CN1238351C - Substituted benzo 1,3-dioxygen pentacyclic ring derivative, preparing process and uses thereof - Google Patents
Substituted benzo 1,3-dioxygen pentacyclic ring derivative, preparing process and uses thereof Download PDFInfo
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- CN1238351C CN1238351C CN 02153717 CN02153717A CN1238351C CN 1238351 C CN1238351 C CN 1238351C CN 02153717 CN02153717 CN 02153717 CN 02153717 A CN02153717 A CN 02153717A CN 1238351 C CN1238351 C CN 1238351C
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Abstract
The present invention discloses a liquid crystal compound of a substituted benzo 1, 3-dioxygen pentacyclic derivative. The compound has the structure disclosed in general formula I, wherein R represents the alkyl or the alkenyl of C1 to 15, and the alkoxyl or the oxyl of C1 to 15; a ring A represents antiform 1, 4 cyclohexylidene, phenylene or phenylene substituted by-F; m represents numbers 0 and 1; X1, X2 and X3 are respectively selected from-H,-CN,-F,-Cl,-Br,-I,-CH3,-OCF3,-CF2CF3,-OCHF2,-CF3 and-NO2. The compound has the advantages of stable structure, wide liquid crystal state temperature range, favorable low temperature mutual solubility, small birefringence, low viscosity and high elastic constant. The compound can be used as a normal nematic phase liquid crystal material with wide temperature and low birefringence. The performance of a liquid crystal composition material and a display is improved. The present invention also discloses the application of the compound disclosed in the general formula I to a liquid crystal material composition and a display and a preparation method of the compound.
Description
Technical field
The present invention relates to a kind of compound, the benzo 1 of Qu Daiing particularly, 3-dioxolane derivative, its preparation method and as the purposes of liquid crystalline cpd belongs to the compound field.
Background technology
Liquid crystal material wherein shows with the nematic liquid crystal material it is a kind of liquid crystal material with fastest developing speed, market occupancy volume maximum along with the development of liquid-crystal display (LCD) develops rapidly.Nematic liquid crystal shows liquid-crystal displays (LCD) such as TN (twisted-nematic phase) pattern, HTN (high twist nematic phase) pattern, STN (supertwist nematic phase) pattern, TFT (thin film transistor) pattern, PDLC (Polymer Dispersed Liquid Crystal) pattern, DS (dynamic scattering) pattern, GH (host and guest) pattern, ECB (electrically conerolled birefringence) pattern, DAP pattern and DSTN (reflection type bistable state) pattern.Particularly TN, STN, TFT type have obtained remarkable development in the Color Liquid Crystal Display in recent years, have dropped into scale operation, and wherein the TFT pattern is extremely many welcomes and attention.Up to now, many liquid-crystal displays that these utilize characteristics such as the distinctive birefringence anisotropy of liquid crystal, dielectric anisotropy to make, be widely used in the indicating meters such as clock and watch, electronic calculator, word processing, portable computer, palm PC, information processing terminal demonstration, televisor, mobile communication and various instrument, and, the demand of liquid crystal indicator is increased year by year along with the developing rapidly of information industry.
Therefore, also obtained very great development, a large amount of liquid crystalline cpds occurred as the liquid crystal material that shows usefulness.Develop into cyclohexyl (connection) benzene class, diphenyl acetylene class, ethyl bridged bond class, alkene end group class liquid crystal and various fluorine-containing aromatic ring class liquid crystalline cpd gradually from biphenyl nitrile, ester class, oxygen heterocyclic ring benzene class, pyrimidine lopps liquid crystalline cpd, Japan synthesizes constitutionally stable difluoroethylene class liquid crystalline cpd recently, its molecular structure is more and more stable, constantly satisfies the performance requriements of TN, STN, TFT-LCD.
Summary of the invention
The object of the present invention is to provide a kind of benzo 1 of replacement, 3-dioxolane derivative, described compound structure is stable, has wide liquid crystal state temperature range, good low temperature mutual solubility, less degree of birefringence, lower viscosity, higher ratio elastic constant, can be used as and show, improve the performance of liquid-crystal composition material and indicating meter with the normal nematic liquid crystal material of wide gentle low-birefringence.
Another object of the present invention is to provide the preparation method of above-mentioned liquid crystalline cpd, described preparation method's raw material is easy to get, synthetic route simple, be fit to large-scale industrial production.
A further object of the present invention is to provide the purposes of above-mentioned liquid crystalline cpd on liquid crystal material composition and indicating meter.
The technical solution used in the present invention is to achieve these goals: a kind of benzo 1 of replacement, and 3-dioxolane derivative, described compound has the structure shown in the general formula I:
Wherein R is C
1-C
15Alkyl, C
1-C
15Thiazolinyl, C
1-C
15Alkoxyl group or C
1-C
15Alkene oxygen base; Ring A is 1,4-cyclohexylidene, phenylene or the phenylene that is replaced by F; M is a numeral 0 or 1; X
1, X
2, X
3Be respectively-H ,-CN ,-F ,-Cl ,-Br ,-I ,-CH
3,-OCF
3,-CF
2CF
3,-OCHF
2,-CF
3,-NO
2Or C
1-C
7Straight chained alkyl.
In the present invention, preferred R is C
1-C
15Straight chained alkyl, C
1-C
15Straight-chain alkenyl, C
1-C
15Straight chain alkoxyl group or C
1-C
15Straight alkenyloxy.
Also preferred R is C
1-C
7Straight chained alkyl, C
1-C
7Straight-chain alkenyl, C
1-C
7Straight chain alkoxyl group or C
1-C
7Straight alkenyloxy.
More preferably R is C
1-C
7Straight chained alkyl.
In the present invention, preferred X
1, X
2, X
3Be respectively-H ,-F ,-Cl ,-CN or CF
3Also preferred X
1, X
3Be respectively-H ,-F or-Cl; X
2For-F ,-Cl ,-CN or CF
3, more preferably X
1, X
3Be respectively-H or-F, X
2For-F or-CN.
It is trans 1 that ring A among the present invention is preferably, 4-cyclohexylidene or phenylene.
The preferred compound of the present invention is: R is C
1-C
7Straight chained alkyl; M is 0 or 1; X
1, X
3Be respectively-H or-F, X
2For-F or-CN.
In the present invention, preferred m is 0.
The typical structure formula of compound of the present invention is as follows:
Preferably wherein R is C
1-C
7Straight chained alkyl, ring A is trans 1,4-cyclohexylidene, phenylene.
The benzo 1 of a kind of replacement of the present invention, 3-dioxolane derivative liquid crystalline cpd Stability Analysis of Structures, has wide liquid crystal state temperature range, good low temperature mutual solubility, less degree of birefringence, lower viscosity, higher ratio elastic constant can be used as and show with the normal nematic liquid crystal material of wide gentle low-birefringence, improve the performance of liquid-crystal composition material and indicating meter.
Among the present invention, the compound shown in the general formula (I) can separately or be formed liquid-crystal composition with other liquid crystalline cpds well known in the prior art and be used as liquid crystal display material, and when being used for liquid-crystal composition, consumption is generally 2-50%.
The compound of formula of of the present invention (I) representative can be by following two kinds of methods preparation.
First kind of preparation method of the compound of formula of of the present invention (I) representative comprises the steps:
With 4-R '-pyrocatechol (A) and 1-(dichloromethyl)-3-X
1-5-X
3Disubstituted benzenes (B) carries out condensation reaction in solvent in the presence of alkali, through aftertreatment, get 2-(3-X
1-5-X
3Di-substituted-phenyl)-and 5-R '-benzo 1,3-dioxolane (C), R ' wherein is
2-(the 3-X that obtains
1-5-X
3Di-substituted-phenyl)-and 5-R '-benzo 1,3-dioxolane (C) is in the general formula I X
2Structure shown in during for-H.
Wherein the solvent of condensation reaction employing is DMSO, and described alkali is sodium hydroxide, potassium hydroxide, yellow soda ash or sodium bicarbonate.
This preparation method also comprises: in solvent, with iodine substitution compound (C), obtain 2-(3-X under the effect of positive fourth lithium under the low temperature
1-5-X
3-two replacement-4-iodophenyls)-and 5-R '-benzo 1,3-dioxolane (D); This 2-(3-X
1-5-X
3-two replacement-4-iodophenyls)-and 5-R '-benzo 1,3-dioxolane (D) is in the general formula I X
2Structure shown in during for-I.
The described low temperature of above-mentioned reaction carries out in-20 to-60 ℃ of following THF solvents.
This preparation method also further comprises: with compound (D) and cuprous compounds back flow reaction in solvent, obtain target compound (E).
Solvent wherein is DMF, and cuprous compounds is CuX
2
Second kind of preparation method of the compound of formula of of the present invention (I) representative comprises the steps:
With 4-R '-pyrocatechol (A) and 3-X
1-4-X
2-5-X
3Trisubstituted xylylene dichlorides (B ') in the presence of alkali, in solvent, carry out condensation reaction, through aftertreatment, get target compound (E).
Wherein the solvent of condensation reaction employing is DMSO, and described alkali is sodium hydroxide, potassium hydroxide, yellow soda ash or sodium bicarbonate, and is fit to other alkali of the present invention.
The preparation method of the starting compound among the preparation method of the present invention (A) is: the phenol compound that contains para-orienting group
With Acetyl Chloride 98Min. in solvent; under the effect of triethylamine, carry out back flow reaction; remove solvent and get acetate-(para-orienting group)-phenol ester; again through the aluminum chloride transposition; aluminum chloride is decomposed in cryosel acid; reacted after aftertreatment gets 4-substituting group-2-acetyl phenol, got compound (A) through oxidizing reaction again.Yield is 65%.Wherein Acetyl Chloride 98Min. and para-orientation phenol are the commercially available prod.
Compound used therefor in the synthetic method of the present invention (B) is made by following method with (B '): substituted benzaldehyde and phosphorus trichloride, phosphorus pentachloride react, and underpressure distillation gets compound (B) or (B ').
As for any method of concrete employing in the reaction, depend on whether compound of reaction has commodity and synthetic difficulty or ease, and this is known for those skilled in the art.
The reaction process of two kinds of methods is as follows:
Or
The reaction signal
Wherein R ' is
Preparation method's raw material of the present invention is easy to get, synthetic route simple, be fit to large-scale industrial production.
Because the application of liquid crystalline cpd of the present invention has improved the low-temperature performance that shows with the nematic liquid crystal material greatly, has improved the response characteristic of liquid-crystal display, has improved response speed, can be used for TN, HTN, STN, TFT indicating meter.Promptly under extensively suitable condition, compound of the present invention has:
1) effect of the clearing point of raising liquid-crystal composition.
2) effect of reduction composition viscosity.
3) prevent the effect that the dielectric anisotropy of composition reduces.
Good low temperature mutual solubility can be used as liquid crystalline cpd of the present invention to improve the wide gentle low birefringence of display performance to show and uses the nematic liquid crystal material.
The invention provides a kind of benzo 1 of replacement, 3-dioxolane derivative liquid crystalline cpd and preparation method thereof, described compound structure is stable, has wide liquid crystal state temperature range, good low temperature mutual solubility, less degree of birefringence, lower viscosity, higher ratio elastic constant, improve the low-temperature performance that shows with the nematic liquid crystal material greatly, improve the response characteristic of liquid-crystal display, improved response speed, can be used as and show with the normal nematic liquid crystal material of wide gentle low-birefringence, improve the performance of liquid-crystal composition material and indicating meter, can be used for TN, HTN, STN, the TFT indicating meter.
Embodiment
Below be embodiments of the invention, the embodiment that the present invention provides is in order to further specify the specific embodiments of the invention scheme, rather than is used for limiting protection scope of the present invention.
Embodiment 1 (method one)
2-(3 ｀, 5 ｀-difluorophenyl)-5-propyl group-benzo 1,3-dioxolane synthetic
(1) acetate-(to propyl group)-phenol ester is synthetic
In the there-necked flask of 500ml, the n-propyl phenol of 1.0mol is dissolved in the 300ml toluene, add the 95ml triethylamine.Install whipping appts and reflux, under heated and stirred, dripping acetyl chloride 1.1mol finished in about 1 hour, refluxed 5 hours, be cooled to room temperature, be washed to neutrality, separatory, abandon water layer, the toluene layer anhydrous sodium sulfate drying, the filtering siccative is spin-dried for solvent, and it is standby to obtain acetate-(to propyl group)-phenol ester.
(2) 4-propyl group-2-acetyl phenol is synthetic
0.8mol acetate-(to propyl group)-phenol ester is moved in the reaction flask, add AlCl
31.6mol, be warming up to 90 ℃ of reactions 15 minutes under stirring, pour into while hot in the hydrochloric acid soln that is made into by 250ml concentrated hydrochloric acid and 500ml frozen water.Stirred 20 minutes, and used the dichloromethane extraction hydrochloric acid soln, dichloromethane layer is washed to neutrality, uses anhydrous sodium sulfate drying; the filtering siccative, be spin-dried for solvent after, underpressure distillation; collect 96～100 ℃/3mmHg cut, get faint yellow 4-propyl group-2-acetyl phenol liquid 103g, yield 90%.
(3) 4-propyl group pyrocatechol is synthetic
0.1mol 4-propyl group-2-acetyl phenol is added in the reaction flask; the solution that adding is made into by 0.1mol NaOH and 40ml water; in 40 minutes, drip the solution that 0.3mol hydrogen peroxide and 66ml water are made into; stirring reaction 4 hours; add the sodium bisulfite saturated solution of new preparation,, use the dichloromethane extraction secondary to remove excessive hydrogen peroxide; the siccative drying; the filtering siccative is spin-dried for underpressure distillation behind the solvent, collects 110～120 ℃/3mmHg fraction; add 50mL sherwood oil (90-105 ℃); the vibration crystallization gets white powder 4-propyl group pyrocatechol solid product, yield 65%; gas chromatographic detection, its purity 〉=99.5%.
(4) 1-(dichloromethyl)-3,5 two fluorobenzene is synthetic
Add 3 in the reaction flask, 5-difluorobenzaldehyde 1.0mol, 200ml phosphorus trichloride and 200ml methylene dichloride are installed whipping appts, under agitation, add the 1.2mol phosphorus pentachloride, finish stirring at room 8 hours.Normal pressure steams most of solvent and phosphorus pentachloride, and 94～99 ℃/40mmHg cut is collected in underpressure distillation, gets colourless 1-(dichloromethyl)-3,5 two fluorobenzene liquid, yield 75%, and the gas-chromatography chromatogram detects, its purity 〉=98%.
(5) 2-(3, the 5-difluorophenyl)-5-propyl group-benzo 1,3-dioxolane synthetic
In reaction flask with 0.2mol 4-propyl group-pyrocatechol; 0.4mol sodium hydroxide is suspended among the 200ml DMSO; logical nitrogen protection; be heated to 100 ℃, stirred 20 minutes, in 1 hour, drip 1-(dichloromethyl)-3; 5-two fluorobenzene 0.2mol; controlled temperature after dripping, continued stirring reaction 6 hours at 95 ± 5 ℃.Be cooled to room temperature, add 300ml water, extract secondary with about 200ml methylene fluoride, the washing dichloromethane layer is abandoned water layer to neutral, with siccative dry methylene chloride layer, filtering siccative, evaporate to dryness methylene dichloride, enriched material are dissolved in 150ml sherwood oil (90-105 ℃) and cross the silicagel column decolouring, elutriant is a sherwood oil, the collection elutriant also steams and removes sherwood oil, and 154～160 ℃/3mmHg cut is collected in the enriched material underpressure distillation, gets weak yellow liquid, yield 60%, gas-chromatography content 99.5%.
Its structure identifies that situation is as follows:
Molecular formula: C
16H
14O
2F
2MS:M
+/ Z=276; Ultimate analysis: theoretical value: C 69.5%, H 5.11%;
Measured value: C 69.50%, H 5.08%.
Embodiment 2
2-(3,5-two fluoro-4-iodophenyls)-5-propyl group-benzo 1,3-dioxolane synthetic
With 100ml THF; logical nitrogen protection; be cooled to-20 ℃; in 30 minutes, drip positive fourth lithium 0.15mol; temperature control is less than 0 ℃ in the dropping process; drip and finish; be cooled to below-60 ℃, dripped the product that embodiment 1 obtains in 1 hour, just 0.1mol 2-(3; the 5-difluorophenyl)-5-propyl group-benzo 1; the 50ml THF solution of 3-dioxolane, controlled temperature is-60～-65 ℃, drips off back stirring reaction 20 minutes; drip the 50ml THF solution of 0.13mol iodine in 40 minutes, controlled temperature is lower than-60～-65 ℃.Drip and finish, nature is warming up to more than 0 ℃ under stirring, and adds 200ml water and 0.1mol S-WAT, stirring and dissolving, with 100ml dichloromethane extraction secondary, united extraction liquid also is washed to neutrality, use the anhydrous sodium sulfate drying solvent layer, the filtering siccative is used activated carbon decolorizing, solvent evaporated, the enriched material recrystallizing methanol gets white powder 2-(3,5-two fluoro-4-iodophenyls)-5-propyl group-benzo 1,3-dioxolane solid, yield 80%, gas-chromatography content 99.5%.
Its structure identifies that situation is as follows:
Molecular formula: C
16H
13F
2IO
2MS:M
+/ Z=402; Ultimate analysis: theoretical value: C 47.7%, H 3.26%;
Measured value: C 47.80%, H 3.24%.
Embodiment 3
2-(3,5-two fluoro-4-cyano-phenyls)-5-propyl group-benzo 1,3-dioxolane synthetic
With 0.04mol 2-(3,5-two fluoro-4-iodophenyls)-5-propyl group-benzo l, 3-dioxolane and 0.06mol cuprous cyanide are dissolved among the 100ml DMF, reflux 5 hours, be cooled to room temperature, filter, add 50ml ammoniacal liquor, with 100ml methylbenzene extraction secondary, the combining methylbenzene layer is also used the siccative drying, evaporate to dryness toluene, underpressure distillation is collected 189～191 ℃/3mmHg cut and is got weak yellow liquid, this weak yellow liquid is dissolved in the 50ml sherwood oil, with the sherwood oil is that elutriant is crossed silicagel column, and elutriant concentrates removes sherwood oil, gets 2-(3,5-two fluoro-4-cyano-phenyls)-5-propyl group-benzo 1,3-dioxolane colourless liquid, yield 60%, gas chromatographic purity 99.5%.
Its structure identifies that situation is as follows:
| Molecular formula | H 1NMR (δ value) (s, unimodal; D, bimodal; T, triplet; M, multiplet) | Characteristic ion (M/Z +) and abundance (%) |
| C 11H 12O 2BF 2CN | 0.900(t，H)、1.577(m，2H)、2.520(t，2H)、 6.683(d，2H)、6.714(s，1H)、6.783(d，1H)、 6.958(s，1H)、7.723(m，4H) | 251(M +、48.73)、236(1.85)、208(7.8)、 179(8.24)、166(20.85)、152(17.63)、 119(7.48)、56(100) |
Ultimate analysis: theoretical value: C 67.77%, H 4.35%, and N 4.65%; Measured value: C 67.79%, H 4.33%, N4.67%.
Embodiment 4 (method two)
2-(4-cyano-phenyl)-5-propyl group-benzo 1,3-dioxolane synthetic
(1) 4-xylylene dichlorides cyanogen is synthetic
Synthetic method with (4) among the embodiment 1, different is to use cyanobenzaldehyde and phosphorus trichloride and phosphorus pentachloride reaction, 216～220 ℃/3mmHg cut is collected in decompression, add the sherwood oil recrystallization, get 4-xylylene dichlorides cyamelide look crystal, yield 75%, mp=40.0 ℃, its purity of gas chromatographic analysis is 98.5%.
(2) 2-(4-cyano-phenyl)-5-propyl group-benzo 1,3-dioxolane synthetic
With 0.25mol 4-propyl group-pyrocatechol; 0.4mol sodium hydroxide is suspended among the 100ml DMSO; logical nitrogen protection; be heated to 100 ℃; stirred 20 minutes, and dripped the 50ml DMSO solution of 0.25mol 4-xylylene dichlorides cyanogen in 30 minutes, controlled temperature is at 95 ± 5 ℃; after dripping, stirring reaction 6 hours.Be cooled to room temperature, add 300ml water, with 300ml dichloromethane extraction secondary, the combined dichloromethane layer also is washed to neutrality, uses the siccative drying, is spin-dried for methylene dichloride behind the filtering siccative, enriched material is dissolved in the 50ml sherwood oil and crosses silicagel column, steam and remove the petroleum ether solution that wash-out goes out, 226～230 ℃/3mmHg cut is collected in remaining enriched material underpressure distillation, get faint yellow 2-(4-cyano-phenyl)-5-propyl group-benzo 1,3-dioxolane liquid, yield 60% is with this weak yellow liquid of sherwood oil recrystallization, get the white powder solid, mp:35.65～37.27 ℃, yield 60%, its purity of gas chromatographic analysis is 99.5%.
After wherein reaction mixture washing, the extraction, also can be with behind the activated carbon decolorizing, dry and concentrated, directly use the sherwood oil recrystallization then, pale yellow powder shape 2-(4-the cyano-phenyl)-5-propyl group-benzo 1 that obtains, 3-dioxolane solid, yield 85%, its purity of gas chromatographic analysis is 92.1%.
Its structure identifies that situation is as follows:
C3H7-B(O2)-B-CN
| Molecular formula | H 1NMR (δ value) (s, unimodal; D, bimodal; T, triplet; M, multiplet) | Characteristic ion (M/Z +) and abundance (%) |
| C 16H 15O 2CN | 0.930(t，3H)、1.589(m，2H)、2.545(t，2H)、 6.685(d，2H)、6.721(s，1H)、6.789(d，1H)、 6.965(s，1H)、7.930(m，2H) | 265(M +、32.33)、236(100)、206(0.86)、 180(2.43)、163(3.36)、105(9.46)、 77(29.01)、51(22.16) |
Ultimate analysis: theoretical value: C 76.96%, H 5.70%, and N 5.28%; Measured value: C 76.93%, H 5.72%, and N 5.31%.
Embodiment 5
2-(4-cyano group benzene)-5-[is anti--(4-propyl group) cyclohexyl] and benzo 1,3-dioxolane synthetic
(1) right-[anti--(4-propyl group) cyclohexyl] phenol is the commercially available prod.
(2) [anti--(4-propyl group) cyclohexyl]-3-ethanoyl-4-hydroxybenzene is synthetic
With the synthetic method of (1) among the embodiment 1-(2), different is, and reactant is to anti--(4-propyl group) cyclohexylphenol, through underpressure distillation, collects 96～100 ℃/3mmHg cut, weak yellow liquid, yield 92%.
(3) [anti--(4-propyl group) cyclohexyl]-3,4-dihydroxy-benzene synthetic
Method with reference to step (4) among the embodiment 1; with 0.1mol[anti--(4-propyl group) cyclohexyl]-3-ethanoyl-4-hydroxybenzene adds in the reaction flask; add 120ml toluene; 0.1mol the solution that sodium hydroxide and 50ml water are made into; stir, drip the solution that 0.3mol hydrogen peroxide and 80ml water are made in 50 minutes, finish; temperature rises to 45 ℃; stirred 4 hours, and reduced to room temperature, add the sodium bisulfite saturated solution of new preparation; to remove excessive hydrogen peroxide; use the dichloromethane extraction secondary, siccative drying, filtering siccative; be spin-dried for solvent; use the toluene recrystallization, [instead-and (4-propyl group) cyclohexyl]-3,4-dihydroxy-benzene solid; yield 72%, its purity of gas chromatographic analysis is 〉=99.0%.
(4) 2-(4-cyano group benzene)-5-[anti--(4-propyl group) cyclohexyl] benzo 1,3-dioxolane synthetic
With reference to the method for embodiment 1, with 0.05mol[anti--(4-propyl group) cyclohexyl]-3, the 4-dihydroxy-benzene; 0.08mol sodium hydroxide is suspended among the 120ml DMSO; logical nitrogen protection is heated with stirring to 100 ℃, drips the DMSO solution of 0.05mol 4-xylylene dichlorides cyanogen.Finish, kept 100 ℃ of stirring reactions 4 hours.Be cooled to room temperature, after reaction mixture washing, the extraction, after solvent layer activated carbon decolorizing, the filtration, dry, filtration and concentrated, using the sherwood oil recrystallization then, the white powder 2-that obtains (4-cyano group benzene)-5-[is anti--(4-propyl group) cyclohexyl] benzo 1,3-dioxolane solid, yield 63%, its purity of gas phase spectrum analysis is 〉=99.0%.
Its structure identifies that situation is as follows: MS:M
+/ Z=347
Ultimate analysis: theoretical value: C 79.51%, H 7.25%, and N 4.03%; Measured value: C 79.52%, H 7.23%, and N 4.07%.
Embodiment 6
With reference to method Synthetic 2-(4-cyano group benzene)-5-(4-propylbenzene)-benzo 1 of embodiment 1, the 3-dioxolane:
(1) be the commercially available prod to (4-propylbenzene) phenol.
(2) 1-(4-propylbenzene)-3-ethanoyl-4-hydroxybenzene is synthetic
With the synthetic method of (1) among the embodiment 1-(2), different is that reactant is to (4-propylbenzene) phenol, through underpressure distillation, collects 96～100 ℃/3mmHg cut, gets weak yellow liquid, yield 85%.
(3) 1-(4-propylbenzene)-3,4-dihydroxy-benzene synthetic
Method with reference to embodiment 1; 0.15mol 1-(4-propylbenzene)-3-ethanoyl-4-hydroxybenzene is added in the reaction flask, add 150ml toluene, 2M sodium hydroxide solution 100ml, drip 10% hydrogen peroxide 140ml in 1 hour; finish, 50 ℃ were reacted 4.5 hours down.Reduce to room temperature treatment,, get 1-(4-propylbenzene)-3,4-dihydroxy-benzene, yield 63%, gas-chromatography content 〉=99.0% through the chloroform recrystallization.
(4) 2-(4-cyano group benzene)-5-(4-propylbenzene)-benzo 1,3-dioxolane synthetic
With reference to the method for embodiment 1, with 0.05mol 1-(4-propylbenzene)-3, the 4-dihydroxy-benzene joins among the 100ml DMSO; add 0.08mol sodium hydroxide again; logical nitrogen protection is heated with stirring to 100 ℃, drips the DMSO solution 20ml of 0.05mol4-xylylene dichlorides cyanogen in 20 minutes.Keep 98 ± 2 ℃, stirring reaction 6 hours.Be cooled to room temperature and carry out aftertreatment, handle through the 100ml ethyl alcohol recrystallization again, get white solid, yield 60%, its purity of gas phase spectrum analysis is 〉=99.0%.
Its structure identifies that situation is as follows: MS:M
+/ Z=341
Ultimate analysis: theoretical value: C 80.92%, H 5.61%, and N 4.10%;
Measured value: C 80.90%, H 5.63%, and N 4.12%.
Embodiment 7-21
With reference to the synthetic method of embodiment 1-6, synthetic following compound:
The compound of embodiment 7-21 can adopt the synthetic method of embodiment 1 or 4 synthetic.Certainly, when R is thiazolinyl, should carry out building-up reactions ,-OCF at first to the thiazolinyl protection
3,-CF
2CF
3,-OCHF
2,-CF
3Or-NO
2Substitution compound synthetic also is group and the reaction that liquid crystalline cpd often adopts, and this is known for those skilled in the art, discloses in the prior art in addition and various commercial get various are arranged
The phenol that base replaces, if but in said structure synthetic, existing does not have disclosed corresponding fortified phenol, then can be with reference to prior art for preparing, and this also is technique known for those skilled in the art, has not just described one by one here.
Claims (15)
1, a kind of benzo 1 of replacement, 3-dioxolane derivative, described compound has the structure shown in the general formula I:
Wherein R is C
1-C
15Alkyl, C
1-C
15Thiazolinyl, C
1-C
15Alkoxyl group or C
1-C
15Alkene oxygen base; Ring A is 1,4-cyclohexylidene, phenylene or the phenylene that is replaced by F; M is a numeral 0 or 1; X
1, X
2, X
3Be respectively-H ,-CN ,-F ,-Cl ,-Br ,-I ,-CH
3,-OCF
3,-CF
2CF
3,-OCHF
2,-CF
3,-NO
2Or C
1-C
7Straight chained alkyl.
2, the benzo 1 of replacement according to claim 1,3-dioxolane derivative, wherein R is C
1-C
15Straight chained alkyl, C
1-C
15Straight-chain alkenyl, C
1-C
15Straight chain alkoxyl group or C
1-C
15Straight alkenyloxy.
3, the benzo 1 of replacement according to claim 1,3-dioxolane derivative, wherein R is C
1-C
7Straight chained alkyl, C
1-C
7Straight-chain alkenyl, C
1-C
7Straight chain alkoxyl group or C
1-C
7Straight alkenyloxy.
4, the benzo 1 of replacement according to claim 1,3-dioxolane derivative, wherein R is C
1-C
7Straight chained alkyl.
5, according to the benzo 1 of any one described replacement of claim 1-4,3-dioxolane derivative, wherein X
1, X
2, X
3Be respectively-H ,-F ,-Cl ,-CN or CF
3
6, the benzo 1 of replacement according to claim 5,3-dioxolane derivative, wherein X
1, X
3Be respectively-H ,-F or-Cl; X
2For-F ,-Cl ,-CN or CF
3
7, the benzo 1 of replacement according to claim 6,3-dioxolane derivative, wherein X
1, X
3Be respectively-H or-F, X
2For-F or-CN.
8, according to the benzo 1 of any one described replacement of claim 1-4,3-dioxolane derivative, wherein the ring A among the present invention is trans 1,4-cyclohexylidene or phenylene.
9, according to the benzo 1 of any one described replacement of claim 5,3-dioxolane derivative, wherein the ring A among the present invention is trans 1,4-cyclohexylidene or phenylene.
10, according to the benzo 1 of any one described replacement of claim 6-7,3-dioxolane derivative, wherein the ring A among the present invention is trans 1,4-cyclohexylidene or phenylene.
11, according to the benzo 1 of any one described replacement of claim 1-7,3-dioxolane derivative, wherein R is C
1-C
7Straight chained alkyl; M is 0 or 1; X
1, X
3Be respectively-H or-F, X
2For-F or-CN.
12, the benzo 1 of replacement according to claim 11,3-dioxolane derivative, wherein m is 0.
13, the benzo 1 of any one described replacement of claim 1-12, the preparation method of 3-dioxolane derivative comprises the steps: 4-R '-pyrocatechol and 1-(dichloromethyl)-3-X
1-5-X
3Disubstituted benzenes carries out condensation reaction in solvent in the presence of alkali, through aftertreatment, get 2-(3-X
1-5-X
3Di-substituted-phenyl)-and 5-R '-benzo 1, the 3-dioxolane, R ' wherein is
2-(the 3-X that obtains
1-5-X
3Di-substituted-phenyl)-and 5-R '-benzo 1, the 3-dioxolane is in the general formula I X
2Structure shown in during for-H; Wherein R is C
1-C
15Alkyl, C
1-C
15Thiazolinyl, C
1-C
15Alkoxyl group or C
1-C
15Alkene oxygen base; Ring A is 1,4-cyclohexylidene, phenylene or the phenylene that is replaced by F; M is a numeral 0 or 1; X
1, X
2, X
3Be respectively-H ,-CN ,-F ,-Cl ,-Br ,-I ,-CH
3,-OCF
3,-CF
2CF
3,-OCHF
2,-CF
3,-NO
2Or C
1-C
7Straight chained alkyl.
14, the benzo 1 of replacement according to claim 13, the preparation method of 3-dioxolane derivative also comprises: in solvent, use the iodine substitution compound under the effect of positive fourth lithium under the low temperature, obtain 2-(3-X
1-5-X
3Two replacement-4-iodophenyls)-and 5-R '-benzo 1, the 3-dioxolane; This 2-(3-X
1-5-X
3Two replacement-4-iodophenyls)-and 5-R '-benzo 1, the 3-dioxolane is in the general formula I X
2Structure shown in during for-I.
15, the benzo 1 of any one described replacement of claim 1-12, the purposes of 3-dioxolane derivative on liquid-crystal composition or liquid-crystal display.
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| CN103087038B (en) * | 2012-12-24 | 2015-07-29 | 石家庄诚志永华显示材料有限公司 | Liquid crystalline cpd containing the sub-methoxyl group bridge of benzo 1,3-dioxolane and difluoro |
| CN103555346B (en) * | 2013-11-06 | 2015-01-14 | 北京八亿时空液晶科技股份有限公司 | 1, 3-dioxolane liquid crystal compound as well as preparation method and application thereof |
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