CN115385774A - Preparation method of di-sec-aromatic alcohol - Google Patents
Preparation method of di-sec-aromatic alcohol Download PDFInfo
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- CN115385774A CN115385774A CN202211016731.6A CN202211016731A CN115385774A CN 115385774 A CN115385774 A CN 115385774A CN 202211016731 A CN202211016731 A CN 202211016731A CN 115385774 A CN115385774 A CN 115385774A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
- C07C45/46—Friedel-Crafts reactions
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
- C07C29/145—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones with hydrogen or hydrogen-containing gases
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Abstract
The invention provides a preparation method of di-sec-aromatic alcohol, belonging to the field of organic synthesis. The invention provides a method for preparing di-sec aromatic alcohol, which has the following reaction formula:
wherein R1 and R2 are independently selected from alkyl groups having any carbon number, and Q is
N =1-5, comprising the following reaction steps: mixing the compound 1, a reducing agent and a solvent for reaction, and performing post-treatment to obtain a compound 2, wherein the reducing agent is borohydride or Ranny Ni/H 2 . The preparation method provided by the application can be used for preparing the di-sec-aromatic alcohol under milder reaction conditions.
Description
Technical Field
The invention relates to the field of organic chemistry, in particular to a preparation method of di-sec-aromatic alcohol.
Background
In the prior art, di-secondary aromatic alcohol compounds have been widely used in many fields, for example, according to the patent JP2004101819A, a series of di-secondary aromatic alcohol compounds represented by 1,2-bis (4- (1-hydroxyethyl) phenyl) ethane can be used as a component of a negative resist. The negative resist containing the di-sec-aromatic alcohol compound has better storage stability, so that the negative resist can be applied to the processing process of a semiconductor device and the processing precision of the semiconductor device is improved.
Also, as reported in the paper of Divinyl Aromatic Compounds and Di (meth) purified by Acid-Catalyzed Transformations of Bis [4- (1-hydroxyethenyl) phenyl ] alkanes (Russian Journal of Applied Chemistry,84 (10), 1783-1794 (2011)), di-sec-aralkyl alcohol Compounds can also be used as monomers to prepare heat-resistant insulating Compounds.
The above-mentioned article also provides a process for the preparation of di-sec-aromatic alcohols, which has the following reaction formula:
however, according to the paper, the above reaction is carried out under the condition of at least 25atm, and the overall reaction yield is low, and the partial substrate yield is only about 40%.
Disclosure of Invention
The present invention has been made to solve the above problems, and an object of the present invention is to provide a process for producing di-sec-aralkyl alcohol under milder reaction conditions and in higher reaction yield.
The invention provides two technical schemes of preparation methods of di-sec-aromatic alcohol.
The first scheme is as follows:
the invention provides a preparation method of di-sec-aromatic alcohol, which is characterized in that the reaction formula is as follows:
wherein R1 and R2 are independently selected from alkyl groups having any carbon number, and Q is
N =1-5, comprising the following reaction steps: and (3) mixing the compound 1, borohydride and a solvent for reaction, and performing post-treatment to obtain a compound 2, wherein the solvent is an alcohol solvent.
The preparation method of the di-sec-aromatic alcohol provided by the invention can also have the following characteristics: wherein the alcohol solvent is one or more of methanol, ethanol, n-propanol or isopropanol.
The preparation method of the di-sec-aromatic alcohol provided by the invention can also have the following characteristics: wherein, the borohydride is sodium borohydride or potassium borohydride, and the molar ratio of the borohydride to the compound is (1.2-1.55): 1.
the preparation method of the di-sec-aromatic alcohol provided by the invention can also have the following characteristics: wherein, the post-treatment comprises the following steps:
adding acid liquor to quench reaction, extracting with an organic solvent, taking an organic phase, washing with water, concentrating, adding a benzene solvent, heating and refluxing, cooling to-20-0 ℃, filtering, taking a filter cake, and drying to obtain the product.
The preparation method of the di-sec-aromatic alcohol provided by the invention can also have the following characteristics: wherein, the post-treatment comprises the following steps:
adding hydrochloric acid aqueous solution to quench reaction, extracting by using ethyl acetate or dichloromethane, taking an organic phase, adding benzene or toluene, heating and refluxing for 0.5h-3h, cooling to-20-0 ℃, filtering, taking a filter cake, and drying to obtain the compound.
Scheme two is as follows:
the invention provides a preparation method of di-sec-aromatic alcohol, which is characterized in that the reaction formula is as follows:
in the formula, R 1 、R 2 Independently of one another, are selected from alkyl groups having any carbon number, Q is
N =1-5,
the method comprises the following reaction steps:
in the hydrogen atmosphere, the compound 1, ranny Ni and a solvent are mixed and reacted, and the post-treatment is carried out to obtain the compound,
wherein the mass ratio of the solvent to the compound 1 is (6-15): 1.
the preparation method of the di-sec-aromatic alcohol provided by the invention can also have the following characteristics: the mass ratio of Ranny Ni to the compound 1 is 1: (3-10).
The preparation method of the di-sec-aromatic alcohol provided by the invention can also have the following characteristics: the reaction temperature is 35-50 ℃.
The preparation method of the di-sec-aromatic alcohol provided by the invention can also have the following characteristics: r is 1 、R 2 Independently of one another, from C1-C5 alkyl, preferably R 1 ＝R 2 ＝Me。
The preparation method of the di-sec-aromatic alcohol provided by the invention can also have the following characteristics: ranny Ni was adjusted to pH 7-8 prior to use.
The preparation method of the di-sec-aromatic alcohol provided by the invention can also have the following characteristics: the reaction pressure is 1.2MPa-1.8MPa.
The preparation method of the di-sec-aromatic alcohol provided by the invention can also have the following characteristics: the solvent is an alcohol solvent, preferably methanol or ethanol.
The preparation method of the di-sec-aromatic alcohol provided by the invention can also have the following characteristics: wherein, the post-treatment comprises the following steps: filtering, collecting filtrate, concentrating under reduced pressure, and drying.
Action and Effect of the invention
According to the preparation method of the di-sec-aromatic alcohol, disclosed by the invention, the borohydride is used as a reducing agent, and the methanol or the ethanol is used as a reaction solvent, so that the di-sec-aromatic alcohol compound can be prepared at normal pressure and high yield.
According to the preparation method of the di-sec-aromatic alcohol, ranny Ni is adopted as a reduction catalyst, and the mass ratio of the reaction solvent to the raw materials is controlled to be (6-15): 1, the preparation method provided by the invention can unexpectedly obtain higher reaction yield at lower pressure and lower reaction temperature.
Detailed Description
In order to make the technical means, the creation features, the achievement purposes and the effects of the invention easy to understand, the invention is specifically described with the embodiment below.
In the following examples, the starting materials were all commercially available unless otherwise indicated.
< example 1>
Preparation of Compound 1a
This example provides a method for preparing compound 1a, having the formula:
the method comprises the following reaction and post-treatment steps:
183g of AlCl were placed in an ice-water bath under nitrogen protection 3 (1.37mol, 2.5eq) is added into 300g of dichloromethane, then 116g of acetyl chloride (1.48mol, 2.7eq) is dripped dropwise, 100g of a mixed solution of compound 4 (0.55mol, 1.0eq) and 200g of dichloromethane is dripped dropwise, after the dripping is finished, the temperature is raised to 40 ℃ for reaction for 2 hours, the mixture is transferred into an ice water bath, 600g of 10wt% hydrochloric acid aqueous solution is added for quenching reaction, 600g of dichloromethane is added for extraction, an organic phase is taken, the concentration is carried out under reduced pressure, the drying is carried out at the temperature of 60 ℃, 133g of compound 1a is obtained, the yield is 91.0%, and the purity is 99.1%.
< example 2>
Preparation of Compound 2a
This example provides a method for the preparation of compound 2a, having the formula:
the method comprises the following reaction and post-treatment steps:
adding 35g of compound 1a (131.4mmol, 1.0eq) into 100g of methanol, heating to 35 ℃, adding 11g of potassium borohydride (203.9mmol, 1.55eq), reacting for 2h, cooling to 10 ℃, adding 175g of 10wt% hydrochloric acid aqueous solution, quenching, adding 420g of ethyl acetate, stirring for 1h, extracting, taking an organic phase, extracting, washing once, concentrating under reduced pressure, and drying at 60 ℃ to obtain 33.5g of compound 2a, wherein the yield is 94.4%, and the purity is 86.1%.
< example 3>
Preparation of Compound 2a
This example provides a method for the preparation of compound 2a, having the formula:
the method comprises the following reaction and post-treatment steps:
adding 35g of compound 1a (131.4mmol, 1.0eq) into 100g of methanol, heating to 35 ℃, adding 11g of potassium borohydride (203.9mmol, 1.55eq), reacting for 2h, cooling to 10 ℃, adding 175g of hydrochloric acid aqueous solution with the concentration of 10wt% to quench the reaction, adding 420g of ethyl acetate, stirring for 1h, extracting, taking an organic phase, extracting, washing once with water, concentrating under reduced pressure to dryness, adding 100g of toluene, heating to 120 ℃, refluxing for 1h, naturally cooling to-10 ℃, filtering, taking a filter cake, and drying at 60 ℃ to obtain 32.6g of compound 2a, wherein the yield is 91.8% and the purity is 99.4%.
< example 4>
Screening of reaction solvent
In this example, a reaction solvent was screened from the reaction solvent in example 3, and the raw materials and the operation steps were the same as those in example 3 except that the contents described in table are different from those in example 3, and the screening results are shown in table 1.
TABLE 1 screening of reaction solvents
| Serial number | Solvent(s) | Yield of | Purity of |
| 1 | Tetrahydrofuran (THF) | 41.3％ | - |
| 2 | Methylene dichloride | Trace amount of | - |
| 3 | Ethanol | 85.3％ | 99.5％ |
| 4 | Isopropanol (I-propanol) | 78.5％ | 98.9％ |
| 5 | Dimethoxy ethyl ether | 37.5％ | - |
As is clear from table 1, the reaction solvent has a large influence on the substrate referred to in the present application, and alcohol solvents such as methanol and ethanol are more suitable for the reaction than other types of solvents.
< example 5>
Preparation of Compound 2a
This example provides a method for the preparation of compound 2a, having the formula:
the method comprises the following reaction and post-treatment steps:
10g of compound 1a are weighed into a hydrogenation kettle and 100g of methanol and 2g of Ranny Ni are added, wherein the Ranny Ni is washed with deionized water to pH 8 before use. Introducing hydrogen into the hydrogenation kettle until the pressure in the hydrogenation kettle is 1.5MPa, heating to 38 ℃, stirring for reacting for 2 hours, centrifuging, filtering, taking filtrate, and concentrating under reduced pressure to obtain 9.75g of compound 2a, wherein the yield is 96.3%, and the purity is 99.8%.
< example 6>
Preparation of Compound 2a
This example is essentially the same as example 5 except that Ranny Ni was washed with deionized water to 14 before use. This example gave 8.60g of Compound 2a in 84.8% yield.
< example 7>
Screening of reaction solvent dosage
In this example, the amount of the reaction solvent used was selected based on example 5, and the materials and the operation steps were the same as those in example 5 except that the contents shown in the table were different from those in example 5, and the results of the selection are shown in table 2.
TABLE 2 screening of reaction solvent amounts
| Serial number | Amount of solvent used | Yield of |
| 1 | 30g | 54.9％ |
| 2 | 60g | 84.0％ |
| 3 | 150g | 96.1％ |
As can be seen from table 2, the applicant unexpectedly found that the amount of the reaction solvent is greatly related to the yield of the final product, and even under a small hydrogen pressure, when the mass ratio of the solvent to the compound 1a is less than 10, the reaction yield is gradually increased with the increase of the amount of the reaction solvent; further, when the mass ratio of the solvent to the compound 1a is greater than 10, the amount of the solvent used for the reaction is further increased, and the yield is not further improved.
< example 8>
Screening of reaction temperature
In this example, the reaction temperature was selected based on example 5, and the raw materials and the operation steps were the same as those in example 5 except that the contents shown in the table are different from those in example 5, and the results of the selection are shown in table 3.
TABLE 3 screening of reaction temperatures
As can be seen from table 3, the applicant unexpectedly found that the reaction yield was rather improved as the reaction temperature was lowered, which is probably due to the side reaction of the reaction raw material at high temperature and high pressure, which resulted in the decrease of the yield of the objective product.
Effects and effects of the embodiments
According to the method for producing di-secondary aromatic alcohols according to examples 2 to 4, the borohydride is used as the reducing agent, and methanol or ethanol is used as the reaction solvent, so that the di-secondary aromatic alcohol compound can be produced at normal pressure with high yield.
Furthermore, the steps of adding toluene, heating and refluxing, cooling and filtering are carried out in the post-treatment process, so that impurities carried in the product can be effectively removed, and the product purity is improved.
According to the preparation method of the di-sec-aromatic alcohol related to the embodiments 5 to 8, because Ranny Ni is adopted as the reduction catalyst, the dosage of the reaction solvent is greatly increased, and the mass ratio of the reaction solvent to the raw material is controlled to be (6-15): 1, the preparation method provided by the invention can unexpectedly obtain higher reaction yield at lower pressure and lower reaction temperature.
Further, since the Ranny Ni is washed before using it to have a pH of 7 to 8, the yield of the objective product is unexpectedly improved to some extent.
The above embodiments are preferred examples of the present invention, and are not intended to limit the scope of the present invention.
Claims (10)
1. The preparation method of the di-sec-aromatic alcohol is characterized by comprising the following reaction formula:
wherein R1 and R2 are independently selected from alkyl groups having any carbon number, and Q is
N =1-5,
the method comprises the following reaction steps:
mixing the compound 1, borohydride and solvent for reaction, and post-treating to obtain a compound 2,
wherein the solvent is an alcohol solvent.
2. The process according to claim 1, wherein:
wherein the alcohol solvent is any one or more of methanol, ethanol, n-propanol or isopropanol.
3. The process according to claim 1, wherein:
wherein the borohydride is sodium borohydride or potassium borohydride,
the molar ratio of said borohydride to said compound is (1.2-1.55): 1.
4. the process according to claim 1, wherein:
wherein the post-treatment comprises the following steps:
adding acid liquor to quench reaction, extracting with an organic solvent, taking an organic phase, washing with water, concentrating, adding a benzene solvent, heating and refluxing, cooling to-20-0 ℃, filtering, taking a filter cake, and drying to obtain the product.
5. A preparation method of di-sec aromatic alcohol is characterized in that the reaction formula is as follows:
in the formula, R 1 、R 2 Independently of one another, are selected from alkyl groups having any carbon number, Q is
N =1-5,
the method comprises the following reaction steps:
in the hydrogen atmosphere, the compound 1, ranny Ni and a solvent are mixed and reacted, and the post-treatment is carried out to obtain the compound,
wherein the mass ratio of the solvent to the compound 1 is (6-15): 1.
6. a process according to claim 5, wherein:
wherein the reaction temperature is 35-50 ℃.
7. The process according to claim 5, wherein the aromatic alcohol is a di-sec-aromatic alcohol,
wherein R is 1 、R 2 Independently of one another, from C1-C5 alkyl groups.
8. The process according to claim 5, wherein the aromatic alcohol is a di-sec-aromatic alcohol,
wherein the Ranny Ni is adjusted to pH 7-8 before use.
9. The process according to claim 5, wherein the aromatic alcohol is a di-sec-aromatic alcohol,
wherein the reaction pressure is 1.2MPa-1.8MPa.
10. A process according to claim 5, wherein the aromatic alcohol is a di-sec-aromatic alcohol,
wherein the solvent is an alcohol solvent.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113372187A (en) * | 2021-06-02 | 2021-09-10 | 西安瑞联新材料股份有限公司 | Industrial synthesis method of BVPE |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113372187A (en) * | 2021-06-02 | 2021-09-10 | 西安瑞联新材料股份有限公司 | Industrial synthesis method of BVPE |
Non-Patent Citations (1)
| Title |
|---|
| B. A. ZAITSEV AND I. D. SHVABSKAYA: "Divinyl Aromatic Compounds and Di(methacrylates) Prepared by Acid-Catalyzed Transformations of Bis[4-(1-hydroxyethyl)phenyl]alkanes", 《RUSSIAN JOURNAL OF APPLIED CHEMISTRY》, vol. 84, no. 10, pages 1784 - 42 * |
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