CN114539013A - Method for synthesizing OLED intermediate material 9, 10-dihydroanthracene - Google Patents
Method for synthesizing OLED intermediate material 9, 10-dihydroanthracene Download PDFInfo
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- CN114539013A CN114539013A CN202210168485.XA CN202210168485A CN114539013A CN 114539013 A CN114539013 A CN 114539013A CN 202210168485 A CN202210168485 A CN 202210168485A CN 114539013 A CN114539013 A CN 114539013A
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- dihydroanthracene
- anthraquinone
- iodine
- hypophosphorous acid
- acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/22—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by reduction
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/22—Ortho- or ortho- and peri-condensed systems containing three rings containing only six-membered rings
- C07C2603/24—Anthracenes; Hydrogenated anthracenes
Abstract
The invention discloses a method for synthesizing OLED intermediate material 9.10-dihydroanthracene, which takes anthraquinone, hypophosphorous acid and elementary iodine as raw materials, and reduces the anthraquinone into 9.10-dihydroanthracene by utilizing the reducibility of the hypophosphorous acid and the elementary iodine, wherein the molar ratio of the anthraquinone to the hypophosphorous acid to the elementary iodine is 1: 2-4: 2 to 4. The invention reduces anthraquinone into 9.10-dihydroanthracene by using a mixed system of elemental iodine and hypophosphorous acid, has mild reaction process, improves the reaction yield, reduces the cost and reduces the reaction risk, and the yield is more than 93 percent.
Description
Technical Field
The invention belongs to the technical field of drug synthesis and material chemistry, and particularly relates to a synthesis method of an OLED intermediate material 9, 10-dihydroanthracene.
Background
In the prior art, hydroiodic acid and a lithium aluminum hydride reduction system are mainly adopted, the former generates most of intermediate product anthracene, the product is less, the yield is low, and the latter adopts elemental lithium aluminum hydride as a raw material and has certain danger.
At present, the synthesis of 9, 10-dihydroanthracene has large pollution, high danger and high cost, so that the development of a new synthesis method of 9, 10-dihydroanthracene is necessary.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a synthesis method of an OLED intermediate material 9, 10-dihydroanthracene.
In order to solve the technical problem, the technical scheme of the invention is as follows:
the synthesis method of the OLED intermediate material 9, 10-dihydroanthracene uses anthraquinone, hypophosphorous acid and elemental iodine as raw materials, and utilizes the reducibility of the hypophosphorous acid and the elemental iodine to reduce the anthraquinone into the 9, 10-dihydroanthracene, wherein the molar ratio of the anthraquinone to the hypophosphorous acid to the elemental iodine is 1: 2-4: 2 to 4.
Preferably, the molar ratio of the anthraquinone to the hypophosphorous acid to the elemental iodine is 1: 3: 3.
preferably, the specific reaction process is as follows: continuously protecting by using inert gas, adding acetic acid into a reaction bottle, adding iodine elementary substance, stirring, dropwise adding hypophosphorous acid, heating to 40-50 ℃ after dropwise adding is finished, adding anthraquinone into the system at one time, heating to 100-120 ℃, reacting for 2-4h to obtain a 9, 10-dihydroanthracene system, and collecting hydroiodic acid gas generated in the reaction process, wherein the dosage ratio of the anthraquinone to the acetic acid is 1 Kg: 3-5L.
Preferably, the inert gas is argon.
Preferably, the hydriodic acid gas generated in the reaction process is used for preparing the hydriodic acid solution.
Preferably, the 9, 10-dihydroanthracene system is subjected to a post-treatment process: cooling the 9, 10-dihydroanthracene system to 30-50 ℃, adding water, stirring for 30min, cooling the system to 25-28 ℃, performing suction filtration, leaching with water to neutrality after filtration, then boiling and washing with ethanol at 50-70 ℃ for 0.5-1 h, cooling to 25-28 ℃, performing suction filtration, and drying at normal pressure for 12-15 h to obtain a white solid 9, 10-dihydroanthracene.
Compared with the prior art, the invention has the advantages that:
(1) the invention reduces anthraquinone into 9, 10-dihydroanthracene by using a mixed system of elemental iodine and hypophosphorous acid, has mild reaction process, improves the reaction yield, reduces the cost and reduces the reaction risk, and the yield is more than 93 percent;
(2) the hydriodic acid generated in the reaction process is collected and prepared into hydriodic acid solution, so that pollution is avoided, and the environmental compatibility is good;
(3) the method has the advantages of simple operation, easy treatment, high yield and convenient expanded production.
Drawings
FIG. 1 shows H-NMR spectra of examples 1 to 3 of the present invention.
Detailed Description
The present invention is illustrated below with reference to specific examples, wherein the raw materials, solvents and catalysts are all conventional commercial products, and the following examples are provided to illustrate the present invention but are not intended to limit the scope of the present invention.
The invention discloses a method for synthesizing an OLED intermediate material 9, 10-dihydroanthracene, which takes anthraquinone, hypophosphorous acid and elementary iodine as raw materials, and reduces the anthraquinone into 9, 10-dihydroanthracene by utilizing the reducibility of the hypophosphorous acid and the elementary iodine, wherein the molar ratio of the anthraquinone to the hypophosphorous acid to the elementary iodine is 1: 2-4: 2 to 4.
Preferably, the molar ratio of the anthraquinone to the hypophosphorous acid to the elemental iodine is 1: 3: 3.
preferably, the specific reaction process is as follows: continuously protecting by using inert gas, adding acetic acid into a reaction bottle, adding iodine elementary substance, stirring, dropwise adding hypophosphorous acid, heating to 40-50 ℃ after dropwise adding is finished, adding anthraquinone into the system at one time, heating to 100-120 ℃, reacting for 2-4h to obtain a 9, 10-dihydroanthracene system, and collecting hydroiodic acid gas generated in the reaction process, wherein the dosage ratio of the anthraquinone to the acetic acid is 1 Kg: 3-5L.
Preferably, the inert gas is argon.
Preferably, the hydriodic acid gas generated in the reaction process is used for preparing the hydriodic acid solution.
Preferably, the 9, 10-dihydroanthracene system is subjected to a post-treatment process: cooling the 9, 10-dihydroanthracene system to 30-50 ℃, adding water, stirring for 30min, cooling the system to 25-28 ℃, performing suction filtration, leaching with water to neutrality after filtration, then boiling and washing with ethanol at 50-70 ℃ for 0.5-1 h, cooling to 25-28 ℃, performing suction filtration, and drying at normal pressure for 12-15 h to obtain a white solid 9, 10-dihydroanthracene.
Example 1
Continuously protecting with argon, adding 30L of acetic acid into the system, adding 12.3kg of iodine simple substance (molecular weight 127, 0.097 mol), stirring, dropwise adding 6.4kg of hypophosphorous acid (molecular weight 65.97, 0.097 mol), heating to 40 ℃, adding 10kg of anthraquinone (molecular weight 208.21, 0.048 mol) into the system at one time, heating to 100 ℃, collecting hydroiodic acid gas generated in the reaction process, preparing hydroiodic acid solution with certain concentration, reacting for 2h, stopping reaction, closing heating, cooling to 30 ℃, adding water, stirring for 30min, performing suction filtration when the system is about 25 ℃, leaching to neutrality with water after filtration, then boiling and washing with ethanol at 50 ℃ for 0.5h, and press-drying for 12h to obtain 8.18kg of white solid with yield of 94.5%.
Example 2
Continuously protecting with argon, adding 50L of acetic acid into the system, adding 18.28kg of iodine simple substance (molecular weight is 127, 0.144 mol), stirring, dropwise adding 9.50kg of hypophosphorous acid (molecular weight is 65.97, 0.144 mol), heating to 45 ℃, adding 10kg of anthraquinone (molecular weight is 208.21, 0.048 mol) into the system at one time, heating to 110 ℃, collecting hydroiodic acid gas generated in the reaction process, preparing hydroiodic acid solution with certain concentration, reacting for 3h, stopping reaction, closing heating, cooling to 40 ℃, adding water, stirring for 30min, filtering to about 25 ℃, leaching with water to neutrality after filtration, then boiling and washing with ethanol at 60 ℃, cooling to 25 ℃, leaching, and drying at normal pressure for 12h to obtain 8.11kg of white solid with yield of 93.7%.
Example 3
Continuously protecting with argon, adding 30L of acetic acid into the system, adding 24.4kg of iodine simple substance (molecular weight 127, 0.192 mol), stirring, dropwise adding 12.66kg of hypophosphorous acid (molecular weight 65.97, 0.192 mol), heating to 50 ℃, adding 10kg of anthraquinone (molecular weight 208.21, 0.048 mol) into the system at one time, heating to 120 ℃, collecting hydroiodic acid gas generated in the reaction process, preparing hydroiodic acid solution with certain concentration, reacting for 4 hours, stopping reaction, closing heating, cooling to 50 ℃, adding water, stirring for 30 minutes, filtering to about 25 ℃, leaching with water to neutrality after filtration, then boiling and washing with ethanol at 70 ℃ for 0.5 hour, cooling to 25 ℃, leaching, and drying under normal pressure for 12 hours to obtain 8.12kg of white solid with the yield of 93.9%.
A nuclear magnetic spectrum of the product of example 1-3 was prepared, and the specific H-NMR spectrum is shown in FIG. 1.
As shown in FIG. 1, the H-NMR spectrum of 9, 10-dihydroanthracene showed chemical shifts of 3.82ppm, 7.21ppm and 7.32ppm for hydrogen atoms, and the peak area ratio was 1/1/1.
The reaction principle of the invention is as follows:
the method comprises the steps of continuously protecting argon, adding acetic acid (3 v-6 v) into a system, adding iodine simple substance (2 eq-4 eq), stirring, dropwise adding hypophosphorous acid (2 eq-4 eq), heating to 40-50 ℃, adding anthraquinone (1 eq) into the system at one time, heating to the temperature of 100-120 ℃, collecting hydroiodic acid gas generated in the reaction process, preparing a hydroiodic acid solution with a certain concentration, reacting for 2-4h, stopping the reaction, closing the heating, cooling to 30-50 ℃, adding water, stirring for 30min, filtering at about 25 ℃, leaching by using water to be neutral after filtration, boiling and washing for 0.5h by using ethanol at 50-70 ℃, cooling to 25 ℃, leaching, and drying for 12h at normal pressure to obtain white solid 9, 10-dihydroanthracene.
The invention reduces anthraquinone into 9, 10-dihydroanthracene by using a mixed system of elemental iodine and hypophosphorous acid, has mild reaction process, improves the reaction yield, reduces the cost and reduces the reaction risk, and the yield is more than 93 percent.
The invention collects the hydriodic acid generated in the reaction process and prepares hydriodic acid solution, thereby avoiding pollution and having good environmental compatibility.
The method has the advantages of simple operation, easy treatment, high yield and convenient expanded production.
While the preferred embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Many other changes and modifications can be made without departing from the spirit and scope of the invention. It is to be understood that the invention is not to be limited to the specific embodiments, but only by the scope of the appended claims.
Claims (6)
1. A synthesis method of an OLED intermediate material 9, 10-dihydroanthracene is characterized by comprising the following steps: anthraquinone, hypophosphorous acid and elementary iodine are used as raw materials, and the reduction of the hypophosphorous acid and the elementary iodine is utilized to reduce the anthraquinone into 9, 10-dihydroanthracene, wherein the molar ratio of the anthraquinone to the hypophosphorous acid to the elementary iodine is 1: 2-4: 2 to 4.
2. The method of claim 1 for the synthesis of an OLED intermediate material of 9, 10-dihydroanthracene, wherein: the molar ratio of the anthraquinone to the hypophosphorous acid to the elemental iodine is 1: 3: 3.
3. the method for synthesizing the OLED intermediate material 9, 10-dihydroanthracene according to claim 2, characterized in that the specific reaction process is as follows: continuously protecting by using inert gas, adding acetic acid into a reaction bottle, adding iodine elementary substance, stirring, dropwise adding hypophosphorous acid, heating to 40-50 ℃ after dropwise adding is finished, adding anthraquinone into the system at one time, heating to 100-120 ℃, reacting for 2-4h to obtain a 9, 10-dihydroanthracene system, and collecting hydroiodic acid gas generated in the reaction process, wherein the dosage ratio of the anthraquinone to the acetic acid is 1 Kg: 3-5L.
4. The method of claim 3, wherein the inert gas is argon.
5. The method of claim 3, wherein the hydroiodic acid gas generated during the reaction is used to prepare a hydroiodic acid solution.
6. The method for synthesizing an OLED intermediate material 9, 10-dihydroanthracene according to claim 3, wherein the post-treatment process of the 9, 10-dihydroanthracene system is as follows: cooling the 9, 10-dihydroanthracene system to 30-50 ℃, adding water, stirring for 30min, cooling the system to 25-28 ℃, performing suction filtration, leaching with water to neutrality after filtration, then boiling and washing with ethanol at 50-70 ℃ for 0.5-1 h, cooling to 25-28 ℃, performing suction filtration, and drying at normal pressure for 12-15 h to obtain a white solid 9, 10-dihydroanthracene.
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| CN202210168485.XA CN114539013A (en) | 2022-02-23 | 2022-02-23 | Method for synthesizing OLED intermediate material 9, 10-dihydroanthracene |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50140434A (en) * | 1974-04-30 | 1975-11-11 | ||
| CN101230126A (en) * | 2007-12-29 | 2008-07-30 | 中国科学院长春应用化学研究所 | Soluble conjugated polymer using 9,10-diaryl anthracene as repeating units and preparation method thereof |
| JP2009155309A (en) * | 2007-12-28 | 2009-07-16 | Tosoh Corp | Anthracene derivative and anthraquinone derivative |
| CN102675128A (en) * | 2011-03-07 | 2012-09-19 | 昆山维信诺显示技术有限公司 | Dihydroanthracene derivative, preparation method and application thereof and luminescent device comprising dihydroanthracene derivative |
| US20140378729A1 (en) * | 2011-12-15 | 2014-12-25 | Dow Global Technologies Llc | Reductive dehydroxylation of vicinal polyols to olefins using an iodine-based catalyst having enhanced solubility |
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- 2022-02-23 CN CN202210168485.XA patent/CN114539013A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50140434A (en) * | 1974-04-30 | 1975-11-11 | ||
| JP2009155309A (en) * | 2007-12-28 | 2009-07-16 | Tosoh Corp | Anthracene derivative and anthraquinone derivative |
| CN101230126A (en) * | 2007-12-29 | 2008-07-30 | 中国科学院长春应用化学研究所 | Soluble conjugated polymer using 9,10-diaryl anthracene as repeating units and preparation method thereof |
| CN102675128A (en) * | 2011-03-07 | 2012-09-19 | 昆山维信诺显示技术有限公司 | Dihydroanthracene derivative, preparation method and application thereof and luminescent device comprising dihydroanthracene derivative |
| US20140378729A1 (en) * | 2011-12-15 | 2014-12-25 | Dow Global Technologies Llc | Reductive dehydroxylation of vicinal polyols to olefins using an iodine-based catalyst having enhanced solubility |
Non-Patent Citations (5)
| Title |
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| ANDREAS J. ATHANS ET AL.: "Hydrogen-protected acenes", 《JOURNAL OF MATERIALS CHEMISTRY》, vol. 17, pages 2636 * |
| LATORYA D. HICKS ET AL.: "Hypophosphorous acid–iodine: a novel reducing system. Part 1: Reduction of diaryl ketones to diaryl methylene", 《TETRAHEDRON LETTERS》, vol. 41, no. 41, pages 7817, XP004235878, DOI: 10.1016/S0040-4039(00)01359-9 * |
| MICHAEL B. SMITH: "Iodine", 《ENCYCLOPEDIA OF REAGENTS FOR ORGANIC SYNTHESIS.》, pages 1 - 16 * |
| 张红等: "10,10-二吡啶甲基-9,10-二氢蒽的合成研究", 《有机化学》, vol. 31, no. 10, pages 1690 - 1694 * |
| 施证伟等: "1,8-二羟基-9,10-二氢蒽的合成", 《高等学校化学学报》, vol. 26, no. 4, pages 667 - 670 * |
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