CN112661610A

CN112661610A - Preparation method of 1, 3-dihydroxy adamantane

Info

Publication number: CN112661610A
Application number: CN202011594934.4A
Authority: CN
Inventors: 蒋小惠; 傅志伟; 毕景峰; 郭颖; 贺宝元
Original assignee: Shanghai Bodong Chemical Technology Co ltd
Current assignee: Shanghai Bodong Chemical Technology Co ltd
Priority date: 2020-12-28
Filing date: 2020-12-28
Publication date: 2021-04-16
Anticipated expiration: 2040-12-28
Also published as: CN112661610B

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

Preparation method of 1, 3-dihydroxy adamantane

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, the metal cocatalyst can promote oxidation, so that 1, 3-dihydroxy adamantane is directly synthesized from adamantane by a one-step method, 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 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 (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

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.

2. The method of claim 1, 3-dihydroxyadamantane preparation according to claim 1, where the nitroxide catalyst is piperidine nitroxide.

3. The method of claim 2, wherein 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.

4. The method of claim 1, 3-dihydroxyadamantane preparation according to claim 1, characterised in that the promoter is one of cobalt acetate, nickel acetate and copper acetate.

5. A method for preparing 1, 3-dihydroxy adamantane according to any of claims 1 to 4, characterized in that the molar ratio of adamantane, sodium hypochlorite and nitroxide catalyst is 1 (2-4): 0.02-0.1, and the molar ratio of nitroxide catalyst and cocatalyst is 5: 1.

6. The method of claim 1, 3-dihydroxyadamantane preparation, wherein the hypochlorite is one of sodium hypochlorite and calcium hypochlorite.