CN110483408A - A kind of N- methyl substituted benzimidazole side fluorine liquid-crystal compounds of big birefringence and preparation method thereof - Google Patents
A kind of N- methyl substituted benzimidazole side fluorine liquid-crystal compounds of big birefringence and preparation method thereof Download PDFInfo
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- C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
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- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- 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
Abstract
The invention discloses N- methyl substituted benzimidazole side fluorine liquid-crystal compounds of a kind of big birefringence and preparation method thereof, and 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 to be prepared using 2- fluorine p-bromobenzaldehyde, 2- methyl -3- butyne-2-alcohol, 1- iodo- 4- (alkoxy) benzene, o-phenylenediamine class compound 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 applied 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 of big birefringence
Side fluorine liquid-crystal compounds and preparation method thereof.
Background technique
Liquid crystal material is widely used in the display fields such as tablet computer, mobile phone, laptop and high definition television, Yi Jiguang
The non-display fields such as modulator, laser beam deflection, adaptive optics.Liquid crystal electro-optical device low, phase tune with driving voltage
The advantages that amount processed is big, light-weight, low in energy consumption.
Liquid crystal material is the key core material of liquid crystal electro-optical device, and the optimization of the performance of liquid crystal electro-optical device is mainly logical
The structure and component of toning control liquid crystal material is realized.In recent years, it is important to be that liquid crystal electro-optical device is pursued always for quick response
Developing direction.In order to improve the response speed of liquid crystal electro-optical device, the liquid-crystal compounds of low viscosity, liquid crystal on the one hand can be used
There are direct relation in the viscosity of compound and the response time of liquid crystal device, i.e. the viscosity of liquid crystal material is lower, the sound of liquid crystal device
It is smaller between seasonable, response speed is faster；On the other hand it is thick that liquid crystal device box can be reduced, liquid crystal device box thickness is lower, response speed
Degree is faster, and (it is thick that Δ n) liquid crystal material can effectively reduce liquid crystal device box in practical applications using large optical anisotropic.
Thus big Δ n liquid crystal is the critical material that liquid crystal electro-optical device realizes quick response.
Liquid-crystal compounds structure is generally constructed by phenyl ring, cyclohexyl, heteroaromatic etc. as rigid backbone, can pass through introducing
Acetylene bond increases phenyl ring, introduces the increase liquid crystal molecule conjugate length such as cyano or isothiocyano, and then promoting the Δ of liquid-crystal compounds
n.Although there is many optical anisotropy liquid crystal materials at present, its Δ n is not big enough, type is insufficient, limits it in liquid
Application in brilliant photoelectric device.It is non-especially to can be used as the big Δ n heteroaromatic class LCD compound species that liquid crystal electro-optical device uses
It is often few.
Summary of the invention
The object of the present invention is to provide a kind of N- methyl substituted benzimidazole side fluorine liquid-crystal compounds of big birefringence, and
A kind of simple preparation method of processing step is provided for the compound.
For above-mentioned purpose, the N- methyl substituted benzimidazole side fluorine liquid-crystal compounds for the big birefringence that the present invention uses
Structural formula it 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 side of the present invention fluorine liquid-crystal compounds is made of following step:
1,4- (4- (1,3- dioxolanes -2- base) -2- fluorophenyl) -2- methyl butyl- 3- alkynes -2- alcohol is prepared
60 DEG C of reaction 6h in chloroform are added in 2- fluorine p-bromobenzaldehyde, p-methyl benzenesulfonic acid, ethylene glycol, decompression steams molten
Agent, then under nitrogen protection, be added 2- methyl -3- butyne-2-alcohol, cuprous iodide, triphenylphosphine, tetrakis triphenylphosphine palladium,
80 DEG C of reaction 8h, isolate and purify in triethylamine, obtain 4- (4- (1,3-dioxolane -2- base) -2- fluorophenyl) -2- methyl butyl-
3- alkynes -2- alcohol, reaction equation are as follows:
2,2- (the fluoro- 4- of 2- ((4- (alkoxy) phenyl) acetenyl) phenyl) -1,3- dioxolanes is prepared
By 1- iodo- 4- (alkoxy) benzene, ethylene glycol shown in 2- (4- acetenyl -2- fluorophenyl) -1,3- dioxolanes, Formulas I
Ether, tetrakis triphenylphosphine palladium are added in toluene, under nitrogen protection 60~80 DEG C of 8~10h of reaction, after reaction, separation
Purifying, obtains 2- (the fluoro- 4- of 2- ((4- (alkoxy) phenyl) acetenyl) phenyl) -1,3-dioxolane, reaction equation is as follows:
3, the fluoro- 4- of 2- ((4- (alkoxy) phenyl) acetenyl) benzaldehyde is prepared
Tetrahydro furan is added in 2- (the fluoro- 4- of 2- ((4- (alkoxy) phenyl) acetenyl) phenyl) -1,3- dioxolanes, formic acid
In muttering, flows back 6~8 hours in 50~70 DEG C of constant temperature, after reaction, isolate and purify, obtain the fluoro- 4- of 2- ((4- (alkoxy) benzene
Base) acetenyl) benzaldehyde, reaction equation is as follows:
4, N- methyl substituted benzimidazole side fluorine liquid-crystal compounds is prepared
N, N- dimethyl methyl is added in the fluoro- 4- of 2- ((4- (alkoxy) phenyl) acetenyl) benzaldehyde, Sodium Metabisulfite
In amide, 120~130 DEG C of constant temperature flow back 1~2 hour under nitrogen protection, and o-phenylenediamine class chemical combination shown in Formula II is then added
Object continues reflux 4~6 hours；After reaction, reaction solution is poured into deionized water and is settled, isolated and purified, obtain formula III
Shown benzimidazole compound containing acetylene bond；Then N, N- bis- is added in obtained benzimidazole compound containing acetylene bond and sodium hydroxide
It in methylformamide, is stirred at room temperature 1~2 hour, then the n,N-Dimethylformamide solution dissolved with potassium iodide is added dropwise, the reaction was continued
5~6 hours, reaction solution is then poured into deionized water sedimentation, is isolated and purified, obtained target compound N- methyl and replace benzo miaow
Azoles side fluorine liquid-crystal compounds.
In above-mentioned steps 1,2- fluorine p-bromobenzaldehyde and p-methyl benzenesulfonic acid, ethylene glycol, 2- methyl -3- crotonylene-are preferably stated
Alcohol, cuprous iodide, triphenylphosphine, tetrakis triphenylphosphine palladium molar ratio 1:0.25~0.4:20~25:0.4~1:0.02~
0.05:0.04~0.1:0.008~0.01.
In above-mentioned steps 2, preferably 4- (4- (1,3-dioxolane -2- base) -2- fluorophenyl) -2- methyl butyl- 3- alkynes -2- alcohol
Molar ratio with 1- iodo- 4- (alkoxy) benzene, sodium hydroxide, ethylene glycol ethyl ether, tetrakis triphenylphosphine palladium is 1:0.8~1.2:
5.5~6.5:9.5~10.5:0.015~0.025.
In above-mentioned steps 3, preferably 2- (the fluoro- 4- of 2- ((4- (alkoxy) phenyl) acetenyl) phenyl) -1,3-dioxolane
Molar ratio with formic acid is 1:170~175.
In above-mentioned steps 4, the fluoro- 4- of preferably 2- ((4- (alkoxy) phenyl) acetenyl) benzaldehyde and o-phenylenediamine class chemical combination
Molar ratio 1:1.0~1.5:1.0~1.5:3.0~3.8:1.0~1.5 of object, Sodium Metabisulfite, sodium hydroxide, iodomethane.
Beneficial effects of the present invention are as follows:
1, liquid-crystal compounds of the present invention is with 2- fluorine p-bromobenzaldehyde, 2- methyl -3- butyne-2-alcohol, the iodo- 4- (alcoxyl of 1-
Base) benzene, o-dihydroxy ammon class compound be raw material, pass through the reactions such as Sonogashira coupling, nucleophilic addition, cyclization prepare, prepare
Method and step is simple.
2, the compounds of this invention had not only had heterocycle liquid crystal mesophase type, but also had biggish birefringence, and had width
Nematic phase section, can be widely applied in liquid crystal electro-optical device, to improve its corresponding speed.
Detailed description of the invention
Fig. 1 is the DSC curve (5 DEG C/min of temperature rate) of liquid-crystal compounds prepared by embodiment 1.
Fig. 2 is the POM photo (100 ×) when liquid-crystal compounds prepared by embodiment 1 is warming up to 160 DEG C.
Fig. 3 is the POM photo (100 ×) when liquid-crystal compounds prepared by embodiment 1 is warming up to 167 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) -2- fluorophenyl) -2- methyl butyl- 3- alkynes -2- alcohol is prepared
It is added in the 250mL single port bottle equipped with condenser pipe and stirrer 2- fluorine p-bromobenzaldehyde 10g (50.0mmol), right
Toluenesulfonic acid 2.2g (12.6mmol), ethylene glycol 70g (1120mmol), and dry chloroform 100mL, In are added thereto
2- methyl -3- butyne-2-alcohol 2.1g is added in back flow reaction 6h at 60 DEG C, evaporating solvent under reduced pressure after having reacted thereto
(23.8mmol), cuprous iodide 0.2g (1mmol), triphenylphosphine 0.6g (2.2mmol), and 80mL triethylamine is added as reaction
Solvent is passed through nitrogen protection, at 80 DEG C after back flow reaction 1 hour, is added tetra-triphenylphosphine palladium 0.5g (0.44mmol), continues
Reaction 8 hours.After reaction, reaction system is diluted with water, is extracted with dichloromethane, separates organic phase, and use methylene chloride
Aqueous phase extracted is repeated, merges organic phase, obtained organic phase is washed three times with saturated aqueous ammonium chloride, anhydrous magnesium sulfate is dry
Dry, vacuum distillation screws out solvent, the sample preparation of 14g silica gel is added thereto, (eluant, eluent is petroleum ether and ethyl acetate to pillar layer separation
Volume ratio is 30:1 mixed liquor), obtain yellow oily liquid 4- (4- (1,3-dioxolane -2- base) -2- fluorophenyl) -2- methyl
Butyl- 3- alkynes -2- alcohol 6.4g, yield 65%, reaction equation is as follows:
2,2- (the fluoro- 4- of 2- ((4- (alkoxy) 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 stirrer and condenser pipe
2- fluorophenyl) -2- methyl butyl- 3- alkynes -2- alcohol 4.8g (19.3mmol), 1- iodo- 4- (amoxy) benzene 6g (21mmol), hydroxide
Sodium 4.6g (114.6mmol), ethylene glycol ethyl ether 17.2g (191.8mmol), and 80mL toluene is added as reaction dissolvent, 70
DEG C thermostatical oil bath in heat and logical nitrogen protection is rapidly added tetrakis triphenylphosphine palladium after reacting 1h under nitrogen protection
Stop reaction after 0.4g (0.4mmol), the reaction was continued 8h.After reaction, reaction system is diluted with water, is extracted with methylene chloride
It takes, separates organic phase, and repeat aqueous phase extracted with methylene chloride, merge organic phase, the organic phase saturated ammonium chloride that will be obtained
Solution washs three times, and anhydrous magnesium sulfate is dry, and vacuum distillation screws out solvent, and the sample preparation of 7g silica gel, pillar layer separation are added thereto
(eluant, eluent is petroleum ether and ethyl acetate volume ratio is 100:1 mixed liquor), obtains faint yellow solid 2- (the fluoro- 4- of 2- ((4- (penta
Oxygroup) phenyl) acetenyl) phenyl) -1,3-dioxolane 4.6g, yield 60%, reaction equation is as follows:
3, the fluoro- 4- of 2- ((4- (alkoxy) phenyl) acetenyl) benzaldehyde is prepared
By 2- (the fluoro- 4- of 2- ((4- (alkoxy) phenyl) acetenyl) phenyl) -1,3- dioxolanes 3.2g (8.6mmol) and
Formic acid 68.12g (1480mmol), tetrahydrofuran 80mL are added in the 250mL single port bottle equipped with stirrer, flow back at 60 DEG C anti-
6h is answered, after reaction, extracts reaction solution with methylene chloride and water, concentrated by rotary evaporation obtains white solid, dehydrated alcohol is added to tie again
Crystalline substance obtains the fluoro- 4- of white solid 2- ((4- (alkoxy) phenyl) acetenyl) benzaldehyde 2.1g, yield 80%, reaction equation
It is as follows:
4, N- methyl substituted benzimidazole side fluorine liquid-crystal compounds is prepared
By the fluoro- 4- of 2- ((4- (alkoxy) phenyl) acetenyl) benzaldehyde 2.1g (6.8mmol), Sodium Metabisulfite 1.5g
(8.2mmol), 40mL n,N-Dimethylformamide are added in the 100mL there-necked flask equipped with condenser pipe and stirrer, protect in nitrogen
Lower 130 DEG C of return stirring 2h are protected, 1.5g (8.2mmol) 4-nitro-o-phenylenediamine is dissolved in 20mL n,N-Dimethylformamide
After be slowly added dropwise into reaction solution, the reaction was continued 5h after being added dropwise to complete.After reaction, reaction solution is poured into deionized water and is sunk
Drop filters drying, the sample preparation of 4g silica gel is added thereto, (eluant, eluent is that petroleum ether is with ethyl acetate volume ratio to pillar layer separation
4:1 mixed liquor), obtain white crystal, i.e. -1 compound of formula III.By -1 compound of gained formula III and sodium hydroxide 0.98g
(24.5mmol), n,N-Dimethylformamide 20mL are added in the 100mL single port bottle equipped with stirrer, and 1h is stirred at room temperature, will
1.5g (10.2mmol) iodomethane is slowly added dropwise after being dissolved in 20mL n,N-Dimethylformamide into reaction solution, is added dropwise to complete
After continue to be stirred to react 5h.After reaction, reaction solution is poured into deionized water and is settled, filter drying, dehydrated alcohol is tied again
Crystalline substance obtains white crystal N- methyl substituted benzimidazole side fluorine liquid-crystal compounds 0.47g, yield 15%, chemical name 2-
(the fluoro- 4- of 2- ((4- (amoxy) phenyl) acetenyl) phenyl) -1- methyl -6- nitro -1H- benzimidazole, reaction equation is such as
Under:
The spectral data of product is as follows:
IR(KBr)v(cm-1): 2947,2866,2205,1899,1605,1554,1518,1330,1244,1016,824,
729.
1H-NMR(400MHz,CDCl3, TMS) and δ (ppm)=8.31-8.20 (m, 1H), 7.95-7.78 (m 1H), 7.74-
7.61 (d, J=8.8Hz, 1H), 7.50-7.47 (m, 2H), 7.47-7.45 (m, 2H), 7.42-7.34 (m, 1H), 6.92-6.83
(d, J=8.4Hz, 2H), 3.99-3.94 (t, J=6Hz, 2H), 3.86-3.80 (s, 3H), 1.83-1.74 (m, 2H), 1.46-
1.34 (m, 4H), 0.95-0.90 (t, J=6.8Hz, 3H)
MS (MALDI-TOF) m/z: theoretical value 457.20, measured value 458.32.
Embodiment 2
It is adjacent with the 4- nitro in 1 step 5 of equimolar 4- methyl-o-phenylenediamine alternative embodiment in the step 5 of the present embodiment
Phenylenediamine, other steps are same as Example 1, obtain the following N- methyl substituted benzimidazole side fluorine liquid-crystal compounds of structural formula
0.44g, yield 15%, chemical name are 2- (the fluoro- 4- of 2- ((4- (amoxy) phenyl) acetenyl) phenyl) -1,6- diformazan
Base -1H- benzimidazole.
The spectral data of generation is as follows:
IR(KBr)v(cm-1): 2939,2870,2355,2203,1608,1510,1337,1250,1208,831,743,
528.
1H-NMR(400MHz,CDCl3, TMS) and δ (ppm)=7.73-7.70 (m, 1H), 7.69-7.66 (m 1H), 7.49-
7.45 (d, J=9.6Hz, 2H), 7.45-7.41 (m, 1H), 7.36-7.27 (m, 2H), 7.20-7.12 (m, 1H), 6.92-6.86
(d, J=9.6Hz, 2H), 3.98-3.92 (t, 2H), 3.76-3.69 (m, 3H), 2.55-2.48 (d, 3H), 1.82-1.77 (m,
2H), 1.45-1.32 (m, 4H), 0.94-0.84 (t, J=5.6Hz, 3H)
MS (MALDI-TOF) m/z: theoretical value 426.23, measured value 425.64.
Embodiment 3
In the step 5 of the present embodiment, with the 4-nitro-o-phenylenediamine in 1 step 5 of equimolar o-phenylenediamine alternative embodiment,
Other steps are same as Example 1, obtain the following N- methyl substituted benzimidazole side fluorine liquid-crystal compounds 0.42g of structural formula,
Yield 15%, chemical name are 2- (the fluoro- 4- of 2- ((4- (amoxy) phenyl) acetenyl) phenyl) -1- methyl-1 H- benzo miaow
Azoles.
The spectral data of product is as follows:
IR(KBr)v(cm-1): 2937,2866,2206,1876,1608,1460,1248,1116,1025,828,750,
629.
1H-NMR(400MHz,CDCl3, TMS) and δ (ppm)=8.43-8.36 (m, 1H), 8.31-8.20 (m1H), 7.91-
7.79 (d, J=7.2Hz 1H), 7.73-7.66 (m, 1H), 7.51-7.47 (m, 2H), 7.47-7.44 (m, 2H), 7.41-7.34
(m, 1H), 6.90-6.85 (d, J=10Hz, 2H), 3.99-3.94 (t, J=6.8Hz, 2H), 3.86-3.79 (s, 3H), 1.83-
1.73 (m, 2H), 1.46-1.32 (m, 4H), 0.95-0.89 (t, J=6.4Hz, 3H)
MS (MALDI-TOF) m/z: theoretical value 412.21, measured value 413.13.
To above-described embodiment 1~3 prepare liquid-crystal compounds optical anisotropy and it is hot can be carried out test, obtain it
Birefringence, phase transition temperature and enthalpy of phase change.Birefringence is to obtain theoretical value by Gaussian09 software, can also pass through Ah
Shellfish refractometer extrapolation obtains experiment value；Phase transition temperature and enthalpy of phase change are obtained by differential scanning calorimeter measurement.As a result see
Tables 1 and 2.
1 birefringence of table
2 phase transition temperature of table and enthalpy of phase change
Note: Cr represents crystalline phase in table；N represents nematic phase；I represents isotropism.
Seen from table 1, liquid-crystal compounds (theoretical value Δ n >=0.5529 of the present invention；Experiment value Δ n >=0.5175) and document
Liquid-crystal compounds in (Liquid Crystals, 2017,44:14-15,2184-2191)(experiment value Δ n=0.305) is compared, and Δ n significantly becomes larger, and is further demonstrate,proved
Bright liquid-crystal compounds of the present invention has excellent optical anisotropy.Table 2 can be seen that liquid-crystal compounds of the present invention all has wider
Nematic phase temperature range, wherein 104.22 DEG C of widest mesomorphic range.And by the DSC curve of Fig. 1 (5 DEG C of temperature rate/
Min) and the POM photo (100 ×) of Fig. 2 and 3 as it can be seen that the compounds of this invention all had in heating and cooling nematic liquid crystal texture and
Liquid crystal phase.
Claims (6)
1. a kind of N- methyl substituted benzimidazole side fluorine liquid-crystal compounds of big birefringence, it is characterised in that the liquid-crystal compounds
Structural formula 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 N- methyl substituted benzimidazole side described in claim 1 fluorine liquid-crystal compounds, feature exist
It is made of in it following step:
(1) 4- (4- (1,3- dioxolanes -2- base) -2- fluorophenyl) -2- methyl butyl- 3- alkynes -2- alcohol is prepared
2- fluorine 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, four (triphens is then added
Base phosphine) palladium, triethylamine, flow back 7~10 hours for 70~80 DEG C under nitrogen protection, isolate and purify product, obtain 4- (4- (1,3-
Dioxolanes -2- base) -2- fluorophenyl) -2- methyl butyl- 3- alkynes -2- alcohol, reaction equation is as follows:
(2) 2- (the fluoro- 4- of 2- ((4- (alkoxy) phenyl) acetenyl) phenyl) -1,3- dioxolanes is prepared
By the iodo- 4- (alkane of 1- shown in 4- (4- (1,3- dioxolanes -2- base) -2- fluorophenyl) -2- methyl butyl- 3- alkynes -2- alcohol, Formulas I
Oxygroup) benzene, ethylene glycol ethyl ether, tetrakis triphenylphosphine palladium be added in toluene, 60~80 DEG C of 8~10h of reaction under nitrogen protection, instead
It after answering, isolates and purifies, obtains 2- (the fluoro- 4- of 2- ((4- (alkoxy) phenyl) acetenyl) phenyl) -1,3-dioxolane, instead
Answer equation as follows:
(3) the fluoro- 4- of 2- ((4- (alkoxy) phenyl) acetenyl) benzaldehyde is prepared
Tetrahydrofuran is added in 2- (the fluoro- 4- of 2- ((4- (alkoxy) phenyl) acetenyl) phenyl) -1,3- dioxolanes, formic acid
In, it flows back 6~8 hours in 50~70 DEG C of constant temperature, after reaction, isolates and purifies, obtain the fluoro- 4- of 2- ((4- (alkoxy) benzene
Base) acetenyl) benzaldehyde, reaction equation is as follows:
(4) N- methyl substituted benzimidazole side fluorine liquid-crystal compounds is prepared
N,N-dimethylformamide is added in the fluoro- 4- of 2- ((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 4~6 hours；After reaction, reaction solution is poured into deionized water and is settled, isolated and purified, obtain formula III chemical combination
Object；Then obtained formula III compound and sodium hydroxide are added in n,N-Dimethylformamide, are stirred at room temperature 1~2 hour,
The n,N-Dimethylformamide solution dissolved with potassium iodide is added dropwise again, the reaction was continued 5~6 hours, then by reaction solution pour into from
Sub- water sedimentation, isolates and purifies, obtains N- methyl substituted benzimidazole side fluorine liquid-crystal compounds；
In formula, X represents H, CH3、NO2In any one.
3. the preparation method of N- methyl substituted benzimidazole side according to claim 2 fluorine liquid-crystal compounds, feature exist
In: in step (1), the 2- fluorine p-bromobenzaldehyde and p-methyl benzenesulfonic acid, ethylene glycol, 2- methyl -3- butyne-2-alcohol, iodate Asia
Copper, triphenylphosphine, tetrakis triphenylphosphine palladium molar ratio 1:0.25~0.4:20~25:0.4~1:0.02~0.05:0.04~
0.1:0.008~0.01.
4. the preparation method of N- methyl substituted benzimidazole side according to claim 2 fluorine liquid-crystal compounds, feature exist
In: in step (2), 4- (4- (1,3-dioxolane -2- base) -2- the fluorophenyl) -2- methyl butyl- 3- alkynes -2- alcohol and 1- are iodo-
4- (alkoxy) benzene, sodium hydroxide, ethylene glycol ethyl ether, tetrakis triphenylphosphine palladium molar ratio be 1:0.8~1.2:5.5~6.5:
9.5~10.5:0.015~0.025.
5. the preparation method of N- methyl substituted benzimidazole side according to claim 2 fluorine liquid-crystal compounds, feature exist
In: in step (3), 2- (the fluoro- 4- of 2- ((4- (alkoxy) phenyl) acetenyl) the phenyl) -1,3-dioxolane and formic acid
Molar ratio is 1:170~175.
6. the preparation method of N- methyl substituted benzimidazole side according to claim 2 fluorine liquid-crystal compounds, feature exist
In: in step (4), the fluoro- 4- of 2- ((4- (alkoxy) phenyl) acetenyl) benzaldehyde and o-phenylenediamine class compound are laid particular stress on
Molar ratio 1:1.0~1.5:1.0~1.5:3.0~3.8:1.0~1.5 of sodium sulfite, sodium hydroxide, iodomethane.
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Citations (7)
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