into tran-4-octeneWhen cis-4-octene was completely converted, the selectivity to tran-4-octene was 98.3%.
Comparative example 1: palladium/copper compound catalyst with different valences
S1: pd (CH) is preliminarily prepared3CN)2Cl2Dispersing in acetonitrile, and stirring at 10-60 ℃ for 10h to obtain Pd (CH)3CN)2Cl2Acetonitrile solution of Pd (CH)3CN)2Cl2The mass percentage concentration is 0.5%.
S2: respectively dispersing 500mg of copper compounds with different valence states in 100mL of acetonitrile, and ultrasonically dispersing uniformly in 50sccm N2Stirring for 15min under atmosphere, and dropwise adding Pd (CH) according to the mass ratio of Pd to copper compound of 0.1: 1003CN)2Cl2And (3) stirring the acetonitrile solution at 60 ℃ for 5h, cooling to room temperature, performing centrifugal separation, washing with ethanol for a plurality of times, and placing in a vacuum drying oven for vacuum drying to obtain a catalyst A, a catalyst B and a catalyst C.
S3: respectively weighing catalyst A, catalyst B and catalyst C according to the amount of 5 mu mol Pd, adding into a 50mL high-pressure reaction bottle, respectively adding 1mmol cis-4-octene, adding 10mL ethanol as solvent, mixing well, and adding into 1bar H2And (3) reacting for 2-10 hours at the temperature of 30 ℃ in the atmosphere, sampling, and measuring the performance of different catalysts for catalyzing the isomerization of cis-4-octene into tran-4-octene by adopting an internal standard method and using gas chromatography for analysis. Table 3 shows the reaction results of catalysts prepared from copper compounds with different valences for catalytic isomerization applications, and it can be seen that only when the valency of copper is +1, the obtained palladium/copper catalyst has high activity and high selectivity for catalyzing the isomerization of cis-olefin to trans-olefin, and the selectivity reaches 98.2%, while the catalysts prepared by selecting Cu with valences of 0 or CuO with valences of +2 cannot achieve the purpose of catalyzing the isomerization of cis-olefin to trans-olefin.
TABLE 4 reaction results for different valency copper compounds to prepare catalysts for catalytic isomerization applications
Copper compound Catalyst and process for preparing same Substrate Product of Conversion (%) Selectivity (%)
Cu2O Catalyst A cis-4-octene tran-4-octene 100 98.2
CuO Catalyst B cis-4-octene tran-4-octene 0 -
Cu Catalyst C cis-4-octene tran-4-octene 0 -
Comparative example 2: cu2Negative on OPd-loaded particles, non-atomic level dispersion
S1: pd (CH) is preliminarily prepared3CN)2Cl2Dispersing in acetonitrile, and stirring at 10-60 ℃ for 10h to obtain Pd (CH)3CN)2Cl2Acetonitrile solution of Pd (CH)3CN)2Cl2The mass percentage concentration is 0.5%.
S2: 500mgCu was taken2Dispersing O in 100mL of acetonitrile, ultrasonically dispersing the O uniformly, and then dispersing the O in 50sccm N2Stirring for 15min under atmosphere, and mixing according to Pd and Cu2Pd (CH) is added dropwise with the mass ratio of O being 1: 103CN)2Cl2Stirring acetonitrile solution at 60 deg.C for 5 hr, cooling to room temperature, centrifuging, washing with ethanol for several times, and vacuum drying in vacuum drying oven to obtain 10% Pd NPs/Cu2And (3) an O catalyst.
S3: weighing 10% PdNPs/Cu in the amount of 5 mu mol Pd2Adding an O catalyst into a 50mL high-pressure reaction bottle, adding 1mmol of cis-4-octene, adding 10mL of ethanol as a solvent, uniformly mixing, and adding the mixture at 1bar H2And (3) reacting for 2-10 hours at the temperature of 30 ℃ in the atmosphere, sampling, and measuring the performance of the catalyst for catalyzing the isomerization of cis-4-octene into tran-4-octene by adopting an internal standard method and using gas chromatography for analysis. 10% Pd NPs/Cu2O can also catalyze the isomerization of cis-4-octene to tran-4-octene at 100%, but the selectivity is only 78%, and over time, the cis-4-octene will be totally hydrogenated to octane. Therefore, only a single atom of Pd favors the isomerization of cis-olefins to trans-olefins.
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims and their equivalents.

Claims (8)

1. A process for isomerizing a cis olefin to a trans olefin comprising the steps of:
adding palladium/copper compound catalyst and cis-olefin into a reaction container, adding organic solvent, mixing uniformly, and reacting in hydrogen atmosphereCarrying out reaction under the surrounding atmosphere to obtain trans-olefin; the palladium in the palladium/copper compound catalyst is dispersed on the surface of the copper compound in an atomic scale; the copper compound is selected from Cu2O、Cu3And N.
2. The method of claim 1, wherein the palladium/cuprate catalyst has a molar ratio of Pd to cis-olefin of (1-10) to 1000.
3. The method according to claim 1, wherein the organic solvent is selected from alcoholic solvents.
4. The method according to claim 3, wherein the alcoholic solvent is at least one selected from the group consisting of ethanol, methanol, propylene glycol, ethylene glycol, n-butanol and isobutanol.
5. The method of claim 1, wherein the conditions of the reaction under hydrogen atmosphere are: the time is 2-10 h; the temperature is 10-60 ℃; the hydrogen pressure is 1 to 1.5 atm.
6. The process according to claim 1, wherein the cis-olefin is at least one selected from the group consisting of cis-4-octene, cis-diphenylethylene, cis-1-phenyl-1-butene, and cis-1-phenyl-1-pentene.
7. The method of claim 1, wherein the palladium/copper compound catalyst is prepared by a method comprising the steps of:
a. dispersing a palladium precursor in acetonitrile in advance, and stirring at 10-60 ℃ to obtain a palladium precursor acetonitrile solution, wherein the mass percentage concentration of the palladium precursor in the palladium precursor acetonitrile solution is 0.001% -1%;
b. dispersing a copper compound in acetonitrile, stirring in an inert gas atmosphere, adding a palladium precursor acetonitrile solution, stirring for 3-7 h at 40-70 ℃, centrifuging, washing, and vacuum drying to obtain a palladium/copper compound catalyst; the palladium in the palladium/copper compound catalyst is dispersed on the surface of the copper compound in an atomic scale.
8. The method of claim 7, wherein the palladium precursor is selected from (Ph)4P)2[Pd2(μ-CO)2Cl4]And at least one of diacetonitrile palladium chloride.
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