CN117924056A - Synthesis method of conjugated diketone compound - Google Patents
Synthesis method of conjugated diketone compound Download PDFInfo
- Publication number
- CN117924056A CN117924056A CN202410337895.1A CN202410337895A CN117924056A CN 117924056 A CN117924056 A CN 117924056A CN 202410337895 A CN202410337895 A CN 202410337895A CN 117924056 A CN117924056 A CN 117924056A
- Authority
- CN
- China
- Prior art keywords
- reaction
- synthesizing
- compound
- diketone compound
- conjugated diketone
- 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.)
- Granted
Links
- -1 diketone compound Chemical class 0.000 title claims abstract description 61
- 238000001308 synthesis method Methods 0.000 title claims description 5
- 238000000034 method Methods 0.000 claims abstract description 49
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 230000035484 reaction time Effects 0.000 claims abstract description 23
- 239000002904 solvent Substances 0.000 claims abstract description 19
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 9
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 9
- 238000000605 extraction Methods 0.000 claims abstract description 5
- 238000006482 condensation reaction Methods 0.000 claims abstract description 4
- XLSMFKSTNGKWQX-UHFFFAOYSA-N hydroxyacetone Chemical compound CC(=O)CO XLSMFKSTNGKWQX-UHFFFAOYSA-N 0.000 claims description 20
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 11
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000008096 xylene Substances 0.000 claims description 11
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 10
- GFAZHVHNLUBROE-UHFFFAOYSA-N 1-hydroxybutan-2-one Chemical compound CCC(=O)CO GFAZHVHNLUBROE-UHFFFAOYSA-N 0.000 claims description 8
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 claims description 8
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 claims description 8
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N pentanal Chemical compound CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 claims description 8
- 150000004696 coordination complex Chemical class 0.000 claims description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims description 5
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 239000003446 ligand Substances 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 9
- 238000003786 synthesis reaction Methods 0.000 abstract description 9
- 125000005594 diketone group Chemical group 0.000 abstract description 8
- 238000007086 side reaction Methods 0.000 abstract description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 abstract description 4
- 238000009833 condensation Methods 0.000 abstract description 4
- 230000005494 condensation Effects 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract 1
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 description 76
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 24
- 239000002262 Schiff base Substances 0.000 description 17
- 150000004753 Schiff bases Chemical class 0.000 description 14
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 13
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 12
- 229910052759 nickel Inorganic materials 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000003921 oil Substances 0.000 description 10
- FJPGAMCQJNLTJC-UHFFFAOYSA-N 2,3-Heptanedione Chemical compound CCCCC(=O)C(C)=O FJPGAMCQJNLTJC-UHFFFAOYSA-N 0.000 description 8
- KVFQMAZOBTXCAZ-UHFFFAOYSA-N 3,4-Hexanedione Chemical compound CCC(=O)C(=O)CC KVFQMAZOBTXCAZ-UHFFFAOYSA-N 0.000 description 8
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical compound CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 description 8
- MWVFCEVNXHTDNF-UHFFFAOYSA-N hexane-2,3-dione Chemical compound CCCC(=O)C(C)=O MWVFCEVNXHTDNF-UHFFFAOYSA-N 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000006071 cream Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- XCBBNTFYSLADTO-UHFFFAOYSA-N 2,3-Octanedione Chemical compound CCCCCC(=O)C(C)=O XCBBNTFYSLADTO-UHFFFAOYSA-N 0.000 description 6
- PQCLJXVUAWLNSV-UHFFFAOYSA-N 5-Methyl-2,3-hexanedione Chemical compound CC(C)CC(=O)C(C)=O PQCLJXVUAWLNSV-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 238000009835 boiling Methods 0.000 description 4
- 235000014121 butter Nutrition 0.000 description 4
- 235000009508 confectionery Nutrition 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- 239000003205 fragrance Substances 0.000 description 4
- 235000013336 milk Nutrition 0.000 description 4
- 239000008267 milk Substances 0.000 description 4
- 210000004080 milk Anatomy 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 235000013351 cheese Nutrition 0.000 description 3
- 239000000796 flavoring agent Substances 0.000 description 3
- 235000019634 flavors Nutrition 0.000 description 3
- SQYNKIJPMDEDEG-UHFFFAOYSA-N paraldehyde Chemical compound CC1OC(C)OC(C)O1 SQYNKIJPMDEDEG-UHFFFAOYSA-N 0.000 description 3
- 229960003868 paraldehyde Drugs 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- MIDXCONKKJTLDX-UHFFFAOYSA-N 3,5-dimethylcyclopentane-1,2-dione Chemical compound CC1CC(C)C(=O)C1=O MIDXCONKKJTLDX-UHFFFAOYSA-N 0.000 description 2
- 244000025352 Artocarpus heterophyllus Species 0.000 description 2
- 235000008725 Artocarpus heterophyllus Nutrition 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- 235000013736 caramel Nutrition 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 235000013599 spices Nutrition 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 244000099147 Ananas comosus Species 0.000 description 1
- 235000007119 Ananas comosus Nutrition 0.000 description 1
- 240000008790 Musa x paradisiaca Species 0.000 description 1
- 235000018290 Musa x paradisiaca Nutrition 0.000 description 1
- 244000183278 Nephelium litchi Species 0.000 description 1
- 244000061176 Nicotiana tabacum Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 235000019219 chocolate Nutrition 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 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 application discloses a method for synthesizing conjugated diketone compounds, which belongs to the technical field of organic chemical industry, and adopts inorganic acid as a catalyst and a low-polarity solvent, and adds aldehyde compounds and hydroxy ketone compounds to carry out condensation reaction under the action of an auxiliary agent; after the reaction is finished, the system is divided into two layers of water and oil by extraction, and the oil phase is rectified to obtain the conjugated diketone compound, so that the method shortens the reaction time, avoids side reactions such as condensation and the like of products, realizes the efficient synthesis of the conjugated diketone compound, reduces the energy consumption cost of recycling solvents, and has high product purity and high yield; and the reaction condition is mild, the reaction time is short, the cost is low, and the method is suitable for industrial production.
Description
Technical Field
The application belongs to the technical field of organic chemical industry, and particularly relates to a method for synthesizing conjugated diketone compounds.
Background
Conjugated diketone compounds such as 2, 3-butanedione, 2, 3-pentanedione, 2, 3-hexanedione, 3, 4-hexanedione, 2, 3-heptanedione and the like have milk fragrance, are milk fragrance type perfumes, and are widely applied to the fields of foods, daily chemicals and the like.
2, 3-Butanedione, pale yellow to yellowish green liquid, melting point-4 to-2 ℃, boiling point 88 ℃, is dissolved in water, ethanol and diethyl ether, has strong spike smell and pleasant cream fragrance after dilution, is mainly used for preparing cream essence, is a main raw material for producing pyrazine spices, and the 2, 3-butanedione can be formed by condensing hydroxyacetone and paraformaldehyde.
2, 3-Pentanedione, yellow green oily liquid, melting point-52 ℃, boiling point 108 ℃, slightly sweet, slightly water-soluble, ethanol-soluble and other organic solvents, has intense milk flavor, is a milk flavor spice, can be used as a food additive, is mainly used for preparing chocolate and cream type essence, can also be used as daily chemical essence, such as soap essence, detergent essence, perfume essence and the like, is also an important intermediate for synthesizing medicines, preservatives, bactericides and the like, and has very wide application range, and the 2, 3-pentanedione can be condensed by adopting hydroxyacetone and paraldehyde as raw materials.
2, 3-Hexanedione, yellow oily liquid with a boiling point of 128 ℃, slightly soluble in water, soluble in organic solvents such as ethanol, and the like, and has sweet cream, caramel and fruit smell; can be used for preparing edible essence such as cheese, butter, caramel, jackfruit, litchi, etc., and the 2, 3-hexanedione can be prepared by condensing hydroxyacetone and propionaldehyde serving as raw materials.
3, 4-Hexanedione, a yellow oily liquid, is practically insoluble in water, in ethanol and oils, is very soluble in propylene glycol, and is creamy in fragrance with slightly unpleasant, irritating odor; the 3, 4-hexanedione can be prepared by condensing 1-hydroxy-2-butanone and acetaldehyde.
5-Methyl-2, 3-hexanedione, light yellow liquid, slightly water-soluble and ethanol-soluble organic solvent. It has the flavor of spiked butter and fruit, and has sweet butter and pineapple taste after dilution. Can be used for preparing edible essence such as jackfruit, banana, butter, cheese, etc. The 5-methyl-2, 3-hexanedione can be prepared by condensing hydroxy acetone and isobutyraldehyde.
2, 3-Heptanedione, a yellowish liquid, slightly soluble in water and ethanol, and is mainly used for essence such as cream, cheese, nutlet, rum and the like; the 2, 3-heptanedione can be prepared by condensing hydroxyacetone and n-butyraldehyde serving as raw materials.
2, 3-Octanedione, yellow oily liquid, slightly water-soluble, dissolve in organic solvent such as ethanol, it has sweet cream aroma, can be used for preparing edible essence and tobacco essence such as coffee, white hair, cream, etc.; the 2, 3-octanedione can be prepared by condensing hydroxyacetone and n-valeraldehyde serving as raw materials.
Patent US2799707a uses hydroxyacetone and paraldehyde as raw materials, and adopts a reaction rectification mode under the catalysis of inorganic acid (HCl, HBr and H 2SO4, preferably HCl) to obtain 2, 3-pentanedione, wherein the reaction time is about 60H, the yield is 48%, and the reaction time in the process route is still long and the yield is low.
In the presence of aqueous solution containing strong organic or inorganic acid with pKa value less than or equal to 4 and phase transfer catalyst, the patent EP1310476A1 takes hydroxy acetone and paraldehyde as raw materials to react at 35-100 ℃ for 7 h, the mixture of 2, 3-pentanedione and water is distilled out at normal pressure, and then the 2, 3-pentanedione with purity of 85-95% is obtained by separation, the yield can reach 85%, the reaction time of the method is still longer, and the purity of the obtained product is lower.
In the prior art, regarding the synthesis process of the conjugated diketone compound, some of the synthesis processes have low yield, some of the synthesis processes have long reaction time, some of the synthesis processes have high energy consumption and some of the synthesis processes have low product purity, and the synthesis method of the conjugated diketone compound has high yield, short reaction time, low cost and high product purity.
Disclosure of Invention
The application provides a method for synthesizing conjugated diketone compounds, which solves the problems of low yield, long reaction time and low product purity in the synthesis process of conjugated diketone compounds.
The embodiment of the application provides a method for synthesizing conjugated diketone compounds, which specifically comprises the following steps:
(1): inorganic acid is used as a catalyst, a low-polarity solvent is adopted, a hydroxy ketone compound and an aldehyde compound are added under the action of an auxiliary agent, and the condensation reaction is carried out by controlling the reaction temperature and the reaction time to obtain a reaction liquid;
(2): after the reaction is finished, the reaction liquid in the step (1) is divided into two layers of water and oil by extraction, and the conjugated diketone compound is obtained by rectifying the oil phase.
Preferably, the hydroxy ketone compound is one of hydroxy acetone and 1-hydroxy-2-butanone, the aldehyde compound is one of formaldehyde, acetaldehyde, propionaldehyde, isobutyraldehyde, n-butyraldehyde or n-valeraldehyde, the structural general formula of the hydroxy ketone compound is formula (I), the structural general formula of the aldehyde compound is formula (II), and the structural general formula of the conjugated diketone compound is formula (III);
wherein R 1、R2 is one of hydrogen group and hydrocarbon group respectively.
Preferably, the inorganic acid is an inorganic weak acid, and the inorganic weak acid is one of silicic acid, carbonic acid, sulfurous acid or phosphoric acid.
Preferably, the auxiliary agent is a water-soluble metal complex, the water-soluble metal complex comprises metal ions and a ligand, the metal ions M are Fe, co, ni, cu or one of Zn, the ligand is a water-soluble Schiff base, and the structural formula of the water-soluble metal complex is as follows:
preferably, the low polarity solvent is one of n-octane, xylene or ethylene glycol diethyl ether.
Preferably, the molar ratio of the aldehyde compound to the hydroxy ketone compound is 0.95-1.05:1, especially 1.0:1.
Preferably, the mass ratio of the catalyst to the hydroxyketone compound is 1.0-5.0% to 1, especially 2.0% to 1.
Preferably, the mass ratio of the auxiliary agent to the hydroxyketone compound is 0.01-0.05% to 1, especially 0.03% to 1.
Preferably, the mass ratio of the low-polarity solvent to the hydroxyketone compound is 1.0-3.0:1, especially 2.0:1.
Preferably, the reaction temperature is 10-30 ℃, especially 20 ℃, and the reaction time is 1-4 h, especially 2-h.
According to the application, by designing the synthesis method of the conjugated diketone compound, the reaction time is shortened, and side reactions such as condensation and the like of products are avoided, so that the efficient synthesis of the conjugated diketone compound is realized, and the energy consumption cost of recovering the solvent is reduced; and the reaction condition is mild, the product purity is high, the cost is low, the universality is high, and the method is suitable for industrial production.
Detailed Description
The invention is further described below with reference to examples. The present invention is not limited to the following examples. The implementation conditions adopted in the embodiments can be further adjusted according to different requirements of specific use, and the implementation conditions which are not noted are conventional conditions in the industry. The technical features of the various embodiments of the present invention may be combined with each other as long as they do not collide with each other.
Example 1
148 G of 4-hydroxyacetone, 220 g mass fraction of 40% aqueous acetaldehyde solution (the molar ratio of 40% aqueous acetaldehyde solution to 4-hydroxyacetone is 1:1), 2.96 g sulfurous acid (the mass ratio of sulfurous acid to 4-hydroxyacetone is 2.0:1), 0.044 g water-soluble Schiff base nickel complex (the mass ratio of water-soluble Schiff base nickel complex to 4-hydroxyacetone is 0.03:1), 296 g xylene (the mass ratio of xylene to 4-hydroxyacetone is 2.0:1) are added into a 1L autoclave with a magnetic stirring and temperature controller, the reaction is carried out at a temperature of 20 ℃ under 500: 500 rpm stirring conditions, after the reaction of 2: 2h is finished, the reaction liquid is extruded, the system is separated into two layers of water and oil, and the oil phase is rectified to obtain the product 2, 3-pentanedione 186.3 g with a purity of 99.5 percent and a yield of 92.7 percent.
Example 2
The procedure of this example was repeated except that xylene was changed to n-octane and the remaining operations were the same, to obtain 2, 3-pentanedione having a purity of 99.5% and a yield of 92.2%.
Example 3
The difference between the method and example 2 is that the water-soluble Schiff base nickel complex is changed into the water-soluble Schiff base iron complex, the n-octane is changed into ethylene glycol diethyl ether, and the other operations are the same, so that the purity of 2, 3-pentanedione is 99.5%, and the yield is 92.5%.
Example 4
The difference between the method and example 1 is that sulfurous acid is changed into silicic acid (H 2SiO3), the water-soluble Schiff base nickel complex is changed into water-soluble Schiff base cobalt complex, and the other operations are the same, so that the purity of 2, 3-pentanedione is 99.3%, and the yield is 89.9%.
Example 5
The difference between the method and example 1 is that sulfurous acid is changed into carbonic acid (H 2CO3), the water-soluble Schiff base nickel complex is changed into water-soluble Schiff base copper complex, and the other operations are the same, so that the purity of 2, 3-pentanedione is 99.5%, and the yield is 91.6%.
Example 6
The difference between the method and example 1 is that sulfurous acid is changed to phosphoric acid (H 3PO4), the water-soluble Schiff base nickel complex is changed to water-soluble Schiff base zinc complex, and the other operations are the same, so that the purity of 2, 3-pentanedione is 99.4%, and the yield is 90.3%.
In comparative examples 1-6, the remaining conditions were the same, and the yield was highest when the catalyst was sulfurous acid, the adjuvant was a water-soluble schiff base nickel complex, the low polarity solvent was xylene, so the optimal catalyst was sulfurous acid, the optimal adjuvant was a water-soluble schiff base nickel complex, and the optimal low polarity solvent was xylene.
Example 7
The difference between the present embodiment and example 1 is that the molar ratio of 40% aqueous acetaldehyde to 4-hydroxyacetone is changed to 0.95:1, and the other operations are the same, so that 2, 3-pentanedione purity is 99.3%, and the yield is 86.4%.
Example 8
The difference between the present embodiment and example 1 is that the molar ratio of 40% aqueous acetaldehyde to 4-hydroxyacetone is changed to 1.05:1, and the other operations are the same, so that 2, 3-pentanedione with a purity of 99.5% and a yield of 92.5% is obtained.
Comparative example 1/7/8, the other conditions were the same, and the 40% aqueous acetaldehyde solution molar ratio was increased from 0.95 to the yield of 1,2, 3-pentanedione from 86.4% to 92.7%, and the yield was increased to 1.05, so that the optimum molar ratio of aldehyde compound to hydroxy ketone compound was 1:1.
Example 9
The difference between the method of this embodiment and example 1 is that the mass ratio of sulfurous acid to 4-hydroxyacetone is 1.0%, and the other operations are the same, so that the purity of 2, 3-pentanedione is 99.3%, and the yield is 87.7%.
Example 10
The difference between the method of this example and example 9 is that the mass ratio of sulfurous acid to 4-hydroxyacetone is 3.5% to 1, and the other operations are the same, so that 2, 3-pentanedione purity is 99.5% and yield is 92.4%.
Example 11
The difference between the method of this embodiment and example 10 is that the mass ratio of sulfurous acid to 4-hydroxyacetone is 5.0% to 1, and the other operations are the same, so that the purity of 2, 3-pentanedione is 99.5%, and the yield is 92.1%.
In comparative example 1/9/10/11, the other conditions were the same, the mass ratio of sulfurous acid to 4-hydroxyacetone was increased from 1.0% to 1 to 2.0% and the yield of 1,2, 3-pentanedione was increased from 87.7% to 92.7%, and the mass ratio of sulfurous acid to 4-hydroxyacetone was further increased to 5.0% and the yield of 1,2, 3-pentanedione was decreased to 92.1%, so that the optimum mass ratio of catalyst to hydroxyketone compound was 2.0% to 1.
Example 12
The difference between the method and example 1 is that the mass ratio of the water-soluble Schiff base nickel complex to the 4-hydroxy acetone is 0.01% to 1, and the rest operation is the same, so that the purity of 2, 3-pentanedione is 99.5%, and the yield is 90.9%.
Example 13
The difference between the method and example 12 is that the mass ratio of the water-soluble Schiff base nickel complex to the 4-hydroxy acetone is 0.05 percent to 1, and the rest operation is the same, so that the purity of the 2, 3-pentanedione is 99.5 percent, and the yield is 92.6 percent.
In comparative example 1/12/13, the other conditions were the same, the mass ratio of the water-soluble Schiff base nickel complex to 4-hydroxyacetone was increased from 0.01% to 1 to 0.03% and the yield of 1,2, 3-pentanedione was increased from 90.9% to 92.7%, and the mass ratio of the water-soluble Schiff base nickel complex to 4-hydroxyacetone was continuously increased to 0.05% and the yield of 1,2, 3-pentanedione was not substantially changed to 92.6%, so that the optimum mass ratio of the auxiliary agent to the hydroxyketone compound was 0.03% to 1.
Example 14
The difference between the present method and example 1 is that the mass ratio of xylene to 4-hydroxyacetone is 1.0:1, and the other operations are the same, so that 2, 3-pentanedione purity is 99.5%, and yield is 92.5%.
Example 15
The difference between the method of this example and example 14 is that the mass ratio of xylene to 4-hydroxyacetone is 3.0:1, and the other operations are the same, so that 2, 3-pentanedione purity is 99.5%, and yield is 90.8%.
In comparative example 1/14/15, the other conditions were the same, and the mass ratio of xylene to 4-hydroxyacetone was increased from 1.0:1 to 2.0:1, 2, 3-pentanedione yield was increased from 92.5% to 92.7%, and the mass ratio of xylene to 4-hydroxyacetone was continuously increased to 3.0:1, 2, 3-pentanedione yield was decreased to 90.8%, so that the optimum mass ratio of the low polarity solvent to the hydroxyketone compound was 2.0:1.
Example 16
The difference between the present method and example 1 is that the reaction temperature is 10℃and the other operations are the same, and the purity of 2, 3-pentanedione obtained is 99.5% and the yield is 86.8%.
Example 17
The difference between the method and example 16 is that the reaction temperature is 30℃and the other operations are the same, and the purity of 2, 3-pentanedione is 99.5% and the yield is 91.9%.
Comparative example 1/16/17, the reaction temperature was increased from 10 to 20℃and the yield of 2, 3-pentanedione was increased from 86.8% to 92.7%, and the reaction temperature was further increased to 30℃and the yield of 2, 3-pentanedione was decreased to 91.9%, so that the optimum reaction temperature was 20 ℃.
Example 18
The difference between the present method and example 1 is that the reaction time is 1 h, and the other operations are the same, so that the purity of 2, 3-pentanedione is 99.5%, and the yield is 87.2%.
Example 19
The difference between the method and example 18 is that the reaction time is 3 h, and the other operations are the same, so that the purity of 2, 3-pentanedione is 99.5%, and the yield is 91.8%.
Example 20
The procedure of this example 19 was repeated except that the reaction time was 4h and the remaining operations were identical, to give 2, 3-pentanedione having a purity of 99.5% and a yield of 90.3%.
In comparative example 1/18/19/20, the reaction time was increased from 1h to 2h, the yield of 2, 3-pentanedione was increased from 87.2% to 92.7%, and the reaction time was further increased to 4h, the yield of 2, 3-pentanedione was decreased to 90.3%, so that the optimal reaction time was 2 h.
2, 3-Pentanedione 186.3 g% pure was prepared in 92.7% yield according to the conditions of example 1.
Example 21
The difference between the method and example 1 is that the aldehyde compound is changed into n-valeraldehyde, the reaction temperature is 30 ℃, the reaction time is 1h, and the other operations are the same, so that the purity of the 2, 3-octanedione is 99.5%, and the yield is 85.3%.
Example 22
The difference between the method and example 1 is that the aldehyde compound is changed into formaldehyde, the low-polarity solvent is changed into n-octane, and the rest operation is the same, so that the purity of the 2, 3-butanedione is 99.3%, and the yield is 70.8%.
Example 23
The procedure of this example was repeated except that the aldehyde compound was changed to propanal, the low-polarity solvent was changed to ethylene glycol diethyl ether, and the remaining operations were the same, to obtain 2, 3-hexanedione having a purity of 99.5% and a yield of 89.9%.
Example 24
The procedure of this example was repeated except that the aldehyde compound was changed to isobutyraldehyde, the catalyst was changed to carbonic acid, and the remaining operations were the same, to obtain 5-methyl-2, 3-hexanedione having a purity of 99.5% and a yield of 90.2%.
Example 25
The difference between the present embodiment and example 1 is that the aldehyde compound is changed to n-butyraldehyde, the catalyst is changed to phosphoric acid, and the rest of the operations are the same, so that the purity of 2, 3-heptanedione is 99.5%, and the yield is 88.1%.
Example 26
The difference between the method and example 1 is that the hydroxy ketone compound is changed into 1-hydroxy-2-butanone, the catalyst is changed into silicic acid, and the rest operation is the same, so that the purity of the 3, 4-hexanedione is 99.5%, and the yield is 82.6%.
The examples 21 to 26 are respectively the optimal examples of the corresponding products, and other condition screening examples are not repeated, and it can be seen from examples 21 to 26 that the conjugated diketone compound can be obtained in high yield by adopting the synthetic route of the application, and the method has the advantages of good universality, short reaction time and high purity.
According to the method, inorganic acid is used as a catalyst, a condensation reaction is carried out on the hydroxyketone compound and the aldehyde compound under the action of an auxiliary agent, a low-polarity solvent is adopted, the product is subjected to reaction extraction, the product continuously enters an oil phase, water and oil phases are layered after the reaction is finished, and the oil phase is rectified to obtain the product of the conjugated diketone compound; the inorganic acid catalyst is cooperated with the water-soluble metal complex, so that the reaction can be promoted to be rapidly carried out at a lower reaction temperature, the reaction time is shortened, and the condensation side reaction of the raw materials is avoided; in addition, the low-polarity solvent is used for extraction, the product is quickly extracted to the water phase where the oil phase is separated from the catalyst after being generated, and the product can be prevented from further carrying out condensation and other side reactions under the action of the catalyst, so that the high-efficiency synthesis of the conjugated diketone compound is realized, the yield can reach more than 90 percent, the boiling point of the adopted low-polarity solvent is lower than that of the product, the solvent and the oil phase of the product only need to rectify the product after the reaction is finished, and the energy consumption cost of the recovered solvent is reduced; in addition, the reaction system has good universality for conjugated diketone compounds, and is suitable for synthesizing most conjugated diketones; as the system has less side reactions, the purity of the product after rectification and purification can reach more than 99 percent, the product yield is high, the reaction condition is mild, the reaction time is short, the product purity is high, the cost is low, and the method is suitable for industrial production.
The foregoing description of the preferred embodiments of the application is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the application.
Claims (10)
1. The synthesis method of the conjugated diketone compound is characterized by comprising the following steps of:
(1): inorganic acid is used as a catalyst, a low-polarity solvent is adopted, a hydroxy ketone compound and an aldehyde compound are added under the action of an auxiliary agent, and the condensation reaction is carried out by controlling the reaction temperature and the reaction time to obtain a reaction liquid;
(2): after the reaction is finished, the reaction liquid in the step (1) is divided into two layers of water and oil by extraction, and the conjugated diketone compound is obtained by rectifying the oil phase.
2. The method for synthesizing conjugated diketone compound according to claim 1, wherein the hydroxy ketone compound is one of hydroxy acetone and 1-hydroxy-2-butanone, and the aldehyde compound is one of formaldehyde, acetaldehyde, propionaldehyde, isobutyraldehyde, n-butyraldehyde or n-valeraldehyde.
3. The method for synthesizing a conjugated diketone compound according to claim 1, wherein the inorganic acid is an inorganic weak acid.
4. The method for synthesizing a conjugated diketone compound according to claim 1, wherein the auxiliary agent is a water-soluble metal complex, and the water-soluble metal complex comprises a metal ion and a ligand.
5. The method for synthesizing a conjugated diketone compound according to claim 1, wherein the low-polarity solvent is one of n-octane, xylene or ethylene glycol diethyl ether.
6. The method for synthesizing conjugated diketone compound according to claim 1, wherein the molar ratio of aldehyde compound to hydroxyketone compound is 0.95-1.05:1.
7. The method for synthesizing conjugated diketone compound according to claim 1, wherein the mass ratio of the catalyst to the hydroxyketone compound is 1.0-5.0%: 1.
8. The method for synthesizing the conjugated diketone compound according to claim 1, wherein the mass ratio of the auxiliary agent to the hydroxyketone compound is 0.01-0.05%: 1.
9. The method for synthesizing conjugated diketone compound according to claim 1, wherein the mass ratio of the low-polarity solvent to the hydroxyketone compound is 1.0-3.0:1.
10. The method for synthesizing a conjugated diketone compound according to claim 1, wherein the reaction temperature in step (1) is 10-30 ℃, and the reaction time is 1-4 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410337895.1A CN117924056B (en) | 2024-03-25 | 2024-03-25 | Synthesis method of conjugated diketone compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410337895.1A CN117924056B (en) | 2024-03-25 | 2024-03-25 | Synthesis method of conjugated diketone compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN117924056A true CN117924056A (en) | 2024-04-26 |
| CN117924056B CN117924056B (en) | 2024-06-11 |
Family
ID=90761370
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410337895.1A Active CN117924056B (en) | 2024-03-25 | 2024-03-25 | Synthesis method of conjugated diketone compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117924056B (en) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2799707A (en) * | 1956-05-14 | 1957-07-16 | Dow Chemical Co | Preparation of alpha-diketones |
| US4638096A (en) * | 1982-10-12 | 1987-01-20 | Henkel Corporation | Process of preparing hydroxyarylaldehydes and catalyst therefor |
| US20030092942A1 (en) * | 2001-11-12 | 2003-05-15 | Stefan Lambrecht | Process for the preparation of 2,3-pentanedione |
| AU2003300727A1 (en) * | 2003-12-31 | 2005-07-21 | Council Of Scientific And Industrial Research | Process for synthesis of alpha-substituted acroleins |
| JP2008037765A (en) * | 2006-08-02 | 2008-02-21 | Osaka Prefecture Univ | Method for producing 1,3-diketone |
| CN103113199A (en) * | 2013-02-28 | 2013-05-22 | 河南华龙香料有限公司 | Clearer production method of 2,3-hexanedione |
| CN103159603A (en) * | 2013-02-28 | 2013-06-19 | 河南华龙香料有限公司 | Clean production method of 2,3-heptadione |
| CN105541588A (en) * | 2016-02-25 | 2016-05-04 | 济南悟通化学科技有限公司 | Synthesis method of butanedione |
| CN108358765A (en) * | 2018-02-08 | 2018-08-03 | 淮阴工学院 | The preparation method of 2,3- pentanediones |
| US20190106370A1 (en) * | 2018-12-07 | 2019-04-11 | Huaiyin Institute Of Technology | Preparation Method for 2,3-pentanedione |
-
2024
- 2024-03-25 CN CN202410337895.1A patent/CN117924056B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2799707A (en) * | 1956-05-14 | 1957-07-16 | Dow Chemical Co | Preparation of alpha-diketones |
| US4638096A (en) * | 1982-10-12 | 1987-01-20 | Henkel Corporation | Process of preparing hydroxyarylaldehydes and catalyst therefor |
| US20030092942A1 (en) * | 2001-11-12 | 2003-05-15 | Stefan Lambrecht | Process for the preparation of 2,3-pentanedione |
| AU2003300727A1 (en) * | 2003-12-31 | 2005-07-21 | Council Of Scientific And Industrial Research | Process for synthesis of alpha-substituted acroleins |
| JP2008037765A (en) * | 2006-08-02 | 2008-02-21 | Osaka Prefecture Univ | Method for producing 1,3-diketone |
| CN103113199A (en) * | 2013-02-28 | 2013-05-22 | 河南华龙香料有限公司 | Clearer production method of 2,3-hexanedione |
| CN103159603A (en) * | 2013-02-28 | 2013-06-19 | 河南华龙香料有限公司 | Clean production method of 2,3-heptadione |
| CN105541588A (en) * | 2016-02-25 | 2016-05-04 | 济南悟通化学科技有限公司 | Synthesis method of butanedione |
| CN108358765A (en) * | 2018-02-08 | 2018-08-03 | 淮阴工学院 | The preparation method of 2,3- pentanediones |
| US20190106370A1 (en) * | 2018-12-07 | 2019-04-11 | Huaiyin Institute Of Technology | Preparation Method for 2,3-pentanedione |
Non-Patent Citations (1)
| Title |
|---|
| 闵恩泽，李成岳等著: "《绿色石化技术的科学与工程基础》", 31 May 2002, 中国石化出版社, pages: 39 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN117924056B (en) | 2024-06-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6195622B2 (en) | Method for producing neopentyl glycol | |
| CN109053407B (en) | Method for synthesizing beta-damascenone | |
| CN103052616A (en) | Method for obtaining ditrimethylolpropane and trimethylolpropane-enriched product streams from side-streams in trimethylolpropane production | |
| CN1310863C (en) | Continuous process for producing pseudoionones and ionones | |
| CN117924056B (en) | Synthesis method of conjugated diketone compound | |
| JP2000119211A (en) | Production of citral | |
| EP1433774A1 (en) | Process for reducing the aldehyde concentration in a mixture comprising cyclohexanone and one or more aldehydes | |
| JPS6136812B2 (en) | ||
| CN104607182A (en) | Preparation of nano-palladium catalyst as well as application of nano-palladium catalyst to synthesis of vanillin compounds | |
| US20200377436A1 (en) | Oxidation of limonene | |
| JP5824735B2 (en) | Food and beverage additives | |
| US7632973B2 (en) | Methods for preparing aldehydes by self-aldol condensation | |
| CN107418735A (en) | A kind of preparation method of citral diethyl acetal natural perfume material | |
| CN108069834B (en) | Method for continuously preparing 3, 4' -dichlorodiphenyl ether | |
| US20030181769A1 (en) | Method for producing branched alcohols and/or hydrocarbons | |
| US5039497A (en) | Process for separating copper from aqueous base solutions | |
| CN113563287B (en) | Preparation method of epoxy caprylate and preparation method of melonal | |
| JP2023054910A (en) | Method for producing 2-acetyltetrahydropyridine compound | |
| CN102584552B (en) | Method for preparing benzalacetone under supercritical condition | |
| CN107983334B (en) | Graphene-loaded tin-tungsten bimetallic catalyst and preparation method and application thereof | |
| JP2711893B2 (en) | Ketones and alcohols | |
| JPS628109B2 (en) | ||
| CN109206300B (en) | Method for synthesizing carvacrol by using dipentene dioxide | |
| CN114773168A (en) | Method for synthesizing cis/trans-prenyl-3-methyl butadiene ether by using methyl butynol and isopentenol | |
| CN101421216B (en) | Process for the preparation of a ketone or an aldehyde using silica as a catalyst |
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 | ||
| GR01 | Patent grant |