CN102603472B - Lateral-difluoro-containing liquid crystal compounds, and preparation method and application thereof - Google Patents
Lateral-difluoro-containing liquid crystal compounds, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses lateral-difluoro-containing liquid crystal compounds, and a preparation method and application thereof. The compounds are disclosed as Formula I. The liquid crystal compounds disclosed by the invention are correct by nuclear magnetic resonance detection, have linear, Z-shaped, banana-shaped or any other molecular structure, can be used as a liquid crystal display material and a liquid crystal monomer, and have important application value.
Description
Technical field
The invention belongs to technical field of organic synthesis, relate to and contain side difluoro class liquid crystalline cpd and preparation method thereof and application.
Background technology
Along with the constantly development of lcd technology, liquid-crystal display has obtained application more and more widely in people's production and life.Because people show more and more higher requirement on quality and quantity to writings and image, the physical properties of working fluid (mixture liquid crystal) and the requirement of photoelectric technology performance to liquid-crystal display are also more and more higher.Low viscosity, to can be used for multichannel driving, fast response time, driving voltage novel liquid crystal low, that have higher dielectric anisotropy, suitable specific refractory power anisotropy, good chemistry and optical stability and good voltage retention be the improved direction of following exploitation.
Liquid-crystal display is to utilize the dielectric anisotropy of liquid crystal material and optically anisotropic characteristic to realize Presentation Function.Traditional TN-TFT and IPS pattern all adopt the liquid crystal material of positive dielectric anisotropy, in order to meet the requirement of Δ ε > 0, are generally the groups of introducing strong polarity on the long axis direction of liquid crystal molecule, such as cyano group, fluorine atom, trifluoromethyl, trifluoromethoxy etc.; And VA-TFT pattern requires the liquid crystal material adopting to have negative dielectric anisotropic, i.e. Δ ε < 0, this just need to, at the short-axis direction of molecule, introduce the group of strong polarity in the side direction of molecule.Although the liquid crystalline cpd negative dielectric anisotropic that contains side direction cyano group is larger, its resistivity is low, and the liquid crystalline cpd resistivity that side direction fluorine atom replaces is high, and has larger dielectric anisotropy, can meet the requirement of VA-TFT pattern.
In recent years, fluorine-containing liquid crystal material has obtained development rapidly, the exploitation of nearly all nematic liquid crystal material is all using fluorochemicals as main composition component, be applied in TN-LCD, STN-LCD, PDLC, LCOS rear-projection, especially indispensable component especially in TFT-LCD display format.
Therefore in order to obtain the liquid crystal material that performance is better, exploitation is an inexorable trend of liquid crystal development containing the fluorine-containing novel liquid crystal compound of aromatic ring side direction.In liquid crystal molecule, introduce fluorine atom, can make liquid crystal there is the significant advantage such as low viscosity, high electric charge conservation rate, high stability.Especially in the time that the cyclohexyl in molecule is connected with difluorobenzene, the viscosity of such liquid crystal molecule is lower, electric charge conservation degree is higher, performance is more superior.
Therefore, the invention provides and contain side difluoro class liquid crystalline cpd, to improve traditional liquid crystal molecule performance.Two rodlike molecules that contain side difluoro are connected by carbochain or the carbochain that contains Sauerstoffatom, shape of molecule is changed, formation has V-arrangement, and U-shaped is Z-shaped, banana-shaped, the difform compound such as linear.
Summary of the invention
The object of this invention is to provide one and contain side difluoro class liquid crystalline cpd and preparation method thereof and application.
The side difluoro class liquid crystalline cpd that contains provided by the invention, its general structure is suc as formula shown in I,
Formula I
In described formula I, R
afor R
1-(Z
1-A
1-Z
2)
x-; R
bfor-(Z
3-A
2-Z
4)
y-R
2;
Wherein, R
1and R
2the alkyl that the total number of carbon atoms that is all selected from hydrogen, fluorine, chlorine, cyano group, alkyl that the total number of carbon atoms is 1-25, alkoxyl group that the total number of carbon atoms is 1-25, normal olefine base that the total number of carbon atoms is 2-25, fluoro is 1-25, any one in the normal olefine base that the alkoxyl group that the total number of carbon atoms of fluoro is 1-25 and the total number of carbon atoms of fluoro are 2-25;
Z
1, Z
2, Z
3and Z
4all be selected from singly-bound ,-O-,-OCO-,-COO-,-CO-,-CH
2o-,-OCH
2-,-CF
2o-,-OCF
2-, at least one in the total number of carbon atoms of thiazolinyl that the total number of carbon atoms of straight chained alkyl that the total number of carbon atoms of straight chained alkyl that the total number of carbon atoms is 1-25, straight-chain alkenyl that the total number of carbon atoms is 2-25, straight-chain alkynyl that the total number of carbon atoms is 2-25, fluoro is 1-25, fluoro is 2-25 and fluoro straight-chain alkynyl that is 1-25;
A
1and A
2all be selected from singly-bound, Isosorbide-5-Nitrae-cyclohexyl, Isosorbide-5-Nitrae-phenyl, 2,5-pyrimidyl, 2,5-pyridyl, 2,5-tetrahydrochysene-2H-pyranyl, 1,3-diox-2,5-base, 1,2,4-oxadiazole-3,1 of 5-base, fluoro, at least one in the Isosorbide-5-Nitrae-phenyl of 4-cyclohexyl, fluoro and the pyranoid ring of fluoro two bases;
N is the integer of 1-4;
X and y are the integer of 0-3;
Described x or y are 2 or at 3 o'clock, structural unit Z
1-A
1-Z
2in, Z
1identical or different, A
1identical or different, Z
2identical or different; Structural unit Z
3-A
2-Z
4in, Z
3identical or different, A
2identical or different, Z
4identical or different.
Above-claimed cpd is preferred:
In described formula I, R
1and R
2all be selected from hydrogen, fluorine, chlorine, cyano group and C
1-C
25any one in alkyl;
Z
1and Z
2all be selected from-CF
2o-and C
1-C
25at least one in straight chained alkyl;
A
1be selected from Isosorbide-5-Nitrae-cyclohexyl, Isosorbide-5-Nitrae-phenyl, 2,5-pyrimidyl, 2,5-pyridyl, 2,5-tetrahydrochysene-2H-pyranyl, 1,3-diox-2,5-base and 1,2,4-oxadiazole-3, at least one in 5-base.
Above-claimed cpd is more preferably: compound shown in described formula I is following compound (wherein, each substituting group defines with upper identical):
The method of the described compound that in preparation formula I provided by the invention, n is 1, comprises the steps:
1) by 4-R
a-1,2-difluorobenzene and n-Butyl Lithium carry out lithiation in solvent, within 1-2 hour, react complete maintenance temperature and add DMF to carry out substitution reaction again, be warming up to room temperature continuation reaction and obtain 5-R after 1-2 hour after 1-2 hour
a-2,3-difluorobenzaldehyde;
2) by described step 1) gained 5-R
a-2,3-difluorobenzaldehyde and sodium borohydride carry out after reduction reaction in solvent, and gained reduction reaction product and sulfur oxychloride are carried out to chlorination reaction or carry out bromination reaction with tribromo oxygen phosphorus, react the complete 5-R of obtaining
a-2,3-difluorophenyl methyl chloride or 5-R
a-2,3-difluorophenyl monobromethane;
3) by 4-R
b-1,2-difluorobenzene and n-Butyl Lithium carry out lithiation in solvent, react complete maintenance temperature and add step 2 again) gained 5-R
a-2,3-difluorophenyl methyl chloride or 5-R
a-2,3-difluorophenyl monobromethane carries out substitution reaction, is warming up to room temperature continuation reaction and obtains the described compound that in described formula I, n is 1 after 1-2 hour after 1-2 hour;
In aforesaid method, described step 1) in, described 4-R
athe mole dosage ratio that feeds intake of-1,2-difluorobenzene, n-Butyl Lithium, DMF is 1: 1.2-1.5: 1.2-1.5, preferably 1: 1.2: 1.5; Described 4-R
a-1,2-difluorobenzene and n-Butyl Lithium carry out in lithiation step in solvent, and temperature is-90 DEG C～-80 DEG C, and preferably-80 DEG C, the time is 1-2 hour, preferably 1 hour;
Described step 2) in, described 5-R
a-2,3-difluorobenzaldehyde is 1 with the mole dosage ratio that feeds intake of sodium borohydride: 1-3, preferably 1: 2; In described reduction reaction step, temperature is 20-60 DEG C, and the time is 1-2 hour, preferably 1 hour; Described reduzate is 1 with the mole dosage ratio that feeds intake of described sulfur oxychloride or tribromo oxygen phosphorus: 1-2, preferably 1: 1.25; In described chlorination reaction or bromination reaction step, temperature is 25-65 DEG C, and preferably 60 DEG C, the time is 1-5 hour, preferably 3 hours;
Described step 3) in, described 4-R
b-1,2-difluorobenzene, n-Butyl Lithium, step 2) gained 5-R
a-2,3-difluorophenyl methyl chloride or 5-R
athe mole dosage ratio that feeds intake of-2,3-difluorophenyl monobromethane is 1: 1.2-1.5: 1-1.5, preferably 1: 1.2: 1.2; Described 4-R
b-1,2-difluorobenzene and n-Butyl Lithium carry out in lithiation step in solvent, and temperature is-90 DEG C～-80 DEG C, and preferably-80 DEG C, the time is 0.5-2 hour, preferably 1 hour;
Described step 1) to step 3) in, described solvent is all selected from least one in tetrahydrofuran (THF), hexane, methyl tertiary butyl ether, anhydrous diethyl ether and 2-methyltetrahydrofuran.
The method of the described compound that in the described formula I of preparation provided by the invention, n is 2, comprises the steps:
1) by 4-R
a-1,2-difluorobenzene and n-Butyl Lithium mix and carry out lithiation in solvent, react complete maintenance temperature and add iodine to carry out iodination reaction again, be warming up to room temperature continuation reaction and obtain 5-R after 1-2 hour after 1-2 hour
a-2,3-difluoro iodobenzene;
2) be 8-14 and Pd (PPh keeping the pH value in reaction system
3)
4under the condition existing as catalyzer, by step 1) gained 5-R
a-2,3-difluoro iodobenzene mixes and reacts with 2-methyl 3-butyne-2-alcohol, reacts the complete 4-of obtaining (the fluoro-5-R of 2,3-bis-
aphenyl)-2-methyl-3-butyne-2-alcohol;
3) by step 2) gained 4-(the fluoro-5-R of 2,3-bis-
aphenyl)-2-methyl-3-butyne-2-alcohol mixes and reacts with highly basic, reacts the complete 5-R of obtaining
a-2,3-difluorophenyl acetylene;
4) by 4-R
b-1,2-difluorobenzene and n-Butyl Lithium carry out lithiation in solvent, within 1-2 hour, react complete maintenance temperature and add iodine to carry out iodination reaction again, be warming up to room temperature continuation reaction and obtain 5-R after 1-2 hour after 1-2 hour
b-2,3-difluoro iodobenzene;
5) be 8-14 and Pd (PPh keeping the pH value in reaction system
3)
4under the condition existing as catalyzer, by step 3) gained 5-R
a-2,3-difluorophenyl acetylene and step 4) gained 5-R
b-2,3-difluoro iodobenzene mixes and reacts, and reacts the complete dibenzenyl compound that obtains;
6) under the condition existing at Pd/C catalyzer, by step 5) gained dibenzenyl compound and hydrogen carries out hydrogenation reduction, obtains the compound that in described formula I, n is 2.
The step 1 of aforesaid method) in, described 4-R
athe mole dosage ratio that feeds intake of-1,2-difluorobenzene, n-Butyl Lithium and iodine is 1: 1.2-1.5: 1.2-1.5, preferably 1: 1.5: 1.5; Described 4-R
a-1,2-difluorobenzene and n-Butyl Lithium carry out in lithiation step in solvent, and temperature is-90 DEG C～-80 DEG C, and preferably-80 DEG C, the time is 1-2 hour, preferably 1 hour; Described solvent is selected from least one in tetrahydrofuran (THF), hexane, methyl tertiary butyl ether, anhydrous diethyl ether and 2-methyltetrahydrofuran;
Described step 2) in, described step 1) gained 5-R
athe molar ratio of-2,3-difluoro iodobenzene and 2-methyl 3-butyne-2-alcohol is 1: 1-3, preferably 1: 2; Described Pd (PPh
3)
4the mole dosage that feeds intake be described step 1) gained 5-R
athe 0.1-0.5% of-2,3-difluoro iodobenzene, preferably 0.5%; In described reactions steps, temperature is 40-70 DEG C, and preferably 60 DEG C, the time is 1-4 hour, preferably 2 hours;
Described step 3) in, described highly basic is selected from least one in sodium hydroxide and potassium hydroxide; Described step 2) gained 4-(the fluoro-5-R of 2,3-bis-
aphenyl) molar ratio of-2-methyl-3-butyne-2-alcohol and highly basic is 1: 1.2-1.5, preferably 1: 1.2; In described reactions steps, temperature is 80-110 DEG C, and preferably 100 DEG C, the time is 2-6 hour, preferably 4 hours;
Described step 4) in, described 4-R
bthe mole dosage ratio that feeds intake of-1,2-difluorobenzene, n-Butyl Lithium and iodine is 1: 1.2-1.5: 1.2-1.5, preferably 1: 1.5: 1.5; Described 4-R
b-1,2-difluorobenzene and n-Butyl Lithium carry out in lithiation step in solvent, and temperature is-90 DEG C～-80 DEG C, and preferably-80 DEG C, the time is 1-2 hour, preferably 1 hour; Described solvent is selected from least one in tetrahydrofuran (THF), hexane, methyl tertiary butyl ether, anhydrous diethyl ether and 2-methyltetrahydrofuran;
Described step 5) in, described step 3) gained 5-R
a-2,3-difluorophenyl acetylene and described step 4) gained 5-R
bthe molar ratio of-2,3-difluoro iodobenzene is 1: 1-1.2, preferably 1: 1; Described Pd (PPh
3)
4the mole dosage that feeds intake be described step 3) gained 5-R
athe 0.1-0.5% of-2,3-difluorophenyl acetylene, preferably 0.5%; In described reactions steps, temperature is 60-110 DEG C, and preferably 85 DEG C, the time is 2-6 hour, preferably 4 hours;
Described step 6) in, the consumption of described Pd/C catalyzer is described step 5) 1%-5% of gained dibenzenyl compound quality consumption, preferably 2%; In described reactions steps, temperature is 20-40 DEG C, and preferably 30 DEG C, the time is 12-24 hour, preferably 12 hours; Pressure is 0.2-1MPa, preferably 1MPa.
The method of arbitrary described compound that in the described formula I of preparation provided by the invention, n is 3, comprises the steps:
1) by 4-R
a-1,2-difluorobenzene and n-Butyl Lithium mix and carry out lithiation in solvent, react complete maintenance temperature and add 1,3-dibromopropane to carry out substitution reaction again, be warming up to room temperature continuation reaction and obtain 5-R after 1-2 hour after 1-2 hour
a-2,3-difluorophenyl N-PROPYLE BROMIDE;
2) by 4-R
b-1,2-difluorobenzene and n-Butyl Lithium mix and carry out lithiation in solvent, react complete maintenance temperature and add described step 1 again) 5-R that obtains
a-2,3-difluorophenyl N-PROPYLE BROMIDE reacts, and is warming up to room temperature and continues reaction 1-2 hour after 0.5-1 hour, reacts the complete described compound that in described formula I, n is 3 that obtains.
The step 1 of described method) in, described 4-R
athe mole dosage ratio that feeds intake of-1,2-difluorobenzene, n-Butyl Lithium and 1,3-dibromopropane is 1: 1.2-1.5: 1.2-1.5, preferably 1: 1.2: 1.2; Described 4-R
a-1,2-difluorobenzene and n-Butyl Lithium carry out in lithiation step in solvent, and temperature is-90 DEG C～-80 DEG C, and preferably-80 DEG C, the time is 1-2 hour, preferably 1 hour; Described solvent is selected from least one in tetrahydrofuran (THF), hexane, methyl tertiary butyl ether, anhydrous diethyl ether and 2-methyltetrahydrofuran;
Described step 2) in, described 4-R
b-1,2-difluorobenzene, n-Butyl Lithium and described step 1) gained 5-R
athe molar ratio of-2,3-difluorophenyl N-PROPYLE BROMIDE is 1: 1.2-1.5: 1.2-1.5, preferably 1: 1.5: 1.2; Described 4-R
b-1,2-difluorobenzene and n-Butyl Lithium carry out in lithiation step in solvent, and temperature is-90 DEG C～-80 DEG C, and preferably-80 DEG C, the time is 1-2 hour, preferably 1 hour; Described solvent is selected from least one in tetrahydrofuran (THF), hexane, methyl tertiary butyl ether, anhydrous diethyl ether and 2-methyltetrahydrofuran;
The method of the described compound that in the described formula I of preparation provided by the invention, n is 4, comprises the steps:
1) by 4-R
a-1,2-difluorobenzene and n-Butyl Lithium mix and carry out lithiation in solvent, react complete maintenance temperature and add Isosorbide-5-Nitrae-dibromobutane to carry out substitution reaction again, be warming up to room temperature continuation reaction and obtain 5-R after 1-2 hour after 1-2 hour
a-2,3-difluorophenyl n-butyl bromide;
2) by 4-R
b-1,2-difluorobenzene and n-Butyl Lithium mix and carry out lithiation in solvent, react complete maintenance temperature and add described step 1 again) 5-R that obtains
a-2,3-difluorophenyl n-butyl bromide is reacted, and is warming up to room temperature and continues reaction 1-2 hour after 0.5-1 hour, reacts the complete arbitrary described compound that in described formula I, n is 4 that obtains.
The step 1 of described method) in, described 4-R
athe mole dosage ratio that feeds intake of-1,2-difluorobenzene, n-Butyl Lithium and Isosorbide-5-Nitrae-dibromobutane is 1: 1.2-1.5: 1.2-1.5, preferably 1: 1.2: 1.2; Described 4-R
a-1,2-difluorobenzene and n-Butyl Lithium carry out in lithiation step in solvent, and temperature is-90 DEG C～-80 DEG C, and preferably-80 DEG C, the time is 1-2 hour, preferably 1 hour; Described solvent is selected from least one in tetrahydrofuran (THF), hexane, methyl tertiary butyl ether, anhydrous diethyl ether and 2-methyltetrahydrofuran;
Described step 2) in, described 4-R
b-1,2-difluorobenzene, n-Butyl Lithium and described step 1) gained 5-R
athe molar ratio of-2,3-difluorophenyl n-butyl bromide is 1: 1.2-1.5: 1.2-1.5, preferably 1: 1.5: 1.2; Described 4-R
b-1,2-difluorobenzene and n-Butyl Lithium carry out in lithiation step in solvent, and temperature is-90 DEG C～-80 DEG C, and preferably-80 DEG C, the time is 1-2 hour, preferably 1 hour; Described solvent is selected from least one in tetrahydrofuran (THF), hexane, methyl tertiary butyl ether, anhydrous diethyl ether and 2-methyltetrahydrofuran;
In addition, in above-mentioned four preparation methods, described 4-R
a-1,2-difluorobenzene and 4-R
bin-1,2-difluorobenzene, described R
aand R
ball identical with aforementioned definitions.
Shown in preparation formula 1 general structure provided by the invention, the synthetic route of liquid crystalline cpd is as follows:
Synthetic route 1 (n=1)
Synthetic route 2 (n=2)
Compound shown in the formula I that the invention described above provides, in the application of preparing in liquid crystal display material, Organic Light Emitting Diode material or semiconductor material, also belongs to protection scope of the present invention.
Liquid crystalline cpd provided by the invention, magnetic resonance detection is correct, has linear, Z-shaped, and banana-shaped equimolecular structure can be used as liquid crystal display material and liquid crystal monomer and uses, and has important using value.
Embodiment
Below in conjunction with specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Described method is ordinary method if no special instructions.Described material all can obtain from open commercial sources if no special instructions.
Following embodiment prepares liquid crystalline cpd shown in gained formula II and all carries out as follows the test of optics anisotropic and dielectric anisotropy and the mensuration of fitting parameter:
Choose the commodity liquid crystalline cpd that is numbered SLC090105 of Shijiazhuang Cheng Zhiyonghua display material company (China) production as parent, liquid crystalline cpd shown in formula II is dissolved in to parent with 5% ratio, test conventional parameter.According to its conventional parameter of institute's adding proportion linear fit in parent (optical anisotropy Δ n (20 DEG C, 589nm), dielectric anisotropy Δ ε (20 DEG C, 1000Hz)).
The preparation of embodiment 1 4-(3-(the fluoro-5-of 2,3-bis-(two (the cyclohexyl)-4-yls of 4 '-amyl group) benzyl)-4,5-difluorophenyl)-4 '-ethyl two (hexanaphthene)
Step 1:5-(two (the cyclohexyl)-4-yls of 4 '-ethyl)-2, the preparation of 3-difluorobenzaldehyde
In 250mL reaction flask, drop into the 4-(4-(4 '-ethyl cyclohexyl) cyclohexyl)-1 of 30mmol, 2-difluorobenzene, then drop into the THF of 100mL and the methyl tertiary butyl ether of 30mL, at N
2under protection, system temperature is down to below-80 DEG C by liquid nitrogen/ethanol bath.Drip the hexane solution of the n-BuLi of 36mmol, after dripping off, remain on-80 DEG C of following reactions 1 hour.The DMF that keeps temperature to drip 45mmol is dissolved in the solution of THF, dropwise rear maintenance thermotonus 1 hour, then rise to gradually room temperature reaction 2 hours, add ethyl acetate and the 30mL saturated common salt aqueous solution of 30mL, separatory, 30mL ethyl acetate extraction 2 times for water, merge organic phase, decompression is spin-dried for and obtains yellow oil, and recycle silicon glue column separating purification obtains 5-(two (the cyclohexyl)-4-yls of 4 '-ethyl)-2,3-difluorobenzaldehyde, white solid, GC:98%, yield: 80%.
The preparation of step 2:4-(3-(brooethyl)-4,5-difluorophenyl)-4 '-ethyl two (hexanaphthene)
In 250mL reaction flask, drop into the 5-(two (the cyclohexyl)-4-yls of 4 '-ethyl)-2 of 12mmol, the THF of 3-difluorobenzaldehyde and 100mL, under room temperature, add the sodium borohydride solids of 24mmol in batches, add rear stirring reaction 1 hour, add the 20mL saturated common salt aqueous solution, separate organic phase, 30mL ethyl acetate extraction 2 times for water, merges organic phase, and decompression is spin-dried for and obtains (5-(two (the cyclohexyl)-4-yls of 4 '-ethyl)-2,3-difluorophenyl) methyl alcohol, white solid, GC:98%, yield: 98%
In 250mL reaction flask, drop into (the 5-(two (the cyclohexyl)-4-yls of 4 '-ethyl)-2 of 12mmol, 3-difluorophenyl) chloroform of methyl alcohol and 100mL, add again the tribromo oxygen phosphorus of 15mmol, reflux stirring reaction 3 hours, decompression is spin-dried for and obtains yellow oil, cross silicagel column decolouring, obtain 4-(3-(brooethyl)-4,5-difluorophenyl)-4 '-ethyl two (hexanaphthene), colorless oil product, GC:92%, yield: 80%.
The preparation of step 3:4-(3-(the fluoro-5-of 2,3-bis-(two (the cyclohexyl)-4-yls of 4 '-amyl group) benzyl)-4,5-difluorophenyl)-4 '-ethyl two (hexanaphthene)
In 100mL reaction flask, drop into 4-(3,4-difluorophenyl)-4 '-amyl group two (hexanaphthene) of 10mmol, then drop into the THF of 40mL and the methyl tertiary butyl ether of 10mL, at N
2under protection, system temperature is down to below-80 DEG C by liquid nitrogen/ethanol bath.Drip the hexane solution of the n-BuLi of 12mmol, after dripping off, be retained to-80 DEG C of following stirring reactions 1 hour, be added dropwise to the 4-(3-(brooethyl)-4 of 12mmol, 5-difluorophenyl) the THF solution of-4 '-ethyl two (hexanaphthenes), dropwise rear maintenance thermotonus 1 hour, then rise to gradually room temperature reaction 2 hours.Add the 30mL saturated common salt aqueous solution, separate organic phase use, 30mL ethyl acetate extraction 2 times for water, merges organic phase, be spin-dried for and obtain yellow oil, add the ether of 40mL to be warming up to boiling, cool to room temperature, filters, obtain target compound, white solid, HPLC:> 99%, yield: 50%.
Experimental result is as follows:
(1)
1HNMR(δ，CDCl
3)：0.84～1.94(50H，m)；2.43(2H，m)；3.71(2H，m)；6.88～6.95(2H，m)；7.16(1H，m)；7.27(1H，m)。Confirm that the product obtaining through above-mentioned polystep reaction is to be formula I-1 (n=1, R really
1=C
2h
5, R
2=C
5h
11) shown in compound 4-(3-(the fluoro-5-of 2,3-bis-(4 '-amyl group two (cyclohexyl)-4-yls) benzyl)-4,5-difluorophenyl)-4 '-ethyl two (hexanaphthene).
(2) melting point compound mp:108.22 DEG C
(3) compound clearing point cp:257.98 DEG C
(4) test synthetic liquid crystal monomer formula I-1 (n=1, R
1=C
2h
5, R
2=C
5h
11) shown in 4-(3-(2, the fluoro-5-of 3-bis-(two (the cyclohexyl)-4-yls of 4 '-amyl group) benzyl)-4,5-difluorophenyl) optical anisotropy and the dielectric anisotropy of-4 '-ethyl two (hexanaphthenes), the fitting parameter of gained is Δ n=0.0656, Δ ε=-0.8.
The preparation of embodiment 2 4-(3-(the fluoro-5-of 2,3-bis-(4-penta cyclohexyl) styroyl)-4,5-difluorophenyl)-4 '-propyl group two (hexanaphthene)
The preparation of step 1:4-(the fluoro-5-iodophenyl of 3,4-bis-)-4 '-propyl group two (hexanaphthene)
In 1000mL reaction flask, drop into 4-(3,4-difluorophenyl)-4 '-propyl group two (hexanaphthene) of 0.10mol, then drop into the THF of 300mL and the methyl tertiary butyl ether of 100mL, at N
2protection is lower is down to system temperature below-80 DEG C by liquid nitrogen/ethanol bath, drips the hexane solution of the n-BuLi of 0.15mol, is retained to-80 DEG C of following stirring reactions 1 hour after dripping off.The iodine that keeps temperature to drip 0.15mol is dissolved in the solution of THF, dropwises rear maintenance thermotonus 1 hour, then rises to gradually room temperature reaction 2 hours.Then add the sodium thiosulfate solution that 100mL is saturated, separate organic phase, with 30mL saturated common salt washing 3 times, organic phase anhydrous sodium sulfate drying, obtains yellow oil after decompression is spin-dried for, and room temperature is placed crystallization, obtain 4-(3, the fluoro-5-iodophenyl of 4-bis-)-4 '-propyl group two (hexanaphthene), GC:95%, yield: 80%
The preparation of step 2:4-(the fluoro-5-of 2,3-bis-(two (the cyclohexyl)-4-yls of 4 '-propyl group) phenyl)-2-methyl-3-butyne-2-alcohol
In 250mL reaction flask, drop into the 5-(4-(4 '-propyl group cyclohexyl) cyclohexyl)-2 of 10mmol, the Pd (PPh of 3-difluoro iodobenzene and 0.5mol%
3)
4, it is 9 that the triethylamine of input 10mL makes the pH value of reaction system, then drops into the anhydrous THF of 20mL, at N
2under protection, be warming up to 60 DEG C; drip the methylbutynol THF solution of 20mmol; stirring reaction 2 hours; decompression is spin-dried for to obtain yellow oil; use silicagel column separation and purification, obtain product 4-(the fluoro-5-of 2,3-bis-(two (the cyclohexyl)-4-yls of 4 '-propyl group) phenyl)-2-methyl-3-butyne-2-alcohol; yellow solid, yield: 95%
The preparation of step 3:4-(3-ethynyl-4,5-difluorophenyl)-4 '-propyl group two (hexanaphthene)
In 250mL reaction flask, drop into the 4-(2 of 10mmol, the fluoro-5-of 3-bis-(4 '-propyl group two (cyclohexyl)-4-yls) phenyl) potassium hydroxide of-2-methyl-3-butyne-2-alcohol and 12mmol, drop into the toluene of 40mL, be heated to 100 DEG C, stirring reaction 4 hours, cool to room temperature, decompression is spin-dried for, resistates silicagel column separation and purification, obtains 4-(3-ethynyl-4,5-difluorophenyl)-4 '-propyl group two (hexanaphthene), yellow solid, yield: 85%
Step 4:1, the preparation of the iodo-5-of the fluoro-3-of 2-bis-(4-amyl group cyclohexyl) benzene
In 1000mL reaction flask, drop into 1 of 0.10mol, the fluoro-4-of 2-bis-(4-amyl group cyclohexyl) benzene, then drop into the THF of 250mL and the methyl tertiary butyl ether of 80mL, at N
2protection is lower is down to system temperature below-80 DEG C by liquid nitrogen/ethanol bath, drips the hexane solution of the n-BuLi of 0.15mol, is retained to-80 DEG C of following stirring reactions 1 hour after dripping off.The iodine that keeps temperature to drip 0.15mol is dissolved in the solution of THF, dropwises rear maintenance thermotonus 1 hour, then rises to gradually room temperature reaction 2 hours.Then add the sodium thiosulfate solution that 100mL is saturated, separate organic phase, with 30mL saturated common salt washing 3 times, organic phase anhydrous sodium sulfate drying, obtains yellow oil after decompression is spin-dried for, and room temperature is placed crystallization, obtain 1, the iodo-5-of the fluoro-3-of 2-bis-(4-amyl group cyclohexyl) benzene, GC:95%, yield: 82%.
The preparation of step 5:4-(3-((the fluoro-5-of 2,3-bis-(4-amyl group cyclohexyl) phenyl) ethynyl)-4,5-difluorophenyl)-4 '-propyl group two (hexanaphthene)
In 250mL reaction flask, drop into 4-(3-ethynyl-4 of 10mmol, 5-difluorophenyl)-4 '-propyl group two (hexanaphthenes) and 10mmol 1, the iodo-5-of the fluoro-3-of 2-bis-(4-amyl group cyclohexyl) benzene, the Pd (PPh of input 0.5mol%
3)
4making the pH value of reaction system with the triethylamine of 10mL is 9, then adds the toluene of 20mL, at N
2under protection, be warming up to 85 DEG C; stirring reaction 4 hours; decompression is spin-dried for, and to the anhydrous diethyl ether that adds 30mL in resistates, after dispersed with stirring, filters; obtain target compound 4-(3-((2; the fluoro-5-of 3-bis-(4-amyl group cyclohexyl) phenyl) ethynyl)-4,5-difluorobenzene)-4 '-propyl group two (cyclohexyl), white solid; HPLC:> 99%, yield: 40%
The preparation of step 6:4-(3-(the fluoro-5-of 2,3-bis-(4-penta cyclohexyl) styroyl)-4,5-difluorophenyl)-4 '-propyl group two (hexanaphthene)
In 500mL autoclave, drop into the 4-(3-((2 of 0.01mol, the fluoro-5-of 3-bis-(4-amyl group cyclohexyl) phenyl) ethynyl)-4, 5-difluorophenyl)-4 '-propyl group two (hexanaphthene) and the THF of 250mL and the methyl alcohol of 50mL, drop into again the 10%Pd/C catalyzer of 0.12g, sealed reactor, logical hydrogen exchange three times, finally make pressure reach 1MPa, stirring at room temperature reaction 12 hours, hydrogen make-up makes still internal pressure maintain 1MPa left and right during this time, shift out reaction solution, filter, filtrate decompression is spin-dried for, silicagel column separation and purification, obtain target product, white solid product, yield: 95%
Experimental result is as follows:
(1)
1HNMR(δ，CDCl
3)：0.84～1.91(46H，m)；2.38(2H，m)；2.52(4H，m)；7.02(2H，m)；7.12(2H，m)。Confirm that the product obtaining through above-mentioned polystep reaction is Compound I-3 (n=2, R really
1=C
3h
7, R
2=C
5h
11) shown in 4-(3-(the fluoro-5-of 2,3-bis-(4-penta cyclohexyl) styroyl)-4,5-difluorophenyl)-4 '-propyl group two (hexanaphthenes).
(2) test synthetic liquid crystal monomer formula I-3 (n=2, R
1=C
3h
7, R
2=C
5h
11) shown in 4-(3-(2, the fluoro-5-of 3-bis-(4-penta cyclohexyl) styroyl)-4,5-difluorophenyl) optical anisotropy and the dielectric anisotropy of-4 '-propyl group two (hexanaphthenes), the fitting parameter of gained is Δ n=0.0856, Δ ε=0.6.
The preparation of embodiment 3 4-(the fluoro-5-of 3,4-bis-(3-(2 ', 4,5,6 '-tetrafluoro-4 '-(4-propyl group cyclohexyl) biphenyl-3-yl) propyl group) phenyl)-4 '-ethyl two (hexanaphthene)
The preparation of step 1:4-(3-(3-bromopropyl)-4,5-difluorophenyl)-4 '-ethyl two (hexanaphthene)
In 100mL reaction flask, drop into 4-(3,4-difluorophenyl)-4 '-ethyl two (hexanaphthene) of 10mmol, then add the anhydrous THF of 40mL and the methyl tertiary butyl ether of 20mL, at N
2under protection, system temperature is down to below-80 DEG C by liquid nitrogen/ethanol bath; drip the hexane solution of the n-BuLi of 12mmol; after dripping off, be retained to-80 DEG C of following stirring reactions 1 hour; in reaction solution, inject rapidly 1 of 12mmol; 3-dibromopropane; dropwise rear maintenance thermotonus 1 hour, then rise to gradually room temperature reaction 2 hours.Then add the common salt aqueous solution that 30mL is saturated, separate organic phase, with 30mL saturated common salt washing 3 times, water extracts 2 times by the ethyl acetate of 30mL again, merge organic phase, anhydrous sodium sulfate drying, filters, after being spin-dried for, filtrate decompression obtains yellow oil, purify with silicagel column, obtain intermediate 4-(3-(3-bromopropyl)-4,5-difluorophenyl)-4 '-ethyl two (hexanaphthene), colorless oil, yield: 80%
The preparation of step 2:4-(the fluoro-5-of 3,4-bis-(3-(2 ', 4,5,6 '-tetrafluoro-4 '-(4-propyl group cyclohexyl) biphenyl-3-yl) propyl group) phenyl)-4 '-ethyl two (hexanaphthene)
In 100mL reaction flask, drop into 2 of 6mmol, 3 ', 4 ', 6-tetrafluoro-4-(4-propyl group cyclohexyl) biphenyl, then add the anhydrous THF of 50mL and the methyl tertiary butyl ether of 15mL, at N
2under protection, system temperature is down to below-80 DEG C by liquid nitrogen/ethanol bath; drip the hexane solution of the n-BuLi of 7.5mmol; after dripping off, be retained to-80 DEG C of following stirring reactions 1 hour; to the 4-(3-(3-bromopropyl)-4 that is slowly added dropwise to 7.2mmol in reaction solution; 5-difluorophenyl)-4 '-ethyl two (hexanaphthenes) is dissolved in the solution of anhydrous THF; dropwise rear maintenance thermotonus half an hour, then rise to gradually room temperature reaction 1 hour.Then add the common salt aqueous solution that 30mL is saturated, separate organic phase, with 30mL saturated common salt washing 3 times, water extracts 2 times by the ethyl acetate of 30mL again, merges organic phase, anhydrous sodium sulfate drying, filter, after filtrate decompression is spin-dried for, obtain yellow oil, add 40mL anhydrous diethyl ether to be heated to boil, cool to room temperature, filter, obtain target compound, white solid, yield: 50%
Experimental result is as follows:
(1)
1HNMR(δ，CDCl
3)：0.84～1.95(42H，m)；2.35(2H，m)；2.66(4H，m)；6.72～6.85(4H，m)；7.42～7.46(2H，m)。Confirm that the product obtaining through above-mentioned polystep reaction is the 4-(3 shown in Compound I really, the fluoro-5-of 4-bis-(3-(2 ', 4,5,6 '-tetrafluoro-4 '-(4-propyl group cyclohexyl) biphenyl-3-yl) propyl group) phenyl)-4 '-ethyl two (hexanaphthene).
(2) melting point compound mp:105.76 DEG C
(3) compound clearing point cp:131.80 DEG C
(4) test the 4-(3 shown in synthetic liquid crystal monomer formula I Compound I, the fluoro-5-of 4-bis-(3-(2 ', 4,5,6 '-tetrafluoro-4 '-(4-propyl group cyclohexyl) biphenyl-3-yl) propyl group) phenyl) optical anisotropy and the dielectric anisotropy of-4 '-ethyl two (hexanaphthenes), the fitting parameter of gained is Δ n=0.0642, Δ ε=-0.3.
The preparation of embodiment 4 4-(3-(4-(5-(two (the cyclohexyl)-4-yls of 4 '-butyl)-2,3-difluorophenyl) butyl)-4,5-difluorophenyl)-4 '-ethyl two (hexanaphthene)
The preparation of step 1:4-(3-(4-brombutyl)-4,5-difluorophenyl)-4 '-ethyl two (hexanaphthene)
In 100mL reaction flask, drop into 4-(3,4-difluorophenyl)-4 '-ethyl two (hexanaphthene) of 10mmol, then add the anhydrous THF of 40mL and the methyl tertiary butyl ether of 20mL, at N
2under protection, system temperature is down to below-80 DEG C by liquid nitrogen/ethanol bath; drip the hexane solution of the n-BuLi of 12mmol; after dripping off, be retained to-80 DEG C of following stirring reactions 1 hour; in reaction solution, inject rapidly 1 of 12mmol; 4-dibromobutane; dropwise rear maintenance thermotonus 1 hour, then rise to gradually room temperature reaction 2 hours.Then add the common salt aqueous solution that 30mL is saturated, separate organic phase, with 30mL saturated common salt washing 3 times, water extracts 2 times by the ethyl acetate of 50mL again, merge organic phase, anhydrous sodium sulfate drying, filters, after being spin-dried for, filtrate decompression obtains yellow oil, purify with silicagel column, obtain intermediate 4-(3-(4-brombutyl)-4,5-difluorophenyl)-4 '-ethyl two (hexanaphthene), white solid, yield: 68%
Step 2:4-(3-(4-(5-(two (the cyclohexyl)-4-yls of 4 '-butyl)-2,3-difluorophenyl) butyl)-4,5-difluorophenyl)-4 '-ethyl two (hexanaphthene) preparation
In 100mL reaction flask, drop into 4-butyl-4 '-(3,4-difluorophenyl) bis cyclohexane of 6mmol, then add the anhydrous THF of 50mL and the methyl tertiary butyl ether of 15mL, at N
2under protection, system temperature is down to below-80 DEG C by liquid nitrogen/ethanol bath; drip the hexane solution of the n-BuLi of 7.5mmol; after dripping off, be retained to-80 DEG C of following stirring reactions 1 hour; to the 4-(3-(4-brombutyl)-4 that is slowly added dropwise to 7.2mmol in reaction solution; 5-difluorophenyl)-4 '-ethyl two (hexanaphthenes) is dissolved in the solution of anhydrous THF; dropwise rear maintenance thermotonus half an hour, then rise to gradually room temperature reaction 1 hour.Then add the common salt aqueous solution that 30mL is saturated, separate organic phase, with 30mL saturated common salt washing 3 times, water extracts 2 times by the ethyl acetate of 50mL again, merges organic phase, anhydrous sodium sulfate drying, filter, after filtrate decompression is spin-dried for, obtain yellow oil, add 50mL anhydrous diethyl ether to be heated to boil, cool to room temperature, filter, obtain target compound, white solid, yield: 45%
Experimental result is as follows:
(1)
1HNMR(δ，CDCl
3)：0.84～1.88(56H，m)；2.35(2H，m)；2.64(4H，m)；6.70～6.72(2H，d)；6.77～6.84(2H，m)。Confirm that the product obtaining through above-mentioned polystep reaction is Compound I-1 (n=4, R really
1=C
2h
5, R
2=C
4h
9) 4-(3-(4-(5-(two (the cyclohexyl)-4-yls of 4 '-butyl)-2,3-difluorophenyl) butyl)-4,5-difluorophenyl)-4 '-ethyl two (hexanaphthene).
(2) melting point compound mp:121.41 DEG C
(3) compound clearing point cp:162.41 DEG C
(4) test synthetic liquid crystal monomer formula I-1 (n=4, R
1=C
2h
5, R
2=C
4h
9) shown in 4-(3-(4-(5-(4 '-butyl two (cyclohexyl)-4-yls)-2,3-difluorophenyl) butyl)-4,5-difluorophenyl) two (hexanaphthene) optical anisotropies of-4 '-ethyl and dielectric anisotropy, the fitting parameter of gained is Δ n=0.0629, Δ ε=0.2.
Embodiment 5
According to the identical step of embodiment 1, only reactant is replaced according to the different substituents group in following product, obtain the target product as shown in the formula different structure shown in I.Nuclear-magnetism structural confirmation data are indicated as target product.The performance of its optical anisotropy and dielectric anisotropy and embodiment 1, without substantive difference, repeat no more herein.
Embodiment 6
According to the identical step of embodiment 2, only reactant is replaced according to the different substituents group in following product, obtain the target product as shown in the formula different structure shown in I.Nuclear-magnetism structural confirmation data are indicated as target product.The performance of its optical anisotropy and dielectric anisotropy and embodiment 2, without substantive difference, repeat no more herein.
Embodiment 7
According to the identical step of embodiment 3, only reactant is replaced according to the different substituents group in following product, obtain the target product as shown in the formula different structure shown in I.Nuclear-magnetism structural confirmation data are indicated as target product.The performance of its optical anisotropy and dielectric anisotropy and embodiment 3, without substantive difference, repeat no more herein.
Embodiment 8
According to the identical step of embodiment 4, only reactant is replaced according to the different substituents group in following product, obtain the target product as shown in the formula different structure shown in I.Nuclear-magnetism structural confirmation data are indicated as target product.The performance of its optical anisotropy and dielectric anisotropy and embodiment 4, without substantive difference, repeat no more herein.
Claims (5)
1. compound shown in formula I,
Specifically be selected from following any one:
Wherein, R
1and R
2all be selected from any one in alkyl, the alkoxyl group of C1 and the normal olefine base of C2-C3 of C1-C5; N is the integer of 1-4.
2. prepare a method for compound described in claim 1, for following method one is to any one in method four,
Wherein, described method one, for preparing the method for arbitrary described compound that the n described in claim 1 is 1, comprises the steps:
1) by 4-R
a-1,2-difluorobenzene and n-Butyl Lithium carry out lithiation in solvent, within 1-2 hour, react complete maintenance temperature and add DMF to carry out substitution reaction again, be warming up to room temperature continuation reaction and obtain 5-R after 1-2 hour after 1-2 hour
a-2,3-difluorobenzaldehyde;
2) by described step 1) gained 5-R
a-2,3-difluorobenzaldehyde and sodium borohydride carry out after reduction reaction in solvent, and gained reduction reaction product and sulfur oxychloride are carried out to chlorination reaction or carry out bromination reaction with tribromo oxygen phosphorus, react the complete 5-R of obtaining
a-2,3-difluorophenyl methyl chloride or 5-R
a-2,3-difluorophenyl monobromethane;
3) by 4-R
b-1,2-difluorobenzene and n-Butyl Lithium carry out lithiation in solvent, react complete maintenance temperature and add step 2 again) gained 5-R
a-2,3-difluorophenyl methyl chloride or 5-R
a-2,3-difluorophenyl monobromethane carries out substitution reaction, is warming up to room temperature continuation reaction and obtains the arbitrary described compound that in described formula I, n is 1 after 1-2 hour after 1-2 hour;
Described method two is the method for preparing arbitrary described compound that n claimed in claim 1 is 2, comprises the steps:
1) by 4-R
a-1,2-difluorobenzene and n-Butyl Lithium mix and carry out lithiation in solvent, react complete maintenance temperature and add iodine to carry out iodination reaction again, be warming up to room temperature continuation reaction and obtain 5-R after 1-2 hour after 1-2 hour
a-2,3-difluoro iodobenzene;
2) be 8-14 and Pd (PPh keeping the pH value in reaction system
3)
4under the condition existing as catalyzer, by step 1) gained 5-R
a-2,3-difluoro iodobenzene mixes and reacts with 2-methyl 3-butyne-2-alcohol, reacts the complete 4-of obtaining (the fluoro-5-R of 2,3-bis-
aphenyl)-2-methyl-3-butyne-2-alcohol;
3) by step 2) gained 4-(the fluoro-5-R of 2,3-bis-
aphenyl)-2-methyl-3-butyne-2-alcohol mixes and reacts with highly basic, reacts the complete 5-R of obtaining
a-2,3-difluorophenyl acetylene;
4) by 4-R
b-1,2-difluorobenzene and n-Butyl Lithium carry out lithiation in solvent, within 1-2 hour, react complete maintenance temperature and add iodine to carry out iodination reaction again, be warming up to room temperature continuation reaction and obtain 5-R after 1-2 hour after 1-2 hour
b-2,3-difluoro iodobenzene;
5) be 8-14 and Pd (PPh keeping the pH value in reaction system
3)
4under the condition existing as catalyzer, by step 3) gained 5-R
a-2,3-difluorophenyl acetylene and step 4) gained 5-R
b-2,3-difluoro iodobenzene mixes and reacts, and reacts the complete dibenzenyl compound that obtains;
6) under the condition existing at Pd/C catalyzer, step 5) gained dibenzenyl compound and hydrogen are carried out to hydrogenation reduction, obtain the arbitrary described compound that in described formula I, n is 2;
Described method three, for preparing the method for arbitrary described compound that n claimed in claim 1 is 3, comprises the steps:
1) by 4-R
a-1,2-difluorobenzene and n-Butyl Lithium mix and carry out lithiation in solvent, react complete maintenance temperature and add 1,3-dibromopropane to carry out substitution reaction again, be warming up to room temperature continuation reaction and obtain 5-R after 1-2 hour after 1-2 hour
a-2,3-difluorophenyl N-PROPYLE BROMIDE;
2) by 4-R
b-1,2-difluorobenzene and n-Butyl Lithium mix and carry out lithiation in solvent, react the 5-R that complete maintenance temperature adds described step 1) to obtain again
a-2,3-difluorophenyl N-PROPYLE BROMIDE reacts, and is warming up to room temperature and continues reaction 1-2 hour after 0.5-1 hour, reacts the complete arbitrary described compound that in described formula I, n is 3 that obtains;
Described method four, for preparing the method for arbitrary described compound that n claimed in claim 1 is 4, comprises the steps:
1) by 4-R
a-1,2-difluorobenzene and n-Butyl Lithium mix and carry out lithiation in solvent, react complete maintenance temperature and add 1,3-dibromobutane to carry out substitution reaction again, be warming up to room temperature continuation reaction and obtain 5-R after 1-2 hour after 1-2 hour
a-2,3-difluorophenyl n-butyl bromide;
2) by 4-R
b-1,2-difluorobenzene and n-Butyl Lithium mix and carry out lithiation in solvent, react the 5-R that complete maintenance temperature adds described step 1) to obtain again
a-2,3-difluorophenyl n-butyl bromide is reacted, and is warming up to room temperature and continues reaction 1-2 hour after 0.5-1 hour, reacts the complete arbitrary described compound that in described formula I, n is 4 that obtains;
Described 4-R
a-1,2-difluorobenzene and 4-R
bin-1,2-difluorobenzene, described R
aand R
ball define identical with claim 1.
3. method according to claim 2, is characterized in that: in described method one, and in described step 1), described 4-R
athe mole dosage ratio that feeds intake of-1,2-difluorobenzene, n-Butyl Lithium, DMF is 1:1.2-1.5:1.2-1.5; Described 4-R
a-1,2-difluorobenzene and n-Butyl Lithium carry out in lithiation step in solvent, and temperature is-90 DEG C～-80 DEG C, and the time is 1-2 hour;
Described step 2) in, described 5-R
a-2,3-difluorobenzaldehyde feeds intake mole dosage than being 1:1-3 with sodium borohydride; In described reduction reaction step, temperature is 20-60 DEG C, and the time is 1-2 hour; Described reduzate feeds intake mole dosage than being 1:1-2 with described sulfur oxychloride or tribromo oxygen phosphorus; In described chlorination reaction or bromination reaction step, temperature is 25-65 DEG C, and the time is 1-5 hour;
In described step 3), described 4-R
b-1,2-difluorobenzene, n-Butyl Lithium, step 2) gained 5-R
a-2,3-difluorophenyl methyl chloride or 5-R
athe mole dosage ratio that feeds intake of-2,3-difluorophenyl monobromethane is 1:1.2-1.5:1-1.5; Described 4-R
b-1,2-difluorobenzene and n-Butyl Lithium carry out in lithiation step in solvent, and temperature is-90 DEG C～-80 DEG C, and the time is 0.5-2 hour;
Described step 1) is to step 3), and described solvent is all selected from least one in tetrahydrofuran (THF), hexane, methyl tertiary butyl ether, anhydrous diethyl ether and 2-methyltetrahydrofuran;
In described method two, in step 1), described 4-R
athe mole dosage ratio that feeds intake of-1,2-difluorobenzene, n-Butyl Lithium and iodine is 1:1.2-1.5:1.2-1.5; Described 4-R
a-1,2-difluorobenzene and n-Butyl Lithium carry out in lithiation step in solvent, and temperature is-90 DEG C～-80 DEG C, and the time is 1-2 hour; Described solvent is selected from least one in tetrahydrofuran (THF), hexane, methyl tertiary butyl ether, anhydrous diethyl ether and 2-methyltetrahydrofuran;
Described step 2) in, described step 1) gained 5-R
athe molar ratio of-2,3-difluoro iodobenzene and 2-methyl 3-butyne-2-alcohol is 1:1-3; Described Pd (PPh
3)
4the mole dosage that feeds intake be described step 1) gained 5-R
athe 0.1-0.5% of-2,3-difluoro iodobenzene; In described reactions steps, temperature is 40-70 DEG C, and the time is 1-4 hour;
In described step 3), described highly basic is selected from least one in sodium hydroxide and potassium hydroxide; Described step 2) gained 4-(the fluoro-5-R of 2,3-bis-
aphenyl) molar ratio of-2-methyl-3-butyne-2-alcohol and highly basic is 1:1.2-1.5; In described reactions steps, temperature is 80-110 DEG C, and the time is 2-6 hour;
In described step 4), described 4-R
bthe mole dosage ratio that feeds intake of-1,2-difluorobenzene, n-Butyl Lithium and iodine is 1:1.2-1.5:1.2-1.5; Described 4-R
b-1,2-difluorobenzene and n-Butyl Lithium carry out in lithiation step in solvent, and temperature is-90 DEG C～-80 DEG C, and the time is 1-2 hour; Described solvent is selected from least one in tetrahydrofuran (THF), hexane, methyl tertiary butyl ether, anhydrous diethyl ether and 2-methyltetrahydrofuran;
In described step 5), described step 3) gained 5-R
a-2,3-difluorophenyl acetylene and described step 4) gained 5-R
bthe molar ratio of-2,3-difluoro iodobenzene is 1:1-1.2; Described Pd (PPh
3)
4the mole dosage that feeds intake be described step 3) gained 5-R
athe 0.1-0.5% of-2,3-difluorophenyl acetylene; In described reactions steps, temperature is 60-110 DEG C, and the time is 2-6 hour;
In described step 6), the consumption of described Pd/C catalyzer is the 1%-5% of described step 5) gained dibenzenyl compound quality consumption; In described reactions steps, temperature is 20-40 DEG C, and the time is 12-24 hour; Pressure is 0.2-1MPa;
In described method three, in described step 1), described 4-R
athe mole dosage ratio that feeds intake of-1,2-difluorobenzene, n-Butyl Lithium and 1,3-dibromopropane is 1:1.2-1.5:1.2-1.5; Described 4-R
a-1,2-difluorobenzene and n-Butyl Lithium carry out in lithiation step in solvent, and temperature is-90 DEG C～-80 DEG C, and the time is 1-2 hour; Described solvent is selected from least one in tetrahydrofuran (THF), hexane, methyl tertiary butyl ether, anhydrous diethyl ether and 2-methyltetrahydrofuran;
Described step 2) in, described 4-R
b-1,2-difluorobenzene, n-Butyl Lithium and described step 1) gained 5-R
athe molar ratio of-2,3-difluorophenyl N-PROPYLE BROMIDE is 1:1.2-1.5:1.2-1.5; Described 4-R
b-1,2-difluorobenzene and n-Butyl Lithium carry out in lithiation step in solvent, and temperature is-90 DEG C～-80 DEG C, and the time is 1-2 hour; Described solvent is selected from least one in tetrahydrofuran (THF), hexane, methyl tertiary butyl ether, anhydrous diethyl ether and 2-methyltetrahydrofuran;
In described method four, in described step 1), in the step 1) of described method, described 4-R
athe mole dosage ratio that feeds intake of-1,2-difluorobenzene, n-Butyl Lithium and 1,3-dibromobutane is 1:1.2-1.5:1.2-1.5; Described 4-R
a-1,2-difluorobenzene and n-Butyl Lithium carry out in lithiation step in solvent, and temperature is-90 DEG C～-80 DEG C, and the time is 1-2 hour; Described solvent is selected from least one in tetrahydrofuran (THF), hexane, methyl tertiary butyl ether, anhydrous diethyl ether and 2-methyltetrahydrofuran;
Described step 2) in, described 4-R
b-1,2-difluorobenzene, n-Butyl Lithium and described step 1) gained 5-R
athe molar ratio of-2,3-difluorophenyl n-butyl bromide is 1:1.2-1.5:1.2-1.5; Described 4-R
b-1,2-difluorobenzene and n-Butyl Lithium carry out in lithiation step in solvent, and temperature is-90 DEG C～-80 DEG C, and the time is 1-2 hour; Described solvent is selected from least one in tetrahydrofuran (THF), hexane, methyl tertiary butyl ether, anhydrous diethyl ether and 2-methyltetrahydrofuran.
4. method according to claim 3, is characterized in that: in described method one, and in described step 1), described 4-R
athe mole dosage ratio that feeds intake of-1,2-difluorobenzene, n-Butyl Lithium, DMF is 1:1.2:1.5; Described 4-R
a-1,2-difluorobenzene and n-Butyl Lithium carry out in lithiation step in solvent, and temperature is-80 DEG C, and the time is 1 hour;
Described step 2) in, described 5-R
a-2,3-difluorobenzaldehyde feeds intake mole dosage than being 1:2 with sodium borohydride; In described reduction reaction step, the time is 1 hour; Described reduzate feeds intake mole dosage than being 1:1.25 with described sulfur oxychloride or tribromo oxygen phosphorus; In described chlorination reaction or bromination reaction step, temperature is 60 DEG C, and the time is 3 hours;
In described step 3), described 4-R
b-1,2-difluorobenzene, n-Butyl Lithium, step 2) gained 5-R
a-2,3-difluorophenyl methyl chloride or 5-R
athe mole dosage ratio that feeds intake of-2,3-difluorophenyl monobromethane is 1:1.2:1.2; Described 4-R
b-1,2-difluorobenzene and n-Butyl Lithium carry out in lithiation step in solvent, and temperature is-80 DEG C, and the time is 1 hour;
In described method two, in step 1), described 4-R
athe mole dosage ratio that feeds intake of-1,2-difluorobenzene, n-Butyl Lithium and iodine is 1:1.5:1.5; Described 4-R
a-1,2-difluorobenzene and n-Butyl Lithium carry out in lithiation step in solvent, and temperature is-80 DEG C, and the time is 1 hour;
Described step 2) in, described step 1) gained 5-R
athe molar ratio of-2,3-difluoro iodobenzene and 2-methyl 3-butyne-2-alcohol is 1:2; Described Pd (PPh
3)
4the mole dosage that feeds intake be described step 1) gained 5-R
a0.5% of-2,3-difluoro iodobenzene; In described reactions steps, temperature is 60 DEG C, and the time is 2 hours;
In described step 3), described highly basic is selected from least one in sodium hydroxide and potassium hydroxide; Described step 2) gained 4-(the fluoro-5-R of 2,3-bis-
aphenyl) molar ratio of-2-methyl-3-butyne-2-alcohol and highly basic is 1:1.2; In described reactions steps, temperature is 100 DEG C, and the time is 4 hours;
In described step 4), described 4-R
bthe mole dosage ratio that feeds intake of-1,2-difluorobenzene, n-Butyl Lithium and iodine is 1:1.5:1.5; Described 4-R
b-1,2-difluorobenzene and n-Butyl Lithium carry out in lithiation step in solvent, and temperature is-80 DEG C, and the time is 1 hour;
In described step 5), described step 3) gained 5-R
a-2,3-difluorophenyl acetylene and described step 4) gained 5-R
bthe molar ratio of-2,3-difluoro iodobenzene is 1:1; Described Pd (PPh
3)
4the mole dosage that feeds intake be described step 3) gained 5-R
a0.5% of-2,3-difluorophenyl acetylene; In described reactions steps, temperature is 85 DEG C, and the time is 4 hours;
In described step 6), the consumption of described Pd/C catalyzer is 2% of described step 5) gained dibenzenyl compound quality consumption; In described reactions steps, temperature is 30 DEG C, and the time is 12 hours; Pressure is 1MP
a;
In described method three, in described step 1), described 4-R
athe mole dosage ratio that feeds intake of-1,2-difluorobenzene, n-Butyl Lithium and 1,3-dibromopropane is 1:1.2:1.2; Described 4-R
a-1,2-difluorobenzene and n-Butyl Lithium carry out in lithiation step in solvent, and temperature is--and 80 DEG C, the time is 1 hour;
Described step 2) in, described 4-R
b-1,2-difluorobenzene, n-Butyl Lithium and described step 1) gained 5-R
athe molar ratio of-2,3-difluorophenyl N-PROPYLE BROMIDE is 1:1.5:1.2; Described 4-R
b-1,2-difluorobenzene and n-Butyl Lithium carry out in lithiation step in solvent, and temperature is-80 DEG C, and the time is 1 hour;
In described method four, in described step 1), in the step 1) of described method, described 4-R
athe mole dosage ratio that feeds intake of-1,2-difluorobenzene, n-Butyl Lithium and 1,3-dibromobutane is 1:1.2:1.2; Described 4-R
a-1,2-difluorobenzene and n-Butyl Lithium carry out in lithiation step in solvent, and temperature is-80 DEG C, and the time is 1 hour;
Described step 2) in, described 4-R
b-1,2-difluorobenzene, n-Butyl Lithium and described step 1) gained 5-R
athe molar ratio of-2,3-difluorophenyl n-butyl bromide is 1:1.5:1.2; Described 4-R
b-1,2-difluorobenzene and n-Butyl Lithium carry out in lithiation step in solvent, and temperature is-80 DEG C, and the time is 1 hour.
Described in claim 1 compound in the application of preparing in liquid crystal display material, Organic Light Emitting Diode material or semiconductor material.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1127517A (en) * | 1993-06-11 | 1996-07-24 | 大不列颠及北爱尔兰联合王国国防大臣 | Liquid crystal materials, mixtures and devices |
| US6210603B1 (en) * | 1996-11-28 | 2001-04-03 | Chisso Corporation | Fluorine-substituted benzene derivative, liquid-crystal composition, and liquid-crystal display element |
| WO2011033937A1 (en) * | 2009-09-18 | 2011-03-24 | チッソ株式会社 | Liquid crystalline compound, liquid crystal composition, and liquid crystal display element |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1127517A (en) * | 1993-06-11 | 1996-07-24 | 大不列颠及北爱尔兰联合王国国防大臣 | Liquid crystal materials, mixtures and devices |
| US6210603B1 (en) * | 1996-11-28 | 2001-04-03 | Chisso Corporation | Fluorine-substituted benzene derivative, liquid-crystal composition, and liquid-crystal display element |
| WO2011033937A1 (en) * | 2009-09-18 | 2011-03-24 | チッソ株式会社 | Liquid crystalline compound, liquid crystal composition, and liquid crystal display element |
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