CN112661610B - Preparation method of 1, 3-dihydroxy adamantane - Google Patents
Preparation method of 1, 3-dihydroxy adamantane Download PDFInfo
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- CN112661610B CN112661610B CN202011594934.4A CN202011594934A CN112661610B CN 112661610 B CN112661610 B CN 112661610B CN 202011594934 A CN202011594934 A CN 202011594934A CN 112661610 B CN112661610 B CN 112661610B
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- adamantane
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- 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
Abstract
The invention belongs to the technical field of organic synthesis, and discloses a preparation method of 1, 3-dihydroxy adamantane, which comprises the following steps: dissolving adamantane in a solvent, adding a nitroxide free radical catalyst and a cocatalyst, adding hypochlorite under an alkaline condition for oxidation, and purifying to obtain 1, 3-dihydroxy adamantane. The invention has simple synthetic route, and the product yield is high due to the matched use of the nitroxide free radical catalyst and the cocatalyst.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a preparation method of 1, 3-dihydroxy adamantane.
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 1, 3-dihydroxyadamantane, it is known that mainly adamantane is brominated and then hydrolyzed at high temperature under a certain pressure or hydrolyzed using an excessive amount of silver sulfate, and the above method uses an excessive amount of bromine as a resource substance, which is expensive and inconvenient in transportation, resulting in high production cost.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects of the prior art and aim to provide a preparation method for synthesizing 1, 3-dihydroxy adamantane with high yield by a one-step method.
In order to solve the technical problems, the invention provides the following technical scheme:
the invention provides a preparation method of 1, 3-dihydroxy adamantane, which comprises the following steps: dissolving adamantane in a solvent, adding a nitroxide free radical catalyst and a cocatalyst, adding hypochlorite for oxidation, and purifying to obtain 1, 3-dihydroxy adamantane.
The synthetic route is as follows:
as a preferred technical scheme of the invention, the nitroxide radical catalyst is piperidine nitroxide radical.
In a preferred embodiment of the present invention, the piperidine nitroxide radical is one of 4-hydroxy-2, 2,6, 6-tetramethylpiperidine-1-oxyl, 4-oxo-2, 2,6, 6-tetramethylpiperidine-1-oxyl and 2,2,6, 6-tetramethylpiperidine-1-oxyl.
As a preferred technical scheme of the invention, the cocatalyst is one of cobalt acetate, nickel acetate and copper acetate.
According to a preferable technical scheme, the molar ratio of the adamantane, the sodium hypochlorite and the nitroxide free radical catalyst is 1 (2-4) to 0.02-0.1, and the molar ratio of the nitroxide free radical catalyst to the cocatalyst is 5 to 1.
Preferably, the molar ratio of adamantane, sodium hypochlorite and nitroxide free radical catalyst is 1:3: 0.05.
As a preferred technical scheme of the invention, the hypochlorite is one of sodium hypochlorite and calcium hypochlorite.
Preferably, the hypochlorite is sodium hypochlorite.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention has simple synthetic route and small pollution without using bromine-containing compounds.
(2) The nitroxide free radical catalyst and the cocatalyst are used in a matched manner, and the metal cocatalyst can promote the oxidation, so that the 1, 3-dihydroxy adamantane is directly synthesized by one step from adamantane, the molar yield of the product is higher than 79.4%, and the by-products are few.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a gas chromatogram of 1, 3-dihydroxyadamantane of example 1;
FIG. 2 is a gas chromatogram of 1, 3-dihydroxyadamantane of example 2;
FIG. 3 is a gas chromatogram of 1, 3-dihydroxyadamantane in example 3.
Detailed Description
The preferred embodiments of the present invention will be described in conjunction with the accompanying drawings, and it will be understood that they are described herein for the purpose of illustration and explanation and not limitation.
Example 1
Adamantane (10g,73.4mmol) was dissolved in methylene chloride (100mL) at 0 ℃ and 2,2,6, 6-tetramethylpiperidine-1-oxyl (0.57g,3.65mmol) and cobalt acetate (0.13g,0.73mmol) were added, followed by addition of a 10% by mass sodium hypochlorite solution (111.66g,150mmol), and the reaction solution was stirred for 3 hours. Separating to obtain an organic phase, washing with water, concentrating, adding into ethyl acetate, centrifuging, and filtering for the first time; pulping the solid after the first filtration, centrifuging again, and filtering for the second time; the solid obtained by the second filtration was dried to give 1, 3-dihydroxyadamantane (10.3g,61.2mmol, molar yield 83.4%).
Example 2
Adamantane (10g,73.4mmol) was dissolved in methylene chloride (100mL) at 0 ℃ and 4-hydroxy-2, 2,6, 6-tetramethylpiperidine-1-oxyl (0.63g,3.66mmol) and nickel acetate (0.13g,0.74mmol) were added, followed by addition of a 10% by mass sodium hypochlorite solution (111.66g,150mmol), and the reaction solution was stirred for 3 hours. Separating to obtain an organic phase, washing with water, concentrating, adding into ethyl acetate, centrifuging, and filtering for the first time; pulping the solid after the first filtration, centrifuging again, and filtering for the second time; the solid obtained by the second filtration was dried to give 1, 3-dihydroxyadamantane (10g,59.4mmol, molar yield 81.0%).
Example 3
Adamantane (10g,73.4mmol) was dissolved in methylene chloride (100mL) at 0 ℃ and 4-oxo-2, 2,6, 6-tetramethylpiperidine-1-oxyl (0.63g,3.70mmol) and copper acetate (0.15g,0.75mmol) were added, and a 10% sodium hypochlorite solution (111.66g,150mmol) was added to stir the reaction solution for 3 hours. Separating to obtain an organic phase, washing with water, concentrating, adding ethyl acetate, centrifuging, and filtering for the first time; pulping the solid after the first filtration, centrifuging again, and filtering for the second time; the solid obtained by the second filtration was dried to give 1, 3-dihydroxyadamantane (9.8g,58.3mmol, molar yield 79.4%).
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (3)
1. A preparation method of 1, 3-dihydroxy adamantane is characterized by comprising the following steps: dissolving adamantane in a solvent, adding a nitroxide free radical catalyst and a cocatalyst, adding hypochlorite for oxidation, and purifying to obtain 1, 3-dihydroxy adamantane; the nitroxide free radical catalyst is piperidine nitroxide free radical, the cocatalyst is one of cobalt acetate, nickel acetate and copper acetate, and the hypochlorite is sodium hypochlorite.
2. The method of claim 1, 3-dihydroxyadamantane, wherein the piperidinyloxy radical is one of 4-hydroxy-2, 2,6, 6-tetramethylpiperidin-1-yloxy radical, 4-oxo-2, 2,6, 6-tetramethylpiperidin-1-yloxy radical, and 2,2,6, 6-tetramethylpiperidin-1-yloxy radical.
3. The method for preparing 1, 3-dihydroxyadamantane according to any one of claims 1 to 2, characterized in that the molar ratio of adamantane, sodium hypochlorite and nitroxide radical catalyst is 1 (2-4) to (0.02-0.1), and the molar ratio of nitroxide radical catalyst to cocatalyst is 5: 1.
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| JP4756719B2 (en) * | 1997-02-17 | 2011-08-24 | ダイセル化学工業株式会社 | Oxidation catalyst system, oxidation method and oxide production method |
| JP4171879B2 (en) * | 2002-07-17 | 2008-10-29 | 三菱瓦斯化学株式会社 | Method for producing adamantanediol |
| JP2005306802A (en) * | 2004-04-23 | 2005-11-04 | Mitsubishi Gas Chem Co Inc | Method for producing adamantanediol |
| JP5168225B2 (en) * | 2009-05-14 | 2013-03-21 | 三菱瓦斯化学株式会社 | Method for producing adamantanols |
| CN104725194B (en) * | 2015-02-03 | 2016-08-17 | 泸州大洲化工有限公司 | A kind of preparation method of adamantane alcohol compound |
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