CN110483407A - N- methyl substituted benzimidazole liquid-crystal compounds containing acetylene bond and preparation method thereof - Google Patents
N- methyl substituted benzimidazole liquid-crystal compounds containing acetylene bond and preparation method thereof Download PDFInfo
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- C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
- C09K19/3441—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom
- C09K19/3477—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom the heterocyclic ring being a five-membered aromatic ring containing at least one nitrogen atom
- C09K19/348—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom the heterocyclic ring being a five-membered aromatic ring containing at least one nitrogen atom containing at least two nitrogen atoms
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Abstract
The invention discloses a kind of N- methyl substituted benzimidazole liquid-crystal compounds and preparation method thereof containing acetylene bond, belongs to field of material technology.The structural formula of the liquid-crystal compounds isR represents C in formula5~C12Straight chained alkyl, X represents hydrogen, methyl or nitro.The compound is prepared using p-bromobenzaldehyde, 2- methyl -3- butyne-2-alcohol, 1- iodo- 4- (alkoxy) benzene, o-phenylenediamine class compound, iodomethane as raw material by reactions such as Sonogashira coupling, nucleophilic addition, cyclizations.Liquid-crystal compounds of the present invention has big birefringence, and preparation methods steps are simple, can be used in liquid crystal electro-optical device, to improve its response speed.
Description
Technical field
The invention belongs to liquid crystal material technical fields, and in particular to a kind of N- methyl substituted benzimidazole liquid crystal containing acetylene bond
Compound and preparation method thereof.
Background technique
Liquid crystal material with tremendous expansion prospect is applied to smart phone, automobile navigation instrument dial plate, plate, portable now
The field of display devicees such as formula laptop and large high-definition screen TV and optical modulator, laser beam deflection, adaptive optics
Etc. non-display field.Liquid crystal material in photoelectric device driving voltage, driving number, viscoplasticity, visual angle, including energy consumption etc.
More than ten of parameter be adjusted and optimize, display superiority can be made more prominent.
In its numerous application, the response speed for promoting liquid crystal display is always that stubborn problem is compared in this field.
In display field, substantially the reason of influence liquid crystal display response speed, has: first is that the coefficient of viscosity of liquid crystal material；Second is that liquid crystal
The size in unit box gap, the i.e. gap of electro-conductive glass substrate, that is, the thickness of liquid crystal layer up and down；Third is that Jie of liquid crystal material
Electrostrictive coefficient and driving voltage.Therefore, the response speed for improving liquid crystal electro-optical device is always the important development direction of field of liquid crystals.
Following scheme a: side can be taken according to the response speed that above influence factor will improve liquid crystal electro-optical device
Face reduces the coefficient of viscosity of liquid crystal material as much as possible, and there are direct pass in the viscosity of liquid crystal material and the response time of liquid crystal device
System, i.e., under conditions of temperature is stablized, the coefficient of viscosity of general liquid crystal material is lower, and liquid crystal can be free high under electric field driven
Speed presses direction of an electric field aligned twisted, and the response speed of display is accelerated；On the other hand, it is thick that liquid crystal device box is reduced as much as possible,
The gap of liquid crystal device unit box is smaller, is torqued into place liquid crystal molecule faster, and response speed will be accelerated, and big light
Learning anisotropy, (Δ n) liquid crystal material can ensure to effectively reduce liquid crystal device unit box gap and be applied in practice.
So studying big Δ n liquid crystal material is the key that night crystalline substance photoelectric device realizes one of quick response.However, that is reported at present is big
Portions of liquid crystal material its Δ n and it is not big enough, type is also seldom, this is far from satisfying answering in this field of liquid crystal electro-optical device
With requiring.It is considerably less especially to can be used as the big Δ n heteroaromatic class LCD compound species that liquid crystal electro-optical device uses.
The study found that the Π electron conjugated length appropriate for increasing liquid crystal molecule is a kind of side for effectively increasing liquid crystal Δ n
Method.The method of traditional increase liquid crystal molecule conjugate length has:
(1) double bond, three keys and unsaturated hexatomic ring are introduced in the rigid central of liquid crystal molecule；Such as Chinese patent
Compound disclosed in CN1436761A
Wherein m, n=2~5, x=1~2.Although double bond, three keys and unsaturated hexatomic ring facilitate to promote the Δ n of liquid crystal,
But it is limited to promote effect.
(2) increase the number of intramolecular phenyl ring, the compound as disclosed in Japan Patent JP02059530A
Wherein R and R ' represents the alkyl substituent, alkoxy substituent, methylene alkoxy substituent of carbochain 1~10.But
Increase phenyl ring number and inevitably result in fusing point raising, fusing point has reached 150 DEG C, and synthetic route is also long.
(3) cyano or isothiocyano are introduced on the terminal sites of liquid crystal molecule.As document " Li Tan, Wang Zhen, Wang Guohua,
Zhang Zhiyong, customs gold unit great waves, study on the synthesis [J] the liquid crystal of the high bicyclic nematic liquid crystal of Δ n value of Dai Zhiqun low melting point and display,
2017,32 (11): the compound reported in 861-867 "
Wherein n=3~5.Although cyano or isothiocyano can be such that the Δ n of liquid crystal increases, biggish dipole significantly
Square makes the effect of the intermolecular electrostatic containing these groups very strong, is unfavorable for reducing liquid crystal viscosity；Moreover, cyano and isothiocyano
Liquid crystal is still extremely difficult to the requirement of active matrix driving even across multiple purification, resistivity.
Summary of the invention
The purpose of the present invention is to provide a kind of, and the N- methyl substituted benzimidazole containing acetylene bond with larger Δ n liquid-crystalizes
Object is closed, and provides a kind of simple preparation method of processing step for the liquid-crystal compounds.
For above-mentioned purpose, the structural formula of liquid-crystal compounds of the present invention is as follows:
R represents C in formula5~C12Straight chained alkyl, X represents H, CH3、NO2In any one.
The preparation method of N- methyl substituted benzimidazole liquid-crystal compounds of the present invention containing acetylene bond is made of following step:
1,4- (4- (1,3- dioxolanes -2- base) phenyl) -2- methyl butyl- 3- alkynes -2- alcohol is prepared
P-bromobenzaldehyde, p-methyl benzenesulfonic acid, ethylene glycol are added in dry chloroform, flowed back at 60~80 DEG C anti-
It answers 6~8 hours, evaporating solvent under reduced pressure, 2- methyl -3- butyne-2-alcohol, cuprous iodide, triphenylphosphine, triethylamine is then added,
60~80 DEG C after back flow reaction 8~10 hours under nitrogen protection, tetrakis triphenylphosphine palladium is added, the reaction was continued 6~8 hours,
Product is isolated and purified after the reaction was completed, obtains 4- (4- (1,3-dioxolane -2- base) phenyl) -2- methyl butyl- 3- alkynes -2- alcohol,
Reaction equation is as follows:
2,2- (4- ((4- (alkoxy) phenyl) acetenyl) phenyl) -1,3- dioxolanes is prepared
By 4- (4- (1,3-dioxolane -2- base) phenyl) -2- methyl butyl- 3- alkynes -2- alcohol, ethylene glycol ethyl ether, hydroxide
Sodium is added in toluene, and 60~80 DEG C of constant temperature flow back 4~5 hours under nitrogen protection, and the iodo- 4- (alcoxyl of 1- shown in Formulas I is then added
Base) benzene, tetrakis triphenylphosphine palladium, the reaction was continued 6~8 hours, isolates and purifies product after the reaction was completed, obtains 2- (4- ((4- (alkane
Oxygroup) phenyl) acetenyl) phenyl) -1,3-dioxolane, reaction equation is as follows:
In Formulas I, R represents C5~C12Straight chained alkyl.
3,4- ((4- (alkoxy) phenyl) acetenyl) benzaldehyde is prepared
2- (4- ((4- (alkoxy) phenyl) acetenyl) phenyl) -1,3-dioxolane, formic acid are added in tetrahydrofuran,
It flows back 6~8 hours in 50~70 DEG C of constant temperature, isolates and purifies product, obtain 4- ((4- (alkoxy) phenyl) acetenyl) benzaldehyde,
Reaction equation is as follows:
4, the N- methyl substituted benzimidazole liquid-crystal compounds containing acetylene bond is prepared
N,N-dimethylformamide is added in 4- ((4- (alkoxy) phenyl) acetenyl) benzaldehyde, Sodium Metabisulfite
In, 120~130 DEG C of constant temperature flow back 1~2 hour under nitrogen protection, o-phenylenediamine class compound shown in Formula II is then added, after
Continuous reflux 6~8 hours, sedimentation is recrystallized to give faint yellow solid in water；N, N- bis- is added in faint yellow solid, sodium hydroxide
It in methylformamide, is stirred at room temperature 2~3 hours, the n,N-Dimethylformamide solution dissolved with iodomethane is added dropwise, the reaction was continued 5
~6 hours, then reaction solution is poured into deionized water and is settled, decompression is filtered and dried, and dehydrated alcohol recrystallization is obtained containing alkynes
The N- methyl substituted benzimidazole liquid-crystal compounds of key, reaction equation are as follows:
In Formula II, X represents H, CH3、NO2In any one.
In above-mentioned steps 1, preferably p-bromobenzaldehyde and p-methyl benzenesulfonic acid, ethylene glycol, 2- methyl -3- butyne-2-alcohol, iodate
Molar ratio 1:0.25~0.3:20~25:0.4~1.0:0.02~0.05 of cuprous, triphenylphosphine, tetrakis triphenylphosphine palladium:
0.04~0.1:0.008~0.02.
In above-mentioned steps 2, preferably 4- (4- (1,3-dioxolane -2- base) phenyl) -2- methyl butyl- 3- alkynes -2- alcohol and second
Glycol ether, sodium hydroxide, 1- iodo- 4- (alkoxy) benzene, tetrakis triphenylphosphine palladium molar ratio be 1:10~12:6~6.5:1
~1.1:0.015~0.025.
In above-mentioned steps 3, preferably 2- (4- ((4- (alkoxy) phenyl) acetenyl) phenyl) -1,3-dioxolane and formic acid
Molar ratio be 1:150~175.
In above-mentioned steps 4, preferably 4- ((4- (alkoxy) phenyl) acetenyl) benzaldehyde and Sodium Metabisulfite, adjacent benzene two
Molar ratio 1:1.0~1.4:1.0~1.3:1.5~2.0:0.5~1.0 of ammoniac compounds, sodium hydroxide, iodomethane.
Beneficial effects of the present invention are as follows:
1, the present invention is with p-bromobenzaldehyde, 2- methyl -3- butyne-2-alcohol, 1- iodo- 4- (alkoxy) benzene, o-dihydroxy ammon class
Compound, iodomethane are raw material, and the N- first containing acetylene bond is prepared by reactions such as Sonogashira coupling, nucleophilic addition, cyclizations
Base substituted benzimidazole liquid-crystal compounds, preparation method are easy to operate.
2, the compounds of this invention had not only had heterocycle liquid crystal mesophase type, but also optical anisotropy with higher, and had
There is wide nematic phase section, can be used in liquid crystal electro-optical device, to improve its response speed.
Detailed description of the invention
Fig. 1 is the thermal analysis curve of liquid-crystal compounds prepared by embodiment 1.
Fig. 2 is polarized light microscopy photo when liquid-crystal compounds prepared by embodiment 1 is warming up to 192 DEG C.
Fig. 3 is polarized light microscopy photo when liquid-crystal compounds prepared by embodiment 1 is cooled to 170 DEG C.
Specific embodiment
The present invention is described in more detail with reference to the accompanying drawings and examples, but protection scope of the present invention is not limited only to
These embodiments.
Embodiment 1
1,4- (4- (1,3- dioxolanes -2- base) phenyl) -2- methyl butyl- 3- alkynes -2- alcohol is prepared
P-bromobenzaldehyde 10g (49.6mmol) is added in the 250mL single-necked flask equipped with condenser pipe and stirrer, to first
Benzene sulfonic acid 2.20g (12.7mmol), ethylene glycol 70mL (1120.0mol), and the chloroform dried with molecular sieve is added
100mL makees solvent, and at 60 DEG C after constant temperature back flow reaction 6 hours, washing is extracted with dichloromethane, evaporating solvent under reduced pressure obtains
White liquid.Gained white liquid is added in the 250mL there-necked flask equipped with stirrer, 2- methyl -3- crotonylene-is then added
Alcohol 2.02g (24.0mmol), cuprous iodide 0.21g (1.1mmol), triphenylphosphine 0.58g (2.2mmol), and triethylamine is added
80 DEG C after back flow reaction 1 hour under nitrogen protection, tetrakis triphenylphosphine palladium 0.50g is added as solvent in 80mL
(0.4mmol), the reaction was continued 8 hours.After reaction, reaction system is diluted with water, is extracted with dichloromethane, anhydrous magnesium sulfate
Dry, vacuum distillation rotation removes solvent, the pillar layer separation (mixing that eluant, eluent is petroleum ether and ethyl acetate volume ratio is 30:1
Liquid), yellow oily liquid 4- (4- (1,3-dioxolane -2- base) phenyl) -2- methyl butyl- 3- alkynes -2- alcohol 4.20g is obtained, is received
Rate 82%, reaction equation is as follows:
2,2- (4- ((4- (amoxy) phenyl) acetenyl) phenyl) -1,3- dioxolanes is prepared
4- (4- (1,3- dioxolanes -2- base) is sequentially added in the 250mL there-necked flask equipped with stirring magneton and condenser pipe
Phenyl) -2- methyl butyl- 3- alkynes -2- alcohol 4.20g (18.1mmol), sodium hydroxide 4.32g (0.1mol), ethylene glycol ethyl ether
16.30g (0.2mol), and 80mL toluene is added and makees solvent is stirred at reflux reaction 4 hours for 80 DEG C under nitrogen protection, then plus
Enter 1- iodo- 4- (amoxy) benzene 5.46g (18.1mmol), tetrakis triphenylphosphine palladium 0.42g (0.3mmol), it is 8 small that the reaction was continued
When.Reaction solution is extracted with methylene chloride and water after reaction, merges organic phase, vacuum distillation removes solvent, pillar layer separation
(mixed liquor that eluant, eluent is petroleum ether and ethyl acetate volume ratio is 100:1), obtains light yellow crystal 2- (4- ((4- (penta oxygen
Base) phenyl) acetenyl) phenyl) -1,3-dioxolane 4.76g, yield 69%, reaction equation is as follows:
3,4- ((4- (amoxy) phenyl) acetenyl) benzaldehyde is prepared
2- (4- ((4- (amoxy) phenyl) acetylene is sequentially added in the 250mL single port bottle equipped with stirrer and condenser pipe
Base) phenyl) -1,3-dioxolane 4.76g (12.5mmol), and formic acid 87.8g (1.9mol), tetrahydrofuran are added thereto
190mL, 60 DEG C of heating reflux reaction 6h in constant temperature oil bath.After reaction, reaction solution, revolving are extracted with methylene chloride and water
Concentration obtains faint yellow solid, and dehydrated alcohol recrystallization is added, obtains white solid 4- ((4- (amoxy) phenyl) acetenyl)
Benzaldehyde 2.55g, yield 70%, reaction equation is as follows:
4,2- (4- ((4- (amoxy) phenyl) acetenyl) phenyl) -1- methyl-1 H- benzimidazole is prepared
4- ((4- (amoxy) phenyl) acetenyl) benzene is sequentially added in the 250mL there-necked flask added with magneton and condenser pipe
Formaldehyde 2.55g (8.7mmol), Sodium Metabisulfite 1.66g (8.7mmol) and dry n,N-Dimethylformamide 75mL, In
The lower 120 DEG C of back flow reaction 2h of nitrogen protection, then o-phenylenediamine 0.94g (8.7mmol) is dissolved in the DMF that 50mL is dried afterwards slowly
It is added drop-wise in reaction system, continues back flow reaction 6h, pour into 500mL deionized water and settle after reaction solution is cooled to room temperature,
It is recrystallized with dehydrated alcohol, 50mL N, N- diformazan is added in gained faint yellow solid and 0.61g (15.2mmol) sodium hydroxide
In base formamide, 2h is stirred at room temperature, 50mL is then added dropwise dissolved with the n,N-Dimethylformamide of iodomethane 0.95g (6.7mmol)
Solution, the reaction was continued 5h.After reaction, reaction solution is poured into deionized water and is settled, decompression is filtered and dried, dehydrated alcohol
Recrystallization, obtains 2- (4- ((4- (amoxy) phenyl) acetenyl) phenyl) -1- methyl-1 H- benzimidazole 0.52g, yield
30%, reaction equation is as follows:
The spectral data of product is as follows:
IR(KBr)v(cm-1): 2933,2862,2210,1596,1502,1460,1384,1244,1001,837,740,
534。
1H NMR(CDCl3,400MHz): 7.85-7.79 (m, 1H), 7.78-7.72 (m, 2H), 7.68-7.72 (m, 2H),
7.50-7.45 (m, 2H), 7.41-7.37 (m, 1H), 7.36-7.28 (m, 2H), 6.90-6.84 (d, J=7.81 2H), 3.97-
3.95 (t,3JH-H=8.25Hz, 2H), 3.89-3.86 (s, 3H), 1.87-1.74 (m, 2H), 1.53-1.30 (m, 4H), 0.94-
0.92 (t,3JH-H=7.23Hz, 3H).
MS m/z (%): theoretical value 394.52, measured value 395.21.
The above Structural Identification is statistics indicate that synthesized compound out is strictly 2- (4- ((4- (amoxy) phenyl) acetylene
Base) phenyl) -1- methyl-1 H- benzimidazole.
Embodiment 2
In the step 4 of the present embodiment, with the adjacent benzene two in 1 step 4 of equimolar 4- methylbenzene -1,2- diamines alternative embodiment
Amine, other steps are same as Example 1, obtain the following 2- of structural formula (4- ((4- (amoxy) phenyl) acetenyl) phenyl)-
1,6- dimethyl -1H- benzimidazole 0.61g, yield 35.5%.
The spectral data of product is as follows:
IR(KBr)v(cm-1): 2927,2862,2356,1598,1502,1458,1386,1242,1026,837,588,
528。
1H NMR(CDCl3, 400MHz): 7.75-7.73 (m, 2H), 7.70-7.68 (m, 1H), 7.64-7.59 (m, 2H),
7.48-7.46 (m, 2H), 7.17-7.12 (m, 2H), 6.88-6.86 (d, J=9.24,2H), 3.97-3.95 (t,3JH-H=
7.83Hz, 2H), 3.88-3.81 (s, 3H), 2.52-2.50 (s, 3H), 1.86-1.74 (m, 2H), 1.49-1.32 (m, 4H),
0.94-0.92 (t,3JH-H=7.70Hz, 3H).
MS m/z (%): theoretical value 408.54, measured value 408.23.
The above Structural Identification is statistics indicate that synthesized compound out is strictly 2- (4- ((4- (amoxy) phenyl) acetylene
Base) phenyl) -1,6- dimethyl -1H- benzimidazole.
Embodiment 3
In the step 4 of the present embodiment, with the adjacent benzene two in 1 step 4 of equimolar 4- nitrobenzene -1,2- diamines alternative embodiment
Amine, other steps are same as Example 1, obtain the following 2- of structural formula (4- ((4- (amoxy) phenyl) acetenyl) phenyl)-
1- methyl -6- nitro -1H- benzimidazole 0.43g, yield 25%.
The spectral data of product is as follows:
IR(KBr)v(cm-1): 2933,2862,2206,1596,1512,1342,1247,1174,1016,823,738,
526。
1H NMR(CDCl3, 400MHz): 8.40-8.34 (m, 1H), 8.26-8.23 (m, 1H), 7.85-7.83 (m, 1H),
7.81-7.73 (m, 2H), 7.68-7.65 (m, 2H), 7.48-7.43 (m, 2H), 6.88-6.86 (d, J=8.61,2H), 4.05-
3.97 (t,3JH-H=758Hz, 2H), 3.97-3.95 (s, 3H), 1.81-1.77 (m, 2H), 1.47-1.36 (m, 4H), 0.94-
0.92 (t,3JH-H=8.61Hz, 3H).
MS m/z (%): theoretical value 439.51, measured value 440.5.
The above Structural Identification is statistics indicate that synthesized compound out is strictly 2- (4- ((4- (amoxy) phenyl) acetylene
Base) phenyl) -1- methyl -6- nitro -1H- benzimidazole.
To Examples 1 to 3 preparation liquid-crystal compounds optical anisotropy and it is hot can be carried out test, it is two-fold to obtain its
Penetrate rate, phase transition temperature and enthalpy of phase change.It is specific as follows:
Phase transition temperature and enthalpy of phase change are tested by differential scanning calorimeter, obtain the liquid crystal phase transition of 1 compound of embodiment
Temperature is Cr 104.79N 193.30I (heating, Cr represent crystalline phase, and N represents nematic phase, and I represents isotropism), nematic phase
Warm area is 88.51 DEG C；The liquid-crystal phase-transition temperature of 2 compound of embodiment is that (heating, Cr represent crystallization to Cr 128.13N 233.56I
Phase, N represent nematic phase, and I represents isotropism), nematic phase warm area is 105.43 DEG C；The liquid crystalline phase alternating temperature of 3 compound of embodiment
Degree is Cr 156.20N 253.75I (heating, Cr represent crystalline phase, and N represents nematic phase, and I represents isotropism), nematic phase temperature
Area is 97.55 DEG C.It can be seen that liquid-crystal compounds of the present invention all has wider nematic phase temperature range, wherein widest liquid
105.43 DEG C of crystal phase section.And by the polarized light microscopy photo (200 of the DSC curve of Fig. 1 (5 DEG C/min of temperature rate) Fig. 2 and 3
×) as it can be seen that the compounds of this invention has nematic liquid crystal texture and all has liquid crystal phase in heating and cooling.
Birefringence is by the theoretical value Δ n that 1 compound of embodiment is calculated in Gaussian09 software theory
0.595, it can also be tested by abbe's refractometer, obtaining experiment value Δ n using extrapolation is 0.499；The reason of 2 compound of embodiment
It is 0.603 by value Δ n, experiment value Δ n is 0.505；The theoretical value Δ n of 3 compound of embodiment is 0.599, and experiment value Δ n is
0.510。
Liquid-crystal compounds (theoretical value Δ n >=0.595, experiment value Δ n >=0.499) of the present invention and document (Zhang Ran, Peng Zeng
Brightness, Liu Yonggang, Xuan Li, the synthesis of Zhang Zhiyong high Δ n low viscosity liquid crystal and performance study [J] liquid crystal and display, 2009,24
(06): 789-793) the diphenylacetylene liquid crystal compounds reported
(experiment value Δ n=0.286) compared to as can be seen that Δ n significantly becomes larger, further proof liquid-crystal compounds of the present invention has excellent
Optical anisotropy.
Claims (6)
1. a kind of N- methyl substituted benzimidazole liquid-crystal compounds containing acetylene bond, it is characterised in that the structural formula of the liquid-crystal compounds
It is as follows:
R represents C in formula5~C12Straight chained alkyl, X represents H, CH3、NO2In any one.
2. a kind of preparation method of the N- methyl substituted benzimidazole liquid-crystal compounds described in claim 1 containing acetylene bond, special
Sign is that it is made of following step:
(1) 4- (4- (1,3- dioxolanes -2- base) phenyl) -2- methyl butyl- 3- alkynes -2- alcohol is prepared
P-bromobenzaldehyde, p-methyl benzenesulfonic acid, ethylene glycol are added in dry chloroform, the back flow reaction 6 at 60~80 DEG C
~8 hours, then 2- methyl -3- butyne-2-alcohol, cuprous iodide, triphenylphosphine, triethylamine is added, in nitrogen in evaporating solvent under reduced pressure
60~80 DEG C after back flow reaction 8~10 hours under gas shielded, tetrakis triphenylphosphine palladium is added, the reaction was continued 6~8 hours, reaction
Product is isolated and purified after the completion, obtains 4- (4- (1,3-dioxolane -2- base) phenyl) -2- methyl butyl- 3- alkynes -2- alcohol, is reacted
Equation is as follows:
(2) 2- (4- ((4- (alkoxy) phenyl) acetenyl) phenyl) -1,3- dioxolanes is prepared
4- (4- (1,3-dioxolane -2- base) phenyl) -2- methyl butyl- 3- alkynes -2- alcohol, ethylene glycol ethyl ether, sodium hydroxide are added
Enter in toluene, 60~80 DEG C of constant temperature flow back 4~5 hours under nitrogen protection, and the iodo- 4- of 1- (alkoxy) shown in Formulas I is then added
Benzene, tetrakis triphenylphosphine palladium, the reaction was continued 6~8 hours, isolates and purifies product after the reaction was completed, obtains 2- (4- ((4- (alcoxyl
Base) phenyl) acetenyl) phenyl) -1,3-dioxolane, reaction equation is as follows:
In Formulas I, R represents C5~C12Straight chained alkyl；
(3) 4- ((4- (alkoxy) phenyl) acetenyl) benzaldehyde is prepared
2- (4- ((4- (alkoxy) phenyl) acetenyl) phenyl) -1,3-dioxolane, formic acid are added in tetrahydrofuran, 50
~70 DEG C of constant temperature flow back 6~8 hours, isolate and purify product, obtain 4- ((4- (alkoxy) phenyl) acetenyl) benzaldehyde, react
Equation is as follows:
(4) the N- methyl substituted benzimidazole liquid-crystal compounds containing acetylene bond is prepared
4- ((4- (alkoxy) phenyl) acetenyl) benzaldehyde, Sodium Metabisulfite are added in n,N-Dimethylformamide, In
120~130 DEG C of constant temperature flow back 1~2 hour under nitrogen protection, and o-phenylenediamine class compound shown in Formula II is then added, continues back
Stream 6~8 hours, sedimentation is recrystallized to give faint yellow solid in water；N, N- dimethyl is added in faint yellow solid, sodium hydroxide
It in formamide, is stirred at room temperature 2~3 hours, the n,N-Dimethylformamide solution dissolved with iodomethane is added dropwise, it is 5~6 small that the reaction was continued
When, then reaction solution is poured into deionized water and is settled, decompression is filtered and dried, and dehydrated alcohol recrystallization is obtained containing acetylene bond
N- methyl substituted benzimidazole liquid-crystal compounds, reaction equation are as follows:
In Formula II, X represents H, CH3、NO2In any one.
3. the preparation method of the N- methyl substituted benzimidazole liquid-crystal compounds according to claim 2 containing acetylene bond, special
Sign is: in step (1), the p-bromobenzaldehyde and p-methyl benzenesulfonic acid, ethylene glycol, 2- methyl -3- butyne-2-alcohol, iodate Asia
Copper, triphenylphosphine, tetrakis triphenylphosphine palladium molar ratio 1:0.25~0.3:20~25:0.4~1.0:0.02~0.05:0.04
~0.1:0.008~0.02.
4. the preparation method of the N- methyl substituted benzimidazole liquid-crystal compounds according to claim 2 containing acetylene bond, special
Sign is: in step (2), 4- (4- (1,3-dioxolane -2- base) the phenyl) -2- methyl butyl- 3- alkynes -2- alcohol and ethylene glycol
Ether, sodium hydroxide, 1- iodo- 4- (alkoxy) benzene, tetrakis triphenylphosphine palladium molar ratio be 1:10~12:5.5~6.5:1~
1.1:0.015~0.025.
5. the preparation method of the N- methyl substituted benzimidazole liquid-crystal compounds according to claim 2 containing acetylene bond, special
Sign is: in step (3), 2- (4- ((4- (alkoxy) phenyl) acetenyl) the phenyl) -1,3-dioxolane and formic acid
Molar ratio is 1:150~175.
6. the preparation method of the N- methyl substituted benzimidazole liquid-crystal compounds according to claim 2 containing acetylene bond, special
Sign is: in step (4), 4- ((4- (alkoxy) phenyl) acetenyl) benzaldehyde and Sodium Metabisulfite, o-dihydroxy ammon
Molar ratio 1:1.0~1.4:1.0~1.3:1.5~2.0:0.5~1.0 of class compound, sodium hydroxide, iodomethane.
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