Preparation method of diaminophenol compound

Abstract

The invention provides a preparation method of a diaminophenol compound, and relates to the field of organic synthesis. The invention provides a preparation method of a diaminophenol compound, which comprises the following steps: in the presence of a metal catalyst, a reducing agent and a reaction solvent, carrying out reduction reaction on a compound 1, and separating a compound 2 crude product from reaction liquid; and dissolving the compound 2 in an acidic aqueous solution, mixing with hydrazine hydrate or a hydrazine hydrate solution, and crystallizing to obtain the compound 2. The method not only can effectively control the content of metal ions formed by the main components of the metal catalyst used in the reduction process in the final product, but also can effectively prevent the final product from being oxidized in the post-treatment process, thereby effectively improving the appearance of the final product. # imgabs0 #

Description

Technical Field

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

[0002] Polyimide materials and polybenzoxazole materials have been widely used in the production and manufacturing of semiconductor buffer coating films, passivation films, interlayer insulation films and other materials due to their excellent properties such as good high temperature resistance, low dielectric constant and high strength.

[0003] Diaminophenol compounds are important intermediates for the preparation of polyimide materials, polybenzoxazoles and other materials, so they have high requirements for metal ion content.

[0004] In the prior art, the most common method for preparing diaminophenol compounds is as shown below:

[0005]

[0006] This preparation method usually requires the use of some metal elements or metal oxides as catalysts, but it is difficult to reduce the metal ions formed by the main components of the catalyst to an ideal level during the subsequent purification process.

[0007] For example, JP2004131386A discloses a method for preparing diaminophenol compounds with low metal ion content by the above-mentioned route. Although the method provided by the patent can reduce the metal ions contained in some non-catalysts to a satisfactory level, its optimal solution can only control the metal ions formed by the main components of the catalyst to about 130 ppb, and cannot further control it to a lower content.

[0008] In addition, the crystallization method provided in JP2004131386A will inevitably cause the product to come into contact with air, causing trace amounts of the product to undergo oxidation and discoloration, thereby affecting the subsequent application of the product in semiconductor materials. Summary of the invention

[0009] The present invention is made to solve the above problems and aims to provide a method for preparing diaminophenol compounds which can control the metal ion content of the catalyst to an ideal level and effectively improve the appearance of the product.

[0010] The present invention provides a method for preparing a diaminophenol compound, which has the following characteristics and comprises the following steps:

[0011] In the presence of a metal catalyst, a reducing agent and a reaction solvent, compound 1 undergoes a reduction reaction, and a crude compound 2 is separated from the reaction solution;

[0012] The compound 2 is dissolved in an acidic aqueous solution, and mixed with hydrazine hydrate or its solution for crystallization to obtain compound 2.

[0013]

[0014] A is

[0015] R 1 , R 2 Each independently is H, C 1-8 Alkyl, or C substituted by one or more halogens 1-8 The plurality is 2, 3, 4, 5 or 6;

[0016] n=1, 2, 3, 4, 5, 6, 7 or 8, 0≤m≤(2n+6), m is an integer;

[0017] R 3 C 1-8 The alkyl groups of each R 3 Same or different.

[0018] In the preparation method of the diaminophenol compound provided by the present invention, the following characteristics may also be present: R 1 , R 2 and R 3 In the C 1-8 The alkyl group is preferably C 1-6 Alkyl, more preferably C 1-4 The alkyl group may be a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group or a tert-butyl group.

[0019] In the preparation method of the diaminophenol compound provided by the present invention, the following characteristics may also be present: R 1 and R 2 In the above, the halogen may be F, Cl, Br or I, preferably F.

[0020] In the preparation method of the diaminophenol compound provided by the present invention, the following characteristics may also be present: A is

[0021] R 1 , R 2 Each independently is H, C 1-4 Alkyl, or C substituted by one or more halogens 1-4 The plurality is 2, 3, 4, 5 or 6;

[0022] n=1, 2, 3, 4, 5, 6, 7 or 8, 0≤m≤(2n+6), m is an integer;

[0023] R 3 C 1-4 The alkyl groups of each R 3 Same or different.

[0024] In the preparation method of the diaminophenol compound provided by the present invention, the following characteristics may also be present: wherein A is any one of the following structural formulas:

[0025]

[0026] The method for preparing the diaminophenol compound provided by the present invention may also have the following feature: wherein the reducing agent is hydrogen or hydrazine hydrate.

[0027] The method for preparing diaminophenol compounds provided by the present invention may also have the following characteristics: when the reducing agent is hydrogen, the metal catalyst is selected from any one or more of a Pt catalyst, a Pd catalyst, a PtO2 catalyst, a Ni catalyst or a Cu catalyst.

[0028] In the preparation method of diaminophenol compounds provided by the present invention, it can also have the following characteristics: wherein, when the reducing agent is hydrogen, the metal catalyst is selected from any one or more of a Pt / C catalyst (preferably a Pt / C catalyst with a Pt content of 3wt%-15wt%), a Pd / C catalyst (preferably a Pt / C catalyst with a Pd content of 3wt%-15wt%), a PtO2 catalyst, a Raney Ni catalyst, and a RaneyCu catalyst.

[0029] In the preparation method of the diaminophenol compound provided by the present invention, it can also have such a feature: wherein, when the reducing agent is hydrogen, the amount of the metal catalyst is 3wt%-20wt% of the mass of compound 1.

[0030] The method for preparing diaminophenol compounds provided by the present invention may also have the following characteristics: when the reducing agent is hydrogen, the reaction is carried out under pressurized conditions, and the hydrogen partial pressure in the reaction system is 0.5-2.0 MPa.

[0031] The method for preparing diaminophenol compounds provided by the present invention may also have the following characteristics: when the reducing agent is hydrazine hydrate, the metal catalyst is selected from any one or more of a Pt catalyst, a Pd catalyst or a trivalent iron salt catalyst.

[0032] In the preparation method of diaminophenol compounds provided by the present invention, it can also have the following characteristics: wherein, when the reducing agent is hydrazine hydrate, the metal catalyst is selected from any one or more of a Pt / C catalyst (preferably a Pt / C catalyst with a Pt content of 3wt%-15wt%), a Pd / C catalyst (preferably a Pt / C catalyst with a Pd content of 3wt%-15wt%), and a FeCl3 catalyst.

[0033] The preparation method of the diaminophenol compound provided by the present invention may also have the following characteristics: when the reducing agent is hydrazine hydrate, the amount of the metal catalyst is 3wt%-20wt% of the mass of the compound 1.

[0034] The method for preparing the diaminophenol compound provided by the present invention may also have the following characteristics: when the reducing agent is hydrazine hydrate, the molar ratio of the reducing agent to the compound 1 is (3-10):1.

[0035] The method for preparing the diaminophenol compound provided by the present invention may also have the following characteristics: wherein the amount of the metal catalyst is 3wt%-15wt% of the mass of the compound 1.

[0036] In the preparation method of the diaminophenol compound provided by the present invention, it can also have the following characteristics: wherein the reaction solvent is selected from any one or more of N,N-dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), toluene, N-methylpyrrolidone (NMP), diethanol dimethyl ether, tetrahydrofuran, methanol or ethanol.

[0037] The method for preparing the diaminophenol compound provided by the present invention may also have the following characteristics: wherein the mass volume ratio of the compound 1 to the reaction solvent is 1 g: (3-15) mL.

[0038] The preparation method of the diaminophenol compound provided by the present invention may also have the following characteristics: comprising the following reaction steps:

[0039] In the presence of a metal catalyst, a reducing agent and a reaction solvent, compound 1 undergoes a reduction reaction to obtain a reaction solution containing compound 2;

[0040] Adding a crystallizing agent to the reaction solution or cooling the reaction solution to precipitate compound 2 to obtain a crude compound 2;

[0041] The crude compound 2 is dissolved in an acidic aqueous solution, and hydrazine hydrate or its solution is added to mix and crystallize to obtain compound 2.

[0042] The preparation method of the diaminophenol compound provided by the present invention may also have the following characteristics: wherein the crystallizing agent is selected from any one or more of water, methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, isobutanol, ethylene glycol or dioxane.

[0043] The method for preparing the diaminophenol compound provided by the present invention may also have the following characteristics: wherein the volume ratio of the crystallizing agent to the reaction solvent is 1:(0.3-1.5).

[0044] The preparation method of the diaminophenol compound provided by the present invention may also have the following characteristics: wherein the pH value of the acidic aqueous solution is 3-4, and the mass volume ratio of the crude compound 2 to the acidic aqueous solution is 1 g: (5-10) mL.

[0045] In the preparation method of the diaminophenol compound provided by the present invention, the following characteristics may also be provided: wherein the hydrazine hydrate solution used for crystallization is a hydrazine hydrate aqueous solution with a mass fraction of 30wt%-60wt%;

[0046] The volume ratio of the hydrazine hydrate solution used for crystallization to the acidic aqueous solution is 1:(5-15).

[0047] Functions and Effects of the Invention

[0048] According to the preparation method of diaminophenol compounds involved in the present invention, because a secondary crystallization method is adopted, especially hydrazine hydrate is used in the second crystallization process, the inventor unexpectedly found that the present invention can not only effectively control the content of metal ions formed by the main component of the metal catalyst used in the reduction process in the final product, but also effectively avoid oxidation of the final product during the post-treatment process, thereby effectively improving the appearance of the final product. BRIEF DESCRIPTION OF THE DRAWINGS

[0049] Figure 1 is a photograph of compound 2a prepared in Example 1 of the present invention;

[0050] Figure 2 is a photograph of compound 2a prepared in Comparative Example 1 of the present invention. DETAILED DESCRIPTION

[0051] In order to make the technical means, creative features, objectives and effects achieved by the present invention easier to understand, the present invention is described in detail below in conjunction with embodiments and drawings.

[0052] In the following examples, unless otherwise specified, all raw materials are commercially available products.

[0053] In the following examples, the hydrochloric acid aqueous solution with a pH of 3 is prepared by adding commercially available concentrated hydrochloric acid to deionized water.

[0054] In the following examples, the 20 wt % NaOH aqueous solution is prepared by adding solid sodium hydroxide to deionized water.

[0055] In the following examples, the metal ion content was measured using an Agilent ICP-MS7900 inductively coupled plasma emission mass spectrometer.

[0056] <Example 1>

[0057] A kind of preparation method of diaminophenol compound

[0058] This embodiment provides a method for preparing a diaminophenol compound, and the reaction formula is as follows:

[0059]

[0060] The steps include:

[0061] 100 g of compound 1a was added to 500 mL of dimethylacetamide, and 10 g of RaneyNi was added. The hydrogen in the reaction system was replaced and pressurized to 0.5 MPa with hydrogen. The temperature was raised to 30°C and the reaction was stirred for 6 h. The mixture was filtered and the filtrate was taken. At room temperature, 750 g of deionized water was added to the filtrate to precipitate a solid. The mixture was stirred at room temperature for 1 h, filtered, and the solid was taken to obtain a crude compound 2a. The crude compound 2a had a purity of 99.0%, and the contents of various ions were Fe: 711 ppb, Ni: 128143 ppb, and Pt: 2 ppb, respectively.

[0062] The obtained crude compound 2a was dissolved in 550 mL of a hydrochloric acid aqueous solution with a pH of 3, and 80 mL of a 40 wt% hydrazine hydrate aqueous solution was added at room temperature. The mixture was stirred at room temperature for 1 h, and a large amount of solid precipitated. The solid was filtered and dried in vacuo at 50°C to obtain 78.4 g of compound 2a with a yield of 94.1% and a purity of 99.9%. The contents of various ions were Fe: 15 ppb, Ni: 17 ppb, and Pt: <1 ppb.

[0063] The compound 2a prepared in this example is Figure 1 shown.

[0064] <Example 2>

[0065] A kind of preparation method of diaminophenol compound

[0066] This embodiment provides a method for preparing a diaminophenol compound, and the reaction formula is as follows:

[0067]

[0068] The steps include:

[0069] 100 g of compound 1a was added to 500 mL of dimethylacetamide, and 3.5 g of Pt / C (Pt content 5%) was added. The hydrogen in the reaction system was replaced and pressurized to 0.5 MPa with hydrogen. The temperature was raised to 30°C and the reaction was stirred for 20 h. The mixture was filtered and the filtrate was taken. At room temperature, 750 g of deionized water was added to the filtrate to precipitate a solid. The mixture was stirred at room temperature for 1 h, filtered, and the solid was taken to obtain a crude compound 2a. The crude compound 2a had a purity of 97.7% and the contents of various ions were Fe: 332 ppb, Ni: 59 ppb, and Pt: 54941 ppb, respectively.

[0070] The obtained crude compound 2a was dissolved in 550 mL of a hydrochloric acid aqueous solution with a pH of 3, and 80 mL of a 40 wt% hydrazine hydrate aqueous solution was added at room temperature. The mixture was stirred at room temperature for 1 h, and a large amount of solid precipitated. The solid was filtered and dried in vacuo at 50°C to obtain 77.4 g of compound 2a with a yield of 92.9% and a purity of 99.9%. The contents of various ions were Fe: 19 ppb, Ni: 12 ppb, and Pt: 76 ppb, respectively.

[0071] <Example 3>

[0072] A preparation method of diaminophenol compounds

[0073] This embodiment provides a method for preparing a diaminophenol compound, and the reaction formula is as follows:

[0074]

[0075] The steps include:

[0076] 100 g of compound 1a was added to 500 mL of dimethylacetamide, and 10 g of RaneyNi was added. The hydrogen in the reaction system was replaced and pressurized to 0.5 MPa with hydrogen. The temperature was raised to 30°C and the reaction was stirred for 6 h. The reaction was filtered and the filtrate was taken. 750 g of methanol was added to the filtrate at room temperature. Solid precipitated. The reaction was stirred at room temperature for 1 h. The reaction was filtered and the solid was taken to obtain a crude compound 2a. The crude compound 2a was tested and the purity of the crude compound 2a was 98.6%.

[0077] The obtained crude compound 2a was dissolved in 550 mL of a hydrochloric acid aqueous solution with a pH of 3, and 80 mL of a 40 wt% hydrazine hydrate aqueous solution was added at room temperature. The mixture was stirred at room temperature for 1 h, and a large amount of solid precipitated. The solid was filtered and dried in vacuo at 50°C to obtain 71.8 g of compound 2a with a yield of 86.2% and a purity of 99.9%. The contents of various ions were Fe: 67 ppb, Ni: 60 ppb, and Pt: <1 ppb.

[0078] <Example 4>

[0079] A preparation method of diaminophenol compounds

[0080] This embodiment provides a method for preparing a diaminophenol compound, and the reaction formula is as follows:

[0081]

[0082] The steps include:

[0083] 100 g of compound 1b was added to 500 mL of dimethylacetamide, and 10 g of RaneyNi was added. The hydrogen in the reaction system was replaced and pressurized to 0.5 MPa with hydrogen. The temperature was raised to 30°C and the reaction was stirred for 6 h. The reaction was filtered and the filtrate was taken. 750 g of deionized water was added to the filtrate at room temperature. Solid precipitated. The reaction was stirred at room temperature for 1 h. The reaction was filtered and the solid was taken to obtain a crude compound 2b. The crude compound 2b was tested and the purity of the crude compound 2b was 98.8%.

[0084] The obtained crude compound 2b was dissolved in 550 mL of a hydrochloric acid aqueous solution with a pH of 3, and 80 mL of a 40 wt% hydrazine hydrate aqueous solution was added at room temperature. The mixture was stirred at room temperature for 1 h, and a large amount of solid precipitated. The solid was filtered and dried in vacuo at 50°C to obtain 78.5 g of compound 2b with a yield of 92.03% and a purity of 99.9%. The contents of various ions were Fe: 37 ppb, Ni: 17 ppb, and Pt: <1 ppb.

[0085] <Example 5>

[0086] A preparation method of diaminophenol compounds

[0087] This embodiment provides a method for preparing a diaminophenol compound, and the reaction formula is as follows:

[0088]

[0089] The steps include:

[0090] 80 g of compound 1c was added to 400 mL of dimethylacetamide, and 8 g of Raney Ni was added. The hydrogen in the reaction system was replaced and pressurized to 0.5 MPa with hydrogen. The temperature was raised to 30°C and the reaction was stirred for 6 h. The mixture was filtered and the filtrate was taken. 600 g of deionized water was added to the filtrate at room temperature. Solid precipitated. The mixture was stirred at room temperature for 1 h, filtered, and the solid was taken to obtain a crude compound 2b. The crude compound 2c was tested and the purity of the crude compound 2c was 97.8%.

[0091] The obtained crude compound 2c was dissolved in 450 mL of a hydrochloric acid aqueous solution with a pH of 3, and 70 mL of a 40 wt% hydrazine hydrate aqueous solution was added at room temperature. The mixture was stirred at room temperature for 1 h, and a large amount of solid precipitated. The solid was filtered and dried in vacuo at 50°C to obtain 59.1 g of compound 2c with a yield of 91.1% and a purity of 99.9%. The contents of various ions were Fe: 30 ppb, Ni: 10 ppb, and Pt: <1 ppb.

[0092] <Comparative Example 1>

[0093] A preparation method of diaminophenol compounds

[0094] This embodiment provides a method for preparing a diaminophenol compound, and the reaction formula is as follows:

[0095]

[0096] The steps include:

[0097] 100 g of compound 1a was added to 500 mL of dimethylacetamide, and 10 g of RaneyNi was added. The hydrogen in the reaction system was replaced and pressurized to 0.5 MPa with hydrogen. The temperature was raised to 30°C and the reaction was stirred for 6 h. The reaction was filtered and the filtrate was taken. 750 g of deionized water was added to the filtrate at room temperature. Solid precipitated. The reaction was stirred at room temperature for 1 h. The reaction was filtered and the solid was taken to obtain a crude compound 2a. The crude compound 2a was tested and the purity of the crude compound 2a was 98.9%.

[0098] The obtained crude compound 2a was dissolved in 550 mL of a hydrochloric acid aqueous solution with a pH of 3, and 80 mL of a 20 wt% NaOH aqueous solution was added at room temperature. The mixture was stirred at room temperature for 1 h, and a large amount of solid precipitated. The solid was filtered and dried in vacuo at 50°C to obtain 78.4 g of compound 2a with a yield of 81.9% and a purity of 99.5%. The contents of various ions were Fe: 303 ppb, Ni: 663 ppb, and Pt: 2 ppb, respectively.

[0099] The compound 2a prepared in this comparative example is Figure 2 shown.

[0100] Functions and Effects of the Embodiments

[0101] According to the preparation method of diaminophenol compounds involved in the above embodiments, because a secondary crystallization method is adopted, especially hydrazine hydrate is used in the second crystallization process, the inventor unexpectedly found that this method can not only effectively control the content of metal ions formed by the main component of the metal catalyst used in the reduction process in the final product, but also effectively avoid oxidation of the final product during the post-treatment process, thereby effectively improving the appearance of the final product.

[0102] Furthermore, the technical solution provided in the above embodiment is not only applicable to the reaction conditions such as Example 1 where Raney Ni is a reaction catalyst, but also to the reaction conditions such as Example 2 where Pt / C is a reaction catalyst, and can control the Ni content and Pt content in the final product at a relatively ideal level, reflecting extremely good universality.

[0103] According to the preparation method of diaminophenol compounds involved in the above embodiment, since Pt / C or RaneyNi is used as a catalyst for the reduction reaction, side reactions can be effectively avoided and the content of impurities in the product can be reduced, thereby effectively improving the yield and purity of the final product.

[0104] The above-mentioned embodiments are preferred examples of the present invention and are not intended to limit the protection scope of the present invention.

Claims

1. A method for preparing a diaminophenol compound, characterized in that: The steps include: In the presence of a metal catalyst, a reducing agent and a reaction solvent, compound 1 undergoes a reduction reaction and a crude compound 2 is separated from the reaction solution; The compound 2 is dissolved in an acidic aqueous solution, and mixed with hydrazine hydrate or its solution for crystallization to obtain compound 2. A is R 1 , R 2 Each independently is H, C 1-8 Alkyl, or C substituted by one or more halogens 1-8 The plurality is 2, 3, 4, 5 or 6; n=1, 2, 3, 4, 5, 6, 7 or 8, 0≤m≤(2n+6), m is an integer; R 3 C 1-8 The alkyl groups of each R 3 Same or different.

2. The method for preparing a diaminophenol compound according to claim 1, wherein: in, A is any one of the following structural formulas:

3. The method for preparing diaminophenol compounds according to claim 1, characterized in that: in, The reducing agent is hydrogen or hydrazine hydrate.

4. The method for preparing diaminophenol compounds according to claim 3, characterized in that: in, When the reducing agent is hydrogen, the metal catalyst is selected from any one or more of a Pt catalyst, a Pd catalyst, a PtO2 catalyst, a Ni catalyst or a Cu catalyst.

5. The method for preparing diaminophenol compounds according to claim 4, characterized in that: in, When the reducing agent is hydrogen, the reaction is carried out under pressurized conditions, and the hydrogen partial pressure in the reaction system is 0.5-2.0 MPa.

6. The method for preparing diaminophenol compounds according to claim 3, characterized in that: in, When the reducing agent is hydrazine hydrate, the metal catalyst is selected from any one or more of a Pt catalyst, a Pd catalyst or a trivalent iron salt catalyst.

7. The method for preparing a diaminophenol compound according to any one of claims 4 to 6, characterized in that: in, The amount of the metal catalyst used is 3%-15% of the mass of compound 1.

8. The method for preparing a diaminophenol compound according to claim 1, characterized in that: in, The reaction solvent is selected from any one or more of DMAc, DMF, toluene, NMP, diethanol dimethyl ether, tetrahydrofuran, methanol or ethanol.

9. The method for preparing a diaminophenol compound according to claim 1, characterized in that: The process comprises the following reaction steps: In the presence of a metal catalyst, a reducing agent and a reaction solvent, compound 1 undergoes a reduction reaction to obtain a reaction solution containing compound 2; Adding a crystallizing agent to the reaction solution or cooling the reaction solution to precipitate compound 2 to obtain a crude compound 2; The crude compound 2 is dissolved in an acidic aqueous solution, and hydrazine hydrate or its solution is added to mix and crystallize to obtain compound 2.

10. The method for preparing diaminophenol compounds according to claim 7, characterized in that: in, The crystallizing agent is selected from any one or more of water, methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, isobutanol, ethylene glycol or dioxane.

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