CN105542793B - A kind of chiral room-temperature ion liquid-crystalization compound and preparation method thereof - Google Patents

A kind of chiral room-temperature ion liquid-crystalization compound and preparation method thereof Download PDF

Info

Publication number
CN105542793B
CN105542793B CN201610108345.8A CN201610108345A CN105542793B CN 105542793 B CN105542793 B CN 105542793B CN 201610108345 A CN201610108345 A CN 201610108345A CN 105542793 B CN105542793 B CN 105542793B
Authority
CN
China
Prior art keywords
chiral
compound
room
halogenated aliphatic
aliphatic acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN201610108345.8A
Other languages
Chinese (zh)
Other versions
CN105542793A (en
Inventor
张静
马成乡
蔡瑾
吴立新
魏学红
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanxi University
Original Assignee
Shanxi University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanxi University filed Critical Shanxi University
Priority to CN201610108345.8A priority Critical patent/CN105542793B/en
Publication of CN105542793A publication Critical patent/CN105542793A/en
Application granted granted Critical
Publication of CN105542793B publication Critical patent/CN105542793B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • 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
    • C09K19/36—Steroidal liquid crystal compounds

Landscapes

  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Steroid Compounds (AREA)

Abstract

The invention provides a kind of chiral room-temperature ion liquid-crystalization compound and preparation method thereof.The compound, its general structure are C30H51NO2BrRmTn, in formula：RmFor alkyl carbon chain (CH2)m, wherein m=5,7,9 or 10；TnFor alkyl carbon chain CnH2n+1, wherein n=1,4,8 or 12.Its preparation process：First, initiation material cholesterol carries out esterification with halogenated aliphatic acid, obtains liquid crystal intermediates halogenated aliphatic acid cholesteryl ester；Then, quaterisation is carried out using above-mentioned liquid crystal intermediates and tertiary amine, target product is made.Present invention utilizes space steric effect to design synthesis of chiral room-temperature ion liquid-crystalization compound, method is simple, raw material is easy to get, such material not only has chirality, and liquid crystalline phase can be shown at room temperature, it is expected to be used widely in liquid crystal display, solar cell, electrochemical device etc..

Description

A kind of chiral room-temperature ion liquid-crystalization compound and preparation method thereof
Technical field
The present invention relates to liquid crystal material field, and in particular to a kind of chiral room-temperature ion liquid-crystalization compound and its preparation side Method.Such room-temperature ion liquid crystal material not only has chirality, and can show liquid crystalline phase at room temperature, is expected in liquid crystal Show, solar cell, electrochemical device etc. are used widely.
Background technology
Chiral liquid crystal forms helical structure because of the presence of chiral centre in molecule, and these helical structures have chiral liquid crystal There are special optical characteristics, such as selective reflecting of optical activity, polarised light, circular dichroism.Chiral liquid crystal is because of its unique light Learn, electrical properties and widely paid attention to.Chiral ion liquid crystal has ionic liquid concurrently as a kind of novel functional material The assembling characteristic of special nature and chiral liquid crystal.Chiral ion liquid crystal in anisotropic ionic conductor material, dye sensitization too Synthesis template of positive energy battery, chemical sensor and nano material etc. has potential application prospect.From practical application Angle is set out, and the liquid crystal of low transition temperature assigns chiral ion liquid crystal with great application space, can show at room temperature Liquid crystal liquid crystal property and with wider liquid crystal section chiral ion liquid crystal material be in practical application required for.But in view of electrostatic The presence of interaction, ionic, which is constructed between primitive, has stronger microphase-separated, most of chiral ion liquid crystal be difficult Liquid crystal liquid crystal property can be shown under room temperature condition.
It is attempted to carry out chemistry cutting by the molecular structure of chiral ion liquid crystal to reduce its liquid crystal transition temperature, Meng Fanbao et al. designs have synthesized imidazoles salt form chiral ion liquid crystal (Li X, Lan X, Ma S, Bai L, Meng containing cholesterol F,Tian M,Synthesis and characterization of imidazolium-based ionic liquid crystals bearing a cholesteryl mesogenic group,Liquid Crystals,2014,41,1843- 1853.), its liquid crystal section is 67-129 DEG C；Warner et al. reports the chiral ion liquid crystal containing dysprosium, and its liquid crystal section is 41.9-98 DEG C, room temperature and liquid crystal section narrow (Lu C, Das S, Siraj N, Magut P K S, Li are not only above M,Warner I M,Spectral and physicochemical characterization of dysprosium- Based multifunctional ionic liquid crystals, J.Phys.Chem.A, 2015,119,4780- 4786.).But up to the present, it yet there are no the report of chiral room-temperature ion liquid crystal material.
In view of the microphase-separated of ion liquid crystal molecule, our utilization space steric effects, by the group courage that volume is larger It is sterol-modified tightly packed between adjacent molecule to destroy in the end of quaternary ammonium molecules of salt, reduce liquid crystal transition temperature to reach Purpose.
The content of the invention
It is an object of the invention to provide a kind of chiral room-temperature ion liquid-crystalization compound and preparation method thereof, preparation method letter Easy row, raw material are easy to get, and consersion unit is simple, and operating condition is gentle, the easily separated purifying of product, and yield is high, and cost is low, is easy to work Industry metaplasia is produced.
A kind of chiral room-temperature ion liquid-crystalization compound provided by the invention, its basic structure is by quaternary ammonium salt cationic hydrophilic head Portion's group, end hydrophobic alkyl chain and counter anion bromine containing larger group cholesterol are formed, and its general structure is C30H51NO2BrRmTn, in formula：RmFor alkyl carbon chain-(CH2)m-, wherein m=5,7,9 or 10；TnFor alkyl carbon chain-CnH2n+1, its Middle n=1,4,8 or 12.Its structural formula is：
A kind of preparation method of chiral room-temperature ion liquid-crystalization compound provided by the invention, is with cholesterol and halogenated aliphatic Acid carries out esterification for raw material, and the intermediate product of gained carries out quaterisation with tertiary amine again, and preparing can be in room temperature bar The chiral ionic compound of liquid crystal liquid crystal property is shown under part.Reaction equation is：
Preparation method comprises the following steps：
1) synthesis of intermediate halogenated aliphatic acid cholesteryl ester
Halogenated aliphatic acid is dissolved in anhydrous chloroform, holding concentration is 8-12 mg/mls, adds courage and consolidates Alcohol, the dosage of the two is controlled, it is 1.2-1.6 to make the mol ratio of cholesterol and halogenated aliphatic acid:1；Catalysis is added at 0-4 DEG C Agent DMAP and water absorbing agent dicyclohexylcarbodiimide, make mole of dicyclohexylcarbodiimide and halogenated aliphatic acid Than for 1.2-1.6:1, under nitrogen protection magnetic agitation reaction 3-7 hours, there is white precipitate；It is anti-to continue stirring under normal temperature Answer 17-21 hours；It is filtered to remove after precipitating with petroleum ether/dichloromethane (volume ratio 2:1) column chromatography point is carried out for eluant, eluent From obtaining intermediate product 11- bromine undecanoic acid cholesteryl esters；
Described halogenated aliphatic acid is 6- bromocaproic acids, 8- bromines octanoic acid, 10- bromines capric acid or 11- bromine undecanoic acids.
2) synthesis of chiral room-temperature ion liquid-crystalization compound
Halogenated aliphatic acid cholesteryl ester is dissolved by heating in acetone, holding concentration is 5-8 mg/mls, adds three Level amine, controls the dosage of the two, and the mol ratio for making tertiary amine and halogenated aliphatic acid cholesteryl ester is 6-10:1, protected in nitrogen Lower back flow reaction 24-48 hours；Rotary evaporation removes solvent, obtains the hand containing cholesterol with chloroform/Diethyl ether recrystallization three times Property quarternary ammonium salt compound；
Described tertiary amine is trimethylamine, N, N- dimethyl ns butylamine, N, N- dimethyl ns octylame or N, N- dimethyl ten Dialkylamine.
Beneficial effects of the present invention compared with prior art：Chiral room-temperature ion liquid-crystalization compound shows at room temperature sells Property liquid crystal liquid crystal property, liquid crystal section are wider.
The equipment that the present invention uses is simple, and method operation facility, preparation condition is gentle, obtains containing cholesterol chiral radicals Ion liquid crystal material.The material is characterized by circular dichroism spectra, differential scanning calorimetry, petrographic microscope and X-ray diffraction to exist Room temperature has chiral liquid crystal.It is expected to be used widely in liquid crystal display, solar cell, electrochemical device etc..
Brief description of the drawings
Fig. 1：C30H51NO2BrR10T12Infrared spectrogram；
Fig. 2：C30H51NO2BrR10T12NMR spectrum；
Fig. 3：C30H51NO2BrR10T12Mass spectrogram；
Fig. 4：C30H51NO2BrR10T12Circular dichroism spectrogram；
Fig. 5：C30H51NO2BrR10T12Differential scanning calorimetric curve；
Fig. 6：C30H51NO2BrR10T12X-ray diffraction pattern；
Fig. 7：C30H51NO2BrR10T12Petrographic microscope photo；
Embodiment
Embodiment 1：
(1) take 1 gram of 11- bromine undecanoic acid to be dissolved in 100 milliliters of anhydrous chloroforms, add 2.04 grams of cholesterol.3 A little catalyst DMAP and 1.09 grams of dicyclohexylcarbodiimides are added at DEG C.The lower magnetic agitation of nitrogen protection is anti- There is white precipitate after answering 5 hours.Continue stirring reaction under normal temperature 19 hours.Filtrate is spin-dried for after being filtered to remove white precipitate, is used Petroleum ether/dichloromethane (volume ratio 2:1) column chromatography for separation is carried out for eluant, eluent, obtains 11- bromine undecanoic acid cholesteryl esters, produced Rate is 78%.
(2) 1 gram of 11- bromine undecanoic acids cholesteryl ester is dissolved by heating in 170 milliliters of acetone, adds 2.70 grams of N, N- bis- Methyl lauryl amine, under nitrogen protection back flow reaction 36 hours.Rotary evaporation removes solvent, with chloroform/Diethyl ether recrystallization Three times, quaternary ionic compound C is obtained30H51NO2BrR10T12, yield 79%.
Fig. 1 is C30H51NO2BrR10T12And infrared spectrogram, 3365cm-1For O-H antisymmetric stretching vibrations；2923, 2850cm-1For CH2Antisymmetry and symmetrical stretching vibration；1735cm-1For C-O stretching vibrations；1467cm-1For CH2Scissoring vibration.
Fig. 2 is C30H51NO2BrR10T12NMR spectrum figure, [1H NMR(500MHz,CDCl3,δ):0.675(s, 3H), 0.854-1.845 (m, 78H), 1.939-2.02 (m, 2H), 2.262 (t, J=7Hz, 2H), 2.296-2.312 (d, J= 8Hz, 2H), 3.408 (s, 6H), 3.506-3.533 (m, 4H), 4.571-4.636 (m, 1H), 5.362-5.371 (m, 1H)], The peak at 5.362-5.371ppm places is pointed out as the proton peak in cholesterol group on unsaturated double-bond, 4.571-4.636ppm places Peak is pointed out to be pointed out for the proton on carbon adjacent with ester group in cholesterol group, the peak at 3.408ppm, 3.506-3.533ppm place For the proton peak of quaternary ammonium salt head methyl and methylene, the peak at 2.296-2.312ppm places is pointed out as the methylene adjacent with ester group On proton peak, integral area matches with the number of proton.
Fig. 3 is C30H51NO2BrR10T12Mass spectrogram, karyoplasmic ratio m/z be 766.7, with liquid-crystal compounds cationic moiety Molecular weight is consistent.With reference to infrared spectrogram, NMR spectrum figure and mass spectrogram, it is determined that successfully synthesizing the ionic liquid of target Crystallization compound.
Embodiment 2：
(1) take 1 gram of 11- bromine undecanoic acid to be dissolved in 100 milliliters of anhydrous chloroforms, add 1.75 grams of cholesterol.3 A little catalyst DMAP and 0.93 gram of dicyclohexylcarbodiimide are added at DEG C.The lower magnetic agitation of nitrogen protection is anti- There is white precipitate after answering 3 hours.Continue stirring reaction under normal temperature 21 hours.Filtrate is spin-dried for after being filtered to remove white precipitate, is used Petroleum ether/dichloromethane (volume ratio 2:1) column chromatography for separation is carried out for eluant, eluent, obtains 11- bromine undecanoic acid cholesteryl esters, produced Rate is 76%.
(2) 1 gram of 11- bromine undecanoic acids cholesteryl ester is dissolved by heating in 125 milliliters of acetone, adds 2.02 grams of N, N- bis- Methyl lauryl amine, under nitrogen protection back flow reaction 24 hours.Rotary evaporation removes solvent, with chloroform/Diethyl ether recrystallization Three times, quaternary ionic compound C is obtained30H51NO2BrR10T12, yield 72%.
Embodiment 3：
(1) take 1 gram of 11- bromine undecanoic acid to be dissolved in 100 milliliters of anhydrous chloroforms, add 2.33 grams of cholesterol.3 A little catalyst DMAP and 1.24 grams of dicyclohexylcarbodiimides are added at DEG C.The lower magnetic agitation of nitrogen protection is anti- There is white precipitate after answering 7 hours.Continue stirring reaction under normal temperature 17 hours.Filtrate is spin-dried for after being filtered to remove white precipitate, is used Petroleum ether/dichloromethane (volume ratio 2:1) column chromatography for separation is carried out for eluant, eluent, obtains 11- bromine undecanoic acid cholesteryl esters, produced Rate is 81%.
(2) 1 gram of 11- bromine undecanoic acids cholesteryl ester is dissolved by heating in 200 milliliters of acetone, adds 3.37 grams of N, N- bis- Methyl lauryl amine, under nitrogen protection back flow reaction 48 hours.Rotary evaporation removes solvent, with chloroform/Diethyl ether recrystallization Three times, quaternary ionic compound C is obtained30H51NO2BrR10T12, yield 83%.
Embodiment 4：
(1) take 1 gram of 6- bromocaproic acid to be dissolved in 100 milliliters of anhydrous chloroforms, add 2.76 grams of cholesterol.At 3 DEG C The a little catalyst DMAP of lower addition and 1.48 grams of dicyclohexylcarbodiimides.The lower magnetic agitation reaction of nitrogen protection There is white precipitate after 4 hours.Continue stirring reaction under normal temperature 20 hours.Filtrate is spin-dried for after being filtered to remove white precipitate, uses stone Oily ether/dichloromethane (volume ratio 2:1) column chromatography for separation is carried out for eluant, eluent, obtains 6- bromocaproic acid cholesteryl esters, yield is 82%.
(2) 1 gram of 6- bromocaproic acids cholesteryl ester is dissolved by heating in 170 milliliters of acetone, adds 3.03 grams of N, N- diformazans Base lauryl amine, under nitrogen protection back flow reaction 36 hours.Rotary evaporation removes solvent, with chloroform/Diethyl ether recrystallization three It is secondary, obtain quaternary ionic compound C30H51NO2BrR5T12, yield 71%.
Embodiment 5：
(1) take 1 gram of 8- bromocaproic acid to be dissolved in 100 milliliters of anhydrous chloroforms, add 2.43 grams of cholesterol.At 3 DEG C The a little catalyst DMAP of lower addition and 1.29 grams of dicyclohexylcarbodiimides.The lower magnetic agitation reaction of nitrogen protection There is white precipitate after 5 hours.Continue stirring reaction under normal temperature 19 hours.Filtrate is spin-dried for after being filtered to remove white precipitate, uses stone Oily ether/dichloromethane (volume ratio 2:1) column chromatography for separation is carried out for eluant, eluent, obtains 8- bromine octanoic acid cholesteryl esters, yield is 81%.
(2) 1 gram of 8- bromine octanoic acids cholesteryl ester is dissolved by heating in 170 milliliters of acetone, adds 2.88 grams of N, N- diformazans Base lauryl amine, under nitrogen protection back flow reaction 36 hours.Rotary evaporation removes solvent, with chloroform/Diethyl ether recrystallization three It is secondary, obtain quaternary ionic compound C30H51NO2BrR7T12, yield 79%.
Embodiment 6：
(1) take 1 gram of 10- bromine capric acid to be dissolved in 100 milliliters of anhydrous chloroforms, add 2.43 grams of cholesterol.At 3 DEG C The a little catalyst DMAP of lower addition and 1.29 grams of dicyclohexylcarbodiimides.The lower magnetic agitation reaction of nitrogen protection There is white precipitate after 6 hours.Continue stirring reaction under normal temperature 18 hours.Filtrate is spin-dried for after being filtered to remove white precipitate, uses stone Oily ether/dichloromethane (volume ratio 2:1) column chromatography for separation is carried out for eluant, eluent, obtains 10- bromine capric acid cholesteryl esters, yield is 77%.
(2) 1 gram of 10- bromine capric acid cholesteryl ester is dissolved by heating in 170 milliliters of acetone, adds 2.75 grams of N, N- diformazans Base lauryl amine, under nitrogen protection back flow reaction 36 hours.Rotary evaporation removes solvent, with chloroform/Diethyl ether recrystallization three It is secondary, obtain quaternary ionic compound C30H51NO2BrR9T12, yield 77%.
Embodiment 7：
(1) take 1 gram of 11- bromine undecanoic acid to be dissolved in 100 milliliters of anhydrous chloroforms, add 2.04 grams of cholesterol.3 A little catalyst DMAP and 1.09 grams of dicyclohexylcarbodiimides are added at DEG C.The lower magnetic agitation of nitrogen protection is anti- There is white precipitate after answering 5 hours.Continue stirring reaction under normal temperature 19 hours.Filtrate is spin-dried for after being filtered to remove white precipitate, is used Petroleum ether/dichloromethane (volume ratio 2:1) column chromatography for separation is carried out for eluant, eluent, obtains 11- bromine undecanoic acid cholesteryl esters, produced Rate is 78%.
(2) 1 gram of 11- bromine undecanoic acids cholesteryl ester is dissolved by heating in 170 milliliters of acetone, adds 2.33 gram 40% Trimethylamine, under nitrogen protection back flow reaction 36 hours.Rotary evaporation removes solvent, obtains with chloroform/Diethyl ether recrystallization three times Quaternary ionic compound C30H51NO2BrR10T1, yield 81%.
Embodiment 8：
(1) take 1 gram of 11- bromine undecanoic acid to be dissolved in 100 milliliters of anhydrous chloroforms, add 2.04 grams of cholesterol.3 A little catalyst DMAP and 1.09 grams of dicyclohexylcarbodiimides are added at DEG C.The lower magnetic agitation of nitrogen protection is anti- There is white precipitate after answering 5 hours.Continue stirring reaction under normal temperature 19 hours.Filtrate is spin-dried for after being filtered to remove white precipitate, is used Petroleum ether/dichloromethane (volume ratio 2:1) column chromatography for separation is carried out for eluant, eluent, obtains 11- bromine undecanoic acid cholesteryl esters, produced Rate is 78%.
(2) 1 gram of 11- bromine undecanoic acids cholesteryl ester is dissolved by heating in 170 milliliters of acetone, adds 1.27 grams of N, N- bis- Methyl n-butylamine, under nitrogen protection back flow reaction 36 hours.Rotary evaporation removes solvent, with chloroform/Diethyl ether recrystallization three times, Obtain quaternary ionic compound C30H51NO2BrR10T4, yield 62%.
Embodiment 9：
(1) take 1 gram of 11- bromine undecanoic acid to be dissolved in 100 milliliters of anhydrous chloroforms, add 2.04 grams of cholesterol.3 A little catalyst DMAP and 1.09 grams of dicyclohexylcarbodiimides are added at DEG C.The lower magnetic agitation of nitrogen protection is anti- There is white precipitate after answering 5 hours.Continue stirring reaction under normal temperature 19 hours.Filtrate is spin-dried for after being filtered to remove white precipitate, is used Petroleum ether/dichloromethane (volume ratio 2:1) column chromatography for separation is carried out for eluant, eluent, obtains 11- bromine undecanoic acid cholesteryl esters, produced Rate is 78%.
(2) 1 gram of 11- bromine undecanoic acids cholesteryl ester is dissolved by heating in 170 milliliters of acetone, adds 1.98 grams of N, N- bis- Methyl n-octyl amine, under nitrogen protection back flow reaction 36 hours.Rotary evaporation removes solvent, with chloroform/Diethyl ether recrystallization three times, Obtain quaternary ionic compound C30H51NO2BrR10T8, yield 68%.
Embodiment 10：
We utilize circular dichroism spectrogram detailed examination compound C30H51NO2BrR10T12Optics in acetonitrile solution is lived Property (see Fig. 4), it has shown a negative, positive gram effect, first negative gram signal respectively at 214nm, 337nm (214nm) shows compound C30H51NO2BrR10T12There is optical activity under the induction of cholesterol group, be that S- configurations are chiral Compound.
Embodiment 11：
Chiral room-temperature ion liquid-crystalization compound C30H51NO2BrR10T12Differential scanning calorimetric curve (see Fig. 5) heating and Multiple phase in version peaks that temperature-fall period is shown show meaning with liquid crystal property and there is multiple phases；Wherein, during cooling Exothermic peak to 145 DEG C of appearance points out phase in version peak for from isotropism state to liquid crystal state, continues to be cooled to -1.7 DEG C and glass occurs Glass transistion peak；There are three phase in version peaks in temperature-rise period, wherein 3 DEG C are glassy transition peak, 81 DEG C are different liquid crystal states Between phase in version peak, be warming up to 151 DEG C and endothermic peak occur, 151 DEG C are clearing point, show liquid crystal state disappear, now to be complete Unordered liquid.Illustrate that the quarternary ammonium salt compound has liquid in -1.7 DEG C to 145 DEG C of temperature-fall period, 3 DEG C to 151 DEG C of temperature-rise period Crystalline substance.
Embodiment 12：
Chiral room-temperature ion liquid-crystalization compound C30H51NO2BrR10T12Alternating temperature X-ray diffraction and petrographic microscope test It is chiral smectic phase ion liquid crystal to show it.From isotropism state for the first time be cooled to 120 DEG C when, X-ray diffracting spectrum it is small There are two equidistant diffraction maximums 001 and 002 (see Fig. 6) in angular region, is shown to be Rotating fields, interlamellar spacing d is 3.84nm；Wide-angle area Occur the unrestrained bag of disperse rather than diffraction maximum at 20 °, show that now alkyl chain is in unordered stacking states.Using interlayer pattern Product carry out the observation of liquid crystal texture to multidomain sample, take and grind uniform sample on a small quantity and be placed in two layers of circular lid slide interlayer, Light cap slide.Above-mentioned prepared sample is placed in the thermal station of petrographic microscope, using cross-polarized light to liquid crystal molecule Thermic assembly behavior is observed.120 DEG C are cooled to from isotropism state, there is broken fan-shaped texture (see a in Fig. 7) appearance. X-ray diffracting spectrum shows that the liquid crystal phase at 120 DEG C is the relatively low chiral smectic A (SmA*) of the degree of order with petrographic microscope Phase；
Embodiment 13：
When being cooled to 60 DEG C for the first time from isotropism state, the small angular region of X-ray diffracting spectrum occurs two at equal intervals Diffraction maximum 001 and 002 (see Fig. 6), is shown to be Rotating fields, and interlamellar spacing d is 4.02nm；There is the unrestrained of disperse at 20 ° in wide-angle area Bag rather than diffraction maximum, show that now alkyl chain is in unordered stacking states.Liquid is carried out to multidomain sample using sandwich type sample The observation of brilliant texture, take and grind uniform sample on a small quantity and be placed in two layers of circular lid slide interlayer, light cap slide.By above-mentioned institute The sample of preparation is placed in the thermal station of petrographic microscope, and the thermic assembly behavior of liquid crystal molecule is seen using cross-polarized light Examine.60 DEG C are cooled to from isotropism state, there is typical conical texture (see b in Fig. 7) appearance.X-ray diffracting spectrum and polarisation Microscope shows that the liquid crystal phase at 60 DEG C is relatively low chiral smectic A (SmA*) phase of the degree of order；
Embodiment 14：
When being warming up to 50 DEG C for the second time, the small angular region of X-ray diffracting spectrum occur two equidistant diffraction maximums 001 and 002 (see Fig. 6), is shown to be Rotating fields, and interlamellar spacing d is 4.02nm；There is the unrestrained bag rather than diffraction of disperse at 20 ° in wide-angle area Peak, show that now alkyl chain is in unordered stacking states.The observation of liquid crystal texture is carried out to multidomain sample using sandwich type sample, Take and grind uniform sample on a small quantity and be placed in two layers of circular lid slide interlayer, light cap slide.Above-mentioned prepared sample is put In the thermal station of petrographic microscope, the thermic assembly behavior of liquid crystal molecule is observed using cross-polarized light.60 DEG C are warming up to, There is fan-shaped conical texture (see c in Fig. 7) appearance.X-ray diffracting spectrum shows that the liquid crystal phase at 60 DEG C is with petrographic microscope Higher chiral smectic C (SmC*) phase of the degree of order；
Embodiment 15：
When being warming up to 110 DEG C for the second time, the small angular region of X-ray diffracting spectrum occur two equidistant diffraction maximums 001 and 002 (see Fig. 6), is shown to be Rotating fields, and interlamellar spacing d is 3.84nm；There is the unrestrained bag rather than diffraction of disperse at 20 ° in wide-angle area Peak, show that now alkyl chain is in unordered stacking states.The observation of liquid crystal texture is carried out to multidomain sample using sandwich type sample, Take and grind uniform sample on a small quantity and be placed in two layers of circular lid slide interlayer, light cap slide.Above-mentioned prepared sample is put In the thermal station of petrographic microscope, the thermic assembly behavior of liquid crystal molecule is observed using cross-polarized light.It is warming up to 110 DEG C, there is conical texture (see d in Fig. 7) appearance.X-ray diffracting spectrum shows that the liquid crystal phase at 110 DEG C is with petrographic microscope Relatively low chiral smectic A (SmA*) phase of the degree of order.

Claims (3)

1. a kind of preparation method of chiral room-temperature ion liquid-crystalization compound, it is characterised in that structural formula of compound is：
Wherein m=5,7,9 or 10；N=4,8 or 12；
The preparation method of compound, comprises the following steps：
1) synthesis of intermediate halogenated aliphatic acid cholesteryl ester
Halogenated aliphatic acid is dissolved in anhydrous chloroform, holding concentration is 8-12 mg/mls, adds cholesterol, control The dosage of the two is made, it is 1.2-1.6 to make the mol ratio of cholesterol and halogenated aliphatic acid:1；Catalyst 4- is added at 0-4 DEG C Dimethylamino naphthyridine and water absorbing agent dicyclohexylcarbodiimide, make dicyclohexylcarbodiimide and halogenated aliphatic acid and mol ratio For 1.2-1.6:1, under nitrogen protection magnetic agitation reaction 3-7 hours, there is white precipitate；Continue stirring reaction under normal temperature 17-21 hours；It is 2 to be filtered to remove after precipitation with volume ratio:1 petroleum ether/dichloromethane is that eluant, eluent carries out column chromatography point From obtaining intermediate product halogenated aliphatic acid cholesteryl ester；
2) synthesis of chiral room-temperature ion liquid-crystalization compound
Halogenated aliphatic acid cholesteryl ester is dissolved by heating in acetone, holding concentration is 5-8 mg/mls, adds three-level Amine, the dosage of the two is controlled, the mol ratio for making tertiary amine and halogenated aliphatic acid cholesteryl ester is 6-10:1, under nitrogen protection Back flow reaction 24-48 hours；Rotary evaporation removes solvent, obtains chiral room-temperature ion liquid with chloroform/Diethyl ether recrystallization three times Crystallization compound.
A kind of 2. preparation method of chiral room-temperature ion liquid-crystalization compound as claimed in claim 1, it is characterised in that step 1) Described in halogenated aliphatic acid be 6- bromocaproic acids, 8- bromines octanoic acid, 10- bromines capric acid or 11- bromine undecanoic acids.
A kind of 3. preparation method of chiral room-temperature ion liquid-crystalization compound as claimed in claim 1, it is characterised in that step 2) Described in tertiary amine be N, N- dimethyl ns butylamine, N, N- dimethyl ns octylame or N, N- dimethyl dodecylamine.
CN201610108345.8A 2016-02-26 2016-02-26 A kind of chiral room-temperature ion liquid-crystalization compound and preparation method thereof Expired - Fee Related CN105542793B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610108345.8A CN105542793B (en) 2016-02-26 2016-02-26 A kind of chiral room-temperature ion liquid-crystalization compound and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610108345.8A CN105542793B (en) 2016-02-26 2016-02-26 A kind of chiral room-temperature ion liquid-crystalization compound and preparation method thereof

Publications (2)

Publication Number Publication Date
CN105542793A CN105542793A (en) 2016-05-04
CN105542793B true CN105542793B (en) 2018-01-02

Family

ID=55822365

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610108345.8A Expired - Fee Related CN105542793B (en) 2016-02-26 2016-02-26 A kind of chiral room-temperature ion liquid-crystalization compound and preparation method thereof

Country Status (1)

Country Link
CN (1) CN105542793B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108373922B (en) * 2018-01-30 2021-03-30 山西大学 Pyrene-containing chiral luminescent liquid crystal compound and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1751111A (en) * 2003-01-24 2006-03-22 默克专利股份有限公司 Ionic mesogenic compounds
CN103343013A (en) * 2013-07-05 2013-10-09 东北大学 Ionic liquid crystal compound containing imidazole and cholesteric ester groups and preparation method thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003288954A (en) * 2002-03-27 2003-10-10 Fuji Photo Film Co Ltd Electrolyte composition and electrochemical cell

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1751111A (en) * 2003-01-24 2006-03-22 默克专利股份有限公司 Ionic mesogenic compounds
CN103343013A (en) * 2013-07-05 2013-10-09 东北大学 Ionic liquid crystal compound containing imidazole and cholesteric ester groups and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
MONOMERIC AND OLIGOMERIC QUATERNARY AMMONIUM DERIVATIVES OF CHOLESTEROL: CONCENTRATED AND DILUTE AQUEOUS SOLUTION PHASE BEHAVIOUR;S. K. ABID，D. C. SHERRINGTON;《Eur.Polym.J》;19931231;第29卷(第2/3期);第153-158页 *
Synthesis, Spectroscopic and Semiempirical Studies of New Quaternary Alkylammonium Conjugates of Sterols;Bogumił Brycki;《molecules》;20131231;第18卷;第14961-14976页 *

Also Published As

Publication number Publication date
CN105542793A (en) 2016-05-04

Similar Documents

Publication Publication Date Title
CN102399246A (en) Metal nickel-imidazole chiral nanometer cage complex and preparation method thereof
KR20090105375A (en) Ionic liquids miscible with various polar/non-polar solvents and method for preparing the same
Ringstrand et al. Anion-driven mesogenicity: ionic liquid crystals based on the [closo-1-CB 9 H 10]− cluster
CN105542793B (en) A kind of chiral room-temperature ion liquid-crystalization compound and preparation method thereof
Hou et al. From smectic to columnar phase of polypedal liquid crystals based on tetrathiafulvalene/1, 3-dithiol-2-thione and cholesterol
CN105623673B (en) A kind of chiral liquid crystal compound containing polyacid and preparation method thereof
CN108129385A (en) A kind of compound quaternary ammonium salt nonlinear optics crystalline state material and preparation method thereof
Chen et al. Bowl liquid crystal based on cyclotriveratrylene derivatives with multiple triphenylene units: The influences of the numbers of triphenylene units on mesomorphic behaviors
CN102875339A (en) Liquid crystal compound and preparation method and application thereof
Styron et al. Alternating stereoregular head, tail–tail, head‐poly (alkylene D‐glucaramides) derived from a homologous series of symmetrical diamido‐di‐d‐glucaric acid monomers
CN106433688B (en) One kind tolane liquid crystal molecule of base containing pyridyl end and its preparation method and application
Liao et al. Low-temperature and wide ferroelectric phase in mixtures of chiral and non-chiral tilted smectic C-type liquid crystals
Majumdar et al. A columnar mesophase from a disc-shaped molecule derived from triphenylamine: synthesis, mesomorphic behaviour and optical properties
Dong et al. Mesomorphic properties of multi-arm chenodeoxycholic acid-derived liquid crystals
Song et al. Synthesis and characterization of hexamethylenetetramine-based ionic liquid crystals
Huzum et al. New cholesteryl containing bent core liquid crystals
CN106117222A (en) Benzophenanthrene dodecyloxy bridging isobutyltrimethylmethane. phenyl porphyrin binary compound discotic mesogenic material synthesis method
Rodríguez-Molina et al. Synthesis and solid state characterization of molecular rotors with steroidal stators: ethisterone and norethisterone
Riesco et al. Monotropic polymorphism in copper (II) decanoate
Goto et al. Synthesis and properties of mono-substituted liquid crystalline polyacetylene derivatives—doping, magnetic orientation, and photo-isomerization
CN107955044B (en) Preparation method of 2-deoxy-D-glucose
Liao et al. Synthesis, characterization, and electro-optic properties of novel bent-core mesogens based on cinnamoyloxy derivatives
CN102875557B (en) Tetranitroglycoluril dipolymer, preparation method and application
MA et al. Synthesis and characterization of a novel cholesteric liquid crystalline containing carboxyl group
Shanavas et al. Trimesic Acid-Based Star Mesogens with Flexible Spacer: Synthesis and Mesophase Characterization

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20180102