CN100509736C - 2,3,2,'3' tetrafluoro diphenyl acetylene derivative, composition, preparation method and use thereof - Google Patents
2,3,2,'3' tetrafluoro diphenyl acetylene derivative, composition, preparation method and use thereof Download PDFInfo
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Abstract
The present invention relates to one kind of 2, 3, 2', 3'-tetrafluoro acetylene derivative and its composition, preparation process and use. The compound has the general expression as shown, relatively great optical anisotropy, relatively great negative dielectric anisotropy, relatively high light and heat stability and relatively low viscosity. The compound may constitute well behaved nematic phase liquid crystal composition with low threshold voltage, low viscosity, high response speed, improved response characteristic and contrast, and the nematic phase liquid crystal composition may be used in liquid crystal display of TN mode, STN mode, TFT mode, PDLC mode, etc. In addition, the compound has facile material and simple synthesis path, and the process is suitable for industrial production.
Description
Technical field
The present invention relates to a kind of 2,3,2`, the 3`-tetrafluoro diphenyl acetylene derivative contains 2,3,2`, the composition and method of making the same of 3`-tetrafluoro diphenyl acetylene derivative and its belong to the compound field as the purposes that shows with liquid crystal material.
Background technology
Liquid crystal material is along with the development of liquid-crystal display develops rapidly, wherein show it is with fastest developing speed with the nematic liquid crystal material, the one type of liquid crystal material of market occupancy volume maximum, nematic liquid crystal shows TN (twisted-nematic phase) pattern, STN (supertwist nematic phase) pattern, TFT (thin film transistor) pattern, PDLC (Polymer Dispersed Liquid Crystal) pattern, GH (host and guest) pattern, liquid-crystal displays such as ECB (electrically conerolled birefringence) pattern, particularly in recent years people to large size, wide visual angle, the demand of fast-response, further promoted the scale operation of colored TFT mode display, up to now, utilize the peculiar birefringence anisotropy of liquid crystal material, many liquid-crystal displays that characteristics such as dielectric anisotropy are made, clock and watch have been widely used in, electronic calculator, portable computer, PDA, intelligent terminal, mobile phone, during televisor and various instrument etc. show, developing rapidly particularly along with information technology, LCD-TV is towards large scale development, demand to liquid crystal indicator increases year by year, simultaneously, higher performance requriements has also been proposed liquid crystal material.
Therefore, also be accompanied by the development of liquid-crystal display and grow in strength, a large amount of liquid crystalline cpds occurred as the liquid crystal material that shows usefulness.From azo, azoxy, benzal, biphenyl nitrile, ester class, oxygen heterocyclic ring class, pyrimidine lopps liquid crystalline cpd develops into cyclohexyl (connection) benzene class, diphenyl acetylene class, ethyl bridged bond class, end alkene class and fluorine-containing aromatic ring class liquid crystalline cpd, its molecular structure is more and more stable, and performance characteristics is more and more outstanding, constantly satisfies the requirement of the display performance of TN-LCD, STN-LCD, TFT-LCD, PDLC etc.
The fluorinated liquid crystal material had obtained development rapidly in recent years, the exploitation of nearly all nematic phase material all is as main ingredient with the fluorinated liquid crystal compound, be applied in TN-LCD, STN-LCD, PDLC, the LCOS rear-projection, especially indispensable especially in TFT-LCD.
According to the service requirements of display device, liquid-crystal composition should have suitable optics anisotropy (Δ n), dielectric anisotropy (Δ ε), viscosity (γ), elastic constant ratio (K
33/ K
11, K
22/ K
11K
33-bend elastic constant, K
22-distortion elastic constant, K
11-open up bent elastic constant), resistivity (ρ), liquid crystal phase temperature range and good mutual solubility.
In order to cut down the consumption of energy and to produce large display screen, it is necessary reducing the liquid-crystal display driving voltage, and driving voltage particularly threshold voltage (Vth) is the function of Δ ε, represents with its equation
[M.F.Leslie, Mol.Cryst.Liq.Cryst., 12,57 (1970)] are as follows:
V
th＝π(K/ε
0Δε)
1/2
In the formula: V
Th: threshold voltage, ε
0: specific inductivity, K: elastic constant, Δ ε: dielectric anisotropy.
As can be seen from the above equation,, need 1. increase Δ ε, or 2. reduce elastic constant K, but usually, it is bigger to reduce the elastic constant difficulty, but select to increase Δ ε in order to realize lower driving voltage.
For the difficult problem at the narrow visual angle of improving liquid-crystal display, various new display format meets the tendency and rises in recent years.Transverse electric field effect (IPS) (nineteen ninety-five) and vertical orientated (VA) (1997) new technology all have the ideal visual angle.The VA pattern is wherein a kind of new LCD technology, occupies very consequence on TV and computer screen, and the VA pattern is that Liquid Crystal Molecules Alignment is become vertical orientation, and (Δ ε＜0) is gone to be arranged in extra electric field and become a right angle to utilize the negative permittivity of liquid crystal poor.
Recent years, flat pannel display is irresistible towards large scale development.LCD occupies sizable share therein.LCD-TV and LCOS rear-projection TV are its main ways of realization, and this just requires that bigger optical anisotropy (Δ n) and photo and thermal stability more should be arranged on the basis of traditional performance.
This will the big Δ ε of negate value, so far, has developed the liquid crystalline cpd of bigger Δ ε of many negativity values and big Δ n, for example, U.S. Patent Publication No. US6,348, the compound of narrating among the 244B:
J.MATER.CHEM., the compound of 2004,14,1219～1277 reports, as:
Mol.Cryst.Liq.Cryst., 1997, Vol, the compound of 304,441～445 reports, as:
And " compound that the liquid crystal device handbook is introduced:
The Δ ε negative value of above-claimed cpd is very big, but Δ n is less, and resistivity and voltage retention are very low.Therefore, these liquid crystalline cpd Δs n, Δ ε remain limited, and the validity deficiency.
Up to the present, also be used in separately in the display unit and need not just can satisfy performance requriements with other compound combinations without any single liquid crystalline cpd.In order to obtain the required various characteristics of display format, liquid crystal material uses with the form of mixtures of various liquid crystalline cpds usually, therefore, needs liquid crystalline cpd all to have good solubility and well matching and synergy each other.
Summary of the invention
The object of the present invention is to provide a kind of 2,3,2`, the 3`-tetrafluoro diphenyl acetylene derivative, this compounds light, electricity, heat, chemical stability are good, and bigger optical anisotropy (Δ n) and the bigger dielectric anisotropy (Δ ε) of negative value are arranged, and use liquid crystal material as showing, can reduce the threshold voltage of mixed liquid crystal, improve the performance of liquid-crystal composition material and indicating meter.
Another object of the present invention is to provide above-mentioned 2,3,2`, the preparation method of 3`-tetrafluoro diphenyl acetylene derivative, this preparation method's raw material is easy to get, and synthetic route is simple, is fit to large-scale industrial production.
It is above-mentioned 2,3 that a further object of the present invention is to provide, 2`, and the 3`-tetrafluoro diphenyl acetylene derivative is as the purposes that shows with liquid crystal material.
Of the present invention 2,3,2`, 3`-tetrafluoro diphenyl acetylene derivative have the structure shown in the general formula (I):
Wherein:
R
1Represent C
1-C
15Alkyl, C
1-C
15Thiazolinyl, C
1-C
15Alkoxyl group, C
1-C
15Alkene oxygen base, fluoro C
1-C
15Alkyl or fluoro C
1-C
15Alkenyl;
R
2Be C
1-C
15Straight chained alkyl, C
1-C
15Alkoxyl group ,-F ,-OCF3 or-OCF
2H;
Z is that singly-bound, vinyl, ethynyl, ethyl, one or more hydrogen are by halogenated-CH
2-CH
2-in a kind of;
Ring A is phenylene, pyrimidine-2,5-two bases, cyclohexyl-1, a kind of in 4-two bases;
N is 0,1 or 2.
Above-claimed cpd is preferred:
R
1Be 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;
R
2Be C
1-C
6Alkyl, C
1-C
6Alkoxyl group ,-OCF
3Or-OCF
2H;
Z is singly-bound, vinyl or ethyl;
Ring A is phenylene or cyclohexyl-1,4-two bases;
N is 0 or 1.
Above-claimed cpd is further preferred:
R
1Be C
1-C
7Straight chained alkyl or C
1-C
7The straight chain alkoxyl group;
R
2Be C
1-C
5Straight chained alkyl or C
1-C
5The straight chain alkoxyl group ,-OCF
3
Z is singly-bound, vinyl or ethyl;
Ring A is a cyclohexyl-1,4-two bases;
N is 0 or 1.
Above-claimed cpd is preferred especially:
R
1Be C
1-C
7Straight chained alkyl or C
1-C
7The straight chain alkoxyl group;
R
2For-CH
3,-C
2H
5,-C
3H
7,-OCH
3Or-OC
2H
5
Z is singly-bound, vinyl or ethyl;
Ring A is a cyclohexyl-1,4-two bases;
N is 0 or 1.
The structural formula of above-claimed cpd can specifically be expressed as follows:
Wherein R is C
1-C
7Straight chained alkyl or C
1-C
7The straight chain alkoxyl group.
Of the present invention 2,3,2`, the preparation method of 3`-tetrafluoro diphenyl acetylene derivative comprises the steps:
Thing (e) can get pure trans through recrystallization again
Product (f); Compound (f) becomes lithium reagent with the n-Butyl Lithium reaction at low temperatures, obtains alkyl trans cyclohexyl-2 again with Iod R, 3-two fluoro-4-iodine compounds
(5) compound
Reacting at low temperatures with n-Butyl Lithium becomes lithium reagent, obtains compound with Iod R again
Compound (h) is at Pd[O] in the presence of (zeroth order palladium), triphenylphosphine, the triethylamine etc. with 1,1-dimethyl-2-propine-1-alcohol coupling and compound
Compound (j) deprotection in the presence of alkali obtains 4-and replaces-2,3-difluoro phenylacetylene compound
(6) compound (A) and compound (B) linked reaction and target product (I).
The said process reaction formula is as follows:
Wherein:
R
1Represent C
1-C
15Alkyl, C
1-C
15Thiazolinyl, C
1-C
15Alkoxyl group, C
1-C
15Alkene oxygen base, fluoro C
1-C
15Alkyl or fluoro C
1-C
15Alkenyl;
R
2Be C
1-C
15Straight chained alkyl, C
1-C
15Alkoxyl group ,-F ,-OCF3 or-OCF
2H;
Z is that singly-bound, vinyl, ethynyl, ethyl, one or more hydrogen are by halogenated-CH
2-CH
2-in a kind of;
Ring A is phenylene, pyrimidine-2,5-two bases, cyclohexyl-1, a kind of in 4-two bases;
N is 0,1 or 2.
Above-claimed cpd is preferred:
R
1Be 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;
R
2Be C
1-C
6Alkyl, C
1-C
6Alkoxyl group ,-OCF
3Or-OCF
2H;
Z is singly-bound, vinyl or ethyl;
Ring A is phenylene or cyclohexyl-1,4-two bases;
N is 0 or 1.
Above-claimed cpd is further preferred:
R
1Be C
1-C
7Straight chained alkyl or C
1-C
7The straight chain alkoxyl group;
R
2Be C
1-C
5Straight chained alkyl or C
1-C
5The straight chain alkoxyl group ,-OCF
3
Z is singly-bound, vinyl or ethyl;
Ring A is a cyclohexyl-1,4-two bases;
N is 0 or 1.
Above-claimed cpd is preferred especially:
R
1Be C
1-C
7Straight chained alkyl or C
1-C
7The straight chain alkoxyl group;
R
2For-CH
3,-C
2H
5,-C
3H
7,-OCH
3Or-OC
2H
5
Z is singly-bound, vinyl or ethyl;
Ring A is a cyclohexyl-1,4-two bases;
N is 0 or 1.
When R is thiazolinyl or alkane alkene oxygen base, should carry out building-up reactions at first to the thiazolinyl protection.
Of the present invention a kind of 2,3,2`, when the 3`-tetrafluoro diphenyl acetylene derivative is used to prepare liquid-crystal composition, comprise the compound that 2-30wt% general formula (I) is asked in the described liquid-crystal composition, wherein be preferably 5-15wt%, most preferably be 7-13wt%, all the other components are liquid crystalline cpd commonly known in the art, compound (II)-(VIII) shown in these compounds are preferably as follows, but be not limited to these compounds:
Wherein R and R, with the substituent R of The compounds of this invention
1, R
2Implication is identical.
Of the present invention 2,3,2`, 3`-tetrafluoro diphenyl acetylene derivative have bigger optical anisotropy (Δ n), and the dielectric anisotropy that negative value is bigger (Δ ε) has light, thermostability preferably, lower viscosity; After using the The compounds of this invention product, obtained a kind of well behaved liquid-crystal composition, said composition be used as demonstration with nematic phase liquid crystal composition after, its threshold voltage significantly reduces, has less viscosity, improve response speed, improved the response characteristic and the contrast gradient of liquid-crystal display, can be used for liquid-crystal displays such as TN, STN pattern, TFT pattern and PDLC pattern.
Embodiment
Embodiment 1
4-propyl group-4`-oxyethyl group-2,3,2`, the preparation of 3`-tetrafluoro diphenyl acetylene.
Step 1-1:4-oxyethyl group-2,3-difluoro iodobenzene synthetic: add 52g (0.37mol) 2 in the there-necked flask, the 3-difluoro ether, the dry tetrafluoro furans of 250ml, nitrogen protection is lowered the temperature-70 ℃ down down, begins to drip the 0.45mol n-Butyl Lithium, drips half an hour approximately, finish, be incubated 1.5 hours down in-70 ℃ ,-50 ℃ of solution that drip 94g (0.37mol) iodine and 230mlTHF dripped 1 hour approximately, drip and finish, kept 1 hour; Slowly add 10%NaHSO
3Solution is to fading separatory, organic layer washing twice, anhydrous MgSO
4Drying, the filtering siccative, evaporate to dryness gets 88g, gas chromatographic purity: 95%, yield: 81%.
Step 2-1:4-propyl group-2; synthesizing of 3-difluoro iodobenzene: in there-necked flask, add 117g (0.75mol) propyl group two fluorobenzene and 600ml dry THF; begin to drip n-Butyl Lithium 0.9mol when being cooled to-70 ℃ under the nitrogen protection; temperature control is no more than-60 ℃; dripped approximately 1.5 hours, and dripped and finish, kept 1 hour about-60 ℃;-50 ℃ drip 190g (0.75mol) iodine down at 600mlTHF solution, dripped approximately 3 hours.Drip and finish, kept again 1 hour, remove cooling bath, pour hydrolysis in about 1L water into.Add 10%NaHSO
3The about 300ml of solution transfers to colourless, separatory, and water Petroleum ether extraction three times merge organic phase, wash twice with saturated NaCl solution, the anhydrous MgSO of organic phase
4Drying, (filter, revolve clean) solvent, the resistates vacuum fractionation gets the cut under 90～92 ℃/4mmHg, gas chromatographic purity: 97%, yield; 85%.
Step 2-2:4-propyl group-2, synthesizing of 3-difluoro phenylacetylene: add 4-propyl group-2 in the there-necked flask, 3-difluoro iodobenzene 96g (0.34mol), 1,1-dimethyl-2-propine-1-alcohol 73g (0.87mol), triethylamine 180ml, the inferior ketone of 0.49g iodate, 200ml toluene, triphenylphosphine 0.5g, add Pd[O under the nitrogen protection] 0.7g, reflux 3 hours is filtered, the toluene flushing, separatory, wash three times, the organic phase drying, filter, desolvate, 85g dark oil liquid; It is added in the there-necked flask, and add the 100ml whiteruss, and add 3g KOH, be heated to more than 80 ℃, being distilled to no low-boiling-point substance steams, reacted about 1 hour down at 90～100 ℃, cold slightly changing in the matrass collected 80～80 ℃/5mmHg cut, obtain the light yellow oily liquid of 47g, gas chromatographic purity: 98%, two step yield is 78%, Mp:34.69 ℃.
Step 3:4-propyl group-4`-oxyethyl group-2,3,2`; synthesizing of 3`-tetrafluoro diphenyl acetylene: there-necked flask adds 4-oxyethyl group-2,3-difluoro iodobenzene 15.6g (0.055mol), 20ml triethylamine; 60ml toluene, 0.2g cuprous iodide, 0.2g triphenylphosphine; under nitrogen protection, add Pd[O] 0.2g, begin to stir, drip 9g (0.05ml) 4-propyl group-2 in room temperature; 3-difluoro phenylacetylene and 20ml toluene solution; dripped approximately 30 minutes, and dripped and finish, continue to stir 5 hours.Filter, the toluene flushing, separatory, organic phase washes with water to neutrality, anhydrous MgSO
4Drying is filtered, and revolves to boil off solvent, with sherwood oil 150ml heating for dissolving, carries out column chromatography, decolouring, 100ml sherwood oil wash-out merges, and is spin-dried for, can get the 12g white crystal twice with 2 times of ethyl alcohol recrystallizations again, yield 75%, gas phase is surveyed spectrum analysis: 99.75%, DSC:mp:80.05～82.15 ℃.
The MS data analysis
| Molecular formula | Characteristic ion (M/Z +) and abundance (%) |
| C 19H 16OF 4 | 336(M+，30.44)，308(18.68)，279(100)250(9.67)，230(6.24) |
Ultimate analysis:
Calculated value: C:67.85%, H:4.80%;
Experimental value: C:67.70%, H:4.72%.
Embodiment 2
Trans-4-propyl group cyclohexyl-4`-oxyethyl group-2,3,2`, the preparation of 3`-tetrafluoro diphenyl acetylene.
Step 1-1: propyl group tetrahydrobenzene-2; synthesizing of 3-two fluorobenzene: add 1,2-Difluorobenzene 114g (1mol) and dry THF 300ml in the there-necked flask; install and stir; be cooled to-70 ℃ under the nitrogen protection, begin to drip the 1.1mol n-Butyl Lithium, controlled temperature-70 ℃; dripped approximately 1 hour; drip and finish, kept 1 hour, then-70 ℃ dropping third cyclic ketones 126g
Dripped approximately 1 hour, and dripped and finish, kept 4-5 hour.Pour hydrolysis in about 1.5L water into,, merge organic phase with 500ml * 3 methylbenzene extraction, be washed to neutrality, divide water purification, add another there-necked flask, add the 5g tosic acid, stir following heat temperature raising, distillation THF in limit is during to internal temperature to 108 ℃, stop distillation, change reflux condensing tube into, backflow 5-6 hour, after the sampling and measuring dehydration finishes, cooling is after room temperature, pour in the separating funnel, be washed to neutrality, divide water purification with 1L * 3, cross 80 purpose silica gel pillars and carry out column chromatography, use 500ml toluene wash-out again, merge, standby.
Step 1-2: trans propyl group cyclohexyl-2,3-two fluorobenzene synthetic: the product of going up the step adds in the single port bottle, adding 50g (5%) Pd/C, fill emptying gas 5 times after, carry out atmospheric hydrogenation, about 30～40 ℃ of temperature control finishes filtering catalyst to inhaling hydrogen.Decompression is spin-dried for toluene, gets white suitable back mixing compound 160g, and with sherwood oil and alcohol mixed solvent, recrystallization twice can get pure trans product 146g, gas chromatographic detection〉99.3%, two step yield 65%.
Step 1-3:4-propyl group cyclohexyl-2,3-difluoro iodobenzene synthetic: add trans third ring-2 of 119g (0.5mol) in the there-necked flask, 3-two fluorobenzene and 300ml dry THF, stir inflated with nitrogen cooling down ,-70 ℃ drip n-Butyl Lithium 0.55mol down, dripped approximately 20 minutes, drip and finish, kept 1 hour.-60 ℃ of solution that drip 122g (0.48mol) iodine and 300mlTHF dripped 1 hour approximately, dripped and finished, and kept 1 hour.Cooling carefully adds 10%NaHSO
3The aqueous solution is till fading.Pour in about 1L water, add toluene 500ml, separatory, 300ml * 3 methylbenzene extraction merges organic phase, and washing is neutral, anhydrous MgSO
4Drying is filtered, and revolves the steaming solvent, with sherwood oil and alcohol mixed solvent recrystallization, can get white crystal 136.5g, yield: 78%, and gas chromatographic purity〉98.2%, DSC:mp:37.6 ℃.
Step 2-1:4-oxyethyl group-2,3-difluoro phenylacetylene synthetic: add 80g (0.5mol) 2 in the there-necked flask, the 3-difluoro ether
1,1-dimethyl-2-propine-1-alcohol 63g (0.75mol), triethylamine 300ml, 0.5g cuprous iodide, 350ml toluene, nitrogen protection adds Pd[O down] 1.0g,, filter toluene 200ml flushing, NH 45～50 ℃ of reactions 4 hours
4The Cl solution washing removes cupric ion, and separatory is washed three times, and anhydrous MgSO4 drying filters, and is spin-dried for solvent, crosses the silica gel pillar with petroleum ether dissolution, and decolouring is spin-dried for solvent again, gets dark-brown oily matter;
Step 2-2: dark-brown oily matter is added in the there-necked flask, and add 200ml paraffin, 3.0g KOH, limit heating edge distillation low-boiling-point substance does not distillate to there being low-boiling-point substance, reacts approximately 2 hours; Change in the matrass after cold slightly, decompression steams product, collects 100～102 ℃/3mmHg fraction, place solid 68g, GC〉96%.Two steps merged yield 76%, DSC:mp:54.69.
Step 3: trans-4-propyl group cyclohexyl-4`-oxyethyl group-2; 3; 2`; synthesizing of 3`-tetrafluoro diphenyl acetylene: add 91g (0.25mol) 4-propyl group cyclohexyl-2 in the there-necked flask, 3-difluoro iodobenzene, 200ml toluene, 30ml triethylamine, 0.5g cuprous iodide; nitrogen protection adds 1.0g Pd[O down]; be warming up to 55 ℃, drip 4-oxyethyl group-2, the solution of 3-difluoro phenylacetylene 47g (0.25mol) and 50ml toluene; dripped approximately 40 minutes; finish,, reacted 10 hours in 50～60 ℃; cooling; filter toluene 200ml flushing, NH again
4The Cl solution washing removes cupric ion, and separatory with 200ml * 3 methylbenzene extraction, merges organic phase, is washed to neutrality, anhydrous MgSO
4Drying is filtered, and is spin-dried for solvent, with about 5 times of petroleum ether dissolutions, cross 80～100 purpose silicagel columns and carry out column chromatography, with 3 times of sherwood oil flushings, merge again, revolve steaming, desolvate,, get white crystal 84g with sherwood oil and alcohol mixed solvent recrystallization twice, yield 79.8%, gas chromatographic purity 99.7%.
Its experimental result:
(1) compound phase texture: C:92.6 ℃ N:214.8 ℃ I.I
(2) MS data analysis
| Molecular formula | Characteristic ion (M/Z +) and abundance (%) |
| C25H26OF4 | 418(M+，100)，390(14.90)，307(7.86)，305(6.85)，292(45.71)，279(22.25)，266(11.07)， |
Ultimate analysis:
Calculated value: C:71.76%, H:6.26%;
Experimental value: C:71.77%, H:6.23%.
Embodiment 3
Trans 4-amyl group cyclohexyl-4`-oxyethyl group-2,3,2`, the preparation of 3`-tetrafluoro diphenyl acetylene
With reference to the synthetic method among the embodiment 2, difference is that third cyclic ketones among the step 1-1 is replaced with penta cyclic ketones, with 2, the reaction of 3-two fluorobenzene lithium reagents, through dehydration, hydrogenation, transposition, iodo gets 4-amyl group cyclohexyl-2,3-difluoro iodobenzene, its again with 4-oxyethyl group-2,3-difluoro phenylacetylene coupling and getting, its overall yield is 38%, and its experimental result is as follows:
(1) gas Chromatographic Determination:〉99.7%.
(2) compound phase structure: C:84.5 ℃ N:208.7 ℃ I.I
(3) MS data analysis
| Molecular formula | Characteristic ion (M/Z +) and abundance (%) |
| C 27H 30F 4O | 446(M+，100)，390(14.80)，305(5.78)，292(42.71)，279(20.15)，266(9.78)， |
Ultimate analysis:
Calculated value: C:72.63%, H:6.77%.
Experimental value: C:72.61%, H:6.79%.
Embodiment 4-7
With reference to embodiment 2, with among the step 1-1
Replace with respectively
Other operation prepares following compound with embodiment 2:
Embodiment 8
Embodiment 9-11
With reference to embodiment 2, with among the step 1-1
Replace with
According to the operation of step 1-1,1-2,1-3, preparation
With among the step 2-1
Replace with
According to step 2-1,2-2, preparation
Itself and above-mentioned three products are reacted according to step 3, prepare following product:
Embodiment 12-15
With reference to embodiment 2, with among the step 1-1
Replace with
According to the operation of step 1-1,1-2,1-3, preparation
With among the step 2-1
Replace with
According to step 2-1,2-2, preparation
Itself and above-mentioned four products are reacted according to step 3, prepare following product:
Embodiment 16-19
With reference to embodiment 1-15 preparation process and the synthetic knowledge of liquid crystal, the preparation following compounds:
Experimental example 1
This experimental example is that the liquid crystal property of embodiment of the invention 1-3 product compound compares:
From the liquid crystal property parameter of above compound as can be seen, The compounds of this invention has the necessary characteristic as liquid crystal material, has bigger optical anisotropy, wide temperature range is arranged, as showing the response speed and the driving voltage that can improve liquid-crystal composition with liquid crystal material, can be used in TN pattern, STN pattern and the TFT mode display.
Claims (5)
1, a kind of 2,3,2`, the 3`-tetrafluoro diphenyl acetylene derivative is characterized in that, described derivative is following structural formula compound:
Wherein R is C
1-C
7Straight chained alkyl.
2, the preparation method of the described compound of claim 1 is characterized in that, described method may further comprise the steps:
(d) in solvent, the Pd/C catalyzer exists down, the room temperature shortening and cis and trans cyclohexyl
Mixture (e) gets pure trans through recrystallization again
Product (f); Compound (f) becomes lithium reagent with the n-Butyl Lithium reaction at low temperatures, obtains alkyl trans cyclohexyl-2 again with Iod R, 3-two fluoro-4-iodine compounds
(2) compound
Reacting at low temperatures with n-Butyl Lithium becomes lithium reagent, obtains compound with Iod R again
Compound (h) is at Pd[O], in the presence of the triphenylphosphine, triethylamine with 1,1-dimethyl-2-propine-1-alcohol coupling and compound (j)
Compound (j) deprotection in the presence of alkali obtains 4-and replaces-2,3-difluoro phenylacetylene compound (B)
(3) compound (A) and compound (B) linked reaction and target product (I), described target product (I) is
R wherein
1Represent C
1-C
7Straight chained alkyl, R
2For-OC
2H
5
3, a kind of liquid-crystal composition is characterized in that, it is described 2,3 that described liquid-crystal composition contains the claim 1 of 7-13wt%, 2`, and the 3`-tetrafluoro diphenyl acetylene derivative, all the other components are liquid crystalline cpd commonly known in the art.
4, liquid-crystal composition according to claim 3 is characterized in that, all the other components in the described liquid-crystal composition are following compound:
R, R` are C
1-C
15Alkyl, C
1-C
15Thiazolinyl, C
1-C
15Alkoxyl group, C
1-C
15Alkene oxygen base, fluoro C
1-C
15Alkyl or fluoro C
1-C
15Alkenyl.
5, claim 1 is described 2,3,2`, and the 3`-tetrafluoro diphenyl acetylene derivative is in the purposes that shows aspect liquid crystal material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| DE102009058574B4 (en) * | 2009-12-17 | 2017-08-31 | Merck Patent Gmbh | Method for isomerization |
| JP5696874B2 (en) * | 2010-05-14 | 2015-04-08 | Dic株式会社 | Fluorobenzene derivative and liquid crystal composition containing the compound |
| DE102011112950A1 (en) * | 2010-10-13 | 2012-04-19 | Merck Patent Gmbh | Compounds for a liquid-crystalline medium and their use for high-frequency components |
| CN102153442B (en) * | 2011-03-04 | 2014-03-19 | 石家庄诚志永华显示材料有限公司 | Alkyl dicyclohexyl 2,3-difluorophenylbutenoid liquid crystal compound and application thereof |
| CN102557896B (en) * | 2011-12-15 | 2015-03-11 | 石家庄诚志永华显示材料有限公司 | (Poly) fluorine substituted phenyl diacetylene (bi) phenyl derivative, and preparation method and application thereof |
| CN102633596B (en) * | 2012-03-13 | 2014-10-08 | 石家庄诚志永华显示材料有限公司 | Side difluorine substituted diphenylacetylene liquid crystal compound, preparation method for same and application thereof |
| CN103012083B (en) * | 2012-12-28 | 2014-12-03 | 福建省邵武市永晶化工有限公司 | Dicyclohexyl fluorinated tolane negative liquid crystal, and synthesis method and application thereof |
| CN108659853B (en) * | 2017-03-29 | 2021-04-02 | 北京八亿时空液晶科技股份有限公司 | Liquid crystal composition containing fluoroalkoxy liquid crystal compound and application thereof |
| CN110903832B (en) * | 2019-12-20 | 2021-02-12 | 上海瓜呱科技有限公司 | Negative liquid crystal compound, liquid crystal composition containing negative liquid crystal compound and application of negative liquid crystal compound |
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