CN104004527A - Liquid crystal compound and its preparation method and use - Google Patents
Liquid crystal compound and its preparation method and use Download PDFInfo
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- CN104004527A CN104004527A CN201410191405.8A CN201410191405A CN104004527A CN 104004527 A CN104004527 A CN 104004527A CN 201410191405 A CN201410191405 A CN 201410191405A CN 104004527 A CN104004527 A CN 104004527A
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Abstract
The invention relates to a liquid crystal compound and its preparation method and use. The liquid crystal compound has a structure shown in the formula (I). Through specific combination of two end groups of the compound shown in the formula (I), the compound has the characteristics of low viscosity and high dielectric anisotropy so that the liquid crystal composition containing the compound solves the problem that the existing TFT-LCD has a response rate not fast enough, voltage not low enough and a charge conservation rate not high enough.
Description
Technical field
The present invention relates to a kind of liquid crystalline cpd and its preparation method and application, relate to liquid crystal material field.
Background technology
At present, liquid crystal is used widely in field of information display, and the application in optical communication simultaneously also makes some progress (S.T.Wu, D.K.Yang.Reflective Liquid Crystal Displays.Wiley, 2001).In recent years, the Application Areas of liquid crystalline cpd had significantly been widened kinds of displays part, electro-optical device, electronic component, sensor.Also propose many different liquid crystal structures, particularly in nematic liquid crystal field, especially in the system for tft active matrix, nematic liquid crystal compound obtains applying the most widely for this reason.
Liquid-crystal display follows the discovery of liquid crystal to experience very long road for development.Within 1888, Austrian botanist Friedrich Reinitzer has found the first liquid crystal material M-nitro benzoic acid cholesterol (cholesteryl benzoate).Within 1917, Manguin has invented friction Directional Method, in order to make single domain liquid crystal and Optical anisotropy.E.Bose in 1909 has set up and has collected together (Swarm) theory, and obtains the people's such as L.S.Ormstein and F.Zernike experiment support (1918), is discussed as statistical fluctuation by De Gennes.G.W.Oseen and H.Zocher1933 found continuum theory, and obtain F.C.Frank perfect (1958).M.Born (1916) and K.Lichtennecker (nineteen twenty-six) have found and have studied the dielectric anisotropy of liquid crystal.1932, W.Kast was divided into nematic phase the large class of positive and negative property two accordingly.Nineteen twenty-seven, V.Freedericksz and V.Zolinao find that nematic liquid crystal, under electric field (or magnetic field) effect, deformation occurs and have voltage threshold (Freederichsz transformation).This making that is found to be liquid-crystal display provides foundation.
The nineteen sixty-eight R.Williams of RCA Corp. of the U.S. finds that nematic liquid crystal forms striped farmland under electric field action, and has light scattering phenomenon.G.H.Heilmeir is with develop into dynamic scattering display format by it, and makes first liquid-crystal display (LCD) in the world.Early seventies, Helfrich and Schadt have invented TN principle, and people utilize TN photovoltaic effect and unicircuit to combine, and are made display device (TN-LCD), for wide prospect has been opened up in the application of liquid crystal.Since the seventies, due to the development of large-scale integrated circuit and liquid crystal material, the people such as the application of liquid crystal aspect demonstration obtained breakthrough development, 1983～1985 years T.Scheffer successively propose supertwist nematic phase (Super Twisred Nematic:STN) pattern and P.Brody is adopted again in active matrix (Active matrix:AM) mode of proposition in 1972.Traditional TN-LCD technology has developed into STN-LCD and TFT-LCD technology, although more than the number of scanning lines of STN can reach 768 row, still exist the problems such as response speed, visual angle and gray scale in the time that temperature raises, therefore big area, high information quantity,
The colored Active Matrix LCD At mode that mostly adopts that shows.TFT-LCD has been widely used in direct viewing type TV, large-curtain projecting TV set, terminal shows and some military instrument shows, believes that TFT-LCD technology has more wide application prospect.
Wherein " active matrix " comprises two types: 1, the OMS on the silicon wafer as substrate (metal-oxide semiconductor (MOS)) or other diode.2, the thin film transistor on the sheet glass as substrate (TFT).
Silicon single crystal has limited display size as substrate material because each several part display device even module assembled there are many problems in its junction.Thereby the second thin film transistor is the promising active matrix type of tool, the photovoltaic effect of utilizing is TN effect normally.TFT comprises compound semiconductor, as Cdse, or taking polycrystalline or amorphous silicon as basic TFT.
At present, TFT-LCD product technology is ripe, has successfully solved the technical barriers such as visual angle, resolving power, fullness of shade and brightness, and its display performance has approached or exceeded CRT monitor.Large size and small-medium size TFT-LCD indicating meter occupy the dominant position of flat-panel monitor gradually in field separately.But because being subject to the restriction of liquid crystal material itself, it is fast not that TFT-LCD still exists response, and voltage is low not, the high not many defects of electric charge conservation rate.Patent DE4222371 discloses the liquid crystal monomer that end is-O (CH2) nF, and this liquid crystal monomer viscosity is low, but dielectric anisotropy is lower.
Therefore find the single crystal compound that has low viscosity, high dielectric anisotropy concurrently fast not to the response that overcomes TFT-LCD and exist, voltage is low not, and the high not many defects of electric charge conservation rate are significant.
Summary of the invention
For the defect of above-mentioned prior art, the invention provides a kind of novel liquid crystalline cpd, this compound one end has ethylene linkage, and have-O of the other end (CH2) nF modular construction, has lower viscosity and larger dielectric anisotropy concurrently.
To achieve these goals, the present invention adopts following technical scheme:
A kind of liquid crystalline cpd, has suc as formula the structure shown in (I):
Wherein, the alkyl that contains separately 1-12 carbon atom that R is selected from H or does not replace or replace;
A
1, A
2and A
3be selected from independently of one another singly-bound, Isosorbide-5-Nitrae-cyclohexyl, one of them CH
2or two not direct-connected CH2 can replace by O or S, Isosorbide-5-Nitrae-cyclohexenyl, piperidines-1,4-bis-bases, Isosorbide-5-Nitrae-Ya bis-encircles [2,2,2] octyl group, Isosorbide-5-Nitrae-phenyl, one of them CH or two not direct-connected CH can be replaced by N, naphthalene-2,6-bis-bases, trans naphthane-2,6-bis-bases, tetraline-2,6-bis-bases, 1,2-indane, indenes, phenanthryl, or diphenylene-oxide, wherein hydrogen can be replaced by one or more halogens independently of one another;
A
4be selected from: Isosorbide-5-Nitrae-phenyl, wherein hydrogen can be replaced by one or more halogens independently of one another;
Z
1, Z
2and Z
3be selected from independently of one another: singly-bound ,-(CH
2)
2-,-(CH
2)
4-,-CH=CHCH
2cH
2-,-CH
2cH
2cH=CH-, CF
2o, OCF
2, CF
2cF
2, CF=CF, CH
2cF
2, CF
2cH
2, OCF
2cF
2o, C
2h
4cF
2o, CH
2cF
2oCH
2, CH
2oCF
2cH
2, OCF
2c
2h
4, C
3h
6o, OC
3h
6, C
2h
4oCH
2, CH
2oC
2h
4, CH
2o, OCH
2,-CH=CH-,-C ≡ C-or COO;
M is 0 or 2;
N is 1,2 or 3.
Preferably:
R is selected from H or does not replace the alkyl that contains 1-3 carbon atom;
A
1, A
2and A
3be selected from independently of one another: singly-bound, Isosorbide-5-Nitrae-cyclohexyl, or Isosorbide-5-Nitrae-phenyl, wherein hydrogen can be replaced by one or more fluorine elements independently of one another;
A
4be selected from: Isosorbide-5-Nitrae-phenyl, wherein hydrogen can be replaced by one or more fluorine elements independently of one another;
Z
1, Z
2and Z
3be selected from independently of one another: singly-bound ,-(CH
2)
2-, CF
2o, OCF
2, CH
2o or OCH
2;
M is 0 or 2;
N is 1,2 or 3.
The liquid crystalline cpd of described general formula (I) is further preferably as follows structure:
Or
R is selected from H or CH
3;
A
1, A
2and A
3be selected from independently of one another: singly-bound, Isosorbide-5-Nitrae-cyclohexyl, or Isosorbide-5-Nitrae-phenyl, wherein hydrogen can be replaced by one or more fluorine elements independently of one another.
A
4be selected from: Isosorbide-5-Nitrae-phenyl, wherein hydrogen can be replaced by one or more fluorine elements independently of one another;
Z
1, Z
2and Z
3be selected from independently of one another: singly-bound ,-(CH
2)
2-, CF
2o, OCF
2, CH
2o or OCH
2.
N is 1,2 or 3.
General formula of the present invention (I) compound is following structure most preferably:
Wherein, R is selected from H or CH
3;
M is 0 or 2.
The present invention also provides the preparation method of above-mentioned general formula (I) liquid crystalline cpd, and its synthetic route is as follows:
A) intermediate
synthetic:
e、K
2CO
3，I(CH
2)nCH
2F；
f、n-BuLi，CH
3PhSO
3H；
g、Raney?Ni；
h、80％HCOOH；
i、t-BuOK，CH
3OCH
2PPh
3Cl；
j、HCl；
k、KOH；
B), in the time that m is 0, the synthetic route of general formula (I) compound is as follows:
A, t-BuOK, RCH
2pPh
3i; Or
In the time that m is 2, the synthetic route of general formula (I) compound is as follows:
b、KBH
4；
c、CH
3SO
2Cl，C
5H
5N；
d、RCH
2＝CHCH
2BrMg，Li
2CuCl
4。
Above-mentioned steps A) specifically comprise the steps:
1) Br-A
3-Z
3-A
4-OH (compound 1) and I (CH
2) nCH
2f is 60-75 DEG C of reaction 3-5h under Anhydrous potassium carbonate effect, generates Br-A
3-Z
3-A
4-O (CH
2f) n-CH
2f (compound 2);
2) Br-A
3-Z
3-A
4-O (CH
2) n-CH
2f (compound 2) carries out after the exchange of lithium halogen with butyllithium in-50--60 DEG C, then with protection reactive ketone, by tosic acid dehydration, Raney's nickel hydrogenation, formic acid deprotection, generates O=A
1-Z
1-A
2-Z
2-A
3-Z
3-A
4-O (CH
2) n-CH
2f (compound 5);
3) O=A
1-Z
1-A
2-Z
2-A
3-Z
3-A
4-O (CH
2) n-CH
2f (compound 5) 0 DEG C with potassium tert.-butoxide and chloromethyl ether phosphonium salt through Wei ladder breath react generation
CH
3oCH=A
1-Z
1-A
2-Z
2-A
3-Z
3-A
4-O (CH
2) n-CH
2f (compound 6);
4) by CH
3oCH=A
1-Z
1-A
2-Z
2-A
3-Z
3-A
4-O (CH
2) n-CH
2f (compound 6) is dissolved in tetrahydrofuran (THF), and dilute hydrochloric acid exists after lower back hydrolysis, then transposition generates in potassium hydroxide methanol solution
(compound 7);
Above-mentioned steps B) in, in the time that m is 0, the synthetic route of general formula (I) compound is as follows:
(compound 7) 0 DEG C with potassium tert.-butoxide and alkyl triphenyl phosphonium iodide through Wei ladder breath react generation
(compound 8);
In the time that m is 2, the synthetic route of general formula (I) compound is as follows:
1)
(compound 7), in 40-50 DEG C through potassium borohydride reduction 2-4 hour, dilute hydrochloric acid hydrolysis, generates HOCH
2-A
1-Z
1-A
2-Z
2-A
3-Z
3-A
4-O (CH
2) n-CH
2f (compound 9);
2) in dichloromethane solution, HOCH
2-A
1-Z
1-A
2-Z
2-A
3-Z
3-A
4-O (CH
2) n-CH
2f (compound 9), at 15-20 DEG C, reacts with Methanesulfonyl chloride under the effect of catalyzer pyridine and within 1-2 hour, is warming up to generation in back flow reaction 3-5 hour
CH
3O
2SOCH
2-A
1-Z
1-A
2-Z
2-A
3-Z
3-A
4-O(CH
2)n-CH
2F
(compound 10);
3) taking cupric chloride lithium as catalyzer,
CH
3o
2sOCH
2-A
1-Z
1-A
2-Z
2-A
3-Z
3-A
4-O (CH
2) n-CH
2f (compound 10) reacts with alkyl allyl bromide 98 generation Grignard reagent in anhydrous ether solution, and temperature control 38-42 DEG C stirring reaction generates for 8 hours
(compound 11).
Further illustrate above-mentioned preparation method with the concrete synthetic route of a certain compound below:
1) intermediate
synthetic:
2) in the time that m is 0, compound
synthetic route as follows:
In the time that m is 2, compound
synthetic route as follows:
The present invention also provides the application of above-mentioned general formula (I) compound in TFT-LCD.
Gained general formula of the present invention (I) liquid crystalline cpd, by the particular combinations to its two ends group, make it have the characteristic of low viscosity, high dielectric anisotropy concurrently, it is fast not that thereby the liquid-crystal composition that makes to contain its composition can overcome the response that current TFT-LCD exists, voltage is low not, the high not defect of electric charge conservation rate.
Embodiment
Following examples are used for illustrating the present invention, but are not used for limiting the scope of the invention.
Embodiment 1: intermediate
the preparation of 4 '-[the fluoro-4-of 2,3-bis-(2-fluorine oxyethyl group)-phenyl] dicyclohexyl formaldehyde (compound 7)
1) 2, the fluoro-4-of 3-bis-(2-fluorine oxyethyl group)-bromobenzene (compound 2) synthetic
In 50mL reaction flask, add 22mL DMF, start stirring, add 5.2g2, the fluoro-4-bromophenol of 3-bis-(compound 1), after solid dissolves completely, then adds 10mL water, 0.25g Tetrabutyl amonium bromide, 4.0g Anhydrous potassium carbonate.Heat temperature raising, 65～72 DEG C of dropping 4.9g2-fluorine iodoethane of temperature control, stirring reaction 4 hours, add 10mL toluene and 15mL water, stir 10 minutes, leave standstill separatory, twice of 5mL for water × 2 methylbenzene extraction (stir 2 minutes, leave standstill 5 minutes), this water is abandoned it.Merge all organic phases, with 10mL × 3 water washing three times.Be spin-dried for solvent, underpressure distillation, obtains compound 2.Theoretical yield: 6.4g, actual output 5.1g, yield: 79.8%.Gas phase purity (GC) 99.0%.
Same method can be prepared:
The fluoro-4-of 2,3-bis-(3-fluorine propoxy-)-bromobenzene
The fluoro-4-of 2,3-bis-(4-fluorine butoxy)-bromobenzene
The fluoro-4-of 3,5-bis-(2-fluorine oxyethyl group)-bromobenzene
The fluoro-4-of 3,5-bis-(3-fluorine propoxy-)-bromobenzene
The fluoro-4-of 3,5-bis-(4-fluorine butoxy)-bromobenzene
2) 8-{4-[2, the fluoro-4-of 3-bis-(2-fluorine oxyethyl group)-phenyl] hexamethylene-3-alkene }-Isosorbide-5-Nitrae-dioxo-spiral shell [4.5] decane (compound 3) synthetic
In 1L there-necked flask, add 35.2g2, the fluoro-4-of 3-bis-(2-fluorine oxyethyl group)-bromobenzene (compound 2), 250mL tetrahydrofuran (THF), be cooled to-50 degree to-60 degree, and temperature control drips 100mL2.5M n-Butyl Lithium, temperature control reaction 1 hour.Temperature control drips 150mL tetrahydrofuran (THF) and the mono-mixed solution of protecting dicyclohexyl diketone of 47.6g, drips and finishes the rear stirring 3 hours that naturally heats up.Drip dilute hydrochloric acid, control temperature not higher than 20 degree.Separatory, 150mL washing 3 times for organic phase.
Reaction solution obtained in the previous step is poured in 1L bottle, added 1g2,6-ditertbutylparacresol, air distillation to 110 degree steams low-boiling-point substance, optionally add toluene, it is 300mL that toluene is added total amount, then adds 1.5g tosic acid, 60mL ethylene glycol, heating point water reaction 5h separatory, ethylene glycol is used 20mL*2 methylbenzene extraction 2 times mutually, adds 10g anhydrous sodium carbonate, 20g anhydrous sodium sulfate drying 1 hour, concentrated solvent.Add 1.5 times of Virahol+0.2 of theoretical amount times toluene heating for dissolving recrystallization, obtain 67.4g compound 3.Theoretical amount: 79.2g, yield: 85.1%.
Same method can be prepared:
8-{4-[2, the fluoro-4-of 3-bis-(3-fluorine propoxy-)-phenyl] hexamethylene-3-alkene }-Isosorbide-5-Nitrae-dioxo-spiral shell [4.5] decane
8-{4-[2, the fluoro-4-of 3-bis-(4-fluorine butoxy)-phenyl] hexamethylene-3-alkene }-Isosorbide-5-Nitrae-dioxo-spiral shell [4.5] decane
8-[2, the fluoro-4-of 3-bis-(2-fluorine oxyethyl group)-phenyl]-Isosorbide-5-Nitrae-dioxo-spiral shell [4.5] last of the ten Heavenly stems-7-alkene
8-[2, the fluoro-4-of 3-bis-(3-fluorine propoxy-)-phenyl]-Isosorbide-5-Nitrae-dioxo-spiral shell [4.5] last of the ten Heavenly stems-7-alkene
8-[2, the fluoro-4-of 3-bis-(4-fluorine butoxy)-phenyl]-Isosorbide-5-Nitrae-dioxo-spiral shell [4.5] last of the ten Heavenly stems-7-alkene
8-{4-[3, the fluoro-4-of 5-bis-(2-fluorine oxyethyl group)-phenyl] hexamethylene-3-alkene }-Isosorbide-5-Nitrae-dioxo-spiral shell [4.5] decane
8-{4-[3, the fluoro-4-of 5-bis-(3-fluorine propoxy-)-phenyl] hexamethylene-3-alkene }-Isosorbide-5-Nitrae-dioxo-spiral shell [4.5] decane
8-{4-[3, the fluoro-4-of 5-bis-(4-fluorine butoxy)-phenyl] hexamethylene-3-alkene }-Isosorbide-5-Nitrae-dioxo-spiral shell [4.5] decane
3) 8-{4-[2, the fluoro-4-of 3-bis-(2-fluorine oxyethyl group)-phenyl] cyclohexyl }-Isosorbide-5-Nitrae-dioxo-spiral shell [4.5] decane (compound 4) synthetic
In 1L there-necked flask, add 64.3g8-{4-[2, the fluoro-4-of 3-bis-(2-fluorine oxyethyl group)-phenyl] hexamethylene-3-alkene }-1,4-dioxo-spiral shell [4.5] decane (compound 3), 200mL toluene, 1.5mL triethylamine, 130g Raney's nickel is also clean with 650ml alcohol flushing, hydrogen pump drainage 3 times.Logical hydrogen, is warming up to 35 DEG C, stops heating, hydrogenation 4 hours.Concentrated solvent, obtains 64.0g compound 4, yield: 99.1%.
Same method can be prepared:
8-{4-[2, the fluoro-4-of 3-bis-(3-fluorine propoxy-)-phenyl] cyclohexyl }-Isosorbide-5-Nitrae-dioxo-spiral shell [4.5] decane
8-{4-[2, the fluoro-4-of 3-bis-(4-fluorine butoxy)-phenyl] cyclohexyl }-Isosorbide-5-Nitrae-dioxo-spiral shell [4.5] decane
8-[2, the fluoro-4-of 3-bis-(2-fluorine oxyethyl group)-phenyl]-Isosorbide-5-Nitrae-dioxo-spiral shell [4.5] decane
8-[2, the fluoro-4-of 3-bis-(3-fluorine propoxy-)-phenyl]-Isosorbide-5-Nitrae-dioxo-spiral shell [4.5] decane
8-[2, the fluoro-4-of 3-bis-(4-fluorine butoxy)-phenyl]-Isosorbide-5-Nitrae-dioxo-spiral shell [4.5] decane
8-{4-[3, the fluoro-4-of 5-bis-(2-fluorine oxyethyl group)-phenyl] cyclohexyl }-Isosorbide-5-Nitrae-dioxo-spiral shell [4.5] decane
8-{4-[3, the fluoro-4-of 5-bis-(3-fluorine propoxy-)-phenyl] cyclohexyl }-Isosorbide-5-Nitrae-dioxo-spiral shell [4.5] decane
8-{4-[3, the fluoro-4-of 5-bis-(4-fluorine butoxy)-phenyl] cyclohexyl }-Isosorbide-5-Nitrae-dioxo-spiral shell [4.5] decane
4) 4 '-[the fluoro-4-of 2,3-bis-(2-fluorine oxyethyl group)-phenyl] bicyclohexanone (compound 5) is synthetic
In 1L there-necked flask, add 66.8g8-{4-[2, the fluoro-4-of 3-bis-(2-fluorine oxyethyl group)-phenyl] cyclohexyl }-Isosorbide-5-Nitrae-dioxo-spiral shell [4.5] decane (compound 4), 300mL toluene, 250mL formic acid, be warming up to 65 DEG C, react 6 hours, separatory, washs with saturated aqueous sodium carbonate, concentrated toluene phase, obtain crude product, add 2 times of sherwood oils and 0.5 times of ethyl acetate heating for dissolving recrystallization, obtain 30.3g compound 5, theoretical amount: 59.5g, yield: 51.0%.
Same method can be prepared:
4 '-[the fluoro-4-of 2,3-bis-(3-fluorine propoxy-)-phenyl] bicyclohexanone
4 '-[the fluoro-4-of 2,3-bis-(4-fluorine butoxy)-phenyl] bicyclohexanone
4-[2, the fluoro-4-of 3-bis-(2-fluorine oxyethyl group)-phenyl] pimelinketone
4-[2, the fluoro-4-of 3-bis-(3-fluorine propoxy-)-phenyl] pimelinketone
4-[2, the fluoro-4-of 3-bis-(4-fluorine butoxy)-phenyl] pimelinketone
4 '-[the fluoro-4-of 3,5-bis-(2-fluorine oxyethyl group)-phenyl] bicyclohexanone
4 '-[the fluoro-4-of 3,5-bis-(3-fluorine propoxy-)-phenyl] bicyclohexanone
4 '-[the fluoro-4-of 3,5-bis-(4-fluorine butoxy)-phenyl] bicyclohexanone
5) 4-[2, the fluoro-4-of 3-bis-(2-fluorine oxyethyl group)-phenyl]-4 '-methoxy methene-bis cyclohexane (compound 6) synthetic
In 1L there-necked flask, add 47.0g chloromethyl ether phosphonium salt, 200mL tetrahydrofuran (THF), is cooled to-10 DEG C, adds 19.3g potassium tert.-butoxide.Temperature control 0～-5 DEG C reaction 1 hour, the mixed solution of dropping 120mL tetrahydrofuran (THF) and 30.6g4 '-[the fluoro-4-of 2,3-bis-(2-fluorine oxyethyl group)-phenyl] bicyclohexanone (compound 5), controls below temperature 0 degree.Naturally heat up, stirring is spent the night.In reaction solution, add 200mL water, 150mL ethyl acetate to stir, separatory, concentrated solvent, adds the sherwood oil of 3 times of theoretical amount to divide dissolving, crosses silica gel aluminum oxide pillar, crosses pillar after 3 bits of 2 times of theoretical amount petroleum ether extractions.Concentrated post liquid, 2 times of theoretical amount alcohol crystals, obtain 30.5g compound 6, theoretical amount 32.8g, yield: 92.9%.
Same method can be prepared:
4-[2, the fluoro-4-of 3-bis-(3-fluorine propoxy-)-phenyl]-4 '-methoxy methene-bis cyclohexane
4-[2, the fluoro-4-of 3-bis-(4-fluorine butoxy)-phenyl]-4 '-methoxy methene-bis cyclohexane
The fluoro-1-of 2,3-bis-(2-fluorine oxyethyl group)-4-(4-methoxy methene hexanaphthene) benzene
The fluoro-1-of 2,3-bis-(3-fluorine propoxy-)-4-(4-methoxy methene hexanaphthene) benzene
The fluoro-1-of 2,3-bis-(4-fluorine butoxy)-4-(4-methoxy methene hexanaphthene) benzene
4-[3, the fluoro-4-of 5-bis-(2-fluorine oxyethyl group)-phenyl]-4 '-methoxy methene-bis cyclohexane
4-[3, the fluoro-4-of 5-bis-(3-fluorine propoxy-)-phenyl]-4 '-methoxy methene-bis cyclohexane
4-[3, the fluoro-4-of 5-bis-(4-fluorine butoxy)-phenyl]-4 '-methoxy methene-bis cyclohexane
6) 4 '-[the fluoro-4-of 2,3-bis-(2-fluorine oxyethyl group)-phenyl] dicyclohexyl formaldehyde (compound 7) is synthetic
In 1L there-necked flask, add 30.6g4-[2, the fluoro-4-of 3-bis-(2-fluorine oxyethyl group)-phenyl]-4 '-methoxy methene-bis cyclohexane (compound 6), 100mL tetrahydrofuran (THF), 0.15g2,6-ditertbutylparacresol, the mixed solution of dropping 14.5mL concentrated hydrochloric acid and 40mL water, be warming up to faint backflow, react 4 hours, leave standstill separatory, water extracts by 100mL ethyl acetate, merge organic phase, temperature is no more than 70 DEG C, for subsequent use after concentrated solvent.
In 1L there-necked flask, add 2.1g KOH and 270mL anhydrous methanol, be stirred to dissolving, temperature control 0 to 10 degree drips the mixed solution of 30mL tetrahydrofuran (THF) and enriched material, and temperature control 0-10 DEG C is reacted 4.5 hours.Add 100mL methylene dichloride and 200mL water, stir separatory, 70 DEG C of following concentrated solvents, obtain 25.4g compound 7, add 50mL tetrahydrofuran (THF), put refrigerator for subsequent use after nitrogen protection.
Same method can be prepared:
4 '-[the fluoro-4-of 2,3-bis-(3-fluorine propoxy-)-phenyl] dicyclohexyl formaldehyde
4 '-[the fluoro-4-of 2,3-bis-(4-fluorine butoxy)-phenyl] dicyclohexyl formaldehyde
4-[2, the fluoro-4-of 3-bis-(2-fluorine oxyethyl group)-phenyl] hexahydrobenzaldehyde
4-[2, the fluoro-4-of 3-bis-(3-fluorine propoxy-)-phenyl] hexahydrobenzaldehyde
4-[2, the fluoro-4-of 3-bis-(4-fluorine butoxy)-phenyl] hexahydrobenzaldehyde
4 '-[the fluoro-4-of 3,5-bis-(2-fluorine oxyethyl group)-phenyl] dicyclohexyl formaldehyde
4 '-[the fluoro-4-of 3,5-bis-(3-fluorine propoxy-)-phenyl] dicyclohexyl formaldehyde
4 '-[the fluoro-4-of 3,5-bis-(4-fluorine butoxy)-phenyl] dicyclohexyl formaldehyde
Embodiment 24-[2, the fluoro-4-of 3-bis-(2-fluorine oxyethyl group)-phenyl]-4 '-vinyl-bis cyclohexane (compound 8) synthetic
In 1L there-necked flask, add 41.8g methyl iodide phosphonium salt, 200mL tetrahydrofuran (THF), is cooled to subzero 10 DEG C, adds 14.3g potassium tert.-butoxide, reaction 1h.Temperature control drips the mixed solution of 50mL tetrahydrofuran (THF) and 25.4g4 '-[the fluoro-4-of 2,3-bis-(2-fluorine oxyethyl group)-phenyl] dicyclohexyl formaldehyde (compound 7), natural temperature reaction, stirring is spent the night, and adds 200mL water, 100mL ethyl acetate, stir, leave standstill separatory, concentrated solvent, adds 3 times of sherwood oils of theoretical amount, be heated to 75 DEG C, cross silica gel aluminum oxide plume, concentrated solvent obtains 24.8g, adds 2 times of dehydrated alcohol recrystallizations three times.Obtain compound 8, theoretical yield: 25.2g, actual output 19.6g, yield: 78.0%.Gas phase purity (GC) 99.9%, Δ ε is that-3.5, γ 1 is 158mPas.Mass spectroscopy fragment: 161,202,366 (molecular ion peaks);
H-NMR nuclear magnetic spectrogram (CDCl
3, 300mhZ): δ H:1.20-1.86 (m, 18H), 2.08-2.92 (m, 2H), 3.90-5.83 (m, 7H), 6.40-6.80 (m, 2H).
Same method can be prepared:
4-[2, the fluoro-4-of 3-bis-(3-fluorine propoxy-)-phenyl]-4 '-vinyl-bis cyclohexane
4-[2, the fluoro-4-of 3-bis-(4-fluorine butoxy)-phenyl]-4 '-vinyl-bis cyclohexane
The fluoro-1-of 2,3-bis-(2-fluorine oxyethyl group)-4-(4-vinyl cyclohexane) benzene
The fluoro-1-of 2,3-bis-(3-fluorine propoxy-)-4-(4-vinyl cyclohexane) benzene
The fluoro-1-of 2,3-bis-(4-fluorine butoxy)-4-(4-vinyl cyclohexane) benzene
4-[3, the fluoro-4-of 5-bis-(2-fluorine oxyethyl group)-phenyl]-4 '-vinyl-bis cyclohexane
4-[3, the fluoro-4-of 5-bis-(3-fluorine propoxy-)-phenyl]-4 '-vinyl-bis cyclohexane
4-[3, the fluoro-4-of 5-bis-(4-fluorine butoxy)-phenyl]-4 '-vinyl-bis cyclohexane
Embodiment 3
4 '-(fourth-3 thiazolinyl)-4-[2, the fluoro-4-of 3-bis-(2-fluorine oxyethyl group)-phenyl] bis cyclohexane (compound 11) synthetic
1) { 4 '-[the fluoro-4-of 2,3-bis-(2-fluorine oxyethyl group)-phenyl]-dicyclohexyl } methyl alcohol (compound 9) is synthetic
77g4 ' in 1L there-necked flask-[2, the fluoro-4-of 3-bis-(2-fluorine oxyethyl group)-phenyl] solution of dicyclohexyl formaldehyde (compound 7) and 200L tetrahydrofuran (THF) composition, 0～10 DEG C of temperature control adds 10.0g solid POTASSIUM BOROHYDRIDE in batches, within approximately 30 minutes, adds.40～50 DEG C are incubated 3 hours.Temperature control, below 20 DEG C, slowly drips the solution of 50mL hydrochloric acid and 100mL water composition, in reactor, adds 100mL water, 100m L methylene dichloride, mild heat to 35 DEG C left and right, leaves standstill separatory, separate lower floor's gas producing formation, 100m L dichloromethane extraction for the water of upper strata, merges organic phase.Steam solvent, with 2 times of sherwood oil heating for dissolving recrystallizations.Obtain 66.8g compound 9, theoretical amount 77.4g, yield: 86.3%.
Same method can be prepared:
{ 4 '-[the fluoro-4-of 2,3-bis-(3-fluorine propoxy-)-phenyl]-dicyclohexyl } methyl alcohol
{ 4 '-[the fluoro-4-of 2,3-bis-(4-fluorine butoxy)-phenyl]-dicyclohexyl } methyl alcohol
4-[2, the fluoro-4-of 3-bis-(2-fluorine oxyethyl group)-phenyl] hexahydrobenzyl alcohol
4-[2, the fluoro-4-of 3-bis-(3-fluorine propoxy-)-phenyl] hexahydrobenzyl alcohol
4-[2, the fluoro-4-of 3-bis-(4-fluorine butoxy)-phenyl] hexahydrobenzyl alcohol
2 ', 3 '-bis-fluoro-4 '-(2-fluorine oxyethyl group)-biphenyl methyl alcohol
2 ', 3 '-bis-fluoro-4 '-(3-fluorine propoxy-)-biphenyl methyl alcohol
2 ', 3 '-bis-fluoro-4 '-(4-fluorine butoxy)-biphenyl methyl alcohol
2) methylsulphonic acid { 4 '-[the fluoro-4-of 2,3-bis-(2-fluorine oxyethyl group)-phenyl]-dicyclohexyl } methyl alcohol ester (compound 10) is synthetic
In 1L there-necked flask, add 250mL methylene dichloride, 23.6g pyridine, starts stirring, adds 48.1g{4 '-[the fluoro-4-of 2,3-bis-(2-fluorine oxyethyl group)-phenyl]-dicyclohexyl } methyl alcohol (compound 9), be stirred to solid and all dissolve.Be cooled to 0 DEG C, 0～10 DEG C of temperature control adds 20.0g Methanesulfonyl chloride in batches, 15～20 DEG C of stirring reactions of temperature control 1.5 hours.Be warming up to back flow reaction 4 hours.In bottle, add 120mL water, stir 20 minutes, leave standstill separatory, point sub-cloud gas producing formation, upper aqueous layer 80mL dichloromethane extraction, merges all organic phases.Temperature control is below 80 DEG C, and steaming desolventizes, and adds 3 times of dehydrated alcohols and 0.5 times of toluene heating for dissolving recrystallization.Obtain 42.0g compound 10, theoretical amount 56.1g, yield: 74.8%.
Same method can be prepared:
Methylsulphonic acid { 4 '-[the fluoro-4-of 2,3-bis-(3-fluorine propoxy-)-phenyl]-dicyclohexyl } methyl alcohol ester
Methylsulphonic acid { 4 '-[the fluoro-4-of 2,3-bis-(4-fluorine butoxy)-phenyl]-dicyclohexyl } methyl alcohol ester
Methylsulphonic acid 4-[2, the fluoro-4-of 3-bis-(2-fluorine oxyethyl group)-phenyl] hexahydrobenzyl alcohol ester
Methylsulphonic acid 4-[2, the fluoro-4-of 3-bis-(3-fluorine propoxy-)-phenyl] hexahydrobenzyl alcohol ester
Methylsulphonic acid 4-[2, the fluoro-4-of 3-bis-(4-fluorine butoxy)-phenyl] hexahydrobenzyl alcohol ester
Fluoro-4 '-(2-fluorine the oxyethyl group)-biphenyl methyl alcohol ester of methylsulphonic acid 2 ', 3 '-bis-
Fluoro-4 '-(3-fluorine the propoxy-)-biphenyl methyl alcohol ester of methylsulphonic acid 2 ', 3 '-bis-
Fluoro-4 '-(4-fluorine the butoxy)-biphenyl methyl alcohol ester of methylsulphonic acid 2 ', 3 '-bis-
3) 4 '-(fourth-3 thiazolinyl)-4-[2, the fluoro-4-of 3-bis-(2-fluorine oxyethyl group)-phenyl] bis cyclohexane (compound 11) synthetic
In 1L there-necked flask, add 15.4g magnesium chips, 160mL anhydrous diethyl ether, starts stirring, the solution initiation reaction that adds 10ml to be made up of 52.4g allyl bromide 98 and 200mL anhydrous diethyl ether.15～25 DEG C of temperature controls, drip the anhydrous ether solution of remaining allyl bromide 98, stirring reaction 1 hour.15～25 DEG C of temperature controls, the solution that slowly adds 48.4g methylsulphonic acid { 4 '-[the fluoro-4-of 2,3-bis-(2-fluorine oxyethyl group)-phenyl]-dicyclohexyl } methyl alcohol ester (compound 10) and 250mL toluene to form, adds for approximately 1 hour.15～25 DEG C of temperature controls, drip 13.0mL cupric chloride lithium solution, slowly heat up, and 38～42 DEG C of stirring reactions of temperature control 8 hours.Cooling, temperature control, below 20 DEG C, drips the solution of 70mL hydrochloric acid and 200mL water composition to there-necked flask, stir hydrolysis 15 minutes.Leave standstill separatory, in water, add 200mL water and 200mL L Petroleum ether extraction once.Steaming desolventizes.By 2 times of sherwood oil heating for dissolving, alumina column (40 DEG C), with 4 times of high sherwood oils flushings of post, steaming desolventizes.Add 2 times of dehydrated alcohol+1 times sherwood oil heating for dissolving, recrystallization three times, obtains 42.0g compound 11, theoretical amount 56.1g, yield: 74.8%.
Gas phase purity (GC) 99.7%.Δ ε is-3.0.
Mass spectroscopy fragment: 161,202,394 (molecular ion peaks);
H-NMR nuclear magnetic spectrogram (CDCl3,300mhZ): δ H:1.23-1.73 (m, 21H), 1.85-2.80 (m, 3H), 3.98-5.81 (m, 7H), 6.41-6.79 (m, 2H).
Same method can be prepared:
4 '-(fourth-3 thiazolinyl)-4-[2, the fluoro-4-of 3-bis-(3-fluorine propoxy-)-phenyl] bis cyclohexane
4 '-(fourth-3 thiazolinyl)-4-[2, the fluoro-4-of 3-bis-(4-fluorine butoxy)-phenyl] bis cyclohexane
1-(4-fourth-3 thiazolinyl cyclohexyl)-2, the fluoro-4-of 3-bis-(2-fluorine oxyethyl group) benzene
1-(4-fourth-3 thiazolinyl cyclohexyl)-2, the fluoro-4-of 3-bis-(3-fluorine propoxy-) benzene
1-(4-fourth-3 thiazolinyl cyclohexyl)-2, the fluoro-4-of 3-bis-(4-fluorine butoxy) benzene
Thiazolinyl-2,4 '-Ding-3, the fluoro-4-of 3-bis-(2-fluorine oxyethyl group) biphenyl
Thiazolinyl-2,4 '-Ding-3, the fluoro-4-of 3-bis-(3-fluorine propoxy-) biphenyl
Thiazolinyl-2,4 '-Ding-3, the fluoro-4-of 3-bis-(4-fluorine butoxy) biphenyl
Comparative example:
Above-described embodiment 2 gained compounds 8, embodiment 3 gained compounds 11 are carried out to viscosity with available liquid crystal monomer and dielectric anisotropy detects contrast, the results are shown in Table 1, table 2.Wherein, Δ ε is illustrated in the dielectric anisotropy under 20 DEG C and 1kHz; γ 1 is illustrated in the rotary viscosity (mPas) at 20 DEG C.
The Performance Detection comparing result of table 1 embodiment 2 and available liquid crystal monomer
From physical property interpretation of result, compound 8 compares its rotary viscosity with compound 12 obvious reduction; Compound 8 compares its dielectric anisotropy with compound 13 and is significantly improved.
The Performance Detection comparing result of table 2 embodiment 3 and available liquid crystal monomer
From physical property interpretation of result, compound 11 is compared with compound 14, and under the basically identical condition of dielectric anisotropy, its rotary viscosity obviously reduces.
Other liquid crystalline cpds that employing the method for the invention obtains and the detected result of compound 8 or compound 11 are basically identical, all have higher dielectric anisotropy and lower viscosity.
Compound 8, compound 11 are joined in liquid-crystal composition as liquid crystal monomer, can obtain response fast, voltage is low, the liquid-crystal composition that electric charge conservation rate is high.
Although above the present invention is described in detail with a general description of the specific embodiments, on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, all belong to the scope of protection of present invention.
Claims (10)
1. a liquid crystalline cpd, is characterized in that, has suc as formula the structure shown in (I):
Wherein, the alkyl that contains separately 1-12 carbon atom that R is selected from H or does not replace or replace;
A
1, A
2and A
3be selected from independently of one another singly-bound, Isosorbide-5-Nitrae-cyclohexyl, one of them CH
2or two not direct-connected CH
2can be replaced by O or S Isosorbide-5-Nitrae-cyclohexenyl, piperidines-1,4-bis-bases, Isosorbide-5-Nitrae-Ya bis-encircles [2,2,2] octyl group, Isosorbide-5-Nitrae-phenyl, one of them CH or two not direct-connected CH can be replaced by N, naphthalene-2,6-bis-bases, trans naphthane-2,6-bis-bases, tetraline-2,6-bis-bases, 1,2-indane, indenes, phenanthryl, or diphenylene-oxide, wherein hydrogen can be replaced by one or more halogens independently of one another;
A
4be selected from: Isosorbide-5-Nitrae-phenyl, wherein hydrogen can be replaced by one or more halogens independently of one another;
Z
1, Z
2and Z
3be selected from independently of one another: singly-bound ,-(CH
2)
2-,-(CH
2)
4-,-CH=CHCH
2cH
2-,-CH
2cH
2cH=CH-, CF
2o, OCF
2, CF
2cF
2, CF=CF, CH
2cF
2, CF
2cH
2, OCF
2cF
2o, C
2h
4cF
2o, CH
2cF
2oCH
2, CH
2oCF
2cH
2, OCF
2c
2h
4, C
3h
6o, OC
3h
6, C
2h
4oCH
2, CH
2oC
2h
4, CH
2o, OCH
2,-CH=CH-,-C ≡ C-or COO;
M is 0 or 2;
N is 1,2 or 3.
2. liquid crystalline cpd according to claim 1, is characterized in that, R is selected from H or does not replace the alkyl that contains 1-3 carbon atom;
A
1, A
2and A
3be selected from independently of one another: singly-bound, Isosorbide-5-Nitrae-cyclohexyl, or Isosorbide-5-Nitrae-phenyl, wherein hydrogen can be replaced by one or more fluorine elements independently of one another;
A
4be selected from: Isosorbide-5-Nitrae-phenyl, wherein hydrogen can be replaced by one or more fluorine elements independently of one another;
Z
1, Z
2and Z
3be selected from independently of one another: singly-bound ,-(CH
2)
2-, CF
2o, OCF
2, CH
2o or OCH
2;
M is 0 or 2;
N is 1,2 or 3.
3. liquid crystalline cpd according to claim 2, is characterized in that, the liquid crystalline cpd structure of described general formula (I) is as follows:
Or
R is selected from H or CH
3;
A
1, A
2and A
3be selected from independently of one another: singly-bound, Isosorbide-5-Nitrae-cyclohexyl, or Isosorbide-5-Nitrae-phenyl, wherein hydrogen can be replaced by one or more fluorine elements independently of one another.
A
4be selected from: Isosorbide-5-Nitrae-phenyl, wherein hydrogen can be replaced by one or more fluorine elements independently of one another;
Z
1, Z
2and Z
3be selected from independently of one another: singly-bound ,-(CH
2)
2-, CF
2o, OCF
2, CH
2o or OCH
2.
N is 1,2 or 3.
4. liquid crystalline cpd according to claim 3, is characterized in that, the liquid crystalline cpd structure of described general formula (I) is as follows:
Wherein, R is selected from H or CH
3;
M is 0 or 2.
5. the preparation method of the arbitrary described liquid crystalline cpd of claim 1-4, is characterized in that, synthetic route is as follows:
1) Br-A
3-Z
3-A
4-OH and I (CH
2) nCH
2f generates Br-A
3-Z
3-A
4-O (CH
2) n-CH
2f;
2) Br-A
3-Z
3-A
4-O (CH
2) n-CH
2f and butyllithium carry out lithium halogen and exchange rear and protection reactive ketone, and through dehydration hydrogenation, formic acid deprotection generates O=A
1-Z
1-A
2-Z
2-A
3-Z
3-A
4-O (CH
2) n-CH
2f.
3) O=A
1-Z
1-A
2-Z
2-A
3-Z
3-A
4-O (CH
2) n-CH
2f and potassium tert.-butoxide and chloromethyl ether phosphonium salt through Wei ladder breath react generation CH
3oCH=A
1-Z
1-A
2-Z
2-A
3-Z
3-A
4-O (CH
2) n-CH
2f;
4) CH
3oCH=A
1-Z
1-A
2-Z
2-A
3-Z
3-A
4-O (CH2) n-CH
2f is dissolved in tetrahydrofuran (THF), reacts generation after hydrolysis with potassium hydroxide
5) in the time that m is 0,
0 DEG C with potassium tert.-butoxide and alkyl triphenyl phosphonium iodide through Wei ladder breath react generation
In the time that m is 2,
A)
in 40-50 DEG C, through potassium borohydride reduction 2-4 hour, dilute hydrochloric acid hydrolysis, generates HOCH
2-A
1-Z
1-A
2-Z
2-A
3-Z
3-A
4-O (CH
2) n-CH
2f;
B) in dichloromethane solution, HOCH
2-A
1-Z
1-A
2-Z
2-A
3-Z
3-A
4-O (CH
2) n-CH2F is at 15-20 DEG C, under the effect of catalyzer pyridine, react with Methanesulfonyl chloride within 1-2 hour, to be warming up to back flow reaction 3-5 hour and to generate CH
3o
2sOCH
2-A
1-Z
1-A
2-Z
2-A
3-Z
3-A
4-O (CH
2) n-CH
2f;
C) taking cupric chloride lithium as catalyzer,
CH
3o
2sOCH
2-A
1-Z
1-A
2-Z
2-A
3-Z
3-A
4-O (CH
2) n-CH
2f reacts with alkyl allyl bromide 98 generation Grignard reagent in anhydrous ether solution, and temperature control 38-42 DEG C stirring reaction generates for 8 hours
6. preparation method according to claim 5, is characterized in that step 1) in, Br-A
3-Z
3-A
4-OH and I (CH
2) nCH
2f is 60-75 DEG C of reaction 3-5h under Anhydrous potassium carbonate effect, generates Br-A
3-Z
3-A
4-O (CH
2) n-CH
2f.
7. preparation method according to claim 5, is characterized in that step 2) in, Br-A
3-Z
3-A
4-O (OH
2) n-CH
2f and butyllithium carry out the exchange of lithium halogen under-50--60 DEG C condition.
8. preparation method according to claim 5, is characterized in that step 3) in, O=A
1-Z
1-A
2-Z
2-A
3-Z
3-A
4-O (CH
2) n-CH
2f 0 DEG C with potassium tert.-butoxide and chloromethyl ether phosphonium salt through Wei ladder breath react generation CH
3oCH=A
1-Z
1-A
2-Z
2-A
3-Z
3-A
4-O (CH
2) n-CH
2f.
9. preparation method according to claim 5, is characterized in that step 4) in, by CH
3oCH=A
1-Z
1-A
2-Z
2-A
3-Z
3-A
4-O (CH
2) n-CH
2f is dissolved in tetrahydrofuran (THF), and dilute hydrochloric acid exists after lower back hydrolysis, then transposition generates in potassium hydroxide methanol solution
10. the application of the arbitrary described general formula of claim 1-4 (I) compound in TFT-LCD.
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