Quinone preparation method

Abstract

The invention relates to the field of organic conversion, in particular to a preparation method of quinone. The method comprises the following step: carrying out contact oxidation on a bisphenol compound and a nitrogen-substituted imide compound in a solvent. According to the method, the p-benzoquinone compound is prepared by oxidizing the bisphenol compound with the nitrogen-substituted imide compound as the oxidizing agent, the reaction condition is mild, and the reaction cost is low.

Description

Technical Field

[0001] The invention relates to the field of organic transformation, and in particular to a method for preparing quinone. Background Art

[0002] 4-Benzoquinone is widely used as an important intermediate in the fields of dyes, polymer materials, fine chemicals, and medicines. It is mainly used in dye intermediates, pesticides, and rubber antioxidants. It can also be used as an initiator for polymerization reactions and an inhibitor for monomers such as unsaturated polyesters.

[0003] The existing preparation methods of p-benzoquinone mainly include:

[0004] 1) Aniline oxidation method: Aniline is directly oxidized to p-benzoquinone using high-valent metal oxides such as MnO2 in sulfuric acid as an oxidant. The oxidation of aniline with sulfuric acid will produce a lot of ammonium sulfate salts, a large amount of wastewater and waste residue, and the catalyst price is relatively high.

[0005] 2) Using metal catalysts to oxidize phenol to p-benzoquinone under the action of oxygen or peroxide. Oxidation using oxygen or peroxide may cause explosion hazard in industry, and metal catalysts are expensive.

[0006] Nitrogen-substituted imide compounds are mainly used as halogenating agents or free radical reaction catalysts, and are not used in the prior art to oxidize bisphenol compounds to prepare quinones. Summary of the invention

[0007] The purpose of the present invention is to overcome the problems of harsh reaction conditions and low reaction yield in the prior art and to provide a method for preparing quinone, which has the characteristics of mild reaction conditions and high reaction yield.

[0008] In order to achieve the above object, the present invention provides a method for preparing quinone, which comprises: contacting and oxidizing a bisphenol compound with a nitrogen-substituted imide compound in a solvent.

[0009] Through the above technical solution, the present invention has the following advantages:

[0010] The invention adopts nitrogen-substituted imide compounds as oxidants to oxidize bisphenol compounds to prepare p-benzoquinone compounds, and the reaction conditions are mild and the reaction cost is low. DETAILED DESCRIPTION

[0011] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0012] The invention provides a method for preparing quinone, which comprises: contacting and oxidizing a bisphenol compound and a nitrogen-substituted imide compound in a solvent.

[0013] The invention adopts nitrogen-substituted imide compounds as oxidants to prepare p-benzoquinone compounds, and the reaction conditions are mild and the reaction cost is low.

[0014] According to a preferred embodiment of the present invention, the bisphenol compound is a para-bisphenol compound, preferably hydroquinone and / or naphthalene diol, and more preferably phenol. By adopting the above preferred embodiment, the reaction efficiency can be further improved.

[0015] According to a preferred embodiment of the present invention, the nitrogen-substituted amide compound is a nitrogen-substituted imide compound, preferably a cyclic nitrogen-substituted imide compound. By adopting the above preferred embodiment, the reaction efficiency can be further improved.

[0016] According to a preferred embodiment of the present invention, the nitrogen-substituted amide compound is at least one of a succinimide compound, a phthalamide compound and a 1,2,4,5-phenyltetracarboxamide compound. By adopting the above preferred embodiment, the reaction efficiency can be further improved.

[0017] According to a preferred embodiment of the present invention, the nitrogen substituted group is selected from halogen and / or hydroxyl, preferably halogen. By adopting the above preferred scheme, the reaction efficiency can be further improved.

[0018] According to a preferred embodiment of the present invention, the nitrogen substituted group is bromine or iodine. By adopting the above preferred embodiment, the reaction efficiency can be further improved.

[0019] In the present invention, as long as the purpose of the present invention can be achieved, there is no special requirement for the selection of the solvent. According to a preferred embodiment of the present invention, the solvent is selected from at least one of benzene, toluene, acetonitrile, dichloromethane, chloroform, carbon tetrachloride, methanol, ethanol, tert-butanol, dimethyl sulfoxide and N,N-dimethylformamide.

[0020] According to a preferred embodiment of the present invention, the contact oxidation conditions include: the ratio of the volume of the solvent to the mass of the bisphenol compound is 50:1-1:1 (mL / g).

[0021] According to a preferred embodiment of the present invention, the contact oxidation conditions include: the reaction temperature is 0°C-120°C, preferably 20-60°C, more preferably 25-40°C.

[0022] According to a preferred embodiment of the present invention, the contact oxidation conditions include: the amount of the nitrogen-substituted imide compound used is 1-10 times, preferably 1-3 times, and more preferably 1.1-1.5 times the molar amount of the bisphenol compound.

[0023] According to a preferred embodiment of the present invention, the method further comprises sequentially performing quenching, extraction separation, concentration and purification after contact oxidation.

[0024] In the present invention, the quenching method can be a conventional choice in the art. According to a preferred embodiment of the present invention, the quenching method is to add water and an organic solvent for liquid extraction, and the quenching agent is selected from water, sodium bicarbonate solution, etc.

[0025] According to a preferred embodiment of the present invention, the extracting agent for extraction and separation is selected from at least one of ethyl acetate, butyl acetate, dichloromethane and chloroform.

[0026] In the present invention, the concentration method can be a conventional choice in the art. According to a preferred embodiment of the present invention, the concentration method is reduced pressure evaporation concentration.

[0027] In the present invention, the purification method can be a conventional choice in the art. According to a preferred embodiment of the present invention, the purification method is rapid column chromatography.

[0028] The present invention will be described in detail below by way of examples. In the following examples, unless otherwise specified, the raw materials are all commercially available products.

[0029] Example 1

[0030] In a 100ml three-necked flask, add 11g of hydroquinone (M=110, 0.1mol), then add 30ml of acetonitrile, stir evenly, keep the water bath at 25°C, then slowly add 22.5g of iodosuccinimide (M=225, 0.11mol), monitor the reaction using thin plate chromatography, and quench the reaction after the reaction of the raw materials is complete. Add 30ml of ethyl acetate to extract and separate the organic phase. The organic phase is then rotary evaporated, and the crude product is subjected to rapid column chromatography to obtain 10.5g of p-benzoquinone (M=108), with a yield of 97.2%

[0031] Example 2

[0032] In a 100ml three-necked flask, add 11g of hydroquinone (M=110, 0.1mol), then add 30ml of acetonitrile, stir evenly, keep the water bath at 25°C, then slowly add 19.6g of bromosuccinimide (M=178, 0.11mol), monitor the reaction using thin plate chromatography, and quench the reaction after the reaction of the raw materials is complete. Add 30ml of ethyl acetate to extract and separate the organic phase. The organic phase is then rotary evaporated, and the crude product is subjected to rapid column chromatography to obtain 10g of p-benzoquinone (M=108), with a yield of 92.6%

[0033] Example 3

[0034] In a 200ml three-necked flask, add 22g of hydroquinone (M=110, 0.2mol), then add 50ml of acetonitrile, stir evenly, keep the water bath at 25°C, then slowly add 29.4g of chlorosuccinimide (M=133.5, 0.22mol), monitor the reaction using thin plate chromatography, and quench the reaction after the reaction of the raw materials is complete. Add 50ml of ethyl acetate to extract and separate the organic phase. The organic phase is then rotary evaporated, and the crude product is subjected to rapid column chromatography to obtain 19.6g of p-benzoquinone (M=108), with a yield of 90.7%

[0035] Example 4

[0036] In a 50ml three-necked flask, add 1.1g of hydroquinone (M=110, 0.01mol), then add 5ml of acetonitrile, stir evenly, keep the water bath at 25°C, then slowly add 1.8g of N-hydroxyphthalimide (M=163, 0.01mol), monitor the reaction using thin plate chromatography, and quench the reaction after the reaction of the raw materials is complete. Add 10ml of ethyl acetate to extract and separate the organic phase. The organic phase is then rotary evaporated, and the crude product is subjected to rapid column chromatography to obtain 0.9g of p-benzoquinone (M=108), with a yield of 83.3%.

[0037] Example 5

[0038] In a 100ml three-necked flask, add 4.4g of hydroquinone (M=110, 0.04mol), then add 30ml of acetonitrile, stir evenly, keep the water bath at 25°C, then slowly add 10.9g of iodophthalimide (M=273, 0.04mol), monitor the reaction using thin plate chromatography, and quench the reaction after the reaction of the raw materials is complete. Add 30ml of ethyl acetate to extract and separate the organic phase. The organic phase is then rotary evaporated, and the crude product is subjected to rapid column chromatography to obtain 4.1g of p-benzoquinone (M=108), with a yield of 94.9%

[0039] Example 6

[0040] In a 100ml three-necked flask, add 4.4g of hydroquinone (M=110, 0.04mol), then add 30ml of acetonitrile, stir evenly, keep the water bath at 25°C, then slowly add 13.6g of iodooctylsuccinimide (M=337, 0.04mol), monitor the reaction using thin plate chromatography, and quench the reaction after the reaction of the raw materials is complete. Add 30ml of ethyl acetate to extract and separate the organic phase. The organic phase is then rotary evaporated, and the crude product is subjected to rapid column chromatography to obtain 3.8g of p-benzoquinone (M=108), with a yield of 87.9%.

[0041] Example 7

[0042] In a 100ml three-necked flask, add 1.4 naphthalene diol 1.6g (M = 160, 0.01mol), then add 10ml acetonitrile, stir evenly, keep the water bath at 25°C, then slowly add iodosuccinimide 2.3g (M = 225, 0.01mol), use thin plate chromatography to monitor the reaction, and after the reaction of the raw materials is completed, quench the reaction. Add 30ml ethyl acetate to extract and separate the organic phase. The organic phase is then rotary evaporated, and the crude product is subjected to rapid column chromatography to obtain 1.4g of naphthoquinone (M = 158), with a yield of 88.6%

[0043] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A method for preparing quinone, characterized in that: The method comprises: contacting and oxidizing a bisphenol compound with a nitrogen-substituted imide compound in a solvent.

2. The preparation method according to claim 1, wherein The bisphenol compound is a p-bisphenol compound, preferably hydroquinone and / or naphthalene diol.

3. The preparation method according to claim 1 or 2, wherein The nitrogen-substituted amide compound is a nitrogen-substituted imide compound, preferably a cyclic nitrogen-substituted imide compound.

4. The preparation method according to any one of claims 1 to 3, wherein The nitrogen-substituted amide compound is selected from at least one of succinimide compounds, phthalamide compounds and 1,2,4,5-phenyltetracarboxamide compounds.

5. The preparation method according to any one of claims 1 to 4, wherein: The nitrogen substituted group is selected from halogen and / or hydroxyl, preferably halogen, more preferably bromine or iodine.

6. The preparation method according to any one of claims 1 to 5, wherein: The solvent is selected from at least one of benzene, toluene, acetonitrile, dichloromethane, chloroform, carbon tetrachloride, methanol, ethanol, tert-butanol, dimethyl sulfoxide and N,N-dimethylformamide.

7. The preparation method according to any one of claims 1 to 6, wherein: The contact oxidation conditions include: The ratio of the volume of the solvent to the mass of the bisphenol compound is 50:1-1:1; and / or The reaction temperature is 0°C-120°C, preferably 20-60°C, more preferably 25-40°C; and / or The amount of the nitrogen-substituted imide compound used is 1-10 times, preferably 1-3 times, and more preferably 1.1-1.5 times, that of the bisphenol compound in terms of molar amount.

8. The preparation method according to any one of claims 1 to 7, wherein: The method also includes sequentially performing quenching, extraction separation, concentration and purification after contact oxidation.

9. The preparation method according to claim 8, wherein: The quenching method is to add water and an organic solvent extractant; and / or The concentration method is evaporation under reduced pressure; and / or The purification method is rapid column chromatography.

10. The preparation method according to claim 8, wherein: The extracting agent for extraction and separation is selected from at least one of ethyl acetate, butyl acetate, dichloromethane and chloroform.