CN112707796A - Synthesis and refining method of electronic grade binaphthol - Google Patents

Synthesis and refining method of electronic grade binaphthol Download PDF

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CN112707796A
CN112707796A CN202011493961.2A CN202011493961A CN112707796A CN 112707796 A CN112707796 A CN 112707796A CN 202011493961 A CN202011493961 A CN 202011493961A CN 112707796 A CN112707796 A CN 112707796A
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binaphthol
refining
antioxidant
organic solvent
crude
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CN112707796B (en
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李灏
王军生
任建坡
纪烈义
蒋志强
刘鹏
邢晓杰
马丹丹
常新月
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Sinochem Hebei Fuheng Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
    • C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
    • C07C37/72—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by liquid-liquid treatment

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention provides a method for synthesizing and refining electronic-grade binaphthol. The synthesis method comprises the following steps: preparing a crude product of binaphthol; and refining the crude product of the binaphthol at 90-102 ℃ in the presence of an antioxidant, a first organic solvent and water to obtain the binaphthol. The antioxidant is added in the refining process, so that the color change probability of the binaphthol caused by oxidation can be greatly reduced, and the chromaticity of the binaphthol is improved. The addition of the first organic solvent and water is beneficial to improving the heating uniformity of the binaphthol in the refining process. Meanwhile, the antioxidant can be dissolved in water, and the binaphthol is dissolved in the organic phase, so that the antioxidant can be removed by separating the inorganic phase from the organic phase after the refining process is finished, and the binaphthol with higher purity can be obtained. In addition, the refining process is carried out at a specific temperature, which is favorable for greatly improving the solubility of the binaphthol in the first organic solvent, thereby improving the recovery rate of the binaphthol.

Description

Synthesis and refining method of electronic grade binaphthol
Technical Field
The invention relates to the field of synthesis and refining of electronic-grade binaphthol, in particular to a method for synthesizing and refining the electronic-grade binaphthol.
Background
1,1' -bi-2-naphthol (binaphthol for short) is white needle crystal or powder, and molecular formula is C20H14O2The structural formula is as follows:
Figure BDA0002841523540000011
the melting point of the binaphthol is 216-218 ℃, the binaphthol is soluble in ether and alkali liquor, slightly soluble in alcohol, insoluble in chloroform, insoluble in water and sublimed at the boiling point, and the binaphthol is widely applied to the fields of organic synthesis, fuels, pesticides, medicines and the like.
Because binaphthol is easily oxidized under the conditions of high temperature, air and light, binaphthol is easily oxidized and discolored in the refining process, which greatly influences the appearance and purity of the product and influences the subsequent application of the product. Therefore, it is desirable to provide a method for synthesizing and purifying electronic grade binaphthol capable of inhibiting oxidative discoloration of binaphthol.
Disclosure of Invention
The invention mainly aims to provide a method for synthesizing and refining electronic-grade binaphthol, which solves the problems that binaphthol is easy to oxidize and discolor and has low yield in the existing binaphthol refining process.
In order to achieve the above object, the present invention provides a method for synthesizing and refining electronic grade binaphthol, comprising: preparing a crude product of binaphthol; and refining the crude product of the binaphthol at 90-102 ℃ in the presence of an antioxidant, a first organic solvent and water to obtain the electronic grade binaphthol.
Further, the antioxidant is selected from one or more of the group consisting of 2-naphthol, oxalic acid and ascorbic acid.
Further, the antioxidant is a mixture of oxalic acid and 2-naphthol, and the weight ratio of the antioxidant to the antioxidant is 1 (1.5-2.5).
Further, the weight ratio of the binaphthol crude product to the antioxidant to the first organic solvent is 100 (0.2-1): (600-700).
Further, the process for preparing crude binaphthol product comprises: in the presence of a copper-ammonia complex and a second organic solvent, 2-naphthol is taken as a raw material to carry out oxidative coupling reaction to prepare a crude binaphthol product.
Further, the first organic solvent and the second organic solvent are each independently selected from one or more of the group consisting of toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, and trichlorobenzene.
By applying the technical scheme of the invention, the antioxidant is added in the refining process, so that the probability of color change of the binaphthol due to oxidation can be greatly reduced, and the chromaticity of the electronic-grade binaphthol is improved. The addition of the first organic solvent and water is beneficial to improving the heating uniformity of the binaphthol in the refining process. Meanwhile, the antioxidant and the impurity metal ions can be dissolved in water, and the binaphthol is dissolved in the organic phase, so that the antioxidant and the metal ions can be removed by separating the inorganic phase from the organic phase after the refining process is finished, and the high-purity electronic grade binaphthol is obtained. In addition, the refining process is carried out at a specific temperature, which is favorable for greatly improving the solubility of the binaphthol in the first organic solvent, thereby improving the recovery rate of the electronic-grade binaphthol.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As described in the background art, the existing binaphthol refining process is easy to be oxidized and discolored and has low yield. In order to solve the technical problem, the present application provides a method for synthesizing and refining an electronic-grade binaphthol, including: preparing a crude product of binaphthol; in the presence of an antioxidant, an organic solvent and water, refining the crude product of the binaphthol at 90-102 ℃ to obtain the electronic grade binaphthol (the purity is 99.7 percent or more, and the content of each impurity metal ion is lower than 1 ppm). The crude binaphthol product needs to be purified because it contains a certain amount of impurities.
According to the preparation method of the binaphthol, the antioxidant is added in the refining process, so that the color change probability of the binaphthol caused by oxidation can be greatly reduced, and the chromaticity of the electronic-grade binaphthol is improved. The addition of the first organic solvent and water is beneficial to improving the heating uniformity of the binaphthol in the refining process. Due to antioxidant and impurity metal ions (such as Na)+、Cu2 +、Fe2+、Ca2+、Mg2+、K+) Can be dissolved in water, and the binaphthol is dissolved in an organic phase, so that after the refining process is finished, the antioxidant and metal ions can be removed by separating the inorganic phase from the organic phase, and the high-purity electronic grade binaphthol is obtained. In addition, the refining process is carried out at a specific temperature, which is favorable for greatly improving the solubility of the binaphthol in the first organic solvent, thereby improving the recovery rate of the electronic-grade binaphthol. In the synthesis and refining method of the electronic grade binaphthol, the antioxidant can be selected from the types commonly used in the field.
In a preferred embodiment, the antioxidants include, but are not limited to, one or more of the group consisting of 2-naphthol, oxalic acid and ascorbic acid. Compared with other antioxidants, the antioxidants have more excellent antioxidant performance, so that the risk of oxidative discoloration of binaphthol is further reduced. More preferably, the antioxidant is oxalic acid. The oxalic acid is favorable for further reducing the risk of oxidizing the binaphthol, and can be complexed with metal ions in the binaphthol, so that the purity and the yield of the electronic-grade binaphthol can be further improved. More preferably, the antioxidant is a mixture of oxalic acid and 2-naphthol, and the weight ratio of the antioxidant to the antioxidant is 1 (1.5-2.5).
The addition of the first organic solvent can make the heating of the binaphthol more uniform in the refining process. In order to further improve the chromaticity of the electronic grade binaphthol and simultaneously improve the purity and the yield of the electronic grade binaphthol, the weight ratio of the binaphthol crude product to the antioxidant and the first organic solvent is preferably 100 (0.2-1): (600-700). When the using amount of the oxidant is less, the chromaticity of the binaphthol is poor; when the amount of the oxidant is large, the purity of the binaphthol is reduced. The amount of water added during the refining process is only required to be sufficient to dissolve the antioxidant and the impurity metal ions.
The crude binaphthol product can be prepared by methods commonly used in the art, for example, the above-mentioned processes for preparing crude binaphthol product include: in the presence of a copper-ammonia complex and a second organic solvent, 2-naphthol is taken as a raw material to carry out oxidative coupling reaction to prepare a crude binaphthol product.
In the above refining process, the first organic solvent and the second organic solvent may be selected from those commonly used in the art. In a preferred embodiment, the first and second organic solvents include, but are not limited to, one or more of the group consisting of toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, and trichlorobenzene.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
Example 1
(1) Preparation of crude binaphthol product
Taking a copper-ammonia complex as a catalyst, and carrying out oxidative coupling reaction on 2-naphthol and toluene to obtain a crude binaphthol product, wherein the adding amount of the copper-ammonia complex and the toluene is 3.3g and 280g based on 100g of 2-naphthol.
(2) Refining of electron-grade binaphthol
And (3) refining and phase splitting the toluene, the crude binaphthol product, the oxalic acid and the water at 90 ℃ to obtain the electronic grade binaphthol, wherein the usage amount of the crude binaphthol product, the oxalic acid, the toluene and the water is 100:0.2:700:10 in sequence. The chroma of the electronic grade binaphthol is 30, the yield is 90 wt%, the purity is 99.8%, and the metal content isIon Na+、Cu2+、Fe2+、Ca2+、Mg2+、K+Are all less than 1 ppm.
Example 2
(1) Crude binaphthol was prepared as in example 1.
(2) Refining of electron-grade binaphthol
And (3) refining and phase splitting the toluene, the crude binaphthol product, the oxalic acid and the water at 90 ℃ to obtain the electronic grade binaphthol, wherein the usage amount of the crude binaphthol product, the oxalic acid, the toluene and the water is 100:1:600:20 in sequence. The chroma of the electronic grade binaphthol is 30, the yield is 88 wt%, the purity is 99.7%, and the metal ion Na+、Cu2+、Fe2+、Ca2+、Mg2+、K+Are all less than 1 ppm.
Example 3
(1) Crude binaphthol was prepared as in example 1.
(2) Refining of electron-grade binaphthol
And (3) refining and phase splitting the toluene, the crude binaphthol product, the oxalic acid and the water at 90 ℃ to obtain the electronic grade binaphthol, wherein the usage amount of the crude binaphthol product, the oxalic acid, the toluene and the water is 100:0.1:500:20 in sequence. The chroma of the electronic grade binaphthol is 40, the yield is 85 wt%, the purity is 99.7%, and the metal ion Na+、Cu2+、Fe2+、Ca2+、Mg2+、K+Are all less than 1 ppm.
Example 4
(1) Crude binaphthol was prepared as in example 1.
(2) Refining of electron-grade binaphthol
And (3) refining and phase splitting the toluene, the crude binaphthol product, the oxalic acid and the water at 90 ℃ to obtain the electronic grade binaphthol, wherein the usage amount of the crude binaphthol product, the oxalic acid, the toluene and the water is 100:1.5:800:20 in sequence. The chroma of the electronic grade binaphthol is 30, the yield is 88 wt%, the purity is 99.7%, and the metal ion Na+、Cu2+、Fe2+、Ca2+、Mg2+、K+Are all less than 1 ppm.
Example 5
(1) Crude binaphthol was prepared as in example 1.
(2) Refining of electron-grade binaphthol
And (3) refining and phase-splitting the toluene, the crude binaphthol product, ascorbic acid and water at 90 ℃ to obtain the electronic grade binaphthol, wherein the usage amount of the crude binaphthol product, oxalic acid, the toluene and the water is 100:0.1:500:20 in sequence. The chroma of the electronic grade binaphthol is 43, the yield is 84 wt%, the purity is 99.7%, and the metal ion Na+、Cu2+、Fe2+、Ca2+、Mg2+、K+Are all less than 1 ppm.
Example 6
(1) Crude binaphthol was prepared as in example 1.
(2) Refining of electron-grade binaphthol
And (3) refining and phase splitting the toluene, the crude binaphthol product, the 2-naphthol and the water at 90 ℃ to obtain the electronic grade binaphthol, wherein the usage amount of the crude binaphthol product, the 2-naphthol, the toluene and the water is 100:0.1:500:20 in sequence. The chroma of the electronic grade binaphthol is 45, the yield is 86 wt%, the purity is 99.7%, and the metal ion Na+、Cu2+、Fe2+、Ca2+、Mg2+、K+Are all less than 1 ppm.
Comparative example 1
The differences from example 6 are: no antioxidant 2-naphthol was added.
The chroma of the refined binaphthol is 50, the yield is 83 wt%, and the purity is 99.7%.
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects: compared with the existing method, the synthesis and refining method of the electronic-grade binaphthol provided by the application is beneficial to greatly reducing the color change probability of the binaphthol due to oxidation, and is also beneficial to improving the recovery rate and purity of the binaphthol.
It is noted that the terms first, second and the like in the description and in the claims of the present application are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the terms so used are interchangeable under appropriate circumstances such that the embodiments of the application described herein are, for example, capable of operation in sequences other than those described or illustrated herein.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. 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 (6)

1. A method for synthesizing and refining electronic-grade binaphthol is characterized by comprising the following steps:
preparing a crude product of binaphthol;
and refining the crude binaphthol product at 90-102 ℃ in the presence of an antioxidant, a first organic solvent and water to obtain the electronic grade binaphthol.
2. The method for synthesizing and refining electronic grade binaphthol according to claim 1, wherein the antioxidant is one or more selected from the group consisting of 2-naphthol, oxalic acid and ascorbic acid.
3. The method for synthesizing and refining the electronic grade binaphthol according to claim 1 or 2, wherein the antioxidant is a mixture of oxalic acid and 2-naphthol, and the weight ratio of the antioxidant to the antioxidant is 1 (1.5-2.5).
4. The method for synthesizing and refining electronic grade binaphthol according to any one of claims 1 to 3, wherein the weight ratio of the binaphthol crude product to the antioxidant and the first organic solvent is 100 (0.2-1): (600-700).
5. The method for synthesizing and refining electronic grade binaphthol according to claim 4, wherein the process for preparing the crude binaphthol product comprises the following steps: under the existence of a copper-ammonia complex and a second organic solvent, 2-naphthol is taken as a raw material to carry out oxidative coupling reaction to prepare the crude binaphthol product.
6. The method for synthesizing and refining electronic grade binaphthol according to claim 5, wherein the first organic solvent and the second organic solvent are respectively and independently selected from one or more of toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene and trichlorobenzene.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115710162A (en) * 2022-11-17 2023-02-24 沈阳化工研究院有限公司 Method for preparing electronic-grade binaphthol by refining at lower temperature

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001039913A (en) * 1999-07-29 2001-02-13 Dainippon Ink & Chem Inc Purification of binaphthol
CN111217680A (en) * 2020-02-14 2020-06-02 乌海时联环保科技有限责任公司 Method for preventing naphthol from discoloring

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001039913A (en) * 1999-07-29 2001-02-13 Dainippon Ink & Chem Inc Purification of binaphthol
CN111217680A (en) * 2020-02-14 2020-06-02 乌海时联环保科技有限责任公司 Method for preventing naphthol from discoloring

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
翁文等: ""1,1-联萘化合物的氧化偶联合成"", 《应用化学》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115710162A (en) * 2022-11-17 2023-02-24 沈阳化工研究院有限公司 Method for preparing electronic-grade binaphthol by refining at lower temperature
CN115710162B (en) * 2022-11-17 2024-03-26 沈阳化工研究院有限公司 Method for refining and preparing electronic cascade naphthol at lower temperature

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