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Preparation method of 1,2-cyclohexanedione

A technology of cyclohexanedione and cyclohexanone, applied in the field of chemistry, can solve the problems of high price, low reaction yield, harsh reaction conditions, etc., and achieves enhanced power supply and steric hindrance, simple post-processing purification, and reaction conditions. mild effect

Active Publication Date: 2021-03-05
SINOSTEEL NANJING NEW MATERIALS RES INST CO LTD
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0007] Among the above-mentioned methods, method one is currently the only method that can be used in industrialized production. This method has a low yield and uses stoichiometric selenium dioxide, which is expensive, and the selenium residue produced by the reaction is difficult to handle, causing serious environmental pollution.
Method 2 has a moderate yield, but its raw material isoamyl nitrite is not easy to obtain, and needs to be self-made and the reaction conditions are harsh; in addition, the reaction system needs to be reacted at a low temperature of -15°C, and a large amount of ether and acid are used to cause three waste pollution, which is not conducive to Clean manufacturing
Method 3 uses elemental iodine to catalyze the reaction, and the reaction conditions are mild, but a mixed solvent of organic solvent and water is used in the reaction process, and there are problems such as difficulty in subsequent organic solvent recovery, large amount of waste water, and low reaction yield.
[0008] In summary, there is not yet a high-yield and environmentally friendly method for the industrial production of 1,2-cyclohexanedione

Method used

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  • Preparation method of 1,2-cyclohexanedione
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  • Preparation method of 1,2-cyclohexanedione

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Experimental program
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Effect test

Embodiment 1

[0033] Under nitrogen protection, 198.0g cyclohexanone (99%, 2.0mol), 3.9g cuprous iodide (99%, 0.02mol), 6.2g ligand L1 (99%, 0.02mmol) were added in a 500mL reaction flask, The structural formula of ligand L1 is as follows:

[0034]

[0035] After feeding, start stirring with a stirring speed of 600rpm, add 38.9g concentration of 35% hydrogen peroxide (35%, 0.4mol) dropwise at room temperature, dropwise time 2hr, after dropwise addition, heat up to 60°C, keep warm for 3hr, after the reaction, Washing and liquid separation, the organic layer was rectified under reduced pressure to recover 156.2g (99.1%, 1.58mol) of cyclohexanone and 44.0g (99.3%, 0.39mol) of 1,2-cyclohexanedione, with a yield of 92.9% (based on cyclohexanone Hexanone meter).

[0036] Such as figure 1 Shown is the present embodiment 1,2-cyclohexanedione 1 H NMR spectrum: 1 H NMR (500MHz, CDCl 3 ): δ2.38-2.41 (t, J=5.5Hz, 6.0Hz, 4H), 1.98-2.04 (m, 4H).

Embodiment 2

[0038] Under nitrogen protection, 237.6g cyclohexanone (99%, 2.4mol), 11.6g cuprous bromide (99%, 0.08mol), 31.2g ligand L2 (99%, 0.08mmol) were added in a 500mL reaction flask, The structural formula of ligand L2 is as follows:

[0039]

[0040] After feeding, start stirring at a stirring speed of 600rpm. Add 54.4g of 50% hydrogen peroxide (50%, 0.8mol) dropwise at room temperature for 1.5hr. , washed with water and separated, and the organic layer was rectified under reduced pressure to obtain 169.9g (99.2%, 1.72mol) of cyclohexanone and 73.5g (99.1%, 0.65mol) of 1,2-cyclohexanedione, with a yield of 95.6% (based on Cyclohexanone meter).

[0041] It should be noted that cuprous chloride is similar in structure to cuprous bromide in this embodiment, so the catalyst in this embodiment can also be replaced by cuprous chloride.

Embodiment 3

[0043] Under nitrogen protection, add 297.0g cyclohexanone (99%, 3.0mol), 0.43g cuprous oxide (99%, 0.003mol), 0.76g ligand L3 (99%, 0.003mol) in the 500mL reaction bottle, formulate The structural formula of body L3 is as follows:

[0044]

[0045] After feeding, start stirring with a stirring speed of 600rpm. Add 40.8g of 25% hydrogen peroxide (25%, 0.3mol) dropwise at room temperature for 1hr. After the dropwise addition, heat up to 40°C and keep the temperature for 6hr. After the reaction, Washing and liquid separation, the organic layer was rectified under reduced pressure to recover 278.2g (99.3%, 2.81mol) of cyclohexanone, 13.6g (99.0%, 0.12mol) of 1,2-cyclohexanedione, and the yield was 63.2% (based on cyclohexanone Hexanone meter).

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Abstract

The invention discloses a preparation method of 1,2-cyclohexanedione, and belongs to the technical field of chemistry. The preparation method comprises the following steps: under the protection of nitrogen, uniformly stirring cyclohexanone, a catalyst and a ligand, dropwise adding hydrogen peroxide at room temperature for 1-2 hours, conducting heating to 40-60 DEG C after dropwise adding is finished, carrying out heat preservation reaction for 3-6 hours, conducting washing with water, separating liquid, and carrying out reduced pressure distillation on an organic layer to obtain 1,2-cyclohexanedione, wherein the catalyst is a copper salt catalyst, and the ligand is a beta-diketimine ligand. Compared with reported methods, the method has the advantages that cheap and easily available hydrogen peroxide is used as an oxidizing agent, a byproduct is water, a reaction system is green and clean, cyclohexanone is used as both a reactant and a solvent in the reaction process, reaction conditions are mild, and operation is convenient. The method is high in yield and green and clean in process, and a new method is provided for synthesis of 1, 2-cyclohexanedione.

Description

technical field [0001] The invention relates to the technical field of chemistry, in particular to a preparation method of 1,2-cyclohexanedione. Background technique [0002] 1,2-Cyclohexanedione is an important organic chemical raw material, which is mainly used as an important intermediate in the synthesis of fine chemicals such as fragrances, medicines, and OLED light-emitting materials. It can also be used in industries such as rubber, leather, coatings, and pesticides. produced solvents. 1,2-cyclohexanedione is mainly prepared by oxidation of cyclohexanone, and according to literature reports, there are mainly the following three types. [0003] [0004] Method 1: In the 1930s, Riley et al. publicly reported a method for preparing 1,2-cyclohexanedione by selenium dioxide oxidation of cyclohexanone. The method used equivalent-level selenium dioxide as an oxidant, and the yield was 30 -50%. (Journal of Chemical Society, 1932, 1875) [0005] Method 2: In 2014, Wang ...

Claims

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Application Information

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IPC IPC(8): C07C45/28C07C49/403B01J31/22
CPCC07C45/28B01J31/1815C07C2601/14B01J2231/70B01J2531/16C07C49/403
Inventor 朱叶峰裴晓东杨修光张玲吴忠凯骆艳华
Owner SINOSTEEL NANJING NEW MATERIALS RES INST CO LTD
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