CN116813455A - Preparation method of 2-adamantanone compound - Google Patents
Preparation method of 2-adamantanone compound Download PDFInfo
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- CN116813455A CN116813455A CN202310771965.XA CN202310771965A CN116813455A CN 116813455 A CN116813455 A CN 116813455A CN 202310771965 A CN202310771965 A CN 202310771965A CN 116813455 A CN116813455 A CN 116813455A
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- Prior art keywords
- adamantanone
- sulfuric acid
- organic solvent
- hydrolysis
- producing
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- -1 2-adamantanone compound Chemical class 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title abstract description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 62
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 claims abstract description 36
- IYKFYARMMIESOX-UHFFFAOYSA-N adamantanone Chemical compound C1C(C2)CC3CC1C(=O)C2C3 IYKFYARMMIESOX-UHFFFAOYSA-N 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000012071 phase Substances 0.000 claims abstract description 23
- 239000003960 organic solvent Substances 0.000 claims abstract description 21
- 239000012074 organic phase Substances 0.000 claims abstract description 20
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 20
- 230000007062 hydrolysis Effects 0.000 claims abstract description 15
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000012043 crude product Substances 0.000 claims abstract description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 10
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 239000012535 impurity Substances 0.000 claims abstract description 7
- 239000000047 product Substances 0.000 claims abstract description 7
- 238000004064 recycling Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 6
- 208000005156 Dehydration Diseases 0.000 claims abstract description 5
- 230000018044 dehydration Effects 0.000 claims abstract description 5
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 5
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000000605 extraction Methods 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000003756 stirring Methods 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 2
- 239000000463 material 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
- VLLNJDMHDJRNFK-UHFFFAOYSA-N adamantan-1-ol Chemical compound C1C(C2)CC3CC2CC1(O)C3 VLLNJDMHDJRNFK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940025250 camphora Drugs 0.000 description 1
- 239000010238 camphora Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Abstract
The application discloses a preparation method of a 2-adamantanone compound. The method comprises the following steps: (1) Dissolving adamantane in a first organic solvent, wherein the first organic solvent is one or more of carbon tetrachloride, 1, 2-dichloroethane and chloroform, and then carrying out oxidation reaction under concentrated sulfuric acid, wherein the reaction temperature is 50-80 ℃; (2) After the oxidation reaction is completed, adding the mixture into water for hydrolysis, and standing and layering after the hydrolysis to obtain an organic phase and a sulfuric acid phase; (3) Extracting the organic phase by a second organic solvent to obtain a 2-adamantanone solution; (4) Extracting impurities from the sulfuric acid phase separated by hydrolysis by a third organic solvent, and then carrying out dehydration treatment to obtain concentrated sulfuric acid for recycling; (5) Removing water from the 2-adamantanone solution obtained in the step (3), concentrating, cooling and crystallizing to obtain a 2-adamantanone crude product; (6) Recrystallizing the 2-adamantanone crude product by a fourth organic solvent to obtain a 2-adamantanone fine product. The application has the advantages of reducing cost and improving yield.
Description
Technical Field
The application relates to a preparation method of alkanone, in particular to a preparation method of 2-adamantanone compound.
Background
The 2-adamantanone is white crystal, has camphora taste, and can be dissolved in organic solvents such as methanol, ethanol, DMSO, etc. The 2-adamantanone can be used for synthesizing pharmaceutical intermediates, photosensitive materials and information technology fields. Currently, 2-adamantanone is mainly obtained by the sulfuric acid oxidation method of adamantane or adamantanol. For example, the prior art discloses a preparation method of 2-adamantanone, the publication number is CN1980877 a, the publication date is 6/13/2007, and the preparation method adopts a sulfuric acid and carboxylic acid mixed oxidation method, so that the production cost cannot be realized. If concentrated sulfuric acid is directly used for oxidation, the cost is reduced, but the carbonization phenomenon of raw materials can occur in the heating process of 98% concentration sulfuric acid, so that the yield is reduced.
Disclosure of Invention
The application aims to provide a preparation method of a 2-adamantanone compound, which reduces cost and improves yield.
In order to achieve the above object, the preparation method of the 2-adamantanone compound of the present application adopts the following technical scheme:
a method for preparing a 2-adamantanone compound, comprising the steps of:
(1) Oxidation reaction: dissolving adamantane in a first organic solvent, wherein the first organic solvent is one or more of carbon tetrachloride, 1, 2-dichloroethane and chloroform, and then carrying out oxidation reaction under concentrated sulfuric acid, wherein the reaction temperature is 50-80 ℃;
(2) Hydrolysis: after the oxidation reaction is completed, adding the mixture into water for hydrolysis, and standing and layering after the hydrolysis to obtain an organic phase and a sulfuric acid phase;
(3) Organic phase extraction: the organic phase separated by hydrolysis is extracted by a second organic solvent to obtain 2-adamantanone solution;
(4) Sulfuric acid phase extraction: the sulfuric acid phase separated by hydrolysis is subjected to impurity extraction by a third organic solvent, and then dehydration treatment is carried out to obtain concentrated sulfuric acid for recycling;
(5) Concentrating and crystallizing: concentrating the 2-adamantanone solution obtained in the step (3), and cooling and crystallizing to obtain a 2-adamantanone crude product;
(6) And (5) recrystallizing: recrystallizing the 2-adamantanone crude product by an alcohol solvent to obtain a 2-adamantanone fine product.
Preferably, the volume weight ratio of the concentrated sulfuric acid to the adamantane is 6:1.
Preferably, the volume weight ratio of the first organic solvent to adamantane is 3:1.
Preferably, the reaction temperature in step (2) is 70 to 80℃and the reaction time is 12 hours.
Preferably, the second organic solvent in step (3) is water.
Preferably, the third organic solvent in step (4) is one or more of petroleum ether, dichloromethane, dichloroethane.
Preferably, the alcohol solvent in the step (6) is one of ethanol, methanol and isopropanol.
Preferably, after the oxidation reaction in the step (2) is completed, cooling and dripping into water at 0-5 ℃ for hydrolysis.
Compared with the prior art, the application has the beneficial effects that:
1. according to the application, adamantane is taken as a raw material and is directly oxidized by sulfuric acid, and the first organic solvent is added to dissolve adamantane, so that the carbonization problem of materials is solved, and simultaneously, the sublimation phenomenon in the adamantane reaction process is also solved, so that the yield can reach 80%, the economic benefit is greatly improved, and the cost is low;
2. the dilute sulfuric acid generated after the oxidation reaction is recycled, impurities in the dilute sulfuric acid are removed through extraction, and concentrated sulfuric acid is obtained after dehydration for recycling, so that the method meets the environmental protection requirement.
Detailed Description
The present application is further illustrated below in conjunction with the specific embodiments, it being understood that these embodiments are meant to be illustrative of the application only and not limiting the scope of the application, and that modifications of the application, which are equivalent to those skilled in the art to which the application pertains, will fall within the scope of the application as defined in the appended claims.
Example 1
Dissolving 10 g of adamantane in 30ml of 1, 2-dichloroethane, dropwise adding the solution into 60ml of 98% sulfuric acid at room temperature, stirring and heating to 75 ℃ for 12 hours, and controlling the adamantane raw material residue in the oxidation reaction liquid to be less than or equal to 0.2% and taking the reaction as complete; then adding 100ml of water into another reaction bottle, stirring and cooling to 0-5 ℃, when the temperature of the reaction liquid reaches about 25 ℃, slowly dropwise adding the oxidation liquid under the condition that the temperature is controlled not to exceed 25 ℃, stirring and hydrolyzing for 2 hours after dropwise adding, standing and layering to form an organic phase and a sulfuric acid phase;
the organic phase is washed by 50ml of water and layered to obtain an organic phase and a water phase, the water phase and the obtained sulfuric acid phase are combined, then petroleum ether is used for extracting impurities, and the obtained water phase is decompressed and dehydrated to obtain sulfuric acid with the concentration of more than 95 percent for recycling;
the organic phase of the water washing is 2-adamantanone solution, the 2-adamantanone solution is concentrated to remove 1, 2-methylene dichloride, 8 g of crude product is separated out, and the crude product is recrystallized by methanol-water again to obtain 7.5 g of 2-adamantanone fine product.
Example 2
Dissolving 10 g of adamantane in 30ml of carbon tetrachloride, dropwise adding the solution into 60ml of 98% sulfuric acid at room temperature, stirring and heating to 70-75 ℃ and preserving heat for 12 hours, and controlling the adamantane raw material residue in the oxidation reaction liquid to be less than or equal to 0.2% and taking the adamantane as the reaction completion; then adding 100ml of water into the other reaction bottle, stirring and cooling to 0-5 ℃, then slowly dropwise adding the oxidation liquid under the condition that the temperature is controlled to be not higher than 25 ℃, stirring and hydrolyzing for 2 hours after dropwise adding, standing and layering to form an organic phase and a sulfuric acid phase; the organic phase is separated into an organic phase and a water phase by 50ml water washing;
combining the water phase and the obtained sulfuric acid phase, extracting impurities by using normal hexane, and carrying out reduced pressure dehydration on the obtained water phase to obtain sulfuric acid with concentration of more than 95%, and recycling;
the organic phase of water washing is 2-adamantanone solution, the 2-adamantanone solution is concentrated to remove carbon tetrachloride, 8 g of crude product is separated out, and the crude product is recrystallized by methanol-water again to obtain 6.5 g of 2-adamantanone fine product.
Example 3
Dissolving 10 g of adamantane in 30ml of chloroform, dropwise adding the solution into 60ml of 98% sulfuric acid at room temperature, stirring and heating to 70-75 ℃ for 12 hours, and controlling the adamantane raw material residue in the oxidation reaction liquid to be less than or equal to 0.2% and taking the reaction as complete; then adding 100ml of water into the other reaction bottle, stirring and cooling to 0-5 ℃, then slowly dropwise adding the oxidation liquid under the condition that the temperature is controlled to be not higher than 25 ℃, stirring and hydrolyzing for 2 hours after dropwise adding, standing and layering to form an organic phase and a sulfuric acid phase; the organic phase is separated into an organic phase and a water phase by 50ml water washing;
mixing the water phase with the obtained sulfuric acid phase, extracting impurities with n-heptane, and dehydrating the obtained water phase under reduced pressure to obtain sulfuric acid with concentration of 95% or higher for recycling;
the organic phase of water washing is 2-adamantanone solution, the 2-adamantanone solution is concentrated to remove chloroform, and 8 g of crude product is separated out, and the crude product is recrystallized by methanol-water again to obtain 5.5 g of 2-adamantanone fine product.
The data for the 2-adamantanones prepared in examples 1-3 of the present application are shown in Table 1 below.
TABLE 1
| Example 1 | Example 2 | Example 3 | |
| Weight of fine product | 7.5 g | 6.5 g | 5.5 g |
| Purity of | 99.3％ | 99.2％ | 99.3％ |
| Melting point | 256-258℃ | 257-259℃ | 258-260℃ |
Claims (8)
1. A method for preparing a 2-adamantanone compound, comprising the steps of:
(1) Oxidation reaction: dissolving adamantane in a first organic solvent, wherein the first organic solvent is one or more of carbon tetrachloride, 1, 2-dichloroethane and chloroform, and then carrying out oxidation reaction under concentrated sulfuric acid, wherein the reaction temperature is 50-80 ℃;
(2) Hydrolysis: after the oxidation reaction is completed, adding the mixture into water for hydrolysis, and standing and layering after the hydrolysis to obtain an organic phase and a sulfuric acid phase;
(3) Organic phase extraction: the organic phase separated by hydrolysis is extracted by a second organic solvent to obtain 2-adamantanone solution;
(4) Sulfuric acid phase extraction: the sulfuric acid phase separated by hydrolysis is subjected to impurity extraction by a third organic solvent, and then dehydration treatment is carried out to obtain concentrated sulfuric acid for recycling;
(5) Concentrating and crystallizing: concentrating the 2-adamantanone solution obtained in the step (3), and cooling and crystallizing to obtain a 2-adamantanone crude product;
(6) And (5) recrystallizing: recrystallizing the 2-adamantanone crude product by an alcohol solvent to obtain a 2-adamantanone fine product.
2. The method for producing a 2-adamantanone compound according to claim 1, wherein: the volume weight ratio of the concentrated sulfuric acid to the adamantane is 6:1.
3. The method for producing a 2-adamantanone compound according to claim 1, wherein: the volume weight ratio of the first organic solvent to adamantane is 3:1.
4. The method for producing a 2-adamantanone compound according to claim 1, wherein: the reaction temperature in the step (2) is 70-80 ℃ and the reaction time is 12 hours.
5. The method for producing a 2-adamantanone compound according to claim 1, wherein: the second organic solvent in step (3) is water.
6. The method for producing a 2-adamantanone compound according to claim 1, wherein: the third organic solvent in the step (4) is one or more of petroleum ether, methylene dichloride and dichloroethane.
7. The method for producing a 2-adamantanone compound according to claim 1, wherein: the alcohol solvent in the step (6) adopts one of ethanol, methanol and isopropanol.
8. The method for producing a 2-adamantanone compound according to claim 1, wherein: and (3) after the oxidation reaction in the step (2) is completed, cooling and dripping the mixture into water at 0-5 ℃ for hydrolysis.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310771965.XA CN116813455A (en) | 2023-06-28 | 2023-06-28 | Preparation method of 2-adamantanone compound |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202310771965.XA CN116813455A (en) | 2023-06-28 | 2023-06-28 | Preparation method of 2-adamantanone compound |
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| CN116813455A true CN116813455A (en) | 2023-09-29 |
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| CN202310771965.XA Withdrawn CN116813455A (en) | 2023-06-28 | 2023-06-28 | Preparation method of 2-adamantanone compound |
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| Country | Link |
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- 2023-06-28 CN CN202310771965.XA patent/CN116813455A/en not_active Withdrawn
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Application publication date: 20230929 |
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