Summary of the invention
The purpose of this invention is to provide a kind of benzo 1 that contains, the inferior methoxyl group bridge of 3-dioxolane and difluoro (CF
2O-) liquid crystalline cpd and preparation method thereof and application.
The benzo 1 that contains provided by the invention, the inferior methoxyl group bridge of 3-dioxolane and difluoro (CF
2O-) liquid crystalline cpd is also compound shown in formula I,
The formula I
In described formula I, R
1And R
2Be group shown in following A or B:
A, be selected from H, Cl, F, OCF
3, CF
3, CHF
2, OCHF
2, C1-C15 the alkoxyl group of alkyl, the alkoxyl group of C1-C15 and the C1-C15 that fluorine or chlorine replaces of the C1-C15 that replaces of alkyl, fluorine or chlorine at least a;
B, with at least one non-conterminous-CH in described A
2-quilt-CH=CH-,-C ≡ C-,-COO-,-OOC-, tetramethylene and-at least one in O-substitute and group;
Described A
1And A
4All be selected from least a in singly-bound and following radicals:
Described A
2And A
3All be selected from least a in singly-bound and following radicals:
L
1, L
2And L
3All be selected from singly-bound ,-CH=CH-,-C ≡ C-,-COO-,-OOC-,-CF
2O-,-OCH
2-,-CH
2O-,-OCF
2-,-CH
2CH
2-,-CF
2CH
2-,-CH
2CF
2-,-C
2F
4-,-CF=CF-and-(CH
2)
4-at least a;
A is the integer of 0-3; B and c are the integer of 1-3, and a+b+c≤5.
Concrete, compound shown in described formula I is compound shown in formula Ia,
Formula I a
In described formula I a, R
1, R
2, A
1, A
4, A
2, A
3And L
1Definition identical with aforementioned definitions;
A is the integer of 0-3; B and c are the integer of 1-3, and a+b+c≤4.
More specifically, compound shown in described formula I be as shown in the formula I 1 to compound shown in I 12:
Wherein, described formula I 1 to I 12, R
1The straight chained alkyl or the carbonatoms that are 1-10 for hydrogen or carbonatoms are the alkoxyl group of 1-10, be specially straight chained alkyl or alkoxyl group that carbonatoms is 1-8,1-6,1-5,2-8,2-6 or 2-5 or 3-5 ,-(F) the fluorine atom substituting group is arranged or be hydrogen on the expression phenyl ring.
Described formula I R
1And R
2Definition in, in the alkoxyl group of the C1-C15 that the alkyl of the C1-C15 that the alkyl of described C1-C15, fluorine or chlorine replace, the alkoxyl group of C1-C15 and fluorine or chlorine replace, the carbon atom of alkyl or alkoxyl group is specially 1-10 or 1-8 or 1-6 or 1-5 or 1-4 or 1-3 or 2-5 or 2-4 or 2-8.
More specifically, shown in described formula I, compound is
Or
The invention provides the method for compound shown in two kinds of preparation formula I;
Method one comprises the steps:
1) will
Sodium hydroxide with
Mixing carries out etherification reaction, reacts complete obtaining
2) with the step 1) gained
With the n-Butyl Lithium mixing, and it is saturated to system to pass into carbonic acid gas, carries out addition reaction, reacts complete obtaining
3) with step 2) gained
1,3-dimercaptopropane and trifluoromethanesulfonic acid mixing carry out the reflux dewatering reaction, tell the water of generation, and after minute water purification, cooling obtains
4) will
With triethylamine in-90 ℃~-60 ℃ with the step 3) gained
The mixing reaction kept temperature to add NEt after 0.5-3 hour again
3Fluoridation is carried out in 3HF and bromine mixing, reacts the complete compound shown in described formula I that obtains;
Described step 1) to step 4) reaction materil structure formula, R
1, R
2, A
1, A
2, A
3, A
4, L
1, L
2, a and b definition as hereinbefore.
The synthetic route of the method is as follows:
In the described step 1) of aforesaid method,
Sodium hydroxide with
Molar ratio be 0.8-1.2:1.5-3.0:0.8-1.5, preferred 1:2:1; In described etherification reaction step, temperature is 80-130 ℃, and preferred 95 ± 5 ℃, the time is 2-8 hour, preferred 6 hours;
Described step 2) in,
With the molar ratio of n-Butyl Lithium be 1-1.2:0.8-1.5, preferred 1:1; In described addition reaction step, temperature is-50 to-90 ℃, and preferred-70 ℃, the time is 0.5-2 hour, preferred 2 hours;
In described step 3),
The mole dosage ratio that feeds intake of 1,3-dimercaptopropane and trifluoromethanesulfonic acid is 0.8-1.2:0.9-1.3:1.0-1.5, preferred 1.0:1.3:1.3;
In described step 4),
Triethylamine,
NEt
3The mole dosage ratio that feeds intake of 3HF and bromine is 0.8-1.2:0.8-1.2:0.8-1.2:2.5-6:2.5-6, preferred 1:1:1:4:4;
Described step 1)-4) reactions steps is all carried out in solvent; Described solvent is selected from least a in tetrahydrofuran (THF), toluene, Virahol and methylene dichloride.
Method two comprises the steps:
1) will
Sodium hydroxide with
Mixing carries out etherification reaction, reacts complete obtaining
2) with the step 1) gained
Carry out negative ionization reaction after 0.5-2.0 hour with n-Butyl Lithium in-55 ℃--60 ℃, add again CF after cooling
2Br
2Mixing carried out substitution reaction 0.5-2.0 hour, reacted complete obtaining
3) with step 2) gained
Anhydrous potassium carbonate,
Carry out Williamson in 65-70 ℃ and become the ether reaction, react compound shown in complete described formula I;
Described step 1) to step 3) reaction materil structure formula, R
1, R
2, A
1, A
2, A
3, A
4, L
1, L
2, a and b definition as hereinbefore.
The synthetic route of the method is as follows:
In the described step 1) of the method,
Sodium hydroxide with
Molar ratio be 0.8-1.2:1.5-3.0:0.8-1.5, preferred 1:2:1; In described etherification reaction step, temperature is 95 ± 5 ℃, and the time is 2-8 hour, preferred 6 hours;
Described step 2) in,
N-Butyl Lithium, CF
2Br
2Molar ratio be 0.8-1.2:0.8-1.5:1.0-2.0, preferred 5:6:7;
In described step 3),
Anhydrous potassium carbonate and
Molar ratio be 1.0-1.2:2.0-3.0:1.0-1.5, preferred 1:2:1.2;
Described step 1)-3) reactions steps is all carried out in solvent;
Described solvent is selected from least a in tetrahydrofuran (THF), toluene, Virahol and methylene dichloride.
In above-mentioned two methods, intermediate benzo 1, the synthetic method of 3-dioxolane is according to described in CN02153717.8., the inferior methoxyl group bridge of difluoro (CF
2Being introduced in " contemporary organic fluorine chemistry " (Wu Yongming translates for original work P.Kirsch, Zhu Shizheng) P287-288 O-) provides.
The compound of structural formula I is due to substituent difference, thereby range of application is more extensive.These compounds can be as the basic ingredient of liquid crystal compound.Also be shown in described formula I at least a in compound therefore contain component A() liquid crystal compound, also belong to protection scope of the present invention, wherein, described component A is specially 1-5 kind compound, is more specifically 2-4 kind compound or 2 kinds of compounds; Described component A accounts for the 1-90% of described liquid crystal mixed solution gross weight, preferred 5-60%, and more preferably 9-40% is specially 9% or 20% or 9-20%.
Described component A is specifically also that shown in formula I1 and formula I3, compound forms by compound shown in two kinds of formula I, and the mass ratio of compound shown in described formula I1 and formula I3 is 4:5 or 8:12 or 4-8:5-12;
Wherein, shown in described formula I1, compound is specially
Shown in described formula I3, compound is specially
Or
More specifically, above-mentioned liquid crystal compound is mixture a or the b that each component by following mass parts forms;
Wherein, in mixture a, each component structure formula and mass parts are as follows:
In mixture b, each component structure formula and mass parts are as follows:
The application in preparation liquid crystal display material or electrooptics display material of compound shown in above-mentioned formula I or described liquid crystal compound, and comprise liquid crystal display material or the electrooptics liquid-crystal display of compound shown in formula I or described liquid crystal compound.Wherein, described indicating meter is TN-TFT indicating meter, STN indicating meter or IPS indicating meter.
The benzo 1 that contains provided by the invention, the inferior methoxyl group bridge of 3-dioxolane and difluoro (CF
2O-) novel cpd has thermostability, moderate △ n, larger positive dielectric anisotropy △ ε preferably, can realize lower threshold voltage when using in optics, also has simultaneously wide nematic phase range and low rotary viscosity γ
1, significant for the quick response that realizes indicating meter, therefore be suitable for very much allocating liquid crystal compound.Lower threshold voltage and low rotary viscosity γ can be realized when optics uses, liquid-crystal composition material and display performance can be improved, significant to the quick response that realizes indicating meter.It is low that the liquid-crystal composition that contains this compounds can be applicable to prepare driving voltage, wide temperature range, the liquid-crystal display of fast response time.
Embodiment
The present invention is further elaborated below in conjunction with specific embodiment, but the present invention is not limited to following examples.Described method is ordinary method if no special instructions.Described material all can get from open commercial sources if no special instructions.
In following embodiment:
1, GC represents gas chromatographic purity (Agilent HP6820 type gas chromatographicanalyzer)
2, MS represents mass spectrum (Agilent MS5975C type)
3,1H-NMR represents nucleus magnetic hydrogen spectrum
4, MP represent fusing point (the micro-thermal analyzer of WRX-1S, set temperature rise rate and be 3 ℃/min)
5, CP represents that (scanner is turned round in plum Teller DSC822e type differential calorimetric to clearing point, heats up or 1 ℃/min of cooling rate; Plum Teller FP-52 type polarizing microscope melting point apparatus, 3 ℃ of heat-up rates/min)
6, △ ε represents dielectric anisotropy (20 ℃, 1000Hz, the HP4284a of Hewlett-Packard), △ ε=ε
11-ε
⊥(ε
11Be the specific inductivity of liquid crystal molecule at long axis direction, ε
⊥Be the specific inductivity of liquid crystal molecule at short-axis direction)
7, △ n represents optical anisotropy (20 ℃, 589nm, Abbérefractometer), △ n=n
11-n
⊥(specific refractory power (n
11) be to measure when polarization direction is parallel with frictional direction, specific refractory power (n
⊥) be to measure when polarization direction is vertical with frictional direction).
Embodiment 1(method one)
Step 1:
In reaction flask with 0.1mol4-amyl group pyrocatechol (reactant); 0.2mol sodium hydroxide (reactant) is suspended in the 100mlDMSO(solvent) in; logical nitrogen protection; be heated to 100 ℃, stirred 20 minutes, dripped the 0.1mol1-(dichloromethyl in 1 hour)-3; 5-difluorobenzene (reactant); control temperature at 95 ± 5 ℃, dropwise, continue to stir and carried out etherification reaction 6 hours.Be cooled to room temperature, add 150ml water, extract twice water layer with 100ml methylene dichloride (solvent), the washing organic layer is to neutral, discard water layer, with the dry organic layer of anhydrous sodium sulphate (siccative), filtering siccative, solvent evaporated, 168 ℃~175 ℃/3mmHg cut is collected in the enriched material underpressure distillation, get weak yellow liquid (1-a), yield 60%, gas chromatographic purity 98.0%.
Step 2:
the 0.1mol (1-a) (reactant) that adds step to obtain in reaction flask, 120ml tetrahydrofuran (THF) (solvent), sealing is installed stirs, logical nitrogen replacement air, be cooled to-70 ℃, dripping 0.1mol concentration is the hexane solution of the n-Butyl Lithium (reactant) of 2.5M, add rear 20 minutes, pass into dry carbon dioxide (reactant), to saturated, carry out addition reaction 2 hours at this temperature, this reaction solution is poured in the beaker of 20ml concentrated hydrochloric acid (regulate pH value) and 100ml water and be hydrolyzed, separatory, 50ml ethyl acetate (solvent) is extracted water once, merge organic phase, saturated common salt is washed to neutrality, anhydrous sodium sulphate (siccative) drying, the concentrated solvent that eliminates, obtain light yellow solid, with Virahol (solvent) recrystallization once, obtain white crystal (1-b).Yield 90%, liquid chromatography purity 98.0%.
Step 3:
add 0.1mol (1-b) in reaction flask, 30ml toluene (solvent) and 30ml octane-iso (solvent), add 14g(0.13mol) 1, 3-dimercaptopropane (reactant), under stirring, above-mentioned suspension is heated to 50 ℃, added trifluoromethanesulfonic acid (reactant) 19.2g(0.13mol in 30 minutes), be warming up to reflux dewatering after adding, tell the water of generation, after minute water purification, cool to 90 ℃, add methyl tertiary butyl ether (solvent) 100ml at 70 ℃ in 45 minutes, continue cooling, crystallize out, filter under nitrogen protection, the crystal that obtains washs with methyl tertiary butyl ether (solvent) (25ml * 4), vacuum-drying obtains orange crystal (dithiane fluoroform sulphonate) (1-c).
Step 4:
Add 0.1mol3 in reaction flask, 4,5-trifluoromethyl phenol (reactant), 0.1mol the mixing solutions of triethylamine (reactant) and 130ml methylene dichloride (solvent) also is cooled to-70 ℃, drip the solution of the 120ml methylene dichloride (solvent) of above-mentioned 0.1mol (1-c) crystal (reactant), added in 45 minutes, and stirred in this temperature and carry out addition reaction after one hour, add 0.4mol NEt in 5 minutes
3The 3HF(reactant).Then under-70 ℃, 30ml methylene dichloride (solvent) solution that adds 0.4mol bromine (reactant) in one hour, then proceed fluoridation one hour under-70 ℃, be warming up to 0 ℃, reaction solution is poured into during 32% 160ml aqueous sodium hydroxide solution (regulating pH value) and 300g ice, and the pH value of coming conditioned reaction liquid by dropping 45g32% aqueous sodium hydroxide solution changes occurrence in this scope into to 6().After separatory, water extracts with 80ml methylene dichloride (solvent), merges organic phase and filters with 4g diatomite (discoloring agent), washing, the lower solvent evaporated of decompression.After the crude product column chromatography that obtains, sherwood oil (solvent) recrystallization, obtain white crystal product (1-d), yield 45%.
Experimental result is as follows:
1、GC:99.5%。
2、MP:26℃
3、MS:m/s%163(62.22)191(7.99)296(8.95)353(63.80)443(100)500(M
+87.45)
4、
1H-NMR:0.906(t,3H)、1.331(m,4H)、1.589(m,2H)、2.547(t,2H)、6.700(d,1H)、6.739(s1H)、6.778(d,1H)、6.897(s,1H)、6.967(t,2H)、7.226(d,2H)
As from the foregoing, this product structure is correct, is compound shown in formula I1.Its liquid crystal property detected result is as follows:
5、△ε:18.0
6、△n:0.17
7、CP:50℃
Embodiment 2(method two)
Step 1
In reaction flask with 0.1mol4-propyl group pyrocatechol (reactant); 0.2mol sodium hydroxide (reactant) is suspended in the 100mlDMSO(solvent) in; logical nitrogen protection; be heated to 100 ℃, stirred 20 minutes, dripped the 0.1mol4-(dichloromethyl in 1 hour)-3 '; 5 '-DfBP (reactant); control temperature at 95 ± 5 ℃, dropwise, continue to stir and carried out etherification reaction 6 hours.Be cooled to room temperature, add 150ml water, extract twice water layer with 100ml methylene dichloride (solvent), the washing dichloromethane layer discards water layer to neutral, with anhydrous sodium sulphate (siccative) dry methylene chloride layer, the filtering siccative, solvent evaporated, gains are dissolved in the 30ml sherwood oil, cross the silicagel column decolouring, with sherwood oil (solvent) wash-out, collect elutriant and solvent evaporated, get weak yellow liquid (2-a), yield 90%, gas chromatographic purity 90%.
Step 2
Add 0.05mol(2-a in reaction flask) (reactant), 90ml tetrahydrofuran (THF) (solvent), logical nitrogen protection; be cooled to-60 ℃, drip 0.06mol n-Butyl Lithium (reactant), drip process temperature control-55 ℃~-60 ℃; drip and finish, continue temperature control stirring and carry out negative ionization reaction 1 hour.Be cooled to-70 ℃, drip 0.07mol difluorodibromomethane (reactant), drip process temperature control-65 ℃~-70 ℃, drip and finish, continue temperature control stirring and carried out substitution reaction 30 minutes, be warming up to room temperature, add 10ml concentrated hydrochloric acid (regulating the pH value)+50ml water (solvent) hydrolysis, separatory, 50ml methylene dichloride (solvent) extracts water, and the washing organic phase is to neutral, and solvent evaporated gets weak yellow liquid (2-b), yield 70%, gas chromatographic purity 78%.
Step 3
Add 0.01mol(2-b in reaction flask) (reactant), the 50mlDMSO(solvent), 0.02mol Anhydrous potassium carbonate (reactant), 0.012mol3,4,5-trifluoromethyl phenol (reactant) is heated with stirring to 70 ℃) carry out Williamson and become ether reaction reaction in 2 hours complete.Be cooled to room temperature, cross filter solid, and with 30ml methylene dichloride (solvent) flush cake, filtrate adds 100ml water, stirs, separatory extracts water layer with 20ml methylene dichloride (solvent), and the washing organic phase is to neutrality, solvent evaporated.Enriched material is dissolved in 20ml sherwood oil (solvent), crosses the silicagel column decolouring, uses sherwood oil (solvent) wash-out, collects elutriant and steams except sherwood oil (solvent), and gains dehydrated alcohol (solvent) recrystallization 3 times obtain white plates solid (2-c), yield 45%
Experimental result is as follows:
1、GC:99.5%
2、MP:45.5℃
3、MS:m/s%186(56.89)239(62.08)267(29.95)401(45.26)519(67.18)548(M
+100)
4、
1H-NMR:0.948(t,3H)、1.627(m,2H)、2.535(t,2H)、6.672(d,1H)、6.729(s,1H)、6.774(d,1H)、6.990(t,3H)、7.226(t,2H)、7.616(d,2H)、7.695(d,2H)
As from the foregoing, this product structure is correct, is compound shown in formula I3.Its liquid crystal property detected result is as follows:
5、△ε:19.2
6、△n:0.216
7、CP:120℃
Embodiment 3 ~ 50
With reference to the method for embodiment 1,2, only with the reactant substituting group according to the corresponding replacement of product, obtain as shown in the formula compound shown in I:
Embodiment 51
With embodiment 2 gained
With embodiment 5 gained
And the liquid crystalline cpd of other following structural formulas, according to following weight ratio mixing, obtain liquid crystal compound:
The physical property of this liquid crystal compound and liquid crystal property detected result are as follows:
CP=103℃
Δn=0.1000
Δε=6.2;
And add embodiment 2 gained
With embodiment 5 gained
Before, the performance test results of the liquid crystal compound of above-mentioned mass ratio is as follows:
CP=93℃,
Δn=0.087,
Δε=4.4。
As from the foregoing, formula I compound adds in liquid crystal compound, can improve the performance of liquid crystal compound, has significantly improved dielectric anisotropy Δ ε and optical anisotropy △ n, and has widened the nematic temperature range of liquid crystal compound.
Embodiment 52
With embodiment 50 gained
With embodiment 5 gained
And the liquid crystalline cpd of other following structural formulas, according to following weight ratio mixing, obtain liquid crystal compound:
The physical property of this mixture and liquid crystal property detected result are as follows:
CP=93℃
Δn=0.089
Δε=6.5。
And add embodiment 50 gained
With embodiment 5 gained
Before, the performance test results of the liquid crystal compound of above-mentioned mass ratio is as follows:
CP=83℃,
Δn=0.075,
Δε=4.5。
As from the foregoing, formula I compound adds in liquid crystal compound, can significantly improve the performance of liquid crystal compound, has obviously improved mixture dielectric anisotropy Δ ε and optical anisotropy △ n, has improved degree of birefringence, has improved the nematic phase range of liquid crystal compound.