CN110229051A - The synthesis of nano-graphene San Ben Bing Pi disc liquid-crystal compounds and photism - Google Patents
The synthesis of nano-graphene San Ben Bing Pi disc liquid-crystal compounds and photism Download PDFInfo
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Abstract
The present invention relates to be based on nano-graphene San Ben Bing Pi disc liquid-crystal compounds and 2, the substitution of bis- (3', 4,4', 5- tetra- (alkoxy)-[1,1'- the biphenyl] -2- base) naphthalenes of 6-.It is characterized in that having structure shown in general formula (I), (II).Wherein R is C6~C16Alkyl chain, above-mentioned general formula (I) compound is self-assembled into hexagonal columnar liquid crystal interphase in wider temperature range and at room temperature.The present invention also provides nano-graphene San Ben Bing Pi disc liquid-crystal compounds and 2, the preparation method of bis- (3', 4,4', 5- tetra- (alkoxy)-[1,1'- biphenyl] -2- base) the naphthalenes substitutions of 6-.Compound can be by compound in general formula (II) in FeCl in general formula (I)3Internal oxidation cyclization obtains.
Description
Technical field
The present invention relates to the synthesis of nano-graphene San Ben Bing Pi disc liquid-crystal compounds and photisms.
Background technique
Currently, discotic mesogenic, which is that one kind is unique, to be had significant conductance and photoconductive property, can pass through self assembly
Form the material of nano-micro structure.It is a kind of discotic molecule with pi bond conjugation, due to its one-dimensional intermolecular column heap
Product, can be self-assembled into column structure, especially hexagonal columnar phase.This for one-dimensional charge carrier system provide it is unique can
It can property.Therefore, application of the discotic mesogenic in fields such as molectronics, photoelectricity, photoconduction, photovoltaic and el light emitting devices
In, discotic mesogenic is considered as promising organic semiconductor.However, accumulation is due to opening up in the column of high molecule liquid crystal interphase
Flutterring defect, heat fluctuation and molecule diffusion etc. can also affect to the parameter of electric charge carrier flow efficiency.These attributes
Improvement need to reach by various methods such as highly stable sensor material, suitable temperature and ideal operating environments
Desired molecular order mode makes reaction facilitate processing, so as to improve the performance of charge migration.
Summary of the invention
Nano-graphene San Ben Bing Pi disc liquid-crystal compounds have been synthesized based on this design.Such compound is main in synthesis
If being coupled by Suzuki.Mainly by the bromo- 3' of 2-, (the alkoxy) -1,1'- biphenyl of 4,4', 5- tetra- and 2,6- are bis-
(4,4,5,5- tetramethyl -1,3,2- dioxaborolane -2- base) naphthalene carries out cyclization after Suzuki coupling occurs.Obtain target
Compound, research has shown that such compound can be formed in wider temperature range at room temperature stable hexagonal columnar phase and
It is a kind of good room temperature liquid crystal.Such compound has certain luminescent properties simultaneously.
In addition, there is a need to provide the preparation method of nano-graphene San Ben Bing Pi disc liquid-crystal compounds.
A kind of nano-graphene San Ben Bing Pi disc liquid-crystal compounds, it is characterised in that there is structure shown in general formula (I):
(Ⅰ)
Wherein R is CnH2n+1, n indicate carbon atom number be 6-16 integer.
A kind of general formula as claimed in claim 2 (II) 2,6- bis- (3', 4,4', 5- tetra- (alkoxy)-[1,1'- biphenyl]
- 2- base) it is characterized by comprising following steps for naphthalene.
Step 1: intermediate is the preparation of b compound:
(a) (b)
Wherein, R is CnH2n+1,N indicates that carbon atom number is 6-16.
Using formula a compound represented as raw material, it is claimed in 250ml round-bottomed flask with bromine simple substance with the molar ratio of 1:1
It takes, 150ml chloroform is added, puts on constant pressure funnel, chloroform (20ml) and bromine simple substance is charged with, by round bottom
Flask is put into the environment of room temperature, and the solution control in constant pressure funnel tracked, instead in 2 seconds every drops every 15 minutes contact plates
It should finish, sodium hydrogensulfite is added and terminates reaction, filtering passes through silica gel column chromatography (eluant, eluent: V methylene chloride: V stone with being spin-dried for
Oily ether=1:2), with ethyl alcohol, re-crystallizing in ethyl acetate, product b is obtained, wherein R1For-CnH2n+1, n expression carbon atom number is 6-16's
Integer.
Step 2: the conjunction of bis- (4,4,5,5- tetramethyl -1,3,2- dioxaborolane -2- base) naphthalenes of intermediate 2,6-
At:
(c)
Wherein, R is CnH2n+1,N indicates that carbon atom number is 6-16.
With molar ratio 2,6- dibromine naphthalene in 200 ml reaction flasks: bis (pinacolato) diboron: CH3COOK: PdCl2(dppf) =
Weigh and be added Isosorbide-5-Nitrae-dioxane 60 ml at 1: 3: 0.1: 6, under protection of argon gas, reacts for 24 hours, is cooled at 90 DEG C
Room temperature is extracted with methylene chloride, the anhydrous MgSO of organic phase4It dries, filters, is spin-dried for, pass through silica gel column chromatography (elution
Agent: V methylene chloride: V petroleum ether=1:3), it is recrystallized with ethyl acetate and ethyl alcohol, obtains white crystal (c).
Step 3: the synthesis of 2,6- bis- (3', 4,4', 5- tetra- (alkoxy)-[1,1'- biphenyl] -2- base) naphthalenes: it is made
Preparation Method are as follows:
(c) (b) (II)
Wherein, R is CnH2n+1,N indicates that carbon atom number is 6-16.
With molar ratio b: c:K in 50 ml reaction tubes2CO3 : Pd(PPh3)4 Weigh at=2: 1: 30: 0.2
And mixed solvent water (3 ml)/THF (10 ml) is added and reacts 48 h at 70 DEG C under protection of argon gas, it is cooled to room temperature, uses
Methylene chloride is extracted, the anhydrous MgSO of organic phase4It dries, filters, is spin-dried for, pass through silica gel column chromatography (eluant, eluent: V dichloro
Methane: V petroleum ether=1:3), it is recrystallized with ethyl acetate and ethyl alcohol, obtains white solid (II).
The preparation of nano-graphene San Ben Bing Pi disc liquid-crystal compounds (I):
(II) (I)
Wherein, R is CnH2n+1,N indicates that carbon atom number is 6-16.
With compound (II) in the round-bottomed flask of 100ml: FeCl3 =1: 6 molar ratio weighs, and is added three
Chloromethanes (60ml), nitromethane (5ml) react at room temperature, track and react every 15min contact plate, and first is added in end of reaction
Alcohol terminates reaction, is extracted with chloroform, MgSO4It dries, filters, is spin-dried for, pass through silica gel column chromatography (eluant, eluent: V bis-
Chloromethanes: V petroleum ether=1:2), it is recrystallized with ethyl acetate and ethyl alcohol, obtains white solid (I).
The preparation method of above-mentioned nano-graphene San Ben Bing Pi disc liquid-crystal compounds, synthetic route is simple and fast and item
Part is mild, such compound is with bromo tetraalkoxy biphenyl and 2,6- bis- (4,4,5,5- tetramethyls -1,3,2- dioxo bora rings
Pentane -2- base) naphthalene carries out cyclization after Suzuki coupling occurs, multiple aryl connected together by way of condensed, in periphery
A plurality of alkoxy flexible chain adjustment effect under, stabilization can be self-assembled into wider temperature range and at room temperature
Hexagonal columnar liquid crystal interphase, have good application value in terms of liquid crystal material.
Detailed description of the invention
Obtained R is C in Fig. 1 embodiment 18H17Intermediate b nucleus magnetic hydrogen spectrum.
The nucleus magnetic hydrogen spectrum of obtained intermediate c in Fig. 2 embodiment 2.
Obtained R is C in Fig. 3 embodiment 38H17When general formula (II) nucleus magnetic hydrogen spectrum.
Obtained R is C in Fig. 4 embodiment 48H17When general formula (I) nucleus magnetic hydrogen spectrum.
Obtained R is C in Fig. 5 embodiment 510H21Intermediate b nucleus magnetic hydrogen spectrum.
Obtained R is C in Fig. 6 embodiment 610H21When general formula (II) nucleus magnetic hydrogen spectrum.
Obtained R is C in Fig. 7 embodiment 710H21When general formula (I) nucleus magnetic hydrogen spectrum.
Obtained R is C in Fig. 8 embodiment 812H25Intermediate b nucleus magnetic hydrogen spectrum.
Obtained R is C in Fig. 9 embodiment 912H25When general formula (II) nucleus magnetic hydrogen spectrum.
Obtained R is C in Figure 10 embodiment 1012H25When general formula (I) nucleus magnetic hydrogen spectrum.
Obtained R is C in Figure 11 embodiment 48H17When general formula (I) Polarized Texture figure.
Obtained R is C in Figure 12 embodiment 710H21When general formula (I) Polarized Texture figure.
Obtained R is C in Figure 13 embodiment 1012H25When general formula (I) Polarized Texture figure.
Obtained R is C in Figure 14 embodiment 48H17When general formula (I) DSC curve figure.
Obtained R is C in Figure 15 embodiment 710H21When general formula (I) DSC curve figure.
Obtained R is C in Figure 16 embodiment 1012H25When general formula (I) DSC curve figure.
Figure 17 is the UV-visible absorption spectrum that compound is tested in embodiment；Wherein D2 is obtained in embodiment 4
R is C8H17When general formula (I) ultraviolet-ray visible absorbing figure.
Figure 17 is the UV-visible absorption spectrum that compound is tested in embodiment；Wherein D4 is obtained in embodiment 4
R is C10H21When general formula (I) ultraviolet-ray visible absorbing figure.
Figure 17 is the UV-visible absorption spectrum that compound is tested in embodiment；Wherein D6 is obtained in embodiment 7
R is C12H25When general formula (I) ultraviolet-ray visible absorbing figure.
Figure 18 is the fluorescence emission spectrogram of compound that compound is tested in embodiment；Wherein D2 is that obtained R is in embodiment 4
C8H17When general formula (I) fluorescence emission spectrogram of compound.
Figure 18 is the fluorescence emission spectrogram of compound that compound is tested in embodiment；Wherein D4 is that obtained R is in embodiment 7
C10H21When general formula (I) fluorescence emission spectrogram of compound.
Figure 18 is the fluorescence emission spectrogram of compound that compound is tested in embodiment；Wherein D6 is that obtained R is in embodiment 10
C12H25When general formula (I) fluorescence emission spectrogram of compound.
Specific embodiment
Examples given below is to specific descriptions of the invention, it is necessary to it is emphasised that example given below is
Of the invention is further described, rather than a kind of limitation to protection scope of the present invention.Those skilled in the art's root
In the actual implementation process according to foregoing invention content, the improvement or adjustment that are related to are if not change on essential meaning, still
So belong to the scope of protection of the present invention.
Synthetic method used in each case study on implementation is the prior art below:
T. Yasuda, T. Shimizu, F. Liu, G. Ungar, T. Kato, J. Am. Chem. Soc. 2011,
133, 13437–13444。
Embodiment 1.
Compound provided in this embodiment is the preparation of the compound intermediate b of general formula (II), and wherein R is C8H17,It is made
It is standby to react as follows:
(b).
With 3,3', 4,4'- tetra- (octane oxygroup) -1,1'- biphenyl (1.50 g, 2.25 mmol) for raw material, by itself and bromine
(0.16 g, 2.2 mmol) simple substance is weighed in 250 ml round-bottomed flasks with 1:1 molar ratio, and 150 ml chloroforms, set is added
Upper constant pressure funnel is charged with chloroform (20 ml) and bromine simple substance, round bottom flask is entered in the environment of room temperature,
Solution control in constant pressure funnel tracked, sodium hydrogensulfite is added in end of reaction in 2 seconds every drops every 15 minutes contact plates
Reaction is terminated, filtering is crossed silica gel column chromatography (eluant, eluent: V methylene chloride: V petroleum ether=1:2), with ethyl alcohol, acetic acid second with being spin-dried for
Ester recrystallization, obtains product b, (1.68g, 90 % of yield).
Nucleus magnetic hydrogen spectrum1H NMR(CDCl3, TMS, 400 MHz), δ:7.10(s, 1H, ArH), 6.94(d, J =
1.2 Hz, 1H, ArH),6.89(s, 1H, ArH), 6.89(d, J = 1.6 Hz, 1H, ArH), 6.84(s, 1H,
ArH),4.02(t, J = 7.6 Hz, 8H, OCH2), 1.78-1.86(m, 8H, CH2), 1.27-1.57(m, 40H,
CH2), 0.89(t, J = 4.8Hz, 12H, CH3)。
Embodiment 2.
Intermediate 2, the preparation of bis- (3', 4,4', 5- tetra- (methane oxygroup)-[1,1'- the biphenyl] -2- base) naphthalenes (c) of 6-:
(c)。
With molar ratio 2 in 200 ml reaction flasks, 6- dibromine naphthalene (2 g, 6.90 mmol): bis (pinacolato) diboron (5.3 g,
20.98 mmol) : CH3COOK (4.10 g, 42.0 mmol): PdCl2(dppf) (0.6 g, 0.70 mmol)=1: 3:6:
0.1 weighs, and 60 ml of Isosorbide-5-Nitrae-dioxane is added, and under protection of argon gas, 24 h is reacted at 90 DEG C, are cooled to room temperature, with two
Chloromethanes is extracted, the anhydrous MgSO of organic phase4It dries, filters, is spin-dried for, pass through silica gel column chromatography (eluant, eluent: V dichloromethane
Alkane: V petroleum ether=1:3), it is recrystallized with ethyl acetate and ethyl alcohol, obtains white crystal (c) (2 g, 77 % of yield).
Nucleus magnetic hydrogen spectrum1H NMR(CDCl3, TMS, 400 MHz), 1H NMR(CDCl3, TMS, 400 MHz), δ:
8.35 (s, 2H, ArH),7.86 (d, J = 12.0 Hz, 2H, ArH), 7.85 (d, J = 12.0 Hz, 2H,
ArH),1.30 (s,24H, CH3). 。
Embodiment 3.
Compound provided in this embodiment is the preparation of the compound of general formula (II), and wherein R is C8H17,It prepares reaction such as
Under:
(II).
With molar ratio b (0.74 g, 0.98 mmol): c (0.15 g, 0.39 mmol) in 50 ml reaction tubes:
K2CO3(1.63 g, 11.80 mmol): Pd (PPh3)4 (0.09 g, 0.08 mmol)=2.5: 1: 30: 0.2 is weighed
And mixed solvent water (3 ml)/THF (10 ml) is added and reacts 48 h at 70 DEG C under protection of argon gas, it is cooled to room temperature, uses
Methylene chloride is extracted, the anhydrous MgSO of organic phase4It dries, filters, is spin-dried for, pass through silica gel column chromatography (eluant, eluent: V dichloro
Methane: V petroleum ether=1:3), it is recrystallized with ethyl acetate and ethyl alcohol, obtains white solid (II) (0.43 g, yield 75
%).
Nucleus magnetic hydrogen spectrum1H NMR(CDCl3, TMS, 400 MHz), δ: 7.65 (s, 2H, ArH), 7.49 (d, J
=8.0 Hz, 2H, ArH), 7.07 (d, J =12.0 Hz, 2H, ArH), 7.00 (d, J =12.0 Hz, 2H,
ArH),6.71 (s, 4H, ArH), 6.62 (s, 2H, ArH), 4.06-4.10 (m , 8H, OCH2), 3.93 (t,J = 8.0 Hz, 4H, OCH2), 3.57 (t, J = 8.0Hz , 4H, OCH2), 1.85-1.90 (m, 8H, CH2),
1,77 (t, J =8.0 Hz, 4H, CH2), 1.47-1.52(m, 14H, CH2), 1.20-1.41 (m, 70H,
CH2), 0.87(t, J = 8 Hz, 24H, CH3) 。
Embodiment 4.
Compound provided in this embodiment is the preparation of general formula (I) compound, and wherein R is C8H17, it is as follows to prepare reaction:
(I).
With compound (II) (0.30 g, 0.21 mmol): FeCl in the round-bottomed flask of 100ml3 (0.20 g,
1.23 mmol)=1: 6 molar ratio weighs, and chloroform (60 ml) is added, nitromethane (5 ml), at room temperature
Reaction is tracked every 15 min contact plates and is reacted, and end of reaction is added methanol and terminates reaction, extracted with chloroform,
MgSO4Dry, filter, be spin-dried for, by silica gel column chromatography (eluant, eluent: V methylene chloride: V petroleum ether=1:2), with ethyl acetate and
Ethyl alcohol is recrystallized, and light yellow solid (I) (0.25g, 83 % of yield) is obtained.
Nucleus magnetic hydrogen spectrum1H NMR(CDCl3, TMS, 400 MHz), δ: 8.99 (d, J = 12.0 Hz, 2H,
ArH), 8.45 (d, J = 8.0 Hz, 2H, ArH), 8.39(s, 2H, ArH), 8.10 (s, 2H, ArH),
7.96 (s, 2H, ArH), 7.94 (s, 2H, ArH), 4.27-4.34(m, 12H, OCH2), 4.17 (t, J =
8.0 Hz, 4H, OCH2), 1.91-2.00 (m, 16H, CH2), 1.54-1.61 (m, 16H, CH2), 1.27-1.43
(m, 64H, CH2), 0.91 (t, J = 8.0 Hz, 24H, CH3) 。
Embodiment 5.
Compound provided in this embodiment is the preparation of the compound intermediate b of general formula (II), and wherein R is C10H21,It is made
It is standby to react as follows:
(b).
With 3,3', 4,4'- tetra- (ten alkoxies) -1,1'- biphenyl (0.63 mg, 0.80 mmol) for raw material, by itself and bromine
(0.11 g, 0.80 mmol) simple substance is weighed in 250 ml round-bottomed flasks with 1:1 molar ratio, and 150 ml chloroforms, set is added
Upper constant pressure funnel is charged with chloroform (20 ml) and bromine simple substance, round bottom flask is entered in the environment of room temperature,
Solution control in constant pressure funnel tracked, sodium hydrogensulfite is added in end of reaction in 2 seconds every drops every 15 minutes contact plates
Reaction is terminated, filtering is crossed silica gel column chromatography (eluant, eluent: V methylene chloride: V petroleum ether=1:2), with ethyl alcohol, acetic acid second with being spin-dried for
Ester recrystallization, obtains product b, (0.65 g, 94 % of yield).
Nucleus magnetic hydrogen spectrum1H NMR(CDCl3, TMS, 400 MHz), 1H NMR(CDCl3, TMS, 400 MHz), δ:
7.10(s, 1H, ArH), 6.95(s, 1H, ArH), 6.89(d, J = 4 Hz, 2H, ArH),6.84(s, 1H,
ArH), 4.02(t, J = 2.8 Hz, 8H, OCH2), 1.76-1.87(m, 8H, CH2), 1.27-1.57(m, 56H,
CH2), 0.88(t, J = 2.8Hz, 12H, CH3) 。
Embodiment 6.
Compound provided in this embodiment is the preparation of the compound of general formula (II), and wherein R is C10H21,It prepares reaction such as
Under:
(II).
With molar ratio b (0.52 g, 0.66 mmol): c (0.10 g, 0.26 mmol) in 50 ml reaction tubes:
K2CO3(1.09 g, 7.89 mmol): Pd (PPh3)4 (0.06 g, 0.05 mmol)=2: 1: 30: 0.2 is weighed simultaneously
Mixed solvent water (3 ml)/THF (10 ml) is added to react 48 h at 70 DEG C under protection of argon gas, be cooled to room temperature, with two
Chloromethanes is extracted, the anhydrous MgSO of organic phase4It dries, filters, is spin-dried for, pass through silica gel column chromatography (eluant, eluent: V dichloromethane
Alkane: V petroleum ether=1:3), it is recrystallized with ethyl acetate and ethyl alcohol, obtains white solid (II) (0.243 g, yield 55
%).
Nucleus magnetic hydrogen spectrum1H NMR(CDCl3, TMS, 400 MHz), 1H NMR(CDCl3, TMS, 400 MHz), δ:
7.64 (s, 2H, ArH), 7.49 (d, J =8.0 Hz, 2H, ArH), 7.06 (d, J =8.0 Hz, 2H,
ArH), 6.99 (d, J =8.0 Hz, 4H, ArH),6.71 (s, 4H, ArH), 6.62 (s, 2H, ArH),
4.08-4.10 (m , 8H, OCH2), 3.91 (t, J = 8.0 Hz, 4H, OCH2), 3.57 (t, J = 8.0Hz ,
4H, OCH2), 1.83-1.90 (m, 10H, CH2), 1,74-1.79 (m, 6H, CH2), 1.46-1.51(m, 12H,
CH2), 1.22-1.28 (m, 100H, CH2), 0.87(t, J = 4 Hz, 24H, CH3) 。
Embodiment 7.
Compound provided in this embodiment is the preparation of general formula (I) compound, and wherein R is C10H21, preparation reaction is such as
Under:
(I).
With compound (II) (0.15 g, 0.09 mmol): FeCl in the round-bottomed flask of 100ml3 (0.09 g,
0.50 mmol)=1: 6 molar ratio weighs, and chloroform (60 ml) is added, nitromethane (5 ml), at room temperature
Reaction is tracked every 15 min contact plates and is reacted, and end of reaction is added methanol and terminates reaction, extracted with chloroform,
MgSO4Dry, filter, be spin-dried for, by silica gel column chromatography (eluant, eluent: V methylene chloride: V petroleum ether=1:2), with ethyl acetate and
Ethyl alcohol is recrystallized, and light yellow solid (I) (0.120g, 81 % of yield) is obtained.
Nucleus magnetic hydrogen spectrum1H NMR(CDCl3, TMS, 400 MHz), δ: 9.00 (d, J = 8.0 Hz, 2H, ArH),
8.47 (d, J = 12.0 Hz, 2H, ArH), 8.41(s, 2H, ArH), 8.12 (s, 2H, ArH), 7.98 (s,
2H, ArH), 7.96 (s, 2H,ArH), 4.29-4.36(m, 12H, OCH2), 4.19 (t, J = 8.0 Hz, 4H,
OCH2), 1.92-2.02 (m, 16H, CH2), 1.61-1.66 (m, 12H, CH2), 1.55 (t, J = 8.0 Hz,
4H, CH2), 1.26-1.46 (m, 96H, CH2), 0.91 (t, J = 8.0 Hz, 24H, CH3) 。
Embodiment 8.
Compound provided in this embodiment is the preparation of the intermediate b of compound in general formula (II), wherein
R1For C12H25:
(b).
With 3,3', 4,4'- tetra- (dodecyloxy) -1,1'- biphenyl (3.29 g, 3.70 mmol) be raw material, by its with
Bromine (0.59 g, 3.70mmol) simple substance is weighed in 250ml round-bottomed flask with 1:1 molar ratio, and 150ml chloroform, set is added
Upper constant pressure funnel is charged with chloroform (20ml) and bromine simple substance, round bottom flask is entered in the environment of room temperature, permanent
It presses the solution control in dropping funel in 2 seconds every drops, is tracked every 15 minutes contact plates, it is whole that sodium hydrogensulfite is added in end of reaction
It only reacts, filters, with being spin-dried for, cross silica gel column chromatography (eluant, eluent: V methylene chloride: V petroleum ether=1:2), with ethyl alcohol, ethyl acetate
Recrystallization, obtains product b, (3.5g, 97 % of yield).
Nucleus magnetic hydrogen spectrum1H NMR(CDCl3, TMS, 400 MHz), δ: 7.10(s, 1H, ArH), 6.94 (s, 1H,
ArH), 6.89 (s, 2H, ArH), 6.84 (s, 1H, ArH), 3.96-4.04 (m, 8H, OCH2), 1.80—
1.84 (m, 8H, CH2), 1.42-1,47 (m, 8H, CH2), 1.26-1.32 (m, 64H, CH2), 0.88 (t, J
=7.2Hz, 12H, CH3) 。
Embodiment 9.
Compound provided in this embodiment be general formula (II) compound wherein R be C12H25,It is as follows that it prepares reaction:
(Ⅱ)。
With molar ratio b (0.32 g, 0.33 mmol): c (0.05 g, 0.13 mmol) in 50 ml reaction tubes:
K2CO3(0.57 g, 3.96 mmol): Pd (PPh3)4 (0.04 g, 0.26 mmol)=2: 1: 30: 0.2 is weighed simultaneously
Mixed solvent water (3 ml)/THF (10 ml) is added to react 48 h at 70 DEG C under protection of argon gas, be cooled to room temperature, with two
Chloromethanes is extracted, the anhydrous MgSO of organic phase4Dry, filter, be spin-dried for, by silica gel column chromatography (eluant, eluent: V methylene chloride:
V petroleum ether=1:3), it is recrystallized with ethyl acetate and ethyl alcohol, obtains white solid (II), (0.124 g, 49 % of yield).
Nucleus magnetic hydrogen spectrum1H NMR(CDCl3, TMS, 400 MHz), 1H NMR(CDCl3, TMS, 400 MHz), δ:
7.60 (s, 2H, ArH), 7.49 (d, J =8.0 Hz, 2H, ArH), 7.06 (d, J =8.0 Hz, 2H,
ArH), 6.99 (d, J =8.0 Hz, 4H, ArH),6.70 (s, 4H, ArH), 6.61 (s, 2H, ArH), 4.
06-4.10 (m , 8H, OCH2), 3.93 (t, J = 8.0 Hz, 4H, OCH2), 3.55 (t, J = 8.0Hz ,
4H, OCH2), 1.83-1.88 (m, 10H, CH2), 1,74-1.79 (m, 6H, CH2), 1.49 (t, J = 8.0
Hz 12H, CH2), 1.21-1.39 (m, 132H, CH2), 0.88 (t, J = 4 Hz, 24H, CH3) 。
Embodiment 10.
Compound provided in this embodiment is the compound of general formula (I), wherein R1For C12H25,It is as follows that it prepares reaction:
(I).
With compound (II) (0.13g, 0.07 mmol): FeCl in the round-bottomed flask of 100ml3(0.07g, 0.41
Mmol molar ratio)=1: 6 weighs, and chloroform (60ml) is added, and nitromethane (5ml) reacts at room temperature, often
It tracks and reacts every 15min contact plate, end of reaction is added methanol and terminates reaction, extracted with chloroform, MgSO4It is dry,
Filtering, is spin-dried for, and by silica gel column chromatography (eluant, eluent: V methylene chloride: V petroleum ether=1:2), carries out weight with ethyl acetate and ethyl alcohol
Crystallization, obtains light yellow solid (I), (0.110g, 84 % of yield).
Nucleus magnetic hydrogen spectrum1H NMR(CDCl3, TMS, 400 MHz), 1H NMR(CDCl3, TMS, 400 MHz), δ:
8.98 (d, J = 8.0 Hz, 2H, ArH), 8.45 (d, J = 12.0 Hz 2H, ArH), 8.38(s, 2H,
ArH), 8.09 (s, 2H, ArH), 7.96 (s, 2H, ArH), 7.94 (s, 2H,ArH), 4.28-4.32(m,
12H, OCH2), 4.18 (t, J = 8.0 Hz, 4H, OCH2), 1.94-2.00 (m, 16H, CH2), 1.63 (t,J = 8.0 Hz, 4H, CH2), 1.51-1.57 (m, 12H, CH2), 1.22-1.42 (m, 128H, CH2), 0.88
(t, J = 8.0 Hz, 24H, CH3)。
Claims (8)
1. nano-graphene San Ben Bing Pi disc liquid-crystal compounds, it is characterised in that have structure shown in general formula (I):
(I).
2. one kind 2, bis- (3', 4,4', 5- tetra- (alkoxy)-[1,1'- the biphenyl] -2- base) naphthalenes of 6-, it is characterised in that have logical
Structure shown in formula (II):
(II).
3. nano-graphene San Ben Bing Pi disc liquid-crystal compounds (I) shown according to claim 1 and claim 2(II) shown in
Bis- (3', 4,4', 5- tetra- (alkoxy)-[1,1'- biphenyl] -2- base) naphthalenes containing 2,6-, it is shown it is characterized in that the R be -
CnH2n+1, n indicate carbon atom number be 6-16 integer.
4. a kind of general formula as claimed in claim 2 (II) 2,6- bis- (3', 4,4', 5- tetra- (alkoxy)-[1,1'- biphenyl]-
2- yl) naphthalene, preparation method are as follows:
Step 1: the preparation of intermediate b (2- bromo- 3', 4,4', 5- tetra- (alkoxy) -1,1'- biphenyl):
(a) (b)
With 3,3', 4,4'- tetra- (alkoxy) -1,1'- biphenyl (a) compound represented of formula for raw material, by it with bromine simple substance with 1:1
Molar ratio weighs in 250ml round-bottomed flask, and 150ml chloroform is added, puts on constant pressure funnel, is charged with trichlorine
Methane (20ml) and bromine simple substance, round bottom flask is entered in the environment of room temperature, and the solution control in constant pressure funnel is every at 2 seconds
Drop tracked, end of reaction every 15 minutes contact plates, and sodium hydrogensulfite is added and terminates reaction, filtering, with being spin-dried for, crossed silica gel column layer
It analyses (eluant, eluent: V methylene chloride: V petroleum ether=1:2), with ethyl alcohol, re-crystallizing in ethyl acetate, obtains product b, wherein R1For-
CnH2n+1, n indicate carbon atom number be 6-16 integer；
Step 2: the synthesis of bis- (4,4,5,5- tetramethyl -1,3,2- dioxaborolane -2- base) naphthalenes of intermediate 2,6-:
(c)
With molar ratio 2,6- dibromine naphthalene in 200 ml reaction flasks: bis (pinacolato) diboron: CH3COOK: PdCl2(dppf)= 1 : 3 :
Weigh and be added Isosorbide-5-Nitrae-dioxane 60 ml at 0.1: 6, under protection of argon gas, reacts for 24 hours at 90 DEG C, is cooled to room temperature, uses
Methylene chloride is extracted, the anhydrous MgSO of organic phase4It dries, filters, is spin-dried for, pass through silica gel column chromatography (eluant, eluent: V dichloro
Methane: V petroleum ether=1:3), it is recrystallized with ethyl acetate and ethyl alcohol, obtains white crystal (c).
5. step 3: the synthesis of 2,6- bis- (3', 4,4', 5- tetra- (alkoxy)-[1,1'- biphenyl] -2- base) naphthalenes:
(c) (b) (Ⅱ)
With molar ratio b: c:K in 50 ml reaction tubes2CO3 : Pd(PPh3)4 Weigh and add at=2: 1: 30: 0.2
Enter mixed solvent water (3 ml)/THF (10 ml) to react 48 h at 70 DEG C under protection of argon gas, be cooled to room temperature, use dichloro
Methane is extracted, the anhydrous MgSO of organic phase4Dry, filter, be spin-dried for, by silica gel column chromatography (eluant, eluent: V methylene chloride:
V petroleum ether=1:3), it is recrystallized with ethyl acetate and ethyl alcohol, obtains white solid (II).
6. nano-graphene San Ben Bing Pi disc liquid-crystal compounds, preparation method in general formula shown in a kind of claim 1 (I)
Are as follows:
(II) (I)
With compound (II) in the round-bottomed flask of 100ml: FeCl3 =1: 6 molar ratio weighs, and three chloromethanes are added
Alkane (60ml), nitromethane (5ml) react at room temperature, track and react every 15min contact plate, and it is whole that methanol is added in end of reaction
It only reacts, is extracted with chloroform, MgSO4It dries, filters, is spin-dried for, pass through silica gel column chromatography (eluant, eluent: V dichloromethane
Alkane: V petroleum ether=1:2), it is recrystallized with ethyl acetate and ethyl alcohol, obtains light yellow solid (I).
7. nano-graphene San Ben Bing Pi disc liquid-crystal compounds are as organic lcd in general formula described in a kind of claim 1 (I)
The purposes of semiconductor material.
8. nano-graphene San Ben Bing Pi disc liquid-crystal compounds are as organic photic in general formula described in a kind of claim 1 (I)
The purposes of luminescent material.
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Cited By (3)
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| CN115477574A (en) * | 2021-06-16 | 2022-12-16 | 四川师范大学 | Synthesis of hexafluorobenzotetraphenyl and tetrafluorotetraphenyl discotic liquid crystal semiconductors |
| CN115820264A (en) * | 2021-09-16 | 2023-03-21 | 四川师范大学 | Synthesis and performance research of bis-benzophenanthrene-pyrene discotic liquid crystal compound |
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| CN115820264A (en) * | 2021-09-16 | 2023-03-21 | 四川师范大学 | Synthesis and performance research of bis-benzophenanthrene-pyrene discotic liquid crystal compound |
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