CN116903454A - Method for preparing 3,4, 7-trimethyl-1-indanone by one-step conversion of 2, 5-hexanedione - Google Patents
Method for preparing 3,4, 7-trimethyl-1-indanone by one-step conversion of 2, 5-hexanedione Download PDFInfo
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- CN116903454A CN116903454A CN202310821698.2A CN202310821698A CN116903454A CN 116903454 A CN116903454 A CN 116903454A CN 202310821698 A CN202310821698 A CN 202310821698A CN 116903454 A CN116903454 A CN 116903454A
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- indanone
- hexanedione
- trimethyl
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- alkali solution
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- OJVAMHKKJGICOG-UHFFFAOYSA-N 2,5-hexanedione Chemical compound CC(=O)CCC(C)=O OJVAMHKKJGICOG-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 39
- FSBIQEDMEKAAMA-UHFFFAOYSA-N 3,4,7-trimethyl-2,3-dihydroinden-1-one Chemical compound CC1=CC=C(C)C2=C1C(C)CC2=O FSBIQEDMEKAAMA-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 21
- 239000003513 alkali Substances 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 238000005882 aldol condensation reaction Methods 0.000 claims abstract description 7
- 239000003208 petroleum Substances 0.000 claims abstract description 6
- 230000009471 action Effects 0.000 claims abstract description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 25
- 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 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 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
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000004587 chromatography analysis Methods 0.000 claims description 2
- 238000004440 column chromatography Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000004809 thin layer chromatography Methods 0.000 claims description 2
- 239000002028 Biomass Substances 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 238000009776 industrial production Methods 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 229940125782 compound 2 Drugs 0.000 abstract description 2
- -1 indanone compound Chemical class 0.000 abstract description 2
- QNXSIUBBGPHDDE-UHFFFAOYSA-N indan-1-one Chemical compound C1=CC=C2C(=O)CCC2=C1 QNXSIUBBGPHDDE-UHFFFAOYSA-N 0.000 description 15
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000005863 Friedel-Crafts acylation reaction Methods 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 150000001555 benzenes Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 2
- XVTQSYKCADSUHN-UHFFFAOYSA-N 3-methyl-2,3-dihydroinden-1-one Chemical compound C1=CC=C2C(C)CC(=O)C2=C1 XVTQSYKCADSUHN-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000003042 antagnostic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- IQZZFVDIZRWADY-UHFFFAOYSA-N isocoumarin Chemical class C1=CC=C2C(=O)OC=CC2=C1 IQZZFVDIZRWADY-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000341 volatile oil Substances 0.000 description 2
- GHAMYXPEZSUOCU-XZOQPEGZSA-N 1-[2-[4-[(1r,3s)-3-(4-fluorophenyl)-2,3-dihydro-1h-inden-1-yl]piperazin-1-yl]ethyl]imidazolidin-2-one Chemical compound C1=CC(F)=CC=C1[C@H]1C2=CC=CC=C2[C@H](N2CCN(CCN3C(NCC3)=O)CC2)C1 GHAMYXPEZSUOCU-XZOQPEGZSA-N 0.000 description 1
- GPNYJXANBXUOLW-UHFFFAOYSA-N 2-(2,3-dihydro-1h-inden-1-yloxy)acetic acid Chemical class C1=CC=C2C(OCC(=O)O)CCC2=C1 GPNYJXANBXUOLW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 102100040611 Endothelin receptor type B Human genes 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 241000234435 Lilium Species 0.000 description 1
- 238000006229 Nazarov cyclization reaction Methods 0.000 description 1
- 102000009493 Neurokinin receptors Human genes 0.000 description 1
- 108050000302 Neurokinin receptors Proteins 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 230000003276 anti-hypertensive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical class C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000002934 diuretic Substances 0.000 description 1
- 230000001882 diuretic effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000003511 endothelial effect Effects 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 229950008734 irindalone Drugs 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Chemical class CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
- C07C45/74—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
- C07C2602/04—One of the condensed rings being a six-membered aromatic ring
- C07C2602/08—One of the condensed rings being a six-membered aromatic ring the other ring being five-membered, e.g. indane
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of pharmaceutical chemicals, and particularly relates to a method for preparing 3,4, 7-trimethyl-1-indanone by one-step conversion of 2, 5-hexanedione. Under the action of alkali solution, the raw material 2, 5-hexanedione is subjected to intermolecular aldol condensation reaction to synthesize the target product 3,4, 7-trimethyl-1-indanone. The invention utilizes biomass platform compound 2, 5-hexanedione to obtain indanone compound through intermolecular aldol condensation reaction, and replaces petroleum-based route from sustainable biomass route; the raw material 2, 5-hexanedione can be directly obtained through renewable biomass resources, and is simple and easy to obtain; the invention has the advantages of simple synthetic route, no metal participation, clean and environment-friendly route, little environmental pollution and suitability for industrial production.
Description
Technical Field
The invention belongs to the technical field of pharmaceutical chemicals, and particularly relates to a method for preparing 3,4, 7-trimethyl-1-indanone by one-step conversion of 2, 5-hexanedione.
Background
Indanone (indione) is an important organic intermediate, is commonly used for pharmaceutical synthesis, such as irindalone with antihypertensive activity, indanoxy acetic acid compounds with salt elimination and diuretic acid activities, SB-209670 and SB-217242 with endothelial ETA/ETB receptor antagonistic activity, trans-1-phenyl-3- (pyrrole-1-yl) -indan-2-carboxamide with neurokinin receptor antagonistic activity and the like, are synthesized from Indanone as an intermediate, can also be synthesized from Indanone to isocoumarin, and metal complexes with indene ring skeletons can also be used as catalysts for styrene polymerization.
Indanone is present in plant essential oils in nature, but can be extracted in very small amounts. According to Chinese pharmacopoeia, 3,4, 7-trimethyl-1-indanone in lily essential oil accounts for only 0.35% (Asian Journal of Chemistry,2014,26,1974-1976). Thus, the production of indanone is largely dependent on organic synthesis techniques.
As early as the 40 th century of 20, the synthesis of indanones was reported using substituted benzene and crotonic acid in AlCl 3 3-methyl-1-indanone is synthesized under catalysis. 3-aryl propionic acid and derivatives thereof are used as substrates, and 1-indanone is obtained through Friedel-Crafts acylation reaction under the action of Lewis acid or protonic acid, as shown in a scheme A (Journal of the Chemical society. Perkin transactions I,1972, 151-155).
From the 50 s of the 20 th century, reports on the synthesis of indanones have been gradually enriched, zhao et al modified by microwave irradiation to catalyze Friedel-Crafts acylation and Nazarov cyclization of substituted benzene and unsaturated acyl chloride to give 1-indanone (Journal of Organic Chemistry,2006,71,4312-4315). The prior method uses metal salt to promote the reaction to different degreesThe reaction proceeds with or without transition metal catalysis, and Shimada reports Tb (OTf) 3 Friedel-Crafts acylation of 3-aryl propionic acids to 1-indanone (Tetrahedron Letters,2004,45,1741-1745) is efficiently catalyzed at 250 ℃. However, the use of metal salts is very difficult for the post purification of the drug or material. Furthermore, from previous literature reports, most of the reaction precursors need to be prepared in advance. Even by 2000, the synthetic raw materials of indanone have been free of substituted benzene. Thus, the complex route for preparing indanone greatly limits its application.
Therefore, it is very important to find a high-efficiency synthesis method with simple and easily available raw materials, mild reaction conditions and no metal participation.
Disclosure of Invention
Aiming at a plurality of problems existing in the technology, the invention provides a preparation method of 3,4, 7-trimethyl-1-indanone with low cost, high yield and high application range, which takes 2, 5-hexanedione as a raw material and performs intermolecular aldol condensation under alkaline condition to synthesize a target product 3,4, 7-trimethyl-1-indanone in one step. The method has the advantages of short synthetic route, high total yield, clean and environment-friendly route, small environmental pollution and suitability for industrial production.
In order to achieve the above object, the technical scheme of the present invention is as follows:
a method for preparing 3,4, 7-trimethyl-1-indanone by one-step conversion of 2, 5-hexanedione comprises the steps of synthesizing a target product 3,4, 7-trimethyl-1-indanone through intermolecular aldol condensation reaction of raw material 2, 5-hexanedione under the action of alkali solution, wherein the reaction equation is as follows:
in the above technical solution, further, the method specifically includes the following steps: sequentially adding raw materials 2, 5-hexanedione and alkali solution into a reactor, reacting for 60-240 min at 20-60 ℃, preferably reacting for 60-120 min at 25-30 ℃, extracting and purifying the product by using methylene dichloride after the reaction is finished, and obtaining the 3,4, 7-trimethyl-1-indanone.
In the above technical solution, in the alkali solution, the alkali is any one of potassium hydroxide, sodium hydroxide, lithium hydroxide, barium hydroxide, and calcium hydroxide, preferably potassium hydroxide.
In the above technical scheme, further, the concentration of the alkali solution is 0.1-0.2Kg/L, preferably 0.1-0.15Kg/L; the concentration of 2, 5-hexanedione in the reactor is 0.05-1Kg/L, and the concentration of alkali in the reactor is 0.05-0.2Kg/L.
In the above technical scheme, further, the purification uses a chromatographic column or thin layer chromatography, and the developing agent used for chromatography is a mixture of petroleum ether and ethyl acetate, and the volume ratio of petroleum ether to ethyl acetate is 10:1-20:1.
The beneficial effects of the invention are as follows:
1. the invention utilizes biomass platform compound 2, 5-hexanedione to obtain indanone compound through intermolecular aldol condensation reaction, and replaces petroleum-based route from sustainable biomass route;
2. the raw material 2, 5-hexanedione can be directly obtained through renewable biomass resources, and is simple and easy to obtain;
3. the invention has the advantages of simple synthetic route, no metal participation, clean and environment-friendly route, little environmental pollution and suitability for industrial production.
In summary, the synthetic method has the advantages of simple and easily obtained raw materials, remarkably reduced production cost, mild reaction conditions, high product yield and easy purification.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of 3,4, 7-trimethyl-1-indanone, which is a product prepared in example 1 of the present invention;
FIG. 2 is a chart showing the nuclear magnetic resonance of 3,4, 7-trimethyl-1-indanone, which is a product obtained in example 1 of the present invention;
FIG. 3 is a high resolution mass spectrum of the product 3,4, 7-trimethyl-1-indanone prepared in example 1 of the present invention.
Detailed Description
The following examples will enable those of ordinary skill in the art to more fully understand the invention and are not intended to limit the invention in any way.
Unless otherwise indicated, all materials used in the examples of the present invention were commercially available or prepared according to conventional methods well known to those skilled in the art.
Example 1
1) The reaction formula:
2) The preparation process comprises the following steps:
a 500mL double-layer reaction flask is added with a magnetic stirrer, and 300mL of 0.1Kg/L KOH solution and 150g of 2, 5-hexanedione are sequentially added; opening a circulating water bath in a jacket of the reaction bottle, and keeping the constant temperature of 25 ℃ for stirring reaction for 60min; after the reaction, 20g of sodium chloride and 100mL of ethyl acetate are added to extract and separate the liquid three times, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and separated by a 200-300 mesh silica gel column to obtain 3,4, 7-trimethyl-1-indanone (71.7 g, purity > 98.0%), wherein the yield of 3,4, 7-trimethyl-1-indanone is 62.6%.
The nuclear magnetic resonance hydrogen spectrum and the carbon spectrum of the product are shown in figures 1 and 2, and the high resolution mass spectrum is shown in figure 3.
Example 2
The preparation procedure and conditions were similar to example 1, except that the concentration of potassium hydroxide was varied, and the results are shown in Table 1.
TABLE 1
As can be seen from Table 1, the yield of 3,4, 7-trimethyl-1-indanone was optimal when the concentration of potassium hydroxide solution was 0.1Kg/L under the same conditions.
Example 3
The preparation procedure and conditions were similar to example 1, except that the reaction temperature was varied, and the results are shown in Table 2.
TABLE 2
As can be seen from Table 2, under the same conditions, the yield was optimal at 25℃at the reaction temperature, which means that the industrial production was kept at room temperature, and that too high a reaction temperature caused a side reaction of aldol condensation of 2, 5-hexanedione itself.
Example 4
The preparation procedure and conditions were similar to example 1, except that the reaction time was varied and the results are shown in Table 3.
TABLE 3 Table 3
As can be seen from Table 3, under the same conditions, the maximum yield was reached by the reaction for 60min, and the yield could not be improved by the extension of the reaction time due to the thermodynamic influence of the reaction.
Comparative example 1
A 500mL double-layer reaction flask is added with a magnetic stirrer, and 300mL of 0.1Kg/L calcium hydroxide solution and 150g of 2, 5-hexanedione are sequentially added; opening a circulating water bath in a jacket of the reaction bottle, and keeping the constant temperature of 25 ℃ for stirring reaction for 60min; after the reaction is finished, 20g of sodium chloride and 100mL of ethyl acetate are added for three times of extraction and liquid separation, anhydrous sodium sulfate is dried, and after decompression concentration, 200-300 meshes of silica gel column separation is adopted to obtain 3,4, 7-trimethyl-1-indanone, and the yield of the 3,4, 7-trimethyl-1-indanone is 10.1%.
Comparative example 2
A 500mL double-layer reaction flask is added with a magnetic stirrer, and 300mL of 0.05Kg/L KOH solution and 150g of 2, 5-hexanedione are sequentially added; opening a circulating water bath in a jacket of the reaction bottle, and keeping the constant temperature of 25 ℃ for stirring reaction for 60min; after the reaction is finished, 20g of sodium chloride and 100mL of ethyl acetate are added for three times of extraction and liquid separation, anhydrous sodium sulfate is used for drying, and after decompression and concentration, 200-300 meshes of silica gel column separation is adopted to obtain 3,4, 7-trimethyl-1-indanone, and the yield of the 3,4, 7-trimethyl-1-indanone is 35.7%.
Comparative example 3
A 500mL double-layer reaction flask is added with a magnetic stirrer, and 300mL of 0.5Kg/L KOH solution and 150g of 2, 5-hexanedione are sequentially added; opening a circulating water bath in a jacket of the reaction bottle, and keeping the constant temperature of 25 ℃ for stirring reaction for 60min; after the reaction is finished, 20g of sodium chloride and 100mL of ethyl acetate are added for three times of extraction and liquid separation, anhydrous sodium sulfate is used for drying, and after decompression and concentration, 200-300 meshes of silica gel column separation is adopted to obtain 3,4, 7-trimethyl-1-indanone, and the yield of the 3,4, 7-trimethyl-1-indanone is 34%.
The above examples are only preferred embodiments of the present invention and are not limiting of the implementation. The protection scope of the present invention shall be subject to the scope defined by the claims. Other variations or modifications may be made in the various forms based on the above description. Obvious variations or modifications of the embodiments are within the scope of the invention.
Claims (8)
1. A method for preparing 3,4, 7-trimethyl-1-indanone by one-step conversion of 2, 5-hexanedione is characterized in that: under the action of alkali solution, the raw material 2, 5-hexanedione is subjected to intermolecular aldol condensation reaction to synthesize a target product 3,4, 7-trimethyl-1-indanone, wherein the reaction equation is as follows:
2. the method according to claim 1, characterized in that: the method comprises the following specific steps: sequentially adding raw materials 2, 5-hexanedione and alkali solution into a reactor, reacting for 60-240 min at 20-60 ℃, and extracting and purifying a product by using methylene dichloride after the reaction is finished to obtain 3,4, 7-trimethyl-1-indanone.
3. The method according to claim 2, characterized in that: the reaction condition is that the reaction is carried out for 60 to 120 minutes at the temperature of 25 to 30 ℃.
4. The method according to claim 2, characterized in that: in the alkali solution, alkali is any one of potassium hydroxide, sodium hydroxide, lithium hydroxide, barium hydroxide and calcium hydroxide.
5. The method according to claim 2, characterized in that: in the alkali solution, the alkali is potassium hydroxide.
6. The method according to claim 2, characterized in that: the concentration of the alkali solution is 0.1-0.2Kg/L; the concentration of 2, 5-hexanedione in the reactor is 0.05-1Kg/L, and the concentration of alkali in the reactor is 0.05-0.2Kg/L.
7. The method according to claim 2, characterized in that: the concentration of the alkali solution is 0.1-0.15Kg/L.
8. The method according to claim 2, characterized in that: the purification uses a chromatographic column or thin layer chromatography, and the developing agent used in the chromatography is a mixture of petroleum ether and ethyl acetate, wherein the volume ratio of petroleum ether to ethyl acetate is 10:1-20:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310821698.2A CN116903454A (en) | 2023-07-05 | 2023-07-05 | Method for preparing 3,4, 7-trimethyl-1-indanone by one-step conversion of 2, 5-hexanedione |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310821698.2A CN116903454A (en) | 2023-07-05 | 2023-07-05 | Method for preparing 3,4, 7-trimethyl-1-indanone by one-step conversion of 2, 5-hexanedione |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116903454A true CN116903454A (en) | 2023-10-20 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310821698.2A Pending CN116903454A (en) | 2023-07-05 | 2023-07-05 | Method for preparing 3,4, 7-trimethyl-1-indanone by one-step conversion of 2, 5-hexanedione |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116903454A (en) |
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2023
- 2023-07-05 CN CN202310821698.2A patent/CN116903454A/en active Pending
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