CN112321399A - Preparation method of chemical intermediate - Google Patents
Preparation method of chemical intermediate Download PDFInfo
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- CN112321399A CN112321399A CN202011382930.XA CN202011382930A CN112321399A CN 112321399 A CN112321399 A CN 112321399A CN 202011382930 A CN202011382930 A CN 202011382930A CN 112321399 A CN112321399 A CN 112321399A
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- cyclopentanone
- methyl
- carbonate
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- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000000126 substance Substances 0.000 title claims description 29
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 claims abstract description 120
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000002608 ionic liquid Substances 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- GYTMUNSNMBRSEW-UHFFFAOYSA-N hydrogen carbonate;1h-imidazol-1-ium Chemical compound OC(O)=O.C1=CNC=N1 GYTMUNSNMBRSEW-UHFFFAOYSA-N 0.000 claims abstract description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000001301 oxygen Substances 0.000 claims abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 14
- 230000035484 reaction time Effects 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 229920004482 WACKER® Polymers 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 7
- GSYBSZRLMHKNIH-UHFFFAOYSA-N 1-butyl-3-methyl-1,2-dihydroimidazol-1-ium;hydrogen carbonate Chemical compound OC([O-])=O.CCCC[NH+]1CN(C)C=C1 GSYBSZRLMHKNIH-UHFFFAOYSA-N 0.000 claims description 6
- NFLCOQPZVBRLKF-UHFFFAOYSA-N C(O)(O)=O.CN1CN(C=C1)CC Chemical compound C(O)(O)=O.CN1CN(C=C1)CC NFLCOQPZVBRLKF-UHFFFAOYSA-N 0.000 claims description 6
- GNLFJTIUHOAVLH-UHFFFAOYSA-N C(O)(O)=O.CN1CN(C=C1)CCCCCC Chemical compound C(O)(O)=O.CN1CN(C=C1)CCCCCC GNLFJTIUHOAVLH-UHFFFAOYSA-N 0.000 claims description 6
- BIAHEUUSFPLXKJ-UHFFFAOYSA-N C(O)(O)=O.CN1CN(C=C1)CCC Chemical compound C(O)(O)=O.CN1CN(C=C1)CCC BIAHEUUSFPLXKJ-UHFFFAOYSA-N 0.000 claims description 5
- POYOHJSEMHRDKG-UHFFFAOYSA-N C(O)(O)=O.CN1CN(C=C1)CCCCC Chemical compound C(O)(O)=O.CN1CN(C=C1)CCCCC POYOHJSEMHRDKG-UHFFFAOYSA-N 0.000 claims description 5
- JVSJZCBXHAONLQ-UHFFFAOYSA-N C(O)(O)=O.CN1CN(C=C1)CCCCCCCC Chemical compound C(O)(O)=O.CN1CN(C=C1)CCCCCCCC JVSJZCBXHAONLQ-UHFFFAOYSA-N 0.000 claims description 5
- 239000013461 intermediate chemical Substances 0.000 claims 3
- 229910002666 PdCl2 Inorganic materials 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 17
- 239000002994 raw material Substances 0.000 description 10
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 7
- 238000004821 distillation Methods 0.000 description 7
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- -1 1-methyl-3-butyl imidazole hexafluorophosphate Chemical compound 0.000 description 3
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 2
- JFYZBXKLRPWSGV-UHFFFAOYSA-N 1-methyl-3-propyl-2h-imidazole Chemical compound CCCN1CN(C)C=C1 JFYZBXKLRPWSGV-UHFFFAOYSA-N 0.000 description 2
- KRNSYSYRLQDHDK-UHFFFAOYSA-N 6,7-dihydro-5h-cyclopenta[b]pyridine Chemical compound C1=CN=C2CCCC2=C1 KRNSYSYRLQDHDK-UHFFFAOYSA-N 0.000 description 2
- 101150003085 Pdcl gene Proteins 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- KVWWIYGFBYDJQC-UHFFFAOYSA-N methyl dihydrojasmonate Chemical compound CCCCCC1C(CC(=O)OC)CCC1=O KVWWIYGFBYDJQC-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- JTHVYOIHZNYRCC-UHFFFAOYSA-N 2-hexylcyclopentan-1-one Chemical compound CCCCCCC1CCCC1=O JTHVYOIHZNYRCC-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- XMLSXPIVAXONDL-PLNGDYQASA-N Jasmone Chemical compound CC\C=C/CC1=C(C)CCC1=O XMLSXPIVAXONDL-PLNGDYQASA-N 0.000 description 1
- 235000006679 Mentha X verticillata Nutrition 0.000 description 1
- 235000002899 Mentha suaveolens Nutrition 0.000 description 1
- 235000001636 Mentha x rotundifolia Nutrition 0.000 description 1
- 229940124599 anti-inflammatory drug Drugs 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 239000002246 antineoplastic agent Substances 0.000 description 1
- 229940041181 antineoplastic drug Drugs 0.000 description 1
- 239000002249 anxiolytic agent Substances 0.000 description 1
- QWCRAEMEVRGPNT-UHFFFAOYSA-N buspirone Chemical compound C1C(=O)N(CCCCN2CCN(CC2)C=2N=CC=CN=2)C(=O)CC21CCCC2 QWCRAEMEVRGPNT-UHFFFAOYSA-N 0.000 description 1
- 229960002495 buspirone Drugs 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- XMLSXPIVAXONDL-UHFFFAOYSA-N trans-jasmone Natural products CCC=CCC1=C(C)CCC1=O XMLSXPIVAXONDL-UHFFFAOYSA-N 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
- C07C45/27—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
-
- 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
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/122—Halides of copper
-
- 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
- B01J27/06—Halogens; Compounds thereof
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
- B01J27/13—Platinum group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
- C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated
Landscapes
- 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)
Abstract
The invention provides a preparation method of cyclopentanone, which is characterized by comprising the following steps: placing cyclopentene in a reaction container, adding ionic liquid imidazole carbonate and a Wacker catalyst, introducing an oxygen source, stirring and heating to react under normal pressure, and performing aftertreatment to obtain cyclopentanone. The imidazole carbonate ionic liquid is used as a solvent, the system can fully react without high pressure, the reaction time is greatly shortened, the higher yield and purity of the product can be ensured, the method is particularly suitable for industrial production, and the unexpected technical effect is achieved.
Description
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a preparation method of a chemical intermediate, and more particularly relates to a preparation method of cyclopentanone, a chemical intermediate.
Background
Cyclopentanone is a colorless transparent oily liquid, has a special ether smell slightly similar to mint, is insoluble in water, and is soluble in most organic solvents such as alcohol and ether. Cyclopentanone is an important fine chemical intermediate, is a raw material of perfume and pharmaceutical industry, can be used for preparing novel perfumes, namely jasmone, methyl dihydrojasmonate, alband ketone, 2-n-hexyl cyclopentanone, 2, 3-cyclopentenopyridine, anxiolytic drug, namely buspirone and various anti-inflammatory and anti-cancer drugs, and is also used for biochemical research and synthesis of pesticides and herbicides. Because of its good solubility to various resins, it is widely used as a solvent in the electronics industry. Cyclopentanone is currently in short supply worldwide.
At present, the methods for preparing cyclopentanone mainly comprise the following methods:
(1) the adipic acid method mainly uses adipic acid as a raw material to prepare cyclopentanone through high-temperature decarboxylation, which is the main method for industrially producing cyclopentanone at present, but is limited by the source of the raw material and a large amount of pollutants, so that the further development of the process is limited.
(2) Using cyclopentene as raw material and N2O is used as an oxidant to prepare cyclopentanone, and although the yield of cyclopentanone is high, the reaction energy consumption is very high due to the adoption of conditions such as high temperature and high pressure, and the industrial development is not facilitated.
(3) The preparation of cyclopentanone by using cyclopentene as a raw material, obtaining cyclopentanol through indirect hydration or direct hydration, and then preparing cyclopentanone through catalytic dehydrogenation generally comprises the steps of hydration reaction of cyclopentene, recovery of unreacted raw materials, refining of a solvent, refining of cyclopentanol, dehydrogenation and refining of cyclopentanol and the like, but has the problems of long flow path and high energy consumption.
(4) The conversion rate is not high, chlorine-containing by-products are generated, the equipment is corroded greatly, and the post-treatment is difficult.
(5) Cyclopentene is used as raw material, a Wacker catalyst is used, a certain amount of water is added in the reaction, and the improvement of the reaction is facilitated
The selectivity is desirable, but as the amount of water continues to increase, palladium inevitably precipitates, and halogenated salts such as LiCl, KCl or NaCl can be added to prevent palladium precipitation, but cause deep oxidation of cyclopentanone, Cl-The introduction of ions also increases the by-products.
(6) Cyclopentene is used as a raw material, a Wacker catalyst is used, and ionic liquid 1-methyl-3-butyl imidazole hexafluorophosphate ([ Bmim) is used]·PF6) The reaction is a solvent, the reaction conversion rate is improved, but the reaction still needs to be carried out under high pressure, the reaction time needs 6-9 hours, and the reaction time is longer.
Disclosure of Invention
The invention aims to overcome the series of defects in the synthesis of cyclopentanone in the prior art, and provides a preparation method of cyclopentanone, which is characterized by comprising the following steps: placing cyclopentene in a reaction container, adding ionic liquid imidazole carbonate and a Wacker catalyst, introducing an oxygen source, stirring and heating to react under normal pressure, and performing aftertreatment to obtain cyclopentanone.
According to the preparation method of the cyclopentanone as the chemical intermediate, the imidazole carbonate is selected from one or more of 1-methyl-3-ethyl imidazole carbonate, 1-methyl-3-propyl imidazole carbonate, 1-methyl-3-butyl imidazole carbonate, 1-methyl-3-pentyl imidazole carbonate, 1-methyl-3-hexyl imidazole carbonate or 1-methyl-3-octyl imidazole carbonate.
According to the preparation method of the chemical intermediate cyclopentanone, the Wacker catalyst is selected from PdCl2-CuCl2A catalyst.
According to the preparation method of cyclopentanone as an intermediate in chemical industry, the oxygen source is selected from air or oxygen.
According to the preparation method of cyclopentanone as a chemical intermediate, the heating temperature is 50-80 ℃.
According to the preparation method of cyclopentanone as an intermediate in chemical industry, the reaction time is 1-3 h.
According to the preparation method of the chemical intermediate cyclopentanone, the feeding ratio of the cyclopentene to the catalyst to the ionic liquid is 1mol: 1-10 g: 100-200 g.
According to the preparation method of the chemical intermediate cyclopentanone, PdCl is contained in the catalyst2And CuCl2The mass ratio of (A) to (B) is 1: 5-10.
According to the preparation method of the cyclopentanone as the chemical intermediate, the stirring speed is 500-1000 r/min.
According to the preparation method of cyclopentanone as a chemical intermediate, the post-treatment process comprises the following steps: after the reaction was completed, the system was slowly returned to room temperature, and distilled under reduced pressure to obtain cyclopentanone.
Further, the present invention also provides a use of an ionic liquid in preparation of cyclopentanone, preferably, the ionic liquid is imidazole carbonate, further preferably, the imidazole carbonate is selected from one or more of 1-methyl-3-ethyl imidazole carbonate, 1-methyl-3-propyl imidazole acid salt, 1-methyl-3-butyl imidazole carbonate, 1-methyl-3-pentyl imidazole carbonate, 1-methyl-3-hexyl imidazole carbonate, or 1-methyl-3-octyl imidazole carbonate.
The main contributions of the present invention with respect to the prior art are the following:
the invention takes cyclopentene as raw material and PdCl2-CuCl2The catalyst is added with the imidazole carbonate ionic liquid as a solvent for reaction, the raw material and the catalyst can be fully dissolved by using the imidazole carbonate ionic liquid, and the reaction efficiency is greatly improved compared with [ Bmim ]]·PF6The imidazole carbonate ionic liquid is used as a solvent, the system can fully react without high pressure, the reaction time is greatly shortened, the higher yield and purity of the product can be ensured, the method is particularly suitable for industrial production, and the unexpected technical effect is achieved.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present disclosure more apparent, the technical solutions of the embodiments of the present disclosure are clearly and completely described. It is to be understood that the described embodiments are only a few embodiments of the present disclosure, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the disclosure without any inventive step, are within the scope of protection of the disclosure.
The invention provides a preparation method of cyclopentanone, which is characterized by comprising the following steps: placing cyclopentene in a reaction container, adding ionic liquid imidazole carbonate and a Wacker catalyst, introducing an oxygen source, stirring and heating to react under normal pressure, and performing aftertreatment to obtain cyclopentanone.
According to the preparation method of the cyclopentanone as the chemical intermediate, the imidazole carbonate is selected from one or more of 1-methyl-3-ethyl imidazole carbonate, 1-methyl-3-propyl imidazole carbonate, 1-methyl-3-butyl imidazole carbonate, 1-methyl-3-pentyl imidazole carbonate, 1-methyl-3-hexyl imidazole carbonate or 1-methyl-3-octyl imidazole carbonate.
According to the preparation method of the chemical intermediate cyclopentanone, the Wacker catalyst is selected from PdCl2-CuCl2A catalyst.
According to the preparation method of cyclopentanone as an intermediate in chemical industry, the oxygen source is selected from air or oxygen.
According to the preparation method of cyclopentanone as a chemical intermediate, the heating temperature is 50-80 ℃.
According to the preparation method of cyclopentanone as an intermediate in chemical industry, the reaction time is 1-3 h.
According to the preparation method of the chemical intermediate cyclopentanone, the feeding ratio of the cyclopentene to the catalyst to the ionic liquid is 1mol: 1-10 g: 100-200 g.
According to the preparation method of the chemical intermediate cyclopentanone, PdCl is contained in the catalyst2And CuCl2The mass ratio of (A) to (B) is 1: 5-10.
According to the preparation method of the cyclopentanone as the chemical intermediate, the stirring speed is 500-1000 r/min.
According to the preparation method of cyclopentanone as a chemical intermediate, the post-treatment process comprises the following steps: after the reaction was completed, the system was slowly returned to room temperature, and distilled under reduced pressure to obtain cyclopentanone.
Further, the present invention also provides a use of an ionic liquid in preparation of cyclopentanone, preferably, the ionic liquid is imidazole carbonate, further preferably, the imidazole carbonate is selected from one or more of 1-methyl-3-ethyl imidazole carbonate, 1-methyl-3-propyl imidazole acid salt, 1-methyl-3-butyl imidazole carbonate, 1-methyl-3-pentyl imidazole carbonate, 1-methyl-3-hexyl imidazole carbonate, or 1-methyl-3-octyl imidazole carbonate.
Example 1
6.8g (0.1mol) of cyclopentene, 20g of 1-methyl-3-butylimidazole carbonate, 0.5g of copper chloride and 0.1g of palladium chloride are sequentially added into a reactor, the mixture is uniformly stirred, oxygen is continuously introduced, the mixture is slowly heated to 50 ℃ under normal pressure, the stirring speed is kept at 500r/min, the reaction time is 3 hours, then the system is slowly cooled to room temperature, and the mixture is subjected to reduced pressure distillation to obtain 8g of cyclopentanone, wherein the yield is 95.2%, and the purity is 99.1%.
Example 2
6.8g (0.1mol) of cyclopentene, 20g of 1-methyl-3-ethylimidazole carbonate, 0.5g of copper chloride and 0.1g of palladium chloride are sequentially added into a reactor, the mixture is uniformly stirred, oxygen is continuously introduced, the mixture is slowly heated to 60 ℃ under normal pressure, the stirring speed is kept at 800r/min, the reaction time is 3 hours, then the system is slowly cooled to room temperature, and the mixture is subjected to reduced pressure distillation to obtain 8.1g of cyclopentanone, wherein the yield is 96.4% and the purity is 99%.
Example 3
6.8g (0.1mol) of cyclopentene, 20g of 1-methyl-3-hexyl imidazole carbonate, 0.9g of copper chloride and 0.1g of palladium chloride are sequentially added into a reactor, the mixture is uniformly stirred, air is continuously introduced, the mixture is slowly heated to 80 ℃ under normal pressure, the stirring speed is kept at 1000r/min, the reaction time is 3 hours, then the system is slowly cooled to room temperature, reduced pressure distillation is carried out, 7.8g of cyclopentanone is obtained, the yield is 92.9%, and the purity is 99.4%.
Example 4
68g (1mol) of cyclopentene, 180g of 1-methyl-3-propyl imidazole carbonate, 9g of copper chloride and 1g of palladium chloride are sequentially added into a reactor, the mixture is uniformly stirred, air is continuously introduced, the mixture is slowly heated to 80 ℃ under normal pressure, the stirring speed is kept at 1000r/min, the reaction time is 3 hours, then the system is slowly cooled to the room temperature, reduced pressure distillation is carried out, and 76.8g of cyclopentanone is obtained, the yield is 91.2%, and the purity is 99.5%.
Example 5
68g (1mol) of cyclopentene, 150g of 1-methyl-3-propyl imidazole carbonate, 8g of copper chloride and 1g of palladium chloride are sequentially added into a reactor, the mixture is uniformly stirred, air is continuously introduced, the mixture is slowly heated to 70 ℃ under normal pressure, the stirring speed is kept at 1000r/min, the reaction time is 3 hours, then the system is slowly cooled to the room temperature, reduced pressure distillation is carried out, 79.8g of cyclopentanone is obtained, the yield is 95%, and the purity is 99.3%.
Comparative example 1
6.8g (0.1mol) of cyclopentene, 20g of 1-methyl-3-butylimidazole hexafluorophosphate, 0.5g of copper chloride and 0.1g of palladium chloride are sequentially added into a reactor, the mixture is uniformly stirred, oxygen is continuously introduced, the mixture is slowly heated to 50 ℃ under normal pressure, the stirring speed is kept at 500r/min, the reaction time is 3 hours, then the system is slowly cooled to room temperature, and the mixture is subjected to reduced pressure distillation to obtain 6.8g of cyclopentanone, the yield is 80.9%, and the purity is 89.2%.
Comparative example 2
6.8g (0.1mol) of cyclopentene, 20g of 1-methyl-3-hexyl imidazole hexafluorophosphate, 0.9g of copper chloride and 0.1g of palladium chloride are sequentially added into a reactor, the mixture is uniformly stirred, oxygen is continuously introduced, the mixture is slowly heated to 80 ℃ under normal pressure, the stirring speed is kept at 1000r/min, the reaction time is 3 hours, then the system is slowly cooled to room temperature, and reduced pressure distillation is carried out to obtain 7g of cyclopentanone, wherein the yield is 83.3%, and the purity is 87.4%.
Finally, it should be noted that: it should be understood that the above examples are only for clearly illustrating the present invention and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the scope of the invention.
Claims (10)
1. A preparation method of cyclopentanone as a chemical intermediate is characterized by comprising the following steps: placing cyclopentene in a reaction container, adding ionic liquid imidazole carbonate and a Wacker catalyst, introducing an oxygen source, stirring and heating to react under normal pressure, and performing aftertreatment to obtain cyclopentanone.
2. The method for preparing cyclopentanone, an intermediate in chemical industry, according to claim 1, wherein the imidazole carbonate is selected from one or more of 1-methyl-3-ethylimidazole carbonate, 1-methyl-3-propyl imidazole carbonate, 1-methyl-3-butylimidazole carbonate, 1-methyl-3-pentylimidazole carbonate, 1-methyl-3-hexylimidazole carbonate, and 1-methyl-3-octylimidazole carbonate.
3. The preparation method of chemical intermediate cyclopentanone as claimed in claim 1 or 2, wherein the Wacker catalyst is selected from PdCl2-CuCl2A catalyst.
4. The method for preparing cyclopentanone, an intermediate in chemical industry, as defined in any one of claims 1 to 3, wherein said oxygen source is selected from air and oxygen.
5. The method for preparing cyclopentanone, an intermediate chemical ring, according to any of claims 1 to 4, wherein the heating temperature is 50 to 80 ℃.
6. The method for preparing cyclopentanone, an intermediate in chemical industry, as claimed in any one of claims 1 to 5, wherein the reaction time is 1-3 h.
7. The method for preparing cyclopentanone, an intermediate chemical ring, as claimed in any one of claims 1 to 6, wherein the charge ratio of cyclopentene to catalyst to ionic liquid is 1mol: 1-10 g: 100-200 g.
8. The method for preparing cyclopentanone, an intermediate in chemical industry, as claimed in any one of claims 1 to 7, wherein said catalyst contains PdCl2And CuCl2The mass ratio of (A) to (B) is 1: 5-10.
9. The method for preparing cyclopentanone, an intermediate in chemical industry, as defined in any one of claims 1 to 8, wherein the stirring speed is 500-1000 r/min.
10. The method for preparing cyclopentanone, an intermediate chemical ring, according to any one of claims 1 to 9, wherein the post-treatment process comprises: after the reaction was completed, the system was slowly returned to room temperature, and distilled under reduced pressure to obtain cyclopentanone.
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| 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 |
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