CN116178119B - Method for preparing alpha-isophorone by taking 3, 5-trimethyl-2-cyclohexene-1-subunit acetone as raw material - Google Patents
Method for preparing alpha-isophorone by taking 3, 5-trimethyl-2-cyclohexene-1-subunit acetone as raw material Download PDFInfo
- Publication number
- CN116178119B CN116178119B CN202211471929.3A CN202211471929A CN116178119B CN 116178119 B CN116178119 B CN 116178119B CN 202211471929 A CN202211471929 A CN 202211471929A CN 116178119 B CN116178119 B CN 116178119B
- Authority
- CN
- China
- Prior art keywords
- raw material
- isophorone
- reaction
- water
- trimethyl
- 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
Links
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 title claims abstract description 73
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000002994 raw material Substances 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 8
- 230000007935 neutral effect Effects 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- -1 hydroxyl-thioamine hydrochloride Chemical compound 0.000 claims description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- ORECNKBJIMKZNX-UHFFFAOYSA-N 1,3-thiazol-3-ium;chloride Chemical compound Cl.C1=CSC=N1 ORECNKBJIMKZNX-UHFFFAOYSA-N 0.000 claims description 4
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- JDIIGWSSTNUWGK-UHFFFAOYSA-N 1h-imidazol-3-ium;chloride Chemical compound [Cl-].[NH2+]1C=CN=C1 JDIIGWSSTNUWGK-UHFFFAOYSA-N 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000000047 product Substances 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 2
- 239000002440 industrial waste Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 238000009833 condensation Methods 0.000 description 10
- 230000005494 condensation Effects 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000012043 crude product Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- DPJRMOMPQZCRJU-UHFFFAOYSA-M thiamine hydrochloride Chemical compound Cl.[Cl-].CC1=C(CCO)SC=[N+]1CC1=CN=C(C)N=C1N DPJRMOMPQZCRJU-UHFFFAOYSA-M 0.000 description 2
- 229960000344 thiamine hydrochloride Drugs 0.000 description 2
- 235000019190 thiamine hydrochloride Nutrition 0.000 description 2
- 239000011747 thiamine hydrochloride Substances 0.000 description 2
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 1
- OZXIZRZFGJZWBF-UHFFFAOYSA-N 1,3,5-trimethyl-2-(2,4,6-trimethylphenoxy)benzene Chemical compound CC1=CC(C)=CC(C)=C1OC1=C(C)C=C(C)C=C1C OZXIZRZFGJZWBF-UHFFFAOYSA-N 0.000 description 1
- DGBNUTJYQXQLSV-UHFFFAOYSA-N 1h-triazol-1-ium;chloride Chemical compound Cl.C1=CNN=N1 DGBNUTJYQXQLSV-UHFFFAOYSA-N 0.000 description 1
- GBURUDXSBYGPBL-UHFFFAOYSA-N 2,2,3-trimethylhexanedioic acid Chemical compound OC(=O)C(C)(C)C(C)CCC(O)=O GBURUDXSBYGPBL-UHFFFAOYSA-N 0.000 description 1
- 241000723346 Cinnamomum camphora Species 0.000 description 1
- PBCJIPOGFJYBJE-UHFFFAOYSA-N acetonitrile;hydrate Chemical compound O.CC#N PBCJIPOGFJYBJE-UHFFFAOYSA-N 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229960000846 camphor Drugs 0.000 description 1
- 229930008380 camphor Natural products 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- SHOJXDKTYKFBRD-UHFFFAOYSA-N mesityl oxide Natural products CC(C)=CC(C)=O SHOJXDKTYKFBRD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000011527 polyurethane coating Substances 0.000 description 1
- XTUSEBKMEQERQV-UHFFFAOYSA-N propan-2-ol;hydrate Chemical compound O.CC(C)O XTUSEBKMEQERQV-UHFFFAOYSA-N 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000000126 substance 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
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing alpha-isophorone by taking 3, 5-trimethyl-2-cyclohexene-1-subunit acetone as a raw material, which comprises the following specific processes: the raw material 3, 5-trimethyl-2-cyclohexene-1-subunit acetone is dissolved in a solvent, the temperature is raised for reaction under the action of an alkaline catalyst and an auxiliary agent, when the GC content of the raw material is lower than 5%, the reaction is stopped, after the reaction is finished, the material is washed to be neutral, and the alpha-isophorone finished product is obtained by rectification. Compared with a pressure rectifying tower, the reaction has low equipment requirement and low equipment cost. The invention has high conversion rate and good selectivity, the isophorone selectivity can reach 96%, and the isophorone is easy to separate after reaction, and can be directly rectified to obtain the alpha-isophorone with the content of 99%. The byproduct acetone obtained by the method can be used as a raw material for continuous use, so that the production cost is reduced, the generation of three industrial wastes is reduced, the economic benefit is effectively improved, and the method has strong economic advantages.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, relates to synthesis of an organic raw material of alpha-isophorone, and in particular relates to a method for preparing alpha-isophorone by taking 3, 5-trimethyl-2-cyclohexene-1-subunit acetone as a raw material.
Background
Alpha-isophorone is colorless or pale yellow liquid, has camphor smell, has higher boiling point, strong dissolving capacity, good dispersibility and stratoscopicity, is an excellent solvent for high polymer materials, and can dissolve acrylic ester, polyester, epoxy resin and the like. Meanwhile, the alpha-isophorone can also be used as a raw material to prepare trimethyl adipic acid, is an important intermediate for synthesizing novel plasticizers, lubricants and the like, can be used for preparing isocyanate through addition, hydrogenation and phosgenation, and is also an important isocyanate raw material in polyurethane coating. Therefore, the industrial production of isophorone has important application and economic value.
The prior method for synthesizing the alpha-isophorone mainly comprises two methods, namely a liquid phase condensation method and a weather condensation method. The liquid phase condensation method means that acetone is carried out under the liquid state condition below a critical point in the reaction, for example, patent CN101050168A adopts preheated acetone, and then the acetone is introduced into a solid sodium alkoxide or strong alkali fixed bed reactor, so that the acetone conversion rate is 16% -40%, and the selectivity of alpha-isophorone is 42.2% -70%. The gas phase condensation method refers to the reaction of acetone in a gaseous state, which usually adopts alkali or solid acid as a catalyst, and the reaction has high temperature requirements. For example, in the patent of US5153156, US4970191 and US5202496, a magnesium-aluminum compound or an organic anion modified magnesium-aluminum compound is used as a catalyst, the reaction temperature is 300-350 ℃, the selectivity of isophorone can reach 70-71.5%, and the total selectivity of mesityl oxide and alpha-isophorone reaches 90%. In both methods, side reactions which cause excessive condensation of acetone often occur, and the generated 3, 5-trimethyl-2-cyclohexene-1-subunit acetone affects the reaction yield, increases the kettle liquid rate of the reaction, and brings about more economic loss. Therefore, the reverse condensation reaction of the acetone-based condensate is also becoming an important point of research for each company.
In recent years, the report of the formation of a-isophorone by reverse condensation of a product of acetone excessive condensation has been increasing. For example: in US 3337423a it is reported that acetone excessive condensate is hydrolyzed in an alkaline aqueous solution at 120-300 ℃ by means of a pressure distillation column; CN 101633610a reports that the polymer over-reacted with acetone is hydrolyzed by a pressure hydrolysis tower under alkaline sodium hydroxide or potassium hydroxide; CN 102367223a discloses that acetone condensed polymer is reacted by passing through a rectifying tower in an alkaline aqueous solution of sodium hydroxide or potassium hydroxide at 190-245 ℃ for 10-120 minutes of liquid phase residence time. CN 110903180a discloses that the polymer high boiling point substance which is excessively reacted enters a hydrolysis tower through a delivery pump and a homogenizer to react under the condition of alkaline sodium hydroxide or potassium hydroxide, so as to obtain isophorone; as can be seen from the above patent, the prior art discloses that the pressure rectifying tower is used for carrying out reverse condensation on the acetone excessive condensate, so that the requirements on reaction equipment are higher, and the operation conditions are more severe; meanwhile, the reaction is heterogeneous reaction, the conversion rate of products of acetone excessive condensation and the selectivity of isophorone are generally low, and the liquid amount of the reaction kettle is large. There is therefore still a need for a more selective and economical process for effecting the reverse condensation of acetone microcondensates to isophorone.
Disclosure of Invention
In view of the shortcomings of the prior art, the invention aims to provide a method for preparing alpha-isophorone, which is used for successfully synthesizing the alpha-isophorone with high selectivity by 3, 5-trimethyl-2-cyclohexene-1-subunit acetone through screening a solvent, a base catalyst, a heterocyclic salt auxiliary agent and temperature.
The invention is realized by the following technical scheme:
the method for preparing the alpha-isophorone by taking 3, 5-trimethyl-2-cyclohexene-1-subunit acetone as a raw material comprises the following steps:
The raw material 3, 5-trimethyl-2-cyclohexene-1-subunit acetone is dissolved in a solvent, the temperature is raised for reaction under the action of an alkaline catalyst and an auxiliary agent, when the GC content of the raw material is lower than 5%, the reaction is stopped, after the reaction is finished, the material is washed to be neutral, and the alpha-isophorone finished product is obtained by rectification.
The reaction equation is shown below:
the invention further improves the mode as follows:
the alkaline catalyst is inorganic alkali or organic alkali.
Further, the alkaline catalyst is one or more than two of potassium hydroxide, calcium hydroxide, sodium hydroxide, barium hydroxide, lithium hydroxide, cesium carbonate, sodium carbonate, potassium carbonate, DBU, TMEDA, triethylamine, potassium tert-butoxide, ethylenediamine or ammonia water.
Preferably, the basic catalyst is one or more of DBU, TMEDA or triethylamine.
Further, the auxiliary agent is heterocyclic salt auxiliary agent,
Further, the auxiliary agent is one or more than two of pyridine hydrochloride, thiazole hydrochloride, imidazole hydrochloride, triazole hydrochloride, hydroxyl-thioamine hydrochloride, thiamine hydrochloride, 3, 4-dimethyl-1, 3-thiazole-3-iodide, 2,3, 4-trimethyl-1, 3-thiazole-3-iodide, 3, 4-dimethyl (2-ethyl alcohol) -1, 3-thiazole-3-iodide or 3, 4-dimethyl (2-ethyl alcohol) -1, 3-thiazole-3-bromide.
Preferably, the auxiliary agent is one or more than two of thiazole hydrochloride, imidazole hydrochloride or hydroxyl-thioamine hydrochloride.
Further, the solvent is one or more than two of methanol/water, ethanol/water, propanol/water, isopropanol/water, n-butanol/water, acetonitrile/water, DMF/water or NMP/water mixed solvent.
Further, the dosage of the alkali catalyst is 0.01% -1% of the mass of the raw material; the consumption of the auxiliary agent is 0.01% -1% of the mass of the raw material; the dosage of the solvent is 0.05-10 times of the mass of the raw materials, and the ratio of the alcohol to the water in the solvent is 1% -100%.
Further, the reaction temperature is 120-250 ℃ and the reaction time is 2-12 hours
Compared with the prior art, the invention has the beneficial effects that:
(1) Compared with a pressure rectifying tower, the reaction has low equipment requirement and low equipment cost.
(2) The invention has high conversion rate and good selectivity, the isophorone selectivity can reach 96%, and the isophorone is easy to separate after reaction, and can be directly rectified to obtain the alpha-isophorone with the content of 99%.
(3) The byproduct acetone obtained by the method can be used as a raw material for continuous use, so that the production cost is reduced, the generation of three industrial wastes is reduced, the economic benefit is effectively improved, and the method has strong economic advantages.
Detailed Description
The present invention will be described in detail with reference to specific examples.
Example 1
500G of raw materials are added into a reaction kettle, 3g of 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU) and 3g of thiazole hydrochloride are added, then 200g of isopropanol water solution is added, the weight ratio of isopropanol to water is 1:5, stirring is started, then the temperature is raised to 220 ℃, stirring is carried out for 4 hours, the raw materials react until the GC content of the raw materials is less than 5%, and the reaction is stopped. After the reaction, the materials are washed by a 1% sulfuric acid solution until the water phase is neutral. Then the washed crude product is rectified, the content of alpha-isophorone is 335.1g, the GC content is 99.1%, and the yield is 91%.
Example 2
500G of raw materials are added into a reaction kettle, 5g of triethylamine and 1g of pyridine hydrochloride are added, then 200g of methanol aqueous solution is added, the weight ratio of methanol to water is 1:10, stirring is started, then the temperature is raised to 190 ℃, stirring is performed for 6 hours, the raw materials react until the GC content of the raw materials is less than 5%, and the reaction is stopped. After the reaction, the material was washed with a 0.5% sulfuric acid solution until the aqueous phase was neutral. Then the washed crude product is rectified to obtain 327.7g of alpha-isophorone with GC content of 97.8 percent and yield of 89 percent.
Example 3
500G of raw materials are added into a reaction kettle, 1g of potassium tert-butoxide and 0.05g of 3, 4-dimethyl (2-ethyl alcohol) -1, 3-thiazole-3-iodide are added, then 150g of acetonitrile water solution is added, the weight ratio of acetonitrile to water is 1:20, stirring is started, then the temperature is raised to 180 ℃, stirring is carried out for 5 hours, the raw materials react until the GC content of the raw materials is less than 5%, and the reaction is stopped. After the reaction, the materials are washed by a 1% sulfuric acid solution until the water phase is neutral. Then the washed crude product is rectified to obtain 320.3g of alpha-isophorone with GC content of 97 percent and yield of 87 percent.
Example 4
500G of raw materials are added into a reaction kettle, 0.1g of lithium hydroxide and 0.3g of thiamine hydrochloride are added, then 250g of acetone aqueous solution is added, the weight ratio of acetone to water is 1:8, stirring is started, then the temperature is raised to 210 ℃, stirring is carried out for 5 hours, the reaction is stopped until the GC content of the raw materials is less than 5%. After the reaction, the materials are washed by a 1% sulfuric acid solution until the water phase is neutral. The washed crude product is then rectified to obtain 316.7g of alpha-isophorone with GC content of 98.5% and yield of 86%.
Example 5
500G of raw materials are added into a reaction kettle, 0.2g of potassium carbonate and 0.1g of 3, 4-dimethyl (2-ethyl alcohol) -1, 3-thiazole-3-bromide are added, then 250g of ethanol aqueous solution is added, the weight ratio of ethanol to water is 1:8, stirring is started, then the temperature is raised to 180 ℃, stirring is carried out for 5 hours, the raw materials react until the GC content of the raw materials is less than 5%, and the reaction is stopped. After the reaction, the materials are washed by a 1% sulfuric acid solution until the water phase is neutral. The washed crude product is then rectified to obtain 353.7g of alpha-isophorone with GC content of 99.4% and yield of 96%.
The foregoing embodiments are merely illustrative of the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the present invention and to implement the same, not to limit the scope of the present invention. All equivalent changes or modifications made according to the spirit of the present invention should be included in the scope of the present invention.
Claims (4)
1. The method for preparing the alpha-isophorone by taking 3, 5-trimethyl-2-cyclohexene-1-subunit acetone as a raw material is characterized by comprising the following steps:
Dissolving raw material 3, 5-trimethyl-2-cyclohexene-1-subunit acetone in a solvent, heating to react under the action of an alkaline catalyst and an auxiliary agent, stopping the reaction when the GC content of the raw material is lower than 5%, washing the material to be neutral after the reaction is finished, and rectifying to obtain an alpha-isophorone finished product;
the reaction equation is shown below:
；
the solvent is one or more than two of methanol/water, ethanol/water, propanol/water, isopropanol/water, n-butanol/water, acetonitrile/water, DMF/water or NMP/water mixed solvents;
The alkaline catalyst is one or more than two of potassium hydroxide, calcium hydroxide, sodium hydroxide, barium hydroxide, lithium hydroxide, cesium carbonate, sodium carbonate, potassium carbonate, DBU, TMEDA, triethylamine, potassium tert-butoxide, ethylenediamine or ammonia water;
The auxiliary agent is one or more than two of thiazole hydrochloride, imidazole hydrochloride or hydroxyl-thioamine hydrochloride;
the reaction temperature is 120-250 ℃.
2. The method for preparing alpha-isophorone by using 3, 5-trimethyl-2-cyclohexene-1-subunit acetone as raw material according to claim 1, wherein the method comprises the following steps: the alkaline catalyst is one or more of DBU, TMEDA or triethylamine.
3. The method for preparing alpha-isophorone by using 3, 5-trimethyl-2-cyclohexene-1-subunit acetone as raw material according to claim 1, wherein the method comprises the following steps: the consumption of the alkali catalyst is 0.01% -1% of the mass of the raw material; the consumption of the auxiliary agent is 0.01% -1% of the mass of the raw material; the solvent dosage is 0.05-10 times of the raw material mass.
4. The method for preparing alpha-isophorone by using 3, 5-trimethyl-2-cyclohexene-1-subunit acetone as raw material according to claim 1, wherein the method comprises the following steps: the reaction time is 2-12 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211471929.3A CN116178119B (en) | 2022-11-23 | 2022-11-23 | Method for preparing alpha-isophorone by taking 3, 5-trimethyl-2-cyclohexene-1-subunit acetone as raw material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211471929.3A CN116178119B (en) | 2022-11-23 | 2022-11-23 | Method for preparing alpha-isophorone by taking 3, 5-trimethyl-2-cyclohexene-1-subunit acetone as raw material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116178119A CN116178119A (en) | 2023-05-30 |
| CN116178119B true CN116178119B (en) | 2024-07-02 |
Family
ID=86431476
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211471929.3A Active CN116178119B (en) | 2022-11-23 | 2022-11-23 | Method for preparing alpha-isophorone by taking 3, 5-trimethyl-2-cyclohexene-1-subunit acetone as raw material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116178119B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4617419A (en) * | 1985-09-26 | 1986-10-14 | International Flavors & Fragrances Inc. | Process for preparing natural benzaldehyde and acetaldehyde, natural benzaldehyde and acetaldehyde compositions, products produced thereby and organoleptic utilities therefor |
| US4709098A (en) * | 1987-02-04 | 1987-11-24 | Mallinckrodt, Inc. | Hydrolysis of activated olefinic ketones and aldehydes |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106892807B (en) * | 2016-11-15 | 2019-05-03 | 广东莱佛士制药技术有限公司 | A kind of preparation method of the isophorone using organic imidazoles system quaternary ammonium strong base catalyst |
-
2022
- 2022-11-23 CN CN202211471929.3A patent/CN116178119B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4617419A (en) * | 1985-09-26 | 1986-10-14 | International Flavors & Fragrances Inc. | Process for preparing natural benzaldehyde and acetaldehyde, natural benzaldehyde and acetaldehyde compositions, products produced thereby and organoleptic utilities therefor |
| US4709098A (en) * | 1987-02-04 | 1987-11-24 | Mallinckrodt, Inc. | Hydrolysis of activated olefinic ketones and aldehydes |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116178119A (en) | 2023-05-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100478338C (en) | Process for preparing annular carbonate | |
| CN111423326B (en) | Method for preparing dimethyl carbonate by alkaline ionic liquid catalysis one-step method | |
| CN110078684B (en) | Method for continuously synthesizing epichlorohydrin by using microchannel reactor | |
| CN107311868B (en) | Method for preparing p-tert-butyl methyl benzoate | |
| JPH0446133A (en) | Production of cyclohexane-1,2-diol | |
| CN102010293A (en) | Method for catalyzing and synthesizing 1, 2-pentanediol by using titanium silicalite | |
| CN116178119B (en) | Method for preparing alpha-isophorone by taking 3, 5-trimethyl-2-cyclohexene-1-subunit acetone as raw material | |
| CN102417445B (en) | Method for synthesizing succinic acid from maleic acid | |
| CN111646921A (en) | Catalyst regeneration method for preparing hexamethylene diamine key intermediate 6-aminocapronitrile by caprolactam method | |
| CN111574378B (en) | Method for efficiently synthesizing dihydroxy ethyl terephthalate without catalysis | |
| CN111808054A (en) | Preparation method of ionic liquid and application of ionic liquid in cyclohexanone synthesis | |
| CN110256397B (en) | Method for extracting biuret in process of preparing cyclic carbonate by reacting urea with polyhydric alcohol | |
| CN109305912B (en) | Method for preparing 2,2, 4-trimethyl-1, 3-pentanediol monoisobutyrate by condensing isobutyraldehyde | |
| CN114014765B (en) | Method and catalyst for preparing 1-amino-2-propanol | |
| CN110903180B (en) | Preparation method and device of isophorone | |
| CN112279781B (en) | Synthetic method of p-hydroxybenzonitrile | |
| CN111187146B (en) | Process for producing 2-methyl-3-buten-2-ol | |
| CN108558639B (en) | Preparation method of calcium formate | |
| KR100921944B1 (en) | Process for preparing of epichlorohydrine | |
| CN110105183A (en) | Acetone through one-step method synthesis MIBK device stop in emergency method and acetone synthesis MIBK method | |
| US11578034B2 (en) | Integrated process for production of glycerol carbonate (4-hydroxymethyl-2-oxo-1, 3-dioxolane) and urea | |
| CN112028805A (en) | Method for continuously producing tert-butyl hydroperoxide | |
| CN108503530B (en) | Process for preparing isooctanoic acid | |
| CN111440140A (en) | Green process for synthesizing 2-acetylthiophene | |
| CN103420800A (en) | Method for preparing dichloropropanol by catalyzing chlorination of glycerol through ionic liquids |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant |