CN109265311B - Phenyl fluorene derivative and preparation method and application thereof - Google Patents
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Abstract
The invention discloses a phenylfluorene derivative, which has a general formula shown in formula I:
in the formula I, R is selected from hydrogen, halogen, alkyl, alkoxy and aryl. The phenylfluorene derivative with a novel structure provided by the invention is simple in preparation method, mild in reaction conditions, non-toxic and harmless, has blue fluorescence, and can be used as a potential organic functional material.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a 9-alkenyl-9-phenylfluorene derivative and a preparation method and application thereof.
Background
9, 9-diarylfluorenes are an important class of aromatic compounds. These compounds have now been found to be useful in electroluminescent devices or other applications. Spirocyclic fluorenes have also been studied extensively because of their unusual pi-systems used in organic light emitting diodes, light trapping arrays and organic electronic devices. The particular fluorene derivatives may also be coordinated with rare earth metals or transition metals to form new catalysts.
The 9-substituted 9-phenylfluorene derivative can be generally obtained from a 9-phenylfluorene cation via an electrophilic reaction. In 2017, the Klumpp topic group takes biphenyl-substituted heterocyclic ketone and aromatic hydrocarbon as substrates and takes trifluoromethanesulfonic acid as a solvent to react at normal temperature to obtain heterocycle-substituted 9, 9-diaryl fluorene (J.Org.chem.2017,82, 6044) -6053).
At present, few reports are made on the synthesis of 9-substituted 9-phenylfluorene compounds, and no document is published on 9-alkenyl-9-phenylfluorene compounds.
Disclosure of Invention
The invention aims to provide a phenylfluorene derivative with a novel structure, which has blue fluorescence and can be used as a potential organic functional material.
Another object of the present invention is to provide a method for preparing the phenylfluorene derivative having a novel structure.
It is still another object of the present invention to provide a use of the phenylfluorene derivative as an organic functional material.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention provides a phenylfluorene derivative with a novel structure, which has a general formula shown in formula I:
in the formula I, R is selected from hydrogen, halogen, alkyl, alkoxy and aryl.
Preferred compounds of the invention are those of formula I wherein R is selected from hydrogen (H), halogen (F, Cl, Br), methyl (CH)3) Methoxy (OCH)3) Tert-butyl, phenyl
And the like.
The most preferred compound of the present invention is that the phenylfluorene derivative is selected from one of the following structures:
in the definition of formula I given above, the terms used in the collection are generally defined as follows:
the term alkyl refers to a straight or branched chain saturated aliphatic hydrocarbon group containing 1 to 7 carbon atoms, for example: methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, methylthio, ethylthio and the like.
The term alkoxy refers to a group having an oxygen atom attached to the alkyl terminus, for example: methoxy, ethoxy, n-propoxy, isopropoxy, and the like.
The term aryl refers to mono-, di-or tricyclic hydrocarbon compounds in which at least one ring is aromatic and each ring contains up to 7 carbon atoms, e.g. phenyl, naphthyl, anthracenyl, biphenyl or indenyl.
The term halogen means chlorine, bromine, iodine or fluorine.
Another aspect of the present invention provides a preparation method of the phenylfluorene derivative, including the steps of:
r is selected from hydrogen, halogen, alkyl, alkoxy and aryl;
mixing 1 equivalent of compound II-1 (9-phenylfluorene-9-ol) and 5% equivalent of catalyst, adding a proper solvent, then adding 1 equivalent of 1, 1-diphenylethylene compound III, reacting at 50-80 ℃ for 1-48 h, cooling to room temperature, spin-drying the solvent, and performing column chromatography separation and purification to obtain the compound phenylfluorene derivative shown in formula I.
The catalyst is at least one of scandium trifluoromethanesulfonate, aluminum trichloride, ferric trichloride, ytterbium trifluoromethanesulfonate and p-toluenesulfonic acid.
The solvent is at least one of 1, 2-dichloroethane, dichloromethane, chloroform and ethyl acetate.
The 1, 1-diphenylethylene compound III is selected from 1, 1-diphenylethylene, 4 '-dimethyl-1, 1-diphenylethylene, 4' -dimethoxy-1, 1-diphenylethylene, 4 '-di-tert-butyl-1, 1-diphenylethylene, 3' -dimethoxy-1, 1-diphenylethylene, 2,2 ' -dimethoxy-1, 1-diphenylethylene, 4 ' -difluoro-1, 1-diphenylethylene, 4 ' -dichloro-1, 1-diphenylethylene, 4 ' -dibromo-1, 1-diphenylethylene, 4 ' -diphenyl-1, 1-diphenylethylene.
The preparation method of the 1, 1-diphenylethylene compound III comprises the following steps:
r is selected from hydrogen, halogen, alkyl, alkoxy and aryl;
carrying out anhydrous and oxygen-free treatment on a 100mL three-neck round-bottom flask, adding redistilled tetrahydrofuran, 1 equivalent of ethyl acetate and 15% equivalent of copper oxide, then adding 3 equivalents of bromobenzene or bromobenzene substitute V and 3 equivalents of magnesium chips, reacting for 1-6 h at 50-80 ℃, monitoring the reaction completion by TLC, adding a saturated ammonium chloride solution into a system to quench the reaction, extracting with ethyl acetate, combining organic phases, washing with brine once, drying the organic phase with anhydrous sodium sulfate, removing the solvent of the organic phase, and separating by column chromatography to obtain a compound IV;
adding 10mmol of compound IV and 5 mol% of iodine into a 50mL single-neck flask, then adding acetonitrile serving as a solvent, reacting for 1-8 hours at room temperature, monitoring the reaction by TLC, removing the solvent, and separating by column chromatography to obtain the 1, 1-diphenylethylene compound III.
The bromobenzene substituent is one of the following structures:
the third aspect of the present invention provides a use of the phenylfluorene derivative as an organic functional material.
Due to the adoption of the technical scheme, the invention has the following advantages and beneficial effects:
the phenylfluorene derivative with a novel structure provided by the invention is simple in preparation method, mild in reaction conditions, non-toxic and harmless, has blue fluorescence, and can be used as a potential organic functional material.
Drawings
FIG. 1 is a fluorescence diagram of compounds I-4, I-5, I-8, I-9, and I-10 prepared in the examples of the present invention, which were subjected to fluorescence measurement.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
The reagents used in the invention are as follows: 9-phenylfluoren-9-ol, scandium trifluoromethanesulfonate, 1-diphenylethylene, 4 ' -dimethyl-1, 1-diphenylethylene, 4 ' -dimethoxy-1, 1-diphenylethylene, 4 ' -di-tert-butyl-1, 1-diphenylethylene, 3,3 '-dimethoxy-1, 1-diphenylethylene, 2' -dimethoxy-1, 1-diphenylethylene, 4 '-difluoro-1, 1-diphenylethylene, 4' -dichloro-1, 1-diphenylethylene, 4 '-dibromo-1, 1-diphenylethylene, 4' -diphenyl-1, 1-diphenylethylene;
the preparation method of the 9-phenylfluorene-9-alcohol comprises the following steps:
a100 mL three necked round bottom flask was treated with anhydrous oxygen free treatment, magnesium turnings (30mmol, 3 equiv.) and iodine (2mmol, 10% equiv.) were added, bromobenzene (30mmol, 1.5 equiv.) was dissolved in redistilled tetrahydrofuran and slowly added dropwise to the round bottom flask through a constant pressure dropping funnel for reaction at 65 ℃. After 2 hours, the 9-fluorenone was dissolved in tetrahydrofuran and slowly added to the reaction system, and the reaction was continued overnight. After the reaction is finished, adding saturated ammonium chloride solution into the system for quenching, then extracting with ethyl acetate (3X 30mL), combining organic phases, washing once with brine, then drying the organic phases with anhydrous sodium sulfate, removing the solvent of the organic phases, and obtaining the 9-phenylfluorene-9-alcohol through column chromatography separation.
The preparation method of the 1, 1-diphenylethylene compound III with different substituents comprises the following steps:
a100 mL three necked round bottom flask was treated with anhydrous oxygen free treatment, followed by addition of 30mL of redistilled tetrahydrofuran, ethyl acetate (10mmol, 1 equiv.), 1.5mmol of copper oxide (15% equiv.), and then bromobenzene or a bromobenzene substituent V (30mmol, 3 equiv.) and magnesium turnings (30mmol, 3 equiv.) and reacted at 60 ℃ for 4 h. When the reaction was terminated by TLC, a saturated ammonium chloride solution was added to the system to quench the reaction, and the reaction was extracted with ethyl acetate (3 × 30mL), and the organic phases were combined, washed once with brine, and then dried over anhydrous sodium sulfate to remove the solvent from the organic phase, and separated by column chromatography to give compound IV.
Adding a compound IV (10mmol) and iodine (5 mol%) into a 50mL single-neck flask, then adding a solvent acetonitrile, reacting for 6 hours at room temperature, monitoring the reaction by TLC, removing the solvent, and separating by column chromatography to obtain the 1, 1-diphenylethylene compound III with different substituents.
In the above reaction, R is hydrogen (H), halogen (F, Cl, Br), methyl (CH)3) Methoxy (OCH)3) Tert-butyl, phenyl
And the like.
Reagents used in the examples of the present invention: 9-fluorenone, 25g, purity ≥ 98.0%, available from Shanghai Dairy Fine Chemicals, Inc.; 1, 1-diphenylethylene, 5g, 98% purity, available from Hadamard reagent, Inc.; 500mL of bromobenzene, analytically pure, purchased from national pharmaceutical group reagents, Inc.; 500g of copper oxide, analytically pure, purchased from chemical reagents of national drug group, ltd; magnesium turnings, 500g, analytically pure, were purchased from national pharmaceutical group chemical reagents, Inc.
Example 1
Mixing 9-phenylfluoren-9-ol (compound II-1, 0.25mmol, 1 equiv.) and scandium trifluoromethanesulfonate (0.0125mmol, 5 mol% equiv.), adding 2mL of 1, 2-dichloroethane as a solvent, adding 1, 1-diphenylethylene (compound III-1, 0.25mmol, 1 equiv.), reacting at 60 deg.C for 12 hours, cooling to room temperature, spin-drying the solvent, and purifying by column chromatography on a dry column (eluent: petroleum ether: ethyl acetate: 100: 2) to obtain the target product (compound I-1) as a white solid with a yield of 95%.
1H NMR(400MHz,CDCl3)δ7.44(d,J＝7.5Hz,2H),7.35–7.28(m,2H),7.27–7.14(m, 13H),7.09–7.00(m,2H),6.89–6.79(m,1H),6.76–6.65(m,2H),6.36–6.13(m,2H).
Example 2
Mixing 9-phenylfluoren-9-ol (compound II-1, 0.25mmol, 1 equiv.) and scandium trifluoromethanesulfonate (0.0125mmol, 5 mol% equiv.), adding 2mL of 1, 2-dichloroethane as a solvent, adding 4, 4' -dimethyl-1, 1-diphenylethylene (compound III-2, 0.25mmol, 1 equiv.), reacting at 60 ℃ for 12 hours, cooling to room temperature, spin-drying the solvent, and purifying by column chromatography (eluent: petroleum ether: ethyl acetate: 100: 2) to obtain the target product (compound I-2) as a white solid with a yield of 94%.
1H NMR(400MHz,CDCl3)δ7.45(d,J＝7.5Hz,2H),7.29(d,J＝7.4Hz,2H),7.26–7.19 (m,2H),7.19–7.11(m,7H),7.08(s,1H),7.07–6.97(m,4H),6.49(d,J＝7.7Hz,2H),6.13(d,J ＝7.8Hz,2H),2.30(s,3H),2.12(s,3H).
Example 3
Mixing 9-phenylfluoren-9-ol (compound II-1, 0.25mmol, 1 equiv.) and scandium trifluoromethanesulfonate (0.0125mmol, 5 mol% equiv.), adding 2mL of 1, 2-dichloroethane as a solvent, adding 4, 4' -dimethoxy-1, 1-diphenylethylene (compound III-3, 0.25mmol, 1 equiv.), reacting at 60 ℃ for 12 hours, cooling to room temperature, spin-drying the solvent, and purifying by column chromatography (eluent: petroleum ether: ethyl acetate: 100: 1) to obtain the target product (compound I-3) as a white solid with a yield of 83%.
1H NMR(400MHz,CDCl3)δ7.52–7.44(m,2H),7.31–7.27(m,2H),7.26–7.22(m,2H), 7.20–7.13(m,7H),7.08–7.00(m,3H),6.81–6.74(m,2H),6.27–6.21(m,2H),6.18–6.11(m, 2H),3.76(s,3H),3.66(s,3H).
Example 4
Mixing 9-phenylfluoren-9-ol (compound II-1, 0.25mmol, 1 equiv.) and scandium trifluoromethanesulfonate (0.0125mmol, 5 mol% equiv.), adding 2mL of 1, 2-dichloroethane as a solvent, adding 4, 4' -di-tert-butyl-1, 1-diphenylethylene (compound III-4, 0.25mmol, 1 equiv.), reacting at 60 deg.C for 12 hours, cooling to room temperature, spin-drying the solvent, and purifying by column chromatography (eluent: petroleum ether: ethyl acetate: 100: 2) to obtain the target product (compound I-4) as a white solid with a yield of 93%.
1H NMR(400MHz,CDCl3)δ7.40(d,J＝7.5Hz,2H),7.34–7.11(m,14H),7.02(dd,J＝8.0, 6.9Hz,2H),6.68(d,J＝8.1Hz,2H),6.14(d,J＝8.0Hz,2H),1.28(s,9H),1.20(s,9H).
Example 5
Mixing 9-phenylfluoren-9-ol (compound II-1, 0.25mmol, 1 equiv.) and scandium trifluoromethanesulfonate (0.0125mmol, 5 mol% equiv.), adding 2mL of 1, 2-dichloroethane as a solvent, adding 3, 3' -dimethoxy-1, 1-diphenylethylene (compound III-5, 0.25mmol, 1 equiv.), reacting at 60 ℃ for 12 hours, cooling to room temperature, spin-drying the solvent, and purifying by column chromatography (eluent: petroleum ether: ethyl acetate: 100: 1) to obtain the target product (compound I-5) as a white solid with a yield of 93%.
1H NMR(400MHz,CDCl3)δ7.50–7.41(m,2H),7.33–7.27(m,2H),7.27–7.13(m,9H), 7.10–7.01(m,2H),6.90–6.83(m,1H),6.81–6.72(m,2H),6.65(m,1H),6.45–6.35(m,1H), 5.96–5.88(m,1H),5.72(m,1H),3.72(s,3H),3.44(s,3H).
Example 6
Mixing 9-phenylfluoren-9-ol (compound II-1, 0.25mmol, 1 equiv.) and scandium trifluoromethanesulfonate (0.0125mmol, 5 mol% equiv.), adding 2mL of 1, 2-dichloroethane as a solvent, adding 2, 2' -dimethoxy-1, 1-diphenylethylene (compound III-6, 0.25mmol, 1 equiv.), reacting at 60 ℃ for 12 hours, cooling to room temperature, spin-drying the solvent, and purifying by column chromatography (eluent: petroleum ether: ethyl acetate: 100: 1) to obtain the target product (compound I-6) as a white solid with a yield of 94%.
1H NMR(400MHz,CDCl3)δ7.40–7.31(m,4H),7.27–7.08(m,8H),7.05–6.94(m,4H), 6.87(d,J＝8.2Hz,1H),6.81–6.73(m,2H),6.36–6.21(m,2H),6.16(d,J＝8.2Hz,1H),3.80(s, 3H),3.29(s,3H).
Example 7
Mixing 9-phenylfluoren-9-ol (compound II-1, 0.25mmol, 1 equiv.) and scandium trifluoromethanesulfonate (0.0125mmol, 5 mol% equiv.), adding 2mL of 1, 2-dichloroethane as a solvent, adding 4, 4' -difluoro-1, 1-diphenylethylene (compound III-7, 0.25mmol, 1 equiv.), reacting at 60 ℃ for 12 hours, cooling to room temperature, spin-drying the solvent, and purifying by column chromatography (eluent: petroleum ether: ethyl acetate: 100: 2) to obtain the target product (compound I-7) as a white solid with a yield of 77%.
1H NMR(400MHz,CDCl3)δ7.46(m,2H),7.32–7.12(m,12H),7.11–7.04(m,2H),6.97– 6.88(m,2H),6.44–6.35(m,2H),6.21–6.11(m,2H).
Example 8
Mixing 9-phenylfluoren-9-ol (compound II-1, 0.25mmol, 1 equiv.) and scandium trifluoromethanesulfonate (0.0125mmol, 5 mol% equiv.), adding 2mL of 1, 2-dichloroethane as a solvent, adding 4, 4' -dichloro-1, 1-diphenylethylene (compound III-8, 0.25mmol, 1 equiv.), reacting at 60 ℃ for 12 hours, cooling to room temperature, spin-drying the solvent, and purifying by column chromatography (eluent: petroleum ether: ethyl acetate: 100: 2) to obtain the target product (compound I-8) as a white solid with a yield of 84%.
1H NMR(400MHz,CDCl3)δ7.53–7.44(m,2H),7.31–7.17(m,11H),7.16(s,1H),7.14– 7.03(m,4H),6.70–6.61(m,2H),6.18–6.07(m,2H).
Example 9
Mixing 9-phenylfluoren-9-ol (compound II-1, 0.25mmol, 1 equiv.) and scandium trifluoromethanesulfonate (0.0125mmol, 5 mol% equiv.), adding 2mL of 1, 2-dichloroethane as a solvent, adding 4, 4' -dibromo-1, 1-diphenylethylene (compound III-9, 0.25mmol, 1 equiv.), reacting at 60 ℃ for 12 hours, cooling to room temperature, spin-drying the solvent, and purifying by column chromatography (eluent: petroleum ether: ethyl acetate: 100: 2) to obtain the target product (compound I-9) as a white solid with a yield of 82%.
1H NMR(400MHz,CDCl3)δ7.47(s,2H),7.38–7.32(m,2H),7.30–7.16(m,9H),7.15(s, 1H),7.12–7.03(m,4H),6.86–6.79(m,2H),6.10–6.02(m,2H).
Example 10
Mixing 9-phenylfluoren-9-ol (compound II-1, 0.25mmol, 1 equiv.) and scandium trifluoromethanesulfonate (0.0125mmol, 5 mol% equiv.), adding 2mL of 1, 2-dichloroethane as a solvent, adding 4, 4' -diphenyl-1, 1-diphenylethylene (compound III-10, 0.25mmol, 1 equiv.), reacting at 60 ℃ for 12 hours, cooling to room temperature, spin-drying the solvent, and purifying by column chromatography (eluent: petroleum ether: ethyl acetate: 100: 3) to obtain the target product (compound I-10) as a white solid with a yield of 99%.
1H NMR(400MHz,CDCl3)δ7.60–7.53(m,2H),7.52–7.47(m,2H),7.46–7.39(m,8H), 7.36–7.30(m,6H),7.29–7.15(m,9H),7.10–7.02(m,2H),6.97–6.89(m,2H),6.38–6.29(m, 2H).
The compounds I-4, I-5, I-8, I-9 and I-10 were subjected to fluorescence test, as shown in FIG. 1, FIG. 1 is a schematic diagram of fluorescence of compounds I-4, I-5, I-8, I-9 and I-10 prepared in the example of the present invention, with an excitation wavelength of 310nm, a scanning range of 200 and 650nm, and a scanning interval of 5 nm. As can be seen from the figure, all the products have a strong fluorescence emission peak at 320-350 nm, and the peak positions are different due to different functional groups of the compounds. In addition, the product I-8 has a strong fluorescence peak around 440 nm.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are given by way of illustration of the principles of the present invention, and that various changes and modifications may be made without departing from the spirit and scope of the invention as defined by the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (3)
1. A phenylfluorene derivative is characterized in that the phenylfluorene derivative is one of the following compounds:
2. a process for preparing a phenylfluorene derivative according to claim 1, which comprises the main steps of: mixing 1 equivalent of the compound II-1 with 5% equivalent of a catalyst, adding a proper solvent, then adding 1 equivalent of the 1, 1-diphenylethylene compound III, reacting at 50-80 ℃ for 1-48 h, cooling to room temperature, spin-drying the solvent, and performing column chromatography separation and purification to obtain a target compound;
wherein, the 1, 1-diphenylethylene compound III is 4,4 '-di-tert-butyl-1, 1-diphenylethylene, 3, 3' -dimethoxy-1, 1-diphenylethylene, 4,4 '-dichloro-1, 1-diphenylethylene or 4, 4' -diphenyl-1, 1-diphenylethylene;
the catalyst is at least one of scandium trifluoromethanesulfonate, aluminum trichloride, ferric trichloride, ytterbium trifluoromethanesulfonate or p-toluenesulfonic acid;
the solvent is at least one of 1, 2-dichloroethane, dichloromethane, chloroform or ethyl acetate.
3. The process according to claim 2, wherein the 1, 1-diphenylethylene compound III is prepared by a preparation process comprising the steps of:
carrying out anhydrous and oxygen-free treatment on a 100mL three-neck round-bottom flask, adding redistilled tetrahydrofuran, 1 equivalent of ethyl acetate and 15% equivalent of copper oxide, then adding 3 equivalent of bromobenzene substituent V and 3 equivalent of magnesium chips, reacting for 1-6 h at 50-80 ℃, monitoring that a raw material point disappears by TLC, adding saturated ammonium chloride solution into a system to quench the reaction, extracting with ethyl acetate, combining organic phases, washing with brine once, drying the organic phase with anhydrous sodium sulfate, removing a solvent of the organic phase, and separating by column chromatography to obtain a compound IV;
adding 10mmol of compound IV and 5 mol% of iodine into a 50mL single-neck flask, then adding solvent acetonitrile, reacting for 1-8 h at room temperature, detecting the disappearance of a raw material point by TLC, removing the solvent, and separating by column chromatography to obtain a target substance;
wherein the bromobenzene substituent V is one of the following compounds:
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| "Iodine-catalyzed Transformation of Aryl-substituted Alcohols Under Solvent-free and Highly Concentrated Reaction Conditions";Marjan Jereb等，;《Acta Chimica Slovenica》;20171201;第64卷(第4期);第751页Table1 * |
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