CN112521365B - Synthesis and degradation method of phenanthrene ketal - Google Patents

Synthesis and degradation method of phenanthrene ketal Download PDF

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CN112521365B
CN112521365B CN202011265911.9A CN202011265911A CN112521365B CN 112521365 B CN112521365 B CN 112521365B CN 202011265911 A CN202011265911 A CN 202011265911A CN 112521365 B CN112521365 B CN 112521365B
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CN112521365A (en
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王奇峰
王东伟
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Jilin University
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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
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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
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    • 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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    • 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
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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

Synthesis and degradation method of phenanthrene ketal
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.
Figure GSB0000199480050000011
Disclosure of Invention
The invention aims to provide a synthesis and degradation method of phenanthrene ketal, and the technical method is shown in figure 2:
Figure GSB0000199480050000012
the method comprises the following specific steps:
(1) adding 0.2mmol of 9-hydroxy phenanthrene into a Schlenk tube under nitrogen atmosphere, adding 2mL of solvent, stirring to completely dissolve the substrate, wherein the solvent is selected from tetrahydrofuran, diethyl ether, toluene, N-dimethylformamide or dimethyl sulfoxide,
(2) 0.75 equivalents of base were added and the Schlenk tube was sealed under a nitrogen atmosphere. The alkali is selected from NaH, NaOH, KOH, CsOH, KOBu-t, Na, Cs 2 CO 3 ，Na 2 CO 3 ，K 2 CO 3 The number of DBUs or DBNs,
(3) stirring at room temperature, reacting for 7h, introducing oxygen into a Schlenk tube, sealing the Schlenk tube, 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 added 2 Cl 2 Extracting, drying the organic phase with anhydrous magnesium sulfate, distilling the organic phase under reduced pressure, separating the obtained crude product by column chromatography, eluting with petroleum ether and ethyl acetate (V: 10: 1) to obtain phenanthrene ketal,
(5) adding 0.1mmol phenanthrene ketal into a Schlenk tube under oxygen atmosphere, adding a solvent, stirring and dissolving, wherein the solvent is selected from tetrahydrofuran, diethyl ether, toluene, N-dimethylformamide or dimethyl sulfoxide,
(6) adding 6 equivalents of alkali, sealing the Schlenk tube under oxygen atmosphere, heating until phenanthrene ketal disappears completely,
(7) after the reaction, dilute HCl solution was added to the reaction mixture to neutralize the reaction mixture, and 3X 5mL of CH was added 2 Cl 2 Extracting, 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.
Drawings
FIG. 1: of the product of example 1 1 H-NMR spectrum;
FIG. 2: of the product of example 1 13 A C-NMR spectrum;
FIG. 3: of the product of example 2 1 H-NMR spectrum;
FIG. 4: of the product of example 2 13 A C-NMR spectrum;
FIG. 5 is a schematic view of: of the product of example 3 1 H-NMR spectrum;
FIG. 6: of the product of example 3 13 C-NMR spectrum;
FIG. 7: of the product of example 4 1 H-NMR spectrum;
FIG. 8: of the product of example 4 13 A 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.
Figure GSB0000199480050000021
The base NaH (0.15mmol, 3.6mg) was added, the Schlenk tube was sealed and stirred at room temperature for 7 h. Introducing oxygen into a Schlenk tube, sealing the Schlenk tube, heating to 80 ℃, and detecting the completion of the reaction of the 9-hydroxy phenanthrene by TLC after 2 h. Adding diluted HCl solution to the reaction solution until the reaction solution is neutral, and adding 3X 3mL CH 2 Cl 2 And (2) extracting, drying an organic phase by using anhydrous magnesium sulfate, then filtering out a drying agent, distilling under reduced pressure to obtain a crude product, separating by using column chromatography, eluting by using an eluent petroleum ether/ethyl acetate (V petroleum ether: V ethyl acetate is 5: 1), and distilling under reduced pressure again to finally obtain the pure phenanthrene ketal 33.6mg with the yield of 84% and the purity of more than 95% through nuclear magnetic resonance detection.
Example 2
Figure GSB0000199480050000031
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 CH 2 Cl 2 And (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
Figure GSB0000199480050000032
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 CH 2 Cl 2 Extracting, 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
Figure GSB0000199480050000033
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 (7)

1. A synthesis method of phenanthrene ketal and a degradation method thereof, and the reaction formula is shown as the following figure.
Figure FSB0000199480040000011
2. The method for synthesizing phenanthrene ketal and degrading the phenanthrene ketal as in claim 1 comprises the following steps:
(1) adding 0.2mmol of 9-hydroxy phenanthrene into a Schlenk tube under nitrogen atmosphere, adding 2mL of solvent, stirring to completely dissolve the substrate, wherein the solvent is selected from tetrahydrofuran, diethyl ether, toluene, N-dimethylformamide or dimethyl sulfoxide,
(2) adding 0.75 equivalent of a base selected from NaH, NaOH, KOH, CsOH, KOBu-t, Na, Cs, into the Schlenk tube under a nitrogen atmosphere 2 CO 3 ，Na 2 CO 3 ，K 2 CO 3 The number of DBUs or DBNs,
(3) stirring at room temperature, reacting for 7h, introducing oxygen into a Schlenk tube, sealing the Schlenk tube, heating until the 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 added 2 Cl 2 Extracting, drying the organic phase with anhydrous magnesium sulfate, distilling the organic phase under reduced pressure, separating the obtained crude product by column chromatography, eluting with petroleum ether and ethyl acetate (V: 10: 1) to obtain phenanthrene ketal,
(5) adding 0.1mmol phenanthrene ketal into a Schlenk tube under oxygen atmosphere, adding a solvent, stirring and dissolving, wherein the solvent is selected from tetrahydrofuran, diethyl ether, toluene, N-dimethylformamide or dimethyl sulfoxide,
(6) adding 6 equivalents of alkali, sealing the Schlenk tube under oxygen atmosphere, heating until phenanthrene ketal disappears completely,
(7) after the reaction, dilute HCl solution was added to the reaction mixture to neutralize the reaction mixture, and 3X 5mL of CH was added 2 Cl 2 Extracting, 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 method for synthesizing and degrading phenanthrene ketal according to claim 2, wherein: the alkali adopted by the reaction system in the steps (2) and (6) is inorganic alkali or organic alkali selected from NaH, NaOH, KOH, CsOH, KOBu-t, Na and Cs 2 CO 3 ，Na 2 CO 3 ，K 2 CO 3 DBU or DBN.
4. The method for synthesizing and degrading phenanthrene ketal according to claim 2, wherein: and (3) adopting oxygen as an oxidant in the reaction system in the steps (3) and (5).
5. The method for synthesizing and degrading phenanthrene ketal of claim 2, wherein: the temperature of the reaction system in the steps (3) and (6) is between 0 and 150 ℃.
6. The method for synthesizing and degrading phenanthrene ketal according to claim 2, wherein: the solvent in the steps (1) and (5) is selected from tetrahydrofuran, diethyl ether, toluene, N-dimethylformamide or dimethyl sulfoxide.
7. The method for synthesizing and degrading phenanthrene ketal according to claim 2, wherein: the structure of the degraded product in the step (7) is 9-fluorenone.
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GB763205A (en) * 1952-03-22 1956-12-12 Merck & Co Inc Polyhydrophenanthrene compounds
CN102775279B (en) * 2012-08-14 2014-03-05 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
CN109111351B (en) * 2017-06-23 2021-08-20 吉林大学 Synthesis method of asymmetric 9-alkoxy phenanthrene dimer

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