CN107513009B - Method for preparing cyclopentanone by oxidizing cyclopentene - Google Patents

Method for preparing cyclopentanone by oxidizing cyclopentene Download PDF

Info

Publication number
CN107513009B
CN107513009B CN201710712477.6A CN201710712477A CN107513009B CN 107513009 B CN107513009 B CN 107513009B CN 201710712477 A CN201710712477 A CN 201710712477A CN 107513009 B CN107513009 B CN 107513009B
Authority
CN
China
Prior art keywords
reaction
cyclopentanone
cyclopentene
ionic liquid
oxidation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201710712477.6A
Other languages
Chinese (zh)
Other versions
CN107513009A (en
Inventor
毛建拥
谢海英
王钰
吴雷
于明
袁浩然
李浩然
陈刚
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shandong Nhu Pharmaceutical Co ltd
Zhejiang University ZJU
Zhejiang NHU Co Ltd
Original Assignee
Shandong Nhu Pharmaceutical Co ltd
Zhejiang University ZJU
Zhejiang NHU Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shandong Nhu Pharmaceutical Co ltd, Zhejiang University ZJU, Zhejiang NHU Co Ltd filed Critical Shandong Nhu Pharmaceutical Co ltd
Priority to CN201710712477.6A priority Critical patent/CN107513009B/en
Publication of CN107513009A publication Critical patent/CN107513009A/en
Application granted granted Critical
Publication of CN107513009B publication Critical patent/CN107513009B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
    • C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
    • 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
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a Br phi nsted acid functionalized ionic liquid [ Bmim ] taking cyclopentene as a raw material, palladium chloride and copper chloride as catalysts]·HPF6Is used as solvent, and can synthesize cyclopentanone by one-step method under the condition of a certain temperature and oxygen source. The invention uses [ Bmim ]]·HPF6The ionic liquid replaces hydrochloric acid in the conventional watt reaction, and the occurrence of side reaction is obviously reduced. The ionic liquid used in the invention can effectively dissolve raw materials, metal salts and the like to form a homogeneous reaction system, thereby greatly improving the reaction conversion rate and selectivity. At the same time, the ionic liquid [ Bmim]·HPF6Also has the advantages of stable performance, easy separation of products and environmental protection. After the reaction is finished, only unreacted raw materials, byproducts and products need to be distilled and separated from the reaction system, and the catalytic system can be repeatedly used. The conversion rate of the reaction is more than 93%, and the selectivity of cyclopentanone is more than 95%.

Description

Method for preparing cyclopentanone by oxidizing cyclopentene
Technical Field
The invention relates to the field of fine chemical engineering, in particular to a method for synthesizing cyclopentanone by one-step catalytic oxidation with cyclopentene as a raw material.
Background
Cyclopentanone is colorless transparent oily liquid, has special ether and a smell similar to mint, is insoluble in water, and is soluble in most organic solvents such as alcohol and ether. The product is an important fine chemical intermediate, and is an important raw material for perfume and pharmaceutical industry. The cyclopentanone can be used for preparing novel spices of methyl dihydrojasmonate, albonone, 2-n-hexyl cyclopentanone and various anti-inflammatory and anticancer drugs, and can also be used for synthesizing pesticides and herbicides. Meanwhile, cyclopentanone is widely used as a solvent in the electronic industry because of its good solubility for various resins.
Ethylene by-product C produced by petroleum cracking5The cyclopentene separated from the fraction can be used as a raw material to produce cyclopentanone, and the main process routes comprise three technical routes of a cyclopentene hydration dehydrogenation method, a nitrous oxide oxidation method and a Wacker reaction oxidation method.
Simdt et al in the 20 th century, 50 s, Wacker, Germany, in ethylene with PdCl2CuCl is introduced into a reaction system for generating acetaldehyde2The PdCl is established2-CuCl2The well-known Wacker process for catalytically oxidizing ethylene to produce acetaldehyde, which is successfully applied to practical production, is one of the important processes for the carbonylation of olefins.
In an absolute ethanol solvent, Takehira et al mainly investigated the oxygen pressure on PdCl2-CuCl2、PdCl2-FeCl3The effect of catalytic oxidation of cyclopentene. At 1.01X 105PdCl at Pa2-CuCl2、PdCl2-FeCl3The catalytic oxidation of cyclopentene was 98% and 50%, respectively, and the selectivity of cyclopentanone was 70% and 90%, respectively. With the increase of the oxygen pressure, the catalytic effects of the two catalytic systems are improved, and the oxygen pressure is applied to PdCl2-CuCl2The effect of the catalytic system is more remarkable when P (O)2) At 490.3kPa, cyclopentene is almost completely converted to cyclopentanone (Takehira K, Orita H, Oh I H, Palladium (II) -catalyzed oxidation of cyclopentene in the presence of spreader (II) -chloride and molecular oxygen, J.mol.Catal.,1987,42: 247-255. ). Under the reaction conditions, though PdCl2-FeCl3CatalysisThe cyclopentene conversion of the system increased to 88%, but the cyclopentanone selectivity decreased to about 75%. Furthermore, in this document, CuCl is used2Or FeCl3Are all hydrates and during the reaction water and HCl are formed, which can cause the precipitation of Pd and the catalyst PdCl2Is damaged and cannot be recycled and reused, industrialization is difficult to realize, and side reactions are increased due to the generated HCl.
Ogufit et al studied PdCl2-CuCl2The cyclopentanone is prepared by reaction in the water phase, the yield is 36.5%, triphenylphosphine oxide is added into the reaction system, the palladium precipitation can be effectively prevented, the reaction speed is accelerated, and the reaction yield can reach 68%. The post-treatment of the reaction system is simple, the catalyst can be recycled, but the required pressure is higher (7MPa), the requirement on equipment is high, and the industrial application value is low.
Omori hideki et al in PdCl2-CuCl2In the system, polyvinyl pyrrole is used as a solvent, the pressure is kept at 0.47MPa, the reaction is carried out for 6 hours at 60 ℃, the conversion rate is 43.1 percent, the selectivity is 95.6 percent, the process is easy for recovering the catalyst and separating the product, and the conversion rate is low.
In PdCl, Mutsuo Yamada et al2-CuCl2Adding benzonitrile and Hexamethylphosphoramide (HMPA) into the system, wherein the benzonitrile can react with PdCl2Formation of the Complex increases PdCl2Solubility in cyclopentene, while HMPA can increase O2The solubility in water and the complex formation with CuCl generated by the reaction increase the contact of CuCl and oxygen, and increase the reaction speed by 8 times.
Takehira K et al propose that adding a certain amount of water in the oxidation reaction of the cyclopentene wacker process is advantageous to improve the selectivity of the reaction, but as the amount of water continues to increase, palladium inevitably precipitates, and a halogenated salt such as LiCl, KCl or NaCl may be added to prevent palladium precipitation, but causes deep oxidation of cyclopentanone. Cl-The introduction of ions also increases the by-products.
The cyclopentene Wacker method for preparing cyclopentanone has numerous advantages, fewer side reactions and higher selectivity, but has more problems which are not solved yet:
1) the conversion per pass of the reaction of the Wacker method is relatively low;
2) the reaction system is complex, a series of oxidation chain reactions exist, and simultaneously, a gas phase (oxygen or air) and a water phase (hydrochloric acid and PdCl) exist in the reaction system process2-CuCl2) Oil phase (solvent, cyclopentene, cyclopentanone) and micro solid phase (PdCl)2-CuCl2Metal palladium and cuprous chloride), many factors affect the yield; the method also has great influence on the post-treatment of the reaction, the separation of products, solvent and water in the post-treatment process is difficult, and the cyclopentanone and water are azeotropic and are easy to form entrainment with more alcohol solvents;
3) in the traditional Wacker reaction, acid with certain concentration is required to be added to maintain the activity of the palladium catalyst, HCl is generated in the reaction, and the hydrochloric acid causes excessive Cl to be introduced into the reaction system-Ions, leading to increased side reactions (α of cyclopentanone)-The site is more active and is easy to form α-Chloro cyclopentanone, α-The elimination reaction of the chloro-cyclopentanone to generate cyclopentenone) to reduce the selectivity of the reaction;
4) the hydrochloric acid can corrode reaction equipment or a container, so that the equipment cost is increased;
5) the catalyst is difficult to recycle, a small amount of intermediate metal palladium and cuprous chloride are generated in the reaction process, and the intermediate metal palladium and the cuprous chloride are easily wrapped by materials such as leftovers and the like to cause the catalyst to lose effectiveness.
Disclosure of Invention
In order to solve the problems existing in the preparation of cyclopentanone by the wacker method, the invention provides a one-step method for synthesizing cyclopentanone by taking cyclopentene as a raw material.
A process for preparing cyclopentanone from cyclopentene by oxidation with PdCl2-CuCl2As a catalyst, Br phi nsted acid functional ionic liquid [ Bmim ]]·HPF6And (3) taking air or oxygen as an oxygen source as a solvent, carrying out a wacker reaction on cyclopentene, and carrying out post-treatment after the reaction is finished to obtain the cyclopentanone.
The Br phi nsted acid functionalized ionic liquid [ Bmim ]]-·HPF6 +(hereinafter referred to as ionic liquid) of [ Bmi ]m]-For 1-butyl-3-methylimidazolyl group, HPF6 +Is hexafluorophosphoric acid with positrons. The ionic liquid is strong acid, can perfectly replace hydrochloric acid used in Wacker reaction in the prior art, and is p-PdCl2-CuCl2The catalyst system activity is improved more than that of hydrochloric acid. The ionic liquid can effectively dissolve the reaction raw materials, the catalyst and the product of the invention to form a gas-liquid two-phase reaction for reacting with oxygen, and the yield and the content of the product are high by adopting the ionic liquid for reaction.
In the invention, after the reaction is finished, the reaction liquid is simply rectified, so that the separation of the product from residual raw materials, ionic liquid, byproducts and the like can be realized. The rectification can not evaporate the ionic liquid, and the liquid ionic liquid containing the catalyst can be directly applied; and the ionic liquid can be evaporated, and the separated catalysts can be respectively reused.
The oxygen source is air or oxygen, preferably CO can be added into the air or oxygen2Gas (the volume of air or oxygen, the ratio of CO2 to oxygen source is 10-100: 100). Adding a certain amount of CO2The gas can obviously increase the solubility of oxygen in the ionic liquid, so that the reaction part of the method is converted into a homogeneous reaction, and the reaction efficiency is improved.
In the reaction system, the mass ratio of copper chloride and palladium chloride serving as catalysts is 5-10: 1, and the mass ratio of cyclopentene to the catalyst is 4-10: 1. in the invention, the weight ratio of the ionic liquid to the cyclopentene is 3-5: 1.
in the invention, the reaction temperature is 40-100 ℃, the reaction pressure is 0.3-2.0 MPa, preferably, the reaction temperature is 60-80 ℃, the reaction pressure is 0.8-1.8 MPa, and the reaction time is 6-9 h.
Compared with the prior art, the invention has the beneficial effects that:
(1) the method has high reaction efficiency and simple post-treatment, and can obtain cyclopentanone fraction with the content of more than 99 percent by simple rectification. Meanwhile, the reaction conversion rate of the method is more than 93%, and the selectivity of cyclopentanone is more than 95%.
(2) The catalyst and the ionic liquid solvent are easy to recycle and can be realized through simple rectification, and the selectivity and the yield are not obviously reduced after recycling and recycling, so that the industrial production is convenient to realize.
(3) The invention selects Br phi nsted acid functional ionic liquid [ Bmim ]]·HPF6The catalyst is a solvent, replaces alcohol used in the Wacker reaction in the prior art, not only increases the activity of a catalyst system and improves the reaction conversion rate, but also converts the reaction into a simple gas-liquid two-phase reaction. The invention provides a green reaction route for synthesizing cyclopentanone.
Detailed Description
Example 1
10g of cyclopentene, 0.20g of palladium chloride, 1.50g of copper chloride, and 30g of an ionic liquid solvent ([ Bmim ] was charged in a 250ml autoclave]·HPF6) Heating to 60 ℃, adding oxygen to 1.0MPa, keeping the pressure at 1.0MPa, stirring for 600r/min, and reacting for 6 h. After the reaction was completed, the reaction solution was collected and analyzed by gas chromatography, cyclopentanone was labeled with cyclohexane as an internal standard, and the conversion of the reaction was calculated to be 93.5%, and the selectivity of cyclopentanone was calculated to be 95.5%. Rectifying the reaction liquid at normal pressure, recovering 0.63g of cyclopentene, and recovering 31.65g of ionic liquid solvent and catalyst to obtain 10.8g of cyclopentanone with content of more than 99%.
Examples 2 to 10
According to the operating method of example 1, the reaction conditions were varied: reaction temperature, reaction pressure, reaction time, and the ratio of copper chloride to palladium chloride as catalysts to obtain a reaction solution, and the detection data are shown in table 1.
TABLE 1 reaction conditions and reaction results of examples 2 to 10
Figure BDA0001383015770000041
Figure BDA0001383015770000051
Remarking: example 5a1: example 4 ion of recovered Palladium chloride and copper chloride catalystThe liquid solution was used indiscriminately (amount added to the table depending on losses during ionic liquid recovery).
Example 7a2: the ionic liquid solutions of the recovered palladium chloride and copper chloride catalysts of example 6 were used indiscriminately (with additional amounts added to the table based on losses during ionic liquid recovery).
Example 10a3: the ionic liquid solutions of the recovered palladium chloride and copper chloride catalysts of example 9 were used repeatedly (with additional amounts added to the table based on losses during ionic liquid recovery).

Claims (8)

1. A method for preparing cyclopentanone by oxidation of cyclopentene is characterized in that PdCl is used2-CuCl2As a catalyst, Br phi nsted acid functional ionic liquid [ Bmim ]]·PF6The solvent is air or oxygen as an oxygen source, the cyclopentene is subjected to Wacker reaction, and the cyclopentanone is obtained through post-treatment after the reaction is finished.
2. The process for preparing cyclopentanone through oxidation of cyclopentene according to claim 1, wherein the post-treatment comprises: rectifying the reaction liquid, and separating to obtain a product cyclopentanone, an ionic liquid and a catalyst.
3. The method for preparing cyclopentanone through oxidation of cyclopentene according to claim 1, wherein CO is added to said oxygen source2A gas;
added CO2The volume ratio of the gas to the oxygen or the air is 10-100: 100.
4. the method for preparing cyclopentanone by oxidizing cyclopentene according to claim 1, wherein a mass ratio of copper chloride to palladium chloride in the catalyst is 5-10: 1, and a mass ratio of cyclopentene to the catalyst is 4-10: 1.
5. the method for preparing cyclopentanone through oxidation of cyclopentene according to claim 1, wherein the weight ratio of ionic liquid to cyclopentene is 3-5: 1.
6. the method for preparing cyclopentanone through oxidation of cyclopentene according to claim 1, wherein the reaction temperature is 40-100 ℃ and the reaction pressure is 0.3-2.0 MPa.
7. The method for preparing cyclopentanone through oxidation of cyclopentene according to claim 6, wherein the reaction temperature is 60-80 ℃ and the reaction pressure is 0.8-1.8 MPa.
8. The method for preparing cyclopentanone through oxidation of cyclopentene according to claim 2, wherein the ionic liquid is separated from the catalyst and then used in the post-treatment, or is used directly without separation.
CN201710712477.6A 2017-08-18 2017-08-18 Method for preparing cyclopentanone by oxidizing cyclopentene Active CN107513009B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710712477.6A CN107513009B (en) 2017-08-18 2017-08-18 Method for preparing cyclopentanone by oxidizing cyclopentene

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710712477.6A CN107513009B (en) 2017-08-18 2017-08-18 Method for preparing cyclopentanone by oxidizing cyclopentene

Publications (2)

Publication Number Publication Date
CN107513009A CN107513009A (en) 2017-12-26
CN107513009B true CN107513009B (en) 2020-04-07

Family

ID=60722183

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710712477.6A Active CN107513009B (en) 2017-08-18 2017-08-18 Method for preparing cyclopentanone by oxidizing cyclopentene

Country Status (1)

Country Link
CN (1) CN107513009B (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112299968B (en) * 2020-11-26 2022-05-06 广州彼西络科技有限公司 Preparation method of chemical raw material
CN112299969A (en) * 2020-11-30 2021-02-02 山东卓俊实业有限公司 Application of imidazole carbonate in preparation of important chemical raw materials
CN112321399B (en) * 2020-12-01 2022-10-18 漯河豫博生物化工有限公司 Preparation method of chemical intermediate
CN112479838A (en) * 2020-12-02 2021-03-12 山东卓俊实业有限公司 Application of imidazole carbonate in preparation of chemical intermediates

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1817841A (en) * 2006-03-17 2006-08-16 浙江大学 Production of unsaturated ketone
CN103664557A (en) * 2012-09-25 2014-03-26 中国石油化工股份有限公司 Method for preparing cyclopentanone by oxidation of cyclopentene

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1817841A (en) * 2006-03-17 2006-08-16 浙江大学 Production of unsaturated ketone
CN103664557A (en) * 2012-09-25 2014-03-26 中国石油化工股份有限公司 Method for preparing cyclopentanone by oxidation of cyclopentene

Also Published As

Publication number Publication date
CN107513009A (en) 2017-12-26

Similar Documents

Publication Publication Date Title
CN107513009B (en) Method for preparing cyclopentanone by oxidizing cyclopentene
Zhang et al. Direct reductive amination of aldehydes with nitroarenes using bio-renewable formic acid as a hydrogen source
Lee et al. Aqueous and biphasic nitrile hydration catalyzed by a recyclable Ru (II) complex under atmospheric conditions
Laval et al. Hydrosiloxane–Ti (OiPr) 4: an efficient system for the reduction of primary amides into primary amines as their hydrochloride salts
WO2017124676A1 (en) Method for synthesizing carvacrol by using limo nene epoxides
Sánchez et al. Catalytic conversion of glycerol to allyl alcohol; effect of a sacrificial reductant on the product yield
CN112390712A (en) Method for preparing 1, 3-butanediol by adopting fixed bed continuous reaction
CN104447261A (en) Method for preparing cyclopentanol and cyclopentanone by using cyclopentane
CN107365244B (en) Method for preparing 1H-perhalo cyclic olefin by hydrogen-halogen exchange reaction through hydrogen source provided by organic solvent
CN101602693B (en) Method for synthesizing acetonitrile by ethanol ammoniation method
CN105384616A (en) Synthetic method for methoxyacetone
US20120116119A1 (en) Production of 2,4-hexadienoic acid and 1,3-pentadiene from 6-methyl-5,6-dihydro-2-pyrone
CN108752217B (en) Synthesis method of dolutegravir key intermediate 2, 4-difluorobenzylamine
CN105777508B (en) A kind of synthetic method of 1- (4- chlorphenyl) -2- cyclopropyl -1- acetone
CN107540520B (en) Method for preparing pyromellitic acid or trimellitic acid from pinacol
CN101948461B (en) Method for synthesizing 1,4-dioxane
CN110903186A (en) Process for producing benzyl salicylate by using supported catalyst
CN107501053A (en) A kind of green synthesis method by the step alcohol ether of alkene one
JP7149424B2 (en) Method for recovering and reusing selective homogeneous hydrogenation catalyst
JPH0748346A (en) Integrated production of di-tert-butyl peroxide
US20020062047A1 (en) Process for producing 2,4,5,-trialkylbenzaldehydes
CN107602516B (en) Method for synthesizing delta-cyclopentanolide under catalysis of amino acid ionic liquid
CN105348061A (en) 2-cyclohexene-1-ketone preparation method
CN111187146A (en) Method for producing 2-methyl-3-buten-2-ol
Bailey et al. Studies on transition metal nitrido and oxo complexes. Part 16 1. The nature of the oxoruthenates involved in some rutheniumcatalysed organic oxidations

Legal Events

Date Code Title Description
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant