CN108315018A - A kind of liquid-crystal compounds and its preparation method and application with negative dielectric anisotropic - Google Patents
A kind of liquid-crystal compounds and its preparation method and application with negative dielectric anisotropic Download PDFInfo
- Publication number
- CN108315018A CN108315018A CN201810315926.8A CN201810315926A CN108315018A CN 108315018 A CN108315018 A CN 108315018A CN 201810315926 A CN201810315926 A CN 201810315926A CN 108315018 A CN108315018 A CN 108315018A
- Authority
- CN
- China
- Prior art keywords
- compound
- compounds
- dried
- spin
- negative dielectric
- 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.)
- Pending
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
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
- C09K19/3001—Cyclohexane rings
- C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
-
- 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
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
- C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
-
- 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
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
- C09K19/3402—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom
-
- 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
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
- C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
- C09K2019/121—Compounds containing phenylene-1,4-diyl (-Ph-)
- C09K2019/123—Ph-Ph-Ph
-
- 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
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
- C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
- C09K2019/121—Compounds containing phenylene-1,4-diyl (-Ph-)
- C09K2019/124—Ph-Ph-Ph-Ph
-
- 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
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
- C09K19/3001—Cyclohexane rings
- C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
- C09K2019/3016—Cy-Ph-Ph
-
- 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
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
- C09K19/3001—Cyclohexane rings
- C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
- C09K2019/3021—Cy-Ph-Ph-Cy
-
- 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
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
- C09K19/3001—Cyclohexane rings
- C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
- C09K2019/3025—Cy-Ph-Ph-Ph
-
- 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
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
- C09K19/3402—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom
- C09K2019/3422—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom the heterocyclic ring being a six-membered ring
Abstract
The present invention relates to a kind of liquid-crystal compounds and its preparation method and application with negative dielectric anisotropic.The invention discloses a kind of liquid-crystal compounds of the general formula I with negative dielectric anisotropic.The liquid-crystal compounds has great dielectric anisotropy absolute value, higher clearing point, preferable stability and anti-UV abilities.
Description
Technical field
The present invention relates to a kind of liquid-crystal compounds and its preparation method and application with negative dielectric anisotropic, belongs to liquid
Brilliant display material field.
Background technology
Liquid crystal display is typically realized using the characteristic of the optical anisotropy of liquid crystal material and dielectric anisotropy
Display function.According to the positive and negative of dielectric anisotropy, liquid crystal can be divided into positive dielectric anisotropy liquid crystal and negative dielectric respectively to different
Property liquid crystal.The liquid crystal applications of negative dielectric anisotropic are very extensive, become one of current research hotspot.Ideal liquid crystalline phase can not
It is simply obtained in this way, this is because when liquid crystal material needs to have significantly negative dielectric anisotropic and long enough
Between stability.Too long for probe response time early period of liquid crystal, viscosity is also required to improve.This will be by rotary viscosity γ 1
Influence, especially low temperature when value.The reduction of kinematic viscosity ν 20 can make vertical orientation edge arrange liquid crystal (such as
ECB and VAN are shown) there is the very short corresponding time.Therefore, it is necessary to effective technical solution be proposed, with great
While dielectric anisotropy absolute value, also there is higher clearing point, preferable stability and anti-UV abilities.
Invention content
The present invention in view of the above shortcomings of the prior art, provides a kind of liquid-crystal compounds with negative dielectric anisotropic.
The liquid-crystal compounds has great dielectric anisotropy absolute value, higher clearing point, preferable stability and anti-UV abilities.
The technical solution that the present invention solves above-mentioned technical problem is as follows：
A kind of liquid-crystal compounds with negative dielectric anisotropic, the compound have logical structure shown in formula I：The compound
With logical structure shown in formula I：
Wherein, R1, R2Can be identical, can be different, separate expression hydrogen atom, carbon atom number is the alkyl of 1-7, and carbon is former
The alkenyl that the alkoxy or carbon atom number that subnumber is 1~6 are 2~6；
Separate expression
WhereinIn (F) indicate F can with, can be without；
M, n are separate to indicate 0 or 1.
Further, the R1, R2It is separate to indicate that carbon atom number is the alkyl of 1-5, the alkane that carbon atom number is 1~5
The alkenyl that oxygroup or carbon atom number are 2~5.
1. it is further, it is describedIt indicates
Further, describedIt indicates
Further, the one kind of the compound of the general formula I in following general formula I -1 to I -24,
Advantageous effect：The liquid-crystal compounds that the present invention obtains has great dielectric anisotropy absolute value, higher clear
Bright spot, preferable stability and anti-UV abilities.
The present invention also provides a kind of methods preparing I structural compounds of general formula, include the following steps：
1) compound a is coupled by suzuki or grignard reaction, hydrogenation synthesize compound b；
2) compound b obtains compound c by boric acid on lithiation；
3) compound c obtains compound d by suzuki coupling reactions；
4) compound d obtains compound e by bromine in diazotising；
5) compound e is coupled by suzuki or grignard reaction synthesizes compound f；
6) compound f is aoxidized, and is reacted with hydroxylamine hydrochloride, is dehydrated to obtain final generalformulaⅰcompound.
The present invention also provides a kind of liquid-crystal compositions, including the liquid described in any one of the above embodiments with negative dielectric anisotropic
Brilliant compound.
The present invention also provides a kind of such as application of the above-mentioned liquid-crystal composition in field of liquid crystal.
Specific implementation mode
Illustrate the present invention below with reference to specific embodiment.It should be noted that the following examples are the present invention
Example, be only used for illustrating the present invention, and be not limited to the present invention.Without departing from present subject matter or range,
It can carry out other combinations and the various improvement in present inventive concept.
Embodiment 1
A kind of compoundPreparation method, wherein preparation route is as follows：
Specifically synthetic method is：
1,2 57.9g, 3- difluoro bromobenzenes make Grignard Reagent with THF, are cooled to -20 DEG C, and 19.1g acetaldehyde is added drop-wise to lattice
In family name's reagent, control temperature is warmed to room temperature naturally at -20 DEG C, is stirred 2h, is spin-dried for, and aqueous ammonium chloride solution is added, is extracted with EA；
EA phases use saturated common salt water washing 2 times, dry；300ml THF, 30ml TFA is added and stirs 12h, is spin-dried for obtaining 40.6g above-mentionedization
Close object 1.
2,40.6g compounds 1, for 0.3g palladiums charcoal in 300ml ethyl alcohol, atmospheric hydrogen adds hydrogen 5h, and filtering is spin-dried for obtaining 41.1g
Above compound 2.
3,41.1g compounds 2 are dissolved in 200mlTHF, are cooled to -78 DEG C, and 119ml butyl lithiums are instilled at -70 DEG C,
- 60 DEG C are warming up to, 1h is stirred；- 78 DEG C are cooled to, 70g butyl borates are instilled, are warmed to room temperature naturally, stirs 6h；It is added
200ml contains the water of 40ml concentrated hydrochloric acids, stirs 0.5h, and layering obtains organic layer；Organic phase is spin-dried for, and 46.5g is obtained with petroleum ether
Compound 3.
4,73.2g 2- amino -5- bromobenzoic acid ethyl esters, 11.9g sodium borohydrides, 0 DEG C of stirring 0.5h of 200ml absolute ethyl alcohols,
Naturally it is warmed to room temperature, stirs 2h；It is quenched with water, is spin-dried for, EA is added, with saturated common salt water washing 3 times；It is spin-dried for obtaining 58.6g chemical combination
Object 4.
5,40.4g compounds 4,40.9g compounds 3,60g potassium phosphates, tetra- triphenyl phosphorus palladiums of 0.5g, 400ml toluene, in nitrogen
The lower 90 DEG C of stirrings 8h of gas shielded；Cooling, EA is added in concentration, with saturated common salt water washing 3 times, anhydrous sodium sulfate drying, and filtering,
It is spin-dried for, obtains 50g compounds 5.
6,50g compounds 5,60ml dense bromic acids are cooled to 0 DEG C under 150ml THF stirrings, will contain 13.8g sodium nitrites
50ml aqueous solutions instill at 5 DEG C, keep stirring 1h at 5 DEG C, 2 g cuprous bromides are added three times, 3h is stirred at room temperature；It is spin-dried for,
200ml water is added, 200ml EA stir 5mins, filtering；Organic layer is washed 2 times, 58.7g compounds 6 are spin-dried for obtaining.
7,58.7g compounds 6,32.8g4- propyl phenyl boric acids, 58g potassium phosphates, tetra- triphenyl phosphorus palladiums of 0.5g, 400ml first
Benzene stirs 8h for 90 DEG C under nitrogen protection；Cooling, EA is added in concentration, and with saturated common salt water washing 3 times, anhydrous sodium sulfate is dry
Dry, filtering is spin-dried for, obtains 62.2g compounds 7.
8,12h is stirred at room temperature in 62.2g compounds 7,15.6g manganese dioxide, 240mlTHF；Filtering, is spin-dried for obtaining 61.9g chemical combination
Object 8.
9,61.9g compounds 8,12.6g hydroxylamine hydrochlorides, 18g triethylamines, 300ml THF are stirred at room temperature 5h, are spin-dried for；It is added
200ml acetic anhydrides are heated to reflux 3h；It is spin-dried for, obtained solid petroleum ether obtains 45g target compounds at crystallization 2 times.
Embodiment 2
A kind of compoundPreparation method, wherein preparation route is as follows：
Specifically synthetic method is：
1, compound 3, synthetic method of the synthetic method with compound 3 in embodiment 1 are synthesized.
2,41g compounds 3,38.2g 1,2- difluoro bromobenzenes, 60g potassium phosphates, tetra- triphenyl phosphorus palladiums of 0.5g, 300ml toluene,
90 DEG C of stirring 8h under nitrogen protection；Cooling, EA is added in concentration, with saturated common salt water washing 3 times, anhydrous sodium sulfate drying,
Filtering, is spin-dried for, obtains 48.3g compounds 9.
3,48.3g compounds 9 are dissolved in 200mlTHF, are cooled to -78 DEG C, and 84ml butyl lithiums are instilled at -70 DEG C, are risen
Temperature arrives -40 DEG C, stirs 1h.- 78 DEG C are cooled to, 48g butyl borates are instilled, are warmed to room temperature naturally, stirs 6h.It is added
200ml contains the water of 40ml concentrated hydrochloric acids, stirs 0.5h, and layering obtains organic layer.Organic phase is spin-dried for, and 51gization is obtained with petroleum ether
Close object 10.
4,51g compounds 10,34.3g compounds 4,55g potassium phosphates, tetra- triphenyl phosphorus palladiums of 0.4g, 280ml toluene, in nitrogen
The lower 90 DEG C of stirrings 8h of gas shielded.Cooling, EA is added in concentration, with saturated common salt water washing 3 times, anhydrous sodium sulfate drying, and filtering,
It is spin-dried for, obtains 60g compounds 11.
5,60g compounds 11,50ml dense bromic acids are cooled to 0 DEG C under 150ml THF stirrings, will contain 12.1g sodium nitrites
40ml aqueous solutions instill at 5 DEG C, keep stirring 1h at 5 DEG C, 1.2g cuprous bromides are added three times, 3h is stirred at room temperature.Rotation
It is dry, 200ml water is added, 200ml EA stir 5mins, filtering.Organic layer is washed 2 times, 66g compounds 12 are spin-dried for obtaining.
6,66g compounds 12 and 16.5g triethylamines are dissolved in 200ml DCM, are cooled to 0 DEG C, by 26.6gSEM-Cl drops
Enter, be raised to room temperature naturally, stirs 8h.With saturated common salt water washing DCM phases 3 times, it is spin-dried for obtaining 85.5g compounds 13.
7,85.5g compounds 13 are made into Grignard Reagent with THF.- 20 DEG C are cooled to, 18g4- methyl cyclohexanones are added dropwise
Into Grignard Reagent, control temperature is slowly increased to room temperature at -20 DEG C, stirs 2h.It is spin-dried for, aqueous ammonium chloride solution is added, is extracted with EA
It takes；EA phases use saturated common salt water washing 2 times, dry.300ml THF, 30ml TFA is added and stirs 12h, is spin-dried for obtaining 87.7g chemical combination
Object 14.
8,87.7g compounds 14, for 0.3g Ranney nickel in 300ml ethyl alcohol, atmospheric hydrogen adds hydrogen 5h.Filtering, is spin-dried for；
82g compounds 15 are recrystallized to obtain with petroleum ether.
9,82g compounds 15,400ml ethyl alcohol, 0.1gTBAF stir 12h.It is spin-dried for obtaining 63.8 compounds 16.
10,12h is stirred at room temperature in 63.8 compound 16,13g manganese dioxide, 240mlTHF.Filtering, is spin-dried for obtaining 63.5g chemical combination
Object 17.
11,63.5g compounds 17,12.3g hydroxylamine hydrochlorides, 17.6g triethylamines, 300ml THF are stirred at room temperature 5h, are spin-dried for；
200ml acetic anhydrides are added and are heated to reflux 3h.It is spin-dried for, obtained solid petroleum ether obtains 42g target compounds at crystallization 2 times.
Embodiment 2
A kind of compoundPreparation method, wherein preparation route is as follows：
Specifically synthetic method is：
1, compound 13, synthetic method of the synthetic method with compound 13 in embodiment 2 are synthesized.
2,85.5g compounds 13 are made into Grignard Reagent with THF；- 20 DEG C are cooled to, 9.3g propionic aldehyde is added drop-wise to grignard
In reagent, control temperature is slowly increased to room temperature at -20 DEG C, stirs 2h；It is spin-dried for, aqueous ammonium chloride solution is added, is extracted with EA；EA
Mutually use saturated common salt water washing 2 times, it is dry；300ml THF, 30ml TFA is added and stirs 12h, is spin-dried for obtaining 74.2g compounds 18.
3,74.2g compounds 18, for 0.3g Ranney nickel in 290ml ethyl alcohol, atmospheric hydrogen adds hydrogen 5h.Filtering, is spin-dried for；
69g compounds 19 are recrystallized to obtain with petroleum ether.
4,69g compounds 19,360ml ethyl alcohol, 0.1gTBAF stir 12h.It is spin-dried for obtaining 52.3g compounds 20.
5,12h is stirred at room temperature in 52.3 compound 20,12.5g manganese dioxide, 200mlTHF.Filtering, is spin-dried for obtaining 52g compounds
21。
6,52g compounds 21,12.1g hydroxylamine hydrochlorides, 17.3g triethylamines, 300ml THF are stirred at room temperature 5h, are spin-dried for；It is added
190ml acetic anhydrides are heated to reflux 3h.It is spin-dried for, obtained solid is recrystallized 2 times with petroleum ether, obtains 38g target compounds.
Embodiment 4
A kind of compoundPreparation method, wherein preparation route is as follows：
Specifically synthetic method is：
1, compound 13, synthetic method of the synthetic method with compound 13 in embodiment 2 are synthesized.
2,57g compounds 13,17g is to propyl phenyl boric acid, 40g potassium phosphates, tetra- triphenyl phosphorus palladiums of 0.5g, 200ml toluene,
The lower 90 DEG C of stirrings 8h of nitrogen protection；Cooling, EA is added in concentration, with saturated common salt water washing 3 times, anhydrous sodium sulfate drying, mistake
Filter, is spin-dried for, obtains 54.7g compounds 22.
3,54.7g compounds 22,360ml ethyl alcohol, 0.1gTBAF stir 12h；It is spin-dried for obtaining 43g compounds 23.
4,12h is stirred at room temperature in 43g compounds 23,8.7g manganese dioxide, 150mlTHF.Filtering, is spin-dried for obtaining 42g compounds
24。
5,42g compounds 24,7.1g hydroxylamine hydrochlorides, 10.3g triethylamines, 300ml THF are stirred at room temperature 5h, are spin-dried for；It is added
120ml acetic anhydrides are heated to reflux 3h；It is spin-dried for, obtained solid is recrystallized 2 times with petroleum ether, obtains 28g target compounds.
Embodiment 5
A kind of compoundPreparation method, wherein preparation route is as follows：
Specifically synthetic method is：
1, the fluoro- 4 ethyl phenyl boric acids of 37g 3-, 38.2g 1,2- difluoro bromobenzenes, 60g potassium phosphates, 0.5 g, tetra- triphenyl phosphorus
Palladium, 300ml toluene stir 8h for 90 DEG C under nitrogen protection；Cooling, EA is added in concentration, anhydrous with saturated common salt water washing 3 times
Sodium sulphate is dried, and filtering is spin-dried for, obtains 44.8g compounds 25.
2,44.8g compounds 25 are dissolved in 200mlTHF, are cooled to -78 DEG C, and 84ml butyl lithiums are instilled at -70 DEG C,
- 60 DEG C are warming up to, 1h is stirred；- 78 DEG C are cooled to, 48g butyl borates are instilled, are warmed to room temperature naturally, stirs 6h；It is added
200ml contains the water of 40ml concentrated hydrochloric acids, stirs 0.5h, and layering obtains organic layer；Organic phase is spin-dried for, and 50.4g is obtained with petroleum ether
Compound 26.
3,50.4g compounds 26,34.3g compounds 4,55g potassium phosphates, tetra- triphenyl phosphorus palladiums of 0.4g, 280ml toluene,
The lower 90 DEG C of stirrings 8h of nitrogen protection；Cooling, EA is added in concentration, with saturated common salt water washing 3 times, anhydrous sodium sulfate drying, mistake
Filter, is spin-dried for, obtains 60.7g compounds 27.
4,60.7g compounds 27,51ml dense bromic acids are cooled to 0 DEG C under 150ml THF stirrings, will contain 12.5g nitrous acid
Sodium 40ml aqueous solutions instill at 5 DEG C, keep stirring 1h at 5 DEG C, 1.2g cuprous bromides are added three times, 3h is stirred at room temperature；
It is spin-dried for, 200ml water is added, 200ml EA stir 5mins, filtering；Organic layer is washed 2 times, 67.4g compounds 28 are spin-dried for obtaining.
5,67.7g compounds 28 and 17.6g triethylamines are dissolved in 200ml DCM, are cooled to 0 DEG C, by 27.6gSEM-Cl drops
Enter, be raised to room temperature naturally, stirs 8h；With saturated common salt water washing DCM phases 3 times, it is spin-dried for obtaining 88g compounds 29.
6,88g compounds 29 are made into Grignard Reagent with THF；- 20 DEG C are cooled to, 18.5g4- methyl cyclohexanones are added dropwise
Into Grignard Reagent, control temperature is slowly increased to room temperature at -20 DEG C, stirs 2h；It is spin-dried for, aqueous ammonium chloride solution is added, is extracted with EA
It takes；EA phases use saturated common salt water washing 2 times, dry.300ml THF, 30ml TFA is added and stirs 12h, is spin-dried for obtaining 83g compounds
30。
7,83g compounds 30, for 0.3g Ranney nickel in 300ml ethyl alcohol, atmospheric hydrogen adds hydrogen 5h.Filtering, is spin-dried for；With
Petroleum ether recrystallizes to obtain 60.5g compounds 31.
8,60.5g compounds 31,400ml ethyl alcohol, 0.1gTBAF stir 12h.It is spin-dried for obtaining 60.6 compounds 32.
9,12h is stirred at room temperature in 60.6 compound 32,13g manganese dioxide, 240mlTHF.Filtering, is spin-dried for obtaining 60.5g compounds
33。
10,60.5g compounds 33,10g hydroxylamine hydrochlorides, 13g triethylamines, 300ml THF are stirred at room temperature 5h, are spin-dried for；It is added
200ml acetic anhydrides are heated to reflux 3h.It is spin-dried for, obtained solid is recrystallized 2 times with petroleum ether, obtains 45g target compounds.
Embodiment 6
A kind of compoundPreparation method, wherein preparation route is as follows：
Specifically synthetic method is：
1, compound 29, synthetic method of the synthetic method with compound 29 in embodiment 5 are synthesized.
2,55.1g compounds 29 are made into Grignard Reagent with THF；- 20 DEG C are cooled to, 6.4g propionic aldehyde is added drop-wise to grignard
In reagent, control temperature is slowly increased to room temperature at -20 DEG C, stirs 2h；It is spin-dried for, aqueous ammonium chloride solution is added, is extracted with EA；EA
Mutually use saturated common salt water washing 2 times, it is dry；300ml THF, 30ml TFA is added and stirs 12h, is spin-dried for obtaining 48.7g compounds 34.
3,48.7g compounds 34, for 0.3g Ranney nickel in 290ml ethyl alcohol, atmospheric hydrogen adds hydrogen 5h, and filtering is spin-dried for；
48.8g compounds 35 are recrystallized to obtain with petroleum ether.
4,48g compounds 35,360ml ethyl alcohol, 0.1gTBAF stir 12h；It is spin-dried for obtaining 36.5g compounds 36.
5,12h is stirred at room temperature in 36.5 compound 36,9.5g manganese dioxide, 200mlTHF；Filtering, is spin-dried for obtaining 36.6g chemical combination
Object 37.
6,36.6g compounds 37,7.5g hydroxylamine hydrochlorides, 10.5g triethylamines, 150ml THF are stirred at room temperature 5h, are spin-dried for；Add
Enter 120ml acetic anhydrides and is heated to reflux 3h；It is spin-dried for, obtained solid is recrystallized 2 times with petroleum ether, obtains 25.8g target compounds.
Embodiment 7
A kind of compoundPreparation method, wherein preparation route is as follows：
Specifically synthetic method is：
1, compound 29, synthetic method of the synthetic method with compound 29 in embodiment 5 are synthesized.
2,55.1g compounds 29,17g is to propyl phenyl boric acid, 40g potassium phosphates, tetra- triphenyl phosphorus palladiums of 0.5g, 200ml toluene,
90 DEG C of stirring 8h under nitrogen protection；Cooling, EA is added in concentration, with saturated common salt water washing 3 times, anhydrous sodium sulfate drying, mistake
Filter, is spin-dried for, obtains 52.7g compounds 38.
3,52.7g compounds 38,360ml ethyl alcohol, 0.1gTBAF stir 12h；It is spin-dried for obtaining 40g compounds 39.
4,12h is stirred at room temperature in 40g compounds 39,8.7g manganese dioxide, 150mlTHF；Filtering, is spin-dried for obtaining 39g compounds
40。
5,39g compounds 40,7.1g hydroxylamine hydrochlorides, 10.3g triethylamines, 300ml THF are stirred at room temperature 5h, are spin-dried for；It is added
120ml acetic anhydrides are heated to reflux 3h；It is spin-dried for, obtained solid is recrystallized 2 times with petroleum ether, obtains 27g target compounds.
Embodiment 8
A kind of compoundPreparation method, wherein preparation route is as follows：
1,33g 4- ethyls phenyl boric acid, 38.6g 1,2- difluoro bromobenzenes, 65g potassium phosphates, tetra- triphenyl phosphorus palladiums of 0.5g,
400ml toluene stirs 8h for 90 DEG C under nitrogen protection；Cooling, EA is added in concentration, with saturated common salt water washing 3 times, anhydrous sulphur
Sour sodium drying, filtering are spin-dried for, obtain 41.4g compounds 41.
2,41.4g compounds 41 are dissolved in 200mlTHF, are cooled to -78 DEG C, and 84ml butyl lithiums are instilled at -70 DEG C,
- 60 DEG C are warming up to, 1h is stirred；- 78 DEG C are cooled to, 48g butyl borates are instilled, are warmed to room temperature naturally, stirs 6h；It is added
200ml contains the water of 40ml concentrated hydrochloric acids, stirs 0.5h, and layering obtains organic layer；Organic phase is spin-dried for, and 45gization is obtained with petroleum ether
Close object 42.
3,20.2g compounds 4,29g compounds 42,40g potassium phosphates, tetra- triphenyl phosphorus palladiums of 0.5g, 300ml toluene, in nitrogen
The lower 90 DEG C of stirrings 8h of gas shielded；Cooling, EA is added in concentration, with saturated common salt water washing 3 times, anhydrous sodium sulfate drying, and filtering,
It is spin-dried for, obtains 32.3g compounds 43.
4,32.3g compounds 43,35ml dense bromic acids are cooled to 0 DEG C under 100ml THF stirrings, will contain 8.4g nitrous acid
Sodium 50ml aqueous solutions instill at 5 DEG C, keep stirring 1h at 5 DEG C, 2g cuprous bromides are added three times, 3h is stirred at room temperature；Rotation
It is dry, 200ml water is added, 200ml EA stir 5mins, filtering.Organic layer is washed 2 times, 36g compounds 44 are spin-dried for obtaining.
5,36g compounds 44,20.8g4- propyl phenyl boric acids, 58g potassium phosphates, tetra- triphenyl phosphorus palladiums of 0.5g, 200ml toluene,
90 DEG C of stirring 8h under nitrogen protection；Cooling, EA is added in concentration, with saturated common salt water washing 3 times, anhydrous sodium sulfate drying,
Filtering, is spin-dried for, obtains 35g compounds 45.
6,12h is stirred at room temperature in 35g compounds 45,8.7g manganese dioxide, 240mlTHF；Filtering, is spin-dried for obtaining 35g compounds
46。
7,35g compounds 46,10.6g hydroxylamine hydrochlorides, 12g triethylamines, 300ml THF are stirred at room temperature 5h, are spin-dried for；It is added
100ml acetic anhydrides are heated to reflux 3h；It is spin-dried for, obtained solid is recrystallized 2 times with petroleum ether, obtains 20g target compounds.
Application examples
For ease of expressing, in following two application examples, the unit structure of liquid-crystal compounds is indicated with the code listed by table 1：
The group structure code of 1 liquid-crystal compounds of table
Percentage in application examples represents weight percent unless otherwise specified.
Cp (DEG C) represents clearing point.
△ n represent optical anisotropy at 20 DEG C, 589nm.
△ ε represent dielectric anisotropy at 25 DEG C.
γ 1 (mPas) represents rotary viscosity at 20 DEG C.
Vo (V) represents 20 DEG C of lower threshold voltages.
Application examples E1：
The formula composition and parameter of 2 application examples E1 of table
Application examples E2：
The formula composition and parameter of 3 application examples E2 of table
It can be seen that from the above application examples, when liquid-crystal compounds proposed by the invention is applied to liquid-crystal composition, composition
With larger dielectric anisotropy absolute value, higher clearing point, optical anisotropy appropriate is wider to list temperature
Range can be used for the display patterns such as VA, MVA, PVA, PSVA, IPS, FFS, TFT.
The present invention relates to a kind of liquid crystal medias, have negative dielectric anisotropy, clearing point ＞ 70 based on polar compound
℃。
Present invention can assure that display there can be the short response time at high or extremely low temperature, improve simultaneously
Stability does not especially have image sticking phenomenon by prolonged operation.
The present invention can be summarized with others without prejudice to the concrete form of the spirit or essential characteristics of the present invention.Therefore, nothing
By from the point of view of which point, the embodiment above of the invention can only all be considered the description of the invention and cannot limit this hair
Bright, claims indicate the scope of the present invention, and above-mentioned explanation does not point out the scope of the present invention, therefore, with this
Any change in the comparable meaning and scope of claims of invention is all considered as being included in the claim of the present invention
In the range of book.
Claims (8)
1. a kind of liquid-crystal compounds with negative dielectric anisotropic, which is characterized in that the compound has logical structure shown in formula I：
Wherein, R1, R2Can be identical, can be different, separate expression hydrogen atom, carbon atom number is the alkyl of 1-7, carbon atom number
The alkenyl that alkoxy or carbon atom number for 1~6 are 2~6；Separate expressionM, n are separate to indicate 0 or 1.
2. the compound according to claim 1 with negative dielectric anisotropic, which is characterized in that the R1, R2Respectively solely
Vertical expression carbon atom number is the alkyl of 1-5, the alkenyl that the alkoxy or carbon atom number that carbon atom number is 1~5 are 2~5.
3. the compound according to claim 1 with negative dielectric anisotropic, which is characterized in that describedIt indicates
4. the compound according to claim 1 with negative dielectric anisotropic, which is characterized in that describedIt indicates
5. the compound according to claim 2 with negative dielectric anisotropic, which is characterized in that the change of the general formula I
It closes object and preferably is selected from one kind in following general formula I -1 to I -24,
6. a kind of method preparing I structural compounds of general formula, which is characterized in that include the following steps：
1) compound a is coupled by suzuki or grignard reaction, hydrogenation synthesize compound b；
2) compound b obtains compound c by boric acid on lithiation；
3) compound c obtains compound d by suzuki coupling reactions；
4) compound d obtains compound e by bromine in diazotising；
5) compound e is coupled by suzuki or grignard reaction synthesizes compound f；
6) compound f is aoxidized, and is reacted with hydroxylamine hydrochloride, is dehydrated to obtain final generalformulaⅰcompound.
7. the liquid-crystal composition with negative dielectric anisotropic compound according to claims 1 to 5.
8. a kind of application of liquid-crystal composition as claimed in claim 7 in field of liquid crystal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810315926.8A CN108315018A (en) | 2018-04-10 | 2018-04-10 | A kind of liquid-crystal compounds and its preparation method and application with negative dielectric anisotropic |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810315926.8A CN108315018A (en) | 2018-04-10 | 2018-04-10 | A kind of liquid-crystal compounds and its preparation method and application with negative dielectric anisotropic |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108315018A true CN108315018A (en) | 2018-07-24 |
Family
ID=62898177
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810315926.8A Pending CN108315018A (en) | 2018-04-10 | 2018-04-10 | A kind of liquid-crystal compounds and its preparation method and application with negative dielectric anisotropic |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108315018A (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0892190A (en) * | 1994-09-26 | 1996-04-09 | Kanto Chem Co Inc | Cyanobiphenyl derivative and liquid crystal composition containing the derivative |
| CN101407719A (en) * | 2008-03-28 | 2009-04-15 | 河北迈尔斯通电子材料有限公司 | Negative dielectric anisotropy liquid crystal material composition and liquid crystal display device using the same |
| CN101735823A (en) * | 2009-12-18 | 2010-06-16 | 北京八亿时空液晶材料科技有限公司 | Negative dielectric anisotropy liquid crystal composition |
| CN102344815A (en) * | 2011-07-12 | 2012-02-08 | 石家庄诚志永华显示材料有限公司 | Negative dielectric anisotrophy liquid crystal mixture |
| CN102492430A (en) * | 2011-11-28 | 2012-06-13 | 江苏和成化学材料有限公司 | Liquid crystal composition and liquid crystal display element containing the same |
| CN103058886A (en) * | 2013-01-29 | 2013-04-24 | 石家庄诚志永华显示材料有限公司 | Poly-fluorine poly-cyanogen liquid crystal compound as well as preparation method and application thereof |
| CN104152155A (en) * | 2014-07-17 | 2014-11-19 | 北京大学 | High negative dielectric anisotropy liquid crystal mixture with high birefringence and low viscosity and application thereof |
| CN106459764A (en) * | 2014-06-19 | 2017-02-22 | Dic株式会社 | Polymerizable-monomer-containing liquid crystal composition and liquid crystal display element using same |
-
2018
- 2018-04-10 CN CN201810315926.8A patent/CN108315018A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0892190A (en) * | 1994-09-26 | 1996-04-09 | Kanto Chem Co Inc | Cyanobiphenyl derivative and liquid crystal composition containing the derivative |
| CN101407719A (en) * | 2008-03-28 | 2009-04-15 | 河北迈尔斯通电子材料有限公司 | Negative dielectric anisotropy liquid crystal material composition and liquid crystal display device using the same |
| CN101735823A (en) * | 2009-12-18 | 2010-06-16 | 北京八亿时空液晶材料科技有限公司 | Negative dielectric anisotropy liquid crystal composition |
| CN102344815A (en) * | 2011-07-12 | 2012-02-08 | 石家庄诚志永华显示材料有限公司 | Negative dielectric anisotrophy liquid crystal mixture |
| CN102492430A (en) * | 2011-11-28 | 2012-06-13 | 江苏和成化学材料有限公司 | Liquid crystal composition and liquid crystal display element containing the same |
| CN103058886A (en) * | 2013-01-29 | 2013-04-24 | 石家庄诚志永华显示材料有限公司 | Poly-fluorine poly-cyanogen liquid crystal compound as well as preparation method and application thereof |
| CN106459764A (en) * | 2014-06-19 | 2017-02-22 | Dic株式会社 | Polymerizable-monomer-containing liquid crystal composition and liquid crystal display element using same |
| CN104152155A (en) * | 2014-07-17 | 2014-11-19 | 北京大学 | High negative dielectric anisotropy liquid crystal mixture with high birefringence and low viscosity and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6137419B2 (en) | Nematic liquid crystal composition and liquid crystal display device using the same | |
| TWI567170B (en) | A liquid crystal compound and a liquid crystal composition containing the same | |
| KR101431935B1 (en) | Cyclohexane compound and liquid crystal composition containing said compound | |
| CN102795974B (en) | Liquid crystal medium and liquid crystal composition | |
| CN104087310B (en) | A kind of high birefringence rate liquid crystal compound and combinations thereof thing | |
| TW201026823A (en) | Liquid-crystalline medium | |
| WO2014183561A1 (en) | Liquid crystal composition and liquid crystal display device | |
| CN103254903A (en) | Liquid crystal compound containing difluoro-methylene key bridge, preparation method thereof and composition containing liquid crystal compound | |
| CN108251128A (en) | A kind of liquid-crystal compounds with negative dielectric anisotropic and its preparation method and application | |
| CN105294526A (en) | High-birefringence liquid crystal compound, preparing method and composition of high-birefringence liquid crystal compound | |
| CN102203214A (en) | Butene-based liquid crystal compounds | |
| TW200946651A (en) | Liquid crystal compound having negative dielectric anisotropy, liquid crystal composition, and liquid crystal display device | |
| CN104610978A (en) | Liquid crystal compounds and liquid crystal medium containing same | |
| CN109749755A (en) | A kind of liquid-crystal compounds and composition improving liquid crystal material environmental suitability | |
| JP6070110B2 (en) | Compound with fluorinated naphthalene structure | |
| CN102153442A (en) | Alkyl dicyclohexyl 2,3-difluorophenylbutenoid liquid crystal compound and application thereof | |
| JP2005272562A (en) | Liquid crystal composition containing trifluoronaphthalene derivative and display element and compound | |
| CN101928199B (en) | Divinyl liquid crystal compound and preparation method thereof | |
| CN108315018A (en) | A kind of liquid-crystal compounds and its preparation method and application with negative dielectric anisotropic | |
| JPH0316331B2 (en) | ||
| CN108315017A (en) | A kind of liquid-crystal compounds and its preparation method and application with negative dielectric anisotropic | |
| JPH03505093A (en) | Fluorinated 4″-cyano-substituted terphenyl | |
| JPH0432067B2 (en) | ||
| JP3899530B2 (en) | Liquid crystal compound and liquid crystal composition | |
| CN103131425A (en) | Fluorine-containing liquid crystal compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180724 |