CN111286343A - Bis-difluoromethoxy bridged biphenyl liquid crystal compound substituted by bis-fluorine-containing group as well as preparation method and application thereof - Google Patents

Bis-difluoromethoxy bridged biphenyl liquid crystal compound substituted by bis-fluorine-containing group as well as preparation method and application thereof Download PDF

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CN111286343A
CN111286343A CN202010088931.7A CN202010088931A CN111286343A CN 111286343 A CN111286343 A CN 111286343A CN 202010088931 A CN202010088931 A CN 202010088931A CN 111286343 A CN111286343 A CN 111286343A
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difluoromethoxy
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刘园
曾卓
王辉
刘银波
刘婷婷
张梅
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South China Normal University
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Abstract

The invention discloses a bifluoromethoxyl bridged biphenyl liquid crystal compound substituted by bifluoromethoxyl and a preparation method and application thereof, and particularly relates to a bifluoromethoxyl bridged biphenyl liquid crystal compound with different fluorine-containing groups (fluorine, fluoromethyl and difluoromethyl) at the lateral position of biphenyl, and the bifluoromethoxyl bridged biphenyl liquid crystal compound is analogousThe compound can effectively regulate and control the physical properties and the liquid crystal performance of the compound by changing the side fluorine-containing group and the terminal alkyl chain of the biphenyl, so that the compound has excellent liquid crystal performance, such as: wide nematic phase range, high dielectric constant, moderate refractive index, etc. The compound has a structure shown in formula 1:
Figure DDA0002383048560000011
wherein n is 3 or 5, m is 1 or 2, R is H or F, CH2F、CHF2。

Description

Bis-difluoromethoxy bridged biphenyl liquid crystal compound substituted by bis-fluorine-containing group as well as preparation method and application thereof
Technical Field
The invention relates to the field of liquid crystal materials, in particular to a bifluoro-group-substituted bifluoro methoxy-bridged biphenyl liquid crystal compound, and a preparation method and application thereof.
Background
As an important information electronic product, the liquid crystal display is one of the leading products of modern displays due to its light weight, small volume and low power consumption.
Fluorine-containing liquid crystals hold a very important position in the display field, particularly in thin film field effect transistor-driven liquid crystal displays. It has the advantages of low viscosity, high response speed, high dielectric constant and the like. The fluorine atoms are substituted close to hydrogen atoms in volume, so that the ordered arrangement of the liquid crystal cannot be influenced by the steric effect. Meanwhile, the fluorine atoms have higher electronegativity, and a certain dipole moment and electronic effect of the fluorine-containing liquid crystal structure can be ensured. At present, the synthesized liquid crystal monomer with high dielectric anisotropy can be mainly divided into the introduction of fluorine atoms or fluorine-containing groups (trifluoromethyl and trifluoromethoxy) to the lateral side and the tail end of a benzene ring, and the dielectric anisotropy of molecules is effectively increased by increasing the molecular polarity.
The biphenyl liquid crystal molecules without the central bridge bond have strong conjugation effect, thereby showing unique physical properties. Meanwhile, the biphenyl liquid crystal molecules have ideal length-width ratio, so that a wide mesomorphic range and a high nematic phase temperature range are presented. Therefore, such liquid crystals are commonly used in commercial mixed liquid crystals, and due to the existence of a plurality of benzene rings in the molecules of the liquid crystals, biphenyl liquid crystals have the defects of high viscosity, low response and the like. In recent years, researches show that the introduction of difluoromethoxy into a bridge bond can reduce the melting point of liquid crystal molecules, inhibit or eliminate smectic phases, widen the nematic phase temperature range, increase the dielectric constant and particularly effectively reduce the viscosity of the liquid crystal molecules.
In conclusion, the fluorine-containing group is combined with the characteristic that the dielectric constant of the liquid crystal molecule can be effectively improved and the viscosity of the liquid crystal molecule can be greatly reduced by the difluoromethoxy bridge bond, so that the synthesis of the bis-difluoromethoxy bridge-linked biphenyl liquid crystal compound with different fluorine-containing groups on the lateral positions of biphenyl has important significance for developing novel lateral high-dielectric anisotropy, low viscosity and high-response display materials.
Disclosure of Invention
One of the objectives of the present invention is to provide a bis-difluoromethoxy bridged biphenyl liquid crystal compound substituted by a bis-fluoro group, which specifically relates to a bis-difluoromethoxy bridged biphenyl liquid crystal compound with different fluoro groups (fluoro, fluoromethyl, difluoromethyl) on the side of biphenyl, wherein the compound can effectively control the physical properties and liquid crystal properties of the compound by changing the fluoro group on the upper side of biphenyl and the terminal alkyl chain, so that the compound has excellent liquid crystal properties, such as: wide nematic phase range, high dielectric constant, moderate refractive index, etc.
In order to achieve the above object, a first technical solution provided by the present invention is: 1. a bis-difluoromethoxy bridged biphenyl liquid crystal compound substituted by a bis-fluorine-containing group is characterized by having a structure shown as a formula 1:
Figure BDA0002383048540000021
wherein n is 3 or 5, m is 1 or 2, R is H or F, CH2F、CHF2。
The second purpose of the invention is to provide a preparation method of the bis-difluoromethoxy-bridged biphenyl liquid crystal compound substituted by the bis-fluorine-containing group; the preparation method comprises the following steps:
1) adding 5-hydroxy-2-bromobenzaldehyde into a dry 100mL single-neck round-bottom flask, adding 40mL methanol, controlling the temperature to be 0 ℃, slowly adding sodium borohydride, and reacting for 2 hours to obtain 5-hydroxy-2-bromobenzaldehyde;
2) adding the 5-hydroxy-2-bromobenzyl alcohol obtained in the step 1) into a 100mL two-neck round-bottom flask, vacuumizing, replacing nitrogen, adding 30mL dichloromethane, adding diethylaminosulfur trifluoride into a reaction system, and reacting for 12h to obtain 4-bromo-3-monofluoromethylphenol; the reaction formula is shown in formula 1:
Figure BDA0002383048540000031
3) adding the 5-hydroxy-2-bromobenzaldehyde obtained in the step 1) into a 100mL two-neck round-bottom flask, vacuumizing, replacing nitrogen, adding 30mL dichloromethane, adding diethylaminosulfur trifluoride into a reaction system, and reacting for 12h to obtain a product 4-bromo-3-difluoromethylphenol shown in a formula 1; the reaction formula is shown in formula 2:
Figure BDA0002383048540000032
4) dissolving Br-R compound in dichloromethane, adding triethylamine, cooling to-78 deg.C, dropping the dichloromethane solution of disulfate into the above reaction solution, stirring for 3 hr, and dropping Et within 30min3N.3 HF, dropwise adding a dichloromethane solution containing NBS, reacting for 3 hours, moving the reaction solution to room temperature, reacting overnight, and obtaining a product 3CCBr-R and/or 5CCBr-R in the formula 2 after the reaction is finished; the reaction formula is shown in formula 3:
Figure BDA0002383048540000041
5) 3CCBr-R and/or 5CCBr-R obtained in the step 4), pinacol ester diboron and PdCl2(dppf)2Dissolving potassium carbonate in dimethyl sulfoxide, heating to 100 ℃, and reacting for 12h to obtain the formula C3-CF2O-R/C5-CF2A liquid crystal compound represented by O-R; the reaction formula is shown as formula 4The following steps:
Figure BDA0002383048540000042
the mixing molar ratio of the 5-hydroxy-2-bromobenzaldehyde and the sodium borohydride in the step 1) is 1 (1-2).
The mixing molar ratio of the 5-hydroxy-2-bromobenzyl alcohol to the diethylamino sulfur trifluoride in the step 2) is 1: (1-2).
The mixing molar ratio of the 5-hydroxy-2-bromobenzaldehyde to the diethylamino sulfur trifluoride in the step 3) is 1: (1-2).
Step 4), the structural formula of the Br-R compound is shown as a formula 2, and the structural formula of the dithio salt is shown as a formula 3:
Figure BDA0002383048540000043
Figure BDA0002383048540000051
the structural formula of the 3CCBr-R and/or the 5CCBr-R in the step 4) is shown as a formula 4:
Figure BDA0002383048540000052
step 4) the Br-R compound, disulfite, triethylamine, Et3The mixed molar ratio of N-3HF to NBS is 1: (1-2): (3-5): (9-11): (9-11).
The dichloromethane solution of the disulfide salt in the step 4) is prepared by the following method: trans-4- (trans-4-n-propylcyclohexyl) cyclohexanecarboxylic acid or trans-4- (trans-4-n-pentylcyclohexyl) cyclohexanecarboxylic acid (3CCA/5CCA), toluene, isooctane and 1, 3-propanedithiol were charged in a dry 100mL round-bottomed flask. The mixture was heated to 50 ℃ with stirring, and trifluoromethanesulfonic acid was slowly added dropwise to the reaction solution using a dropping funnel. Heated to 102 ℃ and 104 ℃ and refluxed for about 4 hours. After the water separation is finished, removing the solvent, and adding 20mL of dichloromethane solution to obtain the product (the whole reaction process is protected by nitrogen).
Step 5) the 3CCBr-R and/or 5CCBr-R, the pinacol ester of diboron and PdCl2(dppf)2And the mixing molar ratio of the potassium carbonate is 1: (0.5-1): (1 mol% -10 mol%).
The invention also aims to provide application of the bifluoro-group-substituted bifluoromethoxybridged biphenyl liquid crystal compound, namely application in preparing liquid crystal display materials.
Compared with the prior art, the invention has the following advantages:
1. the synthetic method of the bifluoro-group-substituted bifluoromethoxybridging biphenyl liquid crystal compound is simple, convenient and easy, the raw materials are simple and easy to obtain, and the yield is good.
2. The bis-difluoromethoxy bridged biphenyl liquid crystal compound substituted by the bis-fluorine-containing group has the advantages of wide mesophase temperature range, high bright point definition, high dielectric constant, low viscosity, high birefringence and the like.
3. The bifluoro-group-substituted bifluoro methoxy-bridged biphenyl liquid crystal compound can adjust the physical properties such as the mesomorphic phase transition temperature, the dielectric constant, the viscosity, the birefringence and the like of a product by connecting different fluorine-containing groups on a benzene ring, and has the advantages of simple and convenient adjustment.
Drawings
FIG. 1 is the product of example 1, 4' -bis (difluoro (4' -propyl [1,1' -bis (cyclohexane))]-4-yl) methoxy) -1,1' -biphenyl (C)3-CF2O-H) differential scanning thermogram (DSC profile);
FIG. 2 is the product of example 2, 4' -bis (difluoro (4' -pentyl [1,1' -bis (cyclohexane) ]]-4-yl) methoxy) -1,1' -biphenyl (C)5-CF2O-H) differential scanning thermogram (DSC profile);
FIG. 3 is the product 4', 4' - (((2,2 '-difluoro- [1,1' -biphenyl) of example 3]-4,4 '-diyl) bis (oxy)) bis (difluoromethylene)) bis (4-propyl-1, 1' -bis (cyclohexane)) (C3-CF2O-F) differential scanning thermogram (DSC profile);
FIG. 4 is the product 4', 4' - (((2,2 '-difluoro- [1,1' -biphenyl) of example 4]-4,4' -diyl) bis(oxy)) bis (difluoromethylene)) bis (4-pentyl-1, 1' -bis (cyclohexane)) (C5-CF2O-F) differential scanning thermogram (DSC profile);
FIG. 5 is the product 4', 4' - (((2,2 '-bis (monofluoromethyl) - [1,1' -biphenyl) of example 5]-4,4 '-diyl) bis (oxy)) bis (difluoromethylene)) bis (4-pentyl-1, 1' -bis (cyclohexane)) (C3-CF2O-CH2F) Differential scanning thermogram (DSC profile);
FIG. 6 is the product 4', 4' - (((2,2 '-bis (monofluoromethyl) - [1,1' -biphenyl) of example 6]-4,4 '-diyl) bis (oxy)) bis (difluoromethylene)) bis (4-pentyl-1, 1' -bis (cyclohexane)) (C5-CF2O-CH2F) Differential scanning thermogram (DSC profile);
FIG. 7 is the product 4', 4' - (((2,2 '-bis (difluoromethyl) - [1,1' -biphenyl) of example 7]-4,4 '-diyl) bis (oxy)) bis (difluoromethylene)) bis (4-propyl-1, 1' -bis (cyclohexane)) (C3-CF2O-CHF2) Differential scanning thermogram (DSC profile);
FIG. 8 is the product 4', 4' - (((2,2 '-bis (difluoromethyl) - [1,1' -biphenyl) of example 8]-4,4 '-diyl) bis (oxy)) bis (difluoromethylene)) bis (4-pentyl-1, 1' -bis (cyclohexane)) (C5-CF2O-CHF2) Differential scanning thermogram (DSC profile);
FIG. 9 is the product of example 1, 4' -bis (difluoro (4' -propyl [1,1' -bis (cyclohexane))]-4-yl) methoxy) -1,1' -biphenyl (C)3-CF2O-H) polarization microscope spectra (POM spectra);
FIG. 10 is the product of example 2, 4' -bis (difluoro (4' -pentyl [1,1' -bis (cyclohexane) ]]-4-yl) methoxy) -1,1' -biphenyl (C)5-CF2O-H) polarization microscope spectra (POM spectra);
FIG. 11 is the product 4', 4' - (((2,2 '-difluoro- [1,1' -biphenyl) of example 3]-4,4 '-diyl) bis (oxy)) bis (difluoromethylene)) bis (4-propyl-1, 1' -bis (cyclohexane)) (C3-CF2O-F) polarization microscope spectra (POM spectra);
FIG. 12 is the product 4', 4' - (((2,2 '-difluoro- [1,1' -biphenyl) of example 4]-4,4' -diyl) Bis (oxy)) bis (difluoromethylene)) bis (4-pentyl-1, 1' -bis (cyclohexane)) (C5-CF2O-F) polarization microscope spectra (POM spectra);
FIG. 13 is the product 4', 4' - (((2,2 '-bis (monofluoromethyl) - [1,1' -biphenyl) of example 5]-4,4 '-diyl) bis (oxy)) bis (difluoromethylene)) bis (4-pentyl-1, 1' -bis (cyclohexane)) (C3-CF2O-CH2F) (ii) a polarizing microscope map (POM map);
FIG. 14 is the product 4', 4' - (((2,2 '-bis (monofluoromethyl) - [1,1' -biphenyl) of example 6]-4,4 '-diyl) bis (oxy)) bis (difluoromethylene)) bis (4-pentyl-1, 1' -bis (cyclohexane)) (C5-CF2O-CH2F) (ii) a polarizing microscope map (POM map);
FIG. 15 is the product 4', 4' - (((2,2 '-bis (difluoromethyl) - [1,1' -biphenyl) of example 7]-4,4 '-diyl) bis (oxy)) bis (difluoromethylene)) bis (4-propyl-1, 1' -bis (cyclohexane)) (C3-CF2O-CHF2) (ii) a polarizing microscope map (POM map);
FIG. 16 is the product 4', 4' - (((2,2 '-bis (difluoromethyl) - [1,1' -biphenyl) of example 8]-4,4 '-diyl) bis (oxy)) bis (difluoromethylene)) bis (4-pentyl-1, 1' -bis (cyclohexane)) (C5-CF2O-CHF2) (ii) a polarizing microscope spectrum (POM spectrum).
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
Example 1
4,4' -bis (difluoro (4' -propyl [1,1' -bis (cyclohexane))]-4-yl) methoxy) -1,1' -biphenyl (C)3-CF2O-H), comprising the following steps:
(1) synthesis of 1- (4- (4- (trans-4-n-propylcyclohexyl) cyclohexyldifluoromethoxy) bromobenzene (3 CCBr-1):
trans-4- (trans-4-n-propylcyclohexyl) cyclohexanecarboxylic acid 3CCA (2.9g, 0.01387mol) (structure
Figure BDA0002383048540000081
)，Toluene (10mL), isooctane (10mL) and 1, 3-propanedithiol (1.5mL, 0.01387mol) were added to a dry 100mL two-necked round bottom flask. The mixture was stirred at 50 ℃ for 1 hour, and trifluoromethanesulfonic acid (1.2mL, 0.01387mol) was slowly added dropwise to the reaction solution using a dropping funnel. Heated to 102 ℃ and 104 ℃ and refluxed for about 4 hours. After the water separation is finished, the solvent is removed by reduced pressure distillation, 20mL of dehydrated dichloromethane solution is added to obtain the dichloromethane solution of the disulfate (3CCB), and the whole reaction process is protected by nitrogen. Subsequently, p-bromophenol (2g, 0.01156mol), triethylamine (8mL, 0.0578mol) and 20mL of dehydrated dichloromethane solution were added to a 250mL dry single-neck round-bottom flask, and the temperature was lowered to-78 ℃ to slowly drop the disulfide salt (3CCB) in dichloromethane into the reaction flask (30min), and the reaction was carried out for 3 hours. Et was then added dropwise over 30 minutes3N.3HF (18.8mL, 0.1156mol), NBS (20.57g, 0.1156mol) dissolved in dichloromethane solution is added dropwise for 1 hour, then the reaction is carried out for 3 hours, the reaction solution is stirred overnight at room temperature, the reaction solution is poured into 30% sodium hydroxide solution with ice blocks, and the pH value is adjusted to 7-8. The mixture was extracted with dichloromethane three times, washed with saturated brine, and the organic layer was collected and dried over anhydrous sodium sulfate. Finally, column chromatography was performed with petroleum ether to obtain a white solid with a yield of 56%.
The structural characterization data for the product are:1H NMR(600MHz,CDCl3)δ7.46(d,2H J＝12Hz),7.06(d,2H,J＝6Hz),2.07-2.00(m,3H),1.86(d,2H,J＝12Hz),1.79-1.73(dd,4H,J＝12Hz,30Hz),1.41-1.28(m,6H),1.17(t,,3H,J＝12Hz),1.10-0.97(m,6H),0.90(t,3H,J＝12Hz)；13C NMR(150MHz,CDCl3)δ149.65,132.25,125.76(t,JC-F＝534Hz),123.44,118.16,43.76(t, JC-F＝52.5Hz),42.66,37.57,30.02,28.78,25.79,20.04,14.43；19F NMR(564MHz,CDCl3)δ -78.22(d,2F,J＝11.28Hz)；LRMS(EI)m/z:428(M)+；Elemental Analysis:C,61.46；H,7.40.
it is deduced from this that the product has the following structure and is 1- (4- (4- (trans-4-n-propylcyclohexyl) cyclohexyldifluoromethoxy) bromobenzene.
Figure BDA0002383048540000091
(2)4,4' -bis (difluoro (4' -propyl [1,1' -bis (cyclohexane))]-4-yl) methoxy) -1,1' -biphenyl (C)3-CF2O-H).
Mixing the product 3CCBr-1(0.5g, 0.00117mol) in (1), pinacol diboron (0.148g, 0.00058mol) and PdCl2(dppf)2(0.034g, 4% mol), potassium carbonate (0.485g, 0.00351mol) were dissolved in DMSO, heated to 100 ℃ and reacted for 12 h. After cooling, the mixture was filtered, extracted with dichloromethane, washed with water, and dried over anhydrous sodium sulfate. Finally, column chromatography is carried out by using petroleum ether to obtain a white solid with the yield of 35 percent.
The structural characterization data for the product are:1H NMR(600MHz,CDCl3)δ7.53(d,4H,J＝6Hz),7.24(d,4H,J＝12Hz),2.10-2.03(m,6H),1.87(d,4H,J＝6Hz),1.79-1.73(dd,8H,J＝12Hz,24Hz),1.44-1.28(m,12H),1.17(t,,6H,J＝12Hz),1.12-0.98(m,12H),0.90(t,6H,J＝12Hz)；19FNMR(564MHz,CDCl3)δ-77.93(d,2F,J＝5.64Hz)；LRMS(EI)m/z:698(M)+；ElementalAnalysis:C,75.49；H,9.04.
the structure of the product, 4' -bis (difluoro (4' -propyl [1,1' -bis (cyclohexane)), was deduced therefrom]-4-yl) methoxy) -1,1' -biphenyl (C)3-CF2O-H)。
Figure BDA0002383048540000101
Example 2
4,4' -bis (difluoro (4' -pentyl [1,1' -bis (cyclohexane) ])]-4-yl) methoxy) -1,1' -biphenyl (C)5-CF2O-H), comprising the following steps:
(1) synthesis of 1- (4- (4- (trans-4-n-pentylcyclohexyl) cyclohexyldifluoromethoxy) bromobenzene (5CCBr-1)
Trans-4- (trans-4-n-pentylcyclohexyl) cyclohexanecarboxylic acid 5CCA (5.835g, 0.02081mol) (structure
Figure BDA0002383048540000102
) Toluene (15mL), isooctane (15mL) and 1, 3-propanedithiolAlcohol (2.2mL, 0.02081mol) was added to a dry 100mL two-necked round bottom flask. The mixture was stirred at 50 ℃ for 1 hour, and trifluoromethanesulfonic acid (1.8mL, 0.02081mol) was slowly added dropwise to the reaction solution using a dropping funnel. Heated to 102 ℃ and 105 ℃, and then refluxed and water-separated for about 4 hours. After the water separation is finished, the solvent is removed by reduced pressure distillation, 20mL of dehydrated dichloromethane solution is added to obtain the dichloromethane solution of the disulfite (5CCB), and the whole reaction process is protected by nitrogen. Subsequently, p-bromophenol (3g, 0.01734mol), triethylamine (12mL, 0.0867mol) and 20mL of dehydrated dichloromethane solution were added to a 250mL dry single-neck round-bottom flask, and the temperature was lowered to-78 ℃, and then a dichloromethane solution of dithio salt (5CCB) was slowly dropped into the reaction flask (30min) to react for 3 hours. Et was then added dropwise over 30 minutes3N.3HF (28mL, 0.1734mol), NBS (30.86g, 0.1156mol) dissolved in dichloromethane solution is added dropwise for 1 hour, then the reaction is carried out for 3 hours, the reaction solution is stirred overnight at room temperature, the reaction solution is poured into 30% sodium hydroxide solution with ice blocks, and the pH value is adjusted to 7-8. The mixture was extracted with dichloromethane three times, washed with saturated brine, and the organic layer was collected and dried over anhydrous sodium sulfate. Finally, column chromatography was performed with petroleum ether to obtain a white solid with a yield of 61%.
The structural characterization data for the product are:1H NMR(600MHz,CDCl3)δ7.42(d,2H,J＝6Hz),7.04 (d,2H,J＝6Hz),2.04-1.96(m,3H),1.84(d,2H,J＝12Hz),1.77-1.70(dd,4H,J＝12Hz,30 Hz),1.38-1.22(m,9H),1.14(t,3H,J＝12Hz),1.06-0.94(m,7H),0.88(t,3H,J＝12Hz)；13C NMR(100MHz,CDCl3)δ149.63,132.21,125.72(t,JC-F＝536Hz),123.40,118.13,43.75(t, JC-F＝52Hz),42.65,37.43,32.22,30.01,28.77,26.66,25.80,22.71,14.11；19F NMR(564 MHz,CDCl3)δ-78.20(d,2F,J＝5.64Hz)；LRMS(EI)m/z:456(M)+；Elemental Analysis:C, 63.00；H,8.06.
it is deduced from this that the product has the following structure and is 1- (4- (4- (trans-4-n-pentylcyclohexyl) cyclohexyldifluoromethoxy) bromobenzene.
Figure BDA0002383048540000111
(2)4,4' -bis (difluoro (4' -pentyl [1,1' -bis (cyclohexane) ])]-4-yl) methoxy) -1,1' -biphenyl (C)5-CF2O-H) Synthesis
Mixing the product 5CCBr-1(0.5g, 0.00109mol) in the step (1), pinacol ester diboron (0.138g, 0.00054mol) and PdCl2(dppf)2(0.032g, 4% mol) and potassium carbonate (0.451g, 0.00327mol) were dissolved in DMSO, heated to 100 ℃ and reacted for 12 h. After cooling, the mixture was filtered, extracted with dichloromethane, washed with water, and dried over anhydrous sodium sulfate. Finally, column chromatography is carried out by using petroleum ether to obtain a white solid with the yield of 40 percent.
The structural characterization data for the product are:1H NMR(400MHz,CDCl3)δ7.47(d,4H,J＝8Hz),7.19(d,4H,J＝8Hz),2.05-1.97(m,6H),1.82(d,4H,J＝16Hz),1.71(t,8H,J＝20Hz),1.40-1.20(m,18H),1.12(t,6H,J＝12Hz),1.05-0.91(m,14H),0.85(t,6H,J＝16Hz)；19F NMR(376MHz,CDCl3)δ-77.96(d,2F,J＝11.28Hz)；Elemental Analysis:C,76.52；H,9.88.
the structure of the product, 4' -bis (difluoro (4' -propyl [1,1' -bis (cyclohexane)), was deduced therefrom]-4-yl) methoxy) -1,1' -biphenyl (C)5-CF2O-H)。
Figure BDA0002383048540000121
Example 3
4', 4' - (((2,2 '-difluoro- [1,1' -biphenyl)) is]-4,4 '-diyl) bis (oxy)) bis (difluoromethylene)) bis (4-propyl-1, 1' -bis (cyclohexane)) (C3-CF2O-F) comprising the following steps:
(1) synthesis of 4- ((4-bromo-3-fluorophenoxy) difluoromethyl) -4 '-propyl-1, 1' -bicyclohexane (3CCBr-2)
Trans-4- (trans-4-n-propylcyclohexyl) cyclohexanecarboxylic acid 3CCA (4.755g, 0.01884mol) (structure
Figure BDA0002383048540000122
) Toluene (15mL), isooctane (15mL) and 1, 3-propanedithiol (2mL, 0.01884mol) were addedInto a dry 100mL two-neck round bottom flask. The mixture was stirred at 50 ℃ for 1 hour, and trifluoromethanesulfonic acid (1.7mL, 0.01884mol) was slowly added dropwise to the reaction solution using a dropping funnel. Heated to 102 ℃ and 105 ℃, and then refluxed and water-separated for about 4 hours. After the water separation is finished, the solvent is removed by reduced pressure distillation, 20mL of dehydrated dichloromethane solution is added to obtain the dichloromethane solution of the disulfite (3CCB), and the whole reaction process is protected by nitrogen. Subsequently, p-4-bromo-3-fluorophenol (3g, 0.0157mol), triethylamine (11mL, 0.0785mol) and 20mL of the dehydrated dichloromethane solution were added to a 250mL dry single-neck round-bottom flask, and the temperature was reduced to-78 ℃, and then the disulfide salt (3CCB) in dichloromethane was slowly added dropwise to the reaction flask (30min) and reacted for 3 hours. Et was then added dropwise over 30 minutes3N.3HF (26mL, 0.157mol), NBS (27.94g, 0.157mol) dissolved in methylene chloride solution was added dropwise for 1 hour, and then reacted for 3 hours, the reaction mixture was stirred overnight at room temperature, and the reaction mixture was poured into 30% sodium hydroxide solution with ice and pH was adjusted to 7 to 8. The mixture was extracted with dichloromethane three times, washed with saturated brine, and the organic layer was collected and dried over anhydrous sodium sulfate. Finally, column chromatography was performed with petroleum ether to obtain a white solid with a yield of 53%.
The structural characterization data for the product are:1H NMR(600MHz,CDCl3)δ7.51(t,1H,JH-F＝18Hz),7.00-6.98(dd,1H,JH-F＝6Hz,JH-H＝12Hz),6.90(d,1H,J＝12Hz),2.06-1.99(m,3H),1.86(d,2H,J＝6Hz),1.79-1.73(dd,4H,J＝12Hz,30Hz),1.40-1.28(m,6H),1.17(t,3H,J＝12Hz),1.10-0.97(m,6H),0.90(t,3H,J＝18Hz)；13C NMR(100MHz,CDCl3)δ158.85(d,JC-F＝247Hz),150.65(d,JC-F＝9Hz),133.22,125.78(t,JC-F＝536Hz),118.42(d,JC-F＝3Hz),110.48(d,JC-F＝25Hz),104.82(d,JC-F＝21Hz),43.69(t,JC-F＝52Hz),42.62,37.55,29.99,28.72,25.70,20.02,14.40；19F NMR(564MHz,CDCl3)δ–78.56(d,2F,J＝11.28Hz), -104.51(t,1F,J＝22.56Hz)；LRMS(EI)m/z:446(M)+；Elemental Analysis:C,59.03；H,6.88.
it is concluded therefrom that the product has the following structure 4- ((4-bromo-3-fluorophenoxy) difluoromethyl) -4 '-propyl-1, 1' -bicyclohexane.
Figure BDA0002383048540000131
(2)4', 4' - (((2,2 '-difluoro- [1,1' -biphenyl)) is]-4,4 '-diyl) bis (oxy)) bis (difluoromethylene)) bis (4-propyl-1, 1' -bis (cyclohexane)) (C3-CF2O-F) synthesis.
Mixing the product 3CCBr-2(0.5g, 0.0011mol) in the step (1), pinacol ester diboron (0.142g, 0.00056mol) and PdCl2(dppf)2(0.032g, 4% mol) and potassium carbonate (0.46g, 0.0033mol) were dissolved in DMSO, heated to 100 ℃ and reacted for 12 hours. After cooling, the mixture was filtered, extracted with dichloromethane, washed with water, and dried over anhydrous sodium sulfate. Finally, column chromatography is carried out by using petroleum ether to obtain a white solid with the yield of 32 percent.
The structural characterization data for the product are:1H NMR(600MHz,CDCl3)δ7.31(t,2H,JH-F＝18Hz),7.04(d,1H,J＝6Hz),7.30(d,1H,J＝6Hz),2.06-2.02(m,6H),1.86(d,4H,J＝6Hz),1.77-1.71(dd,8H,J＝12Hz,24Hz),1.40-1.29(m,12H),1.15(t,6H,J＝18Hz),1.08-0.95(m,12H),0.87(t,6H,J＝18Hz)；19F NMR(564MHz,CDCl3)δ–78.40(d,4F,J＝5.64Hz),-112.18(t, 2F,J＝11.28Hz)；LRMS(EI)m/z:734(M)+；Elemental Analysis:C,71.90；H,8.52.
it is concluded from this that the structure of the product is 4', 4' - (((2,2 '-difluoro- [1,1' -biphenyl) s]-4,4 '-diyl) bis (oxy)) bis (difluoromethylene)) bis (4-propyl-1, 1' -bis (cyclohexane)) (C3-CF2O-F)。
Figure BDA0002383048540000141
Example 4
4', 4' - ((((2, 2 '-difluoro- [1,1' -biphenyl)) s]-4,4 '-diyl) bis (oxy)) bis (difluoromethylene)) bis (4-pentyl-1, 1' -bis (cyclohexane)) (C5-CF2O-F) comprising the following steps:
(1) synthesis of 4- ((4-bromo-3-fluorophenoxy) difluoromethyl) -4 '-pentyl-1, 1' -bicyclohexane (5CCBr-2)
Trans-4- (trans-4-n-propylcyclohexyl) cyclohexanecarboxylic acid 5CCA (5.283g, 0.01884mol) (structure
Figure BDA0002383048540000142
) Toluene (15mL), isooctane (15mL) and 1, 3-propanedithiol (2mL, 0.01884mol) were added to a dry 100mL two-necked round bottom flask. The mixture was stirred at 50 ℃ for 1 hour, and trifluoromethanesulfonic acid (1.7mL, 0.01884mol) was slowly added dropwise to the reaction solution using a dropping funnel. Heated to 102 ℃ and 105 ℃, and then refluxed and water-separated for about 4 hours. After the water separation is finished, the solvent is removed by reduced pressure distillation, 20mL of dehydrated dichloromethane solution is added to obtain the dichloromethane solution of the disulfite (5CCB), and the whole reaction process is protected by nitrogen. Subsequently, p-4-bromo-3-fluorophenol (3g, 0.0157mol), triethylamine (11mL, 0.0785mol) and 20mL of the dehydrated dichloromethane solution were added to a 250mL dry single-neck round-bottom flask, and the temperature was reduced to-78 ℃, and then the disulfide salt (5CCB) in dichloromethane was slowly added dropwise to the reaction flask (30min) and reacted for 3 hours. Et was then added dropwise over 30 minutes3N.3HF (26mL, 0.157mol), NBS (27.94g, 0.157mol) dissolved in methylene chloride solution was added dropwise for 1 hour, and then reacted for 3 hours, the reaction mixture was stirred overnight at room temperature, and the reaction mixture was poured into 30% sodium hydroxide solution with ice and pH was adjusted to 7 to 8. The mixture was extracted with dichloromethane three times, washed with saturated brine, and the organic layer was collected and dried over anhydrous sodium sulfate. Finally, column chromatography was performed with petroleum ether to obtain a white solid with a yield of 62%.
The structural characterization data for the product are:1H NMR(600MHz,CDCl3)δ7.48(t,1H,JH-F＝12Hz),7.00-6.98(dd,1H,JH-F＝6Hz,JH-H＝12Hz),6.87(d,1H,J＝6Hz),2.03-1.96(m,3H),1.84(d,2H,J＝12Hz),1.77-1.70(dd,4H,J＝12Hz,30Hz),1.37-1.23(m,9H),1.14(t,3H,J＝18Hz),1.09-0.95(m,7H),0.88(t,3H,J＝12Hz)；13C NMR(150MHz,CDCl3)δ159.15(d,JC-F＝246Hz),150.95(d,JC-F＝10.5Hz),133.51,126.09(t,JC-F＝538.5Hz),118.72(d,JC-F＝3Hz),110.79(d,JC-F＝24Hz),105.11(d,JC-F＝21Hz),43.98(t,JC-F＝51Hz),42.90,37.68,32.47,30.28,29.00,26.90,25.98,22.96,14.36；19F NMR(564MHz,CDCl3)δ–78.54(d,2F,J＝5.64Hz),-104.52(t,1F,J＝16.92Hz)；LRMS(EI)m/z:474(M)+；Elemental Analysis:C,60.67；H, 7.38.
it is concluded therefrom that the structure of the product is 4- ((4-bromo-3-fluorophenoxy) difluoromethyl) -4 '-pentyl-1, 1' -bicyclohexane.
Figure BDA0002383048540000151
(2)4', 4' - ((((2, 2 '-difluoro- [1,1' -biphenyl)) s]-4,4 '-diyl) bis (oxy)) bis (difluoromethylene)) bis (4-pentyl-1, 1' -bis (cyclohexane)) (C5-CF2O-F)
Mixing the product 5CCBr-2(0.68g, 0.00143mol) in (1), pinacol diboron (0.181g, 0.00071mol) and PdCl2(dppf)2(0.042g, 4% mol), potassium carbonate (0.592g, 0.00429mol) were dissolved in DMSO, heated to 100 ℃ and reacted for 12 h. After cooling, the mixture was filtered, extracted with dichloromethane, washed with water, and dried over anhydrous sodium sulfate. Finally, column chromatography is carried out by using petroleum ether to obtain a white solid with the yield of 39%.
The structural characterization data for the product are:1H NMR(600MHz,CDCl3)δ7.33(t,2H,JH-F＝12Hz),7.07-7.02(m,6H),2.09-2.03(m,6H),1.88(d,4H,J＝12Hz),1.80-1.73(dd,8H,J＝12Hz,30Hz),1.43-1.26(m,21H),1.17(t,6H,J＝12Hz),1.10-0.98(m,11H),0.91(t,6H,J＝12Hz)；13C NMR(150MHz,CDCl3)δ159.63(d,JC-F＝250.5Hz),151.39,131.61,125.96(t,JC-F＝537Hz),119.64(d,JC-F＝10.5Hz),117.05,110.50(d,JC-F＝25.5Hz),43.84(t,JC-F＝52.5Hz),42.70,37.46,32.25,30.06,28.81,26.68,25.79,22.73,14.13；19F NMR(564MHz,CDCl3)δ–78.38(d,4F,J＝11.28Hz),-112.18(t,2F,J＝11.28Hz)；Elemental Analysis:C,72.96；H,8.76.
from which the product is deducedHas the following structure of 4', 4' - (((2,2 '-difluoro- [1,1' -biphenyl) group]-4,4 '-diyl) bis (oxy)) bis (difluoromethylene)) bis (4-propyl-1, 1' -bis (cyclohexane)) (C5-CF2O-F)。
Figure BDA0002383048540000161
Example 5
4', 4' - (((2,2 '-bis (monofluoromethyl) - [1,1' -biphenyl)]-4,4 '-diyl) bis (oxy)) bis (difluoromethylene)) bis (4-pentyl-1, 1' -bis (cyclohexane)) (C3-CF2O-CH2F) The synthesis comprises the following steps:
(1) 5-hydroxy-2-bromobenzyl alcohol (Br-CH)2OH) Synthesis
5-hydroxy-2-bromobenzaldehyde (3g, 0.01395mol) was added to a dry 100mL single neck round bottom flask, 40mL methanol was added, the temperature was controlled at 0 deg.C, and NaBH was slowly added4(0.686g, 0.01814mol), after 2 hours of reaction, the solvent was dried, extracted with ethyl acetate, washed with water, dried over anhydrous sodium sulfate, and finally treated with petroleum ether: column chromatography of ethyl acetate (V: V ═ 3:1) afforded a white solid in 85% yield.
The structural characterization data for the product are:1H NMR(400MHz,(CD3)2SO)δ9.63(s,1H),7.30(d,1H,J＝8Hz),7.00(s,1H),6.61-6.58(dd,1H,J＝4Hz,8Hz),5.38(t,1H,J＝12Hz),4.42(d,2H,J＝4Hz)；13C NMR(100MHz,(CD3)2SO)δ157.40,142.37,132.84,115.80,115.43,109.33,62.89.
it is concluded therefrom that the product has the following structure, 5-hydroxy-2-bromobenzyl alcohol (Br-CH)2OH)。
Figure BDA0002383048540000171
(2) 4-bromo-3-monofluoromethylphenol (Br-CH)2F) Synthesis of (2)
Adding the product (2g, 0.0092mol) in (1) into a 100mL two-neck round-bottom flask, vacuumizing, replacing nitrogen, adding 40mL dichloromethane, adding DAST (1.4mL, 0.0101mol) into the reaction system, reacting for 12h, quenching with saturated sodium bicarbonate solution until no bubbles are emitted, extracting with dichloromethane, washing with water, drying with anhydrous sodium sulfate, and adding petroleum ether: column chromatography of ethyl acetate (V: V ═ 20:1) gave a colorless, transparent liquid with a yield of 95%.
The structural characterization data for the product are:1H NMR(400MHz,(CD3)2SO)δ9.92(s,1H)7.42(d,1H,J＝12Hz),6.98(s,1H),6.79-6.76(dd,1H,JH-H＝8Hz,JH-F＝4Hz),5.49(d,1H,JH-F＝48Hz)；13CNMR(100MHz,(CD3)2SO)δ157.54,136.40(d,JC-F＝16Hz),133.62,117.98,116.98(d, JC-F＝8Hz),110.29(d,JC-F＝4Hz),83.86(d,JC-F＝165Hz)；19F NMR(376MHz,(CD3)2SO)δ–211.49(t,1F,JF-H＝91Hz).
it is concluded from this that the product has the following structure, 4-bromo-3-fluoromethylphenol (Br-CH)2F)。
Figure BDA0002383048540000172
(3) Synthesis of 4- ((4-bromo-3- (monofluoromethyl) phenoxy) difluoromethyl) -4 '-propyl-1, 1' -bis (cyclohexane) (3CCBr-3)
Trans-4- (trans-4-n-propylcyclohexyl) cyclohexanecarboxylic acid 3CCA (2.239g, 0.00887mol) (structure
Figure BDA0002383048540000173
) Toluene (10mL), isooctane (10mL) and 1, 3-propanedithiol (0.9mL, 0.00887mol) were added to a dry 100mL two-necked round bottom flask. The mixture was stirred at 50 ℃ for 1 hour, and trifluoromethanesulfonic acid (0.8mL, 0.00887mol) was slowly added dropwise to the reaction solution using a dropping funnel. Heated to 102 ℃ and 105 ℃, and then refluxed and water-separated for about 4 hours. After the water separation is finished, the solvent is removed by reduced pressure distillation, 20mL of dehydrated dichloromethane solution is added to obtain the dichloromethane solution of the disulfite (3CCB), and the whole reaction process is protected by nitrogen. Subsequently, 4-bromo-3-fluoromethylphenol (1.523g, 0.00739mol), triethylamine (5mL, 0.0369mol) and 20mL the methylene dichloride solution after water removal is added into a 250mL dry single-neck round-bottom flask, the temperature is reduced to-78 ℃, and then the methylene dichloride solution of the disulfite (3CCB) is slowly dripped into a reaction bottle (30min) to react for 3 hours. Et was then added dropwise over 30 minutes3N.3HF (12mL, 0.0739mol), NBS (13.15g, 0.0739mol) dissolved in methylene chloride solution was added dropwise for 1 hour, and then the reaction was further carried out for 3 hours, the reaction mixture was stirred overnight at room temperature, and the reaction mixture was poured into 30% sodium hydroxide solution with ice and the pH was adjusted to 7 to 8. The mixture was extracted with dichloromethane three times, washed with saturated brine, and the organic layer was collected and dried over anhydrous sodium sulfate. Finally, column chromatography was performed with petroleum ether to obtain a white solid with a yield of 67%.
The structural characterization data for the product are:1H NMR(600MHz,CDCl3)δ7.49(d,1H,J＝6Hz),7.27(d,1H,J＝6Hz),7.05-7.03(dd,1H,JH-F＝2.4Hz,J＝8.4Hz),5.43(d,2H,JH-F＝48Hz), 2.05-1.97(m,3H),1.84(d,2H,J＝12Hz),1.77-1.70(dd,4H,J＝18Hz,30Hz),1.39-1.25(m, 6H),1.14(t,3H,J＝12Hz),1.09-0.95(m,6H),0.87(t,3H,J＝12Hz)；13C NMR(150MHz, CDCl3)δ150.02,137.07(d,JC-F＝18Hz),133.19,125.84(t,JC-F＝535.5Hz),122.94,121.51 (d,J＝10.5Hz),116.59(d,JC-F＝6Hz),83.23(d,JC-F＝169.5Hz),43.80(t,JC-F＝55.5Hz), 42.69,37.60,30.05,28.81,25.82,20.07,14.45；19F NMR(564MHz,CDCl3)δ–78.14(d,2F,J ＝5.64Hz),-218.42(t,1F,JF-H＝90.24Hz)；LRMS(EI)m/z:460(M)+；Elemental Analysis: C,61.12；H,7.62.
it is concluded from this that the product has the following structure, 4- ((4-bromo-3- (fluoromethyl) phenoxy) difluoromethyl) -4 '-propyl-1, 1' -bis (cyclohexane) (3 CCBr-3).
Figure BDA0002383048540000191
(4)4', 4' - (((2,2 '-bis (monofluoromethyl) - [1,1' -biphenyl)]-4,4 '-diyl) bis (oxy)) bis (difluoromethylene)) bis (4-propyl-1, 1' -bis (cyclohexane)) (C3-CF2O-CH2F) The synthesis of (4).
Mixing the product 3CCBr-3(0.4975g, 0.00108mol) in the step (3), pinacol diboron (0.137g, 0.00054mol) and PdCl2(dppf)2(0.0315g, 4% mol) and potassium carbonate (0.447g, 0.0034mol) were dissolved in DMSO, heated to 100 ℃ and reacted for 12 hours. After cooling, the mixture was filtered, extracted with dichloromethane, washed with water, and dried over anhydrous sodium sulfate. Finally, column chromatography is carried out by using petroleum ether to obtain a white solid with the yield of 35 percent.
The structural characterization data for the product are:1H NMR(400MHz,CDCl3)δ7.27(s,2H),7.13(d,2H,J＝8Hz),7.06(d,2H,J＝8Hz),4.97(d,4H,J＝48Hz),2.01-1.92(m,6H),1.78(d,4H,J＝12Hz),1.67(t,8H,J＝28Hz),1.36-1.18(m,12H),1.07-0.87(m,18H),0.81(t,6H,J＝12Hz)；13CNMR(100MHz,CDCl3)δ150.79,136.03,(d,JC-F＝16Hz),134.95(d,JC-F＝5Hz),131.23,126.17(t,JC-F＝535.5Hz),121.52(d,JC-F＝8Hz),121.8(d,JC-F＝4Hz),121.66(d,JC-F＝3Hz),82.21(d,JC-F＝166Hz),44.14(t,JC-F＝52Hz),42.95,37.72,30.30,29.08,26.94,22.98, 14.38；19F NMR(376MHz,CDCl3)δ-78.02(d,4F,J＝7.52Hz),-207.79(t,2F,JF-H＝94Hz)
it is concluded from this that the structure of the product is 4', 4' - ((((2, 2 '-bis (monofluoromethyl) - [1,1' -biphenyl)]-4,4 '-diyl) bis (oxy)) bis (difluoromethylene)) bis (4-propyl-1, 1' -bis (cyclohexane)) (C3-CF2O-CH2F)。
Figure BDA0002383048540000201
Example 6
4', 4' - (((2,2 '-bis (monofluoromethyl) - [1,1' -biphenyl)]-4,4 '-diyl) bis (oxy)) bis (difluoromethylene)) bis (4-pentyl-1, 1' -bis (cyclohexane)) (C5-CF2O-CH2F) The synthesis comprises the following steps:
(1) 5-hydroxy-2-bromobenzyl alcohol (Br-CH)2OH) Synthesis
Adding 5-hydroxyPhenyl-2-bromobenzaldehyde (3g, 0.01395mol) was added to a dry 100mL single neck round bottom flask, 40mL methanol was added, the temperature was controlled at 0 deg.C, and NaBH was slowly added4(0.686g, 0.01814mol), after 2 hours of reaction, the solvent was dried, extracted with ethyl acetate, washed with water, dried over anhydrous sodium sulfate, and finally treated with petroleum ether: column chromatography of ethyl acetate (V: V ═ 3:1) afforded a white solid in 85% yield.
The structural characterization data for the product are:1H NMR(400MHz,(CD3)2SO)δ9.63(s,1H),7.30(d,1H,J＝8Hz),7.00(s,1H),6.61-6.58(dd,1H,J＝4Hz,8Hz),5.38(t,1H,J＝12Hz),4.42(d,2H,J＝4Hz)；13C NMR(100MHz,(CD3)2SO)δ157.40,142.37,132.84,115.80,115.43,109.33,62.89.
it is concluded therefrom that the product has the following structure, 5-hydroxy-2-bromobenzyl alcohol (Br-CH)2OH)。
Figure BDA0002383048540000202
(2) 4-bromo-3-monofluoromethylphenol (Br-CH)2F) Synthesis of (2)
Adding the product (2g, 0.0092mol) in (1) into a 100mL two-neck round-bottom flask, vacuumizing, replacing nitrogen, adding 40mL dichloromethane, adding DAST (1.4mL, 0.0101mol) into the reaction system, reacting for 12h, quenching with saturated sodium bicarbonate solution until no bubbles are emitted, extracting with dichloromethane, washing with water, drying with anhydrous sodium sulfate, and adding petroleum ether: column chromatography of ethyl acetate (V: V ═ 20:1) gave a colorless, transparent liquid with a yield of 95%.
The structural characterization data for the product are:1H NMR(400MHz,(CD3)2SO)δ9.92(s,1H)7.42(d,1H,J＝12Hz),6.98(s,1H),6.79-6.76(dd,1H,JH-H＝8Hz,JH-F＝4Hz),5.49(d,1H,JH-F＝48Hz)；13CNMR(100MHz,(CD3)2SO)δ157.54,136.40(d,JC-F＝16Hz),133.62,117.98,116.98(d, JC-F＝8Hz),110.29(d,JC-F＝4Hz),83.86(d,JC-F＝165Hz)；19F NMR(376MHz,(CD3)2SO)δ–211.49(t,1F,JF-H＝91Hz).
it is concluded from this that the product has the following structure, 4-bromo-3-fluoromethylphenol (Br-CH)2F)。
Figure BDA0002383048540000211
(3) Synthesis of 4- ((4-bromo-3- (monofluoromethyl) phenoxy) difluoromethyl) -4 '-pentyl-1, 1' -bis (cyclohexane) (5CCBr-3)
Trans-4- (trans-4-n-pentylcyclohexyl) cyclohexanecarboxylic acid 5CCA (2.487g, 0.00887mol) (structure
Figure BDA0002383048540000212
) Toluene (10mL), isooctane (10mL) and 1, 3-propanedithiol (0.9mL, 0.00887mol) were added to a dry 100mL two-necked round bottom flask. The mixture was stirred at 50 ℃ for 1 hour, and trifluoromethanesulfonic acid (0.8mL, 0.00887mol) was slowly added dropwise to the reaction solution using a dropping funnel. Heated to 102 ℃ and 105 ℃, and then refluxed and water-separated for about 4 hours. After the water separation is finished, the solvent is removed by reduced pressure distillation, 20mL of dehydrated dichloromethane solution is added to obtain the dichloromethane solution of the disulfite (5CCB), and the whole reaction process is protected by nitrogen. Subsequently, 4-bromo-3-fluoromethylphenol (1.523g, 0.00739mol), triethylamine (5mL, 0.0369mol) and 20mL of the dehydrated dichloromethane solution were added to a 250mL dry single-neck round-bottom flask, and the temperature was reduced to-78 deg.C, and then the dithionium salt (5CCB) in dichloromethane was slowly added dropwise to the reaction flask (30min) and reacted for 3 hours. Et was then added dropwise over 30 minutes3N.3HF (12mL, 0.0739mol), NBS (13.15g, 0.0739mol) dissolved in methylene chloride solution was added dropwise for 1 hour, and then the reaction was further carried out for 3 hours, the reaction mixture was stirred overnight at room temperature, and the reaction mixture was poured into 30% sodium hydroxide solution with ice and the pH was adjusted to 7 to 8. The mixture was extracted with dichloromethane three times, washed with saturated brine, and the organic layer was collected and dried over anhydrous sodium sulfate. Finally, column chromatography is carried out by using petroleum ether to obtain a white solid with the yield of 65 percent.
The structural characterization data for the product are:1H NMR(600MHz,CDCl3)δ7.52(d,1H,J＝12Hz),7.30(s,1H),7.08-7.06(dd,1H,JH-F＝2.4Hz,J＝8.4Hz),5.45(d,2H,JH-F＝48Hz),2.07-2.00(m,3H),1.87(d,2H,J＝12Hz),1.80-1.73(dd,4H,J＝12Hz,30Hz),1.42-1.25(m,9H),1.17(t,3H,J＝12Hz),1.09-0.97(m,7H),0.91(t,3H,J＝18Hz)；13C NMR(150MHz,CDCl3)δ 150.20,137.06(d,JC-F＝18Hz),133.18,125.83(t,JC-F＝535.5Hz),122.93,121.51(d,J＝10.5Hz),116.59(d,JC-F＝4.5Hz),83.22(d,JC-F＝201Hz),43.80(t,JC-F＝52.5Hz),42.69,37.45, 32.24,30.05,28.81,26.67,25.81,22.72,14.13；19F NMR(564MHz,CDCl3)δ–78.14(d,2F,J ＝5.64Hz),-218.39(t,1F,JF-H＝95.88Hz)；LRMS(EI)m/z:488(M)+；ElementalAnalysis: C,61.41；H,7.83.
it is concluded therefrom that the product has the following structure 4- ((4-bromo-3- (monofluoromethyl) phenoxy) difluoromethyl) -4 '-pentyl-1, 1' -bis (cyclohexane) (5 CCBr-3).
Figure BDA0002383048540000221
(4)4', 4' - (((2,2 '-bis (monofluoromethyl) - [1,1' -biphenyl)]-4,4 '-diyl) bis (oxy)) bis (difluoromethylene)) bis (4-pentyl-1, 1' -bis (cyclohexane)) (C5-CF2O-CH2F) The synthesis of (4).
Mixing the product 5CCBr-3(0.597g, 0.00122mol) in (3), pinacol diboron (0.154g, 0.00061mol) and PdCl2(dppf)2(0.035g, 4% mol) and potassium carbonate (0.505g, 0.00366mol) were dissolved in DMSO, heated to 100 ℃ and reacted for 12 hours. After cooling, the mixture was filtered, extracted with dichloromethane, washed with water, and dried over anhydrous sodium sulfate. Finally, column chromatography is carried out by using petroleum ether to obtain a white solid with the yield of 38%.
The structural characterization data for the product are:1H NMR(600MHz,CDCl3)δ7.38(s,2H),7.25(d,2H,J＝6Hz),7.18(d,2H,J＝6Hz),5.08(d,4H,J＝48Hz),2.12-2.04(m,6H),1.89(d,4H,J＝12Hz),1.81-1.75(dd,8H,J＝12Hz,24Hz),1.46-1.26(m,18H),1.18(t,6H,J＝12Hz),1.12-1.01(m, 14H),0.91(t,6H,J＝18Hz)；13C NMR(100MHz,CDCl3)δ150.50,135.73(d,JC-F＝17Hz),134.68(d,JC-F＝5Hz),130.97,125.90(t,JC-F＝535.5Hz),121.54(d,JC-F＝7Hz),121.41(d,JC-F＝2Hz),81.97(d,JC-F＝166Hz),43.86(t,JC-F＝53Hz),42.67,37.42,32.21,30.02,28.80, 26.65,25.82,22.70,14.10；19F NMR(564MHz,CDCl3)δ-77.98(d,4F,J＝5.64Hz),-207.76 (t,2F,JF-H＝95.88Hz)；Elemental Analysis:C,73.65；H,9.31.
it is concluded from this that the structure of the product is 4', 4' - ((((2, 2 '-bis (monofluoromethyl) - [1,1' -biphenyl)]-4,4 '-diyl) bis (oxy)) bis (difluoromethylene)) bis (4-pentyl-1, 1' -bis (cyclohexane)) (C5-CF2O-CH2F)。
Figure BDA0002383048540000231
Example 7
4', 4' - (((2,2 '-bis (difluoromethyl) - [1,1' -biphenyl)]-4,4 '-diyl) bis (oxy)) bis (difluoromethylene)) bis (4-propyl-1, 1' -bis (cyclohexane)) (C3-CF2O-CHF2) The synthesis comprises the following steps:
(1) 4-bromo-3-difluoromethylphenol (Br-CHF)2) Synthesis of (2)
Adding 5-hydroxy-2-bromobenzaldehyde (2g, 0.0093mol) into a 100mL two-neck round-bottom flask, vacuumizing, replacing nitrogen, adding 40mL dichloromethane, adding DAST (2.1mL, 0.0158mol) into the reaction system, reacting for 12h, quenching with saturated sodium bicarbonate solution until no bubble appears, extracting with dichloromethane, washing with water, drying with anhydrous sodium sulfate, and adding petroleum ether: column chromatography of ethyl acetate (V: V ═ 20:1) gave a colorless, transparent liquid in 75% yield.
The structural characterization data for the product are:1H NMR(600MHz,(CD3)2SO)δ10.05(s,1H)7.51(d,1H,J＝6Hz),7.05(d,1H,JH-F＝3Hz),7.05(t,1H,JH-F＝108Hz),6.90-6.88(m,1H)；13C NMR(150MHz,(CD3)2SO)δ109.09(t,JC-F＝12Hz),144.41(t,JC-F＝471Hz),144.48(t,JC-F＝13.5Hz),120.35,133.80(t,JC-F＝45Hz),134.72,157.72；19F NMR(564MHz,(CD3)2SO)δ– 114.29(d,2F,J＝56.4Hz).
it is inferred that the product has the following structure and is 4-bromo-3-difluoromethylphenol (Br-CHF)2)。
Figure BDA0002383048540000241
(2) Synthesis of 4- ((4-bromo-3- (difluoromethyl) phenoxy) difluoromethyl) -4 '-propyl-1, 1' -bis (cyclohexane) (3CCBr-4)
Trans-4- (trans-4-n-propylcyclohexyl) cyclohexanecarboxylic acid 3CCA (1.584g, 0.0071mol) (structure
Figure BDA0002383048540000242
) Toluene (10mL), isooctane (10mL) and 1, 3-propanedithiol (0.7mL, 0.0071mol) were added to a dry 100mL two-necked round-bottomed flask. The mixture was stirred at 50 ℃ for 1 hour, and trifluoromethanesulfonic acid (0.6mL, 0.0071mol) was slowly added dropwise to the reaction solution using a dropping funnel. Heated to 102 ℃ and 105 ℃, and then refluxed and water-separated for about 4 hours. After the water separation is finished, the solvent is removed by reduced pressure distillation, 20mL of dehydrated dichloromethane solution is added to obtain the dichloromethane solution of the disulfite (3CCB), and the whole reaction process is protected by nitrogen. Subsequently, 4-bromo-3-difluoromethylphenol (1.4g, 0.0059mol), triethylamine (4.1mL, 0.0295mol), and 20mL of the dehydrated dichloromethane solution were added to a 250mL dry single-neck round-bottom flask, and the temperature was lowered to-78 deg.C, and then the dithionium salt (3CCB) in dichloromethane was slowly dropped into the reaction flask (30min), and reacted for 3 hours. Et was then added dropwise over 30 minutes3N.3HF (9.6mL, 0.059mol), NBS (10.50g, 0.059mol) dissolved in dichloromethane solution is dripped for 1 hour, then the reaction is carried out for 3 hours, the reaction solution is stirred at room temperature overnight, the reaction solution is poured into 30% sodium hydroxide solution with ice blocks, and the pH value is adjusted to 7-8. The mixture was extracted with dichloromethane three times, washed with saturated brine, and the organic layer was collected and dried over anhydrous sodium sulfate.Finally, column chromatography is carried out by using petroleum ether to obtain a white solid with the yield of 58 percent.
The structural characterization data for the product are:1H NMR(600MHz,CDCl3)δ7.58(d,1H,J＝12Hz),7.47(d,1H,JH-F＝6Hz),7.21-7.19(dd,1H,JH-F＝2.4Hz,J＝9Hz),6.88(t,1H,JH-F＝108Hz),2.07-2.00(m,3H),1.87(d,2H,J＝12Hz),1.79-1.73(dd,4H,J＝12Hz,24Hz),1.42-1.28(m,6H),1.17(t,3H,J＝12Hz),1.12-0.97(m,6H),0.90(t,3H,J＝12Hz)；13C NMR(150MHz,CDCl3)δ150.25,134.29(t,JC-F＝46.5Hz),133.95,125.88(t,JC-F＝537Hz),125.35,120.64(t, JC-F＝12Hz),117.08(t,JC-F＝12Hz),113.28(t,JC-F＝475.5Hz),43.76(t,JC-F＝51Hz),42.67, 37.60,30.05,28.78,25.78,20.06,14.45；19F NMR(564MHz,CDCl3)δ-78.27(d,2F,J＝11.28 Hz),-115.08(d,2F,JF-H＝56.4Hz)；LRMS(EI)m/z:478(M)+；ElementalAnalysis:C,57.90；H, 7.07.
it is concluded therefrom that the product has the following structure, 4- ((4-bromo-3- (difluoromethyl) phenoxy) difluoromethyl) -4 '-propyl-1, 1' -bis (cyclohexane)
Figure BDA0002383048540000251
(3)4', 4' - (((2,2 '-bis (difluoromethyl) - [1,1' -biphenyl)]-4,4 '-diyl) bis (oxy)) bis (difluoromethylene)) bis (4-propyl-1, 1' -bis (cyclohexane)) (C3-CF2O-CHF2) Synthesis of (2)
Mixing the product 3CCBr-4(0.49g, 0.0010mol) in the step (2), pinacol ester diboron (0.13g, 0.00051mol) and PdCl2(dppf)2(0.030g, 4% mol) and potassium carbonate (0.426g, 0.0031mol) were dissolved in DMSO, heated to 100 ℃ and reacted for 12 hours. After cooling, the mixture was filtered, extracted with dichloromethane, washed with water, and dried over anhydrous sodium sulfate. Finally, column chromatography is carried out by using petroleum ether to obtain a white solid with the yield of 35 percent.
The structural characterization data for the product are:1H NMR(600MHz,CDCl3)δ7.54(s,2H),7.34(d,2H,J＝12Hz),7.21(d,2H,J＝6Hz),6.27(t,2H,JH-F＝108Hz),2.09-2.03(m,6H),1.87(d,4H,J＝12Hz),1.78-1.72(dd,8H,J＝12Hz,24Hz),1.43-1.25(m,12H),1.15(t,,6H,J＝12Hz),1.09-0.99(m,12H),0.88(t,,6H,J＝12Hz)；13C NMR(150MHz,CDCl3)δ151.25,134.24(t,JC-F＝45Hz),133.10(t,JC-F＝537Hz),132.13,126.23(t,JC-F＝535.5Hz),123.42,118.89(t, JC-F＝10.5Hz),112.46(t,JC-F＝474Hz),44.07(t,JC-F＝51Hz),42.91,37.81,30.27,29.02, 26.03,20.28,14.67；19F NMR(564MHz,CDCl3)δ-78.27(d,4F,J＝5.64Hz),-108.22(d,1F, JF-H＝13.5Hz),-108.76(d,1F,JF-H＝15Hz),-112.78(d,1F,JF-H＝15Hz),-113.32(d,1F,JF-H＝15Hz)；LRMS(EI)m/z:798(M)+；Elemental Analysis:C,69.11；H,8.18.
the structure of the product was deduced as follows, 4' - (((2,2' -bis (difluoromethyl) - [1,1' -biphenyl)]-4,4 '-diyl) bis (oxy)) bis (difluoromethylene)) bis (4-propyl-1, 1' -bis (cyclohexane)) (C3-CF2O-CHF2)。
Figure BDA0002383048540000261
Example 8
4', 4' - (((2,2 '-bis (difluoromethyl) - [1,1' -biphenyl)]-4,4 '-diyl) bis (oxy)) bis (difluoromethylene)) bis (4-pentyl-1, 1' -bis (cyclohexane)) (C5-CF2O-CHF2) The synthesis comprises the following steps:
(1) 4-bromo-3-difluoromethylphenol (Br-CHF)2) Synthesis of (2)
Adding 5-hydroxy-2-bromobenzaldehyde (2g, 0.0093mol) into a 100mL two-neck round-bottom flask, vacuumizing, replacing nitrogen, adding 40mL dichloromethane, adding DAST (2.1mL, 0.0158mol) into the reaction system, reacting for 12h, quenching with saturated sodium bicarbonate solution until no bubble appears, extracting with dichloromethane, washing with water, drying with anhydrous sodium sulfate, and adding petroleum ether: column chromatography of ethyl acetate (V: V ═ 20:1) gave a colorless, transparent liquid in 75% yield.
The structural characterization data for the product are:1H NMR(600MHz,(CD3)2SO)δ10.05(s,1H)7.51(d,1H,J＝6Hz),7.05(d,1H,JH-F＝3Hz),7.05(t,1H,JH-F＝108Hz),6.90-6.88(m,1H)；13C NMR(150MHz,(CD3)2SO)δ109.09(t,JC-F＝12Hz),144.41(t,JC-F＝471Hz),144.48(t,JC-F＝13.5Hz),120.35,133.80(t,JC-F＝45Hz),134.72,157.72；19F NMR(564MHz,(CD3)2SO)δ– 114.29(d,2F,J＝56.4Hz).
it is inferred that the product has the following structure and is 4-bromo-3-difluoromethylphenol (Br-CHF)2)。
Figure BDA0002383048540000271
(2) Synthesis of 4- ((4-bromo-3- (difluoromethyl) phenoxy) difluoromethyl) -4 '-pentyl-1, 1' -bis (cyclohexane) (5CCBr-4)
Trans-4- (trans-4-n-pentylcyclohexyl) cyclohexanecarboxylic acid 5CCA (1.991g, 0.0071mol) (structure
Figure BDA0002383048540000272
) Toluene (10mL), isooctane (10mL) and 1, 3-propanedithiol (0.7mL, 0.0071mol) were added to a dry 100mL two-necked round-bottomed flask. The mixture was stirred at 50 ℃ for 1 hour, and trifluoromethanesulfonic acid (0.6mL, 0.0071mol) was slowly added dropwise to the reaction solution using a dropping funnel. Heated to 102 ℃ and 105 ℃, and then refluxed and water-separated for about 4 hours. After the water separation is finished, the solvent is removed by reduced pressure distillation, 20mL of dehydrated dichloromethane solution is added to obtain the dichloromethane solution of the disulfite (5CCB), and the whole reaction process is protected by nitrogen. Subsequently, 4-bromo-3-difluoromethylphenol (1.4g, 0.0059mol), triethylamine (4.1mL, 0.0295mol), and 20mL of the dehydrated dichloromethane solution were added to a 250mL dry single-neck round-bottom flask, and the temperature was lowered to-78 deg.C, and then the disulfide salt (5CCB) in dichloromethane was slowly added dropwise to the reaction flask (30min), and reacted for 3 hours. Et was then added dropwise over 30 minutes3N·3HF(9.6mL，0.059mol), then adding NBS (10.50g, 0.059mol) dissolved in dichloromethane solution dropwise for 1 hour, then reacting for 3 hours, stirring the reaction solution at room temperature overnight, pouring the reaction solution into 30% sodium hydroxide solution with ice blocks, and adjusting the pH value to 7-8. The mixture was extracted with dichloromethane three times, washed with saturated brine, and the organic layer was collected and dried over anhydrous sodium sulfate. Finally, column chromatography is carried out by using petroleum ether to obtain a white solid with the yield of 55 percent.
The structural characterization data for the product are:1H NMR(600MHz,CDCl3)δ7.58(d,1H,J＝12Hz),7.46(d,1H,JH-F＝6Hz),7.20-7.19(m,1H),6.88(t,1H,JH-F＝108Hz),2.07-2.00(m,3H),1.87(d,2H,J＝12Hz),1.80-1.73(dd,4H,J＝12Hz,30Hz),1.42-1.25(m,9H),1.17(t,3H,J＝12Hz),1.09-0.97(m,7H),0.91(t,3H,J＝18Hz)；13C NMR(100MHz,CDCl3)δ150.18,134.22(t, JC-F＝58Hz),133.87,125.81(t,JC-F＝537Hz),125.28,120.53(t,JC-F＝7Hz),117.02(t,JC-F＝13Hz),113.21(t,JC-F＝476Hz),43.71(t,JC-F＝51Hz),42.62,37.41,32.21,30.00,28.73,26.64,25.72,22.69,14.10；19F NMR(564MHz,CDCl3)δ-78.26(d,2F,J＝11.28Hz), -115.07(d,2F,JF-H＝56.4Hz)；LRMS(EI)m/z:506(M)+；Elemental Analysis:C,59.03；H, 6.95.
it is concluded therefrom that the product has the following structure, 4- ((4-bromo-3- (difluoromethyl) phenoxy) difluoromethyl) -4 '-pentyl-1, 1' -bis (cyclohexane) (5 CCBr-4).
Figure BDA0002383048540000281
(3)4', 4' - (((2,2 '-bis (difluoromethyl) - [1,1' -biphenyl)]-4,4 '-diyl) bis (oxy)) bis (difluoromethylene)) bis (4-pentyl-1, 1' -bis (cyclohexane)) (C5-CF2O-CHF2) Synthesis of (2)
Mixing the product 5CCBr-4(0.54g, 0.00106mol) in the step (2), pinacol ester diboron (0.135g, 0.000532mol), PdCl2(dppf)2(0.031g, 4 mol%) and potassium carbonate (0.441g, 0.0032mol) are dissolved in DMSO, heated to 100 deg.CAnd reacting for 12 hours. After cooling, the mixture was filtered, extracted with dichloromethane, washed with water, and dried over anhydrous sodium sulfate. Finally, column chromatography is carried out by using petroleum ether to obtain a white solid with the yield of 39%.
The structural characterization data for the product are:1H NMR(400MHz,CDCl3)δ7.54(s,2H),7.33(d,2H,J＝8Hz),7.20(d,2H,J＝8Hz),6.26(t,2H,JH-F＝112Hz),2.09-2.02(m,6H),1.87(d,4H,J＝8Hz),1.75(t,8H,J＝28Hz),1.45-1.23(m,18H),1.15-0.95(m,20H),0.88(t,6H,J＝12Hz)；13C NMR(100MHz,CDCl3)δ150.99,134.01(t,JC-F＝44Hz),132.84(t,JC-F＝12Hz),131.83,125.95(t,JC-F＝537Hz),123.10,118.60(t,JC-F＝11Hz),112.18(t,JC-F＝473Hz),43.84(t,JC-F＝52Hz),42.67,37.45,32.24,30.03,28.78,26.68,25.78,22.71,14.09；19F NMR(376MHz, CDCl3)δ-78.22(d,4F,J＝7.52Hz),-107.98(d,1F,JF-H＝56.4Hz),-108.79(d,1F,JF-H＝ 56.4Hz),-112.59(d,1F,JF-H＝56.4Hz),-113.40(d,1F,JF-H＝56.4Hz)；LRMS(EI)m/z: 854.5(M)+；Elemental Analysis:C,70.17；H,8.30.
the structure of the product was deduced as follows, 4' - (((2,2' -bis (difluoromethyl) - [1,1' -biphenyl)]-4,4 '-diyl) bis (oxy)) bis (difluoromethylene)) bis (4-pentyl-1, 1' -bis (cyclohexane)) (C5-CF2O-CHF2)。
Figure BDA0002383048540000291
Example 9
The products of examples 1 to 8 were tested for their phase transition temperature by means of a Differential Scanning Calorimetry (DSC). The results are as follows:
as shown in FIG. 1, the product of example 1, 4' -bis (difluoro (4' -propyl [1,1' -bis (cyclohexane) ]]-4-yl) methoxy) -1,1' -biphenyl (C)3-CF2O — H) the temperature for transition from the crystalline phase to the liquid crystal phase was 136.6 ℃, the temperature for transition to the smectic phase C was 214.1 ℃, the temperature for transition to the smectic phase G was 224.9 ℃ and the temperature for transition to the anisotropic liquid was 230.7 ℃.
As shown in FIG. 2, the product of example 2, 4' -bis (difluoro (4' -pentyl [1,1' -bis (cyclohexane) ]]-4-yl) methoxy) -1,1' -biphenyl (C)5-CF2O — H) the temperature for transition from the crystalline phase to the liquid crystal phase was 138.1 deg.c, the temperature for transition to the smectic phase C was 212.3 deg.c, the temperature for transition to the smectic phase G was 226.8 deg.c, and the temperature for transition to the anisotropic liquid was 236.9 deg.c.
As shown in FIG. 3, the product 4', 4' - (((2,2 '-difluoro- [1,1' -biphenyl) of example 3]-4,4 '-diyl) bis (oxy)) bis (difluoromethylene)) bis (4-propyl-1, 1' -bis (cyclohexane)) (C3-CF2O-F) the temperature at which the crystal phase was transformed into the liquid crystal phase was 127.2 ℃ and the temperature at which the smectic phase B was transformed into the smectic phase was 136.1 ℃ and the temperature at which the smectic liquid was transformed into the anisotropic liquid was 151.9 ℃.
As shown in FIG. 4, the product of example 4,4' - (((2,2' -difluoro- [1,1' -biphenyl), is]-4,4 '-diyl) bis (oxy)) bis (difluoromethylene)) bis (4-pentyl-1, 1' -bis (cyclohexane)) (C5-CF2O-F) the temperature at which the crystal phase was transformed into the liquid crystal phase was 111.2 ℃ and the temperature at which the crystal phase was transformed into the anisotropic liquid was 130.9 ℃.
As shown in FIG. 5, the product of example 5, 4' - (((2,2' -bis (monofluoromethyl) - [1,1' -biphenyl), is]-4,4 '-diyl) bis (oxy)) bis (difluoromethylene)) bis (4-pentyl-1, 1' -bis (cyclohexane)) (C3-CF2O-CH2F) The temperature at which the crystal phase was transformed into the liquid crystal phase was 125.6 deg.C, the temperature at which the smectic phase B was transformed into the smectic phase was 215.6 deg.C, and the temperature at which the smectic phase B was transformed into the anisotropic liquid was 251.1 deg.C.
As shown in FIG. 6, the product of example 6, 4' - (((2,2' -bis (monofluoromethyl) - [1,1' -biphenyl), is]-4,4 '-diyl) bis (oxy)) bis (difluoromethylene)) bis (4-pentyl-1, 1' -bis (cyclohexane)) (C5-CF2O-CH2F) The temperature for transition from the crystalline phase to the other was 139.2 ℃, the temperature for transition to the smectic B was 218.2 ℃ and the temperature for transition to the isotropic liquid was 319.4 ℃.
As shown in FIG. 7, the product of example 7, 4' - (((2,2' -bis (difluoromethyl) - [1,1' -biphenyl), was]-4,4 '-diyl) bis (oxy)) bis (difluoromethylene)) bis (4-propyl-1, 1' -bis (cyclohexane)) (C3-CF2O-CHF2) The temperature for transition from the crystalline phase to the liquid crystalline phase was 138.4 ℃ and the temperature for transition to the anisotropic liquid was 187.3 ℃.
As shown in FIG. 8, the product of example 8, 4' - (((2,2' -bis (difluoromethyl) - [1,1' -biphenyl), was]-4,4 '-diyl) bis (oxy)) bis (difluoromethylene)) bis (4-pentyl-1, 1' -bis (cyclohexane)) (C5-CF2O-CHF2) The temperature for transition from the crystalline phase to the liquid crystalline phase was 185.7 ℃ and the temperature for transition to the anisotropic liquid was 277.5 ℃.
FIG. 9 is the product of example 1, 4' -bis (difluoro (4' -propyl [1,1' -bis (cyclohexane))]-4-yl) methoxy) -1,1' -biphenyl (C)3-CF2O-H) polarization microscope spectra (POM spectra); wherein a and b are POM diagrams of the compound at 204 ℃ and 225 ℃ respectively.
FIG. 10 is the product of example 2, 4' -bis (difluoro (4' -pentyl [1,1' -bis (cyclohexane) ]]-4-yl) methoxy) -1,1' -biphenyl (C)5-CF2O-H) polarization microscope spectra (POM spectra); wherein a and b are POM diagrams of the compound at 208 ℃ and 228 ℃ respectively.
FIG. 11 is the product 4', 4' - (((2,2 '-difluoro- [1,1' -biphenyl) of example 3]-4,4 '-diyl) bis (oxy)) bis (difluoromethylene)) bis (4-propyl-1, 1' -bis (cyclohexane)) (C3-CF2O-F) polarization microscope spectra (POM spectra); wherein a and b are POM diagrams of the compound at 140 ℃ and 148 ℃ respectively.
FIG. 12 is the product 4', 4' - (((2,2 '-difluoro- [1,1' -biphenyl) of example 4]-4,4 '-diyl) bis (oxy)) bis (difluoromethylene)) bis (4-pentyl-1, 1' -bis (cyclohexane)) (C5-CF2O-F) polarization microscope spectra (POM spectra); wherein a and b are POM graphs of the compound at 128 ℃ and 120 ℃ respectively.
FIG. 13 is the product 4', 4' - (((2,2 '-bis (monofluoromethyl) - [1,1' -biphenyl) of example 5]-4,4 '-diyl) bis (oxy)) bis (difluoromethylene)) bis (4-pentyl-1, 1' -bis (cyclohexane)) (C3-CF2O-CH2F) (ii) a polarizing microscope map (POM map); wherein a and b are POM diagrams of the compound at 220 ℃ and 245 ℃ respectively.
FIG. 14 is a block diagramThe product 4', 4' - (((2,2 '-bis (monofluoromethyl) - [1,1' -biphenyl) of example 6]-4,4 '-diyl) bis (oxy)) bis (difluoromethylene)) bis (4-pentyl-1, 1' -bis (cyclohexane)) (C5-CF2O-CH2F) (ii) a polarizing microscope map (POM map); wherein a and b are POM diagrams of the compound at 235 ℃ and 305 ℃ respectively.
FIG. 15 is the product 4', 4' - (((2,2 '-bis (difluoromethyl) - [1,1' -biphenyl) of example 7]-4,4 '-diyl) bis (oxy)) bis (difluoromethylene)) bis (4-propyl-1, 1' -bis (cyclohexane)) (C3-CF2O-CHF2) (ii) a polarizing microscope map (POM map); wherein a and b are POM diagrams of the compound at 180 ℃ and 185 ℃ respectively.
FIG. 16 is the product 4', 4' - (((2,2 '-bis (difluoromethyl) - [1,1' -biphenyl) of example 8]-4,4 '-diyl) bis (oxy)) bis (difluoromethylene)) bis (4-pentyl-1, 1' -bis (cyclohexane)) (C5-CF2O-CHF2) (ii) a polarizing microscope map (POM map); wherein a and b are POM diagrams of the compound at 260 ℃ and 270 ℃ respectively.
Example 10
The phase transition of the compound of the present invention was studied by a polarizing microscope, and the phase transition behavior occurring during the temperature increase and decrease was shown in table 1. Wherein Cr represents a crystal, N represents a nematic phase, SmB, SmC and SmG represent smectic phases B, C and G, respectively. Iso represents an isotropic liquid.
TABLE 1
Figure BDA0002383048540000321
Combining the DSC test results and polarization microscope characterization results of example 9 and example 10, it can be seen that the products of examples 1, 2, 3, 4, 5, 6, 7, 8 have a wide range of mesophase temperatures.
The results of phase transition studies on the compounds of the present invention in combination with table 1 show that all of the bis-difluoromethoxy-bridged biphenyl liquid crystal compounds substituted with a bis-fluoro group of the present invention are nematic. Such liquid crystal compounds have a very wide mesophase temperature range and a high clearing point.
The bis-difluoromethoxy bridged biphenyl liquid crystal compound substituted by the bis-fluorine-containing group has wide phase transition temperature. And the physical and liquid crystal properties of the biphenyl side chain can be effectively regulated and controlled by simply changing the groups of the biphenyl side chain. Although the series of compounds have the problem of relatively high melting point, the series of compounds can still be applied to compounding nematic phase mixtures as a main component for increasing the stability temperature of the nematic phase.
By combining various properties, the bifluoro-group-substituted bifluoromethoxybridged biphenyl liquid crystal compound has unique physical and liquid crystal properties, such as a very wide nematic phase temperature range, and can be used as a liquid crystal display material; can also be used as a liquid crystal component with high bright point, wide temperature and high dielectric constant, and can be added into mixed crystals to adjust the performance in the future.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (10)

1. A bis-difluoromethoxy bridged biphenyl liquid crystal compound substituted by a bis-fluorine-containing group is characterized by having a structure shown as a formula 1:
Figure FDA0002383048530000011
wherein n is 3 or 5, m is 1 or 2, R is H or F, CH2F、CHF2。
2. A method for preparing the bis-difluoromethoxy-bridged biphenyl liquid crystal compound substituted by the bis-fluoro group as claimed in claim 1, comprising the steps of:
1) adding 5-hydroxy-2-bromobenzaldehyde into a dry 100mL single-neck round-bottom flask, adding 40mL methanol, controlling the temperature to be 0 ℃, slowly adding sodium borohydride, and reacting for 2 hours to obtain 5-hydroxy-2-bromobenzaldehyde;
2) adding the 5-hydroxy-2-bromobenzyl alcohol obtained in the step 1) into a 100mL two-neck round-bottom flask, vacuumizing, replacing nitrogen, adding 30mL dichloromethane, adding diethylaminosulfur trifluoride into a reaction system, and reacting for 12h to obtain 4-bromo-3-monofluoromethylphenol;
3) adding the 5-hydroxy-2-bromobenzaldehyde obtained in the step 1) into a 100mL two-neck round-bottom flask, vacuumizing, replacing nitrogen, adding 30mL dichloromethane, adding diethylaminosulfur trifluoride into a reaction system, and reacting for 12h to obtain a product 4-bromo-3-difluoromethylphenol shown in a formula 1;
4) dissolving Br-R compound in dichloromethane, adding triethylamine, cooling to-78 deg.C, dropping the dichloromethane solution of disulfate into the above reaction solution, stirring for 3 hr, and dropping Et within 30min3N.3 HF, dropwise adding a dichloromethane solution containing NBS, reacting for 3 hours, moving the reaction solution to room temperature, reacting overnight, and obtaining a product 3CCBr-R and/or 5CCBr-R in the formula 2 after the reaction is finished;
5) 3CCBr-R and/or 5CCBr-R obtained in the step 4), pinacol ester diboron and PdCl2(dppf)2Dissolving potassium carbonate in dimethyl sulfoxide, heating to 100 ℃, and reacting for 12h to obtain the formula C3-CF2O-R/C5-CF2And O-R.
3. The method for preparing the bis-fluoro-group-substituted bis-difluoromethoxy-bridged biphenyl liquid crystal compound according to claim 2, wherein the mixing molar ratio of the 5-hydroxy-2-bromobenzaldehyde to the sodium borohydride in the step 1) is 1 (1-2).
4. The method for preparing bis-fluoro-substituted bis-difluoromethoxy-bridged biphenyl liquid crystal compounds according to claim 2, wherein the molar ratio of 5-hydroxy-2-bromobenzyl alcohol to diethylaminosulfur trifluoride in step 2) is 1: (1-2).
5. The method for preparing bis-fluoro-substituted bis-difluoromethoxy-bridged biphenyl liquid crystal compounds according to claim 2, wherein the molar ratio of 5-hydroxy-2-bromobenzaldehyde to diethylaminosulfur trifluoride in step 3) is 1: (1-2).
6. The method for preparing the bis-fluoro-group-substituted bis-difluoromethoxy-bridged biphenyl liquid crystal compound according to claim 2, wherein the structural formula of the Br-R compound in step 4) is shown as formula 2, and the structural formula of the dithionate is shown as formula 3:
Figure FDA0002383048530000021
7. the method for preparing the bis-fluoro-group-substituted bis-difluoromethoxy-bridged biphenyl liquid crystal compound according to claim 2, wherein the structural formula of 3CCBr-R and/or 5CCBr-R in step 4) is shown as formula 4:
Figure FDA0002383048530000031
8. the method for preparing bis (difluoromethoxy) bridged biphenyl liquid crystal compounds substituted with bis (fluoro-containing) groups according to claim 2, wherein the Br-R compound, disulfite, triethylamine, Et in step 4) is3The mixed molar ratio of N-3HF to NBS is 1: (1-2): (3-5): (9-11): (9-11).
9. The method for preparing bis (difluoromethoxy) bridged biphenyl liquid crystal compounds substituted with bis (fluoro) groups according to claim 2, wherein the 3CCBr-R and/or 5CCBr-R, pinacol ester diboron diborate, PdCl in step 5)2(dppf)2And the mixing molar ratio of the potassium carbonate is 1: (0.5-1): (1 mol% -10 mol%).
10. The bis-difluoromethoxy-bridged biphenyl liquid crystal compound substituted by the bis-fluoro group as claimed in claim 1, which is used for preparing liquid crystal display materials.
CN202010088931.7A 2020-02-12 2020-02-12 Bis-difluoromethoxy bridged biphenyl liquid crystal compound substituted by bis-fluorine-containing group as well as preparation method and application thereof Pending CN111286343A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101827805A (en) * 2007-09-10 2010-09-08 智索株式会社 Liquid crystalline compound, liquid crystal composition, and liquid crystal display element
CN105130767A (en) * 2015-09-02 2015-12-09 石家庄诚志永华显示材料有限公司 Liquid crystal compound containing methylbenzene and difluoro methyleneoxy linking group and preparing method and application thereof
CN106675577A (en) * 2017-01-04 2017-05-17 陕西师范大学 Biphenyl liquid crystal compound containing pyridine end group and preparation method and application thereof
CN107406407A (en) * 2015-02-17 2017-11-28 捷恩智株式会社 Compound, liquid-crystal composition and liquid crystal display cells with alkoxy or alkoxyalkyl and the yuan of rings of saturation 6

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101827805A (en) * 2007-09-10 2010-09-08 智索株式会社 Liquid crystalline compound, liquid crystal composition, and liquid crystal display element
CN107406407A (en) * 2015-02-17 2017-11-28 捷恩智株式会社 Compound, liquid-crystal composition and liquid crystal display cells with alkoxy or alkoxyalkyl and the yuan of rings of saturation 6
CN105130767A (en) * 2015-09-02 2015-12-09 石家庄诚志永华显示材料有限公司 Liquid crystal compound containing methylbenzene and difluoro methyleneoxy linking group and preparing method and application thereof
CN106675577A (en) * 2017-01-04 2017-05-17 陕西师范大学 Biphenyl liquid crystal compound containing pyridine end group and preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
胡思前等编: "《有机化学》", 31 December 2015, 同济大学出版社 *

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