CN100391923C - Alkylcyclohexyl multiple-fluorine biphenyl derivative and its preparation method and uses - Google Patents
Alkylcyclohexyl multiple-fluorine biphenyl derivative and its preparation method and uses Download PDFInfo
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- CN100391923C CN100391923C CNB2005101090684A CN200510109068A CN100391923C CN 100391923 C CN100391923 C CN 100391923C CN B2005101090684 A CNB2005101090684 A CN B2005101090684A CN 200510109068 A CN200510109068 A CN 200510109068A CN 100391923 C CN100391923 C CN 100391923C
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Abstract
The present invention discloses derivative alkyl cyclohexyl diphenyl polyfluoride and the preparation method and application. The derivative alkyl cyclohexyl diphenyl liquid crystal polyfluoride provided by the present invention has the structural formula that the structural formula can be seen from a formula I, wherein R is a straight chain or branch chain alkyl of one to ten, and A is H or F. Methoxy is introduced in a lateral direction of a diphenyl ring by compounds of the present invention. The volume of the base group space is small, a couple distance is short, and average dipolar directions are arranged in long shaft directions of molecules. Thereby, the present invention is favorable to increase the dielectric anisotropy of compound molecules in molecule long shaft direction, the fusing point of materials is lowered, and solubility is increased. In addition, the existence of multiple fluorine atoms is favorable to increase the dielectric anisotropy of compound molecules in the molecule long shaft direction. Thereby, the driving voltage of liquid crystal materials is reduced. The substance has good application prospects in the field of liquid crystal displays.
Description
Technical field
The present invention relates to compound and preparation method thereof and application, particularly relate to a kind of alkylcyclohexyl multiple-fluorine biphenyl derivative and preparation method thereof, and this compound is in Application in LCD.
Background technology
Develop rapidly along with TFT liquid-crystal display (Thin Solid Film), requirement to the high-performance liquid crystal material is more and more urgent, especially for obtaining wideer operating temperature range, reduce driving voltage, realize the reduce power consumption of display device, the development dielectric anisotropy is big, and fusing point is low, and the wide high-performance liquid crystal material of mesomorphic temperature range is TFT with liquid crystal material research direction from now on.
Cyclohexyl polyfluoro biphenyls liquid crystal compounds is owing to have good heat, chemical stability, high electric charge conservation rate, and high resistivity, low viscosity etc. have been widely used in the TFT liquid-crystal display.The PlachHerbert of Germany Merck company etc. will have
The liquid crystalline cpd of structure is applied to (DE 4139553,1992) in the mixed liquid crystal; Japan Dainippon Inc﹠amp; The Takehara Sadao of Chemicals company etc. will have
The liquid crystalline cpd of structure is applied to (JP 8183749,1996) in the mixed liquid crystal; The HideoIchinose of Germany Merck company etc. will have
The liquid crystalline cpd of structure is applied to (GB 2310428,1997) in the mixed liquid crystal, and all these materials have all shown good physicals.
Summary of the invention
The purpose of this invention is to provide a kind of alkylcyclohexyl multiple-fluorine biphenyl class liquid crystal and preparation method thereof.
Alkylcyclohexyl multiple-fluorine biphenyl class liquid crystal derived thing provided by the present invention, its structural formula is formula I,
Wherein, R is that carbonatoms is 1～10 straight chained alkyl; (A) be H or F.
More specifically, alkylcyclohexyl multiple-fluorine biphenyl derivative of the present invention comprises:
4 '-(4 "-trans-methylcyclohexyl)-3,4,2 '-three fluoro-2-methoxyl biphenyls,
4 '-(4 "-trans-ethyl cyclohexyl)-3,4,2 '-three fluoro-2-methoxyl biphenyls,
4 '-(4 "-trans-propyl group cyclohexyl)-3,4,2 '-three fluoro-2-methoxyl biphenyls,
4 '-(4 "-trans-butyl cyclohexyl)-3,4,2 '-three fluoro-2-methoxyl biphenyls,
4 '-(4 "-trans-amyl group cyclohexyl)-3,4,2 '-three fluoro-2-methoxyl biphenyls,
4 '-(4 "-trans-hexyl cyclohexyl)-3,4,2 '-three fluoro-2-methoxyl biphenyls,
4 '-(4 "-trans-heptyl cyclohexyl)-3,4,2 '-three fluoro-2-methoxyl biphenyls,
4 '-(4 "-trans-octyl group cyclohexyl)-3,4,2 '-three fluoro-2-methoxyl biphenyls,
4 '-(4 "-trans-nonyl cyclohexyl)-3,4,2 '-three fluoro-2-methoxyl biphenyls,
4 '-(4 "-trans-decyl cyclohexyl)-3,4,2 '-three fluoro-2-methoxyl biphenyls,
4 '-(4 "-trans-methylcyclohexyl)-3,4,2 ', 6 '-tetrafluoro-2-methoxyl biphenyl,
4 '-(4 "-trans-ethyl cyclohexyl)-3,4,2 ', 6 '-tetrafluoro-2-methoxyl biphenyl,
4 '-(4 "-trans-propyl group cyclohexyl)-3,4,2 ', 6 '-tetrafluoro-2-methoxyl biphenyl,
4 '-(4 "-trans-butyl cyclohexyl)-3,4,2 ', 6 '-tetrafluoro-2-methoxyl biphenyl,
4 '-(4 "-trans-amyl group cyclohexyl)-3,4,2 ', 6 '-tetrafluoro-2-methoxyl biphenyl,
4 '-(4 "-trans-hexyl cyclohexyl)-3,4,2 ', 6 '-tetrafluoro-2-methoxyl biphenyl,
4 '-(4 "-trans-heptyl cyclohexyl)-3,4,2 ', 6 '-tetrafluoro-2-methoxyl biphenyl,
4 '-(4 "-trans-octyl group cyclohexyl)-3,4,2 ', 6 '-tetrafluoro-2-methoxyl biphenyl,
4 '-(4 "-trans-nonyl cyclohexyl)-3,4,2 ', 6 '-tetrafluoro-2-methoxyl biphenyl,
4 '-(4 "-trans-decyl cyclohexyl)-3,4,2 ', 6 '-tetrafluoro-2-methoxyl biphenyl.
The preparation method of The compounds of this invention has two kinds of technical schemes:
Scheme-, comprise the steps: 1) preparation 3,4-difluoro-2-methoxy boric acid: with 3,4-difluoro-2-methoxyl bromobenzene and MAGNESIUM METAL reaction generate Grignard reagent, with the trimethyl borate reaction, obtain structural formula after the hydrolysis suc as formula 3 of II, 4-difluoro-2-methoxy boric acid then; 2) preparation alkylcyclohexyl multiple-fluorine biphenyl derivative: suc as formula 3 of II, the compound of 4-difluoro-2-methoxy boric acid and structural formula such as formula III carries out linked reaction under catalyst action with structural formula, obtain described 3, the 4-difluoro-2-methoxyl biphenyl derivative; Described catalyzer is that four (triphenylphosphines) close palladium;
Wherein, step 2) temperature of described linked reaction is 60-90 ℃, and reaction solvent is benzene and dehydrated alcohol.
Reaction equation is as follows:
Wherein, the definition of R, (A) is identical with formula I.
Scheme two comprises the steps: 1) the preparation structural formula is the compound of formula IV: with structural formula is that compound and the MAGNESIUM METAL reaction of formula III generates Grignard reagent, reacts with trimethyl borate then, obtains the compound that structural formula is formula IV after the hydrolysis; 2) preparation alkylcyclohexyl multiple-fluorine biphenyl derivative: with structural formula be the compound of formula IV and structural formula suc as formula 3 of V, 4-difluoro-2-methoxyl bromobenzene carries out linked reaction under catalyst action, obtain described alkylcyclohexyl multiple-fluorine biphenyl derivative; Described catalyzer is that four (triphenylphosphines) close palladium;
Wherein, step 2) temperature of reaction of described linked reaction is 60-90 ℃, and reaction solvent is benzene and dehydrated alcohol.
Reaction equation is as follows:
Wherein, the definition of R, (A) is identical with formula (I).
Another object of the present invention provides the purposes of The compounds of this invention.
It is big that The compounds of this invention has a Δ ε; fusing point is low, and fat-soluble advantage such as good is a kind of well behaved liquid crystal display material; therefore, be that the liquid crystal display material of main component also belongs to protection scope of the present invention with alkylcyclohexyl multiple-fluorine biphenyl derivative of the present invention.
The compounds of this invention has been introduced methoxyl group on the side direction of cyclohexyl biphenyl, because such group spatial volume is less, little and the average dipole direction of galvanic couple distance is in the molecular long axis direction, so help increasing the dielectric anisotropy of compound molecule in the molecular long axis direction, reduce the fusing point of material, increase solvability, in addition, the existence of a plurality of fluorine atoms also helps increasing the dielectric anisotropy of compound molecule in the molecular long axis direction, thereby reduce the driving voltage of liquid crystal material, such material has good prospects for application in field of liquid crystal display.
Embodiment
Embodiment 1, preparation 4 '-(4 "-trans-amyl group cyclohexyl)-3,4,2 '-three fluoro-2-methoxyl biphenyls,
1, preparation 3,4-difluoro-2-methoxy boric acid
In the 250ml there-necked flask, add 22.3g (0.1mol) 3,4-difluoro-2-methoxyl bromobenzene, the 50ml tetrahydrofuran (THF), 2.43g (0.1mol) MAGNESIUM METAL and 1～2 iodine, stirring reaction 1 hour after the initiation reaction at room temperature, system temperature is reduced to-70 ℃ with ethanol-liquid nitrogen system then, under this temperature, slowly drip 10.4g (0.1mol) trimethyl borate, dropwising the back makes it rise to room temperature naturally under agitation condition, dripping 10% HCl solution to pH value then is 1, is heated to 100 ℃ and refluxes 1 hour down.With behind the petroleum ether extraction water of 100ml * 3, use the saturated common salt water washing again reaction solution cooling back, spend the night with anhydrous sodium sulfate drying to neutral.Dried solution revolved steam solution, obtain 15.9g 3,4-difluoro-2-methoxy boric acid, yield 85%.
2, preparation 4 '-(4 "-trans-amyl group cyclohexyl)-3,4,2 '-three fluoro-2-methoxyl biphenyls,
In the 500ml there-necked flask, add 15.9g (0.085mol) 3,4-difluoro-2-methoxy boric acid, 27.8g (0.085mol) 4-(4 '-trans-amyl group cyclohexyl)-2-fluoro-bromobenzene, 150ml benzene, the 60ml dehydrated alcohol, 25g yellow soda ash, 6.6g water and 1.96g four (triphenylphosphine) close palladium, are heated to 70 ℃ of 24 hours postcooling that reflux down to room temperature.Tell organic phase,, merge the organic phase after washing, use anhydrous sodium sulfate drying to neutral with 100ml * 3 chloroform extraction waters.Dried solution revolved steam solution, obtain white crude product 29g, use the dehydrated alcohol recrystallization, obtain the white crystal of 20.6g 4 '-(4 "-trans-amyl group cyclohexyl)-3,4,2 '-three fluoro-2-methoxyl biphenyls, yield 62%.
DSC (differential scanning calorimeter): Cr45.9 ℃ of I
IR (wave number/cm
-)
1: 3010,2947,2854,1876,1614,1595,1568,1491,1475,1412,1367,1310,1281,1240,1 178,1132,1080,1041,955,943,864,812,762,669,627,613,538
MS：390(M
+)，375，319，279，278，265，264，251，247，237，219，201，183，175，153，143，109，97，95，83，81，71，69，57，55，43
The proof products therefrom is correct.
Can obtain with identical method:
4 '-(4 "-trans-methylcyclohexyl)-3,4,2 '-three fluoro-2-methoxyl biphenyls,
4 '-(4 "-trans-ethyl cyclohexyl)-3,4,2 '-three fluoro-2-methoxyl biphenyls,
4 '-(4 "-trans-propyl group cyclohexyl)-3,4,2 '-three fluoro-2-methoxyl biphenyls,
4 '-(4 "-trans-butyl cyclohexyl)-3,4,2 '-three fluoro-2-methoxyl biphenyls,
4 '-(4 "-trans-hexyl cyclohexyl)-3,4,2 '-three fluoro-2-methoxyl biphenyls,
4 '-(4 "-trans-heptyl cyclohexyl)-3,4,2 '-three fluoro-2-methoxyl biphenyls,
4 '-(4 "-trans-octyl group cyclohexyl)-3,4,2 '-three fluoro-2-methoxyl biphenyls,
4 '-(4 "-trans-nonyl cyclohexyl)-3,4,2 '-three fluoro-2-methoxyl biphenyls,
4 '-(4 "-trans-decyl cyclohexyl)-3,4,2 '-three fluoro-2-methoxyl biphenyls.
Embodiment 2,4 '-(4 "-trans-propyl group cyclohexyl)-3,4,2 ', 6 '-tetrafluoro-2-methoxyl biphenyl
1, preparation 4-(trans-4 '-propyl group cyclohexyl)-2,6-two fluoro-phenylo boric acids
In the 250ml there-necked flask, add 31.7g (0.1mol) 4-(trans-4 '-propyl group cyclohexyl)-2,6-two fluoro-bromobenzenes, the 100ml tetrahydrofuran (THF), 2.43g (0.1mol) MAGNESIUM METAL and 1～2 iodine, at room temperature stirred 1 hour after the initiation reaction, system temperature is reduced to-70 ℃ with ethanol-liquid nitrogen system then, under this temperature, slowly drip 10.4g (0.1mol) trimethyl borate, dropwising the back makes it rise to room temperature naturally under agitation condition, dripping 10% HCl solution to pH value then is 1, is heated to 100 ℃ and refluxes 1 hour down.With behind the petroleum ether extraction water of 100ml * 3, use the saturated common salt water washing again reaction solution cooling back, spend the night with anhydrous sodium sulfate drying to neutral.Dried solution revolved steam solution, obtain 19.8g4-(trans-4 '-propyl group cyclohexyl)-2,6-two fluoro-phenylo boric acids, yield 70%.
2,4 '-(4 "-trans-propyl group cyclohexyl)-3,4,2 ', 6 '-tetrafluoro-2-methoxyl biphenyl
In the 250ml there-necked flask, add 11.3g (0.04mol) 4-(trans-4 '-propyl group cyclohexyl)-2,6-two fluoro-phenylo boric acids, 9.0g (0.04mol) 3,4-difluoro-2-methoxyl bromobenzene, 100ml benzene, 50ml dehydrated alcohol, 12g yellow soda ash, 4g water and 0.95g four (triphenylphosphine) close palladium, are heated to 70 ℃ of 24 hours postcooling that reflux down to room temperature.Tell organic phase,, merge the organic phase after washing, use anhydrous sodium sulfate drying to neutral with 100ml * 3 chloroform extraction waters.Dried solution revolved steam solution, obtain white crude product 13.9g, use the dehydrated alcohol recrystallization, obtain 10.5g4 '-(4 "-trans-propyl group cyclohexyl)-3,4, the white crystal of 2 ', 6 '-tetrafluoro-2-methoxyl biphenyl, yield 69%.
54.5 ℃ of N I of DSC (differential scanning calorimeter): Cr
IR: wave number/cm
-1=3010,2958,2860,1865,1615,1585,1560,1486,1475,1420,1387,1315,1285,1238,1175,1128,1080,965,945,860,813,772,658,627,615,540
MS(m/z)：380(M
+)，337，322，311，297，296，283，282，269，255，237，219，201，193，188，155，143，127，109，95，85，81，69，55，43
Proof gained compound is correct.
Can obtain with identical method:
4 '-(4 "-trans-methylcyclohexyl)-3,4,2 ', 6 '-tetrafluoro-2-methoxyl biphenyl,
4 '-(4 "-trans-ethyl cyclohexyl)-3,4,2 ', 6 '-tetrafluoro-2-methoxyl biphenyl,
4 '-(4 "-trans-butyl cyclohexyl)-3,4,2 ', 6 '-tetrafluoro-2-methoxyl biphenyl,
4 '-(4 "-trans-amyl group cyclohexyl)-3,4,2 ', 6 '-tetrafluoro-2-methoxyl biphenyl,
4 '-(4 "-trans-hexyl cyclohexyl)-3,4,2 ', 6 '-tetrafluoro-2-methoxyl biphenyl,
4 '-(4 "-trans-heptyl cyclohexyl)-3,4,2 ', 6 '-tetrafluoro-2-methoxyl biphenyl,
4 '-(4 "-trans-octyl group cyclohexyl)-3,4,2 ', 6 '-tetrafluoro-2-methoxyl biphenyl,
4 '-(4 "-trans-nonyl cyclohexyl)-3,4,2 ', 6 '-tetrafluoro-2-methoxyl biphenyl,
4 '-(4 "-trans-decyl cyclohexyl)-3,4,2 ', 6 '-tetrafluoro-2-methoxyl biphenyl.
Claims (7)
1. alkylcyclohexyl multiple-fluorine biphenyl derivative, its structural formula is formula I
Wherein, R is that carbonatoms is 1～10 straight chained alkyl; (A) be H or F.
2. alkylcyclohexyl multiple-fluorine biphenyl derivative according to claim 1 is characterized in that: described alkylcyclohexyl multiple-fluorine biphenyl derivative is:
4 '-(4 "-trans-amyl group cyclohexyl)-3,4,2 '-three fluoro-2-methoxyl biphenyls,
4 '-(4 "-trans-propyl group cyclohexyl)-3,4,2 ', 6 '-tetrafluoro-2-methoxyl biphenyl.
3. the preparation method of the described alkylcyclohexyl multiple-fluorine biphenyl derivative of claim 1, comprise the steps: 1) preparation 3,4-difluoro-2-methoxy boric acid: with 3,4-difluoro-2-methoxyl bromobenzene and MAGNESIUM METAL reaction generate Grignard reagent, react with trimethyl borate then, obtain structural formula after the hydrolysis suc as formula 3 of II, 4-difluoro-2-methoxy boric acid; 2) preparation alkylcyclohexyl multiple-fluorine biphenyl derivative: suc as formula 3 of II, the compound of 4-difluoro-2-methoxy boric acid and structural formula such as formula III carries out linked reaction under catalyst action, obtain described alkylcyclohexyl multiple-fluorine biphenyl derivative with structural formula; Described catalyzer is that four (triphenylphosphines) close palladium;
Wherein, R is that carbonatoms is 1～10 straight chained alkyl; (A) be H or F.
4. preparation method according to claim 3 is characterized in that: step 2) temperature of described linked reaction is 60-90 ℃, reaction solvent is benzene and dehydrated alcohol.
5. the preparation method of the described alkylcyclohexyl multiple-fluorine biphenyl derivative of claim 1, comprising the steps: 1) the preparation structural formula is the compound of formula IV: with structural formula compound and the MAGNESIUM METAL reaction generation Grignard reagent of formula III, with the trimethyl borate reaction, obtain the compound that structural formula is formula IV after the hydrolysis then; 2) preparation alkylcyclohexyl multiple-fluorine biphenyl derivative: with structural formula be the compound of formula IV and structural formula suc as formula 3 of V, 4-difluoro-2-methoxyl bromobenzene carries out linked reaction under catalyst action, obtain described alkylcyclohexyl multiple-fluorine biphenyl derivative; Described catalyzer is that four (triphenylphosphines) close palladium;
Wherein, R is that carbonatoms is 1～10 straight chained alkyl; (A) be H or F.
6. preparation method according to claim 5 is characterized in that: step 2) temperature of reaction of described linked reaction is 60-90 ℃, reaction solvent is benzene and dehydrated alcohol.
7. the application of the arbitrary described alkylcyclohexyl multiple-fluorine biphenyl derivative of claim 1-2 in the preparation liquid crystal display material.
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