CN111170830A - Preparation method of adamantanol compound - Google Patents
Preparation method of adamantanol compound Download PDFInfo
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- CN111170830A CN111170830A CN202010028747.3A CN202010028747A CN111170830A CN 111170830 A CN111170830 A CN 111170830A CN 202010028747 A CN202010028747 A CN 202010028747A CN 111170830 A CN111170830 A CN 111170830A
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- adamantane
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- sulfuric acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/56—Ring systems containing bridged rings
- C07C2603/58—Ring systems containing bridged rings containing three rings
- C07C2603/70—Ring systems containing bridged rings containing three rings containing only six-membered rings
- C07C2603/74—Adamantanes
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of an adamantanol compound, which comprises the following steps: adding a certain amount of adamantane, a solvent and concentrated sulfuric acid into a three-mouth bottle provided with a thermometer and a condensation reflux device, stirring for dissolving, slowly adding a certain amount of oxidant, stirring for reacting for a period of time at 80 ℃, distilling under reduced pressure to remove the solvent, and neutralizing with a 30% sodium hydroxide solution; the process has the advantages of cheap and easily obtained raw materials, simple and convenient operation, mild reaction conditions and the like, and is suitable for industrial production.
Description
Technical Field
The invention relates to the field of preparation of adamantanol compounds, and in particular relates to a preparation method of an adamantanol compound.
Background
Adamantane alcohol compounds obtained by bonding a hydroxyl group to an adamantane skeleton are very important fine chemical products, and can be used for preparing monomers of photoresists, photochromic compounds, pharmaceutical intermediates and the like, and also have wide applications in the fields of coatings, adhesives, films, adsorbing materials and the like.
As for the preparation method of adamantanol compounds, it is known that mainly adamantanes are brominated and then hydrolyzed at high temperature under a certain pressure or hydrolyzed using an excess amount of silver sulfate; for example, in chinese patent application publication No. CN101492348A, adamantane is brominated and then hydrolyzed at high temperature under pressure to prepare 1-adamantanol. The method uses excessive resource substance bromine, and has high price and inconvenient transportation, thus leading to higher production cost. The document j.org.chem.,26.2207(1961) further uses expensive silver sulfate to hydrolyze adamantane bromide.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of an adamantanol compound, and the process has the advantages of cheap and easily obtained raw materials, simple and convenient operation, mild reaction conditions and the like, and is suitable for industrial production.
In order to achieve the aim of the invention, the invention adopts the specific scheme that:
a preparation method of adamantanol compounds comprises the following steps: adding a certain amount of adamantane, a solvent and concentrated sulfuric acid into a three-mouth bottle provided with a thermometer and a condensation reflux device, stirring for dissolving, slowly adding a certain amount of oxidant, stirring for reacting for a period of time at 80 ℃, distilling under reduced pressure to remove the solvent, and neutralizing with a 30% sodium hydroxide solution; three different products appeared depending on the different amounts of oxidant used in the preparation of the 3 products:
(1) concentrating the neutralized mixture, extracting with ethyl acetate for several times, naturally cooling the extractive solution overnight to obtain white solid, recrystallizing with ethanol/ethane, and drying to obtain 1, 3-adamantanediol as white crystal;
(2) filtering the neutralized mixture, washing the filtrate with anhydrous ethanol, concentrating the filtrate, extracting with ethyl acetate for several times, cooling the extractive solution to 5-10 deg.C overnight, and recrystallizing the precipitated solid with ethanol/dichloromethane to obtain 1, 3, 5-adamantanetriol as white crystal;
(3) and (3) carrying out suction filtration on the neutralized mixture, washing the filtrate by absolute ethyl alcohol, distilling the filtrate under reduced pressure to remove the solvent, extracting for a plurality of times by using tetrahydrofuran and isopropanol with the volume ratio of 1, cooling the filtrate to 0-5 ℃, standing overnight to obtain a white solid, and recrystallizing by using methanol/ethanol/acetone to obtain 1, 3, 5, 7-adamantane tetraol and white crystals.
Preferably, the solvent is acetic acid, acetic anhydride.
Preferably, the oxidizing agent is chromic acid or chromium trioxide.
Preferably, the 1, 3-adamantanediol synthesis conditions are: acetic acid is used as a solvent, the molar ratio of chromic acid to adamantane is 4, the molar ratio of sulfuric acid to adamantane is 0.5, and the reaction is carried out for 2 hours at the temperature of 80 ℃.
Preferably, the synthesis conditions of the 1, 3, 5-adamantanetriol are as follows: acetic acid is used as a solvent, the molar ratio of chromic acid to adamantane is 8, the molar ratio of sulfuric acid to adamantane is 0.5, and the reaction is carried out for 3 hours at the temperature of 80 ℃.
Preferably, the 1, 3, 5, 7-adamantanetetraol synthesis conditions are as follows: using acetic acid and acetic anhydride with volume ratio of 0.5 as solvent, chromium trioxide and adamantane with molar ratio of 12, sulfuric acid and adamantane with molar ratio of 1, and reacting at 80 ℃ for 2 h.
The invention has the beneficial effects that:
the process has the advantages of cheap and easily obtained raw materials, simple and convenient operation, mild reaction conditions and the like, and is suitable for industrial production.
Detailed Description
The present invention is further described below by way of specific examples, but the present invention is not limited to only the following examples. Variations, combinations, or substitutions of the invention, which are within the scope of the invention or the spirit, scope of the invention, will be apparent to those of skill in the art and are within the scope of the invention.
A preparation method of adamantanol compounds comprises the following steps: adding a certain amount of adamantane, a solvent and concentrated sulfuric acid into a three-mouth bottle provided with a thermometer and a condensation reflux device, stirring for dissolving, slowly adding a certain amount of oxidant, stirring for reacting for a period of time at 80 ℃, distilling under reduced pressure to remove the solvent, and neutralizing with a 30% sodium hydroxide solution; three different products appeared depending on the different amounts of oxidant used in the preparation of the 3 products:
(1) concentrating the neutralized mixture, extracting with ethyl acetate for several times, naturally cooling the extractive solution overnight to obtain white solid, recrystallizing with ethanol/ethane, and drying to obtain 1, 3-adamantanediol as white crystal;
(2) filtering the neutralized mixture, washing the filtrate with anhydrous ethanol, concentrating the filtrate, extracting with ethyl acetate for several times, cooling the extractive solution to 5-10 deg.C overnight, and recrystallizing the precipitated solid with ethanol/dichloromethane to obtain 1, 3, 5-adamantanetriol as white crystal;
(3) and (3) carrying out suction filtration on the neutralized mixture, washing the filtrate by absolute ethyl alcohol, distilling the filtrate under reduced pressure to remove the solvent, extracting for a plurality of times by using tetrahydrofuran and isopropanol with the volume ratio of 1, cooling the filtrate to 0-5 ℃, standing overnight to obtain a white solid, and recrystallizing by using methanol/ethanol/acetone to obtain 1, 3, 5, 7-adamantane tetraol and white crystals.
The solvent is acetic acid and acetic anhydride.
The oxidant is chromic acid or chromium trioxide.
The synthesis conditions of the 1, 3-adamantanediol are as follows: acetic acid is used as a solvent, the molar ratio of chromic acid to adamantane is 4, the molar ratio of sulfuric acid to adamantane is 0.5, and the reaction is carried out for 2 hours at the temperature of 80 ℃.
The synthesis conditions of the 1, 3, 5-adamantanetriol are as follows: acetic acid is used as a solvent, the molar ratio of chromic acid to adamantane is 8, the molar ratio of sulfuric acid to adamantane is 0.5, and the reaction is carried out for 3 hours at the temperature of 80 ℃.
The synthesis conditions of the 1, 3, 5, 7-adamantanetetraol are as follows: using acetic acid and acetic anhydride with volume ratio of 0.5 as solvent, chromium trioxide and adamantane with molar ratio of 12, sulfuric acid and adamantane with molar ratio of 1, and reacting at 80 ℃ for 2 h.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the present invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (6)
1. A preparation method of an adamantanol compound is characterized by comprising the following steps: will decideAdding a certain amount of adamantane, a solvent and concentrated sulfuric acid into a three-mouth bottle provided with a thermometer and a condensation reflux device, stirring for dissolving, slowly adding a certain amount of oxidant, stirring for reacting for a period of time at 80 ℃, distilling under reduced pressure to remove the solvent, and neutralizing with 30% sodium hydroxide solution; three different products appeared depending on the different amounts of oxidant used in the preparation of the 3 products:
(1) concentrating the neutralized mixture, extracting with ethyl acetate for several times, naturally cooling the extractive solution overnight to obtain white solid, recrystallizing with ethanol/ethane, and drying to obtain 1, 3-adamantanediol as white crystal;
(2) filtering the neutralized mixture, washing the filtrate with anhydrous ethanol, concentrating the filtrate, extracting with ethyl acetate for several times, cooling the extractive solution to 5-10 deg.C overnight, and recrystallizing the precipitated solid with ethanol/dichloromethane to obtain 1, 3, 5-adamantanetriol as white crystal;
(3) and (3) carrying out suction filtration on the neutralized mixture, washing the filtrate by absolute ethyl alcohol, distilling the filtrate under reduced pressure to remove the solvent, extracting for a plurality of times by using tetrahydrofuran and isopropanol with the volume ratio of 1, cooling the filtrate to 0-5 ℃, standing overnight to obtain a white solid, and recrystallizing by using methanol/ethanol/acetone to obtain 1, 3, 5, 7-adamantane tetraol and white crystals.
2. The method of claim 1, wherein the solvent is acetic acid or acetic anhydride.
3. The method of claim 1, wherein the oxidizing agent is chromic acid or chromium trioxide.
4. The method for preparing adamantanol compound according to claim 3, wherein the conditions for synthesizing 1, 3-adamantanediol are as follows: acetic acid is used as a solvent, the molar ratio of chromic acid to adamantane is 4, the molar ratio of sulfuric acid to adamantane is 0.5, and the reaction is carried out for 2 hours at the temperature of 80 ℃.
5. The method for preparing adamantanol compound according to claim 3, wherein the conditions for synthesizing 1, 3, 5-adamantanetriol are as follows: acetic acid is used as a solvent, the molar ratio of chromic acid to adamantane is 8, the molar ratio of sulfuric acid to adamantane is 0.5, and the reaction is carried out for 3 hours at the temperature of 80 ℃.
6. The method for preparing adamantanol compound according to claim 3, wherein the conditions for synthesizing 1, 3, 5, 7-adamantanetetraol are as follows: using acetic acid and acetic anhydride with volume ratio of 0.5 as solvent, chromium trioxide and adamantane with molar ratio of 12, sulfuric acid and adamantane with molar ratio of 1, and reacting at 80 ℃ for 2 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010028747.3A CN111170830A (en) | 2020-01-11 | 2020-01-11 | Preparation method of adamantanol compound |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010028747.3A CN111170830A (en) | 2020-01-11 | 2020-01-11 | Preparation method of adamantanol compound |
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| CN111170830A true CN111170830A (en) | 2020-05-19 |
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| CN202010028747.3A Pending CN111170830A (en) | 2020-01-11 | 2020-01-11 | Preparation method of adamantanol compound |
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| CN (1) | CN111170830A (en) |
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2020
- 2020-01-11 CN CN202010028747.3A patent/CN111170830A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 付长安等: "金刚烷直接氧化制备金刚烷多元醇新工艺", 《化工学报》 * |
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Application publication date: 20200519 |