CN110041344A - Plate-like ion liquid-crystal compounds containing thienopyridine and preparation method thereof - Google Patents
Plate-like ion liquid-crystal compounds containing thienopyridine and preparation method thereof Download PDFInfo
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- C07—ORGANIC CHEMISTRY
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- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
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- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
- C09K19/3491—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having sulfur as hetero atom
- C09K19/3497—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having sulfur as hetero atom the heterocyclic ring containing sulfur and nitrogen atoms
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- C09K2211/1018—Heterocyclic compounds
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Abstract
The invention discloses a kind of ion liquid-crystal compounds of plate-like containing thienopyridine.Such compound has liquid crystal property, and liquid crystal temperature range is wider, and clearing point temperature is high, and good thermal stability has potential application in liquid crystal material field.Such compound has luminescent properties and gelling performance, can be used as optical material.The invention also discloses the preparation methods of such ion liquid-crystal compounds of plate-like containing thienopyridine.
Description
Technical field
The present invention relates to a kind of plate-like ion liquid-crystal compounds and preparation method thereof containing thienopyridine.
Background technique
With the development of liquid crystal and ionic liquid, there is a kind of novel functional material-ion liquid crystal, due to its combination
The property of ionic liquid and liquid crystal and in ion-conductive material, photoelectric material, there is potential application prospect in the fields such as liquid crystal material.
The research of N- substituent group in ion liquid crystal is concentrated mainly on alkyl chain, and with hydrophobic Polyfluoroalkyl chain and there is parent
The research of aqueous chain is relatively fewer.Thiophene unit is a kind of electron rich unit, and there is excellent photoelectric property and charge to transmit
Ability, the research that thiophene unit is introduced into ion liquid crystal are also relatively fewer.It would therefore be highly desirable to both by MOLECULE DESIGN, synthesis
With thiophene unit, while also with the ion liquid crystal molecule of Polyfluoroalkyl chain and hydrophilic chain, it is desirable to which it is in ionic conduction
Material, photoelectric material, the fields such as liquid crystal material are applied.
Summary of the invention
Goal of the invention of the invention is just to provide a kind of plate-like ion liquid crystal material and luminescent material: containing thienopyridine
Columnar phase is presented in plate-like ion liquid-crystal compounds, such compound in wider temperature range, and has good optical property.
The present invention realizes its first goal of the invention, and used technical solution is: a kind of plate-like containing thienopyridine
Ion liquid-crystal compounds, which is characterized in that the compound has the structure of following general formula I, R=C in formula of InH2n+1, n=
9,10,11, R1=CnH2n+1, n=8,9,10；R=CnH2n+1, n=9,10,11, R1=CnH2nCmF2m+1, n=2,3,4, m=5,6,7 or R=
CnH2n+1, n=9,10,11, R1For, X be inorganic anion or organic anion, such as it is inorganic
Anion: F-, Cl-, Br-, I-, NO3 -, BF4 -, PF6 -, SO4 -, H2PO4 -, ClO4 -, SCN-, AsF6 -, organic anion:
In its formula of I, inorganic anion is preferred: Br-, I-, NO3 -, BF4 -, PF6 -, organic anion is preferred:
。
Compared with prior art, general formula of the invention is the beneficial of the ion liquid-crystal compounds of plate-like containing thienopyridine of I
Effect is:
One, altered chemical structure multiplicity can pass through the length, the length of N- substituent group and type, yin-yang of the peripheral alkoxy chain of adjusting
The type and size of ion adjust liquid crystal property, to adapt to the demand of different function；
Two, the ion liquid-crystal compounds of plate-like containing thienopyridine has wider liquid crystal range.It is demonstrated experimentally that substance of the invention
In the compound that has at normal temperature be in mesomorphic state, be a kind of novel liquid crystal material that liquid crystalline phase is presented in wider temperature range
Material, has a good application prospect；
Three, the ion of plate-like containing thienopyridine liquid-crystal compounds shows good gelation and photism, can be applied to shine
Material.
Second goal of the invention of the invention is to provide the ion of plate-like containing thienopyridine that above-mentioned general formula is I and liquid-crystalizes
Close the preparation method of object.
The present invention realizes its second goal of the invention, and used technical solution is: the above-mentioned general formula of one kind is I containing thiophene
The preparation method of pheno and pyridine plate-like ion liquid-crystal compounds, the steps include:
A, 2,3- dibromo thiophene [3,2-c] pyridine is prepared
(1) with 4,5,6,7- thiophane [3,2-c] pyridine hydrochloride and bromine simple substance occur in a solvent bromo-reaction obtain it is double
Neutralization reaction occurs under alkaline condition and obtains 2,3- bis- bromo- 4 for bromination product, (2) double bromination products, and 5,6,7- thiophanes are simultaneously
[3,2-c] pyridine, (3) 2,3- bis- bromo- 4, simultaneously [3,2-c] pyridine and manganese dioxide stir back 5,6,7- thiophanes in a solvent
Stream occurs aromatization reaction and obtains compound 2,3- dibromo thiophene [3,2-c] pyridine；
B, Suzuki coupling reaction
By 2,3- dibromo thiophene [3,2-c] pyridine of 1 molar part, the aryl-boric acid ester of 2.5 molar parts, 10 molar parts carbonic acid
Potassium, 0.25 molar part four (triphenylphosphines) close palladium be added to THF and H2In the mixed solution of O, under nitrogen protection, 70oC
It being stirred to react 36-48 hours, is extracted with dichloromethane after reaction, organic phase is dried, filtered with anhydrous magnesium sulfate, concentration,
Residue silica gel column chromatography separating-purifying after concentration, obtains compound as white solid；
C, intramolecular arene oxidizing coupling reaction
The 1 molar part coupled product dissolution that B is walked in methylene chloride, is slowly added to be dissolved in 3 in nitromethane and rubs
The liquor ferri trichloridi of your part after dripping, is stirred at room temperature reaction 2-3 hours, is tracked to instead in reaction process with thin-layer chromatography
Object fully reacting to be answered, methanol quenching reaction is then added, with saturated common salt water washing, adjusts pH to alkalinity, methylene chloride extracts,
Organic phase is dried, filtered with anhydrous magnesium sulfate, concentration, the residue silica gel column chromatography separating-purifying after concentration, and recrystallization obtains
To compound as white solid be product；
D, alkylated reaction
The coupled product of 1 molar part is dissolved in toluene, the halogenated hydrocarbons of 3-5 molar part, 80-120 is addedoC is stirred to react 24-
36 hours, after reaction, toluene is boiled off, by residue silica gel column chromatography separating-purifying, vacuum drying, what is obtained is faint yellow
Solid chemical compound is alkylate；
E, ion-exchange reactions (metathesis reaction)
In methylene chloride by the alkylate dissolution of D 1 molar part walked, the inorganic salts of 3-5 molar part are added or have
Machine salt is stirred to react 3-5 hours at room temperature, after reaction, is washed with distilled water organic phase 3 times, and anhydrous magnesium sulfate is dry, mistake
Filter, concentration, the residue silica gel column chromatography separating-purifying after concentration, vacuum drying, obtained faint yellow solid compound is i.e.
For the ion liquid-crystal compounds of plate-like containing thienopyridine.
This preparation method yield is higher, post-processing is simple.
The present invention is described in further detail With reference to embodiment.
Detailed description of the invention
Nuclear magnetic resonance spectroscopy of the Fig. 1 by obtaining compound in embodiment 1.
Polarized Texture figure of the Fig. 2 by obtaining compound in embodiment 1.
Fig. 3 is schemed by the DSC for obtaining compound in embodiment 1.
Nuclear magnetic resonance spectroscopy of the Fig. 4 by obtaining compound in embodiment 2.
Polarized Texture figure of the Fig. 5 by obtaining compound in embodiment 2.
Fig. 6 is schemed by the DSC for obtaining compound in embodiment 2.
Nuclear magnetic resonance spectroscopy of the Fig. 7 by obtaining compound in embodiment 3.
Polarized Texture figure of the Fig. 8 by obtaining compound in embodiment 3.
Fig. 9 is schemed by the DSC for obtaining compound in embodiment 3.
Polarized Texture figure of the Figure 10 by obtaining compound in embodiment 4.
Figure 11 is schemed by the DSC for obtaining compound in embodiment 4.
Figure 12 forms gel figure by obtaining compound in embodiment 4 in acetonitrile.
Nuclear magnetic resonance spectroscopy of the Figure 13 by obtaining compound in embodiment 5.
Polarized Texture figure of the Figure 14 by obtaining compound in embodiment 5.
Figure 15 is schemed by the DSC for obtaining compound in embodiment 5.
Nuclear magnetic resonance spectroscopy of the Figure 16 by obtaining compound in embodiment 6.
Polarized Texture figure of the Figure 17 by obtaining compound in embodiment 6.
Figure 18 is schemed by the DSC for obtaining compound in embodiment 6.
Figure 19 is by obtaining fluorescent emission figure of the compound in film in embodiment 1-6.
Specific embodiment
Embodiment 1
A kind of specific embodiment of the invention is: a kind of plate-like ion liquid-crystal compounds containing thienopyridine, has following
The structure of general formula I, wherein R=C10H21, R1=C8H17, X is inorganic anion bromide ion:
R=C in general formula I10H21, R1=C8H17, X is the ion LCD compound of plate-like containing thienopyridine of inorganic anion bromide ion
Object to prepare reaction equation as follows:
Specific preparation step is as follows:
A, 2,3- dibromo thiophene [3,2-c] pyridine is prepared
4,5,6,7- thiophane [3,2-c] pyridine hydrochlorides (1.0 g, 5.69 mmol) are added to the round bottom for being furnished with stirrer
It in flask, is added chloroform (50 mL), then the bromine simple substance (1.8 of chloroform (15 mL) will be dissolved in constant pressure funnel
G, 11.4 mmol) it is added drop-wise in round-bottomed flask, after dripping, agitating and heating (80oC) reaction overnight, after reaction, is filtered
Solid and sodium hydroxide (228 mg, 5.69 mmol) are added to methylene chloride (20 mL) and water (10 mL) by the solid of generation
In the mixed solvent.After being stirred to react 2 hours, liquid separation is extracted by methylene chloride, and vacuum distillation is except after solvent；It is added prior
Activated manganese dioxide (2.5 g, 27.5 mmol), and toluene (5 mL) is added and makees solvent, in heating (130oC it) stirs
It is reacted 12-24 hours under conditions of reflux, determines that raw material fully reacting then terminates reaction with thin-layered chromatography；After reaction,
Manganese dioxide is filtered with funnel, collects organic phase, vacuum distillation obtains residue after removing solvent, passes through silica gel column chromatography
(solvent: methylene chloride: ethyl acetate=10:1) purifying, obtains compound 2,3- dibromo thiophene [3,2-c] pyridine (965 mg),
Yield 57%；
B, Suzuki coupling reaction
By 2,3- dibromo thiophene [3,2-c] pyridine of 1 molar part, the aryl boric acid of 2.5 molar parts, 10 molar parts potassium carbonate,
Four (triphenylphosphines) of 0.25 molar part close palladium and are added to THF and H2In the mixed solution of O, under nitrogen protection, 70oC stirring
Reaction 48 hours, is extracted with dichloromethane after reaction, and organic phase is dried, filtered with anhydrous magnesium sulfate, concentration, after concentration
Residue is purified by silica gel column chromatography (solvent: methylene chloride: ethyl acetate=10:1), obtains compound as white solid, is produced
Rate 75%；
C, intramolecular arene oxidizing coupling reaction
The 1 molar part coupled product dissolution that B is walked in methylene chloride, is slowly added to be dissolved in 3 in nitromethane and rubs
The liquor ferri trichloridi of your part after dripping, is stirred at room temperature reaction 3 hours, tracks to reaction with thin-layer chromatography in reaction process
Then methanol quenching reaction is added in object fully reacting, with saturated common salt water washing, adjust pH to alkalinity, methylene chloride extraction has
Machine is mutually dried, filtered with anhydrous magnesium sulfate, and concentration, the residue after concentration is purified by silica gel column chromatography methylene chloride, second
Acetoacetic ester/dehydrated alcohol recrystallization, obtained compound as white solid is product, yield 76%；
D, alkylated reaction
The C step product of 1 molar part is dissolved in toluene, the 1- bromooctane of 5 molar parts of addition, 120oC is stirred to react 24 hours,
After reaction, toluene is boiled off, residue is used and is purified by silica gel column chromatography (solvent: methylene chloride: ethyl alcohol=10:1),
Ethyl acetate/ethyl alcohol recrystallization, vacuum drying, obtained faint yellow solid compound is R=C10H21, R1=C8H17, X is nothing
The ion liquid-crystal compounds of plate-like containing thienopyridine of machine anion bromide ion, yield 83%；
It is below statistics indicate that, using R=C in product made from the above the example method really general formula I10H21, R1=C8H17, X is
The ion liquid-crystal compounds of plate-like containing thienopyridine of inorganic anion bromide ion,1H NMR (CDCl3, TMS, 400MHz)
δ: 9.94 (s, 1H, ArH), 8.88 (d, J = 5.2 Hz, 1H, ArH), 8.77 (d, J = 5.2 Hz, 1H,
ArH), 7.84 (s, 1H, ArH), 7.51 (s, 1H, ArH), 7.45 (s, 1H, ArH), 6.70 (s, 1H,
ArH), 5.29 (t, J = 6.0 Hz, 2H, NCH2), 4.55 (t, J = 6.4 Hz, 2H, ArOCH2), 4.20
(t, J = 6.4 Hz, 2H, ArOCH2), 3.96 (t, J = 6.8 Hz, 2H, ArOCH2), 1.92-2.04 (m,
10H, CH2), 1.77-1.82 (m, 2H, CH2), 1.54-1.64 (m, 8H, CH2), 1.29-1.45 (m, 50H,
CH2), 1.16-1.23 (m, 6H, CH2), 0.86-0.91 (m, 12H, CH3), 0.81 (t, J = 6.8 Hz,
3H, CH3).
Compound studies its mesomorphism by differential scanning calorimetry, petrographic microscope in the embodiment, finds it in liquid crystal model
There is typical liquid crystal columnar phase texture in enclosing, the optical property of compound is studied, it is found that the compound has fluorescence hair
Penetrate phenomenon.
Embodiment 2
A kind of specific embodiment of the invention is: a kind of plate-like ion liquid-crystal compounds containing thienopyridine, has following
The structure of general formula I, wherein R=C10H21, R1=C8H17, X is the double trifluoromethanesulfonimide radical ions of organic anion:
Wherein R=C in general formula I10H21, R1=C8H17, X is the double trifluoromethanesulfonimide radical ions of organic anion containing thiophene
And pyridine plate-like ion liquid-crystal compounds to prepare reaction equation as follows:
Specific preparation step is as follows:
A, 2,3- dibromo thiophene [3,2-c] pyridine is prepared
4,5,6,7- thiophane [3,2-c] pyridine hydrochlorides (1.0 g, 5.69 mmol) are added to the round bottom for being furnished with stirrer
It in flask, is added chloroform (50 mL), then the bromine simple substance (1.8 of chloroform (15 mL) will be dissolved in constant pressure funnel
G, 11.4 mmol) it is added drop-wise in round-bottomed flask, after dripping, agitating and heating (80oC) reaction overnight, after reaction, is filtered
Solid and sodium hydroxide (228 mg, 5.69 mmol) are added to methylene chloride (20 mL) and water (10 mL) by the solid of generation
In the mixed solvent.After being stirred to react 2 hours, liquid separation is extracted by methylene chloride, and vacuum distillation is except after solvent；It is added prior
Activated manganese dioxide (2.5 g, 27.5 mmol), and toluene (5 mL) is added and makees solvent, in heating (130oC it) stirs
It is reacted 12-24 hours under conditions of reflux, determines that raw material fully reacting then terminates reaction with thin-layered chromatography；After reaction,
Manganese dioxide is filtered with funnel, collects organic phase, vacuum distillation obtains residue after removing solvent, passes through silica gel column chromatography
(solvent: methylene chloride: ethyl acetate=10:1) purifying, obtains compound 2,3- dibromo thiophene [3,2-c] pyridine (965 mg),
Yield 57%；
B, Suzuki coupling reaction
By 2,3- dibromo thiophene [3,2-c] pyridine of 1 molar part, the aryl boric acid of 2.5 molar parts, 10 molar parts potassium carbonate,
Four (triphenylphosphines) of 0.25 molar part close palladium and are added to THF and H2In the mixed solution of O, under nitrogen protection, 70oC stirring
Reaction 36 hours, is extracted with dichloromethane after reaction, and organic phase is dried, filtered with anhydrous magnesium sulfate, concentration, after concentration
Residue is purified by silica gel column chromatography (solvent: methylene chloride: ethyl acetate=10:1), obtains compound as white solid, is produced
Rate 70%；
C, intramolecular arene oxidizing coupling reaction
The 1 molar part coupled product dissolution that B is walked in methylene chloride, is slowly added to be dissolved in 3 in nitromethane and rubs
The liquor ferri trichloridi of your part after dripping, is stirred at room temperature reaction 3 hours, tracks to reaction with thin-layer chromatography in reaction process
Then methanol quenching reaction is added in object fully reacting, with saturated common salt water washing, adjust pH to alkalinity, methylene chloride extraction has
Machine is mutually dried, filtered with anhydrous magnesium sulfate, and concentration, the residue after concentration is purified by silica gel column chromatography methylene chloride, second
Acetoacetic ester/dehydrated alcohol recrystallization, obtained compound as white solid is product, yield 76%；
D, alkylated reaction
The C step product of 1 molar part is dissolved in toluene, the 1- bromooctane of 3 molar parts of addition, 80oC is stirred to react 36 hours, instead
After answering, toluene is boiled off, residue is used and is purified by silica gel column chromatography (solvent: methylene chloride: ethyl alcohol=10:1), second
Acetoacetic ester/ethyl alcohol recrystallization, vacuum drying, obtained faint yellow solid compound is alkylate, yield 80%；
E, ion-exchange reactions (metathesis reaction)
In methylene chloride by the alkylate dissolution of D 1 molar part walked, double fluoroform sulphurs of 5 molar parts are added
Imide li is stirred to react 5 hours at room temperature, after reaction, is washed with distilled water organic phase 3 times, and anhydrous magnesium sulfate is dry,
Filtering, concentration, the residue after concentration are purified by silica gel column chromatography (solvent: methylene chloride: ethyl acetate=1:1), acetic acid
Ethyl ester/ethyl alcohol recrystallization, vacuum drying, obtained faint yellow solid compound is R=C in general formula I10H21, R1=C8H17, X is
The ion liquid-crystal compounds of plate-like containing thienopyridine of the double trifluoromethanesulfonimide radical ions of organic anion, yield 78%；
It is below statistics indicate that, using R=C in product made from the above the example method really general formula I10H21, R1=C8H17, X is
The ion liquid-crystal compounds of plate-like containing thienopyridine of the double trifluoromethanesulfonimide radical ions of organic anion,1H NMR
(CDCl3, TMS, 400MHz) δ: 9.36 (s, 1H, ArH), 8.48 (s, 1H, ArH), 8.37 (s, 1H,
ArH), 7.67 (s, 1H, ArH), 7.60 (s, 1H, ArH), 7.45 (s, 1H, ArH), 6.80 (s, 1H,
ArH), 4.85 (s, 2H, NCH2), 4.30 (s, 2H, ArOCH2), 4.14-4.19 (m, 4H, ArOCH2),
3.92 (s, 2H, ArOCH2), 2.09-2.11 (m, 2H, CH2), 1.88-1.99 (m, 8H, CH2), 1.54-
1.61 (m, 8H, CH2), 1.26-1.44 (m, 58H, CH2), 0.84-0.91 (m, 15H, CH3).
Compound studies its mesomorphism by differential scanning calorimetry, petrographic microscope in the embodiment, finds it in liquid crystal model
There is typical liquid crystal columnar phase texture in enclosing, the optical property of compound is studied, it is found that the compound has fluorescence hair
Penetrate phenomenon.
Embodiment 3
A kind of specific embodiment of the invention is: a kind of plate-like ion liquid-crystal compounds containing thienopyridine, has following
The structure of general formula I, wherein R=C10H21, R1=C3H6C6F13, X is inorganic anion bromide ion:
R=C in general formula I10H21, R1=C3H6C6F13, X is that the ion of plate-like containing thienopyridine of inorganic anion bromide ion liquid-crystalizes
Close object to prepare reaction equation as follows:
THF is tetrahydrofuran in reaction equation；Toluene is toluene, and specific preparation step is as follows:
A, 2,3- dibromo thiophene [3,2-c] pyridine is prepared
4,5,6,7- thiophane [3,2-c] pyridine hydrochlorides (1.0 g, 5.69 mmol) are added to the round bottom for being furnished with stirrer
It in flask, is added chloroform (50 mL), then the bromine simple substance (1.8 of chloroform (15 mL) will be dissolved in constant pressure funnel
G, 11.4 mmol) it is added drop-wise in round-bottomed flask, after dripping, agitating and heating (80oC) reaction overnight, after reaction, is filtered
Solid and sodium hydroxide (228 mg, 5.69 mmol) are added to methylene chloride (20 mL) and water (10 mL) by the solid of generation
In the mixed solvent.After being stirred to react 2 hours, liquid separation is extracted by methylene chloride, and vacuum distillation is except after solvent；It is added prior
Activated manganese dioxide (2.5 g, 27.5 mmol), and toluene (5 mL) is added and makees solvent, in heating (130oC it) stirs
It is reacted 12-24 hours under conditions of reflux, determines that raw material fully reacting then terminates reaction with thin-layered chromatography；After reaction,
Manganese dioxide is filtered with funnel, collects organic phase, vacuum distillation obtains residue after removing solvent, passes through silica gel column chromatography
(solvent: methylene chloride: ethyl acetate=10:1) purifying, obtains compound 2,3- dibromo thiophene [3,2-c] pyridine (965 mg),
Yield 57%；
B, Suzuki coupling reaction
By 2,3- dibromo thiophene [3,2-c] pyridine of 1 molar part, the aryl boric acid of 2.5 molar parts, 10 molar parts potassium carbonate,
Four (triphenylphosphines) of 0.25 molar part close palladium and are added to THF and H2In the mixed solution of O, under nitrogen protection, 70oC stirring
Reaction 48 hours, is extracted with dichloromethane after reaction, and organic phase is dried, filtered with anhydrous magnesium sulfate, concentration, after concentration
Residue is purified by silica gel column chromatography (solvent: methylene chloride: ethyl acetate=10:1), obtains compound as white solid, is produced
Rate 75%；
C, intramolecular arene oxidizing coupling reaction
The 1 molar part coupled product dissolution that B is walked in methylene chloride, is slowly added to be dissolved in 3 in nitromethane and rubs
The liquor ferri trichloridi of your part after dripping, is stirred at room temperature reaction 3 hours, tracks to reaction with thin-layer chromatography in reaction process
Then methanol quenching reaction is added in object fully reacting, with saturated common salt water washing, adjust pH to alkalinity, methylene chloride extraction has
Machine is mutually dried, filtered with anhydrous magnesium sulfate, and concentration, the residue after concentration is purified by silica gel column chromatography methylene chloride, second
Acetoacetic ester/dehydrated alcohol recrystallization, obtained compound as white solid is product, yield 76%；
D, alkylated reaction
The C step product of 1 molar part is dissolved in toluene, the 9- bromo- 1,1,1,2,2,3,3,4,4,5,5,6,6- of 5 molar parts is added
Ten trifluoro nonanes, 120oC is stirred to react 24 hours, after reaction, boils off toluene, and residue is passed through silica gel column chromatography
(solvent: methylene chloride: ethyl alcohol=10:1) purifying, ethyl acetate/ethyl alcohol recrystallization, vacuum drying, obtained faint yellow solid
Closing object is R=C10H21, R1=C3H6C6F13, X is the ion LCD compound of plate-like containing thienopyridine of inorganic anion bromide ion
Object, yield 81%；
It is below statistics indicate that, using R=C in product made from the above the example method really general formula I10H21, R1=C3H6C6F13, X
For the ion liquid-crystal compounds of plate-like containing thienopyridine of inorganic anion bromide ion,1H NMR (CDCl3, TMS, 400MHz)
δ: 10.12 (s, 1H, ArH), 8.69-8.97 (m, 2H, ArH), 7.76 (s, 1H, ArH), 7.45 (s,
2H, ArH), 6.68 (s, 1H, ArH), 5.52 (s, 2H, NCH2), 4.52 (s, 2H, ArOCH2), 4.15-
4.20 (m, 4H, ArOCH2), 4.00 (s, 2H, ArOCH2), 2.47-2.49 (m, 2H, CH2), 1.90-1.95
(m, 10H, CH2), 1.48-1.66 (m, 8H, CH2), 1.42-1.45 (m, 6H, CH2), 1.26-1.37 (m,
42H, CH2), 0.85-0.89 (m, 12H, CH3).
Compound studies its mesomorphism by differential scanning calorimetry, petrographic microscope in the embodiment, finds it in liquid crystal model
There is typical liquid crystal columnar phase texture in enclosing, the optical property of compound is studied, it is found that the compound has fluorescence hair
Penetrate phenomenon.
Embodiment 4
A kind of specific embodiment of the invention is: a kind of plate-like ion liquid-crystal compounds containing thienopyridine, has following
The structure of general formula I, wherein R=C10H21, R1=C3H6C6F13, X is the double trifluoromethanesulfonimide radical ions of organic anion:
R=C in general formula I10H21, R1=C3H6C6F13, X is the double trifluoromethanesulfonimide radical ions of organic anion containing thieno
Pyridine plate-like ion liquid-crystal compounds to prepare reaction equation as follows:
THF is tetrahydrofuran in reaction equation；Toluene is toluene, and specific preparation step is as follows:
A, 2,3- dibromo thiophene [3,2-c] pyridine is prepared
4,5,6,7- thiophane [3,2-c] pyridine hydrochlorides (1.0 g, 5.69 mmol) are added to the round bottom for being furnished with stirrer
It in flask, is added chloroform (50 mL), then the bromine simple substance (1.8 of chloroform (15 mL) will be dissolved in constant pressure funnel
G, 11.4 mmol) it is added drop-wise in round-bottomed flask, after dripping, agitating and heating (80oC) reaction overnight, after reaction, is filtered
Solid and sodium hydroxide (228 mg, 5.69 mmol) are added to methylene chloride (20 mL) and water (10 mL) by the solid of generation
In the mixed solvent.After being stirred to react 2 hours, liquid separation is extracted by methylene chloride, and vacuum distillation is except after solvent；It is added prior
Activated manganese dioxide (2.5 g, 27.5 mmol), and toluene (5 mL) is added and makees solvent, in heating (130oC it) stirs
It is reacted 12-24 hours under conditions of reflux, determines that raw material fully reacting then terminates reaction with thin-layered chromatography；After reaction,
Manganese dioxide is filtered with funnel, collects organic phase, vacuum distillation obtains residue after removing solvent, passes through silica gel column chromatography
(solvent: methylene chloride: ethyl acetate=10:1) purifying, obtains compound 2,3- dibromo thiophene [3,2-c] pyridine (965 mg),
Yield 57%；
B, Suzuki coupling reaction
By 2,3- dibromo thiophene [3,2-c] pyridine of 1 molar part, the aryl boric acid of 2.5 molar parts, 10 molar parts potassium carbonate,
Four (triphenylphosphines) of 0.25 molar part close palladium and are added to THF and H2In the mixed solution of O, under nitrogen protection, 70oC stirring
Reaction 36 hours, is extracted with dichloromethane after reaction, and organic phase is dried, filtered with anhydrous magnesium sulfate, concentration, after concentration
Residue is purified by silica gel column chromatography (solvent: methylene chloride: ethyl acetate=10:1), obtains compound as white solid, is produced
Rate 70%；
C, intramolecular arene oxidizing coupling reaction
The 1 molar part coupled product dissolution that B is walked in methylene chloride, is slowly added to be dissolved in 3 in nitromethane and rubs
The liquor ferri trichloridi of your part after dripping, is stirred at room temperature reaction 3 hours, tracks to reaction with thin-layer chromatography in reaction process
Then methanol quenching reaction is added in object fully reacting, with saturated common salt water washing, adjust pH to alkalinity, methylene chloride extraction has
Machine is mutually dried, filtered with anhydrous magnesium sulfate, and concentration, the residue after concentration is purified by silica gel column chromatography methylene chloride, second
Acetoacetic ester/dehydrated alcohol recrystallization, obtained compound as white solid is product, yield 76%；
D, alkylated reaction
The C step product of 1 molar part is dissolved in toluene, the 9- bromo- 1,1,1,2,2,3,3,4,4,5,5,6,6- of 3 molar parts is added
Ten trifluoro nonanes, 120oC is stirred to react 36 hours, after reaction, boils off toluene, and residue is passed through silica gel column chromatography
(solvent: methylene chloride: ethyl alcohol=10:1) purifying, ethyl acetate/ethyl alcohol recrystallization, vacuum drying, obtained faint yellow solid
Closing object is alkylate, yield 78%；
E, ion-exchange reactions (metathesis reaction)
In methylene chloride by the alkylate dissolution of D 1 molar part walked, double fluoroform sulphurs of 5 molar parts are added
Imide li is stirred to react 5 hours at room temperature, after reaction, is washed with distilled water organic phase 3 times, and anhydrous magnesium sulfate is dry,
Filtering, concentration, the residue after concentration are purified by silica gel column chromatography (solvent: methylene chloride: ethyl alcohol=15:1), acetic acid second
Ester/ethyl alcohol recrystallization, vacuum drying, obtained faint yellow solid compound is R=C in general formula I10H21, R1=C3H6C6F13, X
For the ion liquid-crystal compounds of plate-like containing thienopyridine of the double trifluoromethanesulfonimide radical ions of organic anion, yield 80%；
Compound is due to passing through differential scanning calorimetry, polarisation without surveying nuclear magnetic spectrogram with gelation in the embodiment
Its mesomorphism of microscopic study finds that it has typical liquid crystal columnar phase texture in liquid crystal range, to the optics of compound
Property is studied, it is found that the compound has fluorescent emission phenomenon.
Embodiment 5
A kind of specific embodiment of the invention is: a kind of plate-like ion liquid-crystal compounds containing thienopyridine, has following
The structure of general formula I, wherein R=C10H21, R1For, X is inorganic anion bromide ion:
R=C in general formula I10H21, R1For, X is the pyrrole containing thieno of inorganic anion bromide ion
Pyridine plate-like ion liquid-crystal compounds to prepare reaction equation as follows:
THF is tetrahydrofuran in reaction equation；Toluene is toluene, and specific preparation step is as follows:
A, 2,3- dibromo thiophene [3,2-c] pyridine is prepared
4,5,6,7- thiophane [3,2-c] pyridine hydrochlorides (1.0 g, 5.69 mmol) are added to the round bottom for being furnished with stirrer
It in flask, is added chloroform (50 mL), then the bromine simple substance (1.8 of chloroform (15 mL) will be dissolved in constant pressure funnel
G, 11.4 mmol) it is added drop-wise in round-bottomed flask, after dripping, agitating and heating (80oC) reaction overnight, after reaction, is filtered
Solid and sodium hydroxide (228 mg, 5.69 mmol) are added to methylene chloride (20 mL) and water (10 mL) by the solid of generation
In the mixed solvent.After being stirred to react 2 hours, liquid separation is extracted by methylene chloride, and vacuum distillation is except after solvent；It is added prior
Activated manganese dioxide (2.5 g, 27.5 mmol), and toluene (5 mL) is added and makees solvent, in heating (130oC it) stirs
It is reacted 12-24 hours under conditions of reflux, determines that raw material fully reacting then terminates reaction with thin-layered chromatography；After reaction,
Manganese dioxide is filtered with funnel, collects organic phase, vacuum distillation obtains residue after removing solvent, passes through silica gel column chromatography
(solvent: methylene chloride: ethyl acetate=10:1) purifying, obtains compound 2,3- dibromo thiophene [3,2-c] pyridine (965 mg),
Yield 57%；
B, Suzuki coupling reaction
By 2,3- dibromo thiophene [3,2-c] pyridine of 1 molar part, the aryl boric acid of 2.5 molar parts, 10 molar parts potassium carbonate,
Four (triphenylphosphines) of 0.25 molar part close palladium and are added to THF and H2In the mixed solution of O, under nitrogen protection, 70oC stirring
Reaction 48 hours, is extracted with dichloromethane after reaction, and organic phase is dried, filtered with anhydrous magnesium sulfate, concentration, after concentration
Residue is purified by silica gel column chromatography (solvent: methylene chloride: ethyl acetate=10:1), obtains compound as white solid, is produced
Rate 75%；
C, intramolecular arene oxidizing coupling reaction
The 1 molar part coupled product dissolution that B is walked in methylene chloride, is slowly added to be dissolved in 3 in nitromethane and rubs
The liquor ferri trichloridi of your part after dripping, is stirred at room temperature reaction 3 hours, tracks to reaction with thin-layer chromatography in reaction process
Then methanol quenching reaction is added in object fully reacting, with saturated common salt water washing, adjust pH to alkalinity, methylene chloride extraction has
Machine is mutually dried, filtered with anhydrous magnesium sulfate, and concentration, the residue after concentration is purified by silica gel column chromatography methylene chloride, second
Acetoacetic ester/dehydrated alcohol recrystallization, obtained compound as white solid is product, yield 76%；
D, alkylated reaction
The C step product of 1 molar part is dissolved in toluene, the diethylene glycol -2- Bromoethyl methyl ether of 5 molar parts of addition, 120oC is stirred
Reaction 24 hours is mixed, after reaction, boils off toluene, residue is used and passes through silica gel column chromatography (solvent: methylene chloride: second
Alcohol=6:1) purifying, ethyl acetate/ethyl alcohol recrystallization, vacuum drying, obtained faint yellow solid compound is R=C10H21, R1
For, X is the ion liquid-crystal compounds of plate-like containing thienopyridine of inorganic anion bromide ion,
Yield 80%；
It is below statistics indicate that, using R=C in product made from the above the example method really general formula I10H21, R1For, X is the ion liquid-crystal compounds of plate-like containing thienopyridine of inorganic anion bromide ion,1H
NMR (C6D6, TMS, 400MHz) δ: 10.38 (s, 1H, ArH), 9.52 (s, 1H, ArH), 9.13 (d, J =
6.0 Hz, 1H, ArH), 8.36 (s, 1H, ArH), 7.55 (s, 1H, ArH), 7.41 (s, 1H, ArH),
6.65 (s, 1H, ArH), 6.25 (s, 2H, CH2), 5.23 (s, 2H, CH2), 4.29 (s, 4H, CH2),
4.17 (s, 2H), 4.02 (s, 2H), 3.79 (s, 2H), 3.54 (s, 2H), 3.35 (s, 2H), 3.13
(s, 2H), 2.98 (s, 3H, OCH3), 2.37-2.42 (m, 2H, CH2), 2.01-2.14 (m, 8H, CH2),
1.81-1.84 (m, 2H, CH2), 1.66-1.72 (m, 6H, CH2), 1.55-1.58 (m, 6H, CH2), 1.38-
1.49 (m, 40H, CH2), 0.98 (s, 12H, CH3).
Compound studies its mesomorphism by differential scanning calorimetry, petrographic microscope in the embodiment, finds it in liquid crystal model
There is typical liquid crystal columnar phase texture in enclosing, the optical property of compound is studied, it is found that the compound has fluorescence hair
Penetrate phenomenon.
Embodiment 6
A kind of specific embodiment of the invention is: a kind of plate-like ion liquid-crystal compounds containing thienopyridine, has following
The structure of general formula I, wherein R=C10H21, R1For, X is the double fluoroform sulphonyl of organic anion
Imines radical ion:
R=C in general formula I10H21, R1For, X is the double trifluoromethanesulfonimides of organic anion
The ion liquid-crystal compounds of plate-like containing thienopyridine of radical ion to prepare reaction equation as follows:
THF is tetrahydrofuran in reaction equation；Toluene is toluene, and specific preparation step is as follows:
A, 2,3- dibromo thiophene [3,2-c] pyridine is prepared
4,5,6,7- thiophane [3,2-c] pyridine hydrochlorides (1.0 g, 5.69 mmol) are added to the round bottom for being furnished with stirrer
It in flask, is added chloroform (50 mL), then the bromine simple substance (1.8 of chloroform (15 mL) will be dissolved in constant pressure funnel
G, 11.4 mmol) it is added drop-wise in round-bottomed flask, after dripping, agitating and heating (80oC) reaction overnight, after reaction, is filtered
Solid and sodium hydroxide (228 mg, 5.69 mmol) are added to methylene chloride (20 mL) and water (10 mL) by the solid of generation
In the mixed solvent.After being stirred to react 2 hours, liquid separation is extracted by methylene chloride, and vacuum distillation is except after solvent；It is added prior
Activated manganese dioxide (2.5 g, 27.5 mmol), and toluene (5 mL) is added and makees solvent, in heating (130oC it) stirs
It is reacted 12-24 hours under conditions of reflux, determines that raw material fully reacting then terminates reaction with thin-layered chromatography；After reaction,
Manganese dioxide is filtered with funnel, collects organic phase, vacuum distillation obtains residue after removing solvent, passes through silica gel column chromatography
(solvent: methylene chloride: ethyl acetate=10:1) purifying, obtains compound 2,3- dibromo thiophene [3,2-c] pyridine (965 mg),
Yield 57%；
B, Suzuki coupling reaction
By 2,3- dibromo thiophene [3,2-c] pyridine of 1 molar part, the aryl boric acid of 2.5 molar parts, 10 molar parts potassium carbonate,
Four (triphenylphosphines) of 0.25 molar part close palladium and are added to THF and H2In the mixed solution of O, under nitrogen protection, 70oC stirring
Reaction 36 hours, is extracted with dichloromethane after reaction, and organic phase is dried, filtered with anhydrous magnesium sulfate, concentration, after concentration
Residue is purified by silica gel column chromatography (solvent: methylene chloride: ethyl acetate=10:1), obtains compound as white solid, is produced
Rate 70%；
C, intramolecular arene oxidizing coupling reaction
The 1 molar part coupled product dissolution that B is walked in methylene chloride, is slowly added to be dissolved in 3 in nitromethane and rubs
The liquor ferri trichloridi of your part after dripping, is stirred at room temperature reaction 3 hours, tracks to reaction with thin-layer chromatography in reaction process
Then methanol quenching reaction is added in object fully reacting, with saturated common salt water washing, adjust pH to alkalinity, methylene chloride extraction has
Machine is mutually dried, filtered with anhydrous magnesium sulfate, and concentration, the residue after concentration is purified by silica gel column chromatography methylene chloride, second
Acetoacetic ester/dehydrated alcohol recrystallization, obtained compound as white solid is product, yield 76%；
D, alkylated reaction
The C step product of 1 molar part is dissolved in toluene, the diethylene glycol -2- Bromoethyl methyl ether of 5 molar parts of addition, 80oC stirring
Reaction 36 hours, after reaction, boil off toluene, by residue use by silica gel column chromatography (solvent: methylene chloride: ethyl alcohol=
It 6:1) purifies, ethyl acetate/ethyl alcohol recrystallization, vacuum drying, obtained faint yellow solid compound is alkylate, is produced
Rate 82%；
E, ion-exchange reactions (metathesis reaction)
In methylene chloride by the alkylate dissolution of D 1 molar part walked, double fluoroform sulphurs of 5 molar parts are added
Imide li is stirred to react 5 hours at room temperature, after reaction, is washed with distilled water organic phase 3 times, and anhydrous magnesium sulfate is dry,
Filtering, concentration, the residue after concentration are purified by silica gel column chromatography (solvent: methylene chloride: ethyl alcohol=15:1), acetic acid second
Ester/ethyl alcohol recrystallization, vacuum drying, obtained faint yellow solid compound is R=C in general formula I10H21, R1For, X is the plate-like containing thienopyridine of the double trifluoromethanesulfonimide radical ions of organic anion
Ion liquid-crystal compounds, yield 85%；
It is below statistics indicate that, using R=C in product made from the above the example method really general formula I10H21, R1For, X is the plate-like containing thienopyridine of the double trifluoromethanesulfonimide radical ions of organic anion
Ion liquid-crystal compounds,1H NMR (C6D6, TMS, 400MHz) δ: 9.50 (s, 1H, ArH), 8.22 (d, J =
6.4 Hz, 1H, ArH), 8.13 (d, J = 6.8 Hz, 1H, ArH), 7.91 (s, 1H, ArH), 7.62 (s,
1H, ArH), 7.52 (s, 1H, ArH), 6.61 (s, 1H, ArH), 4.95 (s, 2H), 4.69 (t, J =
6.4 Hz, 2H), 4.28 (t, J = 6.4 Hz, 2H), 4.19 (t, J = 6.0 Hz, 2H), 3.88 (t, J =
6.0 Hz, 2H), 3.73 (s, 2H), 3.33 (t, J = 6.4 Hz, 2H), 3.24 (t, J = 6.4 Hz,
2H), 3.14 (t, J = 6.8 Hz, 2H), 3.01 (t, J = 4.8 Hz, 2H), 2.98 (s, 3H, OCH3),
2.25-2.32 (m, 2H, CH2), 1.91-2.10 (m, 8H, CH2), 1.48-1.82 (m, 18H, CH2), 1.37-
1.43 (m, 36H, CH2), 0.97 (t, J = 6.4 Hz, 12H, CH3).
Compound studies its mesomorphism by differential scanning calorimetry, petrographic microscope in the embodiment, finds it in liquid crystal model
There is typical liquid crystal columnar phase texture in enclosing, and be room temperature liquid crystal, the optical property of compound is studied, finds the change
Closing object has fluorescent emission phenomenon.
Claims (3)
1. a kind of ion liquid-crystal compounds of plate-like containing thienopyridine has the structure of the following general formula I, R=C in general formula InH2n+1, n
=9,10,11, R1=CnH2n+1, n=8,9,10；R=CnH2n+1, n=9,10,11, R1=CnH2nCmF2m+1, n=2,3,4, m=5,6,7 or R
=CnH2n+1, n=9,10,11, R1For, X be inorganic anion or organic anion, such as it is inorganic
Anion: F-, Cl-, Br-, I-, NO3 -, BF4 -, PF6 -, SO4 -, H2PO4 -, ClO4 -, SCN-, AsF6 -, organic anion:
In its formula of I, inorganic anion is preferred: Br-, I-, NO3 -, BF4 -, PF6 -, organic anion is preferred:
。
2. a kind of preparation side for preparing the ion liquid-crystal compounds of plate-like containing thienopyridine that general formula described in claim 1 is I
Method the steps include:
A, 2,3- dibromo thiophene [3,2-c] pyridine is prepared
(1) with 4,5,6,7- thiophane [3,2-c] pyridine hydrochloride and bromine simple substance occur in a solvent bromo-reaction obtain it is double
Neutralization reaction occurs under alkaline condition and obtains 2,3- bis- bromo- 4 for bromination product, (2) double bromination products, and 5,6,7- thiophanes are simultaneously
[3,2-c] pyridine, (3) 2,3- bis- bromo- 4, simultaneously [3,2-c] pyridine and manganese dioxide stir back 5,6,7- thiophanes in a solvent
Stream occurs aromatization reaction and obtains compound 2,3- dibromo thiophene [3,2-c] pyridine；
B, Suzuki coupling reaction
By 2,3- dibromo thiophene [3,2-c] pyridine of 1 molar part, the aryl-boric acid ester of 2.5 molar parts, 10 molar parts carbonic acid
Potassium, 0.25 molar part four (triphenylphosphines) close palladium be added to THF and H2In the mixed solution of O, under nitrogen protection, 70oC
It being stirred to react 36-48 hours, is extracted with dichloromethane after reaction, organic phase is dried, filtered with anhydrous magnesium sulfate, concentration,
Residue silica gel column chromatography separating-purifying after concentration, obtains compound as white solid；
C, intramolecular arene oxidizing coupling reaction
The 1 molar part coupled product dissolution that B is walked in methylene chloride, is slowly added to be dissolved in 3 in nitromethane and rubs
The liquor ferri trichloridi of your part after dripping, is stirred at room temperature reaction 2-3 hours, is tracked to instead in reaction process with thin-layer chromatography
Object fully reacting to be answered, methanol quenching reaction is then added, with saturated common salt water washing, adjusts pH to alkalinity, methylene chloride extracts,
Organic phase is dried, filtered with anhydrous magnesium sulfate, concentration, the residue silica gel column chromatography separating-purifying after concentration, and recrystallization obtains
To compound as white solid be product；
D, alkylated reaction
The coupled product of 1 molar part is dissolved in toluene, the halogenated hydrocarbons of 3-5 molar part, 80-120 is addedoC is stirred to react 24-36
Hour, after reaction, toluene is boiled off, by residue silica gel column chromatography separating-purifying, vacuum drying, obtained pale yellow colored solid
Body compound is alkylate；
E, ion-exchange reactions (metathesis reaction)
In methylene chloride by the alkylate dissolution of D 1 molar part walked, the inorganic salts of 3-5 molar part are added or have
Machine salt is stirred to react 3-5 hours at room temperature, after reaction, is washed with distilled water organic phase 3 times, and anhydrous magnesium sulfate is dry, mistake
Filter, concentration, the residue silica gel column chromatography separating-purifying after concentration, vacuum drying, obtained faint yellow solid compound is i.e.
For the ion liquid-crystal compounds of plate-like containing thienopyridine.
3. this contains thienopyridine plate-like ion liquid-crystal compounds in liquid crystal material, photoelectric material, in terms of ion-conductive material
Potential application: thienopyridine plate-like ion LCD compound object liquid crystal liquid crystal property wider range, interphase is hexagonal columnar phase, in liquid crystal
Material Field has potential application；Such compound has fluorescent emission phenomenon in film, has in fields such as optical materials potential
Application.
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