CN112521365A - Phenanthrene ketal with novel structure and degradation method thereof - Google Patents
Phenanthrene ketal with novel structure and degradation method thereof Download PDFInfo
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- CN112521365A CN112521365A CN202011265911.9A CN202011265911A CN112521365A CN 112521365 A CN112521365 A CN 112521365A CN 202011265911 A CN202011265911 A CN 202011265911A CN 112521365 A CN112521365 A CN 112521365A
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/72—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 spiro-condensed with carbocyclic rings
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- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
- C07C45/57—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom
- C07C45/59—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom in five-membered rings
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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
- C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
- C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
- C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
- C07C2603/18—Fluorenes; Hydrogenated fluorenes
Abstract
An oxidation bond structure and organic degradation method based on 9-hydroxy phenanthrene, belonging to the technical field of organic and polymer synthesis. The 9-hydroxy phenanthrene is an important derivative of phenanthrene, can be used for synthesizing 10, 10 '-dihydroxy-9, 9' -phenanthrene or phenanthrenequinone under an oxidation condition, and has important organic synthesis and material synthesis values. The development of a new type of oxidation reaction of 9-hydroxy phenanthrene can further expand the application range of 9-hydroxy phenanthrene and improve the application value. On the other hand, phenanthrene as polycyclic aromatic hydrocarbon of a large conjugated system can be used for synthesizing engineering plastics with high heat resistance and mechanical strength, and a novel method for intermolecular bonding of phenanthrene derivatives is developed, so that engineering plastics with a novel structure can be developed. The invention provides a novel oxidation reaction mode and a bonding method of 9-hydroxy phenanthrene by researching the reaction of the 9-hydroxy phenanthrene under the synergistic action of alkaline conditions and oxygen, and a phenanthrene ketal structure is obtained, and can be continuously converted and degraded into 9-fluorenone. The invention technically provides a synthesis method and a degradation method of phenanthrene ketal with a novel structure, and the synthesis method and the degradation method can be used for synthesizing degradable high polymer materials. The separation yield of the phenanthrene ketal can reach 84 percent, and the yield of the 9-fluorenone can reach 100 percent. The nuclear magnetic resonance spectrum and single crystal diffraction confirm the structure of phenanthrene ketal, and confirm that the purity of the product is more than 95 percent.
Description
Technical Field
The invention belongs to the technical field of organic and polymer synthesis, and particularly relates to an oxidation bond structure and an organic degradation method based on 9-hydroxy phenanthrene.
Background
The 9-hydroxy phenanthrene is an important derivative of phenanthrene, can be used for synthesizing 10, 10 '-dihydroxy-9, 9' -phenanthrene or phenanthrenequinone under an oxidation condition, and has important organic synthesis and material synthesis values (a and b in figure 1). The development of a new type of oxidation reaction of 9-hydroxy phenanthrene can further expand the application range of 9-hydroxy phenanthrene and improve the application value. On the other hand, phenanthrene as polycyclic aromatic hydrocarbon of a large conjugated system can be used for synthesizing engineering plastics with high heat resistance and mechanical strength, and a novel method for intermolecular bonding of phenanthrene derivatives is developed, so that engineering plastics with a novel structure can be developed. In the invention, a novel bonding method of 9-hydroxy phenanthrene is developed by adopting 9-hydroxy phenanthrene under the conditions of alkaline condition and oxygen, and a phenanthrene ketal structure is obtained, and the structure can be further degraded and converted into 9-fluorenone. Wherein the separation yield of the phenanthrene ketal can reach 84 percent, and the yield of the 9-fluorenone can reach the quantitative generation. The nuclear magnetic resonance spectrum and single crystal diffraction confirm the structure of phenanthrene ketal, and confirm that the purity of the product is more than 95 percent.
Disclosure of Invention
The invention aims to provide a phenanthrene ketal with a novel structure and a degradation method thereof, and the technical method is shown in figure 2:
the method comprises the following specific steps:
(1) under a nitrogen atmosphere, 0.2mmol of 9-hydroxyphenanthrene was added to a Schlenk tube, 2mL of a solvent was added, and the mixture was stirred to completely dissolve the substrate.
(2) Base (0.75equiv.) was added and the Schlenk tube was sealed under nitrogen atmosphere.
(3) Stirring at room temperature, reacting for 7h, introducing oxygen into a Schlenk tube, sealing the Schlenk tube, and heating until 9-hydroxy phenanthrene completely disappears through TLC detection.
(4) After the reaction is finished, adding a dilute HCl solution into the reaction solution for neutralization, extracting with 3X 5mL of CH2Cl2, drying an organic phase with anhydrous magnesium sulfate, distilling the organic phase under reduced pressure, and carrying out column chromatography separation on the obtained crude product, wherein an eluent is V petroleum ether and V ethyl acetate which is 10: 1, so as to obtain the phenanthrene ketal.
(5) Under oxygen atmosphere, 0.1mmol phenanthrene ketal is added into a Schlenk tube, and a solvent is added and stirred to dissolve.
(6) The base (6equiv.) was added, the Schlenk tube was sealed under an oxygen atmosphere, and heated until the phenanthrene ketal completely disappeared.
(7) After the reaction is finished, adding a dilute HCl solution into the reaction liquid for neutralization, extracting by using 3X 5mL CH2Cl2, drying an organic phase by using anhydrous magnesium sulfate, distilling the organic phase under reduced pressure, and carrying out column chromatography separation on the obtained crude product, wherein an eluent is V petroleum ether and V ethyl acetate which are 5: 1 to obtain a pure product, namely 9-fluorenone
Drawings
FIG. 1: of the product of example 11H-NMR spectrum;
FIG. 2: of the product of example 113A C-NMR spectrum;
FIG. 3: of the product of example 21H-NMR spectrum;
FIG. 4: of the product of example 213A C-NMR spectrum;
FIG. 5: of the product of example 31H-NMR spectrum;
FIG. 6: of the product of example 313A C-NMR spectrum;
FIG. 7: of the product of example 41H-NMR spectrum;
FIG. 8: of the product of example 413A C-NMR spectrum;
FIG. 9: the single crystal structure of the product of example 1;
Detailed Description
The invention is illustrated by way of example. The specific material ratios, process conditions and results described in the examples are merely illustrative of the invention and the invention should not be, nor should it be limited by the examples.
Example 1
When using 3X 3mL CH2Cl2And (2) extracting, drying an organic phase by using anhydrous magnesium sulfate, filtering out a drying agent, distilling under reduced pressure to obtain a crude product, separating by using column chromatography, eluting by using an eluant of petroleum ether/ethyl acetate (V petroleum ether: V ethyl acetate is 5: 1), and distilling under reduced pressure again to finally obtain 33.6mg of pure phenanthrene ketal, wherein the yield is 84%, and the purity is more than 95% by nuclear magnetic resonance detection.
Example 2
Schlenk tube, heating to 80 deg.C, TLC after 10h to detect phenanthrene ketal reaction completion. Adding diluted HCl solution to the reaction solution until the reaction solution is neutral, and adding 3X 3mL CH2Cl2And (3) extracting, drying an organic phase by using anhydrous magnesium sulfate, filtering out a drying agent, distilling under reduced pressure to obtain a crude product, separating by using column chromatography, eluting by using an eluant of petroleum ether/ethyl acetate (V petroleum ether: V ethyl acetate is 5: 1), and distilling under reduced pressure again to finally obtain pure phenanthrene ketal 31.6mg, wherein the yield is 88%, and the purity is more than 95% by nuclear magnetic resonance detection.
Example 3
The Schlenk tube was sealed and heated to 80 ℃ for 10h before TLC detection of 3-bromo-9-hydroxyphenanthrene reaction was complete. Adding diluted HCl solution to the reaction solution until the reaction solution is neutral, and adding 3X 3mL CH2Cl2Extracting, drying an organic phase by using anhydrous magnesium sulfate, filtering out a drying agent, carrying out reduced pressure distillation to obtain a crude product, separating by using column chromatography, eluting by using an eluant of petroleum ether/ethyl acetate (V petroleum ether: V ethyl acetate is 10: 1), and carrying out reduced pressure distillation again to obtain pure 3-bromofluorenone 46.9mg, wherein the yield is 91%, and the purity is more than 95% through nuclear magnetic resonance detection.
Example 4
Drying the organic phase with magnesium sulfate, filtering out the drying agent, distilling under reduced pressure to obtain a crude product, separating by column chromatography, eluting with petroleum ether/ethyl acetate (V petroleum ether: V ethyl acetate is 5: 1), distilling under reduced pressure again to obtain pure 3-bromophenanthrene ketal 45.2mg, wherein the yield is 81%, and the purity is more than 95% according to nuclear magnetic resonance detection.
Claims (9)
1. A phenanthrene ketal with a novel structure and a degradation method thereof are disclosed, wherein the reaction formula is shown as the following formula:
2. the phenanthrene ketal with novel structure and the degradation method thereof as claimed in claim 1, the steps are as follows:
(1) under a nitrogen atmosphere, 0.2mmol of 9-hydroxyphenanthrene was added to a Schlenk tube, 2mL of a solvent was added, and the mixture was stirred to completely dissolve the substrate.
(2) Base (0.75equiv.) was added and the Schlenk tube was sealed under nitrogen atmosphere.
(3) Stirring at room temperature, reacting for 7h, introducing oxygen into a Schlenk tube, sealing the Schlenk tube, and heating until 9-hydroxy phenanthrene completely disappears through TLC detection.
(4) After the reaction, dilute HCl solution was added to the reaction mixture to neutralize the reaction mixture, and 3X 5mL of CH was added2Cl2Extracting, drying the organic phase by using anhydrous magnesium sulfate, distilling the organic phase under reduced pressure, and carrying out column chromatography separation on the obtained crude product, wherein an eluent is petroleum ether V and ethyl acetate V which are 10: 1, so as to obtain the phenanthrene ketal.
(5) Under oxygen atmosphere, 0.1mmol phenanthrene ketal is added into a Schlenk tube, and a solvent is added and stirred to dissolve.
(6) The base (6equiv.) was added, the Schlenk tube was sealed under an oxygen atmosphere, and heated until the phenanthrene ketal completely disappeared.
(7) After the reaction, dilute HCl solution was added to the reaction mixture to neutralize the reaction mixture, and 3X 5mL of CH was added2Cl2Extracting, drying the organic phase by using anhydrous magnesium sulfate, distilling the organic phase under reduced pressure, and carrying out column chromatography separation on the obtained crude product, wherein an eluent is petroleum ether V and ethyl acetate V which are 5: 1, so as to obtain a pure product, namely the 9-fluorenone.
3. The phenanthrene ketal with novel structure and the degradation method thereof as claimed in claim 1, wherein the oxidation product is characterized by the following structure: two oxygen atoms are bridged to the phenanthrene ring, one of which forms a carbonyl structure at the C14 position indicated.
4. The phenanthrene ketal with novel structure and the degradation method thereof as claimed in claim 1, wherein: the substrate is 9-hydroxy phenanthrene, including 9-hydroxy phenanthrene with phenanthrene tricyclic structure having alkyl, aryl, methyl, halogen, trimethylsilyl and other substituents.
5. The phenanthrene ketal with novel structure and the degradation method thereof as claimed in claim 2, wherein: the alkali adopted in the reaction system in the steps (2) and (6) is inorganic alkali and organic alkali, and comprises NaH, NaOH, KOH, CsOH, KOBu-t, Na and Cs2CO3，Na2CO3，K2CO3，DBU，DBN。
6. The phenanthrene ketal with novel structure and the degradation method thereof as claimed in claim 2, wherein: and (3) adopting oxygen as an oxidant in the reaction system in the steps (3) and (5).
7. The phenanthrene ketal with novel structure and the degradation method thereof as claimed in claim 2, wherein: the temperature of the reaction system in the steps (3) and (6) is between 0 and 150 ℃.
8. The phenanthrene ketal with novel structure and the degradation method thereof as claimed in claim 2, wherein: the solvent in the steps (1) and (5) is an ether solvent (tetrahydrofuran or diethyl ether), or dichloromethane, chloroform, toluene, or an alcohol solvent (methanol, ethanol or isopropanol), or N, N-dimethylformamide or dimethyl sulfoxide.
9. The phenanthrene ketal with novel structure and the degradation method thereof as claimed in claim 2, wherein: the structure of the degraded product in the step (7) is 9-fluorenone.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB763205A (en) * | 1952-03-22 | 1956-12-12 | Merck & Co Inc | Polyhydrophenanthrene compounds |
| CN102775279A (en) * | 2012-08-14 | 2012-11-14 | 河南省科学院化学研究所有限公司 | 2,7-dibromo-9-hydroxyl phenanthrene derivatives and preparation method thereof |
| CN103254891A (en) * | 2013-05-06 | 2013-08-21 | 华东师范大学 | Mercury ion fluorescence sensor as well as synthetic method and application thereof |
| CN104744263A (en) * | 2013-12-30 | 2015-07-01 | 南开大学 | Novel method for efficiently synthesizing 6-hydroxy-2,3-dimethoxy-9-phenanthrenecarboxylic acid methyl ester |
| CN109111351A (en) * | 2017-06-23 | 2019-01-01 | 吉林大学 | A kind of synthetic method of asymmetry 9- alkoxy phenanthrene dimer |
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- 2020-11-06 CN CN202011265911.9A patent/CN112521365B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB763205A (en) * | 1952-03-22 | 1956-12-12 | Merck & Co Inc | Polyhydrophenanthrene compounds |
| CN102775279A (en) * | 2012-08-14 | 2012-11-14 | 河南省科学院化学研究所有限公司 | 2,7-dibromo-9-hydroxyl phenanthrene derivatives and preparation method thereof |
| CN103254891A (en) * | 2013-05-06 | 2013-08-21 | 华东师范大学 | Mercury ion fluorescence sensor as well as synthetic method and application thereof |
| CN104744263A (en) * | 2013-12-30 | 2015-07-01 | 南开大学 | Novel method for efficiently synthesizing 6-hydroxy-2,3-dimethoxy-9-phenanthrenecarboxylic acid methyl ester |
| CN109111351A (en) * | 2017-06-23 | 2019-01-01 | 吉林大学 | A kind of synthetic method of asymmetry 9- alkoxy phenanthrene dimer |
Non-Patent Citations (4)
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| DAISUKE SUE等: "Synthesis of Spiro Compounds through", 《ORGANIC LETTERS》 * |
| STN: "《STN》", 4 March 2020 * |
| 孙兵: "9-芴酮合成工艺研究进展", 《广东化工》 * |
| 谢颂凯等: "轴不对称联芳香化合物的研究", 《中山大学学报》 * |
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