CN1150297C - Fluoric liquid crystal compound with pyrimidine ring and its application - Google Patents
Fluoric liquid crystal compound with pyrimidine ring and its application Download PDFInfo
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- CN1150297C CN1150297C CNB021465681A CN02146568A CN1150297C CN 1150297 C CN1150297 C CN 1150297C CN B021465681 A CNB021465681 A CN B021465681A CN 02146568 A CN02146568 A CN 02146568A CN 1150297 C CN1150297 C CN 1150297C
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Abstract
The present invention provides a fluorine-containing liquid crystal compound with a pyrimidine ring, which has a basic structure that a normal alkyl radical is connected with the position 5 of the pyrimidine ring, one end of a phenylene radical is connected with the position 2 of the pyrimidine ring, and the position 4 of the other end of the phenylene radical is connected with one end of a bridge radical Z of which the other end is connected with position 1 phenyl which can contain different fluorine groups in position 4 or positions 3 and 4. When X is equal to-F, Rf is equal to-f; when X is equal to-H, Rf is equal to-CF3; when X is equal to-H, Rf is equal to-OCF3. The bridge radical of the fluorine-containing liquid crystal compound with the pyrimidine ring comprises ethane-N, ethene and ethynyl. The normal alkyl comprises normal ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, celiteyl and decyl. The fluorine-containing liquid crystal compound has the application field of mixing liquid crystal.
Description
Technical field
The present invention relates to a kind of liquid crystalline cpd and application, especially, belong to technical field of organic synthesis with the fluorinated liquid crystal compound and the application of pyrimidine ring.
Background technology
The working fluid of liquid-crystal display is to be mixed according to the technical requirementss such as electric light physicals of indicating meter with multiple monomer liquid crystal to form.The mixed liquid crystal that obtains excellent properties must use the monomer liquid crystal of excellent properties, and the synthetic compound that contains different liquid crystal structures is realized the different electric light physicalies of mixed liquid crystal.It requires supertwist nematic liquid crystal (stn liquid crystal): driving voltage is low, and the liquid crystal operating temperature range is wide, suitable photoanisotropy refringence and good thermostability, light stability and chemical stability.In the process that is mixed of stn liquid crystal, often add the monomer liquid crystal that some have a certain property, as add liquid crystal of big Δ n value and Δ ε value etc., to improve the property of mixed liquid crystal system.Band pyrimidine ring fluorinated liquid crystal United States Patent (USP) 5,021,189 (1991), European patent 0391,591, (1990), German Patent 4,334,126 (1995) all have report, and the structure that the present invention designs compound has different abutments and fluoro-containing group, more meets the requirement to use properties.
Summary of the invention
Technical scheme of the present invention is achieved in that the fluorinated liquid crystal basic structure of this band pyrimidine ring comprises: normal chain alkyl links to each other with the 5-position of pyrimidine ring, penylene base one end links to each other with the 2-position of pyrimidine ring, the other end 4-position links to each other with the end of abutment Z, the other end of abutment links to each other with 1-position phenyl, this phenyl can be in 4-or 3,4-contains the position different fluorin radicals, and the structure of compound is shown in general formula (I):
The fluorinated liquid crystal compound structure characteristics of the band pyrimidine ring of the present invention's design are: work as X=-F, R
f=-F, compound is shown in general formula (II):
The fluorine-containing liquefaction compound of described band pyrimidine ring is worked as X=-H, R
f=-CF3, shown in general formula (III):
The fluorinated liquid crystal compound of described band pyrimidine ring is worked as X=-H, R
f=-OCF3, shown in general formula (IV):
Z described in the fluorinated liquid crystal compound general formula of described band pyrimidine ring comprises ethane, ethene, ethynyl.
R described in the fluorinated liquid crystal compound general formula of described band pyrimidine ring is included as ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl and the decyl of positive structure.
The fluorinated liquid crystal application of compound of band pyrimidine ring of the present invention comprises: the alkyl that contains general formula (II) or (III) or (IV) expression in the liquid crystal that is mixed be positive structure ethyl to decyl, abutment is the compound or derivatives thereof of ethane, ethene, ethynyl.
The fluorinated liquid crystal application of compound of band pyrimidine ring also comprises: the alkyl that contains general formula (II) or (III) or (IV) expression between the liquid-crystal display electrode pair be positive structure ethyl to decyl, abutment is the compound or derivatives thereof of ethane, ethene, ethynyl.
The synthetic method of the fluorinated liquid crystal compound of band pyrimidine ring of the present invention is that 215 pages of Molecular Crystals and Liquid Crystals 1997 42 volumes through revising are to the method for 231 pages of synthetic pyrimidine rings with utilize the Wittig reaction (Huang Wenfang writes, ylide chemistry, press of Central China Normal University) method synthesis of constructing etheno forms.
The fluorinated liquid crystal technical feature characteristics of band pyrimidine ring of the present invention are: wide temperature is hanged down threshold value, and the Use Limitation fruit is good.The nitrogen-atoms that the strong polarity cloud density of pyrimidine ring permanent dipole moment is big is consistent with the direction of end group fluorin radical relative position, the additivity that it can be contributed makes that the liquid crystalline cpd specific inductivity with this structure is very big, threshold voltage is low, and driving voltage is also low, is applicable to that multichannel drives demonstration; Compound with this structure has high fusing point and clearing point (170-180 ℃), shows very wide intermediary's phase temperature range; Their elastic constant is than (K in addition
33/ K
11) less, favourable to improving the speed of response and multichannel driving force; The low temperature intermiscibility is good, and add-on can reach 20%, is difficult for separating out at low temperatures crystallization.The existence of end group fluorin radical makes them have good thermal stability, light stability and chemical stability; Abutment has improved their elastic constant during for ethyl group than (K
33/ K
11), abutment has enlarged their specific refractory power anisotropy poor (Δ n=0.2) when being vinyl and ethynyl, and " four bottles system " the middle degree of birefringence of regulating that is specially adapted to stn liquid crystal is used.The detrimentally affect that pyrimidine ring brings is that (8-10 10 for the viscosity number height
-5m
2/ S) be not suitable for the liquid crystal that is mixed of preparation high-speed response value.Weigh the advantages and disadvantages, the scope that generally contains liquid crystal add-on in the prescription that is mixed of pyrimidine ring is below 10%, and individual cases are 14%-15% down.
Embodiment
Be n-pentyl below with R, Z is a hexyl, and vinyl and ethynyl, X are F, R
fDuring for F, compound is embodiment shown in the general formula (II), and the synthetic method of the fluorinated liquid crystal of three kinds of band pyrimidine rings is described.
The structural formula of three kinds of compounds is as follows:
Embodiment 1: preparation R is a n-pentyl, and Z is a vinyl, and X is F, R
fCompound for F
(1), the preparation of 3-oxyethyl group-2-n-pentyl-propenal:
30 gram (0.16 mole) 2-amyl group mdas four oxalic dialdehyde that contracts, 3.5 ml water and 150 milligrams of tosic acid are as catalyzer, 80-85 ℃ of following Hybrid Heating 3 hours, be chilled to room temperature and add 1.6 gram (0.02 mole) sodium bicarbonates, reaction mixture stirred 1.5 hours, add ether, isolated ether layer is washed 3 times with about 80 milliliters branches of 3N aqueous sodium hydroxide solution, washes with water till the neutrality again.Use anhydrous sodium sulfate drying, remove ether, thick product is directly used in down in the step building-up reactions.
(2), the preparation of pyrimidine ring derivative:
With 18.3 gram (0.08 mole) 4-miaow yl benzoic acid ethyl esters and 13.6 gram (0.08 mole) 2-amyl group-3-ethoxy-c olefine aldehydrs and 7.5 gram (0.2 mole) sodium ethylates, be added in 150 milliliters of ethanol and obtain suspension, feed nitrogen, stir under the room temperature and spend the night, continue ethyl esterization behind the hcl acidifying.Leach the solid of generation, water, ethanol and ether washing are air-dry successively, yield 85%.Be further purified and use silica gel column chromatography, irrigation toluene adds 5% acetone, recrystallization in the ethanol.
(3), the preparation of band pyrimidine ring benzylalcohol derivative:
Carboxylic acid, ethyl ester 30 grams (0.1 mole) that make the band pyrimidine ring are dissolved in the anhydrous tetrahydro furan, slowly splash into 5.7 gram (0.15 mole) lithium aluminium hydride anhydrous tetrahydro furan suspension under the nitrogen filled protection stirring, backflow is spent the night.Drip 6 ml waters successively, 12 milliliter of 10% aqueous sodium hydroxide solution and 18 ml waters stirred 20 minutes, with extracted with diethyl ether 3 times, merged organic phase.Saturated common salt is washed to neutrality, anhydrous sodium sulfate drying, and steaming desolventizes, solid ethyl alcohol recrystallization, yield 95%.
(4), the preparation of band pyrimidine ring benzyl br-derivatives:
47% bromine hydracid of 10 gram (0.1 mole) vitriol oils and 35 grams (0.2 mole) is added in the reaction flask, stir under the room temperature, benzylalcohol 25.6 grams (0.1 mole) that make the band pyrimidine ring are dissolved in 25 milliliters of methylene dichloride, slowly splash into heating 2 hours, steam under 40 ℃ to desolventize and continue to reflux 4 hours, be chilled to room temperature with toluene extraction 3 times, successively with 10% sodium bicarbonate aqueous solution be washed to only neutral.Steam and remove toluene, resultant can directly be used, yield 85%.
(5), the preparation of band pyrimidine ring microcosmic salt:
In bottle, add 16 gram (0.06 mole) triphenyl phosphines,, benzyl br-derivatives 16 grams (0.05 mole) that make the band pyrimidine ring are dissolved in the toluene of new steaming too, under nitrogen protection, splash in the triphenyl phosphine solution in the stirring with new toluene dissolving of steaming.Refluxed 12 hours, and be chilled to room temperature, the solid that leaches washs with small amount of toluene, drying, yield 82%.
(6), the preparation of the thiazolinyl derivative of band pyrimidine ring:
Under nitrogen protection, the microcosmic salt that makes 29 grams (0.05 mole) are dissolved in the dimethyl formamide that purifying crosses, add 6.7 gram (0.06 mole) tert.-butoxy potassium and stirred 1 hour.Splash into 7.1 gram (0.05 moles) 3, the dimethyl formamide wiring solution-forming that 4-difluorobenzaldehyde and purifying are crossed refluxed 12 hours.Use 5% hcl acidifying, add excessive water, leach solid.Purifying on silica gel column chromatography, irrigation methylene dichloride: normal hexane (1: 5), recrystallization in ethanol, yield 70%.
Embodiment 2, preparation R are n-pentyl, and Z is an ethyl group, and X is F, R
fCompound for F
(1)-(6) identical with embodiment 1
(7), the preparation of the ethyl group derivative of band pyrimidine ring:
18.2 grams (0.05 mole) are made band pyrimidine ring ethenyl derivatives be dissolved in the ethanol, add 1.0 grams, 10% palladium carbon catalyst.Stir down and feed hydrogen, temperature of reaction maintains 50 ℃ under the normal pressure.With tlc check disappear substantially to ethenyl derivatives till, desolventizing, solid are at toluene: recrystallization in the ethanol (3: 2), yield 95%.
Embodiment 3, preparation R are n-pentyl, and Z is an ethynyl, and X is F, R
fCompound for F
(1)-(6) identical with embodiment 1
(7), the preparation of two br-derivatives of band pyrimidine ring:
Be with the ethenyl derivatives of pyrimidine rings to be dissolved in the methylene dichloride 3.6 grams (0.01 mole) that make, splash into the bromine of 1 gram (0.013 mole) and the solution of 10 milliliters of methylene dichloride under the room temperature.Drip to finish and at room temperature continue to stir 3 hours.Add 50 ml waters, tell water dichloromethane extraction 3 times, merge organic phase, use 10% sodium bicarbonate and water washing successively until neutrality.Use ethyl alcohol recrystallization, yield 85%.
(8), the preparation of the acetylene-derivative of band pyrimidine ring:
With being dissolved in the anhydrous tetrahydro furan under 5.2 gram (0.01 mole) band pyrimidine rings, the two br-derivatives room temperatures that make, add 4.5 gram (0.04 mole) tert.-butoxy potassium, 40 ℃ were stirred 2 hours down.Add water, with toluene extraction, extraction liquid is successively with 10% hydrochloric acid be washed to only neutral.Steaming desolventizes, solid ethyl alcohol recrystallization, yield 80%.
Claims (6)
1, the fluorinated liquid crystal compound of band pyrimidine ring, the structure of compound is shown in general formula (I):
It is characterized in that: X=F or X=H; R
f=F or R
f=CF
3Or R
f=0CF
3Abutment Z is selected from ethyl group, vinyl, ethynyl in the general formula; R is selected from ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl and the decyl of positive structure in the general formula.
2, the fluorinated liquid crystal compound of band pyrimidine ring according to claim 1, it is characterized in that: the structure of compound is X=F, R
f=-F.
3, the fluorinated liquid crystal compound of band pyrimidine ring according to claim 1, the structure that it is characterized in that compound is X=H, R
f=CF3.
4, the fluorinated liquid crystal compound of band pyrimidine ring according to claim 1, the structure that it is characterized in that compound is X=H, R
f=OCF3.
5, the fluorinated liquid crystal application of compound of band pyrimidine ring is characterized in that containing claim 1 or 2 or 3 or 4 described compound or derivatives thereofs in the liquid crystal that is mixed.
6,, it is characterized in that containing between the liquid-crystal display electrode pair claim 1 or 2 or 3 or 4 described compound or derivatives thereofs according to the fluorinated liquid crystal application of compound of the described band pyrimidine ring of claim 5.
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| CN1150297C true CN1150297C (en) | 2004-05-19 |
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