CN115806541A - 5,5' -bis (1, 3, 4-trifluorotetra (alkoxy) triphenylen-2-yl) dithiophene discotic liquid crystals and synthesis thereof - Google Patents
5,5' -bis (1, 3, 4-trifluorotetra (alkoxy) triphenylen-2-yl) dithiophene discotic liquid crystals and synthesis thereof Download PDFInfo
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- 125000003545 alkoxy group Chemical group 0.000 title claims abstract description 19
- -1 triphenylen-2-yl Chemical group 0.000 title claims abstract description 18
- 239000004985 Discotic Liquid Crystal Substance Substances 0.000 title claims abstract description 13
- 230000015572 biosynthetic process Effects 0.000 title claims description 6
- 238000003786 synthesis reaction Methods 0.000 title claims description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 27
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 5
- 238000001308 synthesis method Methods 0.000 claims abstract 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical class ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 238000004440 column chromatography Methods 0.000 claims description 3
- 239000003480 eluent Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 239000012074 organic phase Substances 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 238000001953 recrystallisation Methods 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 239000004065 semiconductor Substances 0.000 claims description 2
- 229960001701 chloroform Drugs 0.000 claims 2
- 239000012266 salt solution Substances 0.000 claims 1
- 229920006395 saturated elastomer Chemical class 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 4
- OHZAHWOAMVVGEL-UHFFFAOYSA-N 2,2'-bithiophene Chemical compound C1=CSC(C=2SC=CC=2)=C1 OHZAHWOAMVVGEL-UHFFFAOYSA-N 0.000 abstract description 3
- 150000002642 lithium compounds Chemical class 0.000 abstract description 3
- 125000003118 aryl group Chemical group 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 150000002900 organolithium compounds Chemical class 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Abstract
The invention relates to a synthesis method and application research of a 5,5 '-bis (1, 3, 4-trifluoro-6, 7,10, 11-tetra- (alkoxy) benzophenanthrene-2-yl) -2,2' -bithiophene discotic liquid crystal compound. It is characterized by having a general formula (I). Wherein R is C 6 ‑C 10 The alkoxy chain of (A) above, the compound of formula (I) can self-assemble into a columnar liquid crystal mesophase in a certain temperature range. The invention also provides a preparation method of the 5,5 '-bis (1, 3, 4-trifluoro-6, 7,10, 11-tetra- (alkoxy) benzophenanthrene-2-yl) -2,2' -dithiophene discotic liquid crystal compound, and the synthetic route is simple and rapid and the conditions are mild. The compound in the general formula (I) can be obtained by reacting bithiophene with n-butyllithium at low temperature to generate an organic lithium compound, and then reacting the organic lithium compound with a tetrafluorotriphenylene derivative compound at 50 ℃.
Description
Technical Field
The invention relates to synthesis and application of 5,5 '-bis (1, 3, 4-trifluoro-6, 7,10, 11-tetra- (alkoxy) benzophenanthrene-2-yl) -2,2' -dithiophene discotic liquid crystal compounds.
Background
Research shows that introducing electron-withdrawing group onto the aromatic nucleus of disc-shaped molecule can improve the Pi-Pi stacking interaction to result in the stability of columnar intermediate phase, and compared with other substituent, the fluorine atom on the aromatic ring has volume near hydrogen atom, and has high electronegativity, so as to reduce Pi electron cloud density on the aromatic ring, strengthen Pi-Pi interaction and stabilize columnar liquid crystal phase.
Disclosure of Invention
Based on the design, 5 '-bis (1, 3, 4-trifluoro-6, 7,10, 11-tetra- (alkoxy) triphenylene-2-yl) -2,2' -dithiophene discotic liquid crystal compounds are synthesized, in the synthesis, bithiophene firstly reacts with n-butyl lithium to generate an organic lithium compound, and then tetrafluorotriphenylene is added to react to obtain the fluorine-containing triphenylene dithiophene derivatives.
In addition, it is also necessary to provide a method for producing 5,5 '-bis (1, 3, 4-trifluoro-6, 7,10, 11-tetra- (alkoxy) triphenylen-2-yl) -2,2' -bithiophene discotic liquid crystal compounds.
A5, 5 '-bis (1, 3, 4-trifluoro-6, 7,10, 11-tetra- (alkoxy) triphenylen-2-yl) -2,2' -dithiophene discotic liquid crystal compound characterized by having a structure represented by the general formula (I):
wherein R is C n H 2n+1 And n represents a number of carbon atoms of 6 to 10.
A5, 5 '-bis (1, 3, 4-trifluoro-6, 7,10, 11-tetra- (alkoxy) triphenylen-2-yl) -2,2' -bithiophene of the general formula (I) according to claim 1, characterized by comprising the following steps.
Step one Synthesis of 5,5 '-bis (1, 3, 4-trifluoro-6, 7,10, 11-tetra- (alkoxy) triphenylen-2-yl) -2,2' -bithiophene (I):
adding compound (a) into a reaction tube, injecting solvent THF under the protection of argon gas, stirring and dissolving, transferring the reaction tube into a cold trap at-78 deg.C, adding four times of compound (a)nBuLi, reacting in cold trap for 0.5 hr, reacting at room temperature for 4 hr, adding tetrafluorobenzophenanthrene derivative (b) twice the amount of compound (a) at low temperature, slowly heating to 50 deg.C, reacting for 12 hr, extracting with chloroform and saturated saline solution, and extracting organic phase with anhydrous MgSO 4 Drying, filtering, spin-drying, purification by column chromatography on silica gel (eluent: V chloroform: V petroleum ether = 1), recrystallization from a mixed solvent of toluene and petroleum ether to give a green solid (I).
Wherein R is C n H 2n+1 And n represents a carbon number of 6 to 10.
The preparation method of the 5,5 '-bis (1, 3, 4-trifluoro-6, 7,10, 11-tetra- (alkoxy) triphenylene-2-yl) -2,2' -dithiophene discotic liquid crystal compound has a simple and rapid synthetic route, the compound is prepared by reacting bithiophene with n-butyllithium to generate an organolithium compound, then reacting the organolithium compound with tetrafluorobenzophenanthrene derivatives to obtain a compound (I), connecting a plurality of aryl groups together in an aryl nucleophilic substitution mode, and under the regulation action of a plurality of peripheral alkoxy flexible chains, the compound can be self-assembled into a stable columnar liquid crystal intermediate phase within a certain temperature range, and has good application value in the aspect of liquid crystal semiconductor materials.
Drawings
FIG. 1R obtained in example 1 is C 6 H 13 Nuclear magnetic hydrogen spectrum of intermediate b.
FIG. 2 the R obtained in example 1 is C 6 H 13 Nuclear magnetic hydrogen spectrum of general formula (I).
FIG. 3 the R obtained in example 1 is C 6 H 13 Nuclear magnetic fluorine spectra of general formula (I).
FIG. 4 the R obtained in example 1 is C 6 H 13 DSC profile of the general formula (I).
FIG. 5 shows that R obtained in example 1 is C 6 H 13 A polarizing weave pattern of the general formula (I).
Detailed Description
The following examples are given by way of illustration of the present invention and it should be emphasized that the examples given below are given by way of illustration only and are not intended to limit the scope of the invention.
Example 1.
This example provides the preparation of a compound of formula (I) wherein R is C 6 H 13 The preparation reaction is as follows:
adding compound (a) (47 mg) into a 50mL reaction tube, adding THF (10 mL) as solvent under the protection of argon gas, stirring to dissolve, transferring the reaction tube into a cold trap at-78 deg.C, and adding compound (a) in an amount four times that of the compoundnBuLi (0.45 mL), reacting in a cold trap for 0.5h, reacting at room temperature for 4h, adding tetrafluorotriphenylene (400 mg) twice as much as compound (a), slowly raising to room temperature, reacting for 12h, extracting with chloroform and saturated saline water, and extracting the organic phase with anhydrous MgSO 4 Drying, filtration, spin-drying, purification by column chromatography on silica gel (eluent: V chloroform: V petroleum ether = 1), recrystallization from a mixed solvent of toluene and petroleum ether to give a green solid (I) (96 mg, yield: 22%).
Nuclear magnetic hydrogen spectrum 1 H NMR(CDCl 3 , TMS, 400 MHz), δ: 8.33 (d, J = 5.5 Hz, 2H, ArH), 8.28 (d, J = 5.4 Hz, 2H, ArH), 7.61 (d, J = 12 Hz, 6H, ArH), 7.33 (s, 2H, ArH), 4.22-4.14 (m, 16H, OCH 2 ), 1.98-1.91 (m, 16H, CH 2 ), 1.58 (t, J = 12 Hz, 18H, CH 2 ), 1.42 (s, 30H, CH 2 ), 0.96 (d, J = 6.0 Hz, 24H, CH 3 )。
Claims (5)
1. A discotic liquid crystal compound 5,5 '-bis (1, 3, 4-trifluoro-6, 7,10, 11-tetra- (alkoxy) triphenylen-2-yl) -2,2' -dithiophene (I) is characterized by having a structure shown in a general formula (I).
2. A5, 5 '-bis (1, 3, 4-trifluoro-6, 7,10, 11-tetra- (alkoxy) triphenylen-2-yl) -2,2' -dithiophene discotic liquid crystal compound (I) according to claim 1, wherein R is-C n H 2n+1 And n represents a carbon number of 6 to 10.
3. A process for preparing 5,5 '-bis (1, 3, 4-trifluoro-6, 7,10, 11-tetra- (alkoxy) triphenylen-2-yl) -2,2' -bithiophene of general formula (I) according to claim 1 by:
step one Synthesis of 5,5 '-bis (1, 3, 4-trifluoro-6, 7,10, 11-tetra- (alkoxy) triphenylen-2-yl) -2,2' -bithiophene (I):
adding compound (a) into a reaction tube, injecting solvent THF under the protection of argon gas, stirring and dissolving, transferring the reaction tube into a cold trap at-78 deg.C, adding four times of compound (a)nBuLi, reacting in cold trap for 0.5 hr, reacting at room temperature for 4 hr, adding the same amount of tetrafluorobenzophenanthrene derivative as compound (a) at low temperature, slowly heating to 50 deg.C, reacting for 12 hr, extracting with trichloromethane and saturated salt solution, and extracting organic phase with anhydrous MgSO 4 Drying, filtering, spin-drying, purification by column chromatography on silica gel (eluent: V chloroform: V petroleum ether = 1), recrystallization from a mixed solvent of toluene and petroleum ether to give a green solid (I).
4. A chemical structure and a synthesis method of a 5,5 '-bis (1, 3, 4-trifluoro-6, 7,10, 11-tetra- (alkoxy) triphenylene-2-yl) -2,2' -bithiophene discotic liquid crystal compound in a general formula (I) as shown in claim 1.
5. Use of 5,5 '-bis (1, 3, 4-trifluoro-6, 7,10, 11-tetra- (alkoxy) triphenylen-2-yl) -2,2' -dithiophene discotic liquid crystal compounds of the general formula (i) according to claim 1 as organic liquid crystal semiconductor materials.
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Citations (6)
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|---|---|---|---|---|
| DE19907063A1 (en) * | 1999-02-19 | 2000-08-24 | Clariant Gmbh | New fluorinated thiophene derivatives useful as components of liquid crystal mixtures for use in switching and display devices |
| US20090169921A1 (en) * | 2008-01-02 | 2009-07-02 | Chien-Hong Cheng | Synthesis of triphenylene and pyrene based aromatics and their application in oleds |
| KR20120129733A (en) * | 2011-05-20 | 2012-11-28 | (주)씨에스엘쏠라 | Organic light compound and organic light device using the same |
| CN104387398A (en) * | 2014-10-14 | 2015-03-04 | 石家庄诚志永华显示材料有限公司 | Liquid crystal compounds, and preparation method and application thereof |
| CN111362783A (en) * | 2018-12-26 | 2020-07-03 | 四川师范大学 | Tetratetrafluoro tetraalkoxy benzophenanthrene discotic liquid crystal compound and preparation method thereof |
| CN112409323A (en) * | 2020-11-20 | 2021-02-26 | 四川师范大学 | Preparation method and mesomorphism of graphene-like conjugated heterocyclic benzophenanthrene discotic liquid crystal |
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2021
- 2021-09-15 CN CN202111082334.4A patent/CN115806541A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19907063A1 (en) * | 1999-02-19 | 2000-08-24 | Clariant Gmbh | New fluorinated thiophene derivatives useful as components of liquid crystal mixtures for use in switching and display devices |
| US20090169921A1 (en) * | 2008-01-02 | 2009-07-02 | Chien-Hong Cheng | Synthesis of triphenylene and pyrene based aromatics and their application in oleds |
| KR20120129733A (en) * | 2011-05-20 | 2012-11-28 | (주)씨에스엘쏠라 | Organic light compound and organic light device using the same |
| CN104387398A (en) * | 2014-10-14 | 2015-03-04 | 石家庄诚志永华显示材料有限公司 | Liquid crystal compounds, and preparation method and application thereof |
| CN111362783A (en) * | 2018-12-26 | 2020-07-03 | 四川师范大学 | Tetratetrafluoro tetraalkoxy benzophenanthrene discotic liquid crystal compound and preparation method thereof |
| CN112409323A (en) * | 2020-11-20 | 2021-02-26 | 四川师范大学 | Preparation method and mesomorphism of graphene-like conjugated heterocyclic benzophenanthrene discotic liquid crystal |
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