CN112457330A - Preparation method of coumarin benzo selenophene compound serving as pearl brightener - Google Patents
Preparation method of coumarin benzo selenophene compound serving as pearl brightener Download PDFInfo
- Publication number
- CN112457330A CN112457330A CN202011060991.4A CN202011060991A CN112457330A CN 112457330 A CN112457330 A CN 112457330A CN 202011060991 A CN202011060991 A CN 202011060991A CN 112457330 A CN112457330 A CN 112457330A
- Authority
- CN
- China
- Prior art keywords
- compound
- coumarin
- benzo
- pearl brightener
- mmol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D517/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having selenium, tellurium, or halogen atoms as ring hetero atoms
- C07D517/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having selenium, tellurium, or halogen atoms as ring hetero atoms in which the condensed system contains two hetero rings
- C07D517/04—Ortho-condensed systems
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The invention discloses a preparation method of coumarin benzo selenophene compound shown in a pearl brightener formula (IV), which comprises the following steps: the o-hydroxy cinnamaldehyde compound shown in the formula (I), the peroxyacetic acid shown in the formula (II) and the phenylselenophenol compound shown in the formula (III) are prepared into a reaction product by taking aluminum chloride as a catalyst and pyridine as a medium, and the reaction product is subjected to post-treatment to obtain the coumarin acenoselenophene compound. The method has the advantages of no heavy metal in the production process, wide raw material source, simple operation, excellent yield and the like. Has important application prospect in the related fine chemical field of pearl brightener.
Description
Technical Field
The invention belongs to the technical field of fine chemical product preparation, and particularly relates to a preparation method of a pearl brightener coumarin benzo selenophene compound.
Background
The pearl brightener is a fine chemical preparation compounded by a surfactant, a penetrating agent, a stabilizer, a solvent and the like. The pearl brightener has the functions of treating and protecting pearl surface, and can eliminate oil stain and oxidized surface impurity on pearl surface to maintain the surface glossiness and smoothness of pearl. The excellent pearl brightener has the characteristics of good brightening effect, no toxicity, environmental friendliness and the like. Researches show that the coumaro-benzo-selenone thiophene compound has great advantages in removing oil stains from pearls and enhancing the brightness of the pearls, and attracts the attention of researchers.
The reported preparation method of the coumarin benzo selenophene compound is mainly prepared through metal catalysis and multi-step substitution and esterification, and has the defects of multiple reaction steps, low reaction efficiency and the like. The method adopts aluminum chloride with low cost and high catalytic efficiency as a catalyst to realize the high-efficiency preparation of the coumarin acene-selenophene compound. The production process does not use heavy metal, and has the advantages of wide raw material source, simple operation, simple post-reaction treatment, excellent yield and the like. Has important application prospect in the related fine chemical field of pearl brightener.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a method for preparing a pearl brightener coumarin benzo selenone thiophene compound.
The invention is realized by the following technical scheme:
a preparation method of coumarin benzo selenone thiophene compound shown in a pearl brightener formula (IV) is characterized by comprising the following steps: the o-hydroxy cinnamaldehyde compound shown in the formula (I), the peroxyacetic acid shown in the formula (II) and the phenylselenophenol compound shown in the formula (III) are prepared into a reaction product by taking metal salt as a catalyst and an organic solvent as a medium, and the reaction product is subjected to post-treatment to obtain a coumarino selenophene compound; the metal salt catalyst is aluminum chloride, and the organic solvent is pyridine;
in the reaction formula, R1Selected from one of the following: hydrogen and methylMethoxy, halogen; r2Selected from one of the following: hydrogen, methyl, chlorine.
A method for preparing a pearl brightener coumarin benzo selenone thiophene compound is characterized in that the ratio of o-hydroxy cinnamaldehyde compounds, peracetic acid and phenylselenophenol compounds is 5 mmol: 15 mmol: 5 mmol.
A preparation method of a pearl brightener coumarin selenophene compound is characterized in that the ratio of o-hydroxycinnamaldehyde compound to peracetic acid to aluminum chloride is 5 mmol: 15 mmol: 0.5 mmol.
A preparation method of a pearl brightener coumarin selenophene compound is characterized in that the ratio of o-hydroxycinnamaldehyde compound, peracetic acid and solvent pyridine is 5 mmol: 15 mmol: 15 mL.
A preparation method of a pearl brightener coumarin benzo selenone thiophene compound is characterized in that the equivalent ratio of o-hydroxy cinnamaldehyde compounds to peracetic acid to phenylselenophenol compounds is 1 (2-3) to 1.
A method for preparing a pearl brightener coumarin benzo selenone thiophene compound is characterized in that the reaction temperature is 100 ℃, and the reaction time is 8 hours.
A preparation method of a pearl brightener coumarin selenophene compound is characterized by comprising the following steps:
1) and (3) extraction: after the reaction product is cooled to room temperature at normal temperature, 20mL of saturated sodium chloride aqueous solution is added into the reaction product, then ethyl acetate is used for extraction for 3 times, 20mL of the ethyl acetate is used for each time, and the extraction liquid is combined;
2) concentration: drying the extract with anhydrous sodium sulfate, and rotary drying with rotary evaporator to obtain concentrate;
3) adsorbing the obtained concentrate by using column chromatography silica gel, adding the concentrate into a 200-mesh 300-mesh chromatography silica gel column, and adding normal hexane: performing flash column chromatography with ethyl acetate according to a certain proportion, mixing eluates, performing rotary evaporation with a rotary evaporator, and pumping with an oil pump to obtain the product of the pearl brightener coumarin and benzoselenophene compound.
A preparation method of a pearl brightener coumarin selenophene compound, which is characterized in that the drying time in the step 2) is 8 hours.
A preparation method of a pearl brightener coumarin selenophene compound is characterized in that the volume ratio of n-hexane to ethyl acetate in the step 3) is 3:1-1: 1.
The method does not use heavy metal in the production process, and has the advantages of wide raw material source, simple operation, excellent yield and the like. Has important application prospect in the related fine chemical field of pearl brightener.
Drawings
FIG. 1 is a drawing of product 4a of the present invention1H NMR spectrum;
FIG. 2 shows the product 4a of the present invention13C NMR spectrum;
FIG. 3 shows the product 4b of the present invention1H NMR spectrum;
FIG. 4 shows the product 4b of the present invention13C-NMR spectrum;
FIG. 5 shows the preparation of 4c according to the invention1H NMR spectrum;
FIG. 6 shows the preparation of 4c according to the invention13C-NMR spectrum;
FIG. 7 shows the product 4d of the present invention1H NMR spectrum;
FIG. 8 is a drawing showing the production of 4d in the present invention13C NMR spectrum;
FIG. 9 shows the preparation of 4e according to the invention1H NMR spectrum;
FIG. 10 shows the preparation of 4e according to the invention13C-NMR spectrum;
FIG. 11 shows the preparation of 4f of the present invention1H NMR spectrum;
FIG. 12 shows the preparation of 4f of the present invention13C NMR spectrum;
FIG. 13 is a graph showing the effect of brightening pearls in control and experimental groups according to the present invention.
Detailed Description
The present invention will be described in more detail with reference to specific examples.
The synthesis method comprises the steps of sequentially adding 5mmol of o-hydroxy cinnamaldehyde compounds 1, 15mmol of peracetic acid 2 and 5mmol of phenylselenol compounds 3 into a 25mL round-bottom flask, then sequentially adding 15mL of pyridine and 0.5mmol of aluminum chloride, and reacting at 100 ℃ for 8 hours under stirring. After cooling, 20mL of saturated sodium chloride aqueous solution is added into the system, extraction is carried out for 3 times by ethyl acetate, 20mL of saturated sodium chloride aqueous solution is carried out each time, organic phases are combined, after drying by anhydrous sodium sulfate, solvent is removed by evaporation, and the pure product of the pearl brightener coumarin and benzo-selenone thiophene compound 4 is obtained by 200-mesh and 300-mesh silica gel column chromatography, wherein the yield is 80-91%. Specific examples and characterization data are as follows.
Example 1: 4a preparation of the product
In a 25mL round-bottom flask was added 5mmol o-hydroxycinnamaldehyde, 15mmol peracetic acid, and 5mmol phenylselenol sequentially at room temperature, followed by 15mL acetonitrile, 0.5mmol aluminum chloride, and the reaction was stirred at 100 ℃ for 8 hours. After cooling, 20mL of saturated sodium chloride aqueous solution is added into the system, extraction is carried out for 3 times by ethyl acetate, 20mL of saturated sodium chloride aqueous solution is carried out for each time, organic phases are combined, after drying by anhydrous sodium sulfate, solvent is distilled off, and the coumarino-benzoselenophene compound 4a (1324mg, yield 80 percent and light yellow powder) is obtained by silica gel column chromatography with 200-mesh and 300-mesh. 4a1The H NMR spectrum is shown in figure 1,13the C NMR spectrum is shown in FIG. 2.
6H-benzo[4,5]selenopheno[3,2-c]chromen-6-one 11,11-dioxide(4a)
1H NMR(500MHz,CDCl3):δ8.15(dd,J＝2.4Hz,6.6Hz,1H),8.05(dd,J＝1.5Hz,7.8Hz,1H),7.68(dd,J＝1.7Hz,6.9Hz,1H),7.60-7.64(m,1H),7.41-7.52(m,4H)；
13C NMR(125MHz,CDCl3):δ160.0,158.1,155.6,153.7,131.9,126.8,125.2,124.7,123.5,121.9,117.5,112.7,111.8,105.9；
HRMS(+ESI)Calcd for C15H9O4Se+[M+H]+:332.9661,found 332.9663.
Example 2: 4b preparation of the product
5mmol of o-hydroxycinnamaldehyde, 15mmol of peracetic acid and 5mmol of 3-methylphenylselenol are added sequentially to a 25mL round-bottomed flask at room temperature, followed by 15mL of acetonitrile and 0.5mmol of aluminum chloride, and the reaction is stirred at 100 ℃ for 8 hours. After cooling, 20mL of saturated sodium chloride aqueous solution is added into the system, extraction is carried out for 3 times by ethyl acetate, 20mL of saturated sodium chloride aqueous solution is carried out for each time, organic phases are combined, after drying by anhydrous sodium sulfate, solvent is distilled off, and 200-mesh and 300-mesh silica gel column chromatography is carried out to obtain the coumarophenylselenophenone compound 4b (1506mg, yield 87%, light yellow powder). 4b1The H NMR spectrum is shown in FIG. 3,13the C NMR spectrum is shown in FIG. 4.
9-methyl-6H-benzo[4,5]selenopheno[3,2-c]chromen-6-one 11,11-dioxide(4b)
1H NMR(500MHz,CDCl3):δ7.98(m,3H),7.91(s,1H),7.55-7.61(m,2H),7.52(d,J＝8.5Hz,1H),7.49(s,1H),7.47(s,1H),7.44(s,1H),7.39(m,2H),7.26(d,J＝8.0Hz,2H),2.52(s,3H),2.49(s,3H)；
13C NMR(125MHz,CDCl3):δ159.9,159.4,158.1,158.0,155.8,153.8,153.4,153.3,137.4,135.0,131.6,131.5,127.8,126.4,124.5,124.4,121.7,121.6,121.5,121.1,117.3,117.2,112.7,112.6,111.8,111.1,105.8,105.5,21.8,21.2；
HRMS(+ESI)calcd for C16H11O4Se+[M+H]+:346.2195,found 346.2197.
Example 3: preparation of 4c product
In a 25mL round-bottom flask were added 5mmol o-hydroxycinnamaldehyde, 15mmol peracetic acid, and 5mmol 4-methylphenylselenol sequentially at room temperature, followed by 15mL acetonitrile, 0.5mmol aluminum chloride, and the reaction was stirred at 100 ℃ for 8 hours. After cooling, 20mL of saturated sodium chloride aqueous solution is added into the system, extraction is carried out for 3 times by ethyl acetate, 20mL of saturated sodium chloride aqueous solution is carried out each time, organic phases are combined, after drying by anhydrous sodium sulfate, solvent is distilled off, and the coumarino-benzoselenophene compound 4c (1484mg, yield 86 percent, light yellow powder) is obtained by silica gel column chromatography with 300 meshes. 4c1The H NMR spectrum is shown in FIG. 5,13the C NMR spectrum is shown in FIG. 6.
8-methyl-6H-benzo[4,5]selenopheno[3,2-c]chromen-6-one 11,11-dioxide(4c)
1H NMR(500MHz,CDCl3):δ7.98(m,3H),7.91(s,1H),7.55-7.61(m,2H),7.52(d,J＝8.5Hz,1H),7.49(s,1H),7.47(s,1H),7.44(s,1H),7.39(m,2H),7.26(d,J＝8.0Hz,2H),2.52(s,3H),2.49(s,3H)；
13C NMR(125MHz,CDCl3):δ159.9,159.4,158.1,158.0,155.8,153.8,153.4,153.3,137.4,135.0,131.6,131.5,127.8,126.4,124.5,124.4,121.7,121.6,121.5,121.1,117.3,117.2,112.7,112.6,111.8,111.1,105.8,105.5,21.8,21.2；
HRMS(+ESI)calcd for C16H11O4Se+[M+H]+:346.2195,found 346.2197.
Example 4: preparation of 4d product
In a 25mL round bottom flask was added 5mmol 3-methyl o-hydroxycinnamaldehyde, 15mmol peracetic acid and 5mmol phenylselenol sequentially at room temperature, followed by 15mL acetonitrile, 0.5mmol aluminum chloride, and the reaction was stirred at 100 ℃ for 8 hours. After cooling, 20mL of saturated sodium chloride aqueous solution is added into the system, extraction is carried out for 3 times by ethyl acetate, 20mL of saturated sodium chloride aqueous solution is carried out for each time, organic phases are combined, after drying by anhydrous sodium sulfate, solvent is distilled off, and the coumarino-benzoselenophene compound 4d (1536mg, 89 percent of yield and light yellow powder) is obtained by silica gel column chromatography with 300 meshes. 4d1The H NMR spectrum is shown in FIG. 7,13the C NMR spectrum is shown in FIG. 8.
2-methyl-6H-benzo[4,5]selenopheno[3,2-c]chromen-6-one 11,11-dioxide(4d)
1H NMR(500MHz,CDCl3):δ8.07-8.18(m,1H),7.80(br s,1H),7.59-7.70(m,1H),7.32-7.51(m,4H),2.48(s,3H)；
13C NMR(125MHz,CDCl3):δ160.0,158.2,155.5,151.9,134.5,133.0,126.6,125.1,123.5,121.8,121.5,117.2,112.3,111.7,105.8,20.9；
HRMS(+ESI)Calcd for C16H11O4Se+[M+H]+:346.2195,found 346.2197.
Example 5: preparation of 4e product
In a 25mL round bottom flask was added 5mmol of 3-methyl o-hydroxycinnamaldehyde, 15mmol of peracetic acid, and 5mmol of naphthaleneselenol in sequence followed by 15mL of acetonitrile, 0.5mmol of aluminum chloride at room temperature, and the reaction was stirred at 100 ℃ for 8 hours. After cooling, 20mL of saturated sodium chloride aqueous solution is added into the system, extraction is carried out for 3 times by ethyl acetate, 20mL of saturated sodium chloride aqueous solution is carried out each time, organic phases are combined, after drying by anhydrous sodium sulfate, solvent is distilled off, and the coumarino-benzoselenophene compound 4e (1779mg, yield 90 percent and light yellow powder) is obtained by silica gel column chromatography with 200-mesh and 300-mesh. 4e1The H NMR spectrum is shown in FIG. 9,13the C NMR spectrum is shown in FIG. 10.
2-methyl-6H-naphtho[2',3':4,5]selenopheno[3,2-c]chromen-6-one 13,13-dioxide(4e)
1H NMR(500MHz,CDCl3):δ8.59s,1H),7.94-8.06(m,3H),7.86(s,1H),7.42-7.56(m,4H),2.51(s,1H)；
13C NMR(125MHz,CDCl3):δ162.4,158.3,153.9,152.4,35.7,134.7,133.7,132.1,128.5,127.9,126.2,125.3,123.4,121.8,20.4,117.3,112.1,107.7,105.2,20.9；
HRMS(+ESI)Calcd for C20H13O4Se+[M+H]+:396.2795,Found 396.2797.
Example 6: preparation of 4f product
In a 25mL round bottom flask was added 5mmol of 4-methoxy-o-hydroxycinnamaldehyde, 15mmol of peracetic acid, and 5mmol of phenylselenol sequentially at room temperature, followed by 15mL of acetonitrile, 0.5mmol of aluminum chloride, and the reaction was stirred at 100 ℃ for 8 hours. After cooling, 20mL of saturated sodium chloride aqueous solution is added into the system, extraction is carried out for 3 times by ethyl acetate, 20mL of saturated sodium chloride aqueous solution is carried out each time, organic phases are combined, after drying by anhydrous sodium sulfate, solvent is distilled off, and the coumarino-benzoselenophene compound 4f (1350mg, yield 91 percent and light yellow powder) is obtained by silica gel column chromatography with 200-mesh and 300-mesh. 4f1The H NMR spectrum is shown in FIG. 11,13the C NMR spectrum is shown in FIG. 12.
3-methoxy-6H-benzo[4,5]selenopheno[3,2-c]chromen-6-one 11,11-dioxide(4f)
1H NMR(500MHz,CDCl3):δ8.04-8.14(m,1H),7.91(dd,J＝1.9Hz,7.3Hz,1H),7.57-7.67(m,1H),7.39-7.47(m,2H),6.94-7.02(m,2H),3.91(s,3H)；
13C NMR 125MHz,CDCl3):δ163.0,160.6,158.3,155.5,155.2,126.0,125.0,23.5,122.8,121.4,113.0,111.4,105.8,103.3,101.3,55.7；
HRMS(+ESI)calcd for C16H11O5Se+[M+H]+:362.9766,found 362.9768.
Brightness test
1. The product 4a in the invention is selected as a research object, the preparation is carried out according to the standard requirements, the obtained preparation does not contain sulfur, phosphorus and additives, the toxic oxidation and the flammability are avoided, and the sewage discharge in the preparation process meets the environmental protection requirements.
2. The main components and the contents thereof are as follows: brightening agent 4a, brightening oleic acid, fatty acid and water, wherein the ratio of the dosage (mass ratio) of the agents is 20: 60: 10: 10.
3. the technical indexes are as follows: pH value: 7.5-8.5; appearance: light yellow viscous liquid; viscosity: 500-.
4. The technological parameters are as follows: specific gravity: 1.4-1.5 g/mL; the use concentration is as follows: 0.5-3%; treatment temperature: normal temperature; treatment time: depending on the material of the workpiece.
5. The experimental process comprises the following steps: the experimental pearls were divided into 2 groups of 50g each and performed in parallel. Washing 2 groups of pearls with purified water, then putting one group of pearls into a brightening solution prepared from a product 4a in a ratio of 1:270 (an experimental group), putting the other group of pearls into clean water with the same volume (a control group), soaking the two groups of pearls for 8 hours respectively, filtering, washing again, and carrying out washing-enzyme washing-rinsing procedures on the two groups of pearls. After cleaning, the mixture is put into a drying oven to be dried for 10 minutes. The brightness enhancement qualification rate of the test group is 90 percent. The brightness yield of the control group is 60%. The data of the groups are obviously different and have statistical significance.
6. And (4) conclusion: the pearl brightener prepared by the invention has good brightening effect and lasting retention. The comparative effect graph is shown in fig. 13.
Claims (9)
1. A preparation method of coumarin benzo selenone thiophene compound shown in a pearl brightener formula (IV) is characterized by comprising the following steps: the o-hydroxy cinnamaldehyde compound shown in the formula (I), the peroxyacetic acid shown in the formula (II) and the phenylselenophenol compound shown in the formula (III) are prepared into a reaction product by taking metal salt as a catalyst and an organic solvent as a medium, and the reaction product is subjected to post-treatment to obtain a coumarino selenophene compound; the metal salt catalyst is aluminum chloride, and the organic solvent is pyridine;
in the reaction formula, R1Selected from one of the following: hydrogen, methyl, methoxy, halogen; r2Selected from one of the following: hydrogen, methyl, chlorine.
2. The method for preparing coumarin benzo selenone thiophene compound as pearl brightener as claimed in claim 1, wherein the ratio of o-hydroxycinnamaldehyde compound, peroxyacetic acid and phenylselenophenol compound is 5 mmol: 15 mmol: 5 mmol.
3. The method for preparing coumarin benzo selenone thiophene compound as pearl brightener as claimed in claim 1, wherein the ratio of o-hydroxycinnamaldehyde compound, peracetic acid and aluminum chloride is 5 mmol: 15 mmol: 0.5 mmol.
4. The method for preparing coumarin benzo selenone thiophene compound as pearl brightener as claimed in claim 1, wherein the ratio of o-hydroxycinnamaldehyde compound, peracetic acid and solvent pyridine is 5 mmol: 15 mmol: 15 mL.
5. The method for preparing coumarin benzo selenone thiophene compound as pearl brightener as claimed in claim 1, wherein the equivalent ratio of o-hydroxycinnamaldehyde compound, peracetic acid and phenylselenophenol compound is 1 (2-3) to 1.
6. The method for preparing coumarin phenylselenophenesin compounds as pearl brightener as claimed in claim 1, wherein the reaction temperature is 100 ℃ and the reaction time is 8 hours.
7. The method for preparing coumarin benzo selenone thiophene compound as pearl brightener as claimed in claim 1, wherein the post-treatment comprises the following steps:
1) and (3) extraction: after the reaction product is cooled to room temperature at normal temperature, 20mL of saturated sodium chloride aqueous solution is added into the reaction product, then ethyl acetate is used for extraction for 3 times, 20mL of the ethyl acetate is used for each time, and the extraction liquid is combined;
2) concentration: drying the extract with anhydrous sodium sulfate, and rotary drying with rotary evaporator to obtain concentrate;
3) adsorbing the obtained concentrate by using column chromatography silica gel, adding the concentrate into a 200-mesh 300-mesh chromatography silica gel column, and adding normal hexane: performing flash column chromatography with ethyl acetate according to a certain proportion, mixing eluates, performing rotary evaporation with a rotary evaporator, and pumping with an oil pump to obtain the product of the pearl brightener coumarin and benzoselenophene compound.
8. The method for preparing coumarin phenylselenophenesin compounds as pearl brightener as claimed in claim 7, wherein the drying time in step 2) is 8 hours.
9. The method for preparing coumarin benzo selenone thiophene compound as pearl brightener as claimed in claim 7, wherein the volume ratio of n-hexane to ethyl acetate in step 3) is 3:1-1: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011060991.4A CN112457330A (en) | 2020-09-30 | 2020-09-30 | Preparation method of coumarin benzo selenophene compound serving as pearl brightener |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011060991.4A CN112457330A (en) | 2020-09-30 | 2020-09-30 | Preparation method of coumarin benzo selenophene compound serving as pearl brightener |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112457330A true CN112457330A (en) | 2021-03-09 |
Family
ID=74833066
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011060991.4A Pending CN112457330A (en) | 2020-09-30 | 2020-09-30 | Preparation method of coumarin benzo selenophene compound serving as pearl brightener |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112457330A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111961062A (en) * | 2020-07-17 | 2020-11-20 | 浙江农林大学暨阳学院 | Method for preparing dithio coumarin benzothiophene compound by platinum catalysis |
| CN113004308A (en) * | 2021-01-06 | 2021-06-22 | 浙江农林大学暨阳学院 | Method for preparing pearl optimizing agent diselenocoumarol benzo selenophene compound |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD272853A1 (en) * | 1988-06-13 | 1989-10-25 | Univ Leipzig | PROCESS FOR PREPARING SUBSTITUTED THIENO / 3,2-C / CUMARIN-2-CARBOXYLIC ACID ESTERS |
| WO2018015788A1 (en) * | 2016-07-21 | 2018-01-25 | Latvian Institute Of Organic Synthesis | ANTIMETASTATIC 2H-SELENOPHENO[3,2-h]CHROMENES, SYNTHESIS THEREOF, AND METHODS OF USING SAME AGENTS |
| CN109678878A (en) * | 2019-02-27 | 2019-04-26 | 陕西科技大学 | A kind of benzothiophene and coumarin kind compound and its synthetic method |
| CN110483460A (en) * | 2019-08-22 | 2019-11-22 | 温州医科大学 | A kind of preparation method of 3- seleno coumarin kind compound |
| CN111440137A (en) * | 2020-04-28 | 2020-07-24 | 华东理工大学 | 3, 4-benzocoumarin derivative and preparation method and application thereof |
| CN111961062A (en) * | 2020-07-17 | 2020-11-20 | 浙江农林大学暨阳学院 | Method for preparing dithio coumarin benzothiophene compound by platinum catalysis |
| CN113004308A (en) * | 2021-01-06 | 2021-06-22 | 浙江农林大学暨阳学院 | Method for preparing pearl optimizing agent diselenocoumarol benzo selenophene compound |
-
2020
- 2020-09-30 CN CN202011060991.4A patent/CN112457330A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD272853A1 (en) * | 1988-06-13 | 1989-10-25 | Univ Leipzig | PROCESS FOR PREPARING SUBSTITUTED THIENO / 3,2-C / CUMARIN-2-CARBOXYLIC ACID ESTERS |
| WO2018015788A1 (en) * | 2016-07-21 | 2018-01-25 | Latvian Institute Of Organic Synthesis | ANTIMETASTATIC 2H-SELENOPHENO[3,2-h]CHROMENES, SYNTHESIS THEREOF, AND METHODS OF USING SAME AGENTS |
| CN109678878A (en) * | 2019-02-27 | 2019-04-26 | 陕西科技大学 | A kind of benzothiophene and coumarin kind compound and its synthetic method |
| CN110483460A (en) * | 2019-08-22 | 2019-11-22 | 温州医科大学 | A kind of preparation method of 3- seleno coumarin kind compound |
| CN111440137A (en) * | 2020-04-28 | 2020-07-24 | 华东理工大学 | 3, 4-benzocoumarin derivative and preparation method and application thereof |
| CN111961062A (en) * | 2020-07-17 | 2020-11-20 | 浙江农林大学暨阳学院 | Method for preparing dithio coumarin benzothiophene compound by platinum catalysis |
| CN113004308A (en) * | 2021-01-06 | 2021-06-22 | 浙江农林大学暨阳学院 | Method for preparing pearl optimizing agent diselenocoumarol benzo selenophene compound |
Non-Patent Citations (1)
| Title |
|---|
| RONGRONG CAI，ET AL.: "A nickel-catalyzed tandem reaction involving cyclic esterification/C–S bond formation for synthesizing 5-oxa-11-thia-benzofluoren-6-ones", 《RSC ADV.》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111961062A (en) * | 2020-07-17 | 2020-11-20 | 浙江农林大学暨阳学院 | Method for preparing dithio coumarin benzothiophene compound by platinum catalysis |
| CN113004308A (en) * | 2021-01-06 | 2021-06-22 | 浙江农林大学暨阳学院 | Method for preparing pearl optimizing agent diselenocoumarol benzo selenophene compound |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112457330A (en) | Preparation method of coumarin benzo selenophene compound serving as pearl brightener | |
| CN102485718B (en) | Sitagliptin intermediate and its preparation method | |
| CN102993184A (en) | Esomeprazole and preparation method of magnesium trihydrate of esomeprazole | |
| CN110183450B (en) | Synthetic method of 2-arylindazolo maleimide fused polycyclic compound | |
| CN113004308A (en) | Method for preparing pearl optimizing agent diselenocoumarol benzo selenophene compound | |
| CN106977411B (en) | Synthetic method of N-methyltyramine hydrochloride | |
| CN115028849A (en) | Preparation method and application of metal triangular supramolecules with room-temperature fluorescence | |
| CN105026384A (en) | Novel approach for synthesis of catechins | |
| CN109734571B (en) | Method for synthesizing alpha-F-beta-OH-carbonyl compound | |
| CN111961062A (en) | Method for preparing dithio coumarin benzothiophene compound by platinum catalysis | |
| CN103709039B (en) | Method for synthesizing methyl (ethyl) gallate through catalysis of Cu-mordenite | |
| CN114573512B (en) | Method for synthesizing C2-difluoro alkyl benzimidazole derivative | |
| CN111533706B (en) | Preparation method of 1,4, 6-trisubstituted 1, 2-dihydro-triazine compound | |
| CN114163313A (en) | Method for selectively synthesizing EZ-stilbene by coupling aryl diazonium salt and cinnamic acid under catalysis of ruthenium | |
| CN111138445B (en) | Method for preparing 5, 12-dioxaanthracene-6, 11-diketone compound by nickel catalysis | |
| CN109956940A (en) | A kind of method that the rich former times cloth intermediate cyano reaction of pa prepares heteroaryl cyanide | |
| CN115028568B (en) | Synthesis method of 3-selenoindole compound promoted by visible light | |
| CN110668960A (en) | Preparation method of alpha-aryl alpha-aminoketone compound | |
| CN110139853A (en) | It is used to prepare the method for killing harmful organism compound | |
| CN116589475B (en) | Preparation method of 2',4',5',7' -tetrachloro-5 (6) -carboxyl-4, 7-dichloro fluorescein | |
| CN110156649B (en) | Method for preparing 3-phenyl-2-phenyl disulfane methyl methacrylate compound by silver catalysis | |
| CN110194760B (en) | Process for preparing 3-benzylidene-2- (7' -quinoline) -2, 3-dihydro-isoindol-1-ones | |
| CN112266386B (en) | 2-chloroadenine derivative, preparation method and application | |
| CN106279158B (en) | A kind of imidazoheterocycles amino acid ester compound and its preparation method and application | |
| CN116462636A (en) | Synthesis method of 3-alkyl quinoxaline-2 (1H) ketone compound mediated by visible light |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20210309 |
|
| WD01 | Invention patent application deemed withdrawn after publication |