CN116640057A - Preparation method of high-quality 4,4' -diacyl chloride diphenyl ether - Google Patents
Preparation method of high-quality 4,4' -diacyl chloride diphenyl ether Download PDFInfo
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- CN116640057A CN116640057A CN202310592525.8A CN202310592525A CN116640057A CN 116640057 A CN116640057 A CN 116640057A CN 202310592525 A CN202310592525 A CN 202310592525A CN 116640057 A CN116640057 A CN 116640057A
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- diphenyl ether
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- diacyl chloride
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- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 title claims abstract description 50
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 22
- WVDRSXGPQWNUBN-UHFFFAOYSA-N 4-(4-carboxyphenoxy)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1OC1=CC=C(C(O)=O)C=C1 WVDRSXGPQWNUBN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 239000011259 mixed solution Substances 0.000 claims abstract description 9
- 238000001704 evaporation Methods 0.000 claims abstract description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 27
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 239000012046 mixed solvent Substances 0.000 claims description 11
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 claims description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 6
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 238000004042 decolorization Methods 0.000 claims description 2
- VPLLTGLLUHLIHA-UHFFFAOYSA-N dicyclohexyl(phenyl)phosphane Chemical compound C1CCCCC1P(C=1C=CC=CC=1)C1CCCCC1 VPLLTGLLUHLIHA-UHFFFAOYSA-N 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 239000007787 solid Substances 0.000 description 5
- 239000004952 Polyamide Substances 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- PGPNJCAMHOJTEF-UHFFFAOYSA-N 1-chloro-4-phenoxybenzene Chemical compound C1=CC(Cl)=CC=C1OC1=CC=CC=C1 PGPNJCAMHOJTEF-UHFFFAOYSA-N 0.000 description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/58—Preparation of carboxylic acid halides
- C07C51/60—Preparation of carboxylic acid halides by conversion of carboxylic acids or their anhydrides or esters, lactones, salts into halides with the same carboxylic acid part
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/58—Preparation of carboxylic acid halides
- C07C51/64—Separation; Purification; Stabilisation; Use of additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation method of high-quality 4,4' -diacyl chloride diphenyl ether, which comprises the following steps: s1: adding 4,4' -diphenyl ether dicarboxylic acid into a solvent, and dissolving carbon tetrachloride and a catalyst by using the same solvent to obtain a mixed solution A, S2: dropwise adding the mixed solution A into a 4,4' -diphenyl ether dicarboxylic acid solution at a low temperature, and reacting at a certain temperature after the dropwise adding is finished; s3: and after the reaction is finished, evaporating the solvent, and performing post-treatment to obtain the high-quality 4,4' -diacyl chloride diphenyl ether. The invention has the beneficial effects that: the preparation method uses a new process system, has the advantages of simple preparation, safe operation, small environmental pollution, high yield and high purity of the synthesized product, and is suitable for large-scale production.
Description
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a preparation method of high-quality 4,4' -diacyl chloride diphenyl ether.
Background
Polyamide is a polymer material having an amide bond in its main chain, and is known for its high toughness, high modulus, and excellent heat stability, and is located at the front end of the polymer material. 4,4' -diacyl chloride diphenyl ether is an important polyamide monomer, and the polyamide synthesized by using the same has wide application prospect.
At present, the common synthesis method mainly takes 4,4 '-diphenyl ether dicarboxylic acid as a raw material, and utilizes thionyl chloride to synthesize 4,4' -diacyl chloride diphenyl ether. The preparation method has the main problems that the reaction needs high temperature and has high energy consumption; the reaction is severe, the reaction is easy to accumulate heat, and the danger of spraying materials exists; the high temperature prepared product has unstable chromaticity and generally poor chromaticity, and can influence the optical performance of the prepared polyamide.
Disclosure of Invention
In view of the above, the invention aims to provide a preparation method of 4,4' -diacyl chloride diphenyl ether, which has the advantages of simple process, low production cost, environmental protection, higher product quality and yield and suitability for large-scale production.
In order to achieve the above purpose, the technical scheme of the invention is realized as follows:
a preparation method of high-quality 4,4' -diacyl chloride diphenyl ether comprises the following steps:
s1: adding 4,4' -diphenyl ether dicarboxylic acid into a solvent, dissolving carbon tetrachloride and a catalyst by using the same solvent to obtain a mixed solution A,
s2: dropwise adding the mixed solution A into a 4,4' -diphenyl ether dicarboxylic acid solution at a low temperature, and reacting at a certain temperature after the dropwise adding is finished;
s3: and after the reaction is finished, evaporating the solvent, and performing post-treatment to obtain the high-quality 4,4' -diacyl chloride diphenyl ether.
Further, the solvent in the step S1 is one or more of tetrahydrofuran, dichloromethane, acetonitrile, diethyl ether and methyl tertiary butyl ether
Preferably, the solvent is tetrahydrofuran.
Further, the catalyst in the step S1 is one or more of triphenylphosphine, tricyclohexylphosphine and phenyldicyclohexylphosphine;
preferably, the catalyst is tricyclohexylphosphorus.
Further, after the dripping in the step S2 is finished, the mol ratio of the solvent, the carbon tetrachloride, the catalyst and the 4,4' -diphenyl ether dicarboxylic acid is 30-50:2.5-4:3-5:1;
the reaction temperature in the step S2 is 30-50 ℃.
Further, in the step S3, the solvent is distilled off, the mixed solvent is added into the residual residue, after heating and dissolution, activated carbon is added for decolorization, the solution is filtered, the filtrate is cooled to separate out white crystals, and the crystals are obtained through filtration and vacuum drying, so that the high-quality 4,4' -diacyl chloride diphenyl ether is obtained.
Further, the mixed solvent in the step S2 is one of n-hexane/acetonitrile, n-hexane/ethyl acetate and n-hexane/isopropyl ether;
preferably, the mixed solvent is n-hexane/acetonitrile;
further, the molar ratio of the n-hexane to the other solvents is 1-3:1.
Further, the molar ratio of the mixed solvent to the 4,4' -diphenyl ether dicarboxylic acid is 10-20:1.
Further, adding the mixed solvent and heating to 50-60 ℃.
Further, the mass ratio of the active carbon to the 4,4' -diphenyl ether dicarboxylic acid is 0.05-0.2:1.
Compared with the prior art, the preparation method of the high-quality 4,4' -diacyl chloride diphenyl ether has the following advantages:
the preparation method uses a new process system, has the advantages of simple preparation, safe operation, small environmental pollution, high yield and high purity of the synthesized product, and is suitable for large-scale production.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention. In the drawings:
FIG. 1 is a synthetic route for 4,4' -diacyl chlorodiphenyl ether prepared in example 1 of the present invention;
FIG. 2 is an HPLC chart of 4,4' -diacyl chlorodiphenyl ether prepared in example 1 of the present invention.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention pertains. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The invention will be described in detail below with reference to the drawings in connection with embodiments.
Example 1
50g of 4,4' -diphenyl ether dicarboxylic acid is added into 420g of tetrahydrofuran, and the mixture is stirred uniformly and is marked as solution A; 89.35g of carbon tetrachloride, 190.03g of tricyclohexylphosphorus were added to 140g of tetrahydrofuran and designated as solution B. And cooling the solution A to 0 ℃, slowly dripping the solution B into the solution A, slowly heating the solution A to 35 ℃ after dripping, and carrying out heat preservation reaction for 5 hours. And (3) detecting through a liquid phase, and finishing the reaction. The solvent is evaporated under reduced pressure at 50 ℃, 40g of acetonitrile and 87g of normal hexane are added into the residual residue, the temperature is raised to 55 ℃, the system is gradually dissolved until the mixture is transparent, 5g of active carbon is added for stirring for 20min, the hot filtration is carried out, the filtrate is slowly cooled to 0 ℃, a large amount of white crystals are separated out, the filtered solid is dried for 12h at 80 ℃ under vacuum to obtain 56.38g of 4,4' -diacyl chloride diphenyl ether, the molar yield is 98.67%, the purity is 99.95%, and YI=0.34.
Example 2
50g of 4,4' -diphenyl ether dicarboxylic acid is added into 400g of methyl tertiary butyl ether, and the mixture is stirred uniformly and is marked as solution A; 80.41g of carbon tetrachloride, 217.17g of tricyclohexylphosphorus were added to 200g of methyl tert-butyl ether, designated as solution B. And cooling the solution A to 5 ℃, slowly dripping the solution B into the solution A, slowly heating the solution A to 35 ℃ after dripping, and carrying out heat preservation reaction for 7h. And (3) detecting through a liquid phase, and finishing the reaction. The solvent was evaporated to dryness under reduced pressure at 50℃and the residue was added to a mixed solution of 57.24g of ethyl acetate and 143.96g of n-hexane, the temperature was raised to 60℃and the system was gradually dissolved to transparency, 20g of activated carbon was added and stirred for 20min, the filtrate was slowly cooled to 0℃and a large amount of white crystals were precipitated, the filtered solid was dried under vacuum at 80℃for 12h to give 55.74g of 4,4' -diacyl-diphenyl ether with a molar yield of 97.54% and a purity of 99.87% and YI=0.47.
Example 3
50g of 4,4' -diphenyl ether dicarboxylic acid is added into 300g of tetrahydrofuran, and the mixture is stirred uniformly and is marked as solution A; 104.24g of carbon tetrachloride, 187.88g of triphenylphosphine were added to 120g of tetrahydrofuran, designated solution B. And cooling the solution A to 0 ℃, slowly dripping the solution B into the solution A, slowly heating the solution A to 40 ℃ after dripping, and carrying out heat preservation reaction for 5 hours. And (3) detecting through a liquid phase, and finishing the reaction. The solvent was evaporated to dryness under reduced pressure at 50℃and the residue was added to a mixed solution of 177.67g isopropyl ether and 150g n-hexane, the temperature was raised to 50℃and the system was gradually dissolved to transparency, 15g activated carbon was added and stirred for 20min, the filtrate was slowly cooled to 0℃and a large amount of white crystals were precipitated, the filtered solid was dried under vacuum at 80℃for 12h to give 54.76g 4,4' -diacyl-chlorodiphenyl ether with a molar yield of 95.83% and a purity of 99.82% and YI=0.49.
Comparative example 1
50g of 4,4' -diphenyl ether dicarboxylic acid is added into a mixed solvent of 500g of toluene and 5g of dimethylformamide, the temperature is raised to 80 ℃, 15mL of thionyl chloride is slowly added dropwise, and after the dropwise addition is finished, the reaction is carried out at 80 ℃ for 12 hours. And (3) detecting through a liquid phase, and finishing the reaction. The solvent was evaporated to dryness under reduced pressure at 50℃and the residue was added to a mixed solution of 177.67g isopropyl ether and 150g n-hexane, the temperature was raised to 50℃and the system was gradually dissolved to transparency, 15g activated carbon was added and stirred for 20min, the filtrate was slowly cooled to 0℃and a large amount of pale yellow solid was precipitated, the filtered solid was dried under vacuum at 80℃for 12h to give 48.98g 4,4' -diacyl-chlorodiphenyl ether with a molar yield of 85.73% and a purity of 99.12% and YI=8.6.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (10)
1. A preparation method of high-quality 4,4' -diacyl chloride diphenyl ether is characterized by comprising the following steps: the method comprises the following steps:
s1: adding 4,4' -diphenyl ether dicarboxylic acid into a solvent, dissolving carbon tetrachloride and a catalyst by using the same solvent to obtain a mixed solution A,
s2: dropwise adding the mixed solution A into a 4,4' -diphenyl ether dicarboxylic acid solution at a low temperature, and reacting at a certain temperature after the dropwise adding is finished;
s3: and after the reaction is finished, evaporating the solvent, and performing post-treatment to obtain the high-quality 4,4' -diacyl chloride diphenyl ether.
2. The method for preparing high-quality 4,4' -diacyl chloride diphenyl ether according to claim 1, wherein the method comprises the following steps: the solvent in the step S1 is one or more of tetrahydrofuran, dichloromethane, acetonitrile, diethyl ether and methyl tertiary butyl ether
Preferably, the solvent is tetrahydrofuran.
3. The method for preparing high-quality 4,4' -diacyl chloride diphenyl ether according to claim 1, wherein the method comprises the following steps: the catalyst in the step S1 is one or more of triphenylphosphine, tricyclohexylphosphine and phenyldicyclohexylphosphine;
preferably, the catalyst is tricyclohexylphosphorus.
4. The method for preparing high-quality 4,4' -diacyl chloride diphenyl ether according to claim 1, wherein the method comprises the following steps: after the dripping in the step S2 is finished, the mol ratio of the solvent, carbon tetrachloride, the catalyst and the 4,4' -diphenyl ether dicarboxylic acid is 30-50:2.5-4:3-5:1;
the reaction temperature in the step S2 is 30-50 ℃.
5. The method for preparing high-quality 4,4' -diacyl chloride diphenyl ether according to claim 1, wherein the method comprises the following steps: and (3) evaporating the solvent in the step (S3), adding a mixed solvent into the residual residues, heating for dissolution, adding active carbon for decolorization, filtering, cooling the filtrate to separate out white crystals, and performing vacuum drying on the filtered crystals to obtain the high-quality 4,4' -diacyl chloride diphenyl ether.
6. The method for preparing high-quality 4,4' -diacyl chloride diphenyl ether according to claim 5, wherein the method comprises the following steps: the mixed solvent in the step S2 is one of n-hexane/acetonitrile, n-hexane/ethyl acetate and n-hexane/isopropyl ether;
preferably, the mixed solvent is n-hexane/acetonitrile.
7. The method for preparing high-quality 4,4' -diacyl chloride diphenyl ether according to claim 6, wherein the method comprises the following steps: the molar ratio of the n-hexane to the other solvents is 1-3:1.
8. The method for preparing high-quality 4,4' -diacyl chloride diphenyl ether according to claim 5, wherein the method comprises the following steps: the molar ratio of the mixed solvent to the 4,4' -diphenyl ether dicarboxylic acid is 10-20:1.
9. The method for preparing high-quality 4,4' -diacyl chloride diphenyl ether according to claim 5, wherein the method comprises the following steps: adding mixed solvent and heating to 50-60 ℃.
10. The method for preparing high-quality 4,4' -diacyl chloride diphenyl ether according to claim 5, wherein the method comprises the following steps: the mass ratio of the active carbon to the 4,4' -diphenyl ether dicarboxylic acid is 0.05-0.2:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310592525.8A CN116640057A (en) | 2023-05-24 | 2023-05-24 | Preparation method of high-quality 4,4' -diacyl chloride diphenyl ether |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310592525.8A CN116640057A (en) | 2023-05-24 | 2023-05-24 | Preparation method of high-quality 4,4' -diacyl chloride diphenyl ether |
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| CN202310592525.8A Pending CN116640057A (en) | 2023-05-24 | 2023-05-24 | Preparation method of high-quality 4,4' -diacyl chloride diphenyl ether |
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| Country | Link |
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| CN (1) | CN116640057A (en) |
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- 2023-05-24 CN CN202310592525.8A patent/CN116640057A/en active Pending
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