CN114853585A - Heterogeneous catalysis double bond isomerization method - Google Patents
Heterogeneous catalysis double bond isomerization method Download PDFInfo
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Abstract
The invention discloses a heterogeneous catalysis double bond isomerization method, which comprises the following steps: putting the compound shown in the formula (I), the catalyst and the auxiliary agent into a hydrogenation kettle, replacing the hydrogenation kettle with nitrogen, heating and raising the temperature under stirring, introducing hydrogen into the hydrogenation kettle, and stirring for reaction to obtain the compound shown in the formula (II). The invention adopts a heterogeneous catalytic reaction system, has high conversion rate of raw materials and high selectivity of double-bond isomerization products in a hydrogen environment, can realize the application of the catalyst, saves the use of expensive catalyst and saves the production cost.
Description
Technical Field
The invention belongs to the technical field of organic chemistry, relates to a double bond isomerization method, and particularly relates to a heterogeneous catalysis double bond isomerization method.
Background
Olefin is used as an important organic compound framework, and is widely applied in the fields of organic synthesis, pharmaceutical synthesis, petrochemical industry, fine chemical industry, bioengineering and the like. However, there are a few naturally occurring olefins and various methods for synthesizing olefins have been reported in succession to meet the demands of various reactions and productions, for example: elimination, coupling, addition, condensation, rearrangement reactions, isomerization reactions, and the like. Among them, the double bond isomerization reaction is becoming a research hotspot in the chemical and chemical fields because it is more consistent with the requirements of atom economy and green chemistry.
Double bond isomerization means that a functional group undergoes cis/trans configuration change or double bond position migrates in a compound, and at present, the migration of the double bond position in the compound is mainly realized by acid catalysis, base catalysis and transition metal catalysis.
Acid catalysis generally involves the formation of a corresponding carbenium intermediate from a carbon-carbon double bond followed by deprotonation to form a new carbon-carbon double bond. In general, hydrochloric acid, sulfuric acid, nitric acid, p-toluenesulfonic acid, acid anhydride and other medium and strong acids are used as catalysts, but in these homogeneous reactions, the strong acids cause severe corrosion to industrial equipment, the catalysts cannot be recycled, and washing in post-treatment generates a large amount of wastewater. In recent years, heterogeneous catalysts such as solid acids, cationic resins and molecular sieves have become one of the hot spots for research on olefin isomerization. These heterogeneous catalysts have the advantages of easy separation after reaction, catalyst application, etc., but they also have the obvious disadvantages, i.e. the catalyst preparation is complicated, the cost is high, the catalytic efficiency is not high, and the reaction selectivity is not good.
Base catalysis is generally the formation of a corresponding allylic anion intermediate from a compound containing a carbon-carbon double bond followed by dehydrogenation to form a new carbon-carbon double bond. At present, the basic olefin isomerization catalysts used in industry are mainly: NaOH, KOH, r-Al 2 O 3 -NaOH、r-Al 2 O 3 NaOH-Na, MgO-NaOH-Na, etc. When solid strong alkali substances are selected as the catalyst, reaction equipment is easy to corrode, simultaneously, more leftovers are generated in the reaction process, the catalyst is easy to poison and not easy to recycle, and the formed environmental pollution is serious.
As described above, the conventional acid catalysis and base catalysis have the disadvantages of easy corrosion of equipment, difficult recycling of catalyst, complicated post-treatment, and more three wastes, and thus the method for catalyzing olefin isomerization by transition metal is becoming a research hotspot in the chemical engineering field. The isomerization of olefin catalyzed by transition metal is a novel atom economic reaction, and uses VB group, VIB group, VIIB group and VIII group metals and complexes thereof as catalysts to produce corresponding intermediates by inserting the metals into carbon-carbon double bonds, and then the intermediates are reduced and eliminated to obtain new carbon-carbon double bonds. The transition metal catalyst has the advantages of high conversion rate, good selectivity, small corrosion to equipment, less production wastewater and more environment-friendly process, and meanwhile, the reaction is heterogeneous reaction, and the catalyst can be repeatedly used, so that the production cost is greatly reduced.
As an efficient catalytic strategy, transition metal catalysis is widely applied to organic synthesis and industrial production. For example: kaliya et al (Applied Catalysis A: General, 297,2, 231-. Although the reaction conversion rate can reach 98%, the reaction conversion rate is lower than 10%, and the catalyst is expensive and is not beneficial to industrial production. In US patent US 4845303A: the beta-isophorone is prepared by using acetylacetone complexes of metals such as iron, cobalt, chromium, aluminum and the like as a catalyst and adopting a-isophorone isomerization. Although the reaction yield can reach 90-95%, the catalyst dosage is only 0.1-1 wt%. However, the space-time yield of the reaction is low, and the catalyst is dissolved in the reaction solution and is difficult to separate from the system, thereby increasing the production and separation cost. In Chinese patent CN112023941A, Pd and metals such as Cu, Co, Ni, Mg, Al are loaded on activated carbon according to a certain proportion, and then double bond isomerization of beta-pinene is carried out by using a self-made catalyst to obtain a corresponding alpha-pinene product. The hydrazine monohydrate used as the raw material in the method is extremely toxic and is easy to explode, and the potential safety hazard in industrial production is large.
In summary, the prior isomerization reaction of double bonds catalyzed by transition metals has wide application in industrial production, and has a series of advantages of high conversion rate, good selectivity, less production wastewater, indiscriminate application of catalysts, more environment-friendly process and the like. Although the method has a series of advantages, the catalyst is still expensive in production and is not beneficial to large-scale use; limited catalytic activity, limited catalyst application times and the like. Therefore, the development of novel, efficient and green transition metal-catalyzed olefin isomerization has important theoretical significance and application value.
The alpha, beta-unsaturated carbonyl compound has important application in the fields of medicine, pesticide, chemical industry and the like. Many of the compounds with alpha, beta-unsaturated carbonyl skeleton structure are useful products or intermediates for preparing other important products. For example, 2-methyl-2-pentenal, 2,6, 6-trimethyl-2-cyclohexene-1, 4-dione, etc. The former can be used as pesticide intermediate, or flavoring agent for food additive and essence perfume; the latter is also called tea scented ketone, can be used in tea essence and tobacco essence, is also an intermediate for synthesizing 2,3, 5-trimethylhydroquinone, and is an important synthon for synthesizing vitamin E.
The isomerization of the outer double bond to the inner double bond of an α, β -unsaturated carbonyl compound has been successively reported. For example, in patent CN104995165A, a series of compounds with a framework structure shown in formula (II) can be obtained by using a catalyst system of palladium (Pd) or platinum (Pt) and molecular hydrogen or a hydrogen source. The method has the main problems that the number of byproducts is large, the yield is low, the used platinum is a precious metal, the unit price is expensive, and the dosage of the catalyst is 0.5-10%, so that the production cost is increased. In the chinese invention patent CN106699528B, n-valeraldehyde and cyclopentanone are added dropwise into an alkaline solution containing a composite catalyst in the presence of a mixed gas, and reacted in one step to synthesize 2-methylene valeraldehyde, wherein the mixed gas is a mixed gas of nitrogen and hydrogen. According to the method, aldol condensation and isomerization reaction are realized in one step, alkaline water used for aldol condensation corrodes a reaction kettle greatly, lead used for a catalyst is a toxic and harmful water pollutant, and the post-treatment of the produced wastewater is complex.
At present, the method for constructing the alpha, beta-unsaturated carbonyl compound by catalyzing double bond isomerization by transition metal has the defects of expensive catalyst, low catalytic selectivity, low catalyst application frequency and the like, so that the isomerization method with higher productivity, high selectivity and high yield is still needed.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for heterogeneously catalyzing double bond isomerization, which adopts a heterogenous catalysis reaction system, has high conversion rate of raw materials and high selectivity of double bond isomerization products in a hydrogen environment, can realize the application of a catalyst, saves the use of expensive catalysts and saves the production cost.
The invention is realized by the following technical scheme:
a method of heterogeneously catalyzed double bond isomerization comprising the steps of: 1. a method of heterogeneously catalyzed double bond isomerization comprising the steps of: putting the compound of the formula (I), a catalyst and an auxiliary agent into a hydrogenation kettle, replacing the hydrogenation kettle with nitrogen, heating and raising the temperature under stirring, introducing hydrogen into the hydrogenation kettle, and stirring for reaction to obtain a compound of the formula (II);
the chemical reaction equation is as follows:
the compounds (I) and (II) according to the invention comprise at least one carbon-carbon double bond, which may have different stereochemistry (i.e.may be in the Z or E configuration). Said compounds the compounds (I) and (II) can be either pure compounds in cis configuration (Z configuration) or trans configuration (E configuration) or mixtures comprising cis and trans isomers in various w/w ratios.
The invention further improves the scheme as follows:
when n, n 1 、n 2 When both are 0, R represents a hydrogen atom or a linear or branched C 1-10 Alkyl or alkenyl of (a); r 1 Represents a hydrogen atom or a linear or branched C 1-10 Alkyl or alkenyl of (a); r is 2 Represents a hydrogen atom or a linear or branched C 1-10 Alkyl or alkenyl of (a); r 3 Represents a hydrogen atom or a linear or branched C 1-10 Alkyl or alkenyl of (a); r 4 Represents a hydrogen atom or a linear or branched C 1-10 Alkyl or alkenyl groups of (a).
Further, the functional group represented by R includes a hydrogen atom, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, isopropyl group,Isobutyl, isopentyl, 2-methylhexyl, 3-methylhexyl, 2-methylheptyl, 2-methyloctyl, 2-methylnonyl or 3-pentenyl; r 1 The functional groups represented include a hydrogen atom, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, isopropyl group, isobutyl group, isopentyl group, 2-methylhexyl group, 3-methylhexyl group, 2-methylheptyl group, 2-methyloctyl group, 2-methylnonyl group, 3-pentenyl group; r 2 The functional groups represented include a hydrogen atom, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, isopropyl group, isobutyl group, isopentyl group, 2-methylhexyl group, 3-pentenyl group; r 3 The functional groups represented include a hydrogen atom, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, isopropyl group, isobutyl group, isopentyl group, 2-methylhexyl group, 3-pentenyl group; r 4 The functional groups represented include a hydrogen atom, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, isopropyl group, isobutyl group, isopentyl group, 2-methylhexyl group, 3-pentenyl group.
Further, R and R 1 Taken together represent C 3-6 Alkyl-substituted polycyclic ring of (a).
Further, R and R 1 The functional groups represented in combination include cyclopentyl, cyclohexyl, cycloheptyl, or cyclooctyl.
Further, R 2 And R 3 Taken together represent C 3-8 Alkyl-substituted polycyclic ring of (a).
Further, R 2 And R 3 The functional groups represented in combination include cyclopentyl, cyclohexyl, cycloheptyl, or cyclooctyl.
Further, R 3 And R 4 Taken together represent C 3-8 Alkyl-substituted polycyclic ring of (a).
Further, R 3 And R 4 The functional groups represented in combination include cyclopentyl, cyclohexyl, cycloheptyl, or cyclooctyl.
Further, the catalyst is palladium, ruthenium or nickel supported on a support material, which means a material capable of depositing such metals and which is inert with respect to the hydrogen source and the substrate.
Furthermore, the catalyst is one or the mixture of more than two of Ru/Al2O3, Pd/C, Ru/C and Raney Ni.
Furthermore, the reaction auxiliary agent is a compound containing nitrogen or sulfur and having a passivation effect on metals.
Further, the reaction auxiliary agent is one or more of thiophene, benzothiophene, sulfur, quinoline, isoquinoline, pyridine, 2-bipyridine, 4-dimethylaminopyridine, 2, 4, 6-trimethylpyridine, barium acetate, barium chloride, barium sulfate, dimethyldisulfide, ethylenediamine tetraacetic acid, diethylamine, triethylamine, ethylenediamine or ammonia water.
Furthermore, the feeding amount of the catalyst is 0.01-1% of the compound shown in the formula (I), and the feeding amount of the auxiliary agent is 0.01-1% of the compound shown in the formula (I).
Further, the reaction temperature is 20-200 ℃, the pressure is 0.1-5 MPa, and the reaction time is 2-12 hours.
Further, after the reaction is finished, the temperature is reduced, the catalyst and the reaction liquid are filtered and separated, the catalyst can be recycled and reused for more than 15 times, and the reaction liquid is purified to obtain a pure compound product of the formula (II).
Compared with the prior art, the invention has the beneficial effects that:
(1) the method has high conversion rate of raw materials and good selectivity of double-bond isomerization products.
(2) The method adopts a heterogeneous catalytic reaction system, and the catalyst can be recycled for more than 15 times, thereby reducing the production cost.
(3) The method of the invention produces less waste water and the process is more environment-friendly.
Detailed Description
Examples 1 to 27
Different conditions of experiments were performed to synthesize 2-propylacrolein by isomerization of trans-2-methyl-2-pentenal.
The experimental steps are as follows: adding 600g of trans-3-methyl-3-penten-2-one into a 1L hydrogenation kettle provided with a thermometer, a pressure gauge and a mechanical stirrer, then adding a catalyst and an auxiliary agent (shown in the table I), performing nitrogen replacement on the hydrogenation kettle for 3 times, heating to 130 ℃, and adjusting hydrogen through a pressure reducing valve to control the pressure in the kettle to be 1 MPa; and hydrogen was continuously introduced, the reaction was maintained at temperature, and the reaction was analyzed by gas chromatography every 30 minutes.
The temperature is controlled to be 130 ℃, the pressure is 1Mpa, various experiments are carried out on the catalyst, the auxiliary agent and the reaction time, and the results show that when the nitrogenous organic base compound is used as the catalyst, the isomerization selectivity of the 2-propyl acrolein is higher, and when the ruthenium/aluminum is used as the catalyst, the conversion rate of the trans-2-methyl-2-pentenal is better. Therefore, we chose ruthenium/aluminium as the catalyst for the reaction in an amount of 0.3% of the charge, triethylamine as an auxiliary for the reaction in an amount of 0.4% of the charge, a reaction time of 3 hours, a final conversion of trans 2-methyl-2-pentenal of 98% and a selectivity of 2-propylacrolein of 95%.
Watch 1
| Examples | Catalyst and process for preparing same | The amount of catalyst Wt% | Auxiliary agent | The amount of the auxiliary agent Wt% | Reaction time | Trans 2-methyl-2-pentenal conversion% | 2-propylacrolein selectivity% |
| 1 | Ru/Al2O3 | 0.1 | Is free of | - | 2 | 37 | 16 |
| 2 | Ru/Al2O3 | 0.1 | Triethylamine | 0.1 | 2 | 82 | 58 |
| 3 | Ru/Al2O3 | 0.1 | Barium chloride | 0.1 | 2 | 68 | 42 |
| 4 | Ru/Al2O3 | 0.1 | Dimethyl disulfide | 0.1 | 2 | 60 | 50 |
| 5 | Ru/Al2O3 | 0.1 | Pyridine compound | 0.1 | 2 | 51 | 48 |
| 6 | Ru/Al2O3 | 0.1 | Thiophene(s) | 0.1 | 2 | 55 | 39 |
| 7 | Ru/Al2O3 | 0.1 | Ethylene diamine tetraacetic acid | 0.1 | 2 | 72 | 47 |
| 8 | Ru/Al2O3 | 0.1 | Diethylamine | 0.1 | 2 | 75 | 51 |
| 9 | Ru/Al2O3 | 0.1 | Ethylene diamine | 0.1 | 2 | 77 | 44 |
| 10 | Ru/Al2O3 | 0.1 | Sulfur | 0.1 | 2 | 48 | 51 |
| 11 | Pd/C | 0.1 | Triethylamine | 0.1 | 2 | 80 | 42 |
| 12 | Pd/C | 0.1 | Diethylamine | 0.1 | 2 | 74 | 42 |
| 13 | Pd/C | 0.1 | Dimethyl disulfide | 0.1 | 2 | 65 | 35 |
| 14 | Ru/C | 0.1 | Triethylamine | 0.1 | 2 | 80 | 55 |
| 15 | Ru/C | 0.1 | Diethylamine | 0.1 | 2 | 77 | 50 |
| 16 | Ru/C | 0.1 | Dimethyl disulfide | 0.1 | 2 | 72 | 51 |
| 17 | Ru/C | 0.1 | Aqueous ammonia | 0.1 | 2 | 60 | 58 |
| 18 | Raney Ni | 0.1 | Triethylamine | 0.1 | 2 | 81 | 38 |
| 19 | Raney Ni | 0.1 | Diethylamine | 0.1 | 2 | 81 | 30 |
| 20 | Raney Ni | 0.1 | Dimethyl disulfide | 0.1 | 2 | 76 | 22 |
| 21 | Ru/Al2O3 | 0.1 | Triethylamine | 0.2 | 2 | 82 | 68 |
| 22 | Ru/Al2O3 | 0.1 | Triethylamine | 0.3 | 2 | 81 | 84 |
| 23 | Ru/Al2O3 | 0.1 | Triethylamine | 0.4 | 2 | 81 | 90 |
| 24 | Ru/Al2O3 | 0.2 | Triethylamine | 0.4 | 2 | 89 | 92 |
| 25 | Ru/Al2O3 | 0.3 | Triethylamine | 0.4 | 2 | 94 | 95 |
| 26 | Ru/Al2O3 | 0.3 | Triethylamine | 0.4 | 3 | 98 | 95 |
| 27 | Ru/Al2O3 | 0.3 | Triethylamine | 0.4 | 4 | 98 | 95 |
Examples 28 to 37
The temperature and pressure are also key factors influencing the olefin isomerization, and based on the above experiment, the experiment is also carried out under different temperatures and pressures, the experimental steps are the same as the above, the experimental data are as follows (as shown in table two), and the results show that the excessively high temperature and the excessively low pressure are both unfavorable for the reaction, the temperature is too high, the 2-propyl acrolein selectivity is reduced, the pressure is too low, the conversion rate of trans 2-methyl-2-pentenal is reduced, therefore, the reaction temperature is finally selected to be 130 ℃, the pressure is selected to be 0.8MPa, the conversion rate of trans 2-methyl-2-pentenal is 98%, and the 2-propyl acrolein selectivity is 95%.
Watch two
| Examples | Catalyst and process for preparing same | Auxiliary agent | Reaction temperature DEG C | Reaction pressure Mpa | Trans 2-methyl-2-pentenal conversion% | 2-propylacrolein selectivity% |
| 28 | Ru/Al2O3 | Triethylamine | 80 | 1 | 30 | 51 |
| 29 | Ru/Al2O3 | Triethylamine | 100 | 1 | 58 | 75 |
| 30 | Ru/Al2O3 | Triethylamine | 120 | 1 | 90 | 84 |
| 31 | Ru/Al2O3 | Triethylamine | 140 | 1 | 98 | 92 |
| 32 | Ru/Al2O3 | Triethylamine | 160 | 1 | 99 | 90 |
| 33 | Ru/Al2O3 | Triethylamine | 180 | 1 | 99 | 80 |
| 34 | Ru/Al2O3 | Triethylamine | 130 | 0.5 | 83 | 91 |
| 35 | Ru/Al2O3 | Triethylamine | 130 | 0.7 | 93 | 94 |
| 36 | Ru/Al2O3 | Triethylamine | 130 | 0.8 | 98 | 95 |
| 37 | Ru/Al2O3 | Triethylamine | 130 | 0.9 | 98 | 95 |
Examples 38 to 52
The reaction using heterogeneous catalysis has the great advantage that the catalyst can be used indiscriminately, so that experiments (as shown in table three) are carried out on the condition of indiscriminate use of the catalyst in the reaction, and the fact that the catalyst can be used indiscriminately for at least 15 times is found, and the reaction result is not changed greatly.
Watch III
| Examples | Catalyst and process for preparing same | The amount of catalyst Wt% | Auxiliary agent | The amount of the auxiliary agent Wt% | Number of times of catalyst application | Trans 2-methyl-2-pentenal conversion% | 2-propyl acrolein selectivity% |
| 38 | Ru/Al2O3 | 0.3 | Triethylamine | 0.4 | 1 | 98 | 95 |
| 39 | Ru/Al2O3 | 0.3 | Triethylamine | 0.4 | 2 | 98 | 95 |
| 40 | Ru/Al2O3 | 0.3 | Triethylamine | 0.4 | 3 | 98 | 95 |
| 41 | Ru/Al2O3 | 0.3 | Triethylamine | 0.4 | 4 | 98 | 95 |
| 42 | Ru/Al2O3 | 0.3 | Triethylamine | 0.4 | 5 | 98 | 95 |
| 43 | Ru/Al2O3 | 0.3 | Triethylamine | 0.4 | 6 | 98 | 95 |
| 44 | Ru/Al2O3 | 0.3 | Triethylamine | 0.4 | 7 | 98 | 95 |
| 45 | Ru/Al2O3 | 0.3 | Triethylamine | 0.4 | 8 | 98 | 95 |
| 46 | Ru/Al2O3 | 0.3 | Triethylamine | 0.4 | 9 | 96 | 95 |
| 47 | Ru/Al2O3 | 0.3 | Triethylamine | 0.4 | 10 | 96 | 95 |
| 48 | Ru/Al2O3 | 0.3 | Triethylamine | 0.4 | 11 | 96 | 95 |
| 49 | Ru/Al2O3 | 0.3 | Triethylamine | 0.4 | 12 | 90 | 93 |
| 50 | Ru/Al2O3 | 0.3 | Triethylamine | 0.4 | 13 | 90 | 93 |
| 51 | Ru/Al2O3 | 0.3 | Triethylamine | 0.4 | 14 | 90 | 92 |
| 52 | Ru/Al2O3 | 0.3 | Triethylamine | 0.4 | 15 | 90 | 92 |
Example 53
Using Ru/Al 2 O 3 Catalytic isomer trans-2-methyl-2-butenal
Into a 1L hydrogenation kettle equipped with a thermometer, a pressure gauge and mechanical stirring, 600g of trans-2-methyl-2-butenal was charged, and Ru/Al was added 2 O 3 Adding 2.4g of auxiliary agent triethylamine into 9 g of catalyst, performing nitrogen replacement on the hydrogenation kettle for 3 times, heating to 100 ℃, and regulating hydrogen through a pressure reducing valve to control the pressure in the kettle to be 0.4 MPa; continuously introducing hydrogen, carrying out heat preservation reaction for 4 hours, stopping introducing the hydrogen, cooling to 30 ℃, and evacuating and relieving pressure to normal pressure; filtering, using the catalyst, and rectifying the crude product to obtain a finished product of the 2-methylene butyraldehyde, wherein the conversion rate of the trans-2-methyl-2-butenal is 97.3 percent, and the selectivity of the 2-methylene butyraldehyde is 88.5 percent.
Example 54
Use of Ru/C catalytic isomer trans 2-methyl-2-butenal
Adding 600g of trans-2-methyl-2-butenal into a 1L hydrogenation kettle equipped with a thermometer, a pressure gauge and a mechanical stirrer, adding 12 g of Ru/C catalyst, adding 1.8g of auxiliary agent barium acetate, performing nitrogen replacement for 3 times, heating to 160 ℃, and regulating the pressure in the hydrogenation kettle to be 0.3MPa by a pressure reducing valve; continuously introducing hydrogen, carrying out heat preservation reaction for 6 hours, stopping introducing the hydrogen, cooling to 30 ℃, and evacuating and relieving pressure to normal pressure; filtering, using the catalyst mechanically, and rectifying the crude product to obtain a finished product of the 2-methylene butyraldehyde, wherein the conversion rate of the trans-2-methyl-2-butenal reaches 90.1%, and the selectivity of the 2-methylene butyraldehyde reaches 78.3%.
Example 55
Use of Raney Ni as a catalytic isomer trans 2-methyl-2-heptenal
Adding 600g of trans-2-methyl-2-heptenal into a 1L hydrogenation kettle provided with a thermometer, a pressure gauge and a mechanical stirrer, adding 6.0g of Raney Ni catalyst and 1.5g of auxiliary agent dimethyl disulfide, performing nitrogen replacement on the hydrogenation kettle for 3 times, heating to 150 ℃, and regulating the pressure in the hydrogenation kettle to be 0.6MPa through a pressure reducing valve; continuously introducing hydrogen, carrying out heat preservation reaction for 8 hours, stopping introducing the hydrogen, cooling to 30 ℃, and evacuating and relieving pressure to normal pressure; filtering, using catalyst, rectifying the product crude product to obtain the finished product of 2-methylene heptanal, wherein the conversion rate of trans-2-methyl-2-heptenal reaches 98.2%, and the selectivity of 2-methylene heptanal reaches 89.5%.
Example 56
Use of Pd/C catalytic isomer trans 2, 5-dimethyl-2-heptenal
Adding 600g of trans-2, 5-dimethyl-2-heptenal, 11.0 g of Pd/C catalyst and 1.2g of auxiliary pyridine into a 1L hydrogenation kettle provided with a thermometer, a pressure gauge and a mechanical stirrer, performing nitrogen replacement on the hydrogenation kettle for 3 times, heating to 150 ℃, and regulating the pressure in the hydrogenation kettle to be 0.7MPa through a pressure reducing valve; continuously introducing hydrogen, carrying out heat preservation reaction for 4 hours, stopping introducing the hydrogen, cooling to 30 ℃, and evacuating and relieving pressure to normal pressure; filtering, using catalyst, rectifying the crude product to obtain the finished product of the 5-methyl-2-methylene heptanal, wherein the conversion rate of the trans-2, 5-dimethyl-2-heptenal reaches 87.8 percent, and the selectivity of the 5-methyl-2-methylene heptanal is 66.6 percent.
Example 57
Use of Raney Ni to catalyze isomer trans 2-ethyl-2-pentenal
Adding 600g of trans-2-ethyl-2-pentenal, 6.0g of Raney Ni catalyst and 1.8g of auxiliary thiophene into a 1L hydrogenation kettle provided with a thermometer, a pressure gauge and a mechanical stirrer, performing nitrogen replacement on the hydrogenation kettle for 3 times, heating to 120 ℃, and regulating the pressure in the hydrogenation kettle to be 0.6MPa through a pressure reducing valve; continuously introducing hydrogen, carrying out heat preservation reaction for 5 hours, stopping introducing the hydrogen, cooling to 30 ℃, and evacuating and relieving pressure to normal pressure; filtering, using the catalyst mechanically, and rectifying the crude product to obtain a finished product of the 2-ethylidene butyraldehyde, wherein the conversion rate of the trans 2-ethyl-2-pentenal reaches 82.7 percent, and the selectivity of the 2-ethylidene butyraldehyde is 69.1 percent.
Example 58
Use of Raney Ni to catalyze the isomer trans 3-methyl-3-ene-2-pentanone
Adding 600g of trans-3-methyl-3-ene-2-pentanone, 9.0 g of Raney Ni catalyst and 1.5g of auxiliary agent barium acetate into a 1L hydrogenation kettle provided with a thermometer, a pressure gauge and a mechanical stirrer, performing nitrogen replacement on the hydrogenation kettle for 3 times, heating to 120 ℃, and regulating the pressure in the hydrogenation kettle to be 0.6MPa through a pressure reducing valve; continuously introducing hydrogen, carrying out heat preservation reaction for 6 hours, stopping introducing the hydrogen, cooling to 30 ℃, and evacuating and relieving pressure to normal pressure; filtering, using a catalyst mechanically, and rectifying a crude product to obtain a finished product of the 3-ethylidene 2-pentanone, wherein the conversion rate of the trans-3-methyl-3-ene-2-pentanone reaches 72.7 percent, and the selectivity of the 3-ethylidene 2-pentanone reaches 81.1 percent.
Example 59
Using Ru/Al 2 O 3 Catalytic isomer trans-4-methyl-4-en-3-hexanone
Into a 1L hydrogenation vessel equipped with a thermometer, a pressure gauge and mechanical stirring, 600g of trans-4-methyl-4-en-3-hexanone was charged, and Ru/Al was added 2 O 3 Adding 1.2g of auxiliary agent 2, 2-bipyridine into 12 g of catalyst, performing nitrogen replacement on the hydrogenation kettle for 3 times, heating to 144 ℃, and regulating hydrogen through a pressure reducing valve to control the pressure in the kettle to be 0.5 MPa; continuously introducing hydrogen, carrying out heat preservation reaction for 4 hours, stopping introducing the hydrogen, cooling to 30 ℃, and emptying to release pressure to normal pressure; filtering, using the catalyst mechanically, and rectifying the crude product to obtain a finished product of the 4-ethylene 3-hexanone, wherein the conversion rate of the trans-4-methyl-4-alkene-3-hexanone reaches 66.4 percent, and the selectivity of the 4-ethylene 3-hexanone reaches 74.5 percent.
Example 60
Use of Pd/C catalytic isomer trans 3-ethyl-3-en-2-pentanone
Adding 600g of trans-3-ethyl-3-ene-2-pentanone, 5g of Pd/C catalyst and 1.4g of auxiliary agent 4-dimethylaminopyridine into a 1L hydrogenation kettle provided with a thermometer, a pressure gauge and a mechanical stirrer, performing nitrogen replacement on the hydrogenation kettle for 3 times, heating to 158 ℃, and regulating the pressure in the hydrogenation kettle to be 0.2MPa through a pressure reducing valve; continuously introducing hydrogen, carrying out heat preservation reaction for 4 hours, stopping introducing the hydrogen, cooling to 30 ℃, and evacuating and relieving pressure to normal pressure; filtering, using the catalyst mechanically, and rectifying the crude product to obtain a finished product of the 3-ethylidene 2-pentanone, wherein the conversion rate of the 3-ethyl-3-ene-2-pentanone reaches 75.4 percent, and the selectivity of the 3-ethylidene 2-pentanone reaches 80.1 percent.
Example 61
Use of Ru/C catalytic isomer 3-cyclopentyl-3-en-2-pentanone
Adding 600g of 3-cyclopentyl-3-ene-2-pentanone into a 1L hydrogenation kettle equipped with a thermometer, a pressure gauge and a mechanical stirrer, adding 11 g of Ru/C catalyst and 1.2g of auxiliary agent ethylene diamine tetraacetic acid, performing nitrogen replacement on the hydrogenation kettle for 3 times, heating to 140 ℃, and regulating the pressure in the hydrogenation kettle to be 0.2MPa through a pressure reducing valve; continuously introducing hydrogen, carrying out heat preservation reaction for 8 hours, stopping introducing the hydrogen, cooling to 30 ℃, and evacuating and relieving pressure to normal pressure; filtering, using a catalyst mechanically, and rectifying the crude product to obtain a finished product of 3-cyclopentenyl-2-pentanone, wherein the conversion rate of 3-cyclopentyl-3-ene-2-pentanone reaches 73.3 percent, and the selectivity of 3-cyclopentenyl-2-pentanone reaches 72.6 percent.
Example 62
Using Ru/Al 2 O 3 Catalytic isomer 2-propylene-2-cyclohexanone
600g of 2-propylene-2-cyclohexanone was charged into a 1L hydrogenation vessel equipped with a thermometer, a pressure gauge and mechanical stirring, and Ru/Al was added 2 O 3 8g of catalyst, 1.2g of additive quinoline is added, nitrogen replacement is carried out on the hydrogenation kettle for 3 times, then the temperature is raised to 110 ℃, hydrogen is adjusted through a pressure reducing valve, and the pressure in the kettle is controlled to be 0.6 MPa; continuously introducing hydrogen, carrying out heat preservation reaction for 2 hours, stopping introducing the hydrogen, cooling to 30 ℃, and evacuating and relieving pressure to normal pressure; filtering, using the catalyst mechanically, and rectifying the product crude product to obtain a finished product of 2-propyl-2-cyclohexenone, wherein the conversion rate of 2-propylene-2-cyclohexanone reaches 83.4 percent, and the selectivity of 2-propyl-2-cyclohexenone reaches 55.2 percent.
Example 63
Use of the Ru/C catalytic isomer 2-heptylidene-2-cyclopentanone
Adding 600g of 2-propylene-2-cyclohexanone into a 1L hydrogenation kettle equipped with a thermometer, a pressure gauge and a mechanical stirrer, adding 12 g of Ru/C catalyst, adding 1.4g of auxiliary agent barium sulfate, performing nitrogen replacement on the hydrogenation kettle for 3 times, heating to 120 ℃, and regulating the pressure of hydrogen through a pressure reducing valve to control the pressure in the kettle to be 0.5 MPa; continuously introducing hydrogen, carrying out heat preservation reaction for 8 hours, stopping introducing the hydrogen, cooling to 30 ℃, and evacuating and relieving pressure to normal pressure; filtering, using a catalyst mechanically, rectifying the crude product to obtain a finished product of the 2-heptyl-2-cyclopentenone, wherein the conversion rate of the 2-heptylidene-2-cyclopentanone reaches 80.0 percent, and the selectivity of the 2-heptyl-2-cyclopentenone reaches 49.5 percent.
Claims (16)
1. A method of heterogeneously catalyzed double bond isomerization comprising the steps of: putting the compound of the formula (I), a catalyst and an auxiliary agent into a hydrogenation kettle, replacing the hydrogenation kettle with nitrogen, heating and raising the temperature under stirring, introducing hydrogen into the hydrogenation kettle, and stirring for reaction to obtain a compound of the formula (II);
the chemical reaction equation is as follows:
2. the method of claim 1, wherein the double bond isomerization is heterogeneously catalyzed by: when n, n 1 、n 2 When both are 0, R represents a hydrogen atom or a linear or branched C 1-10 Alkyl or alkenyl of (a); r 1 Represents a hydrogen atom or a linear or branched C 1-10 Alkyl or alkenyl of (a); r 2 Represents a hydrogen atom or a linear or branched C 1-10 Alkyl or alkenyl of (a); r 3 Represents a hydrogen atom or a linear or branched C 1-10 Alkyl or alkenyl of (a); r 4 Represents a hydrogen atom or a linear or branched C 1-10 Alkyl or alkenyl groups of (a).
3. The method of claim 2, wherein the double bond isomerization is heterogeneously catalyzed by: the functional group represented by R includes a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an isopropyl group, an isobutyl group, an isopentyl group, a 2-methylhexyl group, a 3-methylhexyl group, a 2-methylheptyl group, a 2-methyloctyl group, a 2-methylnonyl group or a 3-pentenyl group; r 1 The functional groups represented include a hydrogen atom, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, isopropyl group, isobutyl group, isopentyl group, 2-methylhexyl group, 3-methylhexyl group, 2-methylheptyl group, 2-methyloctyl group, 2-methylnonyl group, 3-pentenyl group; r 2 The functional groups represented include a hydrogen atom, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, isopropyl group, isobutyl group, isopentyl group, 2-methylhexyl group, 3-pentenyl group; r 3 A function ofThe group includes hydrogen atom, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, isopropyl group, isobutyl group, isopentyl group, 2-methylhexyl group, 3-pentenyl group; r 4 The functional groups represented include a hydrogen atom, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, isopropyl group, isobutyl group, isopentyl group, 2-methylhexyl group, 3-pentenyl group.
4. The method of claim 1, wherein the double bond isomerization is heterogeneously catalyzed by: r and R 1 Taken together represent C 3-6 Alkyl-substituted polycyclic ring of (a).
5. The method of claim 4, wherein the double bond isomerization is heterogeneously catalyzed by: r and R 1 The functional groups represented in combination include cyclopentyl, cyclohexyl, cycloheptyl, or cyclooctyl.
6. The method of claim 1, wherein the double bond isomerization is heterogeneously catalyzed by: r is 2 And R 3 Taken together represent C 3-8 Alkyl-substituted polycyclic ring of (a).
7. The method of claim 6, wherein the double bond isomerization is heterogeneously catalyzed by: r is 2 And R 3 The functional groups represented in combination include cyclopentyl, cyclohexyl, cycloheptyl, or cyclooctyl.
8. The method of claim 1, wherein the double bond isomerization is heterogeneously catalyzed by: r 3 And R 4 Taken together represent C 3-8 Alkyl-substituted polycyclic ring of (a).
9. The method of claim 8, wherein the double bond isomerization is heterogeneously catalyzed by: r 3 And R 4 Is combined atThe functional groups represented together include cyclopentyl, cyclohexyl, cycloheptyl, or cyclooctyl.
10. The method of claim 1, wherein the double bond isomerization is heterogeneously catalyzed by: the catalyst is palladium, ruthenium or nickel supported on a support material, which refers to a material capable of depositing such metals and which is inert with respect to the hydrogen source and the substrate.
11. The method of claim 10, wherein the double bond isomerization is heterogeneously catalyzed by: the catalyst is one or more of Ru/Al2O3, Pd/C, Ru/C or Raney Ni.
12. The method of claim 1, wherein the double bond isomerization is heterogeneously catalyzed by: the reaction auxiliary agent is a compound containing nitrogen or sulfur and having a passivation effect on metal.
13. The method of claim 12, wherein the double bond isomerization is heterogeneously catalyzed by: the reaction auxiliary agent is one or more of thiophene, benzothiophene, sulfur, quinoline, isoquinoline, pyridine, 2-bipyridine, 4-dimethylaminopyridine, 2, 4, 6-trimethylpyridine, barium acetate, barium chloride, barium sulfate, dimethyl disulfide, ethylenediamine tetraacetic acid, diethylamine, triethylamine, ethylenediamine or ammonia water.
14. The method of claim 1, wherein the double bond isomerization is heterogeneously catalyzed by: the feeding amount of the catalyst is 0.01-1% of the compound shown in the formula (I), and the feeding amount of the auxiliary agent is 0.01-1% of the compound shown in the formula (I).
15. The method of claim 1, wherein the double bond isomerization is heterogeneously catalyzed by: the reaction temperature is 20-200 ℃, the pressure is 0.1-5 MPa, and the reaction time is 2-12 hours.
16. The method of claim 1, wherein the double bond isomerization is heterogeneously catalyzed by: and after the reaction is finished, cooling, filtering and separating the catalyst and the reaction liquid, wherein the catalyst can be recycled and reused for more than 15 times, and the reaction liquid is purified to obtain a pure compound product of the formula (II).
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| CN104995165A (en) * | 2013-02-11 | 2015-10-21 | 弗门尼舍有限公司 | Process for the isomerisation of an exo double bond |
| CN106699528A (en) * | 2016-12-27 | 2017-05-24 | 山东新和成药业有限公司 | Method for one-step synthesis of 2-amyl-2-cyclopentenone |
| CN109438197A (en) * | 2018-09-04 | 2019-03-08 | 万华化学集团股份有限公司 | A method of preparing 3- methyl -3- crotonaldehyde |
| CN113233979A (en) * | 2021-04-29 | 2021-08-10 | 上虞新和成生物化工有限公司 | Preparation method of 4-acetoxyl-2-methyl-2-butenal |
| CN113509954A (en) * | 2020-04-09 | 2021-10-19 | 中国石油化工股份有限公司 | Preparation method and application of passivated sulfuration-state hydrocracking catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104995165A (en) * | 2013-02-11 | 2015-10-21 | 弗门尼舍有限公司 | Process for the isomerisation of an exo double bond |
| CN106699528A (en) * | 2016-12-27 | 2017-05-24 | 山东新和成药业有限公司 | Method for one-step synthesis of 2-amyl-2-cyclopentenone |
| CN109438197A (en) * | 2018-09-04 | 2019-03-08 | 万华化学集团股份有限公司 | A method of preparing 3- methyl -3- crotonaldehyde |
| CN113509954A (en) * | 2020-04-09 | 2021-10-19 | 中国石油化工股份有限公司 | Preparation method and application of passivated sulfuration-state hydrocracking catalyst |
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