CN114456033A - Preparation method of fluoranthene derivative - Google Patents
Preparation method of fluoranthene derivative Download PDFInfo
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- CN114456033A CN114456033A CN202210140470.2A CN202210140470A CN114456033A CN 114456033 A CN114456033 A CN 114456033A CN 202210140470 A CN202210140470 A CN 202210140470A CN 114456033 A CN114456033 A CN 114456033A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 125000003914 fluoranthenyl group Chemical class C1(=CC=C2C=CC=C3C4=CC=CC=C4C1=C23)* 0.000 title abstract description 5
- 150000002219 fluoranthenes Chemical class 0.000 claims abstract description 66
- 239000003960 organic solvent Substances 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000007363 ring formation reaction Methods 0.000 claims abstract description 15
- 125000001424 substituent group Chemical group 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 42
- 238000004440 column chromatography Methods 0.000 claims description 21
- 239000012043 crude product Substances 0.000 claims description 21
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 8
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 8
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 claims description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 8
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 8
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 8
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 8
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 8
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 229910006069 SO3H Inorganic materials 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 4
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 4
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 4
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- 229940078552 o-xylene Drugs 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 abstract description 8
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthene Chemical compound C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 abstract description 6
- 150000001345 alkine derivatives Chemical class 0.000 abstract description 4
- 230000002194 synthesizing effect Effects 0.000 abstract description 4
- 229930192474 thiophene Natural products 0.000 abstract description 4
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 230000021615 conjugation Effects 0.000 abstract description 2
- 230000008569 process Effects 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
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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
- C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
- C07C1/321—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a non-metal atom
- C07C1/322—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a non-metal atom the hetero-atom being a sulfur atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/35—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction
- C07C17/358—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction by isomerisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D319/10—1,4-Dioxanes; Hydrogenated 1,4-dioxanes
- C07D319/14—1,4-Dioxanes; Hydrogenated 1,4-dioxanes condensed with carbocyclic rings or ring systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/08—Hydrogen atoms or radicals containing only hydrogen and carbon atoms
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D333/78—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems condensed with rings other than six-membered or with ring systems containing such rings
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/02—Systems containing only non-condensed rings with a three-membered ring
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- 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
- C07C2603/40—Ortho- or ortho- and peri-condensed systems containing four condensed rings
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/52—Ortho- or ortho- and peri-condensed systems containing five condensed rings
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- C07C2603/54—Ortho- or ortho- and peri-condensed systems containing more than five condensed rings
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Abstract
The invention relates to a preparation method of fluoranthene derivatives, which comprises the following steps: taking 1-thiophene-8-alkynyl naphthalene compounds as raw materials, and carrying out cyclization reaction in an organic solvent to obtain the fluoranthene derivative. Compared with the prior art, the invention provides a simple method for synthesizing the fluoranthene derivative through intramolecular [4+2] cyclization between thiophene and alkyne under the condition of no catalysis, and by simply adjusting the substituent groups on the thiophene and alkyne, various functional groups can be accurately introduced into different positions of a fluoranthene skeleton, and the conjugation of fluoranthene can be extended in different directions. The preparation method can be used for synthesizing fluoranthene derivatives with functional substituents at different positions, and has the advantages of few steps, high yield, low cost, easiness in separation and the like.
Description
Technical Field
The invention belongs to the technical field of fluoranthene derivatives, and relates to a preparation method of fluoranthene derivatives.
Background
Fluoranthene is one of the smallest non-alternating hydrocarbon units formed by linking benzene and naphthalene with a five-membered ring. Fluoranthene derivatives have unique photoelectric characteristics and are widely applied at present, and have excellent application values in the fields of organic light-emitting diodes, organic field effect transistors and fluorescent sensors.
However, although researchers have developed several synthetic methods to prepare fluoranthene derivatives, these methods suffer from the general disadvantages of relatively low selectivity and reactivity, and difficulty in functionally modifying the fluoranthene backbone at different positions.
Disclosure of Invention
The invention aims to provide a preparation method of fluoranthene derivatives, which does not need to use a catalyst and has the advantages of high yield, low cost, simple synthetic process and the like.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of fluoranthene derivatives comprises the following steps: taking 1-thiophene-8-alkynyl naphthalene compounds as raw materials, and carrying out cyclization reaction in an organic solvent to obtain the fluoranthene derivative.
Further, the method specifically comprises the following steps: dissolving the 1-thiophene-8-alkynyl naphthalene compound in an organic solvent, carrying out cyclization reaction, and then separating and purifying to obtain the fluoranthene derivative.
Further, the structural formula of the 1-thiophene-8-alkynyl naphthalene compound is as follows:
wherein R is1To R10As substituents, e.g. hydrogen, fatsVarious functional groups such as alkyl, aromatic alkyl, heterocyclic aryl, and condensed ring aryl.
The synthetic route is as follows:
preferably, R1To R10Each independently selected from the group consisting of: hydrogen, -CnH2n+1、-CnH2nOH、 -CnHnOCmH2m+1、-F、-Cl、-Br、-I、-NH2、-NHCnH2n+1、-N(CnH2n+1)2、-N+(CnH2n+1)3、 -NHCOCnH2n+1、-OH、-OCnH2n+1、-OCOCnH2n+1、-OCnHnOCmH2m+1、-COOH、 -COOCmH2m+1、-CnH2nCOOH、-CnH2nCOOCmH2m+1、-NO2、-CF3、-CCl3、-CN、-CHO、 -SO3H、
Wherein n is 1-10, and m is 1-10.
Preferably, R11To R19Each independently selected from the group consisting of: hydrogen, -CnH2n+1、-CnH2nOH、 -CnHnOCmH2m+1、-F、-Cl、-Br、-I、-NH2、-NHCnH2n+1、-N(CnH2n+1)2、-N+(CnH2n+1)3、 -NHCOCnH2n+1、-OH、-OCnH2n+1、-OCOCnH2n+1、-OCnHnOCmH2m+1、-COOH、 -COOCmH2m+1、-CnH2nCOOH、-CnH2nCOOCmH2m+1、-NO2、-CF3、-CCl3、-CN、-CHO、 -SO3H。
Further, the boiling point of the organic solvent is higher than 100 ℃.
Preferably, the organic solvent comprises one or more of o-xylene, N-methylpyrrolidone, N-dimethylformamide, mesitylene, ethylene glycol, cyclohexanone, o-dichlorobenzene, diphenyl ether, nitrobenzene, sulfolane, diethylene glycol dimethyl ether, pyridine, m-xylene, cyclohexanol, o-cresol, formamide, quinoline, N-methylformamide.
Furthermore, in the cyclization reaction process, the reaction temperature is higher than 100 ℃, and the reaction time is longer than 1 hour.
Preferably, the reaction temperature is 120-285 ℃ and the reaction time is 1.5-10 hours in the cyclization reaction process.
Further, the separation and purification process comprises the following steps: the organic solvent is removed to obtain a crude product, which is then subjected to column chromatography.
Compared with the prior art, the invention has the following characteristics:
1) the invention provides a simple method for synthesizing fluoranthene derivatives through intramolecular [4+2] cyclization under the condition of no catalysis between thiophene and alkyne. By simply adjusting the substituents on the thiophene and alkyne, not only can various functional groups be accurately introduced into different positions of the fluoranthene skeleton, but also the conjugation of fluoranthene can be extended in different directions. The preparation method is simple in synthesis process, can be used for synthesizing fluoranthene derivatives with functional substituents at different positions, and also provides an effective way for constructing large polycyclic aromatic hydrocarbons containing fluoranthene parts.
2) The preparation method of the fluoranthene derivative does not need to add any catalyst, has the advantages of few steps, high yield, low cost, easy separation and the like, and has wide application prospect in organic light-emitting devices.
Detailed Description
The present invention will be described in detail with reference to specific examples. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
The invention provides a preparation method of fluoranthene derivatives, which comprises the following steps: taking 1-thiophene-8-alkynyl naphthalene compounds as raw materials, and carrying out cyclization reaction in an organic solvent to obtain the fluoranthene derivative. The method specifically comprises the following steps: dissolving the 1-thiophene-8-alkynyl naphthalene compound in an organic solvent, carrying out cyclization reaction, and then separating and purifying to obtain the fluoranthene derivative.
Wherein, the structural formula of the 1-thiophene-8-alkynyl naphthalene compound is as follows:
R1to R10Is a substituent.
Preferably, R1To R10Each independently selected from the group consisting of: hydrogen, -CnH2n+1、-CnH2nOH、 -CnHnOCmH2m+1、-F、-Cl、-Br、-I、-NH2、-NHCnH2n+1、-N(CnH2n+1)2、-N+(CnH2n+1)3、 -NHCOCnH2n+1、-OH、-OCnH2n+1、-OCOCnH2n+1、-OCnHnOCmH2m+1、-COOH、 -COOCmH2m+1、-CnH2nCOOH、-CnH2nCOOCmH2m+1、-NO2、-CF3、-CCl3、-CN、-CHO、 -SO3H、
Wherein n is 1-10, and m is 1-10.
Preferably, R11To R19Each independently selected from the group consisting of: hydrogen, -CnH2n+1、-CnH2nOH、 -CnHnOCmH2m+1、-F、-Cl、-Br、-I、-NH2、-NHCnH2n+1、-N(CnH2n+1)2、-N+(CnH2n+1)3、 -NHCOCnH2n+1、-OH、-OCnH2n+1、-OCOCnH2n+1、-OCnHnOCmH2m+1、-COOH、 -COOCmH2m+1、-CnH2nCOOH、-CnH2nCOOCmH2m+1、-NO2、-CF3、-CCl3、-CN、-CHO、 -SO3H。
The organic solvent has a boiling point above 100 ℃ and preferably comprises one or more of o-xylene, N-methylpyrrolidone, N-dimethylformamide, mesitylene, ethylene glycol, cyclohexanone, o-dichlorobenzene, diphenyl ether, nitrobenzene, sulfolane, diethylene glycol dimethyl ether, pyridine, m-xylene, cyclohexanol, o-cresol, formamide, quinoline, N-methylformamide.
In the cyclization reaction process, the reaction temperature is higher than 100 ℃, and the reaction time is longer than 1 hour. Preferably, the reaction temperature is 120-285 ℃ and the reaction time is 1.5-10 hours in the cyclization reaction process.
The separation and purification process comprises the following steps: the organic solvent is removed to obtain a crude product, which is then subjected to column chromatography.
Example 1:
preparation of fluoranthene derivative 1:
606mg of 1a was dissolved in 25mL of o-xylene and stirred at 140 ℃ for 8 hours. After the reaction is finished, the organic solvent in the reaction system is removed, and the crude product is separated and purified by column chromatography to obtain 540mg of fluoranthene derivative 1 with the yield of 89%.
Example 2:
preparation of fluoranthene derivative 2:
49mg of 2a were dissolved in 6ml of N-methylpyrrolidone and stirred at 180 ℃ for 4 hours. After the reaction is finished, the organic solvent in the reaction system is removed, and the crude product is separated and purified by column chromatography to obtain 42mg of fluoranthene derivative 2 with the yield of 85%.
Example 3:
preparation of fluoranthene derivative 3:
72mg of 3a were dissolved in 7ml of N, N-dimethylformamide and stirred at 160 ℃ for 7 hours. After the reaction is finished, the organic solvent in the reaction system is removed, and the crude product is separated and purified by column chromatography to obtain 60mg of fluoranthene derivative 3 with the yield of 83 percent.
Example 4:
preparation of fluoranthene derivative 4:
148mg of 4a were dissolved in mesitylene and stirred at 165 ℃ for 6 hours. After the reaction is finished, the organic solvent in the reaction system is removed, and the crude product is separated and purified by column chromatography to obtain 120mg of fluoranthene derivative 4 with the yield of 81%.
Example 5:
preparation of fluoranthene derivative 5:
51mg of 5a was dissolved in 6mL of ethylene glycol and stirred at 200 ℃ for 3 hours. After the reaction is finished, the organic solvent in the reaction system is removed, and the crude product is separated and purified by column chromatography to obtain 40mg of fluoranthene derivative 5 with the yield of 78%.
Example 6:
preparation of fluoranthene derivative 6:
270mg of 6a was dissolved in 18mL of cyclohexanone and stirred at 155 ℃ for 8 hours. After the reaction is finished, the organic solvent in the reaction system is removed, and the crude product is separated and purified by column chromatography to obtain 130mg of fluoranthene derivative 6 with the yield of 48%.
Example 7:
preparation of fluoranthene derivative 7:
303mg of 7a were dissolved in 20mL of o-dichlorobenzene and stirred at 175 ℃ for 4 hours. After the reaction is finished, the organic solvent in the reaction system is removed, and the crude product is separated and purified by column chromatography to obtain 200mg of fluoranthene derivative 7 with the yield of 66%.
Example 8:
preparation of fluoranthene derivative 8:
56mg of 8a was dissolved in 6mL of diphenyl ether and stirred at 240 ℃ for 2 hours. After the reaction was completed, the organic solvent in the reaction system was removed, and the crude product was purified by column chromatography to obtain 39mg of fluoranthene derivative 8 with a yield of 69%.
Example 9:
preparation of fluoranthene derivative 9:
105mg of 9a was dissolved in 10mL of nitrobenzene and stirred at 200 ℃ for 3 hours. After the reaction is finished, the organic solvent in the reaction system is removed, and the crude product is separated and purified by column chromatography to obtain 80mg of fluoranthene derivative 9 with the yield of 76%.
Example 10:
preparation of fluoranthene derivative 10:
80mg of 10a was dissolved in 8mL of sulfolane and stirred at 285 ℃ for 1.5 hours. After the reaction is finished, the organic solvent in the reaction system is removed, and the crude product is separated and purified by column chromatography to obtain 48mg of fluoranthene derivative 10 with the yield of 60%.
Example 11:
preparation of fluoranthene derivative 11:
60mg of 11a was dissolved in 7mL of diethylene glycol dimethyl ether and stirred at 180 ℃ for 5 hours. After the reaction is finished, the organic solvent in the reaction system is removed, and the crude product is separated and purified by column chromatography to obtain 33mg of fluoranthene derivative 11 with the yield of 55%.
Example 12:
preparation of fluoranthene derivative 12:
61mg of 12a was dissolved in 7mL of pyridine, and stirred at 120 ℃ for 10 hours. After the reaction was completed, the organic solvent in the reaction system was removed, and the crude product was purified by column chromatography to obtain 43mg of fluoranthene derivative 12 with a yield of 71%.
Example 13:
preparation of fluoranthene derivative 13:
43mg of 13a was dissolved in 6mL of m-xylene and stirred at 140 ℃ for 7 hours. After the reaction was completed, the organic solvent in the reaction system was removed, and the crude product was purified by column chromatography to obtain 20mg of fluoranthene derivative 13 with a yield of 47%.
Example 14:
preparation of fluoranthene derivative 14:
61mg of 14a was dissolved in 7mL of cyclohexanol and stirred at 165 ℃ for 5.5 hours. After the reaction was completed, the organic solvent in the reaction system was removed, and the crude product was purified by column chromatography to obtain 41mg of fluoranthene derivative 14 with a yield of 67%.
Example 15:
preparation of fluoranthene derivative 15:
69mg of 15a was dissolved in 7mL of o-cresol and stirred at 195 ℃ for 3 hours. After the reaction, the organic solvent in the reaction system was removed, and the crude product was purified by column chromatography to obtain 49mg of fluoranthene derivative 15 with a yield of 71%.
Example 16:
preparation of fluoranthene derivative 16:
124mg of 16a was dissolved in 12mL of formamide and stirred at 220 ℃ for 2 hours. After the reaction, the organic solvent in the reaction system was removed, and the crude product was purified by column chromatography to obtain 82mg of fluoranthene derivative 16 with a yield of 66%.
Example 17:
preparation of fluoranthene derivative 17:
573mg of 17a are dissolved in 23mL of quinoline and stirred at 240 ℃ for 1 hour. After the reaction is finished, the organic solvent in the reaction system is removed, and the crude product is separated and purified by column chromatography to obtain 430mg of fluoranthene derivative 17 with the yield of 75%.
Example 18:
preparation of fluoranthene derivative 18:
50mg of 18a was dissolved in 7mL of N-methylformamide and stirred at 185 ℃ for 4 hours. After the reaction is finished, the organic solvent in the reaction system is removed, and the crude product is separated and purified by column chromatography to obtain 30mg of fluoranthene derivative 18 with the yield of 61%.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A preparation method of fluoranthene derivatives is characterized by comprising the following steps: taking 1-thiophene-8-alkynyl naphthalene compounds as raw materials, and carrying out cyclization reaction in an organic solvent to obtain the fluoranthene derivative.
2. A method of producing a fluoranthene derivative according to claim 1, characterized in that the method specifically is: dissolving the 1-thiophene-8-alkynyl naphthalene compound in an organic solvent, carrying out cyclization reaction, and then separating and purifying to obtain the fluoranthene derivative.
3. A method for producing a fluoranthene derivative according to claim 2, characterized in that the structural formula of the 1-thiophen-8-alkynylnaphthalene compound is as follows:
wherein R is1To R10Is a substituent.
4. A method of producing a fluoranthene derivative according to claim 3, wherein R is1To R10Each independently selected from the group consisting of: hydrogen, -CnH2n+1、-CnH2nOH、-CnHnOCmH2m+1、-F、-Cl、-Br、-I、-NH2、-NHCnH2n+1、-N(CnH2n+1)2、-N+(CnH2n+1)3、-NHCOCnH2n+1、-OH、-OCnH2n+1、-OCOCnH2n+1、-OCnHnOCmH2m+1、-COOH、-COOCmH2m+1、-CnH2nCOOH、-CnH2nCOOCmH2m+1、-NO2、-CF3、-CCl3、-CN、-CHO、-SO3H、
Wherein n is 1-10, and m is 1-10.
5. A method of producing a fluoranthene derivative according to claim 4, wherein R is11To R19Each independently selected from the group consisting of: hydrogen, -CnH2n+1、-CnH2nOH、-CnHnOCmH2m+1、-F、-Cl、-Br、-I、-NH2、-NHCnH2n+1、-N(CnH2n+1)2、-N+(CnH2n+1)3、-NHCOCnH2n+1、-OH、-OCnH2n+1、-OCOCnH2n+1、-OCnHnOCmH2m+1、-COOH、-COOCmH2m+1、-CnH2nCOOH、-CnH2nCOOCmH2m+1、-NO2、-CF3、-CCl3、-CN、-CHO、-SO3H。
6. A method of producing a fluoranthene derivative according to claim 2, characterized in that the boiling point of the organic solvent is higher than 100 ℃.
7. A method of producing a fluoranthene derivative according to claim 6, wherein the organic solvent includes one or more of o-xylene, N-methylpyrrolidone, N-dimethylformamide, mesitylene, ethylene glycol, cyclohexanone, o-dichlorobenzene, diphenyl ether, nitrobenzene, sulfolane, diethylene glycol dimethyl ether, pyridine, m-xylene, cyclohexanol, o-cresol, formamide, quinoline, and N-methylformamide.
8. A method of producing a fluoranthene derivative according to claim 2, characterized in that the reaction temperature is higher than 100 ℃ and the reaction time is longer than 1 hour during the cyclization reaction.
9. A method for preparing a fluoranthene derivative according to claim 8, wherein the reaction temperature is 120-285 ℃ and the reaction time is 1.5-10 hours during the cyclization reaction.
10. The method according to claim 2, wherein the separation and purification process is: the organic solvent is removed to obtain a crude product, which is then subjected to column chromatography.
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