CN111018687B - Synthesis method of 9, 10-anthraquinone - Google Patents
Synthesis method of 9, 10-anthraquinone Download PDFInfo
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- CN111018687B CN111018687B CN201911175323.3A CN201911175323A CN111018687B CN 111018687 B CN111018687 B CN 111018687B CN 201911175323 A CN201911175323 A CN 201911175323A CN 111018687 B CN111018687 B CN 111018687B
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- C07C46/02—Preparation of quinones by oxidation giving rise to quinoid structures
- C07C46/04—Preparation of quinones by oxidation giving rise to quinoid structures of unsubstituted ring carbon atoms in six-membered aromatic rings
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Abstract
The application discloses a method for synthesizing 9, 10-anthraquinone, which comprises the following steps: adding an organic solvent, water, 9-anthracene boric acid and alkali into a reaction container, and stirring for 1-2 h; wherein the molar ratio of the 9-anthraceneboronic acid to the alkali is 1: 1-1: 15; after the color and fluorescence of the reaction solution completely disappear, filtering to obtain solid 9, 10-anthraquinone; the filtrate was washed with saturated brine, dried over anhydrous magnesium sulfate, filtered and the solvent was removed by distillation under reduced pressure to obtain 9, 10-anthraquinone in the filtrate. The synthesis method of the 9, 10-anthraquinone is simple to operate, does not need to use nitric acid as a reaction raw material, avoids the improvement of the strong corrosion resistance of the nitric acid on the corrosion resistance of equipment, reduces the maintenance cost of the equipment, does not need high-temperature heating, reduces the reaction energy consumption, and reduces the reaction intermediate links, the reaction time and the production cost; and the reaction can be completely carried out, so that the yield can be greatly improved.
Description
Technical Field
The invention relates to the field of organic synthesis, in particular to a synthesis method of 9, 10-anthraquinone.
Background
Anthraquinone is a synthetic natural dye. The basic mother nucleus of the anthraquinone compound is anthraquinone, and the mother nucleus is often provided with substituents such as hydroxyl, hydroxymethyl, methyl, methoxyl, carboxyl and the like.
Anthraquinone is a pigment widely existing in plant, and is an effective component of many important Chinese medicinal materials such as rhubarb, polygonum multiflorum, polygonum cuspidatum and the like. Meanwhile, anthraquinone is also an important raw material of high-grade dyeing intermediates in organic synthesis, such as indanthrene vat dyes, acid dyes and partial reactive dyes.
In the prior art, the production methods of anthraquinone mainly comprise a refined anthracene oxidation method, a gas phase fixed bed oxidation method, a liquid phase oxidation method, a carboxyl synthesis method and the like.
The refined anthracene oxidation method is characterized in that refined anthracene is added into a gasification chamber to be heated and gasified and then is mixed with air, and the proportion of the refined anthracene to the air is 1: (50-100); the mixed gas enters an oxidation chamber at V2O5Oxidizing at 389 +/-2 deg.c under catalysis, and thin-wall condensing to obtain the product. The synthesis method needs high-temperature heating and has high energy consumption.
The liquid phase oxidation method is that refined anthracene is measured and added into a reaction kettle, and then trichlorobenzene is added and dissolved under stirring; then dropwise adding nitric acid, controlling the reaction temperature to be 105-110 ℃, removing a by-product NO, reacting for 6-8 h, decompressing, evaporating the solvent, cooling and crystallizing to obtain the product. The equipment of this process is severely corroded.
The carboxyl synthesis method is that metered benzene is added into a reaction kettle, CO is introduced under 4.88MPa, the reaction is carried out for 4 hours at 200 ℃, and the product is obtained after the reaction is finished until the CO pressure is not reduced any more. The synthesis method needs to use nitric acid as a reaction raw material, has high requirements on the corrosion resistance of equipment due to high corrosion resistance of the nitric acid, increases the maintenance cost of the equipment, is not beneficial to reducing the production cost, and has complex process.
Therefore, it is necessary to propose a new synthesis method.
Disclosure of Invention
The embodiment of the application provides a synthesis method of 9, 10-anthraquinone, which is simple to operate, does not need to use nitric acid as a reaction raw material, avoids the improvement of the corrosion resistance of equipment due to the strong corrosion capacity of the nitric acid, reduces the maintenance cost of the equipment, does not need high-temperature heating, reduces the reaction energy consumption, and reduces the production cost.
The embodiment of the application provides a method for synthesizing 9, 10-anthraquinone, which comprises the following steps:
adding an organic solvent, water, 9-anthracene boric acid and alkali into a reaction container, and stirring for 1-2 h; wherein the molar ratio of the 9-anthraceneboronic acid to the alkali is 1: 1-1: 15;
after the color and fluorescence of the reaction solution completely disappear, filtering to obtain solid 9, 10-anthraquinone;
the filtrate was washed with saturated brine, dried over anhydrous magnesium sulfate, filtered and the solvent was removed by distillation under reduced pressure to obtain 9, 10-anthraquinone in the filtrate.
Optionally, the volume ratio of the organic solvent to the water is 1: 1-1: 3.
optionally, the organic solvent is one of tetrahydrofuran, N-dimethylformamide, and dimethyl sulfoxide.
Optionally, the base is one of sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, sodium bicarbonate, sodium phosphate, calcium phosphate, n-propylamine, diethylamine, triethylamine, tetrabutylammonium hydroxide.
Optionally, the reaction temperature is 15-35 ℃.
Alternatively, when the base is a strong base, the molar ratio of 9-anthraceneboronic acid to base is 1: 1.
By adopting the technical scheme, the technical scheme of the embodiment of the application has the following beneficial effects:
the synthesis method of the 9, 10-anthraquinone in the embodiment of the application is simple to operate, does not need to use nitric acid as a reaction raw material, avoids the improvement of the corrosion resistance of equipment due to the strong corrosion capability of the nitric acid, reduces the maintenance cost of the equipment, does not need high-temperature heating, reduces the reaction energy consumption, and reduces the reaction intermediate links, the reaction time and the production cost; the reaction can be completely carried out, and the yield can be greatly improved; the fluorescence and color change in the reaction process can reflect the whole reaction process, and the reaction process is easy to monitor; the synthesis method of the 9, 10-anthraquinone provided by the embodiment of the application provides a new synthesis route, and lays a good foundation for further improving the reaction yield.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a single crystal spectrum of the product of the synthesis process of 9, 10-anthraquinone according to the present application;
FIG. 2 shows the product of a process for the synthesis of 9, 10-anthraquinone according to the examples of the present application1H-NMR spectrum;
FIG. 3 is a diagram of the product of a process for the synthesis of 9, 10-anthraquinone according to the examples of the present application13A C-NMR spectrum;
FIG. 4 is a hydrogen atom signature of the product of a process for the synthesis of 9, 10-anthraquinone according to the examples of the present application.
Detailed Description
The disclosure may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.
For purposes of the following detailed description, it is to be understood that the invention may assume various alternative variations and step sequences, except where expressly specified to the contrary. Moreover, other than in any operating examples, or where otherwise indicated, all numbers expressing, for example, quantities of ingredients used in the specification and claims are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements.
When a range of values is disclosed herein, the range is considered to be continuous and includes both the minimum and maximum values of the range, as well as each value between such minimum and maximum values. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range-describing features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to encompass any and all subranges subsumed therein. For example, a stated range from "1 to 10" should be considered to include any and all subranges between the minimum value of 1 and the maximum value of 10. Exemplary subranges of the range 1 to 10 include, but are not limited to, 1 to 6.1, 3.5 to 7.8, 5.5 to 10, and the like.
The embodiment of the application provides a method for synthesizing 9, 10-anthraquinone, which comprises the following steps:
adding an organic solvent, water, 9-anthracene boric acid and alkali into a reaction container, and stirring for 1-2 h; wherein the molar ratio of the 9-anthraceneboronic acid to the alkali is 1: 1-1: 15;
after the color and fluorescence of the reaction solution completely disappear, filtering to obtain solid 9, 10-anthraquinone;
the filtrate was washed with saturated brine, dried over anhydrous magnesium sulfate, filtered and the solvent was removed by distillation under reduced pressure to obtain 9, 10-anthraquinone in the filtrate.
When 9-anthracene boric acid reacts with alkali, a fluorescent intermediate product is formed, and as the reaction proceeds, the formed product 9, 10-anthraquinone is not fluorescent, so that the change of fluorescent color is accompanied in the reaction process. After the alkali is added, the fluorescence color of the reaction solution gradually becomes colorless as the reaction is finished, so that the reaction solution can be used for monitoring the reaction progress based on the change of fluorescence, and the reaction is finished when the fluorescence color is not present. The fluorescence color change in the reaction process can be applied to the detection of organic amine.
As an optional embodiment, the volume ratio of the organic solvent to the water is 1: 1-1: 3, excessive water can cause 9-anthracene boric acid to be separated out, the reaction efficiency is influenced, and too little water can influence the reaction activity of the formed 9-anthracene boric acid, wherein the volume ratio of the organic solvent to the water is equal to 1:3 as best.
As an alternative embodiment, the organic solvent may be tetrahydrofuran, N, N-dimethylformamide, dimethylsulfoxide, or the like, which is miscible with water, wherein tetrahydrofuran is more preferable because tetrahydrofuran is more easily removed under reduced pressure.
As an alternative embodiment, the base may be an inorganic base including sodium hydroxide, potassium hydroxide, calcium hydroxide, etc., a weak base including sodium carbonate, sodium bicarbonate, sodium phosphate, calcium phosphate, etc., an organic base including primary, secondary, and tertiary amines including n-propylamine, diethylamine, and triethylamine, etc., and a strong organic base such as tetrabutylammonium hydroxide, etc.
As an alternative embodiment, the reaction is carried out at room temperature, where room temperature is 15-35 ℃ and is most preferably 25 ℃.
As an alternative embodiment, when the alkali is strong alkali, the molar ratio of the 9-anthracene boric acid to the strong alkali is 1:1, and the ratio is equal equivalent, and when the weak alkali is used, the molar ratio of the weak alkali is excessive.
The overall synthesis can be represented by the following general reaction:
the present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.
Examples
Example 1:
example 1 provides a method for synthesizing 9, 10-anthraquinone, comprising the following steps:
adding 0.1mmol of 9-anthraceneboronic acid, 100ml of tetrahydrofuran and 300ml of water into a reaction vessel, simultaneously adding 0.1mmol of sodium hydroxide, and stirring at room temperature for 2 hours;
after the color and fluorescence of the reaction solution completely disappear, filtering to obtain solid 9, 10-anthraquinone;
washing the filtrate with saturated saline solution, drying with anhydrous magnesium sulfate, filtering, and distilling under reduced pressure to remove the solvent to obtain 9, 10-anthraquinone in the filtrate;
the two were combined, and the yield of 9, 10-anthraquinone was 99.03%.
Example 2:
adding 0.1mmol of 9-anthraceneboronic acid, 100ml of tetrahydrofuran and 300ml of water into a reaction vessel, simultaneously adding 0.7mmol of triethylamine, and stirring at room temperature for 2 hours;
after the color and fluorescence of the reaction solution completely disappear, filtering to obtain solid 9, 10-anthraquinone;
washing the filtrate with saturated saline solution, drying with anhydrous magnesium sulfate, filtering, and distilling under reduced pressure to remove the solvent to obtain 9, 10-anthraquinone in the filtrate;
the two were combined, and the yield of 9, 10-anthraquinone was 95.6%.
Example 3:
example 3 provides a method for synthesizing 9, 10-anthraquinone, comprising the steps of:
adding 0.1mmol of 9-anthraceneboronic acid, 100ml of tetrahydrofuran and 300ml of water into a reaction vessel, simultaneously adding 0.97mmol of diethylamine, and stirring at room temperature for 2 hours;
after the color and fluorescence of the reaction solution completely disappear, filtering to obtain solid 9, 10-anthraquinone;
washing the filtrate with saturated saline solution, drying with anhydrous magnesium sulfate, filtering, and distilling under reduced pressure to remove the solvent to obtain 9, 10-anthraquinone in the filtrate;
the two were combined, and the yield of 9, 10-anthraquinone was 94.1%.
Example 4:
example 4 provides a method for synthesizing 9, 10-anthraquinone, comprising the steps of:
adding 0.1mmol of 9-anthraceneboronic acid, 100ml of tetrahydrofuran and 300ml of water into a reaction vessel, simultaneously adding 1.2mmol of n-propylamine, and stirring at room temperature for 2 hours;
after the color and fluorescence of the reaction solution completely disappear, filtering to obtain solid 9, 10-anthraquinone;
washing the filtrate with saturated saline solution, drying with anhydrous magnesium sulfate, filtering, and distilling under reduced pressure to remove the solvent to obtain 9, 10-anthraquinone in the filtrate;
the two were combined, and the yield of 9, 10-anthraquinone was 94.5%.
Example 5:
example 5 provides a method of synthesizing 9, 10-anthraquinone, comprising the steps of:
adding 0.1mmol of 9-anthraceneboronic acid, 100ml of tetrahydrofuran and 300ml of water into a reaction vessel, simultaneously adding 0.94mmol of sodium carbonate, and stirring at room temperature for 2 hours;
after the color and fluorescence of the reaction solution completely disappear, filtering to obtain solid 9, 10-anthraquinone;
washing the filtrate with saturated saline solution, drying with anhydrous magnesium sulfate, filtering, and distilling under reduced pressure to remove the solvent to obtain 9, 10-anthraquinone in the filtrate;
the two were combined, and the yield of 9, 10-anthraquinone was 89.3%.
Example 6:
example 6 provides a method of synthesizing 9, 10-anthraquinone, comprising the steps of:
adding 0.1mmol of 9-anthraceneboronic acid, 100ml of tetrahydrofuran and 300ml of water into a reaction vessel, simultaneously adding 1.2mmol of sodium bicarbonate, and stirring at room temperature for 2 hours;
after the color and fluorescence of the reaction solution completely disappear, filtering to obtain solid 9, 10-anthraquinone;
washing the filtrate with saturated saline solution, drying with anhydrous magnesium sulfate, filtering, and distilling under reduced pressure to remove the solvent to obtain 9, 10-anthraquinone in the filtrate;
the two were combined, and the yield of 9, 10-anthraquinone was 84.6%.
Example 7:
example 7 provides a method of synthesizing 9, 10-anthraquinone, comprising the steps of:
adding 0.1mmol of 9-anthraceneboronic acid, 100ml of tetrahydrofuran and 200ml of water into a reaction vessel, simultaneously adding 0.1mmol of sodium hydroxide, and stirring at room temperature for 2 hours;
after the color and fluorescence of the reaction solution completely disappear, filtering to obtain solid 9, 10-anthraquinone;
washing the filtrate with saturated saline solution, drying with anhydrous magnesium sulfate, filtering, and distilling under reduced pressure to remove the solvent to obtain 9, 10-anthraquinone in the filtrate;
the two were combined, and the yield of 9, 10-anthraquinone was 89%.
Example 8:
example 8 provides a method of synthesizing 9, 10-anthraquinone, comprising the steps of:
adding 0.1mmol of 9-anthraceneboronic acid, 100ml of tetrahydrofuran and 100ml of water into a reaction vessel, simultaneously adding 0.1mmol of sodium hydroxide, and stirring at room temperature for 2 hours;
after the color and fluorescence of the reaction solution completely disappear, filtering to obtain solid 9, 10-anthraquinone;
washing the filtrate with saturated saline solution, drying with anhydrous magnesium sulfate, filtering, and distilling under reduced pressure to remove the solvent to obtain 9, 10-anthraquinone in the filtrate;
the two were combined, and the yield of 9, 10-anthraquinone was 54%.
In embodiments 1 to 8, different bases including strong base sodium hydroxide and weak bases such as organic amine, sodium carbonate, and sodium bicarbonate are used, and tetrahydrofuran and water with different volume ratios are used to synthesize the target product. It can be seen that when the volume ratio of the organic solvent to the water is 1:3 and the molar ratio of the 9-anthraceneboronic acid to the strong base sodium hydroxide is 1:1, the reaction yield can reach more than 99 percent; the use of weak bases or a reduced proportion of water, however, greatly reduces the reaction yield.
FIG. 1 is a single crystal spectrum of the product of the synthesis process of 9, 10-anthraquinone of the examples of the present application.
FIG. 2 is a product of the synthesis of 9, 10-anthraquinone of the examples of this application1H-NMR spectrum; in this FIG. 2, the hydrogen atoms in 9, 10-anthraquinone had chemical shifts at 8.33ppm and 7.81ppm, and the peak area ratio was 1: 1.
FIG. 3 is a product of the process for the synthesis of 9, 10-anthraquinone according to the examples of the present application13A C-NMR spectrum; the peaks in FIG. 3 are at 183, 124 and 127ppm, respectively.
FIG. 4 is a hydrogen atom signature of the product of a process for the synthesis of 9, 10-anthraquinone according to the examples of the present application; table 1 shows the chemical shifts of A, B hydrogen atoms corresponding to FIG. 4, which are 8.33ppm and 7.81ppm, respectively.
Table 1:
| atomic number | Chemical shift (ppm) |
| A | 8.33 |
| B | 7.81 |
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.
Claims (6)
1. A method for synthesizing 9, 10-anthraquinone is characterized by comprising the following steps:
adding an organic solvent, water, 9-anthracene boric acid and alkali into a reaction container, and stirring for 1-2 h; wherein the molar ratio of the 9-anthraceneboronic acid to the alkali is 1: 1-1: 15;
after the color and fluorescence of the reaction solution completely disappear, filtering to obtain solid 9, 10-anthraquinone;
the filtrate was washed with saturated brine, dried over anhydrous magnesium sulfate, filtered and the solvent was removed by distillation under reduced pressure to obtain 9, 10-anthraquinone in the filtrate.
2. The method for synthesizing 9, 10-anthraquinone according to claim 1, characterized in that the volume ratio of the organic solvent to water is 1: 1-1: 3.
3. the method for synthesizing 9, 10-anthraquinone according to claim 1, characterized in that said organic solvent is one of tetrahydrofuran, N-dimethylformamide and dimethyl sulfoxide.
4. The method of synthesizing 9, 10-anthraquinone according to claim 1, characterized in that said base is one of sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, sodium bicarbonate, sodium phosphate, calcium phosphate, n-propylamine, diethylamine, triethylamine, tetrabutylammonium hydroxide.
5. The method for synthesizing 9, 10-anthraquinone according to claim 1, characterized in that the reaction temperature is 15-35 ℃.
6. A process for the synthesis of 9, 10-anthraquinone according to claim 1, characterized in that, when the base is a strong base, the molar ratio of 9-anthraceneboronic acid to base is 1: 1.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102795983A (en) * | 2011-05-25 | 2012-11-28 | 海洋王照明科技股份有限公司 | Anthraquinone derivative material and preparation method and application thereof |
| WO2017104798A1 (en) * | 2015-12-18 | 2017-06-22 | 株式会社エースネット | Method for producing oxidation reaction product of hydrocarbon or derivative thereof, and method for producing oxidation reaction product of olefin |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102795983A (en) * | 2011-05-25 | 2012-11-28 | 海洋王照明科技股份有限公司 | Anthraquinone derivative material and preparation method and application thereof |
| WO2017104798A1 (en) * | 2015-12-18 | 2017-06-22 | 株式会社エースネット | Method for producing oxidation reaction product of hydrocarbon or derivative thereof, and method for producing oxidation reaction product of olefin |
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