CN115819202B - Method for synthesizing cyclohexanedione - Google Patents
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- CN115819202B CN115819202B CN202211679636.4A CN202211679636A CN115819202B CN 115819202 B CN115819202 B CN 115819202B CN 202211679636 A CN202211679636 A CN 202211679636A CN 115819202 B CN115819202 B CN 115819202B
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- cyclohexanediol
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- OILAIQUEIWYQPH-UHFFFAOYSA-N cyclohexane-1,2-dione Chemical compound O=C1CCCCC1=O OILAIQUEIWYQPH-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 22
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 16
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 239000007800 oxidant agent Substances 0.000 claims abstract description 12
- 230000001590 oxidative effect Effects 0.000 claims abstract description 11
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 3
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 40
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 34
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 32
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 22
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- 239000012065 filter cake Substances 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 9
- 239000003208 petroleum Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 229960000583 acetic acid Drugs 0.000 claims description 6
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims description 6
- RJWJCQLFAYQGBG-UHFFFAOYSA-L disodium;sulfite;hydrate Chemical compound [OH-].[Na+].[Na+].OS([O-])=O RJWJCQLFAYQGBG-UHFFFAOYSA-L 0.000 claims description 6
- 239000012362 glacial acetic acid Substances 0.000 claims description 6
- 239000000741 silica gel Substances 0.000 claims description 6
- 229910002027 silica gel Inorganic materials 0.000 claims description 6
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 5
- 229920002472 Starch Polymers 0.000 claims description 5
- 230000008859 change Effects 0.000 claims description 5
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 5
- 235000019698 starch Nutrition 0.000 claims description 5
- 239000008107 starch Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000012074 organic phase Substances 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 13
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 10
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 8
- 238000004128 high performance liquid chromatography Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- DCZFGQYXRKMVFG-UHFFFAOYSA-N cyclohexane-1,4-dione Chemical compound O=C1CCC(=O)CC1 DCZFGQYXRKMVFG-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- PFURGBBHAOXLIO-UHFFFAOYSA-N cyclohexane-1,2-diol Chemical compound OC1CCCCC1O PFURGBBHAOXLIO-UHFFFAOYSA-N 0.000 description 4
- HJSLFCCWAKVHIW-UHFFFAOYSA-N cyclohexane-1,3-dione Chemical compound O=C1CCCC(=O)C1 HJSLFCCWAKVHIW-UHFFFAOYSA-N 0.000 description 4
- JQPFYXFVUKHERX-UHFFFAOYSA-N 2-hydroxy-2-cyclohexen-1-one Natural products OC1=CCCCC1=O JQPFYXFVUKHERX-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 2
- RLMGYIOTPQVQJR-UHFFFAOYSA-N cyclohexane-1,3-diol Chemical compound OC1CCCC(O)C1 RLMGYIOTPQVQJR-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- DKMROQRQHGEIOW-UHFFFAOYSA-N Diethyl succinate Chemical compound CCOC(=O)CCC(=O)OCC DKMROQRQHGEIOW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- KSKWGMNRWCYVAT-UHFFFAOYSA-N diethyl 2,5-dioxocyclohexane-1,4-dicarboxylate Chemical compound CCOC(=O)C1CC(=O)C(C(=O)OCC)CC1=O KSKWGMNRWCYVAT-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of chemical synthesis, and provides a method for synthesizing cyclohexanedione, which comprises the following steps: s1, mixing and stirring cyclohexanediol, a solvent, a catalyst and a phase transfer catalyst until the mixture is uniform; s2, dropwise adding an oxidant to perform an oxidation reaction; s3, after the reaction is finished, performing post-treatment. By the technical scheme, the problems of low cyclohexanedione yield and low cyclohexanedione purity in the prior art are solved.
Description
Technical Field
The invention relates to the technical field of chemical synthesis, in particular to a method for synthesizing cyclohexanedione.
Background
Cyclohexanediones of formula C 6 H 8 O 2 Is colorless oily substance, and is soluble in ethanol and diethyl ether, and insoluble in water. Cyclohexanediones are classified into three types including 1, 2-cyclohexanedione, 1, 3-cyclohexanedione and 1, 4-cyclohexanedione.
Currently, 1, 2-cyclohexanediones are prepared mainly by the following methods: and heating cyclohexanone, dropwise adding an ethanol solution of selenium dioxide, heating for refluxing, evaporating, separating out selenium, distilling under reduced pressure, and purifying to obtain 1, 2-cyclohexanedione.
1, 3-cyclohexanedione is prepared mainly by the following method: mixing resorcinol and sodium hydroxide solution, adding nickel catalyst, reacting for 10-12h under hydrogen atmosphere, cooling, filtering to remove catalyst, acidifying the filtrate, cooling, filtering to remove crystal, and recrystallizing to obtain 1, 3-cyclohexanedione product.
1, 4-cyclohexanedione is prepared mainly by the following method: sequentially mixing sodium ethoxide, diethyl ether and diethyl succinate, refluxing in a water bath for 3 days, cooling, adjusting pH to be acidic, filtering out crystals, washing with water, and drying to obtain a crude product of diethyl succinyl succinate; recrystallizing the crude product to obtain a pure product, adding a mixture of concentrated sulfuric acid, water and ethanol, refluxing for 5 days with oil solution, cooling, adjusting pH to alkalescence, extracting with chloroform, recovering chloroform to obtain the crude product, distilling the crude product under reduced pressure, pouring the distillate into petroleum ether, filtering, and drying to obtain the 1, 4-cyclohexanedione product.
However, the existing method for synthesizing cyclohexanedione generally has the problems of low product yield and low purity, so that the improvement of the yield and purity of cyclohexanedione is a technical problem which needs to be solved by the technicians in the field.
Disclosure of Invention
The invention provides a method for synthesizing cyclohexanedione, which solves the problems of low cyclohexanedione yield and low cyclohexanedione purity in the related art.
The technical scheme of the invention is as follows:
a method of synthesizing cyclohexanedione comprising the steps of:
s1, mixing and stirring cyclohexanediol, a solvent, a catalyst and a phase transfer catalyst until the mixture is uniform;
s2, dropwise adding an oxidant to perform an oxidation reaction;
s3, after the reaction is finished, performing post-treatment;
the catalyst comprises piperidine and potassium bromide.
As a further technical scheme, the mass ratio of the cyclohexanediol to the catalyst to the phase transfer catalyst in the S1 is 1 (0.05-0.1): 0.01.
As a further technical scheme, the mass ratio of the piperidine to the potassium bromide is 1 (0.1-0.25).
As a further technical scheme, the mass ratio of the piperidine to the potassium bromide is 1 (0.15-0.2).
As a further technical scheme, the phase transfer catalyst comprises one of benzyl triethyl ammonium chloride, tetrabutyl ammonium bromide and trioctylmethyl ammonium chloride.
As a further technical scheme, the mass ratio of the cyclohexanediol to the solvent in the S1 is 1 (4-5).
As a further technical scheme, the solvent comprises dichloromethane and glacial acetic acid.
As a further technical scheme, the mass ratio of the dichloromethane to the glacial acetic acid is 1 (0.2-0.3).
As a further technical scheme, the oxidant in S2 is sodium hypochlorite.
As a further technical scheme, the mass ratio of the oxidant to the cyclohexanediol is (7-8): 1.
As a further technical scheme, the temperature of the process of dropwise adding the oxidant in the S2 is 0-10 ℃ and the time is 5-7 h.
As a further technical scheme, after the oxidant is added dropwise in the step S2, stirring is continued for 1-2 h at the temperature of 0-10 ℃.
As a further technical scheme, the post-treatment in the step S3 is specifically that sodium sulfite-water solution is added until starch potassium iodide test paper does not change blue, extraction and washing are carried out, silica gel is added for pressure filtration, filter cake flushing is carried out, reduced pressure distillation is carried out, ethyl acetate and petroleum ether are added for heating to reflux, and then cooling, filtering and drying are carried out, so that cyclohexanedione is obtained.
As a further technical scheme, the mass-volume ratio of sodium sulfite of the sodium sulfite-water solution to water is 1kg:10L.
As a further embodiment, the washing is performed using an aqueous solution of sodium bicarbonate.
As a further technical scheme, the mass volume ratio of the cyclohexanediol to the aqueous solution of the sodium bicarbonate is 1kg (2-4) L.
As a further technical scheme, the mass ratio of the silica gel to the cyclohexanediol is 1 (10-20).
As a further technical solution, when the filter cake is washed, dichloromethane is used for washing.
As a further technical scheme, the mass volume ratio of the cyclohexanediol to the methylene dichloride is 1kg (0.2-0.6) L.
As a further technical scheme, the volume ratio of the ethyl acetate to the petroleum ether is 1:1.
As a further technical scheme, the mass volume ratio of the cyclohexanediol to the ethyl acetate is 1kg (1-3) L.
As a further technical scheme, the temperature of the reflux is 90-120 ℃ and the time is 30min.
As a further technical scheme, when the temperature is reduced, the temperature is reduced to 25-30 ℃ firstly and then reduced to-5 ℃.
The working principle and the beneficial effects of the invention are as follows:
according to the invention, cyclohexanediol is used as a raw material, and cyclohexanedione (1, 2-cyclohexanedione, 1, 3-cyclohexanedione and 1, 4-cyclohexanedione) corresponding to the cyclohexanedione can be generated by adjusting cyclohexanediol (1, 2-cyclohexanediol, 1, 3-cyclohexanediol and 1, 4-cyclohexanedione) in the raw material under the action of a catalyst, a phase transfer catalyst and an oxidant, and the synthesis process is simple.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by one of ordinary skill in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
S1, 150kg of 1, 2-cyclohexanediol, 400L of dichloromethane, 150kg of glacial acetic acid, 9kg of piperidine, 1.5kg of potassium bromide and 1.5kg of benzyl triethyl ammonium chloride are mixed and stirred, after the temperature is reduced to 5 ℃, 1143kg of sodium hypochlorite is added dropwise after 6 hours, and stirring is continued for 1.5 hours;
s2, adding 9% sodium sulfite-water solution into the solution obtained in the step S1 until the starch potassium iodide test paper does not change blue after detection, standing for 20min, and separating to obtain a first organic phase and a water phase;
s3, extracting the water phase with 400L of dichloromethane, stirring for 10min, standing for 30min, separating to obtain a second organic phase, and combining the second organic phase with the first organic phase to obtain an organic phase;
s4, adding 600L of water into the organic phase, stirring for 10min, standing for 10min, separating liquid, washing the organic phase with 400L of sodium bicarbonate aqueous solution, washing the organic phase with water to be neutral, adding 10kg of silica gel for filter pressing, washing a filter cake with 60L of dichloromethane, distilling the filter cake under reduced pressure, adding 300L of ethyl acetate and 300L of petroleum ether, refluxing at 90 ℃ for 30min, cooling to 30 ℃ firstly, cooling to-5 ℃, filtering, and drying the filter cake to obtain 117.6kg of solid with a yield of 81.4% and a purity (HPLC) of 98.5%.
Example 2
S1, 150kg of 1, 3-cyclohexanediol, 350L of dichloromethane, 140kg of glacial acetic acid, 6.5kg of piperidine, 1kg of potassium bromide and 1.5kg of tetrabutylammonium bromide are mixed and stirred, after the temperature is reduced to 0 ℃, 1050kg of sodium hypochlorite is added dropwise, after 5 hours are completed, stirring is continued for 1 hour;
s2, adding 9% sodium sulfite-water solution into the solution obtained in the step S1 until the starch potassium iodide test paper does not change blue after detection, standing for 20min, and separating to obtain a first organic phase and a water phase;
s3, extracting the water phase with 300L of dichloromethane, stirring for 10min, standing for 30min, separating to obtain a second organic phase, and combining the second organic phase with the first organic phase to obtain an organic phase;
s4, adding 300L of water into the organic phase, stirring for 10min, standing for 10min, separating liquid, washing the organic phase with 300L of sodium bicarbonate aqueous solution, washing to be neutral, adding 7.5kg of silica gel for filter pressing, washing a filter cake with 30L of dichloromethane, distilling the filter cake under reduced pressure, adding 150L of ethyl acetate and 150L of petroleum ether, refluxing at 100 ℃ for 30min, cooling to 25 ℃ firstly, cooling to-5 ℃, filtering, and drying the filter cake to obtain 117.2kg of solid with the yield of 81.1% and the purity (HPLC) of 98.4%.
Example 3
S1, 150kg of 1, 4-cyclohexanediol, 472L of methylene dichloride, 125kg of glacial acetic acid, 12.5kg of piperidine, 2.5kg of potassium bromide and 1.5kg of trioctyl methyl ammonium chloride are mixed and stirred, after the temperature is reduced to 10 ℃, 1200kg of sodium hypochlorite is added dropwise, after 7 hours, stirring is continued for 2 hours;
s2, adding 9% sodium sulfite-water solution into the solution obtained in the step S1 until the starch potassium iodide test paper does not change blue after detection, standing for 20min, and separating to obtain a first organic phase and a water phase;
s3, extracting the water phase with 600L of dichloromethane, stirring for 10min, standing for 30min, separating to obtain a second organic phase, and combining the second organic phase with the first organic phase to obtain an organic phase;
s4, adding 900L of water into the organic phase, stirring for 10min, standing for 10min, separating, washing the organic phase with 600L of sodium bicarbonate aqueous solution, washing to be neutral, adding 15kg of silica gel for filter pressing, washing a filter cake with 90L of dichloromethane, distilling the filter cake under reduced pressure, adding 450L of ethyl acetate and 450L of petroleum ether, refluxing at 120 ℃ for 30min, cooling to 30 ℃ firstly, cooling to-5 ℃, filtering, and drying the filter cake to obtain 117.5kg of solid with the yield of 81.3% and the purity (HPLC) of 98.2%.
Example 4
The difference from example 1 is only 9.5kg of piperidine and 1kg of potassium bromide in S1; 116.8kg of solid was obtained in 80.8% yield and 97.7% purity (HPLC).
Example 5
The difference from example 1 is only 8.4kg of piperidine and 2.1kg of potassium bromide in S1; 116.5kg of solid was obtained in 80.6% yield and 97.4% purity (HPLC).
Comparative example 1
The only difference from example 1 is the substitution of piperidine for equal amounts of potassium bromide; 114.9kg of solid was obtained in 79.5% yield with a purity (HPLC) of 96.8%.
Comparative example 2
The only difference from example 1 is that potassium bromide is replaced by an equivalent amount of piperidine; 115.2kg of solid was obtained in 79.7% yield and 97.1% purity (HPLC).
The method for synthesizing cyclohexanedione provided by the invention has few byproducts, and the obtained final product has high purity and high yield.
Example 4 differs from example 1 only in that 9.5kg of piperidine and 1kg of potassium bromide are present in S1, example 5 differs from example 1 only in that 8.4kg of piperidine and 2.1kg of potassium bromide are present in S1, and the yields and purities of cyclohexanone obtained in examples 4 to 5 are not the same as those of example 1, so that the yields and purities of the obtained products are the highest only when the mass ratio of piperidine to potassium bromide in the catalyst is 1 (0.15 to 0.2).
Comparative example 1 differs from example 1 only in that the catalyst is potassium bromide, and comparative example 2 differs from example 1 only in that the catalyst is piperidine, and the yields and purities of cyclohexanone obtained in comparative examples 1 to 2 are lower than those of example 1, so that the yields and purities of cyclohexanone obtained are optimal only when piperidine and potassium bromide are used as the composite catalyst.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (8)
1. A method of synthesizing cyclohexanedione comprising the steps of:
s1, mixing and stirring cyclohexanediol, a solvent, a catalyst and a phase transfer catalyst until the mixture is uniform;
s2, dropwise adding an oxidant to perform an oxidation reaction;
s3, after the reaction is finished, performing post-treatment;
the catalyst comprises piperidine and potassium bromide;
the mass ratio of the piperidine to the potassium bromide is 1 (0.15-0.2);
the solvent consists of dichloromethane and glacial acetic acid with the mass ratio of (0.2-0.3);
the phase transfer catalyst comprises one of benzyl triethyl ammonium chloride, tetrabutyl ammonium bromide and trioctyl methyl ammonium chloride;
the oxidant in the S2 is sodium hypochlorite.
2. The method for synthesizing cyclohexanedione according to claim 1, wherein the mass ratio of cyclohexanediol to the catalyst to the phase transfer catalyst in S1 is 1 (0.05 to 0.1): 0.01.
3. The method for synthesizing cyclohexanedione according to claim 1, wherein the mass ratio of cyclohexanediol to the solvent in S1 is 1 (4-5).
4. The method for synthesizing cyclohexanedione according to claim 1, wherein the mass ratio of the oxidizing agent to cyclohexanediol is (7-8): 1.
5. The method for synthesizing cyclohexanedione according to claim 1, wherein the temperature of the process of dropwise adding the oxidant in the step S2 is 0-10 ℃ for 5-7 hours.
6. The method for synthesizing cyclohexanedione according to claim 1, wherein after the oxidant is added dropwise in the step S2, stirring is continued for 1-2 hours at 0-10 ℃.
7. The method for synthesizing cyclohexanedione according to claim 1, wherein the post-treatment in S3 is specifically that sodium sulfite-water solution is added until starch potassium iodide test paper does not change blue, the mixture is extracted and washed, silica gel is added for press filtration, filter cake washing is performed, reduced pressure distillation is performed after filter cake washing, ethyl acetate and petroleum ether are added for heating to reflux, and then cooling, filtering and drying are performed to obtain cyclohexanedione.
8. The method for synthesizing cyclohexanedione according to claim 7, wherein the volume ratio of ethyl acetate to petroleum ether is 1:1.
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| CN101020627A (en) * | 2007-01-22 | 2007-08-22 | 河北大学 | Process of synthesizing 1,4-cyclohexyl dione |
| CN113956140A (en) * | 2021-11-16 | 2022-01-21 | 八叶草健康产业研究院(厦门)有限公司 | Preparation method of 1, 2-cyclohexanedione |
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| CN101020627A (en) * | 2007-01-22 | 2007-08-22 | 河北大学 | Process of synthesizing 1,4-cyclohexyl dione |
| CN113956140A (en) * | 2021-11-16 | 2022-01-21 | 八叶草健康产业研究院(厦门)有限公司 | Preparation method of 1, 2-cyclohexanedione |
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| 合成盐酸普拉克索的工艺改进;张昭;朱小华;陈国华;;化工时刊(05);29-31 * |
| 抗高血压药物阿利克仑的合成研究;叶赛赛;张拥军;张兴贤;;中国药物化学杂志(05);386-390 * |
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