CN115385774B - Preparation method of di-secondary aromatic alcohol - Google Patents
Preparation method of di-secondary aromatic alcohol Download PDFInfo
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- CN115385774B CN115385774B CN202211016731.6A CN202211016731A CN115385774B CN 115385774 B CN115385774 B CN 115385774B CN 202211016731 A CN202211016731 A CN 202211016731A CN 115385774 B CN115385774 B CN 115385774B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical group OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 19
- 229940125904 compound 1 Drugs 0.000 claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 125000000217 alkyl group Chemical group 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 229940125782 compound 2 Drugs 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 239000007810 chemical reaction solvent Substances 0.000 description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- YLEIFZAVNWDOBM-ZTNXSLBXSA-N ac1l9hc7 Chemical compound C([C@H]12)C[C@@H](C([C@@H](O)CC3)(C)C)[C@@]43C[C@@]14CC[C@@]1(C)[C@@]2(C)C[C@@H]2O[C@]3(O)[C@H](O)C(C)(C)O[C@@H]3[C@@H](C)[C@H]12 YLEIFZAVNWDOBM-ZTNXSLBXSA-N 0.000 description 11
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- GVOISEJVFFIGQE-YCZSINBZSA-N n-[(1r,2s,5r)-5-[methyl(propan-2-yl)amino]-2-[(3s)-2-oxo-3-[[6-(trifluoromethyl)quinazolin-4-yl]amino]pyrrolidin-1-yl]cyclohexyl]acetamide Chemical compound CC(=O)N[C@@H]1C[C@H](N(C)C(C)C)CC[C@@H]1N1C(=O)[C@@H](NC=2C3=CC(=CC=C3N=CN=2)C(F)(F)F)CC1 GVOISEJVFFIGQE-YCZSINBZSA-N 0.000 description 8
- 238000012216 screening Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- -1 aromatic alcohol compound Chemical group 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 229920002120 photoresistant polymer Polymers 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Natural products CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 125000003158 alcohol group Chemical group 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- ZRUHIGBQPRZIQJ-UHFFFAOYSA-N 1-[4-[2-[4-(1-hydroxyethyl)phenyl]ethyl]phenyl]ethanol Chemical compound C1=CC(C(O)C)=CC=C1CCC1=CC=C(C(C)O)C=C1 ZRUHIGBQPRZIQJ-UHFFFAOYSA-N 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 150000001337 aliphatic alkines Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- DEZRYPDIMOWBDS-UHFFFAOYSA-N dcm dichloromethane Chemical compound ClCCl.ClCCl DEZRYPDIMOWBDS-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The application provides a preparation method of di-secondary aromatic alcohol, belonging to the field of organic synthesis. The reaction formula of the method for preparing the di-secondary aromatic alcohol provided by the application is as follows:wherein R1 and R2 are independently selected from alkyl groups having any carbon number, and Q isN=1-5, comprising the following reaction steps: mixing compound 1, reducing agent and solvent for reaction, and post-treating to obtain compound 2, wherein the reducing agent is borohydride or Ranny Ni/H 2 . The preparation method provided by the application can prepare the di-secondary aromatic alcohol under milder reaction conditions.
Description
Technical Field
The application relates to the field of organic chemistry, in particular to a preparation method of di-secondary aromatic alcohol.
Background
Among the prior art, a range of di-secondary aromatic alcohol compounds are widely used in various fields, and as described in patent JP2004101819A, a range of di-secondary aromatic alcohol compounds typified by 1, 2-bis (4- (1-hydroxyethyl) phenyl) ethane can be used as a constituent of a negative resist. The negative resist containing the di-secondary aromatic alcohol compound has better storage stability, so that the negative resist can be applied to the processing process of the semiconductor device and the processing precision of the semiconductor device can be improved.
As another example, paper Divinyl Aromatic Compounds and Di (metacrylates) Prepared by Acid-Catalyzed Transformations of Bis [4- (1-hydroxyetyl) phenyl ] alkines (Russian Journal of Applied Chemistry,84 (10), 1783-1794 (2011)) reports that di-secondary aromatic alcohol compounds can also be used as monomers to prepare heat resistant insulating compounds.
The above paper also provides a process for the preparation of di-secondary aromatic alcohols having the following reaction scheme:
however, according to the paper, the above reaction needs to be 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 application has been made to solve the above problems, and an object of the present application is to provide a process for producing a di-secondary aromatic alcohol having a milder reaction condition and a higher reaction yield.
The application provides a technical scheme of two sets of preparation methods of di-secondary aromatic alcohol.
Scheme one:
the application provides a preparation method of di-secondary aromatic alcohol, which has the characteristics 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-secondary aromatic alcohol provided by the application 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-secondary aromatic alcohol provided by the application 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-secondary aromatic alcohol provided by the application can also have the following characteristics: wherein the post-treatment comprises the following steps:
adding acid liquor to quench reaction, extracting with organic solvent, taking organic phase, washing with water, concentrating, adding benzene solvent, heating to reflux, cooling to-20-0 ℃, filtering, taking filter cake, and drying.
The preparation method of the di-secondary aromatic alcohol provided by the application can also have the following characteristics: wherein the post-treatment comprises the following steps:
adding aqueous hydrochloric acid solution to quench reaction, extracting with ethyl acetate or dichloromethane, taking organic phase, adding benzene or toluene, heating and refluxing for 0.5-3 h, cooling to-20-0 ℃, filtering, taking filter cake, and drying to obtain the final product.
Scheme II:
the application provides a preparation method of di-secondary aromatic alcohol, which has the characteristics that the reaction formula is as follows:
wherein R is 1 、R 2 Independently of one another, are selected from alkyl groups having any carbon number, Q is N=1 to 5,
the method comprises the following reaction steps:
in the hydrogen atmosphere, the compound 1, ranny Ni and solvent are mixed for reaction, and then the post-treatment is carried out, thus obtaining the catalyst,
wherein the mass ratio of the solvent to the compound 1 is (6-15): 1.
the preparation method of the di-secondary aromatic alcohol provided by the application can also have the following characteristics: the mass ratio of Ranny Ni to compound 1 is 1: (3-10).
The preparation method of the di-secondary aromatic alcohol provided by the application can also have the following characteristics: the reaction temperature is 35-50 ℃.
The preparation method of the di-secondary aromatic alcohol provided by the application can also have the following characteristics: r is R 1 、R 2 Independently of one another, from C1-C5 alkyl, preferably R 1 ＝R 2 ＝Me。
The preparation method of the di-secondary aromatic alcohol provided by the application can also have the following characteristics: ranny Ni was adjusted to pH 7-8 prior to use.
The preparation method of the di-secondary aromatic alcohol provided by the application can also have the following characteristics: the reaction pressure is 1.2Mpa-1.8Mpa.
The preparation method of the di-secondary aromatic alcohol provided by the application can also have the following characteristics: the solvent is an alcohol solvent, preferably methanol or ethanol.
The preparation method of the di-secondary aromatic alcohol provided by the application can also have the following characteristics: wherein the post-treatment comprises the following steps: filtering, concentrating under reduced pressure, and drying.
Effects and effects of the application
According to the method for producing a di-secondary aromatic alcohol of the present application, since borohydride is used as a reducing agent and methanol or ethanol is used as a reaction solvent, the present application can produce a di-secondary aromatic alcohol compound at a high yield under normal pressure.
According to the preparation method of the di-secondary aromatic alcohol, ranny Ni is used 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 process provided by the application makes it possible, surprisingly, to obtain higher reaction yields at lower pressures and lower reaction temperatures.
Detailed Description
The present application will be described in detail with reference to the following examples, so that the technical means, the creation characteristics, the achievement of the purpose and the effect achieved by the present application are easily understood.
In the examples below, each of the reaction materials was commercially available unless otherwise specified.
Example 1 ]
Preparation of Compound 1a
This example provides a process for the preparation of compound 1a, having the following formula:
the method comprises the following reaction and post-treatment steps:
under the protection of nitrogen, 183g of AlCl is treated in an ice water bath 3 (1.37 mol,2.5 eq) was added to 300g of methylene chloride, then 116g of acetyl chloride (1.48 mol,2.7 eq) was added dropwise, then a mixed solution of 100g of compound 4 (0.55 mol,1.0 eq) and 200g of methylene chloride was added dropwise, after the addition was completed, the temperature was raised to 40 ℃ for 2 hours, the reaction was transferred to an ice water bath, 600g of 10wt% aqueous hydrochloric acid solution was added for quenching reaction, 600g of methylene chloride was added for extraction, an organic phase was taken, and the mixture was concentrated under reduced pressure and dried at 60 ℃ to obtain 133g of compound 1a, the yield was 91.0%, and the purity was 99.1%.
Example 2 ]
Preparation of Compound 2a
This example provides a method for preparing compound 2a, which has the following reaction formula:
the method comprises the following reaction and post-treatment steps:
35g of Compound 1a (131.4 mmol,1.0 eq) was added to 100g of methanol, the temperature was raised to 35℃and 11g of potassium borohydride (203.9 mmol,1.55 eq) was added, the reaction was cooled to 10℃and quenched by adding 175g of 10wt% aqueous hydrochloric acid, then 420g of ethyl acetate was added and stirred for 1h, the organic phase was extracted, washed once with water, concentrated under reduced pressure and dried at 60℃to give 33.5g of Compound 2a in 94.4% yield and 86.1% purity.
Example 3 ]
Preparation of Compound 2a
This example provides a method for preparing compound 2a, which has the following reaction formula:
the method comprises the following reaction and post-treatment steps:
35g of compound 1a (131.4 mmol,1.0 eq) was added to 100g of methanol, the temperature was raised to 35 ℃, 11g of potassium borohydride (203.9 mmol,1.55 eq) was added, the reaction was cooled to 10 ℃ and quenched by adding 175g of 10wt% aqueous hydrochloric acid, then 420g of ethyl acetate was added, stirred for 1h, then extracted, the organic phase was taken, extracted, washed once with water, concentrated to dryness under reduced pressure, 100g of toluene was added, the temperature was raised to 120 ℃ and refluxed for 1h, naturally cooled to-10 ℃, the filter cake was filtered, and the cake was taken and dried at 60 ℃ to obtain 32.6g of compound 2a, the yield was 91.8% and the purity was 99.4%.
Example 4 ]
Screening of reaction solvents
In this example, the reaction solvent was screened on the basis of example 3, and the screening results are shown in Table 1, except that the contents described in the table are different from those in example 3, and the other raw materials and the procedure were the same as those in example 3.
TABLE 1 screening of reaction solvents
| Sequence number | Solvent(s) | Yield is good | Purity of |
| 1 | Tetrahydrofuran (THF) | 41.3％ | - |
| 2 | Dichloromethane (dichloromethane) | Trace amount of | - |
| 3 | Ethanol | 85.3％ | 99.5％ |
| 4 | Isopropyl alcohol | 78.5％ | 98.9％ |
| 5 | Dimethoxy diethyl ether | 37.5％ | - |
As is clear from Table 1, the reaction solvents have a large influence on the substrate according to the present application, and alcohol solvents such as methanol and ethanol are more suitable for the present reaction than other types of solvents.
Example 5 ]
Preparation of Compound 2a
This example provides a method for preparing compound 2a, which has the following reaction formula:
the method comprises the following reaction and post-treatment steps:
10g of compound 1a was weighed into a hydrogenation kettle and 100g of methanol and 2g of Ranny Ni were added, wherein Ranny Ni was washed with deionized water to pH 8 prior to use. Introducing hydrogen to the pressure of 1.5MPa in the hydrogenation kettle, heating to 38 ℃, stirring for reaction for 2h, 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 is washed to 14 with deionized water prior to use. This example produced 8.60g of compound 2a in 84.8% yield.
Example 7 ]
Screening of the amount of the reaction solvent
In this example, the amount of the reaction solvent was selected based on example 5, and the selection results are shown in Table 2, except that the contents of the materials and the procedure are the same as those in example 5.
TABLE 2 screening of the amounts of reaction solvents used
| Sequence number | Solvent dosage | Yield is good |
| 1 | 30g | 54.9％ |
| 2 | 60g | 84.0％ |
| 3 | 150g | 96.1％ |
As can be seen from Table 2, the applicant has unexpectedly found that the amount of the reaction solvent used has a greater correlation with the yield of the final product, and that even at a smaller hydrogen pressure, when the mass ratio of the solvent to the compound 1a is less than 10:1, the reaction yield increases gradually with increasing amount of the reaction solvent used; further, when the mass ratio of the solvent to the compound 1a is more than 10:1, the solvent is further used for reaction, 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 selection results are shown in Table 3, except that the contents of the materials and the procedure are the same as those in example 5 except that the contents of the materials and the procedure are different from those in example 5.
TABLE 3 screening of reaction temperatures
As shown in Table 3, the applicant has unexpectedly found that the reaction yield is improved as the reaction temperature is lowered, which is probably due to the occurrence of side reactions of the reaction raw materials at high temperature and high pressure, resulting in a decrease in the yield of the target product.
Effects and effects of the examples
According to the process for producing a di-secondary aromatic alcohol of examples 2 to 4, since borohydride is used as a reducing agent and methanol or ethanol is used as a reaction solvent, a di-secondary aromatic alcohol compound can be produced at normal pressure and high yield.
Furthermore, the steps of adding toluene, heating, refluxing, cooling, filtering and the like are performed in the post-treatment process, so that impurities carried in the product can be effectively removed, and the purity of the product is improved.
According to the preparation method of the di-secondary aromatic alcohol related to the examples 5 to 8, since Ranny Ni is used as a reduction catalyst, the amount of the reaction solvent is greatly increased, and the mass ratio of the reaction solvent to the raw materials is controlled to be (6 to 15): 1, the preparation process provided by the application makes it possible, surprisingly, to obtain higher reaction yields at lower pressures and lower reaction temperatures.
Further, since the pH of Ranny Ni is 7-8 by washing before using Ranny Ni, the yield of the target product is unexpectedly improved to some extent.
The above embodiments are preferred examples of the present application, and are not intended to limit the scope of the present application.
Claims (2)
1. A preparation method of di-secondary aromatic alcohol is characterized by comprising the following reaction formula:
wherein R is 1 、R 2 Independently of one another, from C1-C5 alkyl, Q is N=1 to 5,
the method comprises the following reaction steps:
in the hydrogen atmosphere, the compound 1, rannyNi and solvent are mixed for reaction, and then the mixture is post-treated to obtain the catalyst,
wherein the mass ratio of the solvent to the compound 1 is (6-15): 1,
the reaction pressure is 1.2Mpa-1.8Mpa,
the reaction temperature is between 35 and 50 ℃,
the solvent is methanol or ethanol.
2. A process for producing a di-secondary aromatic alcohol according to claim 1, wherein,
wherein the RannyNi is adjusted to pH 7-8 prior to use.
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| 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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| 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 |
|---|
| 刘建周 等.《工业催化工程》.中国矿业大学出版社,2018,第78页. * |
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