CN114933518A - Synthesis method of ethyl heptenone and application of heteropoly acid catalyst - Google Patents
Synthesis method of ethyl heptenone and application of heteropoly acid catalyst Download PDFInfo
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- CN114933518A CN114933518A CN202210694469.4A CN202210694469A CN114933518A CN 114933518 A CN114933518 A CN 114933518A CN 202210694469 A CN202210694469 A CN 202210694469A CN 114933518 A CN114933518 A CN 114933518A
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- heptenone
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- 239000003054 catalyst Substances 0.000 title claims abstract description 52
- 239000011964 heteropoly acid Substances 0.000 title claims abstract description 42
- SAXWRVSDVXCTEL-UHFFFAOYSA-N 6-methyloct-5-en-2-one Chemical compound CCC(C)=CCCC(C)=O SAXWRVSDVXCTEL-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000001308 synthesis method Methods 0.000 title abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 26
- YOWQWFMSQCOSBA-UHFFFAOYSA-N 2-methoxypropene Chemical group COC(C)=C YOWQWFMSQCOSBA-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 230000009471 action Effects 0.000 claims abstract description 5
- 230000002194 synthesizing effect Effects 0.000 claims description 15
- HFYAEUXHCMTPOL-UHFFFAOYSA-N 3-Methyl-1-penten-3-ol Chemical compound CCC(C)(O)C=C HFYAEUXHCMTPOL-UHFFFAOYSA-N 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 8
- 238000006116 polymerization reaction Methods 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000011734 sodium Substances 0.000 description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 239000012071 phase Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 6
- 238000000605 extraction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000007605 air drying Methods 0.000 description 3
- -1 aluminum compound Chemical class 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 235000021190 leftovers Nutrition 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- WASQWSOJHCZDFK-UHFFFAOYSA-N diketene Chemical compound C=C1CC(=O)O1 WASQWSOJHCZDFK-UHFFFAOYSA-N 0.000 description 2
- 150000002085 enols Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- KRLBLPBPZSSIGH-CSKARUKUSA-N (6e)-3,7-dimethylnona-1,6-dien-3-ol Chemical compound CC\C(C)=C\CCC(C)(O)C=C KRLBLPBPZSSIGH-CSKARUKUSA-N 0.000 description 1
- SAXWRVSDVXCTEL-SOFGYWHQSA-N (e)-6-methyloct-5-en-2-one Chemical compound CC\C(C)=C\CCC(C)=O SAXWRVSDVXCTEL-SOFGYWHQSA-N 0.000 description 1
- GOQHETSWCBLHDM-UHFFFAOYSA-N 1-chloro-3-methylpent-2-ene Chemical compound CCC(C)=CCCl GOQHETSWCBLHDM-UHFFFAOYSA-N 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-N Acetoacetic acid Natural products CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 description 1
- 238000006563 Carroll rearrangement reaction Methods 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000911 decarboxylating effect Effects 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000012113 quantitative test Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—Molybdenum
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- 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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
-
- 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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- 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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
- B01J27/198—Vanadium
- B01J27/199—Vanadium with chromium, molybdenum, tungsten or polonium
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the technical field of ethyl heptenone preparation, and in particular relates to a synthesis method of ethyl heptenone, which takes 3-methyl-1-pentene-3-alcohol and 2-methoxy propylene as raw materials to generate a Saucy-Marbet reaction under the action of a heteropoly acid catalyst to generate the ethyl heptenone. The invention also relates to the use of a heteropolyacid catalyst for the synthesis of ethylheptenone. The heteropolyacid catalyst is adopted for catalytic reaction, the reaction temperature and the reaction pressure are both reduced, the polymerization of the 2-methoxypropene in the reaction raw materials is effectively avoided, and the cost is reduced. The catalyst has good stability, and the recovery method is simple and easy to apply.
Description
Technical Field
The invention relates to the technical field of ethyl heptenone preparation, and particularly relates to a synthesis method of ethyl heptenone and application of a heteropoly acid catalyst.
Background
Currently, ethyl heptenone, i.e. 6-methyl-5-octen-2-one, of formula C 10 H 18 O is an important fine chemical intermediate and an important intermediate for industrially preparing the ethyl linalool, and the current ethyl heptenone synthesis method mainly comprises the following steps:
(1) US2815380 reports a method for synthesizing ethyl heptenone from 1-chloro-3-methyl-2-pentene and ethyl acetoacetate, which specifically comprises the steps of reacting the raw materials under the action of sodium methoxide at 60 ℃ overnight, then generating corresponding carboxylate under the alkaline condition of potassium hydroxide, and further decarboxylating under the action of concentrated hydrochloric acid to generate ethyl heptenone.
(2) CN1251832A adopts an organic aluminum compound as a catalyst, and takes acetoacetic acid alkyl ester and unsaturated enol as raw materials to carry out Carroll reaction to obtain unsaturated ketone. The process has the disadvantages of poor atom economy and difficult processing of aluminum-containing leftovers.
(3) CN1218792A adopts an organic aluminum compound as a catalyst, takes diketene and unsaturated enol as raw materials, and generates unsaturated ketone by condensation reaction. The method has the defects that the raw material diketene is a highly toxic product, the transportation is limited, the production operation is dangerous, and the method is not suitable for industrial mass production.
(4) EP3541774A1 describes a method for synthesizing ethyl heptenone by taking 3-methyl-1-pentene-3-alcohol and 2-methoxypropene as raw materials and phenyl phosphonic acid as a catalyst, wherein the molar ratio of ethyl butenol to 2-methoxypropene is 1:7-1:2, the reaction temperature is 100-.
Compared with the Saucy-Marbet process, the other processes have the defects of low product yield, poor atom economy and the like, and also have the problems of waste gas generation, low efficiency and the like in the reaction process, which are not beneficial to industrial production. The method for obtaining unsaturated ketone by Saucy-Marbet reaction has the advantages of less side reaction, high selectivity and environmental friendliness, and has wide industrial application prospect. However, the existing technology for synthesizing ethyl heptenone by taking 3-methyl-1-pentene-3-alcohol and 2-methoxypropene as raw materials through the Saucy-Marbet reaction has the problems of high reaction temperature, high pressure, difficult application of a catalyst, high unit consumption and high cost of the 2-methoxypropene and complex separation, purification and raw material recovery processes.
Disclosure of Invention
The present invention is intended to solve at least one of the technical problems of the prior art, and therefore an aspect of the present invention is to provide a method for synthesizing ethyl heptenone.
It is an object of another aspect of the present invention to provide the use of a heteropolyacid catalyst in the synthesis of ethylheptenone.
In order to achieve the above purpose, an embodiment of one aspect of the invention provides a method for synthesizing ethyl heptenone, which has the advantages of mild reaction conditions, application of a catalyst and low production cost.
A synthetic method of ethyl heptenone comprises the following specific steps:
taking 3-methyl-1-pentene-3-alcohol and 2-methoxy propylene as raw materials, and carrying out Saucy-Marbet reaction under the action of a heteropoly acid catalyst to generate ethyl heptenone.
According to an embodiment of the present invention, the heteropoly acid catalyst employs a Keggin-type heteropoly acid.
According to one embodiment of the invention, the heteropolyacid catalyst has the general formula: h m XY 12 O 40 ；
Wherein m is 3,4, 5; x is P, Si or Al; y is one or more of Mo, W and V; wherein, the heteropolyacid catalyst can achieve the same effect with or without crystal water.
According to one embodiment of the invention, the Saucy-Marbet reaction is carried out in a nitrogen atmosphere.
According to one embodiment of the invention, the pressure of the Saucy-Marbet reaction is atmospheric pressure and the temperature is 5-30 ℃.
According to one embodiment of the invention, the heteropolyacid catalyst is used in an amount of 0.5% to 3.0% by weight based on the 3-methyl-1-penten-3-ol.
According to one embodiment of the invention, the molar ratio of 3-methyl-1-penten-3-ol to 2-methoxypropene is from 1:1.0 to 1.2.
According to one embodiment of the invention, after the Saucy-Marbet reaction is finished, the heteropoly acid catalyst is recycled and reused.
According to one embodiment of the present invention, the heteropolyacid catalyst is recovered for reuse by solid-liquid separation.
According to one embodiment of the invention, the heteropoly acid catalyst is recycled and reused by filtration, and the solid phase after filtration is the heteropoly acid catalyst.
According to one embodiment of the invention, the number of applications is 15-25.
According to one embodiment of the invention, the product after the Saucy-Marbet reaction is rectified and separated to obtain the ethyl heptenone product.
Embodiments of another aspect of the invention provide the use of a heteropolyacid catalyst in the synthesis of ethyl heptenone. The structural property of the heteropoly acid catalyst is adopted to obviously reduce the activation energy of the Saucy-Marbet reaction.
In the invention, Keggin type heteropoly acid H is adopted m XY 12 O 40 As a catalyst, the Keggin type heteropoly acid is a tetrahedron XO formed by central coordination of hetero atoms 4 Octahedral YO with polyacid ligands 6 Large molecules of cage-like structure linked by oxygen bridges. This structure of heteropoly acids, like natural zeolites, is a very stable, symmetrical structure. In a bulk phase, large anions of the heteropoly acid have certain porosity, so that 3-methyl-1-pentene-3-ol and 2-methoxypropene molecules can freely enter and exit, and the contact area of reactants in a heteropoly acid structural bulk phase is greatly increased. The activity change generated by the Saucy-Marbet reaction on the surface layer of the heteropoly acid can be quickly expanded to each part in the structural body phase, so that the heteropoly acid can effectively reduce the activation energy of the Saucy-Marbet reaction in the heterogeneous catalytic reaction and enhance the reaction capability, the solid heteropoly acid catalyst has the characteristic of homogeneous catalytic reaction to form a 'pseudo liquid phase effect', further better catalytic activity is expressed, the reaction is realized at lower temperature and normal pressure, and the polymerization reaction is easy to occur at high temperature and high pressure.
The heteropoly acid in the present application can be prepared by methods known in the art, including but not limited to acid-ether extraction.
According to one embodiment of the invention, the heteropolyacid catalyst H 3 PMo 12 O 40 The preparation method specifically comprises the following steps:
acidifying Na 2 HPO 4 ·12H 2 The O solution was heated to 50 ℃ and acidified Na was added slowly dropwise at this temperature 2 MoO 4 ·2H 2 Keeping the temperature of the O solution for reaction for 2 hours; adding ether for extraction, separating to obtain lower layer transparent oily substance, air drying to obtain powder as heteropoly acid H 3 PMo 12 O 40 。
According to one embodiment of the invention, acidified Na 2 HPO 4 ·12H 2 The preparation method of the O solution comprises the following steps: na (Na) 2 HPO 4 ·12H 2 Dissolving O in water, and then dripping 98% concentrated H 2 SO 4 The pH value is adjusted to 1.5, and the mixture is stirred for 0.5 h.
According to one embodiment of the invention, acidified Na 2 MoO 4 ·2H 2 The preparation method of the O solution comprises the following steps: na (Na) 2 MoO 4 ·2H 2 Dissolving O in water, and then dropwise adding 98% concentrated H 2 SO 4 The pH was adjusted to 1.5 and stirred for 0.5 h.
According to an embodiment of the present invention, in the preparation of the heteropoly acid catalyst by the acidification-ether extraction method, the metal acid salts are used as raw materials, and can be respectively acidified and then mixed, or can be dissolved and mixed to be acidified. A catalyst which meets the objects of the present invention can be obtained.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention has high catalytic efficiency, good selectivity and high yield up to 96%.
(2) The method adopts the heteropoly acid catalyst to catalyze the reaction, reduces the reaction temperature and the pressure, effectively avoids the polymerization of the 2-methoxypropene in the reaction raw materials, and reduces the cost.
(3) The catalyst of the invention has good stability, and the recovery method is simple and easy to apply.
(4) The method has simple process operation and is easy to realize industrialization.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all of the embodiments. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments in the present application without making any creative effort belong to the protection scope of the present application.
It should be noted that: in the present application, all embodiments and preferred methods mentioned herein can be combined with each other to form new solutions, if not specifically stated. In the present application, all the technical features mentioned herein and preferred features may be combined with each other to form new solutions, if not specifically stated. In the present application, percentages (%) or parts refer to percent by weight or parts by weight relative to the composition, unless otherwise specified. In the present application, the components referred to or the preferred components thereof may be combined with each other to form new embodiments, if not specifically stated. In this application, unless otherwise stated, the numerical range "a-b" represents a shorthand representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, a numerical range of "6-22" indicates that all real numbers between "6-22" have been listed herein, and "6-22" is only an abbreviated representation of the combination of these numbers. The "ranges" disclosed herein may be in the form of lower limits and upper limits, and may be one or more lower limits and one or more upper limits, respectively. In the present application, unless otherwise indicated, the individual reactions or operational steps may be performed sequentially or in an ordered sequence. Preferably, the reaction processes herein are carried out sequentially.
Unless otherwise defined, technical and scientific terms used herein have the same meaning as is familiar to those skilled in the art. In addition, any methods or materials similar or equivalent to those described herein can also be used in the present application.
The test materials used in the following examples were purchased from a conventional biochemical reagent store unless otherwise specified.
In the quantitative tests in the following examples, three replicates were set, and the data are the mean or the mean ± standard deviation of the three replicates.
Example 1
Into a 250ml flask were charged 100g of 3-methyl-1-penten-3-ol (1mol), 75.6g of 2-methoxypropene (1.05mol) and 1.5g of heteropolyacid catalyst H 3 PMo 12 O 40 And reacting for 2 hours under the protection of nitrogen and under the conditions of normal pressure and 25 ℃ of reaction temperature. After the reaction end point is reached, the catalyst is separated out by filtration, the reaction liquid is subjected to gas phase detection, the conversion rate is 99.9 percent, the selectivity is 96.3 percent, 148g of ethyl heptenone is obtained by separation by rectification, and the yield is 96.1 percent.
As shown in Table 1, the catalyst after filtration and separation can be recycled for 25 times, and the yield is 95.9-96.3%, namely the catalyst has good stability.
TABLE 1 used batch and yield of catalyst
| Application batch | Yield/% |
| 1 | 96.2 |
| 2 | 96.1 |
| 3 | 96.3 |
| 4 | 96.2 |
| 5 | 96.1 |
| 6 | 96.0 |
| 7 | 95.9 |
| 8 | 96.0 |
| 9 | 96.1 |
| 10 | 96.0 |
| 11 | 96.1 |
| 12 | 96.2 |
| 13 | 96.1 |
| 14 | 96.0 |
| 15 | 96.0 |
| 16 | 95.9 |
| 17 | 96.0 |
| 18 | 96.1 |
| 19 | 96.2 |
| 20 | 96.1 |
| 21 | 96.0 |
| 22 | 96.2 |
| 23 | 96.3 |
| 24 | 96.2 |
| 25 | 96.1 |
Examples 2 to 6
The results of changing the type of catalyst in addition to example 1 are shown in Table 2. The catalysts are recycled for 20 times, and the yield fluctuation of the ethyl heptenone is +/-0.2 percent, namely the catalysts have good stability.
Table 2 effect of catalyst on reaction results.
Examples 8 to 22
Based on example 1, with H 3 PMo 12 O 40 The reaction conditions (amount of catalyst, molar ratio of raw materials, temperature) were changed for the catalyst, and the results are shown in table 3. The catalysts in the table 3 are respectively recycled and reused for 20 times under different reaction conditions corresponding to the examples 8-18, and the yield fluctuation of the ethyl heptenone is +/-0.2 percent under the conditions of the temperature of 5-30 ℃ and the normal pressure, namely the catalysts have good stability.
TABLE 3 influence of the reaction conditions on the reaction results
Example 23
H 3 PMo 12 O 40 The preparation of (1): mixing 1.074g of Na 2 HPO 4 ·12H 2 O dissolved in 10ml water and 8.712g Na 2 MoO 4 ·2H 2 Dissolving O in 20ml of water to prepare water solutions respectively, and stirring at room temperature until the O is completely dissolved; to Na 2 HPO 4 ·12H 2 Dripping 98% concentrated H into O water solution 2 SO 4 Adjusting pH to 1.5, adding Na 2 MoO 4 ·2H 2 Dripping 98% concentrated H into O aqueous solution 2 SO 4 Adjusting the pH value to 1.5, and stirring for 0.5h respectively to complete the acidification of the aqueous solution of the disodium hydrogen phosphate and the sodium molybdate; acidifying Na 2 HPO 4 ·12H 2 The O solution was heated to 50 ℃ and acidified Na was added slowly dropwise at this temperature 2 MoO 4 ·2H 2 Keeping the temperature of the O solution for reaction for 2 hours; adding ether for extraction, separating to obtain lower layer transparent oily substance, air drying to obtain powder as heteropoly acid H 3 PMo 12 O 40 。
Example 24
H 4 PMo 11 VO 40 The preparation of (1): mixing 1.074g of Na 2 HPO 4 ·12H 2 O and 7.986g of Na 2 MoO 4 ·2H 2 Dissolving O in 50ml water, heating to boil, reacting for 0.5h, slowly adding 0.366g NaVO 3 Continuously keeping the temperature and reacting for 0.5H, adding 98 percent concentrated H under stirring 2 SO 4 Adjusting the pH value to 1.5, and continuously stirring for 0.5 h; adding diethyl ether; adding ether for extraction, separating to obtain lower layer transparent oily substance, air drying to obtain powder as heteropoly acid H 4 PMo 11 VO 40 。
Comparative example 1
100g of 3-methyl-1-penten-3-ol (1mol), 75.6g of 2-methoxypropene (1.05mol) and 1.5g of phenylphosphonic acid catalyst are added into a 250ml flask, and the mixture is reacted for 2 hours under the conditions of normal pressure and 25 ℃ of reaction temperature under the protection of nitrogen, wherein the conversion rate is 7.3 percent and the selectivity is 80.6 percent through gas phase detection. Meanwhile, after the reaction time is prolonged, the reaction is slowly carried out, and the conversion rate is basically unchanged.
Comparative example 2
Into a 250ml flask were charged 75.6g of 2-methoxypropene (1.05mol) and 1.5g of heteropolyacid catalyst H 3 PMo 12 O 40 Under the protection of nitrogen, the reaction is carried out for 2h under the conditions of 0.8MPa and the reaction temperature of 150 ℃, and the residual 36.4g of 2-methoxypropene and the conversion rate of 51.8 percent are detected by a gas phase internal standard, so that the 2-methoxypropene is supposed to generate a side polymerization reaction to generate a high-boiling polymer. Because the product of the polymerization reaction is high-boiling leftover material and the gas phase can not be detected, the polymerization reaction is judged to occur according to the fact that the raw material consumes new substances which are not detected in the gas phase, and the reaction liquid becomes viscous, so that the leftover material is generated.
Comparative example 3
Into a 250ml flask were charged 75.6g of 2-methoxypropene (1.05mol) and 1.5g of heteropolyacid catalyst H 3 PMo 12 O 40 Under the protection of nitrogen, the reaction is carried out for 2 hours under the conditions of normal pressure and the reaction temperature of 25 ℃, the residual 73.8g of 2-methoxypropene and the conversion rate of 2.4 percent are detected by a gas phase internal standard, and the 2-methoxypropene is supposed to generate a side polymerization reaction to generate a high-boiling polymer.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and substitutions can be made without departing from the technical principle of the present invention, and these modifications and substitutions should also be regarded as the protection scope of the present invention.
Claims (10)
1. A method for synthesizing ethyl heptenone is characterized in that,
taking 3-methyl-1-pentene-3-alcohol and 2-methoxy propylene as raw materials, and generating a Saucy-Marbet reaction under the action of a heteropoly acid catalyst to generate ethyl heptenone.
2. The method for synthesizing ethyl heptenone according to claim 1, wherein the heteropolyacid catalyst has the following general formula: h m XY 12 O 40 ；
Wherein m is 3,4, 5; x is P, Si or Al; y is one or more of Mo, W and V.
3. The method for synthesizing ethylheptenone according to claim 1, wherein the Saucy-Marbet reaction is carried out in a nitrogen atmosphere.
4. The method for synthesizing ethyl heptenone according to claim 1, wherein the pressure of the Saucy-Marbet reaction is normal pressure, and the temperature is 5-30 ℃.
5. The method for synthesizing ethyl heptenone according to claim 1, wherein the amount of the heteropoly acid catalyst is 0.5% -3.0% of the weight of 3-methyl-1-pentene-3-ol.
6. The method for synthesizing ethyl heptenone according to claim 1, wherein the molar ratio of the 3-methyl-1-penten-3-ol to the 2-methoxypropene is 1: 1.0-1.2.
7. The method for synthesizing ethylheptenone according to any one of claims 1 to 6, wherein the heteropolyacid catalyst is recovered and reused after the Saucy-Marbet reaction is completed.
8. The method for synthesizing ethyl heptenone according to claim 7, wherein the heteropolyacid catalyst is recovered and reused by solid-liquid separation.
9. The method for synthesizing ethyl heptenone according to any one of claims 1 to 6, characterized in that the product after Saucy-Marbet reaction is separated by rectification to obtain ethyl heptenone product.
10. Application of heteropolyacid catalyst in synthesizing ethyl heptenone.
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| CN1539807A (en) * | 2003-10-28 | 2004-10-27 | 浙江大学 | Technique for synthesizing methylheptenone |
| CN1914143A (en) * | 2004-02-04 | 2007-02-14 | 帝斯曼知识产权资产管理有限公司 | Process for the preparation of methylheptenone |
| WO2018091623A1 (en) * | 2016-11-18 | 2018-05-24 | Dsm Ip Assets B.V. | Novel process for the manufacture of gamma, delta-unsaturated ketones |
| WO2020140414A1 (en) * | 2019-01-02 | 2020-07-09 | 浙江新和成股份有限公司 | Method for preparing unsaturated ketone |
| CN112495404A (en) * | 2020-11-19 | 2021-03-16 | 万华化学集团股份有限公司 | Solid phosphoric acid catalyst, preparation method and recovery method of Saucy-Marbet reaction light component |
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| CN1539807A (en) * | 2003-10-28 | 2004-10-27 | 浙江大学 | Technique for synthesizing methylheptenone |
| CN1914143A (en) * | 2004-02-04 | 2007-02-14 | 帝斯曼知识产权资产管理有限公司 | Process for the preparation of methylheptenone |
| WO2018091623A1 (en) * | 2016-11-18 | 2018-05-24 | Dsm Ip Assets B.V. | Novel process for the manufacture of gamma, delta-unsaturated ketones |
| WO2020140414A1 (en) * | 2019-01-02 | 2020-07-09 | 浙江新和成股份有限公司 | Method for preparing unsaturated ketone |
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